Ultrastructure of selected struvite-containing urinary calculi from cats.

PubMed

Neumann, R D; Ruby, A L; Ling, G V; Schiffman, P S; Johnson, D L

1996-01-01

To elucidate the ultrastructural details of struvite-containing urinary calculi from cats. Specimens studied were inclusive of the range of textures visible during preliminary analysis by use of a stereoscopic dissecting microscope. Textural types, which were used to infer crystal growth conditions, were differentiated with regard to crystal habit, crystal size, growth orientation, and primary porosity. Thirty specimens were selected from a collection of approximately 1,600 feline urinary calculi: 20 of these were composed entirely of struvite, and 10 consisted of struvite and calcium phosphate (apatite). Qualitative and quantitative analyses of specimens included use of plain and polarized light microscopy, x-ray diffractometry, scanning electron microscopy with backscattered electron imagery, x-ray fluorescence scans, and electron probe microanalysis. Four textural types were recognized among struvite calculi, whereas 2 textural types of struvite-apatite calculi were described. The presence of minute, well interconnected primary pores in struvite-containing urinary calculi from cats is an important feature, which may promote possible interaction of calculi with changes in urine composition. Primary porosity, which can facilitate interaction between the calculus and changing urine composition, may explain the efficacy of dietary or medicinal manipulations to promote the dissolution of struvite-containing uroliths from this species.

Amelogenin as a promoter of nucleation and crystal growth of apatite

NASA Astrophysics Data System (ADS)

Uskoković, Vuk; Li, Wu; Habelitz, Stefan

2011-02-01

Human dental enamel forms over a period of 2-4 years by substituting the enamel matrix, a protein gel mostly composed of a single protein, amelogenin with fibrous apatite nanocrystals. Self-assembly of amelogenin and the products of its selective proteolytic digestion are presumed to direct the growth of apatite fibers and their organization into bundles that eventually comprise the mature enamel, the hardest tissue in the mammalian body. This work aimed to establish the physicochemical and biochemical conditions for the growth of apatite crystals under the control of a recombinant amelogenin matrix (rH174) in combination with a programmable titration system. The growth of apatite substrates was initiated in the presence of self-assembling amelogenin particles. A series of constant titration rate experiments was performed that allowed for a gradual increase of the calcium and/or phosphate concentrations in the protein suspensions. We observed a significant amount of apatite crystals formed on the substrates following the titration of rH174 sols that comprised the initial supersaturation ratio equal to zero. The protein layers adsorbed onto the substrate apatite crystals were shown to act as promoters of nucleation and growth of calcium phosphates subsequently formed on the substrate surface. Nucleation lag time experiments have showed that rH174 tends to accelerate precipitation from metastable calcium phosphate solutions in proportion to its concentration. Despite their mainly hydrophobic nature, amelogenin nanospheres, the size and surface charge properties of which were analyzed using dynamic light scattering, acted as a nucleating agent for the crystallization of apatite. The biomimetic experimental setting applied in this study proves as convenient for gaining insight into the fundamental nature of the process of amelogenesis.

Time and the crystallization of apatite in seawater

USGS Publications Warehouse

Gulbrandsen, R.A.; Roberson, C.E.; Neil, S.T.

1984-01-01

Carbonate fluorapatite has been synthesized in seawater in an experiment of nearly 10-years duration. The addition of phosphate to seawater whose fluoride concentration had been increased to 7.6 mg/l brought about an initial amorphous phosphate precipitate. After 20 months, a crystalline magnesium phosphate phase developed within the amorphous phosphate. Crystallization of apatite, which occurred during the last 3 years of the experiment, was accompanied by dissolution of the crystalline magnesium phosphate phase. The MgO content of the apatite (1.9 percent) is high in comparison to Tertiary and older apatite but similar to some young apatite; the CO2 content (3.6 percent) is medium, and the fluorine content (2.2 percent) is low but again similar to some young apatite. The hydroxyl ion (OH-) likely fills the need for additional fluorine-position atoms. The mole ratio of Ca plus substituent elements to P plus substituent elements (1.50) is low in comparison to the expected ratio of 1.67. The substitution of the hydronium ion (H3O+) for Ca may account for this difference. The synthesis of apatite in seawater demonstrates that the factor of time overcomes the well known inhibiting effect of magnesium upon the crystallization of apatite. It also implies that given an adequate supply of phosphate, apatite can form in most ocean environments and likely plays a major pan in the control of the phosphate content of seawater. ?? 1984.

Polycrystalline apatite synthesized by hydrothermal replacement of calcium carbonates

NASA Astrophysics Data System (ADS)

Kasioptas, Argyrios; Geisler, Thorsten; Perdikouri, Christina; Trepmann, Claudia; Gussone, Nikolaus; Putnis, Andrew

2011-06-01

Aragonite and calcite single crystals can be readily transformed into polycrystalline hydroxyapatite pseudomorphs by hydrothermal treatment in a (NH 4) 2HPO 4 solution. Scanning electron microscopy of the reaction products showed that the transformation of aragonite to apatite is characterised by the formation of a sharp interface between the two phases and by the development of intracrystalline porosity in the hydroxyapatite phase. In addition, electron backscattered diffraction (EBSD) imaging showed that the c-axis of apatite is predominantly oriented perpendicular to the reaction front with no crystallographic relationship to the aragonite lattice. However, the Ca isotopic composition of the parent aragonite, measured by thermal ionization mass spectrometry was inherited by the apatite product. Hydrothermal experiments conducted with use of phosphate solutions prepared with water enriched in 18O (97%) further revealed that the 18O from the solution is incorporated in the product apatite, as measured by micro-Raman spectroscopy. Monitoring the distribution of 18O with Raman spectroscopy was possible because the incorporation of 18O in the PO 4 group of apatite generates four new Raman bands at 945.8, 932, 919.7 and 908.8 cm -1, in addition to the ν1(PO 4) symmetric stretching band of apatite located at 962 cm -1, which can be assigned to four 18O-bearing PO 4 species. The relative intensities of these bands reflect the 18O content in the PO 4 group of the apatite product. By using equilibrated and non-equilibrated solutions, with respect to the 18O distribution between aqueous phosphate and water, we could show that the concentration of 18O in the apatite product is linked to the degree of 18O equilibration in the solution. The textural and chemical observations are indicative of a coupled mechanism of aragonite dissolution and apatite precipitation taking place at a moving reaction interface.

Adaptation of BAp crystal orientation to stress distribution in rat mandible during bone growth

NASA Astrophysics Data System (ADS)

Nakano, T.; Fujitani, W.; Ishimoto, T.; Umakoshi, Y.

2009-05-01

Biological apatite (BAp) c-axis orientation strongly depends on stress distribution in vivo and tends to align along the principal stress direction in bones. Dentulous mandible is subjected to a complicated stress condition in vivo during chewing but few studies have been carried out on the BAp c-axis orientation; so the adaptation of BAp crystal orientation to stress distribution was examined in rat dentulous mandible during bone growth and mastication. Female SD rats 4 to 14 weeks old were prepared, and the bone mineral density (BMD) and BAp crystal orientation were analyzed in a cross-section of mandible across the first molar focusing on two positions: separated from and just under the tooth root on the same cross-section perpendicular to the mesiodistal axis. The degree of BAp orientation was analyzed by a microbeam X-ray diffractometer using Cu-Kα radiation equipped with a detector of curved one-dimensional PSPC and two-dimensional PSPC in the reflection and transmission optics, respectively. BMD quickly increased during bone growth up to 14 weeks, although it was independent of the position from the tooth root. In contrast, BAp crystal orientation strongly depended on the age and the position from the tooth root, even in the same cross-section and direction, especially along the mesiodistal and the biting axes. With increased biting stress during bone growth, the degree of BAp orientation increased along the mesiodistal axis in a position separated from the tooth root more than that near the tooth root. In contrast, BAp preferential alignment clearly appeared along the biting axis near the tooth root. We conclude that BAp orientation rather than BMD sensitively adapts to local stress distribution, especially from the chewing stress in vivo in the mandible.

Sulfur-in-apatite: An indicator of the volatile evolution during lunar magmatism

NASA Astrophysics Data System (ADS)

Konecke, B.; Fiege, A.; Simon, A. C.; Holtz, F.

2017-12-01

The volatile content of lunar magmas remains controversial despite nearly five decades of interrogating samples from the NASA Apollo missions. Recently, the mineral apatite in lunar mare basalts has been investigated owing to its potential to constrain the volatile (F, Cl, H, S) budget of magmas [1-3]. The F-Cl-H signatures of lunar apatite were interpreted to record fractional crystallization, with nucleation and growth of apatite from a late-stage, interstitial, nearly anhydrous (<10 μg/g H2O), rhyolitic melt that evolved from a sulfide-undersaturated mare basalt [1]. The enigmatic S signature reported for those apatite grains was not interpreted due to the absence of published thermodynamic (partitioning) data for S. Here, we report new experimentally determined apatite/melt partition coefficients for S (DSap/m) at conditions applicable to lunar systems. The DSap/m values and thermodynamically modeled S content (XS) of lunar residual melt were used to constrain plausible S contents of lunar apatite produced by crystal fractionation (Sap = XS * DSap/m). Our results demonstrate that apatite crystallizing under lunar-like conditions from rhyolitic melt cannot obtain the reported 430 μg/g of S [2] by fractional crystallization. The results indicate that 5-35x higher S contents than feasible in sulfide-undersaturated, hydrous and dry rhyolitic melt, respectively, would be required to support crystal fractionation models [1]. Even elevated water concentrations in a sulfide-saturated rhyolitic melt cannot explain the S contents of lunar apatite rims. We propose two plausible scenarios: (A) The necessary concentration of S in rhyolitic melts may be achieved at >5 orders of magnitude higher fO2 (>ΔFMQ+1.2) than reported for lunar magmas, where S6+ is the prevalent oxidation state of S in rhyolitic melt, related to the significant degassing and preferential loss of H2 that drives oxidation of the residual melt [4]. (B) The volatile (F-Cl-H-S) signatures of lunar apatites may reflect cryptic metasomatic reactions between apatite and a S-Cl-rich, F-poor volatile phase released by underlying magma reservoirs. [1] Boyce et at., 2014, Science 344:400-402. [2] Greenwood et al., 2011, Nat. Geosci 4:79-82. [3] Webster et al., 2009, Geochim. Cosmochim. Acta 73, 559-581. [4] McCanta et al., 2017, Icarus 285, 95-102.

The Perils of Electron Microprobe Analysis of Apatite

NASA Astrophysics Data System (ADS)

Henderson, C. E.; Essene, E. J.; Wang, K. L.; Zhang, Y.

2010-12-01

Accurate electron microprobe analysis of apatite is problematic, especially for F and Cl, whose concentrations are essential in calculating a non-analyzable OH component. The issues include beam-induced sample damage and temporal variation of F and Cl X-rays; both effects are mainly dependent on beam current, beam spot size and apatite orientation [1]. To establish a rigorous analytical procedure, several oriented apatite samples, including the well-known Durango and Wilberforce fluorapatites, were analyzed for a large suite of elements, including oxygen. Careful X-ray spectroscopy was performed, including selection of appropriate analytical standards, background measurement positions and comparison of area peak factors. Polarized infrared spectra on oriented apatite samples were also collected for complementary information. The results show that when apatite samples are oriented with the c-axis parallel to the electron beam, there is significant nonlinear variation (an increase or decrease, depending on measurement conditions) of F and Cl X-ray intensities during analyses, and systematically higher-than-expected F apparent concentrations, despite the careful selection of electron beam conditions from a series of X-ray time scans and zero-time count rate extrapolation. On the other hand, when the electron beam is oriented perpendicular to the c-axis, with a ≤ 15 nA beam current and a ≥ 5 µm diameter defocused beam, F and Cl X-ray intensities do not vary or vary slowly and predictably with time, yielding quantitative analysis results for the Durango and Wilberforce apatites (both containing little OH) which are in good agreement with published wet chemical analyses. Furthermore, the OH and CO2 contents inferred for three other analyzed apatite samples are roughly consistent with infrared analyses. For example, for an apatite from Silver Crater Mine in Ontario, significant deficiency in the P site, as well as extra F, was inferred from microprobe analyses. Infrared spectra show a strong band of (CO3)2- for this apatite, which indicates a possible substitution of (CO3)2-(F)- for (PO4)3-. Other techniques to mitigate temporal variation of F and Cl, including alternative metal coatings, concurrent stage movement, and cryogenic sample-cooling were attempted, but did not eliminate the disparity in measured F concentrations between the two sample orientations. Thus, we believe that F measurements on F-rich apatite samples of unknown orientation are immediately suspect and should be regarded as upper limits of true F concentration. X-ray mapping, CL imaging and subsequent quantitative analyses show compositional variations in Na, S, Si, and REE in the Durango and Wilberforce fluorapatite samples used in this study. Problems of electron beam sensitivity, X-ray intensity anisotropy due to sample orientation, and compositional heterogeneity call into question their continued use as routine microanalysis reference materials. Microanalysts are encouraged to use more robust calibration standards, such as Cl-rich or other F-poor apatites for Ca, P, O and Cl, and MgF2 for F measurements. [1] Stormer, J.C., Pierson, M.L, and Tacker, R.C. (1993) Variation of F and Cl X-ray intensity due to anisotropic diffusion in apatite during electron microprobe analysis. Am. Min., 78, 641-648.

Magnetite-apatite mineralization in Khanlogh iron deposit, northwest of Neyshaboor, NE Iran

NASA Astrophysics Data System (ADS)

Najafzadeh Tehrani, Parvin; Asghar Calagari, Ali; Velasco Roldan, Francisco; Simmonds, Vartan; Siahcheshm, Kamal

2016-04-01

Khanlogh iron deposit lies on Sabzehvar-Ghoochan Cenozoic magmatic belt in northwest of Neyshaboor, NE Iran. The lithologic units in this area include a series of sub-volcanic intrusive rocks like diorite porphyry, quartz-diorite porphyry, and micro-granodiorite of Oligocene age. Mineralization in this area occurred as veins, dissemination, and open space filling in brecciated zones within the host sub-volcanic intrusive bodies. Three distinct types of mineral associations can be distinguished, (1) diopside-magnetite, (2) magnetite-apatite, and (3) apatite-calcite. Microscopic examinations along with SEM and EPMA studies demonstrated that magnetite is the most common ore mineral occurring as solitary crystals. The euhedral magnetite crystals are accompanied by lamellar destabilized ilmenite and granular fluorapatite in magnetite-apatite ores. The results of EPMA revealed that the lamellar ilmenite, relative to host magnetite crystal, is notably enriched in MgO and MnO (average of 3.3 and 2.6 wt%, respectively; n=5), whereas magnetite is slighter enriched in Ti (TiO2 around 1.8 wt%) being average of MgO, MnO and V2O3 of 0.6wt%, 0.2wt%, and 0.6 wt% (respectively; n=20). Minerals such as chlorapatite, calcite, and chalcedony are also present in the magnetite-apatite ores. The samples from apatite-calcite ores contain coarse crystals of apatite and rhomboedral calcite. The plot of the EPMA data of Khanlogh iron ore samples on diagram of TiO2-V2O5 (Hou et al, 2011) illustrated that the data points lies between the well-known Kiruna and El Laco (Chile) iron deposits. The magnetite crystals in the sub-volcanic host rocks were possibly formed by immiscible iron oxide fluids during magmatic stage. However, the magnetite and apatite existing in the veins and breccia zones may have developed by high temperature hydrothermal fluids. Studies done by Purtov and Kotelnikova (1993) proved that the proportion of Ti in magnetite is related to fluoride complex in the hydrothermal fluids. The high fluorine content of the apatite at Khanlogh may testify to the presence of Ti-fluoride complex in the fluids. Formation of apatite crystals was concurrent with development of titanium lamellae in magnetite. The apatite possesses high REE content which is possibly associated with monazite inclusions. The SEM studies better show these inclusions are occasionally present at the margin of apatite crystals and veins. Based upon field relations, microscopic examinations, and the results of XRD analyses, sodic (albite), propylitic (epidote, chlorite, calcite), and argillic (montmorillonite) alterations are developed in the study area. The principal minerals in these alteration zones are albite, epidote, sericite, chlorite, quartz, calcite, and montmorllonite. Mineralogy, alteration, geochemistry, structure, and texture of the ores at Khanlogh indicate that the magnetite and apatite were chiefly formed by hydrothermal solutions which were enriched in iron mainly transported by F- and Cl- rich fluids. Reference Hou,,T., Zhaochong, Z., Timothy, K., (2011). Gushan magnetite-apatite deposit in the Ningwu basin, Lower Yangtze River Valley, SE China: Hydrothermal or Kiruna-type? Ore geology review, 43, 333-346. Purtov, V.K., Kotelnikova, A.L. (1993). Solubility of titanium in chloride and fluoride hydrothermal solution. International Geology Review 35, 274 -287.

Raman study of apatite amorphised with swift heavy ions under various irradiation conditions

NASA Astrophysics Data System (ADS)

Weikusat, Christian; Glasmacher, Ulrich A.; Schuster, Beatrice; Trautmann, Christina; Miletich, Ronald; Neumann, Reinhard

2011-04-01

Crystallographically oriented Durango fluorapatites were exposed to swift heavy ions (Xe, Ta, Au, U) at different irradiation conditions. Beam-induced sample modifications were investigated with respect to the effect of fluence (109-1013 ions/cm2), electronic energy loss (18-27 keV/nm), and pressure (3.6-11.5 GPa) applied during irradiation. In situ high-pressure irradiation was performed in diamond anvil cells. Confocal Raman spectroscopy was used to trace the occurring changes in the crystal lattice. Fragmentation of the crystal specimen depends on the orientation and sample thickness and was found to scale with energy loss and fluence. The radiation damage for irradiation along the c-axis was found to be larger than for the < hk0> direction, independent of the confining pressure. Observations on samples irradiated at high pressures indicate a stabilising effect, leading to reduced amorphisation in comparison to the samples irradiated without pressure.

Altered self-assembly and apatite binding of amelogenin induced by N-terminal proline mutation

PubMed Central

Zhu, Li; Uskoković, Vuk; Le, Thuan; DenBesten, Pamela; Huang, Yulei; Habelitz, Stefan; Li, Wu

2012-01-01

Objective A single Pro-70 to Thr (p.P70T) mutation of amelogenin is known to result in hypomineralized amelogenesis imperfecta (AI). This study aims to test the hypothesis that the given mutation affects the self-assembly of amelogenin molecules and impairs their ability to conduct the growth of apatite crystals. Design Recombinant human full-length wild-type (rh174) and p.P70T mutated amelogenins were analyzed using dynamic light scattering (DLS), protein quantification assay and atomic force microscopy (AFM) before and after the binding of amelogenins to hydroxyapatite crystals. The crystal growth modulated by both amelogenins in a dynamic titration system was observed using AFM. Results As compared to rh174 amelogenin, p.P70T mutant displayed significantly increased sizes of the assemblies, higher binding affinity to apatite, and decreased crystal height. Conclusions Pro-70 plays an important structural role in the biologically relevant amelogenin self-assembly. The disturbed regularity of amelogenin nanospheres by this single mutation resulted in an increased binding to apatite and inhibited crystal growth. PMID:21081224

Fabrication of biporous low-crystalline apatite based on mannitol dissolution from apatite cement.

PubMed

Tajima, Shinya; Kishi, Yuji; Oda, Makoto; Maruta, Michito; Matsuya, Shigeki; Ishikawa, Kunio

2006-09-01

Biporous (macro- and microporous) calcium phosphate gains much attention as a bone substitute material because of its large surface area and that it improves cell penetration. In the present study, we evaluated the feasibility of biporous, low-crystalline apatite based on dissolution of mannitol from self-setting apatite cement (Biopex). Mannitol--known as a biocompatible, easily dissolved monosaccharide alcohol--was recrystallized to obtain larger crystals. It was crushed with pestle and mortar, sieved to obtain crystals which passed through a 500-microm mesh but which remained against a 300-microm mesh, and then used as porogen. Although Biopex containing 60 wt% mannitol was not able to be taken out of the mold, addition of mannitol caused no initial setting inhibition to Biopex if the amount was 40 wt% or less. Similarly, transformation to apatitic product was confirmed when the apatite cement was immersed in 0.9% saline kept at 37 degrees C for seven days. The set mass became low-crystalline, biporous apatite with approximately 60% porosity.

Influence of disodium EDTA on the nucleation and growth of struvite and carbonate apatite

NASA Astrophysics Data System (ADS)

Prywer, Jolanta; Olszynski, Marcin

2013-07-01

The effect of disodium EDTA, as an additive, on the crystallization of struvite and carbonate apatite was studied. The growth of struvite crystals and carbonate apatite occurred in the solution of artificial urine at 37 °C and at the condition emulating real urinary tract infection. The results demonstrate that the addition of disodium EDTA increases the induction time and decreases the growth efficiency compared to the baseline (without disodium EDTA). The struvite crystal mean and median diameters were found to decrease in the presence of disodium EDTA but the crystal morphology and habit remain almost unchanged. Disodium EDTA has demonstrated its potential to be further investigated in the presence of bacteria and in vivo conditions.

In-situ measurement of sulfur isotopic ratios in zoned apatite crystals via SIMS: a new tool for interpreting dynamic sulfur behavior in magmas

NASA Astrophysics Data System (ADS)

Economos, R. C.; Boehnke, P.; Burgisser, A.

2017-12-01

Sulfur is an important element in igneous systems due to its impact on magma redox, its role in the formation of economically valuable ore deposits, and the influence of catastrophic volcanogenic sulfur degassing on global climate. The mobility and geochemical behavior of sulfur in magmas is complex due to its multi-valent (from S2- to S6+) and multi-phase (solid, immiscible liquid, gaseous, dissolved ions) nature. Sulfur behavior is closely linked with the evolution of oxygen fugacity (fO2) in magmas; the record of fO2 evolution is often difficult to extract from rock records, particularly for intrusive systems that undergo cyclical magmatic processes and crystallize to the solidus. We apply a novel method of measuring S isotopic ratios via secondary ion mass spectrometry (SIMS) in zoned apatite crystals that we interpret as a record of open-system magmatic processes. We analyzed the S concentration and isotopic variations preserved in multiple apatite crystals from single hand specimens from the Cadiz Valley Batholith, CA via electron microprobe and ion microprobe at UCLA. A single, isotopically homogeneous crystal of Durango apatite was characterized for absolute isotopic ratio for this study (UCLA-D1). Isotopic variations in single apatite crystals ranged from 0 to 3.8‰ δ34S and total variation within a single hand sample was 6.1‰ δ34S. High S concentration cores yielded high isotopic ratios while low S concentration rims yielded low isotopic ratios. We favor an explanation of a combination of magma mixing and open-system, ascent-driven degassing under moderately reduced conditions: fO2 at or below NNO +1, although the synchronous crystallization of apatite and anhydrite is also a viable scenario. These findings have implications for the coupled S and fO2 evolution of granitic plutons and suggest that in-situ apatite S isotopic measurements could be a powerful new tool for evaluating redox and S systematics in magmatic systems.

Site-specific equilibrium isotopic fractionation of oxygen, carbon and calcium in apatite

NASA Astrophysics Data System (ADS)

Aufort, Julie; Ségalen, Loïc; Gervais, Christel; Paulatto, Lorenzo; Blanchard, Marc; Balan, Etienne

2017-12-01

The stable isotope composition of biogenic apatite is an important geochemical marker that can record environmental parameters and is widely used to infer past climates, biomineralization processes, dietary preferences and habitat of vertebrates. In this study, theoretical equilibrium isotopic fractionation of oxygen, carbon and calcium in hydroxyapatite and carbonate-bearing hydroxyapatite is investigated using first-principles methods based on density-functional theory and compared to the theoretical isotopic fractionation properties of calcite, CO2 and H2O. Considering the variability of apatite crystal-chemistry, special attention is given to specific contributions of crystal sites to isotopic fractionation. Significant internal fractionation is calculated for oxygen and carbon isotopes in CO3 between the different structural sites occupied by carbonate groups in apatite (typically 7‰ for both 18O/16O and 13C/12C fractionation at 37 °C). Compared with calcite-water oxygen isotope fractionation, occurrence of A-type substitution in apatite structure, in addition to the main B-type substitution, could explain the larger temperature dependence of oxygen isotope fractionation measured at low temperature between carbonate in apatite and water. Theoretical internal fractionation of oxygen isotopes between carbonate and phosphate in B-type carbonated apatite (∼8‰ at 37 °C) is consistent with experimental values obtained from modern and well-preserved fossil bio-apatites. Concerning calcium, theoretical results suggest a small fractionation between apatite and calcite (-0.17‰ at 37 °C). Internal fractionation reaching 0.8‰ at 37 °C occurs between the two Ca sites in hydroxyapatite. Furthermore, the Ca isotopic fractionation properties of apatite are affected by the occurrence of carbonate groups, which could contribute to the variability observed on natural samples. Owing to the complexity of apatite crystal-chemistry and in light of the theoretical results, measurements of site-specific isotopic fractionation properties could improve our understanding and the interpretation of isotopic records in apatites.

He, U, and Th Depth Profiling of Apatite and Zircon Using Laser Ablation Noble Gas Mass Spectrometry and SIMS

NASA Astrophysics Data System (ADS)

Monteleone, B. D.; van Soest, M. C.; Hodges, K. V.; Hervig, R.; Boyce, J. W.

2008-12-01

Conventional (U-Th)/He thermochronology utilizes single or multiple grain analyses of U- and Th-bearing minerals such as apatite and zircon and does not allow for assessment of spatial variation in concentration of He, U, or Th within individual crystals. As such, age calculation and interpretation require assumptions regarding 4He loss through alpha ejection, diffusive redistribution of 4He, and U and Th distribution as an initial condition for these processes. Although models have been developed to predict 4He diffusion parameters, correct for the effect of alpha ejection on calculated cooling ages, and account for the effect of U and Th zonation within apatite and zircon, measurements of 4He, U, and Th distribution have not been combined within a single crystal. We apply ArF excimer laser ablation, combined with noble gas mass spectrometry, to obtain depth profiles within apatite and zircon crystals in order to assess variations in 4He concentration with depth. Our initial results from pre-cut, pre-heated slabs of Durango apatite, each subjected to different T-t schedules, suggest a general agreement of 4He profiles with those predicted by theoretical diffusion models (Farley, 2000). Depth profiles through unpolished grains give reproducible alpha ejection profiles in Durango apatite that deviate from alpha ejection profiles predicted for ideal, homogenous crystals. SIMS depth profiling utilizes an O2 primary beam capable of sputtering tens of microns and measuring sub-micron resolution variation in [U], [Th], and [Sm]. Preliminary results suggest that sufficient [U] and [Th] zonation is present in Durango apatite to influence the form of the 4He alpha ejection profile. Future work will assess the influence of measured [U] and [Th] zonation on previously measured 4He depth profiles. Farley, K.A., 2000. Helium diffusion from apatite; general behavior as illustrated by Durango fluorapatite. J. Geophys. Res., B Solid Earth Planets 105 (2), 2903-2914.

Sulfur concentration and isotopic variation in apatites from granitic to granodioritic plutons of a Cretaceous Cordilleran Batholith

NASA Astrophysics Data System (ADS)

Economos, R. C.

2012-12-01

Apatite is a common igneous accessory mineral with a high saturation temperature which can therefore crystallize over a significant portion of magmatic compositional space. Sulfur presents an opportunity to identify zoning in apatites. Unlike other trace elements, sulfur is relatively immobile in the apatite crystal structure and can be present in typical concentrations up to 1500 - 2000 ppm (or 0.5 to 1 wt% SO3). Sulfur concentration zoning in igneous apatites from ore producing magmatic systems has been identified (Streck and Dilles, 1998), but the interpretation of the cause of this zoning remains an open question. δ34S isotopic ratios of whole apatites have been used to track isotopic evolution associated with changes in magma fO2 and eruptive degassing (Rye, 2005). The presented work combines sulfur concentration mapping in zoned apatite crystals with in-situ SIMS 34S and 32S isotope measurements. Apatites were extracted from granite to granodiorite samples from the Cadiz Valley Batholith in the central Mojave Desert. This batholith is related to the pulse of Cretaceous Cordilleran magmatism that generated large batholiths in the Sierra Nevada and the Penninsular Ranges. The Mojave segment of the Cretaceous arc is unique in their construction into a full thickness of continental crust which exerted a strong influence on magmatic compositions. Apatite grains were mounted parallel to C axes, ground until grains were approximately bisected, and analyzed by Electron Microprobe at UCLA, for CaO, P2O5, SO3 and SiO2. Grains were surveyed and those yielding anomalous SO3 contents were investigated by micron-scale concentration mapping. Typical SO3 concentrations of apatites from all samples were ~0.2 wt%, while 8 to 10% of apatite grains from two samples contained cores with concentrations ranging up to 0.5 wt%. The sulfur zoning in these samples is oscillatory, in some grains representing 5 to 6 repetitions of high and low concentrations. Based on these textures, our initial interpretation is that this zoning is magmatic. Ratios of 32S to 34S in these grains were analyzed by Secondary Ionization Mass Spectrometry at UCLA in multi-collector mode utilizing a Cs+ primary ion beam and two electron multiplier ion counters. Although absolute δ34S values cannot be calculated without further standard, samples were analyzed relative to demonstrably isotopically homogeneous fragments of Durango apatite. Zoned apatite cores displayed δ34S variation well outside of analytical uncertainty. Analytical errors on individual isotopic measurements were ± 1.5‰ and reproducibility on standard grains through the analytical session was ± 0.5‰. Grains mounted parallel and perpendicular to the C axis displayed no discernible isotopic fractionation. Cores with high S concentrations displayed isotopic enrichment in 34S up to 11‰ relative to rims and core-free grains. Concentration variations may track trajectories of S solubility in evolving magmas (Ducea et al., 1994). Meanwhile heavier S isotopic ratios may suggest either dynamic crystallization/resorption behavior of S bearing species or an oxidizing environment for these earliest crystallizing apatites.

Electron microscopy of octacalcium phosphate in the dental calculus.

PubMed

Kakei, Mitsuo; Sakae, Toshiro; Yoshikawa, Masayoshi

2009-12-01

The purpose of this study was to morphologically demonstrate the presence of octacalcium phosphate in the dental calculus by judging from the crystal lattice image and its rapid transformation into apatite crystal, as part of our serial studies on biomineral products. We also aimed to confirm whether the physical properties of octacalcium phosphate are identical with those of the central dark lines observed in crystals of ordinary calcifying hard tissues. Electron micrographs showed that crystals of various sizes form in the dental calculus. The formation of each crystal seemed to be closely associated with the organic substance, possibly originating from degenerated microorganisms at the calcification front. Many crystals had an 8.2-A lattice interval, similar to that of an apatite crystal. Furthermore, some crystals clearly revealed an 18.7-A lattice interval and were vulnerable to electron bombardment. After electron beam exposure, this lattice interval was quickly altered to about half (i.e. 8.2 A), indicating structural conversion. Consequently, a number of apatite crystals in the dental calculus are possibly created by a conversion mechanism involving an octacalcium phosphate intermediate. However, we also concluded that the calcification process in the dental calculus is not similar to that of ordinary calcifying hard tissues.

Apatite (U-Th)/He thermochronology dataset interpretation: New insights from physical point of view

NASA Astrophysics Data System (ADS)

Gautheron, Cécile; Mbongo-Djimbi, Duval; Gerin, Chloé; Roques, Jérôme; Bachelet, Cyril; Oliviero, Erwan; Tassan-Got, Laurent

2015-04-01

The apatite (U-Th)/He (AHe) system has rapidly become a very popular thermochronometer to constrain burial and exhumation phases in a variety of geological contexts. However, the interpretation of AHe data depends on a precise knowledge of He diffusion in apatite. Several studies suggest that radiation damage generated by U and Th decay can create traps for He atoms, increasing He retention for irradiated minerals. The radiation damage also anneals with temperature and the amount of damage in an apatite crystal is at any time a balance between production and annealing, controlled by U-Th concentration, grain chemistry and thermal history (Flowers et al., 2009; Gautheron et al., 2009; 2013). However the models are not well constrained and do not fully explain the mechanism of He retention. In order to have a deeper insight on this issue, multidisciplinary studies on apatite combining diffusion experiments by Elastic Recoil Diffusion Analysis (ERDA) with a multi-scale theoretical diffusion calculation based on Density Functional Theory (DFT) and Kinetic Monte Carlo were performed. ERDA experiments were conducted on different macro-crystals, and we probed the shape of a He profile implanted into a planar and polished surface of the crystal. The helium profile evolves with temperature and allows quantifying the He diffusivity and damage impact. Additionally, DFT calculations of a damage-free crystal of apatite with different F and Cl compositions, in similar proportion as natural ones, have been run to find the favored paths of a helium atom between interstitial sites, leading to a computation of the activation energy and the diffusion coefficient. We show that damage free apatite crystals are characterized by low retention behavior and closure temperature range from 33-36°C for pure F-apatite to higher value for Cl riche apatite (up to 12°C higher), for typical grain size and cooling rate (Mbongo-Djimbi et al., in review). Using ERDA and DFT approaches, we demonstrate that in addition to grain chemistry, He diffusivity will be strongly influenced by damage and propose a new physical model. Finally, we propose a new way of interpreting AHe datasets and practical geological examples will be given. Flowers, R., Ketcham, R.A., Shuster, D., Farley, K.A., 2009. Apatite (U-Th)/He thermochronology using a radiation damage accumulation and annealing model. Geochimica et Cosmochimica Acta 73, 2347-2365. Gautheron, C., Tassan-got, L., Barbarand, J., Pagel, M., 2009. Effect of alpha-damage annealing on apatite (U-Th)/He thermochronology. Chemical Geology 266, 166-179. Gautheron, C., Barbarand, J., Ketcham R.A., Tassan-got, L., van der Beek, P., Pagel, M., Pinna-Jamme, R., Couffignal, F., Fialin, M., 2013. Chemical influence on α-recoil damage annealing in apatite: implications for (U-Th)/He dating. Chemical Geology 351, 257-267. Mbongo-Djimbi D., Gautheron C., Roques, J., Tassan-Got, L., Gerin, C., Simoni, E.. Apatite composition effect on (U-Th)/He thermochronometer: an atomistic point of view. In review at Geochimica Cosmochimica Acta.

Carbonate substitution in the mineral component of bone: Discriminating the structural changes, simultaneously imposed by carbonate in A and B sites of apatite

NASA Astrophysics Data System (ADS)

Madupalli, Honey; Pavan, Barbara; Tecklenburg, Mary M. J.

2017-11-01

The mineral component of bone and other biological calcifications is primarily a carbonate substituted calcium apatite. Integration of carbonate into two sites, substitution for phosphate (B-type carbonate) and substitution for hydroxide (A-type carbonate), influences the crystal properties which relate to the functional properties of bone. In the present work, a series of AB-type carbonated apatites (AB-CAp) having varying A-type and B-type carbonate weight fractions were prepared and analyzed by Fourier transform infrared spectroscopy (FTIR), powder X-ray diffraction (XRD), and carbonate analysis. A detailed characterization of A-site and B-site carbonate assignment in the FTIR ν3 region is proposed. The mass fractions of carbonate in A-site and B-site of AB-CAp correlate differently with crystal axis length and crystallite domain size. In this series of samples reduction in crystal domain size correlates only with A-type carbonate which indicates that carbonate in the A-site is more disruptive to the apatite structure than carbonate in the B-site. High temperature methods were required to produce significant A-type carbonation of apatite, indicating a higher energy barrier for the formation of A-type carbonate than for B-type carbonate. This is consistent with the dominance of B-type carbonate substitution in low temperature synthetic and biological apatites.

Apatite Mineral Chemistry From IOA Deposits in Northern Chile

NASA Astrophysics Data System (ADS)

Palma, G.; Barra, F.; Reich, M.; Valencia, V.; Simon, A. C.; Vervoort, J. D.

2017-12-01

The Carmen, Fresia and Mariela iron-oxide apatite (IOA) deposits of Cretaceous age, located in the Coastal Cordillera of northern Chile, comprise massive bodies of magnetite with minor apatite and actinolite crystals spatially related to diorite intrusions. In order to provide new insights on the origin of Andean IOA deposits, we provide geochemical data of apatite grains collected from these three deposits. All studied apatite grains are zoned with respect to Cl and F, and show a decoupled behaviour between fluorapatite and chlorapatite. Carmen apatite grains are mostly F-rich, whereas in Mariela apatite grains are Cl-rich. Fresia apatite grains show a variable composition between fluorapatite and chlorapatite. Carmen apatite grains show a high REE content reaching up to 7000 ppm, and both Fresia and Mariela have lower REE content (<1400 ppm). REE patterns for all analyzed apatite grains show the typical LREE enrichment relative to the HREE and pronounced negative Eu anomaly, which indicates crystallization of plagioclase in the source magmas [1]. Chlorapatite zones are characterized by high S, Na, Sr and Fe content relative to fluorapatite zones. Notably S and Na show a coupled behaviour with Cl. Conversely LREE are depleted in chlorapatite zones, which is compatible with metasomatism through dissolution-reprecipitation mechanism and formation of monazite inclusions [2]. These results indicate a magmatic origin for fluorapatite in these Andean IOA deposits followed by variable degrees of hydrothermal overprint which resulted in the formation of Cl-rich apatites.[1] Frietsch & Perdahl (1995) Ore Geology Rev. 9 489-510. [2]Harlov et al. (2005) Contrib Mineral Petrol 150: 268-286

Strontium ranelate changes the composition and crystal structure of the biological bone-like apatite produced in osteoblast cell cultures.

PubMed

Querido, William; Campos, Andrea P C; Martins Ferreira, Erlon H; San Gil, Rosane A S; Rossi, Alexandre M; Farina, Marcos

2014-09-01

We evaluate the effects of strontium ranelate on the composition and crystal structure of the biological bone-like apatite produced in osteoblast cell cultures, a system that gave us the advantage of obtaining mineral samples produced exclusively during treatment. Cells were treated with strontium ranelate at concentrations of 0.05 and 0.5 mM Sr(2+). Mineral substances were isolated and analyzed by using a combination of methods: Fourier transform infrared spectroscopy, solid-state (1)H nuclear magnetic resonance, X-ray diffraction, micro-Raman spectroscopy and energy dispersive X-ray spectroscopy. The minerals produced in all cell cultures were typical bone-like apatites. No changes occurred in the local structural order or crystal size of the minerals. However, we noticed several relevant changes in the mineral produced under 0.5 mM Sr(2+): (1) increase in type-B CO3 (2-) substitutions, which often lead to the creation of vacancies in Ca(2+) and OH(-) sites; (2) incorporation of Sr(2+) by substituting slightly less than 10 % of Ca(2+) in the apatite crystal lattice, resulting in an increase in both lattice parameters a and c; (3) change in the PO4 (3-) environments, possibly because of the expansion of the lattice; (4) the Ca/P ratio of this mineral was reduced, but its (Ca+Sr)/P ratio was the same as that of the control, indicating that its overall cation/P ratio was preserved. Thus, strontium ranelate changes the composition and crystal structure of the biological bone-like apatite produced in osteoblast cell cultures.

Co-variability of S 6+ , S 4+ , and S 2- in apatite as a function of oxidation state: Implications for a new oxybarometer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Konecke, Brian A.; Fiege, Adrian; Simon, Adam C.

In this study, we use micro-X-ray absorption near-edge structures (μ-XANES) spectroscopy at the S K-edge to investigate the oxidation state of S in natural magmatic-hydrothermal apatite (Durango, Mexico, and Mina Carmen, Chile) and experimental apatites crystallized from volatile-saturated lamproitic melts at 1000 °C and 300 MPa over a broad range of oxygen fugacities [( Embedded Image , FMQ+1.2, FMQ+3; FMQ = fayalite-magnetite-quartz solid buffer]. The data are used to test the hypothesis that S oxidation states other than S6+ may substitute into the apatite structure. Peak energies corresponding to sulfate S6+ (~2482 eV), sulfite S4+ (~2478 eV), and sulfide S2-more » (~2470 eV) were observed in apatite, and the integrated areas of the different sulfur peaks correspond to changes in Embedded Image and bulk S content. Here, multiple tests confirmed that the S oxidation state in apatite remains constant when exposed to the synchrotron beam, at least for up to 1 h exposure (i.e., no irradiation damages). To our knowledge, this observation makes apatite the first mineral to incorporate reduced (S2-), intermediate (S4+), and oxidized (S6+) S in variable proportions as a function of the prevailing Embedded Image of the system. Apatites crystallized under oxidizing conditions (FMQ+1.2 and FMQ+3), where the S6+/STotal peak area ratio in the coexisting glass (i.e., quenched melt) is ~1, are dominated by S6+ with a small contribution of S4+, whereas apatites crystallizing at reduced conditions (FMQ) contain predominantly S2-, lesser amounts of S6+, and possibly traces of S4+. A sulfur oxidation state vs. S concentration analytical line transect across hydrothermally altered apatite from the Mina Carmen iron oxide-apatite (IOA) deposit (Chile) demonstrates that apatite can become enriched in S4+ relative to S6+, indicating metasomatic overprinting via a SO2-bearing fluid or vapor phase. This XANES study demonstrates that as the Embedded Image increases from FQM to FMQ+1.2 to FMQ+3 the oxidation state of S in igneous apatite changes from S2- dominant to S6+ > S4+ to S6+ >> S4+. Furthermore, these results suggest that spectroscopic studies of igneous apatite have potential to trace the oxidation state of S in magmas. The presence of three S oxidations states in apatite may in part explain the non-Henrian partitioning of S between apatite and melt. Our study reveals the potential to use the S signature of apatite to elucidate both oxygen and sulfur fugacity in magmatic and hydrothermal systems.« less

Comparative in vitro studies on disodium EDTA effect with and without Proteus mirabilis on the crystallization of carbonate apatite and struvite

NASA Astrophysics Data System (ADS)

Prywer, Jolanta; Olszynski, Marcin; Torzewska, Agnieszka; Mielniczek-Brzóska, Ewa

2014-06-01

Effect of disodium EDTA (salt of ethylenediamine tetraacetic acid) on the crystallization of struvite and carbonate apatite was studied. To evaluate such an effect we performed an experiment of struvite and carbonate apatite growth from artificial urine. The crystallization process was induced by Proteus mirabilis to mimic the real urinary tract infection, which usually leads to urinary stone formation. The results demonstrate that disodium EDTA exhibits the effect against P. mirabilis retarding the activity of urease - an enzyme produced by these microorganisms. The spectrophotometric results demonstrate that, with and without P. mirabilis, the addition of disodium EDTA increases the induction time and decreases the growth efficiency compared to the baseline (without disodium EDTA). These results are discussed from the standpoint of speciation of complexes formed in the solution of artificial urine in the presence of disodium EDTA. The size of struvite crystals was found to decrease in the presence of disodium EDTA. However, struvite crystals are larger in the presence of bacteria while the crystal morphology and habit remain unchanged.

Posttranslational Amelogenin Processing and Changes in Matrix Assembly during Enamel Development

PubMed Central

Pandya, Mirali; Lin, Tiffani; Li, Leo; Allen, Michael J.; Jin, Tianquan; Luan, Xianghong; Diekwisch, Thomas G. H.

2017-01-01

The extracellular tooth enamel matrix is a unique, protein-rich environment that provides the structural basis for the growth of long and parallel oriented enamel crystals. Here we have conducted a series of in vivo and in vitro studies to characterize the changes in matrix shape and organization that take place during the transition from ameloblast intravesicular matrices to extracellular subunit compartments and pericrystalline sheath proteins, and correlated these changes with stages of amelogenin matrix protein posttranslational processing. Our transmission electron microscopic studies revealed a 2.5-fold difference in matrix subunit compartment dimensions between secretory vesicle and extracellular enamel protein matrix as well as conformational changes in matrix structure between vesicles, stippled materials, and pericrystalline matrix. Enamel crystal growth in organ culture demonstrated granular mineral deposits associated with the enamel matrix framework, dot-like mineral deposits along elongating initial enamel crystallites, and dramatic changes in enamel matrix configuration following the onset of enamel crystal formation. Atomic force micrographs provided evidence for the presence of both linear and hexagonal/ring-shaped full-length recombinant amelogenin protein assemblies on mica surfaces, while nickel-staining of the N-terminal amelogenin N92 His-tag revealed 20 nm diameter oval and globular amelogenin assemblies in N92 amelogenin matrices. Western blot analysis comparing loosely bound and mineral-associated protein fractions of developing porcine enamel organs, superficial and deep enamel layers demonstrated (i) a single, full-length amelogenin band in the enamel organ followed by 3 kDa cleavage upon entry into the enamel layer, (ii) a close association of 8–16 kDa C-terminal amelogenin cleavage products with the growing enamel apatite crystal surface, and (iii) a remaining pool of N-terminal amelogenin fragments loosely retained between the crystalline phases of the deep enamel layer. Together, our data establish a temporo-spatial correlation between amelogenin protein processing and the changes in enamel matrix configuration that take place during the transition from intracellular vesicle compartments to extracellular matrix assemblies and the formation of protein coats along elongating apatite crystal surfaces. In conclusion, our study suggests that enzymatic cleavage of the amelogenin enamel matrix protein plays a key role in the patterning of the organic matrix framework as it affects enamel apatite crystal growth and habit. PMID:29089900

Posttranslational Amelogenin Processing and Changes in Matrix Assembly during Enamel Development.

PubMed

Pandya, Mirali; Lin, Tiffani; Li, Leo; Allen, Michael J; Jin, Tianquan; Luan, Xianghong; Diekwisch, Thomas G H

2017-01-01

The extracellular tooth enamel matrix is a unique, protein-rich environment that provides the structural basis for the growth of long and parallel oriented enamel crystals. Here we have conducted a series of in vivo and in vitro studies to characterize the changes in matrix shape and organization that take place during the transition from ameloblast intravesicular matrices to extracellular subunit compartments and pericrystalline sheath proteins, and correlated these changes with stages of amelogenin matrix protein posttranslational processing. Our transmission electron microscopic studies revealed a 2.5-fold difference in matrix subunit compartment dimensions between secretory vesicle and extracellular enamel protein matrix as well as conformational changes in matrix structure between vesicles, stippled materials, and pericrystalline matrix. Enamel crystal growth in organ culture demonstrated granular mineral deposits associated with the enamel matrix framework, dot-like mineral deposits along elongating initial enamel crystallites, and dramatic changes in enamel matrix configuration following the onset of enamel crystal formation. Atomic force micrographs provided evidence for the presence of both linear and hexagonal/ring-shaped full-length recombinant amelogenin protein assemblies on mica surfaces, while nickel-staining of the N-terminal amelogenin N92 His-tag revealed 20 nm diameter oval and globular amelogenin assemblies in N92 amelogenin matrices. Western blot analysis comparing loosely bound and mineral-associated protein fractions of developing porcine enamel organs, superficial and deep enamel layers demonstrated (i) a single, full-length amelogenin band in the enamel organ followed by 3 kDa cleavage upon entry into the enamel layer, (ii) a close association of 8-16 kDa C-terminal amelogenin cleavage products with the growing enamel apatite crystal surface, and (iii) a remaining pool of N-terminal amelogenin fragments loosely retained between the crystalline phases of the deep enamel layer. Together, our data establish a temporo-spatial correlation between amelogenin protein processing and the changes in enamel matrix configuration that take place during the transition from intracellular vesicle compartments to extracellular matrix assemblies and the formation of protein coats along elongating apatite crystal surfaces. In conclusion, our study suggests that enzymatic cleavage of the amelogenin enamel matrix protein plays a key role in the patterning of the organic matrix framework as it affects enamel apatite crystal growth and habit.

Factors controlling sulfur concentrations in volcanic apatite

USGS Publications Warehouse

Peng, G.; Luhr, J.F.; McGee, J.J.

1997-01-01

Apatite crystals from two types of samples were analyzed by electron microprobe for 15 major and trace elements: (1) apatite in H2O- and S-saturated experimental charges of the 1982 El Chicho??n trachyandesite and (2) apatite in volcanic rocks erupted from 20 volcanoes. The SO3 contents of the experimental apatite increase with increasing oxygen fugacity (fo2), from ???0.04 wt% in reduced charges buffered by fayalite-magnetite-quartz (FMQ), to 1.0-2.6 wt% in oxidized charges buffered by manganosite-hausmanite (MNH) or magnetite-hematite (MTH). The SO3 contents of MNH- and MTH-buffered apatite also generally increase with increasing pressure from 2 to 4 kbar and decreasing temperature from 950 to 800??C. The partition coefficient for SO3 between apatite and oxidized melt increases with decreasing temperature but appears to be independent of pressure. Apatites in volcanic rocks show a wide range of SO3 contents (<0.04 to 0.63 wt%). Our sample set includes one group known to contain primary anhydrite and a second group inferred to have been free of primary anhydrite. No systematic differences in apatite S contents are observed between these two groups. Our study was initiated to define the factors controlling S contents in apatite and to evaluate the hypothesis that high S contents in apatite could be characteristic of S-rich anhydrite-bearing magmas such as those erupted from El Chicho??n in 1982 and Pinatubo in 1991. This hypothesis is shown to be invalid, probably chiefly a consequence of the slow intra-crystaline diffusion that limits re-equilibration between early formed apatite and the evolving silicate melt. Contributing factors include early crystallization of most apatite over a relatively small temperature interval, common late-stage magmatic enrichment of S, progressive oxidation during magmatic evolution, and strong controls on S contents in apatite exerted fo2, temperature, and pressure.

Partitioning of F and Cl Between Apatite and a Synthetic Shergottite Liquid (QUE 94201) at 4 Gpa from 1300 TO 1500 C

NASA Technical Reports Server (NTRS)

McCubbin, F. M.; Barnes, J. J.; Vander Kaaden, K. E.; Boyce, J. W.

2017-01-01

Apatite [Ca5(PO4)3(F,Cl,OH)] is present in a wide range of planetary materials. Due to the presence of volatiles within its crystal structure (Xsite), many recent studies have attempted to use apatite to constrain the volatile contents of planetary magmas and mantle sources. In order to use the volatile contents of apatite to accurately determine the abundances of volatiles in coexisting silicate melt or fluids, thermodynamic models for the apatite solid solution and for the apatite components in multicomponent silicate melts and fluids are required. Although some thermodynamic models for apatite have been developed, they are incomplete. Furthermore, no mixing model is available for all of the apatite components in silicate melts or fluids, especially for F and Cl components. Several experimental studies have investigated the apatite-melt and apatite-fluid partitioning behavior of F, Cl, and OH in terrestrial and planetary systems, which have determined that apatite-melt partitioning of volatiles are best described as exchange equilibria similar to Fe-Mg partitioning between olivine and silicate melt. However, McCubbin et al., recently reported that the exchange coefficients vary in portions of apatite compositional space where F, Cl, and OH do not mix ideally in apatite. In particular, solution calorimetry data of apatite compositions along the F-Cl join exhibit substantial excess enthalpies of mixing, and McCubbin et al. reported substantial deviations in the Cl-F exchange Kd along the F-Cl apatite join that could be explained by the preferential incorporation of F into apatite. In the present study, we assess the effect of apatite crystal chemistry on F-Cl exchange equilibria between apatite and melt at 4 GPa over the temperature range of 1300-1500 C. The goal of these experiments is to assess the variation in the Ap-melt Cl-F exchange Kd over a broad range of F:Cl ratios in apatite. The results of these experiments could be used to understand at what composition apatite shifts from a hexagonal unit cell with space group P63/m to a unit cell with monoclinic symmetry within space group P21/b. We anticipate that this transition occurs at >70% chlorapatite based on solution calorimetry data.

In vitro bioactivity of a biocomposite fabricated from HA and Ti powders by powder metallurgy method.

PubMed

Ning, C Q; Zhou, Y

2002-07-01

Traditionally, hydroxyapatite was used as a coating material on titanium substrate by various techniques. In the present work, a biocomposite was successfully fabricated from hydroxyapatite and titanium powders by powder metallurgy method. Bioactivity of the composite in a simulated body fluid (SBF) was investigated. Main crystal phases of the as-fabricated composite are found to be Ti2O, CaTiO3, CaO, alpha-Ti and a TiP-like phase. When the composite is immersed in the simulated body fluid for a certain time, a poor-crystallized, calcium-deficient, carbonate-containing apatite film will form on the surface of the composite. The time required to induce apatite nucleation is within 2 h. In addition, the apatite is also incorporated with a little magnesium and chlorine element. It is found that Ti2O has the ability to induce the formation of bone-like apatite in the SBF. And a dissolve of the CaO phase could also provide favorable conditions for the apatite formation, by forming open pores on the surface of the composite and increasing the degree of supersaturation of the SBF with respect to the apatite.

Nanodimensional and Nanocrystalline Apatites and Other Calcium Orthophosphates in Biomedical Engineering, Biology and Medicine

PubMed Central

Dorozhkin, Sergey V.

2009-01-01

Recent developments in biomineralization have already demonstrated that nanosized particles play an important role in the formation of hard tissues of animals. Namely, the basic inorganic building blocks of bones and teeth of mammals are nanodimensional and nanocrystalline calcium orthophosphates (in the form of apatites) of a biological origin. In mammals, tens to hundreds nanocrystals of a biological apatite were found to be combined into self-assembled structures under the control of various bioorganic matrixes. In addition, the structures of both dental enamel and bones could be mimicked by an oriented aggregation of nanosized calcium orthophosphates, determined by the biomolecules. The application and prospective use of nanodimensional and nanocrystalline calcium orthophosphates for a clinical repair of damaged bones and teeth are also known. For example, a greater viability and a better proliferation of various types of cells were detected on smaller crystals of calcium orthophosphates. Thus, the nanodimensional and nanocrystalline forms of calcium orthophosphates have a great potential to revolutionize the field of hard tissue engineering starting from bone repair and augmentation to the controlled drug delivery devices. This paper reviews current state of knowledge and recent developments of this subject starting from the synthesis and characterization to biomedical and clinical applications. More to the point, this review provides possible directions of future research and development.

Experimental Constraints on the Partitioning Behavior of F, Cl, and OH Between Apatite and Basaltic Melt

NASA Technical Reports Server (NTRS)

McCubbin, Francis M.; Barnes, Jessica J.; Vander Kaaden, Kathleen E.; Boyce, Jeremy W.; Ustunisik, Gokce; Whitson, Eric S.

2017-01-01

The mineral apatite is present in a wide range of planetary materials. The presence of volatiles (F, Cl, and OH) within its crystal structure (X-site) have motivated numerous studies to investigate the partitioning behavior of F, Cl, and OH between apatite and silicate melt with the end goal of using apatite to constrain the volatile contents of planetary magmas and mantle sources. A number of recent experimental studies have investigated the apatite-melt partitioning behavior of F, Cl, and OH in magmatic systems. Apatite-melt partitioning of volatiles are best described as exchange equilibria similar to Fe-Mg partitioning between olivine and silicate melt. However, the partitioning behavior is likely to change as a function of temperature, pressure, oxygen fugacity, apatite composition, and melt composition. In the present study, we have conducted experiments to assess the partitioning behavior of F, Cl, and OH between apatite and silicate melt over a pressure range of 0-6 gigapascals, a temperature range of 950-1500 degrees Centigrade, and a wide range of apatite ternary compositions. All of the experiments were conducted between iron-wustite oxidation potentials IW minus 1 and IW plus 2 in a basaltic melt composition. The experimental run products were analyzed by a combination of electron probe microanalysis and secondary ion mass spectrometry (NanoSIMS). Temperature, apatite crystal chemistry, and pressure all play important roles in the partitioning behavior of F, Cl, and OH between apatite and silicate melt. In portions of apatite ternary space that undergo ideal mixing of F, Cl, and OH, exchange coefficients remain constant at constant temperature and pressure. However, exchange coefficients vary at constant temperature (T) and pressure (P) in portions of apatite compositional space where F, Cl, and OH do not mix ideally in apatite. The variation in exchange coefficients exhibited by apatite that does not undergo ideal mixing far exceeds the variations induced by changes in temperature (T) or pressure (P) . In regions where apatite undergoes ideal mixing of F, Cl, and OH, temperature has a stronger effect than pressure on the partitioning behavior, but both are important. Furthermore, fluorine becomes less compatible in apatite with increasing pressure and temperature. We are still in the process of analyzing our experimental run products, but we plan to quantify the effects of P and T on apatite-melt partitioning of F, Cl, and OH.

Stone formation and calcification by nanobacteria in the human body

NASA Astrophysics Data System (ADS)

Ciftcioglu, Neva; Bjorklund, Michael; Kajander, E. Olavi

1998-07-01

The formation of discrete and organized inorganic crystalline structures within macromolecular extracellular matrices is a widespread biological phenomenon generally referred to as biomineralization. Recently, bacteria have been implicated as factors in biogeochemical cycles for formation of many minerals in aqueous sediments. We have found nanobacterial culture systems that allow for reproducible production of apatite calcification in vitro. Depending on the culture conditions, tiny nanocolloid-sized particles covered with apatite, forming various size of aggregates and stones were observed. In this study, we detected the presence of nanobacteria in demineralized trilobit fossil, geode, apatite, and calcite stones by immunofluorescence staining. Amethyst and other quartz stones, and chalk gave negative results. Microorganisms are capable of depositing apatite outside the thermodynamic equilibrium in sea water. We bring now evidence that this occurs in the human body as well. Previously, only struvite kidney stones composed of magnesium ammonium phosphate and small amounts of apatite have been regarded as bacteria related. 90 percent of demineralized human kidney stones now screened, contained nanobacteria. At least three different distribution patterns of nanobacteria were conditions, and human kidney stones that are formed from small apatite units. Prerequisites for the formation of kidney stones are the supersaturation of urine and presence of nidi for crystallization. Nanobacteria are important nidi and their presence might be of special interest in space flights where supersaturation of urine is present due to the loss of bone. Furthermore, we bring evidence that nanobacteria may act as crystallization nidi for the formation of biogenic apatite structures in tissue calcification found in e.g., atherosclerotic plaques, extensive metastatic and tumoral calcification, acute periarthritis, malacoplakia, and malignant diseases. In nanaobacteria-infected fibroblasts, electron microscopy revealed intra- and extra-cellular needle-like crystal deposits, which were stainable with von Kossa stain and resemble calcospherules found in pathological calcification. Thus bacteria-mediated apatite formation takes place in aqueous environments, in humans and in geological sediments.

Insight into He diffusion in apatite by ion beam experiments and quantum calculations: implication for the (U-Th)/He thermochronometer

NASA Astrophysics Data System (ADS)

Gautheron, C.; Mbongo-Djimbi, D.; Gerin, C.; Roques, J.; Bachelet, C.; Oliviero, E.; Tassan-Got, L.

2015-12-01

The apatite (U-Th)/He (AHe) system has rapidly become a very popular thermochronometer, however, interpretation of AHe age depends on a precise knowledge of He diffusion. Several studies suggest that He retention is function of the amount of damage that is controlled by U-Th concentration, grain chemistry and thermal history. Still, the models are not well constrained and do not fully explain the mechanism of He retention. In order to have a deeper insight into this issue, a multidisciplinary study on apatite combining physical methods such as multi-scale theoretical diffusion calculations based on Density Functional Theory (DFT) with diffusion experiments by ion beam Elastic Recoil Diffusion Analysis (ERDA) were performed. Quantum calculations permit to quantify He diffusivity base level for damage-free crystal and to estimate the additional energy cost to extract He atoms trapped in point defects (i.e. vacancies). On the other hand ion beam ERDA experiments allow to measure He diffusivity in artificially damaged crystals. We show that damage-free apatite crystals are characterized by low retention behavior and closure temperature of ~35°C for pure F-apatite to higher value for Cl rich apatite (up to 12°C higher), for typical grain size and cooling rate (Mbongo-Djimbi et al., 2015). Our computed closure temperature is slightly lower than previously reported experimental values (~50°C). Using ERDA and DFT modeling of damage, we show how He diffusivity is influenced by damage. Finally, we are able to propose a new modeling of He diffusion incorporating mechanisms not included in classical damage models, and taking into account the level of damage and apatite chemistry. We show that it could affect significantly AHe age interpretation. Mbongo-Djimbi D. et al. 2015. Apatite composition effect on (U-Th)/He thermochronometer: an atomistic point of view. Geohimica Cosmochim. Acta.

Preparation of a non-woven poly(ε-caprolactone) fabric with partially embedded apatite surface for bone tissue engineering applications by partial surface melting of poly(ε-caprolactone) fibers.

PubMed

Kim, In Ae; Rhee, Sang-Hoon

2017-07-01

This article describes a novel method for the preparation of a biodegradable non-woven poly(ε-caprolactone) fabric with a partially embedded apatite surface designed for application as a scaffold material for bone tissue engineering. The non-woven poly(ε-caprolactone) fabric was generated by the electro-spinning technique and then apatite was coated in simulated body fluid after coating the PVA solution containing CaCl 2 ·2H 2 O. The apatite crystals were partially embedded or fully embedded into the thermoplastic poly(ε-caprolactone) fibers by controlling the degree of poly(ε-caprolactone) fiber surface melting in a convection oven. Identical apatite-coated poly(ε-caprolactone) fabric that did not undergo heat-treatment was used as a control. The features of the embedded apatite crystals were evaluated by FE-SEM, AFM, EDS, and XRD. The adhesion strengths of the coated apatite layers and the tensile strengths of the apatite coated fabrics with and without heat-treatment were assessed by the tape-test and a universal testing machine, respectively. The degree of water absorbance was assessed by adding a DMEM droplet onto the fabrics. Moreover, cell penetrability was assessed by seeding preosteoblastic MC3T3-E1 cells onto the fabrics and observing the degrees of cell penetration after 1 and 4 weeks by staining nuclei with DAPI. The non-woven poly(ε-caprolactone) fabric with a partially embedded apatite surface showed good water absorbance, cell penetrability, higher apatite adhesion strength, and higher tensile strength compared with the control fabric. These results show that the non-woven poly(ε-caprolactone) fabric with a partially embedded apatite surface is a potential candidate scaffold for bone tissue engineering due to its strong apatite adhesion strength and excellent cell penetrability. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 1973-1983, 2017. © 2017 Wiley Periodicals, Inc.

Calibration for Infrared Measurements of OH in Apatite

NASA Astrophysics Data System (ADS)

Wang, K. L.; Naab, F.; Zhang, Y.

2010-12-01

Apatite is a common accessory mineral, and OH in apatite can indicate the fluid conditions of crystal formation. Previously, water (OH) concentration in apatite has often been estimated through electron microprobe analyses combined with mineral stoichiometry. However, the detection limit, precision, and accuracy of this method are not high. In this work, we calibrated the infrared spectroscopy (IR) method for measurement of OH concentration in apatite by using elastic recoil detection (ERD) analysis to obtain the absolute OH concentration. Large apatite wafers were cut perpendicular to the c-axis of each crystal and doubly polished. ERD measurements were carried out in the Michigan Ion Beam Laboratory at the University of Michigan to determine the hydrogen concentration in each sample. Each ERD spectrum was fitted and a hydrogen standard was used to quantify the hydrogen concentrations. Polarized transmission IR was used on apatite sections that were cut parallel to the c-axis, and doubly polished. IR measurements were made for E-vector parallel to the c-axis. Because the OH peak is intense, very thin samples must be used to avoid absorbance saturation; the thinnest sample (corresponding to the highest OH content) used was 17 µm thick. Four different apatite crystals were successfully analyzed using both the IR and ERD methods. Two were from Durango, Mexico; one from Imilchil, High Atlas Mountains, Morocco; and one from an unknown locality, purchased online from gem dealers. The OH peak near 3550 cm-1 was a relatively simple peak in all four samples. Therefore peak height was used for the absorbance value, A. Using the Beer-Lambert Law, a calibration line was established (R2= 0.95, for IR aperture of 50 µm x 50 µm) where the weight % of H2O is 0.013 times A/d, where d is the thickness in mm. The detection limit of H2O concentration in apatite by IR approaches ppm level for 0.1 mm wafers, the precision is better than 1% relative (depending on H2O content), and the accuracy based on our calibration is 7% relative (2σ).

Preparation of bioactive titania films on titanium metal via anodic oxidation.

PubMed

Cui, X; Kim, H-M; Kawashita, M; Wang, L; Xiong, T; Kokubo, T; Nakamura, T

2009-01-01

To research the crystal structure and surface morphology of anodic films on titanium metal in different electrolytes under various electrochemical conditions and investigate the effect of the crystal structure of the oxide films on apatite-forming ability in simulated body fluid (SBF). Titanium oxide films were prepared using an anodic oxidation method on the surface of titanium metal in four different electrolytes: sulfuric acid, acetic acid, phosphoric acid and sodium sulfate solutions with different voltages for 1 min at room temperature. Anodic films that consisted of rutile and/or anatase phases with porous structures were formed on titanium metal after anodizing in H(2)SO(4) and Na(2)SO(4) electrolytes, while amorphous titania films were produced after anodizing in CH(3)COOH and H(3)PO(4) electrolytes. Titanium metal with the anatase and/or rutile crystal structure films showed excellent apatite-forming ability and produced a compact apatite layer covering all the surface of titanium after soaking in SBF for 7d, but titanium metal with amorphous titania layers was not able to induce apatite formation. The resultant apatite layer formed on titanium metal in SBF could enhance the bonding strength between living tissue and the implant. Anodic oxidation is believed to be an effective method for preparing bioactive titanium metal as an artificial bone substitute even under load-bearing conditions.

The predominant role of collagen in the nucleation, growth, structure and orientation of bone apatite

NASA Astrophysics Data System (ADS)

Wang, Yan; Azaïs, Thierry; Robin, Marc; Vallée, Anne; Catania, Chelsea; Legriel, Patrick; Pehau-Arnaudet, Gérard; Babonneau, Florence; Giraud-Guille, Marie-Madeleine; Nassif, Nadine

2012-08-01

The involvement of collagen in bone biomineralization is commonly admitted, yet its role remains unclear. Here we show that type I collagen in vitro can initiate and orientate the growth of carbonated apatite mineral in the absence of any other vertebrate extracellular matrix molecules of calcifying tissues. We also show that the collagen matrix influences the structural characteristics on the atomic scale, and controls the size and the three-dimensional distribution of apatite at larger length scales. These results call into question recent consensus in the literature on the need for Ca-rich non-collagenous proteins for collagen mineralization to occur in vivo. Our model is based on a collagen/apatite self-assembly process that combines the ability to mimic the in vivo extracellular fluid with three major features inherent to living bone tissue, that is, high fibrillar density, monodispersed fibrils and long-range hierarchical organization.

[A study of bone-like apatite formation on calcium phosphate ceramics in different kinds of animals in vivo].

PubMed

Duan, Yourong; Wu, Yao; Wang, Chaoyuan; Chen, Jiyong; Zhang, Xingdong

2003-03-01

Bone-like apatite formation on the surface of calcium phosphate ceramics has been believed to be necessary for new bone to grow on the ceramics and to be related to the osteoinductivity of the material. The research of bone-like apatite formation is a great help to understanding the mechanism of osteoinduction. Synthetic porous calcium phosphate ceramics (HA/TCP = 70/30) were implanted intramuscularly in pigs, dogs, rabbits and rats to make a comparative study of the bone-like apatite formation onto the porous HA/TCP ceramics in different animals. Specimens were harvested at 14 days after implantation. Samples were detected for the surface morphology with SEM. The chemical composition of the sample surface after implantation was analyzed with reflection infrared (R-IR). Obvious bone-like apatite formation could be detected in the sections of porous specimens harvested from all animals after 14 days intramuscular implantation. Crystal deposition could be only observed on the surface of the concave regions of the samples collected from dogs, rabbits and rat. On the contrary, evenly distributed flake-shaped crystal could be found on the pore surface and also on the outer surface of the materials implanted in pigs. The morphology of bone-like apatite in pigs was different from that in the others animals. Bone-like apatite was not observed in dense specimen implanted intramuscularly. Bone-like apatite formed faster on specimens implanted in rabbit than that in other animals. This formation sequence is different from the sequence of osteoinductivity of biphasic calcium phosphate ceramics implanted in these animals. The results demonstrated that the formation of bone-like apatite on materials is a prerequisite condition to their osteoinduction but other factors also play important roles in osteoinduction.

Oriented and Ordered Biomimetic Remineralization of the Surface of Demineralized Dental Enamel Using HAP@ACP Nanoparticles Guided by Glycine

PubMed Central

Wang, Haorong; Xiao, Zuohui; Yang, Jie; Lu, Danyang; Kishen, Anil; Li, Yanqiu; Chen, Zhen; Que, Kehua; Zhang, Qian; Deng, Xuliang; Yang, Xiaoping; Cai, Qing; Chen, Ning; Cong, Changhong; Guan, Binbin; Li, Ting; Zhang, Xu

2017-01-01

Achieving oriented and ordered remineralization on the surface of demineralized dental enamel, thereby restoring the satisfactory mechanical properties approaching those of sound enamel, is still a challenge for dentists. To mimic the natural biomineralization approach for enamel remineralization, the biological process of enamel development proteins, such as amelogenin, was simulated in this study. In this work, carboxymethyl chitosan (CMC) conjugated with alendronate (ALN) was applied to stabilize amorphous calcium phosphate (ACP) to form CMC/ACP nanoparticles. Sodium hypochlorite (NaClO) functioned as the protease which decompose amelogenin in vivo to degrade the CMC-ALN matrix and generate HAP@ACP core-shell nanoparticles. Finally, when guided by 10 mM glycine (Gly), HAP@ACP nanoparticles can arrange orderly and subsequently transform from an amorphous phase to well-ordered rod-like apatite crystals to achieve oriented and ordered biomimetic remineralization on acid-etched enamel surfaces. This biomimetic remineralization process is achieved through the oriented attachment (OA) of nanoparticles based on non-classical crystallization theory. These results indicate that finding and developing analogues of natural proteins such as amelogenin involved in the biomineralization by natural macromolecular polymers and imitating the process of biomineralization would be an effective strategy for enamel remineralization. Furthermore, this method represents a promising method for the management of early caries in minimal invasive dentistry (MID). PMID:28079165

Oriented and Ordered Biomimetic Remineralization of the Surface of Demineralized Dental Enamel Using HAP@ACP Nanoparticles Guided by Glycine

NASA Astrophysics Data System (ADS)

Wang, Haorong; Xiao, Zuohui; Yang, Jie; Lu, Danyang; Kishen, Anil; Li, Yanqiu; Chen, Zhen; Que, Kehua; Zhang, Qian; Deng, Xuliang; Yang, Xiaoping; Cai, Qing; Chen, Ning; Cong, Changhong; Guan, Binbin; Li, Ting; Zhang, Xu

2017-01-01

Achieving oriented and ordered remineralization on the surface of demineralized dental enamel, thereby restoring the satisfactory mechanical properties approaching those of sound enamel, is still a challenge for dentists. To mimic the natural biomineralization approach for enamel remineralization, the biological process of enamel development proteins, such as amelogenin, was simulated in this study. In this work, carboxymethyl chitosan (CMC) conjugated with alendronate (ALN) was applied to stabilize amorphous calcium phosphate (ACP) to form CMC/ACP nanoparticles. Sodium hypochlorite (NaClO) functioned as the protease which decompose amelogenin in vivo to degrade the CMC-ALN matrix and generate HAP@ACP core-shell nanoparticles. Finally, when guided by 10 mM glycine (Gly), HAP@ACP nanoparticles can arrange orderly and subsequently transform from an amorphous phase to well-ordered rod-like apatite crystals to achieve oriented and ordered biomimetic remineralization on acid-etched enamel surfaces. This biomimetic remineralization process is achieved through the oriented attachment (OA) of nanoparticles based on non-classical crystallization theory. These results indicate that finding and developing analogues of natural proteins such as amelogenin involved in the biomineralization by natural macromolecular polymers and imitating the process of biomineralization would be an effective strategy for enamel remineralization. Furthermore, this method represents a promising method for the management of early caries in minimal invasive dentistry (MID).

Inhibition of crystallization caused by Proteus mirabilis during the development of infectious urolithiasis by various phenolic substances.

PubMed

Torzewska, Agnieszka; Rozalski, Antoni

2014-01-01

Infectious urolithiasis is a consequence of persistent urinary tract infections caused by urease producing bacteria e.g. Proteus mirabilis. These stones are composed of struvite and carbonate apatite. Their rapid growth and high recurrence indicate that so far appropriate methods of treatment have not been found. In the present study, the inhibitory effect of phenolic compounds was investigated in vitro against formation of struvite/apatite crystals. The impact of these substances with different chemical structures on crystallization caused by clinical isolates of P. mirabilis was tested spectrophotometrically using a microdilution method. Among the 11 tested compounds resveratrol, epigallocatechin gallate, peralgonidin, vanillic and coffee acids at the concentrations 250-1000 μg/ml inhibited P. mirabilis urease activity and crystallization. However, only vanillic acid had such an effect on all tested strains of P. mirabilis. Therefore, using an in vitro model, bacterial growth, crystallization, urease activity and pH were examined for 24h in synthetic urine with vanillic acid. Effect of vanillic acid was compared with that of other known struvite/apatite crystallization inhibitors (acetohydroxamic acid, pyrophosphate) and it was shown that vanillic acid strongly inhibited bacterial growth and the formation of crystals. It can be assumed that this compound, after further studies, can be used in the treatment or prophylaxis of infectious urolithiasis. Copyright © 2013 Elsevier GmbH. All rights reserved.

Apatite in carbonatitic rocks: Compositional variation, zoning, element partitioning and petrogenetic significance

NASA Astrophysics Data System (ADS)

Chakhmouradian, Anton R.; Reguir, Ekaterina P.; Zaitsev, Anatoly N.; Couëslan, Christopher; Xu, Cheng; Kynický, Jindřich; Mumin, A. Hamid; Yang, Panseok

2017-03-01

Apatite-group phosphates are nearly ubiquitous in carbonatites, but our understanding of these minerals is inadequate, particularly in the areas of element partitioning and petrogenetic interpretation of their compositional variation among spatially associated rocks and within individual crystals. In the present work, the mode of occurrence, and major- and trace-element chemistry of apatite (sensu lato) from calcite and dolomite carbonatites, their associated cumulate rocks (including phoscorites) and hydrothermal parageneses were studied using a set of 80 samples from 50 localities worldwide. The majority of this set represents material for which no analytical data are available in the literature. Electron-microprobe and laser-ablation mass-spectrometry data ( 600 and 400 analyses, respectively), accompanied by back-scattered-electron and cathodoluminescence images and Raman spectra, were used to identify the key compositional characteristics and zoning patterns of carbonatitic apatite. These data are placed in the context of phosphorus geochemistry in carbonatitic systems and carbonatite evolution, and compared to the models proposed by previous workers. The documented variations in apatite morphology and zoning represent a detailed record of a wide range of evolutionary processes, both magmatic and fluid-driven. The majority of igneous apatite from the examined rocks is Cl-poor fluorapatite or F-rich hydroxylapatite (≥ 0.3 apfu F) with 0.2-2.7 wt.% SrO, 0-4.5 wt.% LREE2O3, 0-0.8 wt.% Na2O, and low levels of other cations accommodated in the Ca site (up to 1000 ppm Mn, 2300 ppm Fe, 200 ppm Ba, 150 ppm Pb, 700 ppm Th and 150 ppm U), none of which show meaningful correlation with the host-rock type. Silicate, (SO4)2 - and (VO4)3 - anions, substituting for (PO4)3 -, tend to occur in greater abundance in crystals from calcite carbonatites (up to 4.2 wt.% SiO2, 1.5 wt.% SO3 and 660 ppm V). Although (CO3)2 - groups are very likely present in some samples, Raman micro-spectroscopy proved inconclusive for apatites with small P-site deficiencies and other substituent elements in this site. Indicator REE ratios sensitive to redox conditions (δCe, δEu) and hydrothermal overprint (δY) form a fairly tight cluster of values (0.8-1.3, 0.8-1.1 and 0.6-0.9, respectively) and may be used in combination with trace-element abundances for the development of geochemical exploration tools. Hydrothermal apatite forms in carbonatites as the product of replacement of primary apatite, or is deposited in fractures and interstices as euhedral crystals and aggregates associated with typical late-stage minerals (e.g., quartz and chlorite). Hydrothermal apatite is typically depleted in Sr, REE, Mn and Th, but enriched in F (up to 4.8 wt.%) relative to its igneous precursor, and also differs from the latter in at least some of key REE ratios [e.g., shows (La/Yb)cn ≤ 25, or a negative Ce anomaly]. The only significant exception is Sr(± REE,Na)-rich replacement zones and overgrowths on igneous apatite from some dolomite(-bearing) carbonatites. Their crystallization conditions and source fluid appear to be very different from the more common Sr-REE-depleted variety. Based on the new evidence presented in this work, trace-element partitioning between apatite and carbonatitic magmas, phosphate solubility in these magmas, and compositional variation of apatite-group minerals from spatially associated carbonatitic rocks are critically re-evaluated.

Optical characteristics of novel bulk and nanoengineered laser host materials

NASA Astrophysics Data System (ADS)

Prasad, Narasimha S.; Sova, Stacey; Kelly, Lisa; Bevan, Talon; Arnold, Bradley; Cooper, Christopher; Choa, Fow-Sen; Singh, N. B.

2018-02-01

The hexagonal apatite single crystals have been investigated for their applications as laser host materials. Czochralksi and flux growth methods have been utilized to obtain single crystals. For low temperature processing (<100 0C), several techniques for crystal growth have been developed. The hexagonal apatite structure (space group P63/m) is characteristic of several compounds, some of which have extremely interesting and useful properties as laser hosts and bone materials. Calcium lanthanum silicate (Nd-doped) and lanthanum aluminate material systems were studied in detail. Nanoengineered calcium and lanthanum based silicates were synthesized by a solution method and their optical and morphological characteristics were compared with Czochralski grown bulk hydroxyapatite single crystals. Materials were evaluated by absorbance, fluorescence and Raman characteristics. Neodymium, iron and chromium doped crystals grown by a solution method showed weak but similar optical properties to that of Czochralski grown single crystals.

The volatile content of Vesta: Clues from apatite in eucrites

NASA Astrophysics Data System (ADS)

Sarafian, Adam Robert; Roden, Michael F.; PatiñO-Douce, Alberto E.

2013-11-01

Apatite was analyzed by electron microprobe in 3 cumulate and 10 basaltic eucrites. Eucritic apatite is fluorine-rich with minor chlorine and hydroxyl (calculated by difference). We confirmed the hydroxyl content by measuring hydroxyl directly in apatites from three representative eucrites using secondary ionization mass spectroscopy. Overall, most eucritic apatites resemble fluorine-rich lunar mare apatites, but intriguing OH- and Cl-rich apatites suggest a role for water and/or hydrothermal fluids in the Vestan interior or on other related differentiated asteroids. Most late-stage apatite found in mesostasis has little hydroxyl or chlorine and is thought to have crystallized from a degassed magma; however, several apatites exhibit atypical compositions and/or textural characteristics. For example, the isotopically anomalous basaltic eucrite Pasamonte has apatite in the mesostasis with significant OH. Apatites in Juvinas also have significant OH and occur as veinlets crosscutting silicates. Euhedral apatites in the Moore County cumulate eucrite occur as inclusions in pyroxene and are also hydroxyl-rich (0.62 wt% OH). The OH was confirmed by SIMS analysis and this apatite clearly points to the presence of water, at least locally, in the Vestan interior. Portions of Elephant Moraine (EET) 90020 have large and abundant apatites, which may be the product of apatite accumulation in a zone of melt-rock reaction. Relatively chlorine-rich apatites occur in basaltic eucrite Graves Nunataks (GRA) 98098 (approximately 1 wt% Cl). Particularly striking is the compositional similarity between apatite in GRA 98098 and apatites in lunar KREEP, which may indicate the presence of residual magmas from an asteroid-wide magma ocean on Vesta.

[Synthesis and characterization of CO-3(2-) doping nano-hydroxyapatite].

PubMed

Liao, Jian-Guo; Li, Yan-Qun; Duan, Xing-Ze; Liu, Qiong

2014-11-01

CO3(2-) doping is an effective method to increase the biological activity of nano-hydroxyapatite (n-HA). In the present study, calcium nitrate and trisodium phosphate were chosen as raw materials, with a certain amount of Na2CO3 as a source of CO-3(2-) ions, to synthesize nano-carbonate hydroxyapatite (n-CHA) slurry by solution precipitation method. The structure and micro-morphology of n-CHA were characterized by transmission electron microscope (TEM), X-ray diffraction (XRD), Fourier transform-infrared spectroscopy (FTIR) and Raman spectroscopy (RS). The results revealed that the synthetic n-HA crystals are acicular in nanometer scale and have a crystal size of 20-30 nm in diameter and 60-80 nm in length, which are similar to natural bone apatite. And the crystallinity of n-CHA crystals decreases to the increment of CO3(2-). Samples with more CO3(2) have composition and structure more similar to the bone apatite. The value of lattice parameters a decreases, value of c increases, and c/a value increases with the increase in the amount of CO3(2-), in accordance with crystal cell parameters change rule of type B replacement. In the AB mixed type (substitution OH- and PO4(3-)) CHA, IR characteristic peak of CO3(2-) out-of-plane bending vibration appears at 872 cm(-1), meanwhile, the asymmetry flexible vibration band is split into band at 1 454 cm(-1) and band at 1 420 cm(-1), while weak CO3(2)-peak appears at 1 540 cm(-1). CO3(2-) Raman peak of symmetric stretching vibration appears at 1 122 cm(-1). CO3(2-) B-type (substitution PO4(3-)) peak appeared at 1 071 cm(-1). Through the calculation of integral area ratio of PO4(3-)/ CO3(2-), OH-/CO3(2-), and PO4(3-)/OH-, low quantity CO3(2-) is B-type and high quantity CO3(2-) is A-type (substitution OH-). The results show that the synthesized apatite crystals are AB hybrid substitued nano-carbonate hydroxyapatite, however B-type replacement is the main substitute mode. Due to similarity inthe shape, size, crystal structure and growth mode, the synthesized apatite crystals can be called a kind of bone-like apatite.

Mineralization of the vertebral bodies in Atlantic salmon (Salmo salar L.) is initiated segmentally in the form of hydroxyapatite crystal accretions in the notochord sheath

PubMed Central

Wang, Shou; Kryvi, Harald; Grotmol, Sindre; Wargelius, Anna; Krossøy, Christel; Epple, Mattias; Neues, Frank; Furmanek, Tomasz; Totland, Geir K

2013-01-01

We performed a sequential morphological and molecular biological study of the development of the vertebral bodies in Atlantic salmon (Salmo salar L.). Mineralization starts in separate bony elements which fuse to form complete segmental rings within the notochord sheath. The nucleation and growth of hydroxyapatite crystals in both the lamellar type II collagen matrix of the notochord sheath and the lamellar type I collagen matrix derived from the sclerotome, were highly similar. In both matrices the hydroxyapatite crystals nucleate and accrete on the surface of the collagen fibrils rather than inside the fibrils, a process that may be controlled by a template imposed by the collagen fibrils. Apatite crystal growth starts with the formation of small plate-like structures, about 5 nm thick, that gradually grow and aggregate to form extensive multi-branched crystal arborizations, resembling dendritic growth. The hydroxyapatite crystals are always oriented parallel to the long axis of the collagen fibrils, and the lamellar collagen matrices provide oriented support for crystal growth. We demonstrate here for the first time by means of synchroton radiation based on X-ray diffraction that the chordacentra contain hydroxyapatite. We employed quantitative real-time PCR to study the expression of key signalling molecule transcripts expressed in the cellular core of the notochord. The results indicate that the notochord not only produces and maintains the notochord sheath but also expresses factors known to regulate skeletogenesis: sonic hedgehog (shh), indian hedgehog homolog b (ihhb), parathyroid hormone 1 receptor (pth1r) and transforming growth factor beta 1 (tgfb1). In conclusion, our study provides evidence for the process of vertebral body development in teleost fishes, which is initially orchestrated by the notochord. PMID:23711083

Mineralization of the vertebral bodies in Atlantic salmon (Salmo salar L.) is initiated segmentally in the form of hydroxyapatite crystal accretions in the notochord sheath.

PubMed

Wang, Shou; Kryvi, Harald; Grotmol, Sindre; Wargelius, Anna; Krossøy, Christel; Epple, Mattias; Neues, Frank; Furmanek, Tomasz; Totland, Geir K

2013-08-01

We performed a sequential morphological and molecular biological study of the development of the vertebral bodies in Atlantic salmon (Salmo salar L.). Mineralization starts in separate bony elements which fuse to form complete segmental rings within the notochord sheath. The nucleation and growth of hydroxyapatite crystals in both the lamellar type II collagen matrix of the notochord sheath and the lamellar type I collagen matrix derived from the sclerotome, were highly similar. In both matrices the hydroxyapatite crystals nucleate and accrete on the surface of the collagen fibrils rather than inside the fibrils, a process that may be controlled by a template imposed by the collagen fibrils. Apatite crystal growth starts with the formation of small plate-like structures, about 5 nm thick, that gradually grow and aggregate to form extensive multi-branched crystal arborizations, resembling dendritic growth. The hydroxyapatite crystals are always oriented parallel to the long axis of the collagen fibrils, and the lamellar collagen matrices provide oriented support for crystal growth. We demonstrate here for the first time by means of synchroton radiation based on X-ray diffraction that the chordacentra contain hydroxyapatite. We employed quantitative real-time PCR to study the expression of key signalling molecule transcripts expressed in the cellular core of the notochord. The results indicate that the notochord not only produces and maintains the notochord sheath but also expresses factors known to regulate skeletogenesis: sonic hedgehog (shh), indian hedgehog homolog b (ihhb), parathyroid hormone 1 receptor (pth1r) and transforming growth factor beta 1 (tgfb1). In conclusion, our study provides evidence for the process of vertebral body development in teleost fishes, which is initially orchestrated by the notochord. © 2013 Anatomical Society.

Using Apatite to Model Chlorine Contents of High SiO2 Magmas: An Enhanced Methodological Approach

NASA Astrophysics Data System (ADS)

Flesch, R.; Webster, J. D.; Nadeau, P. A.

2015-12-01

Hydrothermal experiments were conducted on high-silica (73-75 wt% SiO2), fluid-saturated melts at 844-862°C and ca. 50 MPa using crushed glass of the Los Posos rhyolite. Water and salts including NaCl, KCl, Ca(OH)2, and CaHPO4 and HCl were added proportionally to the experiments to restrict the variability of the aluminosity of the melt. The Durango apatite, which contains 3.53 wt% F and 0.41% Cl, was added as "seeds"<5µm in diameter to stimulate apatite growth during the experiments. Samples were loaded into gold capsules and run in cold-seal pressure vessels for durations of 286-1008 hours. Temperature was cycled at ±20˚C to promote apatite crystallization. Electron microprobe analyses of run-product glasses and embedded apatite grains support calculation of a range of partition coefficients ( = wt% Cl in apatite/wt% Cl in melt) of 4.7 to 15.9. The mole fraction of Cl in experimental apatites, or XCl, ranges from 0.19 to 0.56, while XF ranges from 0.08 to 0.63. The computed values for XOH range from 0.24 to 0.38. We find that normalizing XCl to XOH of apatites dramatically improves the precision when using apatite compositions to model Cl contents of melts. We compare our Los Posos rhyolite experiments with published data on 50 MPa rhyodacite experiments and find that Cl partitioning is significantly different in each system. Given the importance of chlorine in fluid equilibria, ore transport, and magma evolution, applications of apatite as a proxy for Cl contents in melts are unbounded. It is found that in order to accurately use the volatile composition of natural and synthetic apatites to calculate the volatile composition of melts in felsic systems, several chemical factors, including wt% SiO2 and the aluminosity/alkalinity of melts, should be incorporated as parameters to enhance relevant modeling. This allows geochemists to place better constraints on processes associated with crystallizing Cl-bearing magmatic systems.

The oxidation state of sulfur in apatite: A new oxybarometer?

NASA Astrophysics Data System (ADS)

Fiege, A.; Konecke, B.; Kim, Y.; Simon, A. C.; Becker, U.; Parat, F.

2016-12-01

Oxygen fugacity (fO2) of magmatic and hydrothermal systems influences, for instance, crystallization and degassing processes as well as metal solubilities in melts and fluids. Apatite is a ubiquitous mineral in magmatic and hydrothermal environments that can record and preserve volatile zonation. It can contain several thousand μg/g of the redox sensitive element sulfur (S), making S-in-apatite a potential fO2 sensor. Despite the polyvalent properties of S (e.g., S2-, S4+, S6+), the oxidation state and incorporation mechanisms of S in the apatite structure are poorly understood. In this study, the oxidation state of S-in-apatite as a function of fO2 is investigated using X-ray absorption near-edge structures (XANES) spectroscopy at the S K-edge. Apatites crystallized from lamproitic melts at 1000°C, 300 MPa and over a broad range of fO2 and sulfur fugacities (fS2) were measured. Peaks corresponding to S6+ ( 2482 eV), S4+ ( 2478 eV) and S2- ( 2470 eV) were identified in apatite. The integrated S6+/STotal (STotal = S6+ + S4+ + S2-) peak area ratios show a distinct positive correlation with fO2, increasing from 0.17 at FMQ+0 to 0.96 at FMQ+3. Ab-initio calculations were performed to further understand the energetics and geometry of incorporation of S6+, S4+ and S2- into the apatite (F-, Cl-, OH-) end-members. The results confirm that apatite can contain three different oxidations states of S (S6+, S4+, S2-) as a function of fO2. This makes apatite probably the first geologically relevant mineral to incorporate reduced (S2-), intermediate (S4+), and oxidized (S6+) S in variable proportions. We emphasize that the strong dependence of the S oxidation state in apatite as a function of fO2 is also coupled with changing S content of apatite and co-existing melt (i.e., with changing fS2), resulting in a complex correlation between [1] apatite-melt (or fluid) partitioning, [2] redox conditions and [3] the melt and/or fluid composition, making the application of previously determined S apatite-melt partitioning coefficient debatable. Upon calibration over a range of geologically relevant T-P-X-fO2-fS2, S-in-apatite can serve as a powerful oxybarometer to quantify fO2.

Absence of bacterial imprints on struvite-containing kidney stones: a structural investigation at the mesoscopic and atomic scale.

PubMed

Bazin, Dominique; André, Gilles; Weil, Raphael; Matzen, Guy; Emmanuel, Veron; Carpentier, Xavier; Daudon, M

2012-04-01

Bacterial imprints are always observed on highly carbonated apatite kidney stones but not struvite kidney stones. Struvite and carbonated apatite stones with a high CO(3)(2-)/PO(4)(3-) rate are believed to develop from infections, but their structural differences at the mesoscopic scale lack explanation. We investigated 17 urinary calculi composed mainly of struvite or carbonated apatite by Fourier transform infrared, scanning electron microscopy, and powder neutron diffraction techniques. Carbonated apatite but not struvite stones showed bacterial imprints. If the same stone contained both carbonated apatite and struvite components, bacterial imprints were observed on the carbonated apatite but not the struvite part. Moreover, neutron powder diffraction experiments revealed the crystal size of struvite stones were larger than that of carbonated apatite stones (250 ± 50 vs 50 nm). Bacterial imprints may appear more easily on kidney stones with small nanocrystals, such as carbonated apatite than with large nanocrystals, such as struvite. This approach may help identify bacteria contributing to stone formation, perhaps with negative results of urine culture. Copyright © 2012 Elsevier Inc. All rights reserved.

Apatite-Melt Partitioning at 1 Bar: An Assessment of Apatite-Melt Exchange Equilibria Resulting from Non-Ideal Mixing of F and Cl in Apatite

NASA Technical Reports Server (NTRS)

McCubbin, F. M.; Ustunisik, G.; Vander Kaaden, K. E.

2016-01-01

The mineral apatite [Ca5(PO4)3(F,Cl,OH)] is present in a wide range of planetary materials. Due to the presence of volatiles within its crystal structure (X-site), many recent studies have attempted to use apatite to constrain the volatile contents of planetary magmas and mantle sources. In order to use the volatile contents of apatite to precisely determine the abundances of volatiles in coexisting silicate melt or fluids, thermodynamic models for the apatite solid solution and for the apatite components in multi-component silicate melts and fluids are required. Although some thermodynamic models for apatite have been developed, they are incomplete. Furthermore, no mixing model is available for all of the apatite components in silicate melts or fluids, especially for F and Cl components. Several experimental studies have investigated the apatite-melt and apatite-fluid partitioning behavior of F, Cl, and OH in terrestrial and planetary systems, which have determined that apatite-melt partitioning of volatiles are best described as exchange equilibria similar to Fe-Mg partitioning between olivine and silicate melt. However, McCubbin et al. recently reported that the exchange coefficients may vary in portions of apatite compositional space where F, Cl, and OH do not mix ideally in apatite. In particular, solution calorimetry data of apatite compositions along the F-Cl join exhibit substantial excess enthalpies of mixing. In the present study, we conducted apatite-melt partitioning experiments in evacuated, sealed silica-glass tubes at approximately 1 bar and 950-1050 degrees Centigrade on a synthetic Martian basalt composition equivalent to the basaltic shergottite Queen Alexandria Range (QUE) 94201. These experiments were conducted dry, at low pressure, to assess the effects of temperature and apatite composition on the partitioning behavior of F and Cl between apatite and basaltic melt along the F-Cl apatite binary join, where there is non-ideal mixing of F and Cl in apatite.

Quantitatively and Kinetically Identifying Binding Motifs of Amelogenin Proteins to Mineral Crystals Through Biochemical and Spectroscopic Assays

PubMed Central

Zhu, Li; Hwang, Peter; Witkowska, H. Ewa; Liu, Haichuan; Li, Wu

2014-01-01

Tooth enamel is the hardest tissue in vertebrate animals. Consisting of millions of carbonated hydroxyapatite crystals, this highly mineralized tissue develops from a protein matrix in which amelogenin is the predominant component. The enamel matrix proteins are eventually and completely degraded and removed by proteinases to form mineral-enriched tooth enamel. Identification of the apatite-binding motifs in amelogenin is critical for understanding the amelogenin–crystal interactions and amelogenin–proteinases interactions during tooth enamel biomineralization. A stepwise strategy is introduced to kinetically and quantitatively identify the crystal-binding motifs in amelogenin, including a peptide screening assay, a competitive adsorption assay, and a kinetic-binding assay using amelogenin and gene-engineered amelogenin mutants. A modified enzyme-linked immunosorbent assay on crystal surfaces is also applied to compare binding amounts of amelogenin and its mutants on different planes of apatite crystals. We describe the detailed protocols for these assays and provide the considerations for these experiments in this chapter. PMID:24188774

Development of Solid State Laser Materials for Application in Lasers for Atmospheric Ozone and Water Vapor Sensing

NASA Technical Reports Server (NTRS)

Noginov, Makhail A.; Loutts, G. B.

2002-01-01

We have grown neodymium doped mixed apatite crystals, (Sr(x)Ba(l-x)5(PO4)3F, Sr5(P(1-x)V(x)O4)3F, and Ba5(P(1-x)V(x)O4)3F, and spectroscopically studied them as potential gain media for a laser source for atmospheric water sensing operating at 944.11 nm0. We conclude that an appropriate apatite host material for a 944.11 nm laser should be a mixture of Sr5(PO4)3F with a small fraction of Ba5(PO4)3F. The precise wavelength tuning around 944.11 nm can be accomplished by varying the host composition, temperature, and threshold population inversion. In apatite crystals of mixed composition, the Amplified Spontaneous Emission (ASE) loss at 1.06 microns is predicted to be significantly smaller than that in the end members.

Influences of Sr dose on the crystal structure parameters and Sr distributions of Sr-incorporated hydroxyapatite.

PubMed

Guo, D G; Hao, Y Z; Li, H Y; Fang, C Q; Sun, L J; Zhu, H; Wang, J; Huang, X F; Ni, P F; Xu, K W

2013-10-01

Stoichiometric strontium-incorporated hydroxyapatite (Sr-HA) with different Sr concentrations [Sr/(Sr+Ca)] were synthesized using a wet chemical approach and characterized by X-ray diffraction, Fourier-transformed infrared absorption, X-ray photoelectron spectroscopy, and Rietveld Structure Refinement. The crystal lattice parameter, Sr distribution, chemical state of Sr, and also the relationships between their variations and the Sr concentrations have been intensively studied. The results show that both the crystal lattice parameters and crystal plane space of Sr-HA remarkably increase with the Sr concentration increasing. Whether Sr preferably occupies the Ca(I) site or Ca(II) site after incorporated into apatite lattice depends on the Sr number incorporated into apatite. All the Sr ions completely occupy the Ca(II) sites when the Sr concentration is below 5%. With the exception of partial Sr ions occupying the Ca(II) sites, the other Sr ions start to occupy the Ca(I) sites when the Sr concentration doped in HA is beyond 10%. The ratio of Sr ions occupying the Ca(I) sites increases with the further raising Sr concentration up to 20%. The Sr ions inherit the chemical state and environment of the original Ca(I) or Ca(II) site after incorporated into apatite. Copyright © 2013 Wiley Periodicals, Inc.

Interrogating the Effects of Radiation Damage Annealing on Helium Diffusion Kinetics in Apatite

NASA Astrophysics Data System (ADS)

Willett, C. D.; Fox, M.; Shuster, D. L.

2015-12-01

Apatite (U-Th)/He thermochronology is commonly used to study landscape evolution and potential links between climate, erosion and tectonics. The technique relies on a quantitative understanding of (i) helium diffusion kinetics in apatite, (ii) an evolving 4He concentration, (iii) accumulating damage to the crystal lattice caused by radioactive decay[1], and (iv) the thermal annealing of such damage[2],[3], which are each functions of both time and temperature. Uncertainty in existing models of helium diffusion kinetics has resulted in conflicting conclusions, especially in settings involving burial heating through geologic time. The effects of alpha recoil damage annealing are currently assumed to follow the kinetics of fission track annealing (e.g., reference [3]), although this assumption is difficult to fully validate. Here, we present results of modeling exercises and a suite of experiments designed to interrogate the effects of damage annealing on He diffusivity in apatite that are independent of empirical calibrations of fission track annealing. We use the existing experimental results for Durango apatite[2] to develop and calibrate a new function that predicts the effects of annealing temperature and duration on measured diffusivity. We also present a suite of experiments conducted on apatite from Sierra Nevada, CA granite to establish whether apatites with different chemical compositions have the same behavior as Durango apatite. Crystals were heated under vacuum to temperatures between 250 and 500°C for 1, 10, or 100 hours. The samples were then irradiated with ~220 MeV protons to produce spallogenic 3He, the diffusant then used in step-heating diffusion experiments. We compare the results of these experiments and model calibrations to existing models. Citations: [1]Shuster, D., Flowers R., and Farley K., (2006), EPSL 249(3-4), 148-161; [2]Shuster, D. and Farley, K., (2009), GCA 73 (1), 6183-6196; [3]Flowers, R., Ketcham, R., Shuster, D. and Farley, K., (2009), GCA 73, 2347-2365.

Fabrication of carbonate apatite block based on internal dissolution-precipitation reaction of dicalcium phosphate and calcium carbonate.

PubMed

Daitou, Fumikazu; Maruta, Michito; Kawachi, Giichiro; Tsuru, Kanji; Matsuya, Shigeki; Terada, Yoshihiro; Ishikawa, Kunio

2010-05-01

In this study, we investigated a novel method for fabrication of carbonate apatite block without ionic movement between precursor and solution by using precursor that includes all constituent ions of carbonate apatite. A powder mixture prepared from dicalcium phosphate anhydrous and calcite at appropriate Ca/P ratios (1.5, 1.67, and 1.8) was used as starting material. For preparation of specimens, the slurry made from the powder mixture and distilled water was packed in a split stainless steel mold and heat - treated, ranging from 60 degrees C to 100 degrees C up to 48 hours at 100% humidity. It appeared that carbonate apatite could be obtained above 70 degrees C and monophasic carbonate apatite could be obtained from the powder mixture at Ca/P ratio of 1.67. Carbonate content of the specimen was about 5-7%. Diametral tensile strength of the carbonate apatite blocks slightly decreased with increasing treatment temperature. The decrease in diametral tensile strength is thought to be related to the crystal size of the carbonate apatite formed.

Magnetite-apatite-dolomitic rocks of Ust-Chulman (Aldan shield, Russia): Seligdar-type carbonatites?

NASA Astrophysics Data System (ADS)

Prokopyev, Ilya R.; Doroshkevich, Anna G.; Redina, Anna A.; Obukhov, Andrey V.

2018-04-01

The Ust-Chulman apatite ore body is situated within the Nimnyrskaya apatite zone at the Aldan shield in Russia. The latest data confirm the carbonatitic origin of the Seligdar apatite deposit (Prokopyev et al. in Ore Geol Rev 81:296-308, 2017). The results of our investigations demonstrate that the magnetite-apatite-dolomitic rocks of the Ust-Chulman are highly similar to Seligdar-type dolomitic carbonatites in terms of the mineralogy and the fluid regime of formation. The ilmenite and spinel mineral phases occur as solid solutions with magnetite, and support the magmatic origin of the Ust-Chulman ores. The chemical composition of REE- and SO3-bearing apatite crystals and, specifically, monazite-(Ce) mineralisation and the formation of Nb-rutile, late hydrothermal sulphate minerals (barite, anhydrite) and haematite are typical for carbonatite complexes. The fluid inclusions study revealed similarities to the evolutionary trend of the Seligdar carbonatites that included changes of the hydrothermal solutions from highly concentrated chloride to medium-low concentrated chloride-sulphate and oxidized carbonate-ferrous.

Apatite: A New Tool For Understanding The Temporal Variability Of Magmatic Volatile Contents

NASA Astrophysics Data System (ADS)

Stock, M. J.; Humphreys, M.; Smith, V.; Pyle, D. M.; Isaia, R.

2015-12-01

The apatite crystal structure is capable of incorporating H2O, F and Cl, as well as trace CO2 and sulphur. These can be related to parental magma compositions through application of a series of pressure and temperature-dependent exchange reactions (Piccoli and Candela, 1994), permitting apatite crystals to preserve a record of all major volatile species in the melt. Furthermore, due to the general incompatibility of P in other rock-forming minerals, apatite is ubiquitous in igneous systems and often begins crystallising early, such that apatite inclusions within phenocrysts record melt volatile contents throughout magmatic differentiation. In this work, we compare the compositions of apatite inclusions and microphenocrysts with pyroxene-hosted melt inclusions from the Astroni 1 eruption of Campi Flegrei, Italy. These data are coupled with magmatic differentiation models (Gualda et al., 2012), experimental volatile solubility data (Webster et al., 2014) and thermodynamic models of apatite compositional variations (Piccoli and Candela, 1994) to determine a time-series of magmatic volatile evolution in the build-up to eruption. We find that apatite halogen/OH ratios decreased through magmatic differentiation, while melt inclusion F and Cl concentrations increased. Melt inclusion H2O contents are constant at ~2.5 wt%. These data are best explained by volatile-undersaturated differentiation over most of the crystallisation history of the Astroni 1 melt, with melt inclusion H2O contents reset during ascent, due to rapid H diffusion through the phenocryst hosts (Woods et al., 2000). Given the rapid diffusivity of volatiles in apatite (Brenan, 1993), preservation of undersaturated compositions in microphenocrysts suggests that saturation was only achieved a few days to months before eruption and that it may have been the transition into a volatile-saturated state that ultimately triggered eruption. Piccoli and Candela, 1994. Am. J. of Sc., 294, 92-135. Gualda et al., 2012. J. Pet., 53, 875-890. Webster et al., 2014. J. Pet., 55, 2217-2248. Woods et al., 2000. Am. Min., 85, 480-487. Brenan, 1993. Chem. Geol., 110, 195-210.

Helium diffusion experiments on synthetic apatite crystals and single-grain fragments: can we retrieve the He diffusion profiles?

NASA Astrophysics Data System (ADS)

Kasanzu, C.; Beucher, R.; Brown, R. W.; Persano, C.; Stuart, F.

2011-12-01

Apatite (U-Th)/he thermochronometry is one of the most widely used methods of quantifying thermal histories of rocks within the vicinity of the surface. Theoretical and practical development carried out during the last decade, among which was the release of affordable LASERs, have led to standard practice of analyzing single grain rather than multigrain aliquots. The standard theoretical basis for interpreting these ages assumes that the technique is used on full grains. However, the natural weak cleavage of apatite leads to fragmentation of these individual prismatic crystals during the rock crushing and mineral separation process. Apatites are most often broken along a weak cleavage perpendicular to the c-axis. It is therefore common practice to analyze fragments of whole grains, not complete crystals. It is also well known that dating often leads to single ages being more dispersed than expected whatever the efforts to avoid perturbations on the He system. Using a theoretical numerical model and considering both axial and radial diffusion, we demonstrate thata largepart (most?) of the dispersion is due to analyses of single apatite fragments. This effect is larger for older grains which have exprienced a slow cooling history and have well rounded diffusive profiles. Ages are a strongfunction of the fragment size (length specifically), we show that ages from apatite fragments with 1 prismatic termination (1T) can be used to retrieve the helium diffusion profile, provided a sufficient number of single fragment analyses are carried out. The shape of the helium diffusion profile provides a strong constraint on the style of the thermal history and so we propose to use single crystal fragment analyses to extract a mean diffusion profile, and deduce the thermal history of the sample. In order to test these ideas, we performed a set of experiments with natural samples and semi-synthetic grains of apatite. Synthetic grains are obtained by drilling cores of various length/width ratios within standard Durango crystals while natural grains are separated from a deep borehole in south-Africa (BK1) and from the Australian craton. Several experiences are presented: 1) (U-Th)/He dating of about 100 1T single-fragment aliquots of different shape ratio from the BK1 borehole; 2) (U-Th)/He dating of 20 2T single-fragment aliquot from an Australian sample previously dated following standard procedure. 3) (U-Th)/He dating of synthetic fragmentsfrom synthetic grains previously degassed by a known percentageusing a thermo-regulated furnace. The results of the experiments lead to important new insight into the natural dispersion of (U-Th)/He single-grain ages. They show that far from being problematic, highly dispersed data may indeed contain first-order information on the thermal history of rocks. We discuss all the details of the standard (U-Th)/He approach such as the effects of temporally variable diffusivity (e.g. radiation damage models), zonation of U and Th and arbitrary grain size variations.

Properties and Crystallization Phenomena in Li2Si2O5–Ca5(PO4)3F and Li2Si2O5–Sr5(PO4)3F Glass–Ceramics Via Twofold Internal Crystallization

PubMed Central

Rampf, Markus; Dittmer, Marc; Ritzberger, Christian; Schweiger, Marcel; Höland, Wolfram

2015-01-01

The combination of specific mechanical, esthetic, and chemical properties is decisive for the application of materials in prosthodontics. Controlled twofold crystallization provides a powerful tool to produce special property combinations for glass–ceramic materials. The present study outlines the potential of precipitating Ca5(PO4)3F as well as Sr5(PO4)3F as minor crystal phases in Li2Si2O5 glass–ceramics. Base glasses with different contents of CaO/SrO, P2O5, and F− were prepared within the glasses of the SiO2–Li2O–K2O–CaO/SrO–Al2O3–P2O5–F system. Preliminary studies of nucleation by means of XRD and scanning electron microscopy (SEM) of the nucleated base glasses revealed X-ray amorphous phase separation phenomena. Qualitative and quantitative crystal phase analyses after crystallization were conducted using XRD in combination with Rietveld refinement. As a main result, a direct proportional relationship between the content of apatite-forming components in the base glasses and the content of apatite in the glass–ceramics was established. The microstructures of the glass–ceramics were investigated using SEM. Microstructural and mechanical properties were found to be dominated by Li2Si2O5 crystals and quite independent of the content of the apatite present in the glass–ceramics. Biaxial strengths of up to 540 MPa were detected. Ca5(PO4)3F and Sr5(PO4)3F influence the translucency of the glass–ceramics and, hence, help to precisely tailor the properties of Li2Si2O5 glass–ceramics. The authors conclude that the twofold crystallization of Li2Si2O5–Ca5(PO4)3F or Li2Si2O5–Sr5(PO4)3F glass–ceramics involves independent solid-state reactions, which can be controlled via the chemical composition of the base glasses. The influence of the minor apatite phase on the optical properties helps to achieve new combinations of features of the glass–ceramics and, hence, displays new potential for dental applications. PMID:26389112

Properties and Crystallization Phenomena in Li2Si2O5-Ca5(PO4)3F and Li2Si2O5-Sr5(PO4)3F Glass-Ceramics Via Twofold Internal Crystallization.

PubMed

Rampf, Markus; Dittmer, Marc; Ritzberger, Christian; Schweiger, Marcel; Höland, Wolfram

2015-01-01

The combination of specific mechanical, esthetic, and chemical properties is decisive for the application of materials in prosthodontics. Controlled twofold crystallization provides a powerful tool to produce special property combinations for glass-ceramic materials. The present study outlines the potential of precipitating Ca5(PO4)3F as well as Sr5(PO4)3F as minor crystal phases in Li2Si2O5 glass-ceramics. Base glasses with different contents of CaO/SrO, P2O5, and F(-) were prepared within the glasses of the SiO2-Li2O-K2O-CaO/SrO-Al2O3-P2O5-F system. Preliminary studies of nucleation by means of XRD and scanning electron microscopy (SEM) of the nucleated base glasses revealed X-ray amorphous phase separation phenomena. Qualitative and quantitative crystal phase analyses after crystallization were conducted using XRD in combination with Rietveld refinement. As a main result, a direct proportional relationship between the content of apatite-forming components in the base glasses and the content of apatite in the glass-ceramics was established. The microstructures of the glass-ceramics were investigated using SEM. Microstructural and mechanical properties were found to be dominated by Li2Si2O5 crystals and quite independent of the content of the apatite present in the glass-ceramics. Biaxial strengths of up to 540 MPa were detected. Ca5(PO4)3F and Sr5(PO4)3F influence the translucency of the glass-ceramics and, hence, help to precisely tailor the properties of Li2Si2O5 glass-ceramics. The authors conclude that the twofold crystallization of Li2Si2O5-Ca5(PO4)3F or Li2Si2O5-Sr5(PO4)3F glass-ceramics involves independent solid-state reactions, which can be controlled via the chemical composition of the base glasses. The influence of the minor apatite phase on the optical properties helps to achieve new combinations of features of the glass-ceramics and, hence, displays new potential for dental applications.

A bio-recognition device developed onto nano-crystals of carbonate apatite for cell-targeted gene delivery.

PubMed

Chowdhury, E H; Akaike, Toshihiro

2005-05-20

The DNA delivery to mammalian cells is an essential tool for analyzing gene structure, regulation, and function. The approach holds great promise for the further development of gene therapy techniques and DNA vaccination strategies to treat and control diseases. Here, we report on the establishment of a cell-specific gene delivery and expression system by physical adsorption of a cell-recognition molecule on the nano-crystal surface of carbonate apatite. As a model, DNA/nano-particles were successfully coated with asialofetuin to facilitate uptake by hepatocyte-derived cell lines through the asialoglycoprotein receptor (ASGPr) and albumin to prevent non-specific interactions of the particles with cell-surface. The resulting composite particles with dual surface properties could accelerate DNA uptake and enhance expression to a notable extent. Nano-particles coated with transferrin in the same manner dramatically enhanced transgene expression in the corresponding receptor-bearing cells and thus our newly developed strategy represents a universal phenomenon for anchoring a bio-recognition macromolecule on the apatite crystal surface for targeted gene delivery, having immediate applications in basic research laboratories and great promise for gene therapy. (c) 2005 Wiley Periodicals, Inc.

Structural change in lead fluorapatite at high pressure

NASA Astrophysics Data System (ADS)

Fleet, Michael E.; Liu, Xi; Shieh, Sean R.

2010-01-01

The structure of lead fluorapatite [PbFAP; Pb10(PO4)6F2], crystallized from the melt in a platinum capsule at 1,000°C and 1 atm, has been investigated by single-crystal X-ray diffraction. Crystal data are a = 9.7638 (6), c = 7.2866 (4) Å, space group P63/ m, R = 0.043, R w = 0.034. We have also studied the compressional behaviour of the c-axis channel of PbFAP up to 9 GPa at 25°C, using a diamond-anvil cell, synchrotron X-radiation, and Rietveld powder structure refinement. Pressure-volume data for the channel polyhedron of PbFAP fitted to the third-order Birch-Murnaghan equation resulted in K T = 33.2 ± 1.2 GPa when K T ' is fixed at 4. The c-axis channel of PbFAP is about twice as compressible as the unit-cell volume of PbFAP and the channel of calcium apatites. This is attributed to the anomalous narrowing of the channel of PbFAP with increase in confining pressure. Flexibility of the apatite channel is a key factor in the scavenging of toxic heavy metals by calcium apatites.

­­­Experimental Quantifications of Radiation Damage Annealing and Helium Diffusion Kinetics in Apatite

NASA Astrophysics Data System (ADS)

Willett, C. D.; Shuster, D. L.

2017-12-01

(U-Th)/He thermochronology in apatite requires a quantitative description of He diffusivity as a function of temperature and through geologic time. Although variability in diffusion kinetics across a range of natural apatite samples has revealed that higher concentrations of alpha-recoil radiation damage correlates with lower He diffusivity (i.e., at a given temperature, [1]), only one published study has experimentally quantified the effects of annealing for a single apatite specimen (Durango apatite, [2]). Although these effects have been incorporated into now widely applied numerical models, underlying assumptions in these models—in particular, that He diffusivity in all apatite crystals responds with the same rate of damage annealing—have been called into question, and further evaluation is warranted (e.g., [3], [4]). Here, we will describe a suite of experiments conducted on apatite from a single hand sample of granite from Sierra Nevada, CA as well as Durango apatite, to establish whether these two apatites with different chemical compositions and thermal pasts exhibit the same response to annealing conditions. Crystals from both samples were heated under vacuum to temperatures between 220 and 500 °C for 1, 10, 100 or 1000 hours. The samples were then irradiated with 220 MeV protons to produce spallation 3He, the diffusant used in subsequent step-heating degassing experiments. Our preliminary results indicate different minima in closure temperatures of 55 oC and 65 oC for the Durango and Sierra apatite, respectively, when exposed to sufficiently high temperatures (>350 oC) for durations > 1 hour, yet similar transitions from low diffusivities at T <200 oC (and higher activation energy, Ea) to higher diffusivity (lower Ea) across a range of experimental annealing temperatures and durations. We will interpret these results with a new model framework for describing the effects of annealing on diffusivity, and will discuss potential implications of our experimental results, the required assumptions in our analyses, and potential limitations of such empirical quantifications. References: [1] Shuster, D. et al. (2006), EPSL 294, 148-161; [2] Shuster, D., Farley, K. (2009), GCA 73 (1), 6183-6196; [3] Gautheron, C. et al. (2013), Chem. Geol. 351, 257-267; [4] Fox, M., Shuster, D. (2014), EPSL 397, 174-183.

Visualization of structural organization of ventral membranes of sheared-open resorbing osteoclasts attached to apatite pellets.

PubMed

Akisaka, Toshitaka; Yoshida, Atsushi

2015-05-01

Osteoclasts are highly polarized cells from both morphological and functional points of view. Using quick-freeze, rotary-replication methods combined with cell-shearing, we clarified the variability of cytoplasmic surface of the polarized membranes of osteoclasts seeded on apatite. As to the organization of actin filaments and clathrin sheets, we confirmed almost the same ventral membrane specializations of osteoclasts on apatite as seen on glass plates. The organized actin filaments and membrane-associated particles supported the ruffled border membranes. Inside the actin sealing zone, membrane specializations were not always occupied with the ruffled border but also with other types of membranes. Some osteoclasts formed an actin ring but lacked the ruffled border projections. We report a unique and distinctive membrane modification of apatite-attached osteoclasts, i.e., the presence of dense aggregates of membrane-associated particles and related structures not found in the osteoclasts seeded on glass plates. Actin filament polarity in the podosomes was determined by decoration with myosin S1. The actin filament polarity within podosome appears to be oriented predominantly with its barbed ends toward the core, whereas the interconnecting F-actin appears to be mixed oriented. Two different types of clathrin plaques displayed different distributions: clathrin-dependent endocytosis was observed in the ruffled border regions, whereas flat clathrin sheets were found in the leading edge of lamellipodia and near podosomes. The clathrin sheets adhered to the apatite surface tightly on the ventral membranes overlaying the resorption lacunae. All these membrane specializations as mentioned above may indicate the functional variability of osteoclasts seeded on apatite.

Crystallization conditions and controls on trace element residence in the main minerals from the Pedra Branca Syenite, Brazil: An electron microprobe and LA-ICPMS study

NASA Astrophysics Data System (ADS)

Carvalho, Bruna Borges; Janasi, Valdecir de Assis

2012-11-01

Major and trace-element microanalyses of the main minerals from the 610 Ma Pedra Branca Syenite, southeast Brazil, allow inferences on intensive parameters of magmatic crystallization and on the partition of trace-elements among these minerals, with important implications for the petrogenetic evolution of the pluton. Two main syenite types make up the pluton, a quartz-free syenite with tabular alkali feldspar (laminated silica-saturated syenite, LSS, with Na-rich augite + phlogopite + hematite + magnetite + titanite + apatite) and a quartz-bearing syenite (laminated silica-oversaturated syenite, LSO, with scarce corroded plagioclase plus diopside + biotite ± hornblende + ilmenite ± magnetite + titanite + apatite). Both types share a remarkable enrichment in incompatible elements as K, Ba, Sr, P and LREE. Apatite saturation temperatures of ~ 1060-1090 °C are the best estimates of liquidus, whereas the pressure of emplacement, based on Al-in-hornblende barometry, is estimated as 3.3 to 4.8 kbar. Although both units crystallized under oxidizing conditions, oxygen fugacity was probably higher in LSS, as shown by higher mg# of the mafic minerals and higher hematite contents in Hem-Ilmss. In contrast with the Ca-bearing alkali-feldspar from LSO, which hosts most of the whole-rock Sr and Pb, virtually Ca-free alkali-feldspar from LSS hosts ~ 50% of whole-rock Sr and ~ 80% of Pb, the remainder of these elements being shared by apatite, pyroxene and titanite. This contrast reflects a strong crystal-chemical control, whereby a higher proportion of an element with similar ratio and charge (Ca2 +) enhances the residence of Sr and Pb in the M-site of alkali feldspar. The more alkaline character of the LSS magma is inferred to have inhibited zircon saturation; Zr + Hf remained in solution until late in the crystallization, and were mostly accommodated in the structure of Ca-Na pyroxene and titanite, which are one order of magnitude richer in these elements compared to the same minerals in LSO, where most of Zr and Hf are inferred to reside in zircon. The REE, Th and U reside mostly in titanite and apatite; D(REE)Tit/Ap raises steadily from 1 to 6 from La to Tb then remains constant up to Lu in the LSO sample; these values are about half as much in the LSS sample, where lower contents of incompatible elements in titanite are attributed to its greater modal abundance and earlier crystallization.

Preparation of a bonelike apatite-polymer fiber composite using a simple biomimetic process.

PubMed

Yokoyama, Yoshiro; Oyane, Ayako; Ito, Atsuo

2008-08-01

A bonelike apatite-polymer fiber composite may be useful as an implant material to replace bone, the enthesis of a tendon, and the joint part of a ligament. We treated an ethylene-vinyl alcohol copolymer (EVOH) plate and knitted EVOH fibers with an oxygen plasma to produce oxygen-containing functional groups on their surfaces. The plasma-treated samples were alternately dipped in alcoholic calcium and phosphate ion solutions three times to deposit apatite precursors onto their surfaces. The surface-modified samples formed a dense and uniform bonelike surface apatite layer after immersion for 24 h in a simulated body fluid with ion concentrations approximately equal to those of human blood plasma. The adhesive strength between the apatite layer and the sample's surface increased with increasing power density of the oxygen plasma. The apatite-EVOH fiber composite obtained by our process has similarities to natural bone in that apatite crystals are deposited on organic polymer fibers. The resulting composite would possess osteoconductivity due to the apatite phase. With proper polymer selection and optimized synthesis techniques, a composite could be made that would have bonelike mechanical properties. Hence, the present surface modification and coating process would be a promising route to obtain new implant materials with bonelike mechanical properties and osteoconductivity. (c) 2007 Wiley Periodicals, Inc.

Ultra-structural defects cause low bone matrix stiffness despite high mineralization in osteogenesis imperfecta mice☆

PubMed Central

Vanleene, Maximilien; Porter, Alexandra; Guillot, Pascale-Valerie; Boyde, Alan; Oyen, Michelle; Shefelbine, Sandra

2012-01-01

Bone is a complex material with a hierarchical multi-scale organization from the molecule to the organ scale. The genetic bone disease, osteogenesis imperfecta, is primarily caused by mutations in the collagen type I genes, resulting in bone fragility. Because the basis of the disease is molecular with ramifications at the whole bone level, it provides a platform for investigating the relationship between structure, composition, and mechanics throughout the hierarchy. Prior studies have individually shown that OI leads to: 1. increased bone mineralization, 2. decreased elastic modulus, and 3. smaller apatite crystal size. However, these have not been studied together and the mechanism for how mineral structure influences tissue mechanics has not been identified. This lack of understanding inhibits the development of more accurate models and therapies. To address this research gap, we used a mouse model of the disease (oim) to measure these outcomes together in order to propose an underlying mechanism for the changes in properties. Our main finding was that despite increased mineralization, oim bones have lower stiffness that may result from the poorly organized mineral matrix with significantly smaller, highly packed and disoriented apatite crystals. Using a composite framework, we interpret the lower oim bone matrix elasticity observed as the result of a change in the aspect ratio of apatite crystals and a disruption of the crystal connectivity. PMID:22449447

Ultra-structural defects cause low bone matrix stiffness despite high mineralization in osteogenesis imperfecta mice.

PubMed

Vanleene, Maximilien; Porter, Alexandra; Guillot, Pascale-Valerie; Boyde, Alan; Oyen, Michelle; Shefelbine, Sandra

2012-06-01

Bone is a complex material with a hierarchical multi-scale organization from the molecule to the organ scale. The genetic bone disease, osteogenesis imperfecta, is primarily caused by mutations in the collagen type I genes, resulting in bone fragility. Because the basis of the disease is molecular with ramifications at the whole bone level, it provides a platform for investigating the relationship between structure, composition, and mechanics throughout the hierarchy. Prior studies have individually shown that OI leads to: 1. increased bone mineralization, 2. decreased elastic modulus, and 3. smaller apatite crystal size. However, these have not been studied together and the mechanism for how mineral structure influences tissue mechanics has not been identified. This lack of understanding inhibits the development of more accurate models and therapies. To address this research gap, we used a mouse model of the disease (oim) to measure these outcomes together in order to propose an underlying mechanism for the changes in properties. Our main finding was that despite increased mineralization, oim bones have lower stiffness that may result from the poorly organized mineral matrix with significantly smaller, highly packed and disoriented apatite crystals. Using a composite framework, we interpret the lower oim bone matrix elasticity observed as the result of a change in the aspect ratio of apatite crystals and a disruption of the crystal connectivity. Copyright © 2012 Elsevier Inc. All rights reserved.

Apatite (U-Th)/He thermochronometry using a radiation damage accumulation and annealing model

NASA Astrophysics Data System (ADS)

Flowers, Rebecca M.; Ketcham, Richard A.; Shuster, David L.; Farley, Kenneth A.

2009-04-01

Helium diffusion from apatite is a sensitive function of the volume fraction of radiation damage to the crystal, a quantity that varies over the lifetime of the apatite. Using recently published laboratory data we develop and investigate a new kinetic model, the radiation damage accumulation and annealing model (RDAAM), that adopts the effective fission-track density as a proxy for accumulated radiation damage. This proxy incorporates creation of crystal damage proportional to α-production from U and Th decay, and the elimination of that damage governed by the kinetics of fission-track annealing. The RDAAM is a version of the helium trapping model (HeTM; Shuster D. L., Flowers R. M. and Farley K. A. (2006) The influence of natural radiation damage on helium diffusion kinetics in apatite. Earth Planet. Sci. Lett.249, 148-161), calibrated by helium diffusion data in natural and partially annealed apatites. The chief limitation of the HeTM, now addressed by RDAAM, is its use of He concentration as the radiation damage proxy for circumstances in which radiation damage and He are not accumulated and lost proportionately from the crystal. By incorporating the RDAAM into the HeFTy computer program, we explore its implications for apatite (U-Th)/He thermochronometry. We show how (U-Th)/He dates predicted from the model are sensitive to both effective U concentration (eU) and details of the temperature history. The RDAAM predicts an effective He closure temperature of 62 °C for a 28 ppm eU apatite of 60 μm radius that experienced a 10 °C/Ma monotonic cooling rate; this is 8 °C lower than the 70 °C effective closure temperature predicted using commonly assumed Durango diffusion kinetics. Use of the RDAAM is most important for accurate interpretation of (U-Th)/He data for apatite suites that experienced moderate to slow monotonic cooling (1-0.1 °C/Ma), prolonged residence in the helium partial retention zone, or a duration at temperatures appropriate for radiation damage accumulation followed by reheating and partial helium loss. Under common circumstances the RDAAM predicts (U-Th)/He dates that are older, sometimes much older, than corresponding fission-track dates. Nonlinear positive correlations between apatite (U-Th)/He date and eU in apatites subjected to the same temperature history are a diagnostic signature of the RDAAM for many but not all thermal histories. Observed date-eU correlations in four different localities can be explained with the RDAAM using geologically reasonable thermal histories consistent with independent fission-track datasets. The existence of date-eU correlations not only supports a radiation damage based kinetic model, but can significantly limit the range of acceptable time-temperature paths that account for the data. In contrast, these datasets are inexplicable using the Durango diffusion model. The RDAAM helps reconcile enigmatic data in which apatite (U-Th)/He dates are older than expected using the Durango model when compared with thermal histories based on apatite fission-track data or other geological constraints. It also has the potential to explain at least some cases in which (U-Th)/He dates are actually older than the corresponding fission-track dates.

Maruyamaite, a new K-dominant tourmaline coexisting with diamond -an important accessory mineral in UHP rocks

NASA Astrophysics Data System (ADS)

Stock, M. J.; Humphreys, M.; Smith, V.; Pyle, D. M.; Isaia, R.

2014-12-01

The apatite crystal structure is capable of incorporating H2O, F and Cl, as well as trace CO2 and sulphur. These can be related to parental magma compositions through application of a series of pressure and temperature-dependent exchange reactions (Piccoli and Candela, 1994), permitting apatite crystals to preserve a record of all major volatile species in the melt. Furthermore, due to the general incompatibility of P in other rock-forming minerals, apatite is ubiquitous in igneous systems and often begins crystallising early, such that apatite inclusions within phenocrysts record melt volatile contents throughout magmatic differentiation. In this work, we compare the compositions of apatite inclusions and microphenocrysts with pyroxene-hosted melt inclusions from the Astroni 1 eruption of Campi Flegrei, Italy. These data are coupled with magmatic differentiation models (Gualda et al., 2012), experimental volatile solubility data (Webster et al., 2014) and thermodynamic models of apatite compositional variations (Piccoli and Candela, 1994) to determine a time-series of magmatic volatile evolution in the build-up to eruption. We find that apatite halogen/OH ratios decreased through magmatic differentiation, while melt inclusion F and Cl concentrations increased. Melt inclusion H2O contents are constant at ~2.5 wt%. These data are best explained by volatile-undersaturated differentiation over most of the crystallisation history of the Astroni 1 melt, with melt inclusion H2O contents reset during ascent, due to rapid H diffusion through the phenocryst hosts (Woods et al., 2000). Given the rapid diffusivity of volatiles in apatite (Brenan, 1993), preservation of undersaturated compositions in microphenocrysts suggests that saturation was only achieved a few days to months before eruption and that it may have been the transition into a volatile-saturated state that ultimately triggered eruption. Piccoli and Candela, 1994. Am. J. of Sc., 294, 92-135. Gualda et al., 2012. J. Pet., 53, 875-890. Webster et al., 2014. J. Pet., 55, 2217-2248. Woods et al., 2000. Am. Min., 85, 480-487. Brenan, 1993. Chem. Geol., 110, 195-210.

(U-Th-Sm)/He thermochronological age distribution in a slowly cooled plutonic complex (Ploumanac'h intrusion, France): insights into helium diffusion processes.

NASA Astrophysics Data System (ADS)

Recanati, A. C.; Gautheron, C.; Barbarand, J.; Tassan-Got, L.; Missenard, Y.; Pinna-Jamme, R.

2015-12-01

(U-Th-Sm)/He thermochronology is widely used to determine the thermal histories of mountain ranges and sedimentary basins. Apatite crystals retain helium at low temperatures, thus giving an insight into upper crustal evolution (e.g. exhumation, subsidence, erosion). Advanced models predict He production and diffusion rates in apatite crystals, thereby allowing determination of helium dates by integration over time/temperature paths (e.g. Gautheron et al., 2009). However, scattered dates and discordance between predicted and measured dates suggest that other parameters than time or temperature may also influence helium contents in apatite. The present study determines the variables that affect He diffusion in apatite over long timescales. We report the (U-Th-Sm)/He date distribution within a slowly cooled intrusion, along with AFT data, as well as extensive petrological and chemical characterization. The Ploumanac'h site (Brittany, France) was chosen because it includes small-scale spatial variations in petrology and chemistry (6-9106 tracks/cm2). GAUTHERON C., TASSAN-GOT L., BARBARAND J., PAGEL M., 2009. Effect of alpha-damage annealing on apatite (U-Th)/He thermochronology. Chem. Geol. 266, 166-179.

Framework 'interstitial' oxygen in La(10)(GeO(4))(5-)(GeO(5))O(2) apatite electrolyte.

PubMed

Pramana, Stevin S; Klooster, Wim T; White, T J

2007-08-01

Oxygen conduction at low temperatures in apatites make these materials potentially useful as electrolytes in solid-oxide fuel cells, but our understanding of the defect structures enabling ion migration is incomplete. While conduction along [001] channels is dominant, considerable inter-tunnel mobility has been recognized. Using neutron powder diffraction of stoichiometric 'La(10)(GeO(4))(6)O(3)', it has been shown that this compound is more correctly described as an La(10)(GeO(4))(5-)(GeO(5))O(2) apatite, in which high concentrations of interstitial oxygen reside within the channel walls. It is suggested that these framework interstitial O atoms provide a reservoir of ions that can migrate into the conducting channels of apatite, via a mechanism of inter-tunnel oxygen diffusion that transiently converts GeO(4) tetrahedra to GeO(5) distorted trigonal bipyramids. This structural modification is consistent with known crystal chemistry and may occur generally in oxide apatites.

Biomimetic growth and substrate dependent mechanical properties of bone like apatite nucleated on Ti and magnetron sputtered TiO2 nanostructure

NASA Astrophysics Data System (ADS)

Sarma, Bimal K.; Das, Apurba; Barman, Pintu; Pal, Arup R.

2016-04-01

This report presents findings on biomimetic growth of hydroxyapatite (HAp) nanocrystals on Ti and sputtered TiO2 substrates. The possibility of TiO2 nanostructure as candidate materials for future biomedical applications has been explored through the comparison of microstructural and mechanical properties of bone like apatite grown on Ti and nano-TiO2 surfaces. Raman spectroscopy and x-ray diffraction studies reveal formation of carbonate apatite with apparent domain size in the nanoscale range. A better interaction at the nano-TiO2/nano-HAp interface due to higher interfacial area could promote the growth of bone like apatite. The crystal phases, crystallinity, and surface morphology of nano-TiO2 are considered as parameters to understand the nucleation and growth of apatite with different mechanical properties at the nanoscale. The methodology of x-ray line profile analysis encompasses deconvolution of merged peaks by preserving broadening due to nanosized HAp aggregates. The Young’s modulus of bone like apatite exhibits crystallographic directional dependence which suggests the presence of elastic anisotropy in bone like apatite. The lattice contraction in the c-direction is associated with the degree of carbonate substitution in the apatite lattice. The role of residual stress is critical for the lattice distortion of HAp deposited at physiological conditions of temperature and pH of human blood plasma. The ion concentration is crucial for the uniformity, crystallinity, and mechanical behaviour of the apatite.

A review of phosphate mineral nucleation in biology and geobiology.

PubMed

Omelon, Sidney; Ariganello, Marianne; Bonucci, Ermanno; Grynpas, Marc; Nanci, Antonio

2013-10-01

Relationships between geological phosphorite deposition and biological apatite nucleation have often been overlooked. However, similarities in biological apatite and phosphorite mineralogy suggest that their chemical formation mechanisms may be similar. This review serves to draw parallels between two newly described phosphorite mineralization processes, and proposes a similar novel mechanism for biologically controlled apatite mineral nucleation. This mechanism integrates polyphosphate biochemistry with crystal nucleation theory. Recently, the roles of polyphosphates in the nucleation of marine phosphorites were discovered. Marine bacteria and diatoms have been shown to store and concentrate inorganic phosphate (Pi) as amorphous, polyphosphate granules. Subsequent release of these P reserves into the local marine environment as Pi results in biologically induced phosphorite nucleation. Pi storage and release through an intracellular polyphosphate intermediate may also occur in mineralizing oral bacteria. Polyphosphates may be associated with biologically controlled apatite nucleation within vertebrates and invertebrates. Historically, biological apatite nucleation has been attributed to either a biochemical increase in local Pi concentration or matrix-mediated apatite nucleation control. This review proposes a mechanism that integrates both theories. Intracellular and extracellular amorphous granules, rich in both calcium and phosphorus, have been observed in apatite-biomineralizing vertebrates, protists, and atremate brachiopods. These granules may represent stores of calcium-polyphosphate. Not unlike phosphorite nucleation by bacteria and diatoms, polyphosphate depolymerization to Pi would be controlled by phosphatase activity. Enzymatic polyphosphate depolymerization would increase apatite saturation to the level required for mineral nucleation, while matrix proteins would simultaneously control the progression of new biological apatite formation.

Surface functional group dependent apatite formation on bacterial cellulose microfibrils network in a simulated body fluid.

PubMed

Nge, Thi Thi; Sugiyama, Junji

2007-04-01

The apatite forming ability of biopolymer bacterial cellulose (BC) has been investigated by soaking different BC specimens in a simulated body fluid (1.5 SBF) under physiological conditions, at 37 degrees C and pH 7.4, mimicking the natural process of apatite formation. From ATR-FTIR spectra and ICP-AES analysis, the crystalline phase nucleated on the BC microfibrils surface was calcium deficient carbonated apatite through initial formation of octacalcium phosphate (OCP) or OCP like calcium phosphate phase regardless of the substrates. Morphology of the deposits from SEM, FE-SEM, and TEM observations revealed the fine structure of thin film plates uniting together to form apatite globules of various size (from <1 mum to 3 mum) with respect to the substrates. Surface modification by TEMPO (2,2,6,6-tetramethylpyperidine-1-oxyl)-mediated oxidation, which can readily form active carboxyl functional groups upon selective oxidation of primary hydroxyl groups on the surface of BC microfibrils, enhanced the rate of apatite nucleation. Ion exchanged treatment with calcium chloride solution after TEMPO-mediated oxidation was found to be remarkably different from other BC substrates with the highest deposit weight and the smallest apatite globules size. The role of BC substrates to induce mineralization rate differs according to the nature of the BC substrates, which strongly influences the growth behavior of the apatite crystals. (c) 2006 Wiley Periodicals, Inc.

Advantages of conducting in-situ U-Pb age dating of multiple U-bearing minerals from a single complex: Case in point - the Oka Carbonatite Complex

NASA Astrophysics Data System (ADS)

Chen, W.; Simonetti, A.

2012-12-01

A detailed radiometric investigation is currently underway focusing on U-bearing accessory minerals apatite, perovskite, and niocalite from the Oka Carbonatite Complex (Canada). One of the main objectives is to obtain a comparative chronology of melt crystallization for the complex. Unlike other commonly adopted U-bearing minerals (e.g., zircon, monazite) for in-situ dating investigations, apatite, perovskite, and niocalite contain relatively high contents of common Pb. Hence, careful assessment of the proportion and composition of the common Pb, and usage of appropriate matrix-matched external standards are imperative. The Madagascar apatite was utilized as the external standard for apatite dating, and the Emerald Lake and Durango apatites were adopted as secondary standards; the latter yield ages of 92.6 ±1.8 and 32.2 ±1.1 Ma, respectively, and these are identical to their accepted ages. Pb/U ages for apatite from Oka were obtained for different rock types, including 8 carbonatites, 4 okaites, 3 ijolites and 3 alnoites, and these define a range of ages between ~105 and ~135 Ma; this result suggests a protracted crystallization history. In total, 266 individual analyses define two peaks at ~115 and ~125Ma. For perovskite dating, the Ice River perovskite standard was utilized as the external standard. The perovskites from one okaite sample yield an age of 112.2 ±1.9 Ma, and is much younger than the previously reported U-Pb perovskite age of 131 ±7 Ma. Hence, the combined U-Pb perovskite ages also suggest a rather prolonged time of melt crystallization. Niocalite is a rare, accessory silicate mineral that occurs within the carbonatites at Oka. The international zircon standard BR266 was selected for use as the external standard and rastering was employed to minimize the Pb-U fractionation. Two niocalite samples give young ages at 110.6 ±1.2 and 115.0 ±1.9 Ma, and are identical to their respective apatite ages (given associated uncertainties) from the same sample. The niocalite for a carbonatite sample Oka153 defines a bimodal age distribution, with weighted average 206Pb/238U ages of 110.1 ±5.0 and 133.2 ±6.1 Ma. Apatite from the same sample also records a similar bimodal age distribution of 111.4 ±2.8 and 126.9 ±1.8 Ma. The combined in situ U-Pb dating results for apatite, pervoskite, niocalite from Oka clearly support a protracted history of magmatic activity (~30 Myr) for this carbonatite complex. Of importance, the U-Pb results from this study clearly indicate the significance of conducting a thorough geochronological investigation rather than defining the age of any one alkaline complex solely on the basis of a single radiometric age determination.

Endogenous Lunar Volatiles: Insights into the Abundances of Volatiles in the Moon from Lunar Apatite

NASA Technical Reports Server (NTRS)

McCubbin, Francis

2016-01-01

At the time of publication of New Views of the Moon, it was thought that the Moon was bone dry with less than about 1 ppb H2O. However in 2007, initial reports at the 38th Lunar and Planetary Science Conference speculated that H-species were present in both apatites and pyroclastic volcanic lunar glasses. These early reports were later confirmed through peer-review, which motivated many subsequent studies on magmatic volatiles in and on the Moon within the last decade. Some of these studies have cast into question the post-Apollo view of lunar formation, the distribution and sources of volatiles in the Earth-Moon system, and the thermal and magmatic evolution of the Moon. The mineral apatite has been one of the pillars of this new field of study, and it will be the primary focus of this abstract. Although apatite has been used both to understand the abundances of volatiles in lunar systems as well as the isotopic compositions of those volatiles, the focus here will be on the abundances of F, Cl, and H2O. This work demonstrates the utility of apatite in advancing our understanding of lunar volatiles, hence apatite should be among the topics covered in the endogenous lunar volatile chapter in NVM II. Truncated ternary plot of apatite X-site occupancy (mol%) from highlands apatite and mare basalt apatite plotted on the relative volatile abundance diagram from. The solid black lines delineate fields of relative abundances of F, Cl, and H2O (on a weight basis) in the melt from which the apatite crystallized. The diagram was constructed using available apatite/melt partitioning data for fluorine, chlorine, and hydroxyl.

Biomimetic whisker-shaped apatite coating of titanium powder.

PubMed

Sim, Young Uk; Kim, Jong Hee; Yang, Tae Young; Yoon, Seog Young; Park, Hong Chae

2010-05-01

Biomimetic apatite coatings on chemically modified titanium powder have been processed and the resulting coating layers evaluated in terms of morphology, composition and structure, using TF-XRD, XPS, SEM, TEM and FTIR analysis. After 7 days immersion in a simulated body fluid (SBF), nanometer-sized fine precipitates with an amorphous whisker-like phase and a Ca/P atomic ratio of 1.94 were obtained on the external surface of the titanium particles. When the immersion time in SBF was extended to 16 days, the coating layer consisted of the whisker-like nanostructured crystals of carbonated hydroxyapatite with a atomic ratio of 3; in such a case, a double coating layer was developed. The double layer could be divided into two regions and could be clearly distinguished: an inner dense region (approximately 200 nm in thickness) which may include hard agglomerated crystals and an outer less dense region (> 500 nm in thickness) in which crystals are loosely distributed.

Amelogenin in Enamel Tissue Engineering.

PubMed

Uskoković, Vuk

2015-01-01

In this chapter the basic premises, the recent findings and the future challenges in the use of amelogenin for enamel tissue engineering are being discoursed on. Results emerging from the experiments performed to assess the fundamental physicochemical mechanisms of the interaction of amelogenin, the main protein of the enamel matrix, and the growing crystals of apatite, are mentioned, alongside a moderately comprehensive literature review of the subject at hand. The clinical importance of understanding this protein/mineral interaction at the nanoscale are highlighted as well as the potential for tooth enamel to act as an excellent model system for studying some of the essential aspects of biomineralization processes in general. The dominant paradigm stating that amelogenin directs the uniaxial growth of apatite crystals in enamel by slowing down the growth of (hk0) faces on which it adheres is being questioned based on the results demonstrating the ability of amelogenin to promote the nucleation and crystal growth of apatite under constant titration conditions designed to mimic those present in the developing enamel matrix. The role of numerous minor components of the enamel matrix is being highlighted as essential and impossible to compensate for by utilizing its more abundant ingredients only. It is concluded that the three major aspects of amelogenesis outlined hereby--(1) the assembly of amelogenin and other enamel matrix proteins, (2) the proteolytic activity, and (3) crystallization--need to be in precise synergy with each other in order for the grounds for the proper imitation of amelogenesis in the lab to be created.

Physico-chemical and thermochemical studies of the hydrolytic conversion of amorphous tricalcium phosphate into apatite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Somrani, Saida; Banu, Mihai; Jemal, Mohamed

2005-05-15

The conversion of amorphous tricalcium phosphate with different hydration ratio into apatite in water at 25 deg. C has been studied by microcalorimetry and several physical-chemical methods. The hydrolytic transformation was dominated by two strong exothermic events. A fast, relatively weak, wetting process and a very slow but strong heat release assigned to a slow internal rehydration and the crystallization of the amorphous phase into an apatite. The exothermic phenomenon related to the rehydration exceeded the crystalline transformation enthalpy. Rehydration occurred before the conversion of the amorphous phase into apatite and determined the advancement of the hydrolytic reaction. The apatiticmore » phases formed evolved slightly with time after their formation. The crystallinity increased whereas the amount of HPO{sub 4}{sup 2-} ion decreased. These data allow a better understanding of the behavior of biomaterials involving amorphous phases such as hydroxyapatite plasma-sprayed coatings.« less

κ-Carrageenan Enhances the Biomineralization and Osteogenic Differentiation of Electrospun Polyhydroxybutyrate and Polyhydroxybutyrate Valerate Fibers.

PubMed

Goonoo, Nowsheen; Khanbabaee, Behnam; Steuber, Marc; Bhaw-Luximon, Archana; Jonas, Ulrich; Pietsch, Ullrich; Jhurry, Dhanjay; Schönherr, Holger

2017-05-08

Novel electrospun materials for bone tissue engineering were obtained by blending biodegradable polyhydroxybutyrate (PHB) or polyhydroxybutyrate valerate (PHBV) with the anionic sulfated polysaccharide κ-carrageenan (κ-CG) in varying ratios. In both systems, the two components phase separated as shown by FTIR, DSC and TGA. According to the contact angle data, κ-CG was localized preferentially at the fiber surface in PHBV/κ-CG blends in contrast to PHB/κ-CG, where the biopolymer was mostly found within the fiber. In contrast to the neat polyester fibers, the blends led to the formation of much smaller apatite crystals (800 nm vs 7 μm). According to the MTT assay, NIH3T3 cells grew in higher density on the blend mats in comparison to neat polyester mats. The osteogenic differentiation potential of the fibers was determined by SaOS-2 cell culture for 2 weeks. Alizarin red-S staining suggested an improved mineralization on the blend fibers. Thus, PHBV/κ-CG fibers resulted in more pronounced bioactive and osteogenic properties, including fast apatite-forming ability and deposition of nanosized apatite crystals.

Solid state solubility of copper oxides in hydroxyapatite

NASA Astrophysics Data System (ADS)

Zykin, Mikhail A.; Vasiliev, Alexander V.; Trusov, Lev A.; Dinnebier, Robert E.; Jansen, Martin; Kazin, Pavel E.

2018-06-01

Samples containing copper oxide doped hydroxyapatite with the composition Ca10(PO4)6(CuxOH1-x-δ)2, x = 0.054 - 0.582, in the mixture with CuO/Cu2O were prepared by a solid-state high-temperature treatment at varying annealing temperatures and at different partial water vapor and oxygen pressures. The crystal structures of the apatite compounds were refined using powder X-ray diffraction patterns and the content of copper ions x in the apatite was determined. Copper ions enter exclusively into the apatite trigonal channels formally substituting protons of OH-groups and the hexagonal cell parameters grow approximately linearly with x, the channel volume mostly expanding while the remaining volume of the crystal lattice changing only slightly. The equilibrium copper content in the apatite increases drastically, by almost a factor of 10 with the annealing temperature rising from 800° to 1200°C. The reduction of the water partial pressure leads to a further increase of x, while the dependence of x on the oxygen partial pressure exhibits a maximum. The observed relations are consistent with the proposed chemical reactions implying the copper introduction is followed by the release of a considerable quantity of gaseous products - water and oxygen. The analysis of interatomic distances suggests that the maximum content of copper ions in the channel cannot exceed 2/3.

Modification of bone-like apatite nanoparticle size and growth kinetics by alizarin red S

NASA Astrophysics Data System (ADS)

Ibsen, Casper Jon Steenberg; Birkedal, Henrik

2010-11-01

The formation of nanocrystals in biomineralization such as in bone occurs under the influence of organic molecules. Prompted by this fact, the effect of alizarin red S, a dye used in in vivo bone labeling methods, on bone-like carbonated apatite nanocrystal formation was investigated as a function of alizarin red S additive concentration. The obtained nanoparticles were investigated by powder X-ray diffraction (XRD), FTIR as well thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) while the kinetics of nanoparticle formation was investigated by in situ pH and synchrotron XRD measurements. Increasing alizarin red S concentration lead to amorphous particles over a threshold concentration and to smaller crystallites in a dose-dependent fashion. Alizarin red S induced a macroscopic lattice strain that scaled linearly with the alizarin red S concentration; this effect is reminiscent of that seen in biogenic calcium carbonates. TGA showed that the amorphous particles contained significantly more water than the crystalline samples and the DSC data showed that crystallization occurs after loss of most of the included organic material. The in situ studies showed that the formation of apatite goes via the very rapid formation of an amorphous precursor that after a certain nucleation time crystallizes into apatite. This nucleation time increased exponentially with alizarin red S concentration showing that this additive strongly stabilizes the amorphous precursor phase.

Process and kinetics of bonelike apatite formation on sintered hydroxyapatite in a simulated body fluid.

PubMed

Kim, Hyun-Min; Himeno, Teruyuki; Kokubo, Tadashi; Nakamura, Takashi

2005-07-01

The surfaces of two hydroxyapatites (HA), which have been sintered at different temperatures of 800 and 1200 degrees C, was investigated as a function of soaking time in simulated body fluid (SBF) using transmission electron microscopy (TEM) attached with energy-dispersive spectrometry (EDX) and laser electrophoresis spectroscopy. The TEM-EDX indicated that after soaking in SBF, both the HAs form bonelike apatite by undergoing the same surface structural change, i.e., formations of a Ca-rich amorphous or nano-crystalline calcium phosphate (ACP) and a Ca-poor ACP, which eventually crystallized into bonelike apatite. Zeta potential characterized by the electrophoresis indicated that during exposure to SBF, the HA surfaces reveal negative surface charge, thereby interacting with the positive calcium ions in the fluid to form the Ca-rich ACP, which gains positive surface charge. The Ca-rich ACP on the HAs then interacts with the negative phosphate ions in the fluid to form the Ca-poor ACP, which stabilizes by being crystallized into bonelike apatite with a low solubility in the SBF. The exposure times for formations of these phases of the Ca-rich ACP, the Ca-poor ACP as well as the apatite were, however, all late on HA sintered at 1200 degrees C, compared with the HA sintered at 800 degrees C. This phenomenon was attributed to a lower initial negative surface charge of the HA sintered at 800 degrees C than of that one sintered at 1200 degrees C, owing to poverty in surface hydroxyl and phosphate groups which are responsible for the surface negativity of the HA. These indicate that sintered temperature of HA might influence not in terms of the process but in terms of the rate of formation of biologically active bonelike apatite on its surface, through which the HA integrates with living bone.

Fast synthesis of La-substituted apatite by the dry mechanochemical method and analysis of its structure

NASA Astrophysics Data System (ADS)

Bulina, Natalia V.; Chaikina, Marina V.; Prosanov, Igor Yu.; Dudina, Dina V.; Solovyov, Leonid A.

2017-08-01

Compared to pure apatite, La-substituted apatites have improved thermal, mechanical and biological characteristics. In this article, a fast synthesis of La-substituted apatites by a dry mechanochemical method is presented. Structural studies by X-ray diffraction and Fourier transform infrared spectroscopy indicated the formation of a single-phase nanosized product after 30 min of high-energy ball milling of the reaction mixtures. The dry mechanochemical method is technologically attractive for the preparation of La-substituted apatites, as it allows reducing the processing time down to half an hour and does not require prolonged high-temperature annealing normally used in the synthesis practice of the substituted apatite. As the mechanochemically synthesized samples are nanosized, it is difficult to determine the details of their crystal structure by the Rietveld refinement method. Therefore, a series of the mechanochemically synthesized samples with different concentrations of lanthanum were annealed at 1000°C for 5 h. It was found that the annealed powders are microcrystalline La-substituted apatites Ca10-xLax(PO4)6Ox(OH)2-x, where 0 ≤ x ≤2. In their structure, the Ca2+ ions are replaced by the La3+ ions localized near the Ca2 sites, and the OH- groups are replaced by the O2- ions in the hexagonal channels.

REE partitioning between apatite and melt in a peralkaline volcanic suite, Kenya Rift Valley

USGS Publications Warehouse

Macdonald, R.; Baginski, B.; Belkin, H.E.; Dzierzanowski, P.; Jezak, L.

2009-01-01

Electron microprobe analyses are presented for fluorapatite phenocrysts from a benmoreite-peralkaline rhyolite volcanic suite from the Kenya Rift Valley. The rocks have previously been well characterized petrographically and their crystallization conditions are reasonably well known. The REE contents in the M site increase towards the rhyolites, with a maximum britholite component of ~35 mol.%. Chondrite-normalized REE patterns are rather flat between La and Sm and then decrease towards Yb. Sodium and Fe occupy up to 1% and 4%, respectively, of the M site. The major coupled substitution is REE3+ + Si4+ ??? Ca2+ + P5+. The substitution REE3+ + Na+ ??? 2Ca2+ has been of minor importance. The relatively large Fe contents were perhaps facilitated by the low fo2 conditions of crystallization. Zoning is ubiquitous and resulted from both fractional crystallization and magma mixing. Apatites in some rhyolites are relatively Y-depleted, perhaps reflecting crystallization from melts which had precipitated zircon. Mineral/glass (melt) ratios for two rhyolites are unusually high, with maxima at Sm (762, 1123). ?? 2008 The Mineralogical Society.

Rare-earth-element minerals in martian breccia meteorites NWA 7034 and 7533: Implications for fluid-rock interaction in the martian crust

NASA Astrophysics Data System (ADS)

Liu, Yang; Ma, Chi; Beckett, John R.; Chen, Yang; Guan, Yunbin

2016-10-01

Paired martian breccia meteorites, Northwest Africa (NWA) 7034 and 7533, are the first martian rocks found to contain rare-earth-element (REE) phosphates and silicates. The most common occurrence is as clusters of anhedral monazite-(Ce) inclusions in apatite. Occasionally, zoned, irregular merrillite inclusions are also present in apatite. Monazite-bearing apatite is sometimes associated with alkali-feldspar and Fe-oxide. Apatite near merrillite and monazite generally contains more F and OH (F-rich region) than the main chlorapatite host and forms irregular boundaries with the main host. Locally, the composition of F-rich regions can reach pure fluorapatite. The chlorapatite hosts are similar in composition to isolated apatite without monazite inclusions, and to euhedral apatite in lithic clasts. The U-Th-total Pb ages of monazite in three apatite are 1.0 ± 0.4Ga (2σ), 1.1 ± 0.5Ga (2σ), and 2.8 ± 0.7Ga (2σ), confirming a martian origin. The texture and composition of monazite inclusions are mostly consistent with their formation by the dissolution of apatite and/or merrillite by fluid at elevated temperatures (>100 °C). In NWA 7034, we observed a monazite-chevkinite-perrierite-bearing benmoreite or trachyandesite clast. Anhedral monazite and chevkinite-perrierite grains occur in a matrix of sub-micrometer REE-phases and silicates inside the clast. Monazite-(Ce) and -(Nd) and chevkinite-perrierite-(Ce) and -(Nd) display unusual La and Ce depletion relative to Sm and Nd. In addition, one xenotime-(Y)-bearing pyrite-ilmenite-zircon clast with small amounts of feldspar and augite occurs in NWA 7034. One xenotime crystal was observed at the edge of an altered zircon grain, and a cluster of xenotime crystals resides in a mixture of alteration materials. Pyrite, ilmenite, and zircon in this clast are all highly altered, zircon being the most likely source of Y and HREE now present in xenotime. The association of xenotime with zircon, low U and Th contents, and the low Yb content relative to Gd and Dy in xenotime suggest the possible formation of xenotime as a byproduct of fluid-zircon reactions. On the basis of relatively fresh apatite grains and lithic clasts in the same samples, we propose that the fluid-rock/mineral reactions occurred in the source rocks before their inclusion in NWA 7034 and 7533. Additionally, monazite-bearing apatite and REE-mineral-bearing clasts are possibly derived from different crustal origins. Thus, our results imply the wide-occurrence of hydrothermal fluids in the martian crust at 1 Ga or older, which were probably induced by impacts or large igneous intrusions.

Prospects for Practical Laser Ablation U/Pb and (U-Th)/He Double-Dating (LADD) of Detrital Apatite

NASA Astrophysics Data System (ADS)

Horne, A.; Hodges, K. V.; Van Soest, M. C.

2017-12-01

A laser ablation micro-analytical technique for (U-Th)/He dating has been shown to be an effective approach to the thermochronologic study of detrital zircons (Tripathy-Lang et al., J. Geophys. Res., 2013), while Evans et al. (J. Anal. At. Spectrom., 2015) and Horne et al. (Geochim. Cosmochim. Acta, 2016) demonstrated how the technique could be modified to enable laser ablation U/Pb and (U-Th)/He double-dating (LADD) of detrital zircon and titanite. These successes beg the question of whether or not LADD is viable for another commonly encountered detrital mineral: apatite. Exploratory LADD studies in Arizona State University's Group 18 Laboratories - using Durango fluorapatite, apatite from the Fish Canyon tuff, and detrital apatite from modern fluvial sediments in the eastern Sierra Nevada of California - illustrate that the method is indeed viable for detrital apatite. However, the method may not be appropriate for all detrital samples. For example, many apatite grains encountered in detrital samples from young orogenic settings have low concentrations of U and Th and small crystal sizes. This can lead to imprecise laser ablation (U-Th)/He dates, especially for very young grains potentially obscuring or inhibiting relevant interpretations of the data set.

Effect of hot water and heat treatment on the apatite-forming ability of titania films formed on titanium metal via anodic oxidation in acetic acid solutions.

PubMed

Cui, Xinyu; Kim, Hyun-Min; Kawashita, Masakazu; Wang, Longbao; Xiong, Tianying; Kokubo, Tadashi; Nakamura, Takashi

2008-04-01

Titanium and its alloys have been widely used for orthopedic implants because of their good biocompatibility. We have previously shown that the crystalline titania layers formed on the surface of titanium metal via anodic oxidation can induce apatite formation in simulated body fluid, whereas amorphous titania layers do not possess apatite-forming ability. In this study, hot water and heat treatments were applied to transform the titania layers from an amorphous structure into a crystalline structure after titanium metal had been anodized in acetic acid solution. The apatite-forming ability of titania layers subjected to the above treatments in simulated body fluid was investigated. The XRD and SEM results indicated hot water and/or heat treatment could greatly transform the crystal structure of titania layers from an amorphous structure into anatase, or a mixture of anatase and rutile. The abundance of Ti-OH groups formed by hot water treatment could contribute to apatite formation on the surface of titanium metals, and subsequent heat treatment would enhance the bond strength between the apatite layers and the titanium substrates. Thus, bioactive titanium metals could be prepared via anodic oxidation and subsequent hot water and heat treatment that would be suitable for applications under load-bearing conditions.

"Fabrication of arbitrarily shaped carbonate apatite foam based on the interlocking process of dicalcium hydrogen phosphate dihydrate".

PubMed

Sugiura, Yuki; Tsuru, Kanji; Ishikawa, Kunio

2017-08-01

Carbonate apatite (CO 3 Ap) foam with an interconnected porous structure is highly attractive as a scaffold for bone replacement. In this study, arbitrarily shaped CO 3 Ap foam was formed from α-tricalcium phosphate (α-TCP) foam granules via a two-step process involving treatment with acidic calcium phosphate solution followed by hydrothermal treatment with NaHCO 3 . The treatment with acidic calcium phosphate solution, which is key to fabricating arbitrarily shaped CO 3 Ap foam, enables dicalcium hydrogen phosphate dihydrate (DCPD) crystals to form on the α-TCP foam granules. The generated DCPD crystals cause the α-TCP granules to interlock with each other, inducing an α-TCP/DCPD foam. The interlocking structure containing DCPD crystals can survive hydrothermal treatment with NaHCO 3 . The arbitrarily shaped CO 3 Ap foam was fabricated from the α-TCP/DCPD foam via hydrothermal treatment at 200 °C for 24 h in the presence of a large amount of NaHCO 3 .

Rare earth patterns in shergottite phosphates and residues

NASA Technical Reports Server (NTRS)

Laul, J. C.

1987-01-01

Leaching experiments with 1M HCl on ALHA 77005 powder show that rare earth elements (REE) are concentrated in accessory phosphate phases (whitlockite, apatite) that govern the REE patterns of bulk shergottites. The REE patterns of whitlockite are typically light REE-depleted with a negative Eu anomaly and show a hump at the heavy REE side, while the REE pattern of apatite (in Shergotty) is light REE-enriched. Parent magmas are calculated from the modal compositions of residues of ALHA 77005, Shergotty, and EETA 79001. The parent magmas lack a Eu anomaly, indicating that plagioclase was a late-stage crystallizing phase and that it probably crystallized before the phosphates. The parent magmas of ALHA 77005 and Shergotty have similar REE patterns, with a subchondritic Nd/Sm ratio. However, the Sm/Nd isotopoics require a light REE-depleted source for ALHA 77005 (if the crystallization age is less than 600 Myr) and a light REE-enriched source for Shergotty. Distant Nd and Sr isotopic signatures may suggest different source regions for shergottites.

Crystallization, fluoridation and some properties of apatite thin films prepared through rf-sputtering from CaO-P2O5 glasses.

PubMed

Yamashita, K; Matsuda, M; Arashi, T; Umegaki, T

1998-07-01

Using calcium phosphate glass targets with the CaO/P2O5 molar ratios of 1.50-0.50, much lower than the stoichiometric value of 3.3 for hydroxyapatite, thin films of stoichiometric hydroxy-, nonstoichiometric oxyhydroxy- and Ca-deficient oxyhydroxy-apatites were prepared on alumina ceramic substrates by rf-sputtering followed by post-annealing. Based on the present results, a phase diagram for CaO-P2O5 at low temperatures in the ambience of air was depicted for thin films. The ambient H2O vapor had an influence on the phase diagram: Tricalcium phosphate was changed to apatite in the presence of H2O vapor. Dense fluorohydroxyapatite thin films were prepared by fluoridation of those apatite thin films at a low temperature such as 200 degrees C. In the present report, some functional properties of thin films thus prepared were also shown.

High resolution rare-earth elements analyses of natural apatite and its application in geo-sciences: Combined micro-PIXE, quantitative CL spectroscopy and electron spin resonance analyses

NASA Astrophysics Data System (ADS)

Habermann, D.; Götte, T.; Meijer, J.; Stephan, A.; Richter, D. K.; Niklas, J. R.

2000-03-01

The rare-earth element (REE) distribution in natural apatite is analysed by micro-PIXE, cathodoluminescence (CL) microscopy and spectroscopy and electron spin resonance (ESR) spectroscopy. The micro-PIXE analyses of an apatite crystal from Cerro de Mercado (Mexico) and the summary of 20 analyses of six francolite (conodonts of Triassic age) samples indicate that most of the REEs are enriched in apatite and francolite comparative to average shale standard (NASC). The analyses of fossil francolite revealing the REE-distribution not to be in balance with the REE-distribution of seawater and fish bone debris. Strong inhomogenous lateral REE-distribution in fossil conodont material is shown by CL-mapping and most probably not being a vital effect. Therefore, the resulting REE-signal from fossil francolite is the sum of vital and post-mortem incorporation. The necessary charge compensation for the substitution of divalent Ca by trivalent REE being done by different kind of electron defects and defect ions.

Synthesis and characterization of nanocrystalline apatites from solution modeling human blood

NASA Astrophysics Data System (ADS)

Solodyankina, Anna; Nikolaev, Anton; Frank-Kamenetskaya, Olga; Golovanova, Olga

2016-09-01

Present paper is devoted to the research of the calcification processes in the blood plasma of human body. Spontaneous crystallization from the solution modeling the inorganic part of the blood plasma has been carried out. Obtained precipitates were studied by the various instrumental methods (X-ray powder diffraction, Fourier-transformed infrared spectroscopy, scanning electron microscopy, electron probe microanalysis and gas-volumetric method). All gathered data allow to summarize that nonstoichiometric carbonated hydroxyapatite with low crystallinity (CSD lengths 18-28 nm), high water content and small amount of chlorine ion was obtained throughout the syntheses. Part of vacancies at the Ca sites varies from 0.17 to 0.87; the value of the Cat/(P + C) ratio-from 1.52 to 1.64 (where Cat = Ca2+ + Na+ + K+ + Mg2+). The poor crystallized synthetic apatites with high carbonate ion content (from 4.34 to 5.54 wt%) and c parameter (6.888-6.894 Å) are analogues of the apatites of the pathological cardiovascular deposits. They can be obtained from the solution modeling human blood plasma by the inorganic components with calcium phosphate supersaturation 25 and 50 and with 10 and 12 weeks experiment time.

Materials Engineering by Ameloblasts

PubMed Central

2015-01-01

Enamel is unique. It is the only epithelial-derived mineralized tissue in mammals and has a distinct micro- and nanostructure with nanofibrous apatite crystals as building blocks. It is synthesized by a highly specialized cell, the ameloblast, which secretes matrix proteins with little homology to any other known amino acid sequence, but which is composed of a primary structure that makes it competent to self-assemble and control apatite crystal growth at the nanometer scale. The end-product of ameloblast activity is a marvel of structural engineering: a material optimized to provide the tooth with maximum biting force, withstanding millions of cycles of loads without catastrophic failure, while also protecting the dental pulp from bacterial attack. This review attempts to bring into context the mechanical behavior of enamel with the developmental process of amelogenesis and structural development, since they are linked to tissue function, and the importance of controlling calcium phosphate mineralization at the nanometer scale. The origins of apatite nanofibers, the development of a stiffness gradient, and the biological processes responsible for the synthesis of a hard and fracture-resistant dental tissue are discussed with reference to the evolution of enamel from a fibrous composite to a complex, tough, and damage-tolerant coating on dentin. PMID:25800708

Influence of carbonate ion in the crystallization medium on the formation and chemical composition of CaHA-SrHA solid solutions

NASA Astrophysics Data System (ADS)

Nikolaev, Anton; Kuz'mina, Maria; Frank-Kamenetskaya, Olga; Zorina, Maina

2015-06-01

The study of the influence of carbonate ions in a solution to Sr-distribution in system «solution-crystal» and to ion substitutions and the non-stoichiometry of formed CaHA-SrHA solid solutions was carried out. The CaHA-SrHA solid solutions were synthesized by precipitation from aqueous solutions with the atomic C/P ratio equal to 0, 0.05 and 0.1 at T = 90 °C. Resulting precipitates were studied using various methods including X-ray powder diffraction, infrared spectroscopy and different chemical analyses. The results of the study have shown that in the range of values of (Ca + Sr)/P in the water solution from 40% to 85%, the presence of carbonate ions (C/P = 0.05-0.1) promotes the incorporation of strontium in the apatite. Crystalline apatite solid solutions formed from water solutions of such composition are more defective compared to apatites that are mainly calcium or strontium. They are characterized by a smaller size coherence scattering domain length along [0 0 1] direction and a greater number of carbonate ions, water molecules and vacancies at the Ca-sites.

Protein-free formation of bone-like apatite: New insights into the key role of carbonation

PubMed Central

Deymier, Alix C.; Nair, Arun K.; Depalle, Baptiste; Qin, Zhao; Arcot, Kashyap; Drouet, Christophe; Yoder, Claude H.; Buehler, Markus J.; Thomopoulos, Stavros; Genin, Guy M.; Pasteris, Jill D.

2017-01-01

The nanometer-sized plate-like morphology of bone mineral is necessary for proper bone mechanics and physiology. However, mechanisms regulating the morphology of these mineral nanocrystals remain unclear. The dominant hypothesis attributes the size and shape regulation to organic-mineral interactions. Here, we present data supporting the hypothesis that physicochemical effects of carbonate integration within the apatite lattice control the morphology, size, and mechanics of bioapatite mineral crystals. Carbonated apatites synthesized in the absence of organic molecules presented plate-like morphologies and nanoscale crystallite dimensions. Experimentally-determined crystallite size, lattice spacing, solubility and atomic order were modified by carbonate concentration. Molecular dynamics (MD) simulations and density functional theory (DFT) calculations predicted changes in surface energy and elastic moduli with carbonate concentration. Combining these results with a scaling law predicted the experimentally observed scaling of size and energetics with carbonate concentration. The experiments and models describe a clear mechanism by which crystal dimensions are controlled by carbonate substitution. Furthermore, the results demonstrate that carbonate substitution is sufficient to drive the formation of bone-like crystallites. This new understanding points to pathways for biomimetic synthesis of novel, nanostructured biomaterials. PMID:28279923

Electronic structure, bonding, charge distribution, and x-ray absorption spectra of the (001) surfaces of fluorapatite and hydroxyapatite from first principles

NASA Astrophysics Data System (ADS)

Rulis, Paul; Yao, Hongzhi; Ouyang, Lizhi; Ching, W. Y.

2007-12-01

Fluorapatite (FAP) and hydroxyapatite (HAP) are two very important bioceramic crystals. The (001) surfaces of FAP and HAP crystals are studied by ab initio density functional calculations using a supercell slab geometry. It is shown that in both crystals, the O-terminated (001) surface is more stable with calculated surface energies of 0.865 and 0.871J/m2 for FAP and HAP, respectively. In FAP, the two surfaces are symmetric. In HAP, the orientation of the OH group along the c axis reduces the symmetry such that the top and bottom surfaces are no longer symmetric. It is revealed that the atoms near the surface and subsurface are significantly relaxed especially in the case of HAP. The largest relaxations occurred via the lateral movements of the O ions at the subsurface level. The electronic structures of the surface models in the form of layer-by-layer resolved partial density of states for all the atoms show systematic variation from the surface region toward the bulk region. The calculated Mulliken effective charge on each type of atom and the bond order values between cations (Ca, P) and anions (O, F) show different charge transfers and bond strength variations from the bulk crystal values. Electron charge density calculations show that the surfaces of both FAP and HAP crystals are mostly positively charged due to the presence of Ca ions at the surface. The positively charged surfaces have implications for the absorption on apatite surfaces of water and other organic molecules in an aqueous environment which are an important part of its bioactivity. The x-ray absorption near-edge structure (XANES) spectra ( Ca-K , O-K , F-K , P-K , and P-L3 edges) of both the surface models and the bulk crystals are calculated and compared. The calculations use a supercell approach which takes into account the electron-core-hole interaction. It is shown that the site-specific XANES spectra show significant differences between atoms near the surface and in the bulk and are very sensitive to the local atomic environment of each atom. This information will be very valuable for characterizing the apatite materials and in the interpretation of experimental data. Comparisons of several sets of experimental data with the weighted sums of the calculated spectra at different sites for the same element show very good agreement.

Calcium pyrophosphate dihydrate gout and other crystal deposition diseases.

PubMed

Reginato, A J

1991-08-01

The number of crystal or birefringent particles associated with arthritis is increasing, and a uniform taxonomy is needed. The term gout has been proposed as a generic term for these diseases based on historical, clinical, and crystallographic reasons. Calcium pyrophosphate dihydrate gout follows monosodium urate gout in frequency, and its spectrum of clinical manifestations continues to grow. Familial calcium pyrophosphate dihydrate gout was described for the first time in kindreds studied in England and Tunisia; new Jewish and Spanish kindreds were also reported. Type I collagen was shown to nucleate nativelike calcium pyrophosphate dihydrate crystals, and pyrophosphate elaboration was explored in cartilage explants in an attempt to reproduce the in vivo metabolic or endocrine disorders associated with calcium pyrophosphate dihydrate gout. The effect of pyrophosphatase and different cofactors such as magnesium in dissolving calcium pyrophosphate dihydrate crystals was investigated. High-resolution electron microscopy was used to study the interrelation between apatite and other basic calcium phosphate crystals in apatite gout. Raman microscopy was applied for the first time to identify crystals in biologic specimens. A simple and specific technique for basic calcium phosphate crystal identification is necessary to understand the relationship between different calcium phosphate crystals and osteoarthritis. Several reports about children and young patients with primary oxalate gout described the effect of oxalate on eyes, periodontal tissues, and bone. Multicenter studies showed poor results of renal transplantation, but favored combined liver and renal transplantation.(ABSTRACT TRUNCATED AT 250 WORDS)

Carbon Concentration Excursions in Apatite Phenocrysts from the Cerro Galan Ignimbrite: A SIMS View into the Transient pre-Eruptive Volatile History of a Supervolcano

NASA Astrophysics Data System (ADS)

Boyce, J. W.; Hervig, R. L.

2006-12-01

In nearly all igneous rock compositions, apatite is the most abundant mineral that regularly incorporates significant quantities of volatile elements into its structure, making it a potentially useful tool for exploring magmatic processing of volatiles (as well as REEs, Sr, Nd, and Pb isotopes, all of which are typically abundant in apatite). We have developed an analytical protocol that permits measurement of C, H, F, S, and Cl in ~8μm diameter regions of apatite using the Cameca 6f SIMS. A primary Cs+ beam (4-10 nA) is used in conjunction with electron gun charge-compensation to sputter negative ions from polished sections and unpolished crystal faces mounted in volatile-free indium mounts. We operated at mass resolving powers sufficient to separate all potential interferences (such as ^{31}PH and 16O2 from ^{32}S, and 17O from 16OH). Quantifying the SIMS data requires a set of standards that are 1) homogeneous at the few-micron scale; and 2) well-calibrated with multiple, reliable, independent volatile content measurements. Using values combed from the literature and other unpublished sources, we have assembled a set of apatite standards, none of which are proven to meet either criteria. Nevertheless, these materials allow us to create calibration curves for all of the volatile elements listed above. Traverses across polished basal sections of apatite phenocrysts from the ~1000 km3 Cerro Galan ignimbrite, Argentina (courtesy of C. Schirnick) yield the following results: Apatites are fluorine-rich, and contain significant and reproducible intracrystalline variations in C, H, S, and Cl. Positive carbon concentration excursions (up to 360 ppm) are factors of 2-7 greater than apatite baseline concentrations (40-60 ppm), the largest of which correlate with position in different grains. In the majority of the traverses, these carbon excursions also correlate spatially with 25-30% increases in sulfur concentration. We suggest that these dramatic increases in carbon and sulfur concentrations record a transient increase in magmatic SO4^{2- } and CO2 activities, perhaps the result of an underplating/recharge event, followed by a return to baseline magma chemistry. Hydrogen-poor rims are observed in all studied crystals, and are accompanied by chlorine-impoverished rims in a majority of the traverses, perhaps recording the pre- or syn-eruption exsolution of a vapor phase enriched in H and Cl.

Bioactive calcium pyrophosphate glasses and glass-ceramics.

PubMed

Kasuga, Toshihiro

2005-01-01

Calcium phosphate glass-based materials in the pyrophosphate region are briefly reviewed. Calcium pyrophosphate glasses can be prepared by including a small amount of TiO(2) (

Removal of phosphorus, fluoride and metals from a gypsum mining leachate using steel slag filters.

PubMed

Claveau-Mallet, Dominique; Wallace, Scott; Comeau, Yves

2013-03-15

The objective of this work was to evaluate the capacity of steel slag filters to treat a gypsum mining leachate containing 11-107 mg P/L ortho-phosphates, 9-37 mg/L fluoride, 0.24-0.83 mg/L manganese, 0.20-3.3 zinc and 1.7-8.2 mg/L aluminum. Column tests fed with reconstituted leachates were conducted for 145-222 days and sampled twice a week. Two types of electric arc furnace (EAF) slags and three filter sequences were tested. The voids hydraulic retention time (HRT(v)) of columns ranged between 4.3 and 19.2 h. Precipitates of contaminants present in columns were sampled and analyzed with X-ray diffraction at the end of tests. The best removal efficiencies over a period of 179 days were obtained with sequential filters that were composed of Fort Smith EAF slag operated at a total HRT(v) of 34 h which removed 99.9% of phosphorus, 85.3% of fluoride, 98.0% of manganese and 99.3% of zinc. Mean concentration at this system's effluent was 0.04 mg P/L ortho-phosphates, 4 mg/L fluoride, 0.02 mg/L manganese, 0.02 zinc and 0.5 mg/L aluminum. Thus, slag filters are promising passive and economical systems for the remediation of mining effluents. Phosphorus was removed by the formation of apatite (hydroxyapatite, Ca(5)(PO(4))(3)OH or fluoroapatite, Ca(5)(PO(4))(3)F) as confirmed by visual and X-ray diffraction analyses. The growth rate of apatite was favored by a high phosphorus concentration. Calcite crystals were present in columns and appeared to be competing for calcium and volume needed for apatite formation. The calcite crystal growth rate was higher than that of apatite crystals. Fluoride was removed by precipitation of fluoroapatite and its removal was favored by a high ratio of phosphorus to fluoride in the wastewater. Copyright © 2012 Elsevier Ltd. All rights reserved.

Bioactive bredigite coating with improved bonding strength, rapid apatite mineralization and excellent cytocompatibility.

PubMed

Yi, Deliang; Wu, Chengtie; Ma, Bing; Ji, Heng; Zheng, Xuebin; Chang, Jiang

2014-05-01

Previous studies have shown that bredigite (Ca7MgSi4O16) bioceramics possessed excellent biocompatibility, apatite-mineralization ability and mechanical properties. In this paper, the bredigite coating on Ti-6Al-4 V substrate was prepared by plasma spraying technique. The main compositions of the coating were bredigite crystal phase with small parts of amorphous phases. The bonding strength of the coating to Ti-6Al-4 V substrate reached 49.8 MPa, which was significantly higher than that of hydroxyapatite coating and other silicate-based bioceramic coatings prepared by same method. After immersed in simulated body fluid for 2 days, a distinct apatite layer was deposited on the surface of bredigite coating, indicating that the prepared bredigite coating has excellent apatite-mineralization ability. The prepared bredigite coating supported the attachment and proliferation of rabbit bone marrow stem cells. The proliferation level of bone marrow stem cells was significantly higher than that on the hydroxyapatite coating. Our further study showed that the released SiO4 (4-) and Mg(2+) ions from bredigite coating as well as the formed nano-apatite layer on the coating surface might mainly contribute to the improvement of cell proliferation. The results indicated that the bredigite coating may be applied on orthopedic implants due to its excellent bonding strength, apatite mineralization and cytocompatibility.

Genesis of rare-metal pegmatites and alkaline apatite-fluorite rocks of Burpala massi, Northern Baikal folded zone

NASA Astrophysics Data System (ADS)

Sotnikova, Irina; Vladykin, Nikolai

2015-04-01

Burpalinsky rare metal alkaline massif in the Northern Baikal folded zone in southern margin of Siberian Platform, is a of intrusion central type, created 287 Ma covering area of about 250 km2. It is composed of nepheline syenites and pulaskites grading to quartz syenites in the contacts. Veines and dykes are represented by shonkinites, sodalite syenite, leucocratic granophyres, alkali granites and numerous rare metal alkaline syenite pegmatites and two dykes of carbonatites. All rocks except for granites are cut by a large apatite-fluorite dyke rocks with mica and magnetite, which in turn is cut by alaskite granites dyke. The massif has been studied by A.M. Portnov, A.A. Ganzeev et al. (1992) Burpalinsky massif is highly enriched with trace elements, which are concentrated in pegmatite dykes. About 70 rare-metal minerals we found in massif. Zr-silicates: zircon, eudialyte, lovenite, Ti-lovenite, velerite, burpalite, seidozerite, Ca- seidozerite, Rosenbuschite, vlasovite, katapleite, Ca-katapleite, elpidite. Ti- minerals:- sphene, astrophyllite, ramsaite, Mn-neptunite bafertisite, chevkinite, Mn-ilmenite, pirofanite, Sr-perrerit, landauite, rutile, anatase, brookite; TR- minerals - loparite, metaloparite, britolite, rinkolite, melanocerite, bastnesite, parisite, ankilite, monazite, fluocerite, TR-apatite; Nb- minerals - pyrochlore, loparite. Other rare minerals leucophanite, hambergite, pyrochlore, betafite, torite, thorianite, tayniolite, brewsterite, cryolite and others. We have proposed a new scheme massif: shonkinites - nepheline syenites - alkaline syenite - quartz syenites - veined rocks: mariupolites, rare-metal pegmatites, apatite, fluorite rock alyaskite and alkaline granites and carbonatites (Sotnikova, 2009). Apatite-fluorite rocks are found in the central part of massif. This is a large vein body of 2 km length and a 20 m width cutting prevailing pulaskites. Previously, these rocks were regarded as hydrothermal low-temperature phase. New geological and thermobarometric evidence suggests that apatite-fluorite rocks were formed from the residual fluid-melt, separated after crystallization of rare-metal pegmatites. Petrochemical and geochemical data Burpalinsky are in accord of general trend of crystal differentiation of alkaline magma containing small concentrations of CO2 and higher P2O5 and F, which accumulated significantly separated from the pegmatite melts. In some pegmatites fluorite with rare-metal minerals (flyuocerit etc) are separating in schlieren. Apatite-fluorite rocks are cut by leucogranite dyke, having genetic connection with rare-metal pegmatites. Late granitic phases has its own association of rare-metal minerals described by A.A. Ganzeev (1972). Thermobarometric geochemical study of apatite-fluorite rocks Burpala massif found a large number of primary fluid inclusions (15-50 micrometers). Thermal and cryometric research of 60 individual fluid inclusions in fluorite showed the domination of Na, Ca, Mg chlorides and high temperatures salt inclusions in fluorites (above 550C) and melt inclusions in apatites (800C). Apatite-fluorite rocks in massif are similar to foskorites in carbonatite complexes, with similar high Ca content, but instead fluorite, together with other "foskoritovymi" minerals - apatite, magnetite, mica, and pyroxene were formed instead for calcite. Isotopic studies (Sr-Nd) indicate the mantle source of primary magma Burpala massif close to EM-2, which is characteristic of alkaline intrusions in the folded belts (Vladykin 2009). RBRF grant 14-45-04057

Arsenic in hydrothermal apatite: Oxidation state, mechanism of uptake, and comparison between experiments and nature

NASA Astrophysics Data System (ADS)

Liu, Weihua; Mei, Yuan; Etschmann, Barbara; Brugger, Joël; Pearce, Mark; Ryan, Chris G.; Borg, Stacey; Wykes, Jeremey; Kappen, Peter; Paterson, David; Boesenberg, Ulrike; Garrevoet, Jan; Moorhead, Gareth; Falkenberg, Gerald

2017-01-01

Element substitution that occurs during fluid-rock interaction permits assessment of fluid composition and interaction conditions in ancient geological systems, and provides a way to fix contaminants from aqueous solutions. We conducted a series of hydrothermal mineral replacement experiments to determine whether a relationship can be established between arsenic (As) distribution in apatite and fluid chemistry. Calcite crystals were reacted with phosphate solutions spiked with As(V), As(III), and mixed As(III)/As(V) species at 250 °C and water-saturated pressure. Arsenic-bearing apatite rims formed in several hours, and within 48 h the calcite grains were fully replaced. X-ray Absorption Near-edge Spectroscopy (XANES) data show that As retained the trivalent oxidation state in the fully-reacted apatite grown from solutions containing only As(III). Extended X-ray Fine Spectroscopy (EXAFS) data reveal that these As(III) ions are surrounded by about three oxygen atoms at an Assbnd O bond length close to that of an arsenate group (AsO43-), indicating that they occupy tetrahedral phosphate sites. The three-coordinated As(III)-O3 structure, with three oxygen atoms and one lone electron pair around As(III), was confirmed by geometry optimization using ab initio molecular simulations. The micro-XANES imaging data show that apatite formed from solutions spiked with mixed As(III) and As(V) retained only As(V) after completion of the replacement reaction; in contrast, partially reacted samples revealed a complex distribution of As(V)/As(III) ratios, with As(V) concentrated in the center of the grain and As(III) towards the rim. Most natural apatites from the Ernest Henry iron oxide copper gold deposit, Australia, show predominantly As(V), but two grains retained some As(III) in their core. The As-anomalous amphibolite-facies gneiss from Binntal, Switzerland, only revealed As(V), despite the fact that these apatites in both cases formed under conditions where As(III) is expected to be the dominant As form in hydrothermal fluids. These results show that incorporation of As in apatite is a complicated process, and sensitive to the local fluid composition during crystallization, and that some of the complexity in As zoning in partially reacted apatite may be due to local fluctuations of As(V)/As(III) ratios in the fluid and to kinetic effects during the mineral replacement reaction. Our study shows for the first time that As(III) can be incorporated into the apatite structure, although not as efficiently as As(V). Uptake of As(III) is probably highly dependent on the reaction mechanism. As(III)O33- moieties replace phosphate groups, but cause a high strain on the lattice; as a result, As(III) is easily exchanged (or oxidized) for As(V) during hydrothermal recrystallization, and the fully reacted grains only record the preferred oxidation state (i.e., As(V)) from mixed-oxidation state solutions. Overall this study shows that the observed oxidation state of As in apatite may not reflect the original As(III)/As(V) ratio of the parent fluid, due to the complex nature of As(III) uptake and possible in situ oxidation during recrystallization.

Crystal structure details of La- and Bi-substituted hydroxyapatites: Evidence for LaO{sup +} and BiO{sup +} with a very short metal–oxygen bond

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kazin, Pavel E., E-mail: kazin@inorg.chem.msu.ru; Pogosova, Mariam A.; Trusov, Lev A.

Crystal structures of substituted apatites with general formula Ca{sub 10−x}M{sub x}(PO{sub 4}){sub 6}(OH{sub 1−δ}){sub 2−x}O{sub x}, where M=La, Bi, 0≤x<2, were refined using high-resolution X-ray powder diffraction patterns. Individual positions for Ca{sup 2+} and M{sup 3+}-ions localized near Ca2-site were determined. The M{sup 3+}-ion was found shifted toward the hexagonal channel center with respect to the Ca{sup 2+}-ion, forming very short bond with the intrachannel O{sup 2−}, while leaving considerably longer distances to other oxygen atoms, which suggested the existence of a MO{sup +} ion. Distinct bands of stretching M–O modes were observed in the Raman and FT-IR spectra ofmore » the compounds. The bond lengths for BiO{sup +} and LaO{sup +} were estimated to be 2.05(1) and 2.09(1) Å correspondingly. The latter was almost 0.3 Å lower than the shortest La–O bond in La{sub 2}O{sub 3}. The realization of such a strong lanthanide–oxygen bond in a crystal lattice could provide a very high axial ligand field and might be implemented to develop high-energy-barrier single-molecule magnets as well as to tune properties of lanthanide-based luminophores. - Graphical abstract: A fragment of the La-for-Ca substituted apatite crystal structure focusing on the La–O bond. - Highlights: • Individual positions in the apatite crystal lattice for a doping atom (La, Bi) and Ca. • The doping atom shifts toward the center of the hexagonal channel. • BiO{sup +} and LaO{sup +} with estimated short bond lengths of 2.05 and 2.09 Å respectively.« less

Possible secondary apatite fission track age standard from altered volcanic ash beds in the middle Jurassic Carmel Formation, Southwestern Utah

USGS Publications Warehouse

Kowallis, B.J.; Christiansen, E.H.; Everett, B.H.; Crowley, K.D.; Naeser, C.W.; Miller, D.S.; Deino, A.L.

1993-01-01

Secondary age standards are valuable in intra- and interlaboratory calibration. At present very few such standards are available for fission track dating that is older than Tertiary. Several altered volcanic ash beds occur in the Middle Jurassic Carmel Formation in southwestern Utah. The formation was deposited in a shallow marine/sabhka environment. Near Gunlock, Utah, eight ash beds have been identified. Sanidines from one of the ash beds (GUN-F) give a single-crystal laser-probe 40Ar/39Ar age of 166.3??0.8 Ma (2??). Apatite and zircon fission track ages range from 152-185 Ma with typically 15-20 Ma errors (2??). Track densities in zircons are high and most grains are not countable. Apatites are fairly common in most of the ash beds and have reasonable track densities ranging between 1.2-1.5 ?? 106 tracks/cm2. Track length distributions in apatites are unimodal, have standard deviations <1??m, and mean track lengths of about 14-14.5 ??m. High Cl apatites (F:Cl:OH ratio of 39:33:28) are particularly abundant and large in ash GUN-F, and are fairly easy to concentrate, but the concentrates contain some siderite, most of which can be removed by sieving. GUN-F shows evidence of some reworking and detriaal contamination based on older single grain 40Ar/39Ar analyses and some rounding of grains, but the apatite population appears to be largely uncontaminated. At present BJK has approximately 12 of apatite separate from GUN-F. ?? 1993.

A temporal record of pre-eruptive magmatic volatile contents at Campi Flegrei: Insights from texturally-constrained apatite analyses

NASA Astrophysics Data System (ADS)

Stock, Michael J.; Isaia, Roberto; Humphreys, Madeleine C. S.; Smith, Victoria C.; Pyle, David M.

2016-04-01

Apatite is capable of incorporating all major magmatic volatile species (H2O, CO2, S, Cl and F) into its crystal structure. Analysis of apatite volatile contents can be related to parental magma compositions through the application of pressure and temperature-dependent exchange reactions (Piccoli and Candela, 1994). Once included within phenocrysts, apatite inclusions are isolated from the melt and preserve a temporal record of magmatic volatile contents in the build-up to eruption. In this work, we measured the volatile compositions of apatite inclusions, apatite microphenocrysts and pyroxene-hosted melt inclusions from the Astroni 1 eruption of Campi Flegrei, Italy (Stock et al. 2016). These data are coupled with magmatic differentiation models (Gualda et al., 2012), experimental volatile solubility data (Webster et al., 2014) and thermodynamic models of apatite compositional variations (Piccoli and Candela, 1994) to decipher pre-eruptive magmatic processes. We find that apatite halogen/OH ratios decreased through magmatic differentiation, while melt inclusion F and Cl concentrations increased. Melt inclusion H2O contents are constant at ~2.5 wt%. These data are best explained by volatile-undersaturated differentiation over most of the crystallisation history of the Astroni 1 melt, with melt inclusion H2O contents reset at shallow levels during ascent. Given the high diffusivity of volatiles in apatite (Brenan, 1993), the preservation of volatile-undersaturated melt compositions in microphenocrysts suggests that saturation was only achieved 10 - 103 days before eruption. We suggest that late-stage transition into a volatile-saturated state caused an increase in magma chamber overpressure, which ultimately triggered the Astroni 1 eruption. This has major implications for monitoring of Campi Flegrei and other similar volcanic systems. Piccoli and Candela, 1994. Am. J. of Sc., 294, 92-135. Stock et al., 2016, Nat. Geosci. Gualda et al., 2012. J. Pet., 53, 875-890. Webster et al., 2014. J. Pet., 55, 2217-2248. Brenan, 1993. Chem. Geol., 110, 195-210.

Full-Field Calcium K-Edge X-ray Absorption Near-Edge Structure Spectroscopy on Cortical Bone at the Micron-Scale: Polarization Effects Reveal Mineral Orientation.

PubMed

Hesse, Bernhard; Salome, Murielle; Castillo-Michel, Hiram; Cotte, Marine; Fayard, Barbara; Sahle, Christoph J; De Nolf, Wout; Hradilova, Jana; Masic, Admir; Kanngießer, Birgit; Bohner, Marc; Varga, Peter; Raum, Kay; Schrof, Susanne

2016-04-05

Here, we show results on X-ray absorption near edge structure spectroscopy in both transmission and X-ray fluorescence full-field mode (FF-XANES) at the calcium K-edge on human bone tissue in healthy and diseased conditions and for different tissue maturation stages. We observe that the dominating spectral differences originating from different tissue regions, which are well pronounced in the white line and postedge structures are associated with polarization effects. These polarization effects dominate the spectral variance and must be well understood and modeled before analyzing the very subtle spectral variations related to the bone tissue variations itself. However, these modulations in the fine structure of the spectra can potentially be of high interest to quantify orientations of the apatite crystals in highly structured tissue matrices such as bone. Due to the extremely short wavelengths of X-rays, FF-XANES overcomes the limited spatial resolution of other optical and spectroscopic techniques exploiting visible light. Since the field of view in FF-XANES is rather large the acquisition times for analyzing the same region are short compared to, for example, X-ray diffraction techniques. Our results on the angular absorption dependence were verified by both site-matched polarized Raman spectroscopy, which has been shown to be sensitive to the orientation of bone building blocks and by mathematical simulations of the angular absorbance dependence. As an outlook we further demonstrate the polarization based assessment of calcium-containing crystal orientation and specification of calcium in a beta-tricalcium phosphate (β-Ca3(PO4)2 scaffold implanted into ovine bone. Regarding the use of XANES to assess chemical properties of Ca in human bone tissue our data suggest that neither the anatomical site (tibia vs jaw) nor pathology (healthy vs necrotic jaw bone tissue) affected the averaged spectral shape of the XANES spectra.

FT-IR microscopic mappings of early mineralization in chick limb bud mesenchymal cell cultures

NASA Technical Reports Server (NTRS)

Boskey, A. L.; Camacho, N. P.; Mendelsohn, R.; Doty, S. B.; Binderman, I.

1992-01-01

Chick limb bud mesenchymal cells differentiate into chondrocytes and form a cartilaginous matrix in culture. In this study, the mineral formed in different areas within cultures supplemented with 4 mM inorganic phosphate, or 2.5, 5.0, and 10 mM beta-glycerophosphate (beta GP), was characterized by Fourier-transform infrared (FT-IR) microscopy. The relative mineral-to-matrix ratios, and distribution of crystal sizes at specific locations throughout the matrix were measured from day 14 to day 30. The only mineral phase detected was a poorly crystalline apatite. Cultures receiving 4 mM inorganic phosphate had smaller crystals which were less randomly distributed around the cartilage nodules than those in the beta GP-treated cultures. beta GP-induced mineral consisted of larger, more perfect apatite crystals. In cultures receiving 5 or 10 mM beta GP, the relative mineral-to-matrix ratios (calculated from the integrated intensities of the phosphate and amide I bands, respectively) were higher than in the cultures with 4 mM inorganic phosphate or in the in vivo calcified chick cartilage.

Structurally bound sulfide and sulfate in apatite from the Philips Mine iron oxide - apatite deposit, New York, USA: A tracer of redox changes

NASA Astrophysics Data System (ADS)

Sadove, G.; Konecke, B.; Fiege, A.; Simon, A. C.

2017-12-01

Multiple competing hypotheses attempt to explain the genesis of iron oxide-apatite (IOA) ore deposits. Many studies have investigated the chemistry of apatite because the abundances of F and Cl can distinguish magmatic vs. hydrothermal processes. Recent experiments demonstrate that apatite incorporates S6+, S4+, and S2-, and that total sulfur (∑S) as well as the S6+/∑S ratio in apatite vary systematically as a function of oxygen fugacity [1], providing information about sulfur budget and redox. Here, we present results from X-ray absorption near-edge structure (XANES) spectroscopy at the S K-edge, electron microprobe analyses, cathodoluminescence (CL) imaging, and element mapping of apatite from the Philip's Mine IOA deposit, southern Adirondack Mountains, USA. The Philip's Mine apatite contains inclusions of pyrite and pyrrhotite, where the latter includes iron oxide and Ni-rich domains. The apatite also contains inclusions of monazite, and exhibits complex CL zonation coincident with variations in the abundances of REE and S. The presence of monazite fingerprints fluid-mediated dissolution-reprecipitation of originally REE-enriched apatite [2]. The S XANES spectra reveal varying proportions of structurally bound S6+ and S2-, as the S6+/∑S ratio ranges from sulfide-only to sulfate-only. Notably, sulfide-dominated domains contain higher S contents than sulfate-dominated regions. These observations are consistent with co-crystallization of apatite and monosulfide solid solution (MSS) at reducing conditions, followed by decomposition of MSS to pyrrhotite, pyrite and intermediate solid solution (ISS, which is not preserved; [3]). Metasomatism of that assemblage by an oxidized fluid resulted in formation of monazite in apatite and iron oxide domains in pyrrhotite. We conclude that the deposit formed by a H2S-Fe-rich volatile phase, possibly evolved from a rather primitive magmatic source, which is consistent with the low Ti content of magnetite. The deposit was subsequently altered by a rather oxidized SO2-poor volatile phase more typical of evolved felsic source regions. [1] Konecke et al. (2017) American Mineralogist 102-3, 548-557; [2] Harlov (2015) Elements 11-3, 171-176; [3] Edmonds & Mather (2017) Elements 13-2, 105-110.

Magnesian anorthosites and associated troctolites and dunite in Apollo 14 breccias

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lindstrom, M.M.; Knapp, S.A.

1984-11-15

Magnesian anorthosite, a new type of pristine lunar highlands rock, has been found in Apollo 14 breccias. It has primitive (high Ca and Mg) silicate mineral compositions, and high and variable REE concentrations. Variations in REE contents can be accounted for by variations in modal abundance of REE-rich apatite. Magnesian anorthosites are associated with troctolites and a dunite with very similar mineral compositions and it is suggested that all crystallized from a differentiated troctolitic intrusion. The origin of the REE-rich apatite is enigmatic. It is unlikely to have crystallized from an igneous liquid in equilibrium with the major minerals inmore » the anorthosite. Possible origins are assimilation of urKREEP or metasomatism by REE-rich fluids. REE-rich alkali anorthosites and gabbronorites are also found and are likely to be related to KREEP basalt magmas. Lunar compositional associations are distributed in a regional rather than global manner.« less

Method for fabricating apatite crystals and ceramics

DOEpatents

Soules, Thomas F.; Schaffers, Kathleen I.; Tassano, Jr., John B.; Hollingsworth, Joel P.

2013-09-10

The present invention provides a method of crystallizing Yb:C-FAP [Yb.sup.3+:Ca.sub.5(PO.sub.4).sub.3F], by dissolving the Yb:C-FAP in an acidic solution, following by neutralizing the solution. The present invention also provides a method of forming crystalline Yb:C-FAP by dissolving the component ingredients in an acidic solution, followed by forming a supersaturated solution.

Preparation of fluoride substituted apatite cements as the building blocks for tooth enamel restoration

NASA Astrophysics Data System (ADS)

Wei, Jie; Wang, Jiecheng; Liu, Xiaochen; Ma, Jian; Liu, Changsheng; Fang, Jing; Wei, Shicheng

2011-06-01

Fluoride substituted apatite cement (fs-AC) was synthesized by using the cement powders of tetracalcium phosphate (TTCP) and sodium fluoride (NaF), and the cement powders were mixed with diluted phosphoric acid (H 3PO 4) as cement liquid to form fs-AC paste. The fs-AC paste could be directly filled into the carious cavities to repair damaged dental enamel. The results indicated that the fs-AC paste was changed into fluorapatite crystals with the atom molar ratio for calcium to phosphorus of 1.66 and the F ion amount of 3 wt% after self-hardening for 2 days. The solubility of fs-AC in Tris-HCl solution (pH 6) was slightly lower than hydroxyapatite cement (HAC) that was similar to the apatite in enamel, indicating the fs-AC was much insensitive to the weakly acidic solution than the apatite in enamel. The fs-AC was tightly combined with the enamel surface because of the chemical reaction between the fs-AC and the apatite in enamel after the caries cavities was filled with fs-AC. The extracts of fs-AC caused no cytotoxicity on L929 cells, which satisfied the relevant criterion on dental biomaterials, revealing good cytocompatibility. The fs-AC had potential prospect for the reconstitution of carious lesion of dental enamel.

Behavior of carbonate and magnesium ions in the initial crystallites at the early developmental stages of the rat calvaria.

PubMed

Kakei, M; Nakahara, H; Tamura, N; Itoh, H; Kumegawa, M

1997-08-01

Analysis of the contents of calcium (Ca), magnesium (Mg), phosphate, and carbonate ions in the mineral phase of rat calvaria specimens obtained at different developmental stages indicated that the mineral at the newborn stage contained a negligible amount of carbonate, but a high content of Mg. There was no significant difference in Ca and phosphate (as PO4) contents between the newborn material and that from later stages. A relatively large amount of carbonate was detected in the calvaria from 6-day-old rats, in which only immature crystals were observed, thus indicating the beginning of apatite formation. Furthermore, using laser Raman microprobe analysis we confirmed that the Raman peak at 1120 cm-1 band, indicative of a Mg-CO3 compound, appeared at the 6-day stage. We also observed that the Raman peak at 988 cm-1 found in the samples from the newborn seemed to have shifted to 963-962 cm-1 in the case of those obtained from 6-day-old rats, a shift which suggests the conversion from the non-apatitic to the apatitic form. These results indicate that carbonate ions might facilitate the initiation of crystal development by converting the inhibitory Mg ion into its inactive form (Mg-carbonate compound).

Transformation of apatite phosphorus and non-apatite inorganic phosphorus during incineration of sewage sludge.

PubMed

Li, Rundong; Zhang, Ziheng; Li, Yanlong; Teng, Wenchao; Wang, Weiyun; Yang, Tianhua

2015-12-01

The recovery of phosphorus from incinerated sewage sludge ash (SSA) is assumed to be economical. Transformation from non-apatite inorganic phosphorus (NAIP) to apatite phosphorus (AP), which has a higher bioavailability and more extensive industrial applications, was studied at 750-950°C by sewage sludge incineration and model compound incineration with a calcium oxide (CaO) additive. Thermogravimetric differential scanning calorimetry analysis and X-ray diffraction measurements were used to analyze the reactions between NAIP with CaO and crystallized phases in SSA. High temperatures stimulated the volatilization of NAIP instead of AP. Sewage sludge incineration with CaO transformed NAIP into AP, and the percentage of AP from the total phosphorus reached 99% at 950°C. Aluminum phosphate reacted with CaO, forming Ca2P2O7 and Ca3(PO4)2 at 750-950°C. Reactions between iron phosphate and CaO occurred at lower temperatures, forming Ca(PO3)2 before reaching 850°C. Copyright © 2015 Elsevier Ltd. All rights reserved.

Apatite and sodalite based glass-bonded waste forms for immobilization of 129I and mixed halide radioactive wastes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Goel, Ashutosh; McCloy, John S.; Riley, Brian J.

The goal of the project was to utilize the knowledge accumulated by the team, in working with minerals for chloride wastes and biological apatites, toward the development of advanced waste forms for immobilizing 129I and mixed-halide wastes. Based on our knowledge, experience, and thorough literature review, we had selected two minerals with different crystal structures and potential for high chemical durability, sodalite and CaP/PbV-apatite, to form the basis of this project. The focus of the proposed effort was towards: (i) low temperature synthesis of proposed minerals (iodine containing sodalite and apatite) leading to the development of monolithic waste forms, (ii)more » development of a fundamental understanding of the atomic-scale to meso-scale mechanisms of radionuclide incorporation in them, and (iii) understanding of the mechanism of their chemical corrosion, alteration mechanism, and rates. The proposed work was divided into four broad sections. deliverables. 1. Synthesis of materials 2. Materials structural and thermal characterization 3. Design of glass compositions and synthesis glass-bonded minerals, and 4. Chemical durability testing of materials.« less

Crystallographic orientation of the c-axis of biological apatite as a new index of the quality of subchondral bone in knee joint osteoarthritis.

PubMed

Lee, Jee-Wook; Kobayashi, Akio; Nakano, Takayoshi

2017-05-01

The aim of the present study was to investigate the preferred orientation of biological apatite (BAp) as a new index of the quality of subchondral bone (SB) in knee joint osteoarthritis (OA). Ten OA and five normal knee joints were obtained. Thickness, quantity and bone mineral density (BMD) of SB were analyzed at the medial condyle of the femur in dry conditions by peripheral quantitative computed tomography. In addition, the preferred crystallographic orientation of the c-axis of BAp was evaluated as bone quality parameter using a microbeam X-ray diffractometer technique. BMD and thickness of SB were significantly increased in OA specimens compared to normal knee specimens (P < 0.01), and the preferred orientation of the c-axis of BAp along the normal direction of SB surface was significantly higher in OA specimens (P < 0.01), reflecting the change in stress of concentration in the pathological portion without cartilage. SB sclerosis in OA results in both proliferation of bone tissues and enhanced degree of preferential alignment of the c-axis of BAp. Our findings could have major implications for the diagnosis of clinical studies, including pathologic elucidation in OA.

The Orientation of Nanoscale Apatite Platelets in Relation to Osteoblastic-Osteocyte Lacunae on Trabecular Bone Surface.

PubMed

Shah, Furqan A; Zanghellini, Ezio; Matic, Aleksandar; Thomsen, Peter; Palmquist, Anders

2016-02-01

The orientation of nanoscale mineral platelets was quantitatively evaluated in relation to the shape of lacunae associated with partially embedded osteocytes (osteoblastic-osteocytes) on the surface of deproteinised trabecular bone of adult sheep. By scanning electron microscopy and image analysis, the mean orientation of mineral platelets at the osteoblastic-osteocyte lacuna (Ot.Lc) floor was found to be 19° ± 14° in the tibia and 20° ± 14° in the femur. Further, the mineral platelets showed a high degree of directional coherency: 37 ± 7% in the tibia and 38 ± 9% in the femur. The majority of Ot.Lc in the tibia (69.37%) and the femur (74.77%) exhibited a mean orientation of mineral platelets between 0° and 25°, with the largest fraction within a 15°-20° range, 17.12 and 19.8% in the tibia and femur, respectively. Energy dispersive X-ray spectroscopy and Raman spectroscopy were used to characterise the features observed on the anorganic bone surface. The Ca/P (atomic %) ratio was 1.69 ± 0.1 within the Ot.Lc and 1.68 ± 0.1 externally. Raman spectra of NaOCl-treated bone showed peaks associated with carbonated apatite: ν1, ν2 and ν4 PO4(3-), and ν1 CO3(2-), while the collagen amide bands were greatly reduced in intensity compared to untreated bone. The apatite-to-collagen ratio increased considerably after deproteinisation; however, the mineral crystallinity and the carbonate-to-phosphate ratios were unaffected. The ~19°-20° orientation of mineral platelets in at the Ot.Lc floor may be attributable to a gradual rotation of osteoblasts in successive layers relative to the underlying surface, giving rise to the twisted plywood-like pattern of lamellar bone.

[Does carbonate originate from carbonate-calcium crystal component of the human urinary calculus?].

PubMed

Yuzawa, Masayuki; Nakano, Kazuhiko; Kumamaru, Takatoshi; Nukui, Akinori; Ikeda, Hitoshi; Suzuki, Kazumi; Kobayashi, Minoru; Sugaya, Yasuhiro; Morita, Tatsuo

2008-09-01

It gives important information in selecting the appropriate treatment for urolithiasis to confirm the component of urinary calculus. Presently component analysis of the urinary calculus is generally performed by infrared spectroscopy which is employed by companies providing laboratory testing services in Japan. The infrared spectroscopy determines the molecular components from the absorption spectra in consequence of atomic vibrations. It has the drawback that an accurate crystal structure cannot be analyzed compared with the X-ray diffraction method which analyzes the crystal constituent based on the diffraction of X-rays on crystal lattice. The components of the urinary calculus including carbonate are carbonate apatite and calcium carbonate such as calcite. Although the latter is reported to be very rare component in human urinary calculus, the results by infrared spectroscopy often show that calcium carbonate is included in calculus. The infrared spectroscopy can confirm the existence of carbonate but cannot determine whether carbonate is originated from carbonate apatite or calcium carbonate. Thus, it is not clear whether calcium carbonate is included in human urinary calculus component in Japan. In this study, we examined human urinary calculus including carbonate by use of X-ray structural analysis in order to elucidate the origin of carbonate in human urinary calculus. We examined 17 human calculi which were reported to contain calcium carbonate by infrared spectroscopy performed in the clinical laboratory. Fifteen calculi were obtained from urinary tract, and two were from gall bladder. The stones were analyzed by X-ray powder method after crushed finely. The reports from the clinical laboratory showed that all urinary culculi consisted of calcium carbonate and calcium phosphate, while the gallstones consisted of calcium carbonate. But the components of all urinary calculi were revealed to be carbonate apatite by X-ray diffraction. The components of gallstones were shown to be calcium carbonate (one calcite and the other aragonite) not only by infrared spectroscopy but by X-ray diffraction. It was shown that component analysis of the calculus could be more accurately performed by adding X-ray diffraction method to infrared spectroscopy. It was shown that calcium carbonate existed in a gallstone. As for the carbonate in human urinary calculi, present study showed that it was not calcium carbonate origin but carbonate apatite origin.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Carneiro, Karina M. M.; Zhai, Halei; Zhu, Li

We report that enamel, the outermost layer of teeth, is an acellular mineralized tissue that cannot regenerate; the mature tissue is composed of high aspect ratio apatite nanocrystals organized into rods and inter-rod regions. Amelogenin constitutes 90% of the protein matrix in developing enamel and plays a central role in guiding the hierarchical organization of apatite crystals observed in mature enamel. To date, a convincing link between amelogenin supramolecular structures and mature enamel has yet to be described, in part because the protein matrix is degraded during tissue maturation. Here we show compelling evidence that amelogenin self-assembles into an amyloid-likemore » structure in vitro and in vivo. We show that enamel matrices stain positive for amyloids and we identify a specific region within amelogenin that self-assembles into β-sheets. Lastly, we propose that amelogenin nanoribbons template the growth of apatite mineral in human enamel. This is a paradigm shift from the current model of enamel development.« less

Calcium Apatite Deposition Disease: Diagnosis and Treatment

PubMed Central

2016-01-01

Calcium apatite deposition disease (CADD) is a common entity characterized by deposition of calcium apatite crystals within and around connective tissues, usually in a periarticular location. CADD most frequently involves the rotator cuff. However, it can theoretically occur in almost any location in the musculoskeletal system, and many different locations of CADD have been described. When CADD presents in an unexpected location it can pose a diagnostic challenge, particularly when associated with pain or swelling, and can be confused with other pathologic processes, such as infection or malignancy. However, CADD has typical imaging characteristics that usually allows for a correct diagnosis to be made without additional imaging or laboratory workup, even when presenting in unusual locations. This is a review of the common and uncommon presentations of CADD in the appendicular and axial skeleton as well as an updated review of pathophysiology of CADD and current treatments. PMID:28042481

Insight into Bone-Derived Biological Apatite: Ultrastructure and Effect of Thermal Treatment

PubMed Central

Liu, Quan; Pan, Haobo; Chen, Zhuofan; Matinlinna, Jukka Pekka

2015-01-01

Objectives. This study aims at examining the ultrastructure of bone-derived biological apatite (BAp) from a series of small vertebrates and the effect of thermal treatment on its physiochemical properties. Materials and Methods. Femurs/fin rays and vertebral bodies of 5 kinds of small vertebrates were firstly analyzed with X-ray microtomography. Subsequently, BAp was obtained with thermal treatment and low power plasma ashing, respectively. The properties of BAp, including morphology, functional groups, and crystal characteristics were then analyzed. Results. The bones of grouper and hairtail were mainly composed of condensed bone. Spongy bone showed different distribution in the bones from frog, rat, and pigeon. No significant difference was found in bone mineral density of condensed bone and trabecular thickness of spongy bone. Only platelet-like crystals were observed for BAp obtained by plasma ashing, while rod-like and irregular crystals were both harvested from the bones treated by sintering. A much higher degree of crystallinity and larger crystal size but a lower content of carbonate were detected in the latter. Conclusion. Platelet-like BAp is the common inorganic component of vertebrate bones. BAp distributing in condensed and spongy bone may exhibit differing thermal reactivity. Thermal treatment may alter BAp's in vivo structure and composition. PMID:25695088

Apatite mineralization in elasmobranch skeletons via a polyphosphate intermediate

NASA Astrophysics Data System (ADS)

Omelon, Sidney; Lacroix, Nicolas; Lildhar, Levannia; Variola, Fabio; Dean, Mason

2014-05-01

All vertebrate skeletons are stiffened with apatite, a calcium phosphate mineral. Control of apatite mineralization is essential to the growth and repair of the biology of these skeletons, ensuring that apatite is deposited in the correct tissue location at the desired time. The mechanism of this biochemical control remains debated, but must involve increasing the localized apatite saturation state. It was theorized in 1923 that alkaline phosphatase (ALP) activity provides this control mechanism by increasing the inorganic phosphate (Pi) concentration via dephosphorylation of phosphorylated molecules. The ALP substrate for biological apatite is not known. We propose that polyphosphates (polyPs) produced by mitochondria may be the substrate for biological apatite formation by ALP activity. PolyPs (PO3-)n, also known as condensed phosphates, represent a concentrated, bioavailable Pi-storage strategy. Mitochondria import Pi and synthesize phosphate polymers through an unknown biochemical mechanism. When chelated with calcium and/or other cations, the effective P-concentration of these neutrally charged, amorphous, polyP species can be very high (~ 0.5 M), without inducing phosphate mineral crystallization. This P-concentration in the low Pi-concentration biological environment offers a method of concentrating P well above an apatite supersaturation required for nucleation. Bone is the most studied mineralized skeletal tissue. However, locating and analyzing active mineralizing areas is challenging. We studied calcified cartilage skeletons of elasmobranch fishes (sharks, stingrays and relatives) to analyse the phosphate chemistry in this continually mineralizing skeleton. Although the majority of the elasmobranch skeleton is unmineralized cartilage, it is wrapped in an outer layer of mineralized tissue comprised of small tiles called tesserae. These calcified tesserae continually grow through the formation of new mineral on their borders. Co-localization of ALP and polyPs were identified at the mineralizing tessera borders using Raman spectroscopy, fluorescence microscopy and histological methods. Application of exogenous ALP to skeletal tissue cross-sections resulted in polyP disappearance, and Pi production. It is proposed that elasmobranch skeletal cells produce polyP-containing granules as a concentrated P-source, while ALP activity controls when and where Pi is cleaved from polyP, increasing the apatite supersaturation to nucleate apatite minerals in the skeleton. These data support not only interaction of polyP and ALP as a cell-mediated apatite mineralization control mechanism, but also suggest that this mechanism arose millions of years ago and is common to both bony and cartilaginous skeletal systems.

Laser ablation U-Th-Sm/He dating of detrital apatite

NASA Astrophysics Data System (ADS)

Guest, B.; Pickering, J. E.; Matthews, W.; Hamilton, B.; Sykes, C.

2016-12-01

Detrital apatite U-Th-Sm/He thermochronology has the potential to be a powerful tool for conducting basin thermal history analyses as well as complementing the well-established detrital zircon U-Pb approach in source to sink studies. A critical roadblock that prevents the routine application of detrital apatite U-Th-Sm/He thermochronology to solving geological problems is the costly and difficult whole grain approach that is generally used to obtain apatite U-Th-Sm/He data. We present a new analytical method for laser ablation thermochronology on apatite. Samples are ablated using a Resonetics™ 193 nm excimer laser and liberated 4He is measured using an ASI (Australian Scientific Instruments) Alphachron™ quadrupole mass spectrometer system; collectively known as the Resochron™. The ablated sites are imaged using a Zygo ZescopeTM optical profilometer and ablated pit volume measured using PitVol, a custom MatLabTM algorithm. The accuracy and precision of the method presented here was confirmed using well-characterized Durango apatite and Fish Canyon Tuff (FCT) apatite reference materials, with Durango apatite used as a primary reference and FCT apatite used as a secondary reference. The weighted average of our laser ablation Durango ages (30.5±0.35 Ma) compare well with ages obtained using conventional whole grain degassing and dissolution U-Th-Sm/He methods (32.56±0.43 Ma) (Jonckheere et.al., 1 993; Farley, 2000; McDowell et.al., 2005) for chips of the same Durango crystal. These Durango ages were used to produce a K-value to correct the secondary references and unknown samples. After correction, FCT apatite has a weighted average age of 28.37 ± 0.96 Ma, which agrees well with published ages. As a further test of this new method we have conducted a case study on a set of samples from the British Mountains of the Yukon Territory in NW Canada. Sandstone samples collected across the British Mountains were analyzed using conventional U-Th-Sm/He whole grain methods and then reanalyzed using our new Laser ablation approach. The laser ablation results are consistent with those obtained using conventional methods, confirming that apatite laser ablation U-Th-Sm/He thermochronology is a viable alternative for collecting large low temperature thermochronology data sets from detrital samples.

Porous SiO2 nanofiber grafted novel bioactive glass-ceramic coating: A structural scaffold for uniform apatite precipitation and oriented cell proliferation on inert implant.

PubMed

Das, Indranee; De, Goutam; Hupa, Leena; Vallittu, Pekka K

2016-05-01

A composite bioactive glass-ceramic coating grafted with porous silica nanofibers was fabricated on inert glass to provide a structural scaffold favoring uniform apatite precipitation and oriented cell proliferation. The coating surfaces were investigated thoroughly before and after immersion in simulated body fluid. In addition, the proliferation behavior of fibroblast cells on the surface was observed for several culture times. The nanofibrous exterior of this composite bioactive coating facilitated homogeneous growth of flake-like carbonated hydroxyapatite layer within a short period of immersion. Moreover, the embedded porous silica nanofibers enhanced hydrophilicity which is required for proper cell adhesion on the surface. The cells proliferated well following a particular orientation on the entire coating by the assistance of nanofibrous scaffold-like structural matrix. This newly engineered composite coating was effective in creating a biological structural matrix favorable for homogeneous precipitation of calcium phosphate, and organized cell growth on the inert glass surface. Copyright © 2016 Elsevier B.V. All rights reserved.

Probing the limit of magnesium uptake by β-tricalcium phosphate in biphasic mixtures formed from calcium deficient apatites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumar, P. Nandha; Mishra, Sandeep K.; Kannan, S., E-mail: para_kanna@yahoo.com

2015-11-15

A series of magnesium doped non-stoichiometric calcium deficient apatites were synthesized through an aqueous precipitation route. The resultant structural changes during heat treatment were investigated by X-ray diffraction, Raman and FT-IR spectroscopy and Rietveld refinement. The results confirmed the formation of biphasic mixtures comprising Ca{sub 10}(PO{sub 4}){sub 6}(OH){sub 2} and β-Ca{sub 3}(PO{sub 4}){sub 2} after heat treatment at 1000 °C with the preferential occupancy of Mg{sup 2+} at the crystal lattice of β-Ca{sub 3}(PO{sub 4}){sub 2}. The concentration of Mg{sup 2+} uptake in β-Ca{sub 3}(PO{sub 4}){sub 2} is limited till reaching the stoichiometric ratio of (Ca+Mg)/P=1.67 and beyond this stoichiometricmore » value [(Ca+Mg)/P>1.67], Mg{sup 2+} precipitates as Mg(OH){sub 2} and thereafter gets converted to MgO during heat treatment. Any kind of Mg{sup 2+} uptake in the crystal lattice of Ca{sub 10}(PO{sub 4}){sub 6}(OH){sub 2} is discarded from the investigation. - Highlights: • Aqueous co-precipitation of calcium deficient apatites with excess magnesium (Mg{sup 2+}) additions. • Heat treatments beyond 800 °C results in the formation of biphasic apatite mixtures. • Mg{sup 2+} gets accommodated at the β-Ca{sub 3}(PO{sub 4}){sub 2} lattice of biphasic mixtures. • Mg{sup 2+} additions exceeding stoichiometric value (Ca/P>1.67) results in its formation as MgO. • Mg{sup 2+} occupancy at β-Ca{sub 3}(PO{sub 4}){sub 2} lattice delays its allotropic conversion α-Ca{sub 3}(PO{sub 4}){sub 2} till 1350 °C.« less

LA-ICP-MS depth profile analysis of apatite: Protocol and implications for (U-Th)/He thermochronometry

NASA Astrophysics Data System (ADS)

Johnstone, Samuel; Hourigan, Jeremy; Gallagher, Christopher

2013-05-01

Heterogeneous concentrations of α-producing nuclides in apatite have been recognized through a variety of methods. The presence of zonation in apatite complicates both traditional α-ejection corrections and diffusive models, both of which operate under the assumption of homogeneous concentrations. In this work we develop a method for measuring radial concentration profiles of 238U and 232Th in apatite by laser ablation ICP-MS depth profiling. We then focus on one application of this method, removing bias introduced by applying inappropriate α-ejection corrections. Formal treatment of laser ablation ICP-MS depth profile calibration for apatite includes construction and calibration of matrix-matched standards and quantification of rates of elemental fractionation. From this we conclude that matrix-matched standards provide more robust monitors of fractionation rate and concentrations than doped silicate glass standards. We apply laser ablation ICP-MS depth profiling to apatites from three unknown populations and small, intact crystals of Durango fluorapatite. Accurate and reproducible Durango apatite dates suggest that prolonged exposure to laser drilling does not impact cooling ages. Intracrystalline concentrations vary by at least a factor of 2 in the majority of the samples analyzed, but concentration variation only exceeds 5x in 5 grains and 10x in 1 out of the 63 grains analyzed. Modeling of synthetic concentration profiles suggests that for concentration variations of 2x and 10x individual homogeneous versus zonation dependent α-ejection corrections could lead to age bias of >5% and >20%, respectively. However, models based on measured concentration profiles only generated biases exceeding 5% in 13 of the 63 cases modeled. Application of zonation dependent α-ejection corrections did not significantly reduce the age dispersion present in any of the populations studied. This suggests that factors beyond homogeneous α-ejection corrections are the dominant source of overdispersion in apatite (U-Th)/He cooling ages.

Apatite (U-Th-Sm)/He age dispersion arising from analysis of variable grain sizes and broken crystals - examples from the Scottish Southern Uplands

NASA Astrophysics Data System (ADS)

Łuszczak, Katarzyna; Persano, Cristina; Stuart, Finlay; Brown, Roderick

2016-04-01

Apatite (U-Th-Sm)/He (AHe) thermochronometry is a powerful technique for deciphering denudation of the uppermost crust. However, the age dispersion of single grains from the same rock is typical, and this hampers establishing accurate thermal histories when low grain numbers are analysed. Dispersion arising from the analysis of broken crystal fragments[1] has been proposed as an important cause of age dispersion, along with grain size and radiation damage. A new tool, Helfrag[2], allows constraints to be placed on the low temperature history derived from the analysis of apatite crystal fragments. However, the age dispersion model has not been fully tested on natural samples yet. We have performed AHe analysis of multiple (n = 20-25) grains from four rock samples from the Scottish Southern Uplands, which were subjected to the same exhumation episodes, although, the amount of exhumation varied between the localities. This is evident from the range of AFT ages (˜60 to ˜200 Ma) and variable thermal histories showing either strong, moderate and no support for a rapid cooling event at ˜60 Ma. Different apatite size and fragment geometry were analysed in order to maximise age dispersion. In general, the age dispersion increases with increasing AFT age (from 47% to 127%), consistent with the prediction from the fragmentation model. Thermal histories obtained using Helfrag were compared with those obtained by standard codes based on the spherical approximation. In one case, the Helfrag model was capable of resolving the higher complexity of the thermal history of the rock, constraining several heating/cooling events that are not predicted by the standard models, but are in good agreement with the regional geology. In other cases, the thermal histories are similar for both Helfrag and standard models and the age predictions for the Helfrag are only slightly better than for standard model, implying that the grain size has the dominant role in generating the age dispersion. Rather than suggesting that grain size is the predominant factor in controlling age dispersion in all data sets, our results may be linked to the actual size of the picked grains; for grain widths smaller than 100 μm, the He profile within the crystal may not be differentiated enough to produce a dispersion measureable outside the uncertainty associated with the age. It is also easier for long-thin and short-thick than long-thick and short-thin grains to be preserved; this minimises the age dispersion that can be generated from fragmentation. We suggest, that in order to obtain valuable information from both fragmentation and grain size >20 large (width >100 μm) grain fragments of variable length have to be analyzed, together with a few smaller grains. Our results point to a strategy that favours multiple single-grain AHe ages determinations on carefully selected samples, with good quality apatite crystals of variable dimensions rather than fewer determinations on many samples. [1] Brown, R. et al. 2013.Geochim. Cosmochim. Acta.122, 478-497 [2] Beucher, R. et al. 2013.Geochim. Cosmochim. Acta. 120, 395-416.

Bone mineral as an electrical energy reservoir.

PubMed

Nakamura, Miho; Hiratai, Rumi; Yamashita, Kimihiro

2012-05-01

Mechanical stress in bone induces an electrical potential generated by piezoelectricity arising from displacement of collagen fibrils. Where and for how long the potential is stored in bone; however, are still poorly understood. We investigated the electrical properties of collagen fibrils and apatite minerals and found that bone, when polarized electrically by applying an external voltage, depolarizes by two mechanisms. Plots of thermally stimulated depolarization current show two significant peaks: one at 100°C, attributed to collagen fibrils because decalcified bone exhibits depolarization peak at 100°C, and the other at 500°C, attributed to apatite minerals because calcined bone exhibits depolarization peak at 500°C and has activation energy similar to that for synthesized apatite. The crystallographic c-axis orientation of calcined bone depends on the direction in which the bone is cut, either transverse or longitudinal, and strongly affects the polarization efficacy. Copyright © 2012 Wiley Periodicals, Inc.

Hierarchical and non-hierarchical mineralisation of collagen

PubMed Central

Liu, Yan; Kim, Young-Kyung; Dai, Lin; Li, Nan; Khan, Sara; Pashley, David H.; Tay, Franklin R.

2010-01-01

Biomineralisation of collagen involves functional motifs incorporated in extracellular matrix protein molecules to accomplish the objectives of stabilising amorphous calcium phosphate into nanoprecursors and directing the nucleation and growth of apatite within collagen fibrils. Here we report the use of small inorganic polyphosphate molecules to template hierarchical intrafibrillar apatite assembly in reconstituted collagen in the presence of polyacrylic acid to sequester calcium and phosphate into transient amorphous nanophases. The use of polyphosphate without a sequestration analogue resulted only in randomly-oriented extrafibrillar precipitations along the fibrillar surface. Conversely, the use of polyacrylic acid without a templating analogue resulted only in non-hierarchical intrafibrillar mineralisation with continuous apatite strands instead of discrete crystallites. The ability of using simple non-protein molecules to recapitulate different levels of structural hierarchy in mineralised collagen signifies the ultimate simplicity in Nature’s biomineralisation design principles and challenges the need for using more complex recombinant matrix proteins in bioengineering applications. PMID:21040969

The influence of channel anion identity on the high-pressure crystal structure, compressibility, and stability of apatite

NASA Astrophysics Data System (ADS)

Skelton, Richard; Walker, Andrew M.

2018-03-01

The material properties of the common phosphate mineral apatite are influenced by the identity of the channel anion, which is usually F-, Cl-, or (OH)-. Density functional theory calculations have been used to determine the effect of channel anion identity on the compressibility and structure of apatite. Hydroxyapatite and fluorapatite are found to have similar zero pressure bulk moduli, of 79.2 and 82.1 GPa, respectively, while chlorapatite is considerably more compressible, with K 0 = 55.0 GPa. While the space groups of hydroxyapatite and fluorapatite do not change between 0 and 25 GPa, symmetrization of the Cl- site in chlorapatite at 7.5 GPa causes the space group to change from P2 1 /b to P6 3 /m. Examination of the valence electron density distribution in chlorapatite reveals that this symmetry change is associated with a change in the coordination of the Cl- anion from threefold to sixfold coordinated by Ca. We also calculate the pressure at which apatite decomposes to form tuite, a calcium orthophosphate mineral, and find that the transition pressure is sensitive to the identity of the channel anion, being lowest for fluorapatite (13.8 GPa) and highest for chlorapatite (26.9 GPa). Calculations are also performed within the DFT-D2 framework to investigate the influence of dispersion forces on the compressibility of apatite minerals.

Multiphase inclusions in plagioclase from anorthosites in the Stillwater Complex, Montana: implications for the origin of the anorthosites

USGS Publications Warehouse

Loferski, P.J.; Arculus, R.J.

1993-01-01

Multiphase inclusions, consisting of clinopyroxene+ilmenite+apatite, occur within cumulus plagioclase grains from anorthosites in the Stillwater Complex, Montana, and in other rocks from the Middle Banded series of the intrusion. The textures and constant modal mineralogy of the inclusions indicate that they were incorporated in the plagioclase as liquid droplets that later crystallized rather than as solid aggregates. Their unusual assemblage, including a distinctive manganiferous ilmenite and the presence of baddeleyite (ZrO2), indicates formation from an unusual liquid. A process involving silicater liquid immiscibility is proposed, whereby small globules of a liquid enriched in Mg, Fe, Ca, Ti, P, REE, Zr and Mn exsolved from the main liquid that gave rise to the anorthosites, became trapped in the plagioclase, and later crystallized to form the inclusions. The immiscibility could have occurred locally within compositional boundaries around crystallizing plagioclase grains or it could have occurred pervasively throughout the liquid. It is proposed that the two immiscible liquids were analogous, n terms of their melt structures, to immiscible liquid pairs reported in the literature both in experiments and in natural basalts. For the previously reported pairs, immiscibility is between a highly polymerized liquid, typically granitic in composition, and a depolymerized liquid, typically ferrobasaltic in composition. In the case of the anorthosites, the depolymerized liquid is represented by the inclusions, and the other liquid was a highly polymerized aluminosilicate melt with a high normative plagioclase content from which the bulk of the anorthosites crystallized. Crystallization of the anorthosites from this highly polymerized liquid accounts for various distinctive textural and chemical features of the anorthosites compared to other rocks in the Stillwater Complex. A lack of correlation between P contents and chondrite-normalized rare earth element (REE) ratios of plagioclase separates indicates that the amount of apatite in the inclusions is too low to affect the REE signature of the plagioclase separates. Nevertheless, workers should use caution when attempting REE modelling studies of cumulates having low REE contents, because apatite-bearing inclusions can potentially cause problems. ?? 1993 Springer-Verlag.

Volatile Concentrations and H-Isotope Composition of Unequilibrated Eucrites

NASA Technical Reports Server (NTRS)

Sarafian, Adam R.; Nielsen, Sune G.; Marschall, Horst R.; Gaetani, Glenn A.; Hauri, Erik H.; Righter, Kevin; Berger, Eve L.

2017-01-01

Eucrites are among the oldest and best studied asteroidal basalts (1). They represent magmatism that occurred on their parent asteroid, likely 4-Vesta, starting at 4563 Ma and continuing for approx. 30 Myr. Two hypotheses are debated for the genesis of eucrites, a magma ocean model (2), and a mantle partial melting model. In general, volatiles (H, C, F, Cl) have been ignored for eucrites and 4-Vesta, but solubility of wt% levels of H2O are possible at Vestan interior PT conditions. Targeted measurements on samples could aid our understanding considerably. Recent studies have found evidence of volatile elements in eucrites, but quantifying the abundance of volatiles remains problematic (6). Volatile elements have a disproportionately large effect on melt properties and phase stability, relative to their low abundance. The source of volatile elements can be elucidated by examining the hydrogen isotope ratio (D/H), as different H reservoirs have drastically different H isotope compositions. Recent studies of apatite in eucrites have shown that the D/H of 4-Vesta matches that of Earth and carbonaceous chondrites, however, the D/H of apatites may not represent the D/H of a primitive 4-Vesta melt due to the possibility of degassing prior to the crystallization of apatite. Therefore, the D/H of early crystallizing phases must be measured to determine if the D/H of 4-Vesta is equal to that of the Earth and carbonaceous chondrites.

The effect of secondary apatite on the initial 87Sr/86Sr ratio determination in granitic rocks: a case study of the Tadamigawa pluton, northeastern Japan

NASA Astrophysics Data System (ADS)

Wakasugi, Y.; Ichino, K.; Tanioka, Y.; Wakaki, S.; Tsuboi, M.; Ishikawa, T.

2017-12-01

Apatite is a major accessory mineral in igneous rocks. Because Rb contents in apatite are very low, 87Sr/86Sr ratios of magmatic apatite are useful to estimate the initial 87Sr/86Sr ratio (SrI) of igneous rocks. Secondary post-magmatic event such as hydrothermal alteration may also crystallize secondary apatite, which may inhibit the estimation of SrI of igneous rocks. In this study, we examine the effects of secondary apatite on the initial 87Sr/86Sr ratio determination of granitic rocks by using acid leaching technique. Leached apatite samples were first separated from the whole rock powder as a heavy mineral fraction by heavy liquid technique, and the heavy mineral fraction was then leached by 3 M HNO3. The isotopic ratios of Sr and the concentrations of Rb and Sr were analyzed by TIMS and ICP-MS at Kochi Core Center, respectively. The Tadamigawa Older-stage granites, which locate in the Taishaku Mountains at the northeastern part of Japan, intrude into the Ashio Jurassic complex, and the ages of these rocks are late Cretaceous to Paleogene. The U-Pb ages of zircon and the K-Ar ages of biotite for these rocks are c. 100 Ma [1, 2]. Rb-Sr whole-rock isochron age of the pluton is 96.5 ± 1.3 Ma (SrI = 0.70534 ± 0.00003) and it is concordant with other radiometric ages. Rb-Sr mineral isochron ages range from 84.4 to 97.3 Ma and these ages are relatively younger than the Rb-Sr whole-rock isochron age. The difference among radiometric ages may reflect the difference of the closure temperature in each isotopic system. The Tadamigawa Older-stage granites have SrI for Rb-Sr mineral isochron range from 0.7053 to 0.7061 and are very similar to that (0.70534) for Rb-Sr whole-rock isochron. These may suggest that the Tadamigawa Older-stage granites are generated from same parental magma. However, 87Sr/86Sr ratios of the leached apatite samples were 0.70544-0.70856 and are relatively higher than SrI obtained from the Rb-Sr mineral isochrons (0.7053-0.7061). This result suggests that leached apatite samples contain not only magmatic apatite but also secondary apatite. A careful apatite separation is needed to obtain the magmatic initial 87Sr/86Sr ratios by the isotopic analyses of apatite. [1] Tanioka et al. (2014) Japan. Mag. Mineral. Petrol. Sci. 43, 215-227. [2] Wakasugi et al. (2014) 121st Ann. Meet. Geo. Soc. Japan, Abstr., 57.

The essential role of fetuin in the serum-induced calcification of collagen.

PubMed

Toroian, Damon; Price, Paul A

2008-02-01

The mineral in bone is located primarily within the collagen fibril, and during mineralization the fibril is formed first and then water within the fibril is replaced with mineral. Our goal is to understand the mechanism of fibril mineralization, and as a first step we recently determined the size exclusion characteristics of the fibril. This study indicates that apatite crystals up to 12 unit cells in size can access the water within the fibril while molecules larger than a 40-kDa protein are excluded. We proposed a novel mechanism for fibril mineralization based on these observations, one that relies exclusively on agents excluded from the fibril. One agent generates crystals outside the fibril, some of which diffuse into the fibril and grow, and the other selectively inhibits crystal growth outside of the fibril. We have tested this mechanism by examining the impact of removing the major serum inhibitor of apatite growth, fetuin, on the serum-induced calcification of collagen. The results of this test show that fetuin determines the location of serum-driven mineralization: in fetuin's presence, mineral forms only within collagen fibrils; in fetuin's absence, mineral forms only in solution outside the fibrils. The X-ray diffraction spectrum of serum-induced mineral is comparable to the spectrum of bone crystals. These observations show that serum calcification activity consists of an as yet unidentified agent that generates crystal nuclei, some of which diffuse into the fibril, and fetuin, which favors fibril mineralization by selectively inhibiting the growth of crystals outside the fibril.

Effect of ZrO(2) additions on the crystallization, mechanical and biological properties of MgO-CaO-SiO(2)-P(2)O(5)-CaF(2) bioactive glass-ceramics.

PubMed

Li, H C; Wang, D G; Meng, X G; Chen, C Z

2014-06-01

A series of ZrO(2) doped MgO-CaO-SiO(2)-P(2)O(5)-CaF(2) bioactive glass-ceramics were obtained by sintering method. The crystallization behavior, phase composition, morphology and structure of glass-ceramics were characterized. The bending strength, elastic modulus, fracture toughness, micro-hardness and thermal expansion coefficient (TEC) of glass-ceramics were investigated. The in vitro bioactivity and cytotoxicity tests were used to evaluate the bioactivity and biocompatibility of glass-ceramics. The sedimentation mechanism and growth process of apatites on sample surface were discussed. The results showed that the mainly crystalline phases of glass-ceramics were Ca(5)(PO4)3F (fluorapatite) and β-CaSiO(3). (β-wollastonite). m-ZrO(2) (monoclinic zirconia) declined the crystallization temperatures of glasses. t-ZrO(2) (tetragonal zirconia) increased the crystallization temperature of Ca(5)(PO4)(3)F and declined the crystallization temperature of β-CaSiO(3). t-ZrO(2) greatly increased the fracture toughness, bending strength and micro-hardness of glass-ceramics. The nanometer apatites were induced on the surface of glass-ceramic after soaking 28 days in SBF (simulated body fluid), indicating the glass-ceramic has good bioactivity. The in vitro cytotoxicity test demonstrated the glass-ceramic has no toxicity to cell. Copyright © 2014 Elsevier B.V. All rights reserved.

Probing the limit of magnesium uptake by β-tricalcium phosphate in biphasic mixtures formed from calcium deficient apatites

NASA Astrophysics Data System (ADS)

Kumar, P. Nandha; Mishra, Sandeep K.; Kannan, S.

2015-11-01

A series of magnesium doped non-stoichiometric calcium deficient apatites were synthesized through an aqueous precipitation route. The resultant structural changes during heat treatment were investigated by X-ray diffraction, Raman and FT-IR spectroscopy and Rietveld refinement. The results confirmed the formation of biphasic mixtures comprising Ca10(PO4)6(OH)2 and β-Ca3(PO4)2 after heat treatment at 1000 °C with the preferential occupancy of Mg2+ at the crystal lattice of β-Ca3(PO4)2. The concentration of Mg2+ uptake in β-Ca3(PO4)2 is limited till reaching the stoichiometric ratio of (Ca+Mg)/P=1.67 and beyond this stoichiometric value [(Ca+Mg)/P>1.67], Mg2+ precipitates as Mg(OH)2 and thereafter gets converted to MgO during heat treatment. Any kind of Mg2+ uptake in the crystal lattice of Ca10(PO4)6(OH)2 is discarded from the investigation.

Corrosion behavior of mesoporous bioglass-ceramic coated magnesium alloy under applied forces.

PubMed

Zhang, Feiyang; Cai, Shu; Xu, Guohua; Shen, Sibo; Li, Yan; Zhang, Min; Wu, Xiaodong

2016-03-01

In order to research the corrosion behavior of bioglass-ceramic coated magnesium alloys under applied forces, mesoporous 45S5 bioactive glass-ceramic (45S5 MBGC) coatings were successfully prepared on AZ31 substrates using a sol-gel dip-coating technique followed by a heat treatment at the temperature of 400°C. In this work, corrosion behavior of the coated samples under applied forces was characterized by electrochemical tests and immersion tests in simulated body fluid. Results showed that the glass-ceramic coatings lost the protective effects to the magnesium substrate in a short time when the applied compressive stress was greater than 25MPa, and no crystallized apatite was formed on the surface due to the high Mg(2+) releasing and the peeling off of the coatings. Whereas, under low applied forces, apatite deposition and crystallization on the coating surface repaired cracks to some extent, thus improving the corrosion resistance of the coated magnesium during the long-term immersion period. Copyright © 2015 Elsevier Ltd. All rights reserved.

Helium diffusion in apatite assessed by ERDA and implications for (U-Th)/He dating

NASA Astrophysics Data System (ADS)

Stuebner, K.; Jonckheere, R.; Ratschbacher, L.

2006-12-01

The strength of a low-temperature geochronometer, like (U-Th)/He(apatite), lies in the low activation energy of He-diffusion, which makes the system sensitive to temperatures <100°C. A thorough understanding of the diffusion kinetics of He in apatite is crucial for the interpretation of (U-Th)/He ages. Diffusion parameters derived from high temperature step heating experiments and reported in the literature span a broad range: E_a=30-40 kcal/mol (1σ-error ~2 kcal/mol); ln(D0/a2)=8-26 s^-^1 or ln(D0)=8- 130 cm2/s and with the standard experimental setup it is not possible to determine the grain size independent parameter D0. We employ a new approach using Elastic Recoil Detection Analysis (ERDA) to characterise He diffusion at low temperatures. ERDA allows to measure element-concentration profiles across the upper 2 μm of 1x1cm plane surface samples. Implantation of high-dose (5E+15 ions cm2), low- energy Helium ions (50-250 keV) in polished thin sections of a large Durango apatite crystal produces narrow, near-Gaussian distribution of Helium at a depth <1 μm beneath the crystal surface. Diffusion results in normally distributed concentration-profiles across the initial layer. The He-profile is approximated by a Gaussian curve with variance σ2 = 2 D t = D0 exp(-E_a/RT) t. Dt increases exponentially with T and linearly with t, so that knowledge of the t-T conditions of a set of samples allows to calculate the diffusion parameters from the fitted Gauss-distributions. With this approach Helium diffusion is observed on a sub-μm scale, which allows not only a precise determination of E_a and D0, but also circumvents assumptions that are necessary for the step-heating approach (spherical diffusion geometry, dimension of the diffusion domain) and is independent of grain size or shape. It facilitates investigation of the dependence of diffusion on the crystallographic direction, on the anion composition (OH, F, Cl) of apatite and on the degree of radiogenic lattice damage.

Step down Vascular Calcification Analysis using State-of-the-Art Nanoanalysis Techniques

PubMed Central

Curtze, Sven C.; Kratz, Marita; Steinert, Marian; Vogt, Sebastian

2016-01-01

New insights into the architecture and formation mechanisms of calcific lesions down to the nanoscale open a better understanding of atherosclerosis and its pathogenesis. Scanning electron – and atomic force microscope based nano-analytical characterization techniques were adapted to the assessment of an ex-vivo calcified coronary artery. Human atherosclerotic tissue and bone tissue reside a typical chemistry of Magnesium and Sodium rich Calcium phosphates, identified as whitlockite and Calcium apatite, respectively. Despite the obvious similarities in both chemistry and crystallography, there are also clear differences between calcified vascular tissue and bone such as the highly oriented growth in bone, revealing meso-crystal character, as opposed to the anisotropic character of calcified vascular lesions. While the grain size in vascular calcified plaques is in the range of nanometers, the grain size in bone appears larger. Spherical calcific particles present in both the coronary artery wall and embedded in plaques reveal concentric layers with variations in both organic content and degree of hydration. PMID:26980376

Step down Vascular Calcification Analysis using State-of-the-Art Nanoanalysis Techniques.

PubMed

Curtze, Sven C; Kratz, Marita; Steinert, Marian; Vogt, Sebastian

2016-03-16

New insights into the architecture and formation mechanisms of calcific lesions down to the nanoscale open a better understanding of atherosclerosis and its pathogenesis. Scanning electron - and atomic force microscope based nano-analytical characterization techniques were adapted to the assessment of an ex-vivo calcified coronary artery. Human atherosclerotic tissue and bone tissue reside a typical chemistry of Magnesium and Sodium rich Calcium phosphates, identified as whitlockite and Calcium apatite, respectively. Despite the obvious similarities in both chemistry and crystallography, there are also clear differences between calcified vascular tissue and bone such as the highly oriented growth in bone, revealing meso-crystal character, as opposed to the anisotropic character of calcified vascular lesions. While the grain size in vascular calcified plaques is in the range of nanometers, the grain size in bone appears larger. Spherical calcific particles present in both the coronary artery wall and embedded in plaques reveal concentric layers with variations in both organic content and degree of hydration.

Experimental Study into the Partitioning Behavior of Fluorine, Chlorine, Hydroxyl, and Sulfur (S2-) Between Apatite and a Synthetic Kreep Basalt Melt

NASA Technical Reports Server (NTRS)

Turner, Amber; Vander Kaaden, Kathleen; McCubbin, Francis; Danielson, Lisa R.

2017-01-01

The mineral apatite (Ca5 (PO4)3(F, Cl, OH)) is known for its ability to constrain the petrogenesis of the rock in which it is hosted and for its ubiquity throughout the Solar System, as it is found in lunar, martian, and terrestrial rocks alike (McCubbin et. al, 2015). The abundance of volatile elements, and for this particular study, the elevated abundance of sulfur (S2-) in high-Al basalt samples bearing apatite, could provide more insight for inquiries posed about the behavior of volatiles in lunar and martian magmatic systems (Boyce et. al, 2010). Oxygen fugacity will be an important parameter for these experiments, as the Moon, Mars, and Earth have different redox states (Herd, 2008). The objective of this experimental endeavor is to determine apatite-melt partition coefficients for the volatile elements (F-, Cl-, OH-, S2-) that make up the X-site (i.e., the typically monovalent anion site) in the mineral apatite in a lunar melt composition under lunar oxygen fugacity conditions approx.1-2 log units below the iron-wüstite buffer). All experiments will be conducted at NASA, Johnson Space Center in the High Pressure Experimental Petrology Laboratory. In order to conduct apatite-melt partition experiments with oxygen fugacity as an additional parameter, we will create a synthetic mix of the lunar KREEP basalt 15386, a sample retrieved during Apollo 15 that is believed to represent an indigenous volcanic melt derived from the lunar interior (Rhodes, J.M et. al, 2006). Other geochemically significant elements including C, Co, Ni, Mo, and rare earth elements will be included in the mix at trace abundances in order to assess their partitioning behavior without effecting the overall behavior of the system. The synthetic mix will then be loaded into a piston cylinder, an apparatus used to simulate high-pressure/high-temperature conditions of planetary interiors, and exposed to 0.5 GPa of pressure, the pressure observed in the upper mantle of the Moon, and heated to the melting temperature of the materials. To make sure crystals grow large enough for the necessary analyses, the sample will be kept at the crystallization temperature for 8 hours. This extended run time should also allow the sample to achieve a steady state which is necessary to accurately assess the partitioning of these elements between apatite and melt. The results from this experimental study will allow us to determine the fate of F-, Cl-, OH-, and S2- during the magmatic evolution of the Moon.

Using apatite to discriminate synchronous ore-associated and barren granitoid rocks: A case study from the Edong metallogenic district, South China

NASA Astrophysics Data System (ADS)

Duan, Deng-Fei; Jiang, Shao-Yong

2018-06-01

In order to find criteria to discriminate the synchronous ore-associated and barren granitoid rocks, we have determined apatite chemistry associated with ore-associated (Cu-Au) and barren granitoid rocks in the Edong district of the Middle and Lower Yangtze River metallogenic belt, South China. Both rock types give zircon U-Pb ages between 135.0 and 138.7 Ma. Apatite has a higher volatile and Li content (Cl: 0.19-0.57 wt%, average 0.35 wt%, SO3: 0.08-0.71 wt%, average 0.32 wt%, Li: 0.49-7.99 ppm, average 3.23 ppm) in ore-associated rocks than those in barren rocks (Cl: 0.09-0.31 wt%, average 0.16 wt%, SO3: 0.06-0.28 wt%, average 0.16 wt%, Li: 0.15-0.89 ppm, average 0.36 ppm). Apatite (La/Yb)N ratios and Eu/Eu* values are relatively high and show wider variation in ore-associated rocks than those in barren rocks. Apatite (La/Sm)N and (Yb/Sm)N show positive correlation in ore-associated rocks but negative in barren rocks. The higher volatile content occurs in ore-associated magma, favoring Cu-Au transportation and deposition. Furthermore, amphibole fractional crystallization in ore-associated magma further enriched the ore elements in the residual melt. Barren rocks may have undergone fluid exsolution before emplacement, which makes it barren in Cl, S and ore elements (Cu, S). These signatures emphases the significance of volatile and magma evolution in mineralization and indicate that analyses of magmatic apatite can serve to distinguish ore-associated from barren intrusions.

Amyloid-like ribbons of amelogenins in enamel mineralization

DOE PAGES

Carneiro, Karina M. M.; Zhai, Halei; Zhu, Li; ...

2016-03-24

We report that enamel, the outermost layer of teeth, is an acellular mineralized tissue that cannot regenerate; the mature tissue is composed of high aspect ratio apatite nanocrystals organized into rods and inter-rod regions. Amelogenin constitutes 90% of the protein matrix in developing enamel and plays a central role in guiding the hierarchical organization of apatite crystals observed in mature enamel. To date, a convincing link between amelogenin supramolecular structures and mature enamel has yet to be described, in part because the protein matrix is degraded during tissue maturation. Here we show compelling evidence that amelogenin self-assembles into an amyloid-likemore » structure in vitro and in vivo. We show that enamel matrices stain positive for amyloids and we identify a specific region within amelogenin that self-assembles into β-sheets. Lastly, we propose that amelogenin nanoribbons template the growth of apatite mineral in human enamel. This is a paradigm shift from the current model of enamel development.« less

In vitro remineralization of acid-etched human enamel with Ca 3SiO 5

NASA Astrophysics Data System (ADS)

Dong, Zhihong; Chang, Jiang; Deng, Yan; Joiner, Andrew

2010-02-01

Bioactive and inductive silicate-based bioceramics play an important role in hard tissue prosthetics such as bone and teeth. In the present study, a model was established to study the acid-etched enamel remineralization with tricalcium silicate (Ca 3SiO 5, C 3S) paste in vitro. After soaking in simulated oral fluid (SOF), Ca-P precipitation layer was formed on the enamel surface, with the prolonged soaking time, apatite layer turned into density and uniformity and thickness increasingly from 250 to 350 nm for 1 day to 1.7-1.9 μm for 7 days. Structure of apatite crystals was similar to that of hydroxyapatite (HAp). At the same time, surface smoothness of the remineralized layer is favorable for the oral hygiene. These results suggested that C 3S treated the acid-etched enamel can induce apatite formation, indicating the biomimic mineralization ability, and C 3S could be used as an agent of inductive biomineralization for the enamel prosthesis and protection.

Raman spectroscopy of apatite irradiated with swift heavy ions with and without simultaneous exertion of high pressure

NASA Astrophysics Data System (ADS)

Liu, J.; Glasmacher, U. A.; Lang, M.; Trautmann, C.; Voss, K.-O.; Neumann, R.; Wagner, G. A.; Miletich, R.

2008-04-01

Durango apatite was irradiated with energetic U ions of 2.64 GeV and Kr ions of 2.1 GeV, with and without simultaneous exposure to a pressure of 10.5 GPa. Analysis by confocal Raman spectroscopy gives evidence of vibrational changes being marginal for fluences below 5×1011 ions/cm2 but becoming dominant when increasing the fluence to 8×1012 ions/cm2. Samples irradiated with U ions experience severe strain resulting in crystal cracking and finally breakage at high fluences. These radiation effects are directly linked to the formation of amorphous tracks and the fraction of amorphized material increasing with fluence. Raman spectroscopy of pressurized irradiated samples shows small shifts of the band positions with decreasing pressure but without a significant change of the Grüneisen parameter. Compared to irradiations at ambient conditions, the Raman spectra of apatite irradiated at 10.5 GPa exhibit fewer modifications, suggesting a higher radiation stability of the lattice by the pressure applied.

Ytterbium- and neodymium-doped vanadate laser hose crystals having the apatite crystal structure

DOEpatents

Payne, Stephen A.; Kway, Wayne L.; DeLoach, Laura D.; Krupke, William F.; Chai, Bruce H. T.

1994-01-01

Yb.sup.3+ and Nd.sup.3+ doped Sr.sub.5 (VO.sub.4).sub.3 F crystals serve as useful infrared laser media that exhibit low thresholds of oscillation and high slope efficiencies, and can be grown with high optical quality. These laser media possess unusually high absorption and emission cross sections, which provide the crystals with the ability to generate greater gain for a given amount of pump power. Many related crystals such as Sr.sub.5 (VO.sub.4).sub.3 F crystals doped with other rare earths, transition metals, or actinides, as well as the many structural analogs of Sr.sub.5 (VO.sub.4).sub.3 F, where the Sr.sup.2+ and F.sup.- ions are replaced by related chemical species, have similar properties.

Modeling and Measuring the Effects of Radiation Damage Annealing on Helium Diffusion Kinetics in Apatite

NASA Astrophysics Data System (ADS)

Willett, C. D.; Fox, M.; Shuster, D. L.

2016-12-01

Understanding helium diffusion kinetics in apatite is critical for the accurate interpretation of (U-Th)/He thermochronometric data. This problem is complicated by the observation that helium diffusivity is not a simple function of temperature, but may evolve as a function of damage to the apatite crystal lattice resulting from alpha recoil. This `radiation damage' increases as a function of the amount of radiometric parent products, or effective uranium concentration, and time, but decreases due to thermal annealing of damage, necessitating a detailed understanding of radiation damage production and annealing in cases of burial heating over geologic timescales. Published observations [1,2] suggest that annealing rates of damage caused by alpha recoil and fission tracks in apatite differ. Existing models, however, assume the diffusion kinetics resulting from the two sources of damage are identical [3], demonstrating the need for further investigation of these damage sources. We present modeling and experimental work designed to interrogate the effects of radiation damage and its annealing on helium diffusion kinetics in apatite. Using previously published results [4] that investigated the effects of annealing temperature and duration on measured helium diffusivity, we fit a set of functions that are then integrated into a numerical model that tracks the evolution of radiation damage and apparent (U-Th)/He age. We compare the results of this model calibration to existing models [3]. In addition, we present data from two suites of diffusion experiments. The first suite, intended to test the published methodology and results, uses Durango apatite, while the second uses Sierran (CA) granite as a first test to determine if apatite of varying chemistry and age responds differently to the thermal annealing of radiation damage. Ultimately, the updated model and experimental results will benefit the interpretation of the effects of radiation damage accumulation and annealing in apatite and expand the range of geologic settings that can be studied using low-temperature thermochronology. References: [1] Fox, M., Shuster, D. (2014), EPSL 397, 174-183; [2] Gautheron, C. et al. (2013), Chem. Geol. 351, 257-267; [3] Flowers, R. et al. (2009), GCA 73, 2347-2365; [4] Shuster, D., Farley, K. (2009), GCA 73, 6183-6196.

Apatite U-Pb thermochronolgy applied to complex geological settings - insights from geo/thermochronology and geochemistry

NASA Astrophysics Data System (ADS)

Paul, Andre; Spikings, Richard; Ulyanov, Alexey; Chew, David

2016-04-01

Application of high temperature (>350oC) thermochronology is limited to the U-Pb system of accessory minerals, such as apatite, under the assumption that radiogenic lead is lost to thermally activated volume diffusion into an infinite reservoir. Cochrane et al. (2015) have demonstrated a working example from the northern Andes of South America. Predictions from volume diffusion theory were compared with measured single grain U-Pb date correlated to shortest diffusion radius and in-situ profiles measured by LA-ICP-MS. Results from both techniques were found to be in agreement with predictions from thermally activated, volume diffusion. However, outliers from the ID-TIMS data suggested some complexity, as grains were found to be too young relative to their diffusion radius. Interaction of multiple processes can be responsible for the alteration of apatite U-Pb dates such as: (1) metamorphic (over)growth, (2) fluid aided alteration/recrystallization and (3) metamictization and fracturing of the grain. Further, predictions from volume diffusion rely on the input parameters: (a) diffusivity, (b) activation energy and (c) shortest diffusion radius. Diffusivity and activation energy are potentially influenced by the chemical composition and subsequent changes in crystal structure. Currently there is one value for diffusion parameter and activation energy established for (Durango) apatite (Cherniak et al., 1991). Correlation between diffusivity/activation energy and composition has not been established. We investigate if correlations exist between diffusivity/activation energy and composition by obtaining single grain apatite U-Pb date and chemical compostion and correlating these to their diffusion radius. We test the consistency of apatite closure temperature, by comparing the apatite U-Pb dates with lower temperature thermochronometers such as white mica and K-feldspar Ar/Ar and by petrographic observations. We test if chemical information can be a proxy to identify metamorphic (over)growth and fluid aided alteration/recrystallization. We seek to evaluate if apatite U-Pb thermochronology can be applied to a broad range of rock types and geological environments or if limitations must be drawn.

Sub-µm structure and volatile distribution of shocked lunar apatite

NASA Astrophysics Data System (ADS)

Cernok, A.; White, L. F.; Darling, J.; Dunlop, J.; Fougerouse, D.; William, R. D. A.; Reddy, S.; Saxey, D. W.; Zhao, X.; Franchi, I.; Anand, M.

2017-12-01

Apatite is a key mineral broadly used for studying volatiles in planetary materials. Most studies in this recent frontier of planetary exploration focus on volatile content and respective isotopic composition in apatite. However, there is an imperative to contextualize geochemical data with impact-induced features, given that most planetary materials experienced at least some shock deformation. This study aims at understanding the effect of high-level shock deformation on volatile distribution in apatite from lunar highlands samples. Combining Electron Backscatter Diffraction (EBSD), NanoSIMS and Atom Probe Microscopy (APM) analyses we are gaining an insight into the µm- and nm-scale structural variation in apatite from a shocked, maskelynite- and impact-melt-bearing norite. EBSD revealed degraded crystallinity, high density of low angle grain boundaries and domains of sub-µm granular features that appear amorphous at this length scales ( 80 x 40 nm). Texture component maps show up to 25° misorientation within a single grain - evidence of severe crystal-plastic deformation, but with no obvious evidence of recrystallization. APM revealed complex microstructure of the apparently amorphous domains defined by well developed, straight to slightly curved grain boundaries meeting at 120° triple junctions. This equilibrium texture is probably accommodated by annealing and recrystallization of apatite due to the post-shock heating. Crystallites range in size from 50 to 100 nm. Grain boundaries are defined by segregation of Mg, Si and Fe impurities, which possibly originate from surrounding phases. Cl and F show homogenous distribution over the length scale of the APM analysis (1 to 500 nm). H2O content measurements of 250-600 ppm by NanoSIMS are consistent with the lower range of previously reported values for this rock, with no obvious correlation with the level of crystallinity. δD values are confirmed to be terrestrial-like and relatively constant. These preliminary data suggest that impact event(s) either did not disturb the volatile distribution and composition of homogenous magmatic apatite, or that it induced diffusion and homogenisation of primary volatile species during annealing. Apatites in a range of variably shocked lunar samples are currently being examined to further clarify this question.

Combined apatite fission track and U-Pb dating by LA-ICPMS

NASA Astrophysics Data System (ADS)

Chew, D. M.; Donelick, R. A.

2012-04-01

Apatite is a common accessory mineral in igneous, metamorphic and clastic sedimentary rocks. It is a nearly ubiquitous accessory phase in igneous rocks, is common in metamorphic rocks of pelitic, carbonate, basaltic, and ultramafic composition and is virtually ubiquitous in clastic sedimentary rocks. In contrast to the polycyclic behavior of the stable heavy mineral zircon, apatite is unstable in acidic groundwaters and has limited mechanical stability in sedimentary transport systems. Apatite has many potential applications in provenance studies, particularly as it likely represents first-cycle detritus. Fission track and U-Pb dating are very powerful techniques in apatite provenance studies. They yield complementary information, with the apatite fission-track system yielding low-temperature exhumation ages and the U-Pb system yielding high-temperature cooling ages which constrain the timing of apatite crystallization. This study focuses on integrating apatite fission track and U-Pb dating by the LA-ICPMS method. Our approach is intentionally broad in scope, and is applicable to any quadrupole or rapid-scanning magnetic-sector LA-ICPMS system. Calculating uranium concentrations in fission-track dating by LA-ICPMS increases the speed of analysis and sample throughput compared to the conventional external detector method and avoids the need for neutron irradiation (Hasebe et al., 2004). LA-ICPMS-based uranium measurements in apatite are measured relative to an internal concentration standard (typically 43Ca). Ca in apatite is not always stochiometric as minor cations (Mn2+, Sr2+, Ba2+ and Fe2+) and REE can substitute with Ca2+. These substitutions must be quantified by multi-elemental LA-ICPMS analyses. Such data are also useful for discriminating between different apatite populations in sedimentary or volcaniclastic rocks based on their trace-element chemistry. Low U, Th and radiogenic Pb concentrations, elevated common Pb / radiogenic Pb ratios and U-Pb elemental fractionation are challenges in apatite U-Pb dating by LA-ICPMS. Isochron-based approaches to common Pb correction require a significant spread in common Pb / radiogenic Pb ratios. This is not usually possible on individual detrital apatite grains and hence the 204Pb-, 207Pb- and 208Pb-correction methods are preferred. Uranium concentration measurements by ICPMS employ large peak jumps (the internal standard is a Ca isotope) which require a quadrupole or a rapid-scanning magnetic-sector LA-ICPMS system. These single-collector instruments require a prohibitively long dwell time on the low intensity 204Pb peak to measure it accurately and hence the 207Pb- and 208Pb-correction methods are preferred. Uranium-concentration measurements in fission-track dating require well-constrained ablation depths during analysis and hence spot analyses are preferred to rastering. Laser-induced U-Pb fractionation is corrected for by sample-standard bracketing using a variety of apatite standards (Durango, Emerald Lake, Fish Canyon Tuff, Kovdor, Otter Lake and McClure Mountain syenite). Of these, Emerald Lake (Chew et al., 2011) and McClure Mountain syenite apatite are recommended as primary standards with Durango apatite making a suitable secondary standard. Offline data-reduction uses custom-written software for ICPMS data processing (the UPbICP package of Ray Donelick) or the freeware IOLITE data-reduction package of Paton et al. (2010).

Synthetic hydroxyapatites doped with Zn(II) studied by X-ray diffraction, infrared, Raman and thermal analysis

NASA Astrophysics Data System (ADS)

Guerra-López, José R.; Echeverría, Gustavo A.; Güida, Jorge A.; Viña, Raúl; Punte, Graciela

2015-06-01

Calcium hydroxyapatite (CaHap) formation when different amounts of Zn(II) are present in the mother solution has been investigated by atomic absorption, infrared and Raman spectroscopies, X-ray diffraction and thermal analysis (DTA and TG). The studied samples have been synthesized at T=95 °C and pH 9 in air. The analysis of the results have shown that the pure CaHap sample crystallizes in the monoclinic form P21/b. Concentrations up to 20% of Zn(II) in the mother solution, equivalent to smaller concentrations in solid (up to 9.1% in wt), favor the formation of the hexagonal apatite, P63/m, while Zn(II) concentrations higher than 20% in solution help an amorphous phase development where vibrational spectra indicated coexistence of two phases: an apatite and ZnNH4PO4·H2O. Infrared data of thermal treated samples endorse that HPO42- ion had not been incorporated in Zn(II) doped samples during the synthesis process. Present results also allow to conclude that Zn(II) cation exhibits a preference to occupy the Ca2 site of the apatite structure and induces water adsorption and a small quantity of CO32- cation incorporation, leading to formation of a less crystalline Ca deficient apatite.

Yb3+/Ho3+ Co-Doped Apatite Upconversion Nanoparticles to Distinguish Implanted Material from Bone Tissue.

PubMed

Li, Xiyu; Chen, Haifeng

2016-10-07

The exploration of bone reconstruction with time requires the combination of a biological method and a chemical technique. Lanthanide Yb 3+ and Ho 3+ co-doped fluorapatite (FA:Yb 3+ /Ho 3+ ) and hydroxyapatite (HA:Yb 3+ /Ho 3+ ) particles with varying dopant concentrations were prepared by hydrothermal synthesis and thermal activation. Controllable green and red upconversion emissions were generated under 980 nm near-infrared excitation; the FA:Yb 3+ /Ho 3+ particles resulted in superior green luminescence, while HA:Yb 3+ /Ho 3+ dominated in red emission. The difference in the green and red emission behavior was dependent on the lattice structure and composition. Two possible lattice models were proposed for Yb 3+ /Ho 3+ co-doped HA and FA along the hydroxyl channel and fluorine channel of the apatite crystal structure. We first reported the use of the upconversion apatite particles to clearly distinguish implanted material from bone tissue on stained histological sections of harvested in vivo samples. The superposition of the tissue image and material image is a creative method to show the material-tissue distribution and interrelation. The upconversion apatite particles and image superposition method provide a novel strategy for long-term discriminable fluorescence tracking of implanted material or scaffold during bone regeneration.

Natural age dispersion arising from the analysis of broken crystals. Part I: Theoretical basis and implications for the apatite (U-Th)/He thermochronometer

NASA Astrophysics Data System (ADS)

Brown, Roderick W.; Beucher, Romain; Roper, Steven; Persano, Cristina; Stuart, Fin; Fitzgerald, Paul

2013-12-01

Over the last decade major progress has been made in developing both the theoretical and practical aspects of apatite (U-Th)/He thermochronometry and it is now standard practice, and generally seen as best practice, to analyse single grain aliquots. These individual prismatic crystals are often broken and are fragments of larger crystals that have broken during mineral separation along the weak basal cleavage in apatite. This is clearly indicated by the common occurrence of only 1 or no clear crystal terminations present on separated apatite grains, and evidence of freshly broken ends when grains are viewed using a scanning electron microscope. This matters because if the 4He distribution within the whole grain is not homogeneous, because of partial loss due to thermal diffusion for example, then the fragments will all yield ages different from each other and from the whole grain age. Here we use a numerical model with a finite cylinder geometry to approximate 4He ingrowth and thermal diffusion within hexagonal prismatic apatite crystals. This is used to quantify the amount and patterns of inherent, natural age dispersion that arises from analysing broken crystals. A series of systematic numerical experiments were conducted to explore and quantify the pattern and behaviour of this source of dispersion using a set of 5 simple thermal histories that represent a range of plausible geological scenarios. In addition some more complex numerical experiments were run to investigate the pattern and behaviour of grain dispersion seen in several real data sets. The results indicate that natural dispersion of a set of single fragment ages (defined as the range divided by the mean) arising from fragmentation alone varies from c. 7% even for rapid (c. 10 °C/Ma), monotonic cooling to over 50% for protracted, complex histories that cause significant diffusional loss of 4He. The magnitude of dispersion arising from fragmentation scales with the grain cylindrical radius, and is of a similar magnitude to dispersion expected from differences in absolute grain size alone (spherical equivalent radii of 40-150 μm). This source of dispersion is significant compared with typical analytical uncertainties on individual grain analyses (c. 6%) and standard deviations on multiple grain analyses from a single sample (c. 10-20%). Where there is a significant difference in the U and Th concentration of individual grains (eU), the effect of radiation damage accumulation on 4He diffusivity (assessed using the RDAAM model of Flowers et al. (2009)) is the primary cause of dispersion for samples that have experienced a protracted thermal history, and can cause dispersion in excess of 100% for realistic ranges of eU concentration (i.e. 5-100 ppm). Expected natural dispersion arising from the combined effects of reasonable variations in grain size (radii 40-125 μm), eU concentration (5-150 ppm) and fragmentation would typically exceed 100% for complex thermal histories. In addition to adding a significant component of natural dispersion to analyses, the effect of fragmentation also acts to decouple and corrupt expected correlations between grain ages and absolute grain size and to a lesser extent between grain age and effective uranium concentration (eU). Considering fragmentation explicitly as a source of dispersion and analysing how the different sources of natural dispersion all interact with each other provides a quantitative framework for understanding patterns of dispersion that otherwise appear chaotic. An important outcome of these numerical experiments is that they demonstrate that the pattern of age dispersion arising from fragmentation mimics the pattern of 4He distribution within the whole grains, thus providing an important source of information about the thermal history of the sample. We suggest that if the primary focus of a study is to extract the thermal history information from (U-Th)/He analyses then sampling and analytical strategies should aim to maximise the natural dispersion of grain ages, not minimise it, and should aim to analyse circa 20-30 grains from each sample. The key observations and conclusions drawn here are directly applicable to other thermochronometers, such as the apatite, rutile and titanite U-Pb systems, where the diffusion domain is approximated by the physical grain size.

Raman microspectrometry of laser-reshaped rabbit auricular cartilage: preliminary study on laser-induced cartilage mineralization

NASA Astrophysics Data System (ADS)

Heger, Michal; Mordon, Serge R.; Leroy, Gérard; Fleurisse, Laurence; Creusy, Collette

2006-03-01

Laser-assisted cartilage reshaping (LACR) is a relatively novel technique designed to noninvasively and permanently restructure cartilaginous tissue. It is believed that heat-induced stress relaxation, in which a temperature-mediated disruption of H2O binding is associated with conformational alterations in the proteoglycan and collagen-rich matrix, constitutes the underlying mechanism of LACR. Several reports have suggested that laser-mediated cartilage mineralization may contribute to the permanent shape change of laser-reshaped cartilage. In an effort to validate these results in the context of Er:glass LACR, we performed a preliminary Raman microspectrometric study to characterize the crystal deposits in laser-irradiated chondrocytes and extracellular matrix. For the first time, we identified intracellular calcium sulfate deposits and extracellular calcium phosphate (apatite) crystals in laser-reshaped rabbit auricular cartilage. Calcium carbonate deposits are localized in both irradiated and nonirradiated samples, suggesting that this mineral plays no role in conformational retention. In our discussion, we elaborate on the possible molecular and cellular mechanisms responsible for intra- and extracellular crystallization, and propose a novel hypothesis on the formation of apatite, inasmuch as the biological function of this mineral (providing structure and rigidity in bones and dental enamel) may be extrapolated to the permanent shape change of laser-irradiated cartilage.

Parent zonation in thermochronometers - resolving complexity revealed by ID-TIMS U-Pb dates and implications for the application of decay-based thermochronometers

NASA Astrophysics Data System (ADS)

Navin Paul, Andre; Spikings, Richard; Chew, David; Daly, J. Stephen; Ulyanov, Alexey

2017-04-01

High temperature (>350℃) U-Pb thermochronometers primarily use accessory minerals such as apatite, titanite and rutile, and assume that daughter isotopes are lost by thermally activated volume diffusion while the parent remains immobile. Studies exploiting such behaviour have been successfully used to reconstruct thermal histories spanning several hundred million years (e.g. Cochrane et al., 2014). However, outliers in date (ID-TIMS) vs diffusion length space are frequently observed, and grains are frequently found to be either too young or too old for expected thermal history solutions using the diffusion data of Cherniak et al. (2010). These deviations of single grain apatite U-Pb dates from expected behaviour could be caused by a combination of i) metamorphic (over-)growth, ii) fluid-aided Pb mobilisation during alteration/recrystallization, iii) parent isotope zonation, iv) metamictisation, and v) changes in diffusion length with time (e.g. fracturing). We present a large data set from the northern Andes of South America, where we compare apatite U-Pb ID-TIMS-(TEA) data with LA-ICP-MS element maps and in-situ apatite U-Pb LA-(MC)-ICP-MS dates. These are combined with U-Pb zircon and 40Ar/39Ar (muscovite) data to attempt to distinguish between thermally activated volume diffusion and secondary overgrowth/recrystallization. We demonstrate that in young (e.g. Phanerozoic) apatites that have not recrystallized or experienced metasomatic overgrowths, U-Pb dates are dominantly controlled by volume diffusion and intra-crystal uranium zonation. This implies that ID-TIMS analyses of apatites with zoned parent isotope distributions will not usually recover accurate thermal history solutions, and an in-situ dating method is required. Recovering the uranium distribution during in-situ analysis provides a means to account for parent zonation, substantially increasing the accuracy of the modelled t-T-paths. We present in-situ data from apatites where scatter in date v diffusion length scale is observed and compare t-T-paths from single grain and in-situ modelling. Modelling of in-situ data will further show if all apatites from a single hand specimen record the same thermal history using Cherniak et al. (2010) diffusion data, or if the Pb-in-apatite diffusion parameters are a function of composition. U zonation is ubiquitous in the studied rocks (Triassic apatites extracted from peraluminous leucosomes), implying that these conclusions may also apply to lower temperature thermochronometers that are based on uranium decay, such as (U-Th)/He dating.

Water Content of Lunar Alkali Fedlspar

NASA Technical Reports Server (NTRS)

Mills, R. D.; Simon, J. I.; Wang, J.; Alexander, C. M. O'D.; Hauri, E. H.

2016-01-01

Detection of indigenous hydrogen in a diversity of lunar materials, including volcanic glass, melt inclusions, apatite, and plagioclase suggests water may have played a role in the chemical differentiation of the Moon. Spectroscopic data from the Moon indicate a positive correlation between water and Th. Modeling of lunar magma ocean crystallization predicts a similar chemical differentiation with the highest levels of water in the K- and Th-rich melt residuum of the magma ocean (i.e. urKREEP). Until now, the only sample-based estimates of water content of KREEP-rich magmas come from measurements of OH, F, and Cl in lunar apatites, which suggest a water concentration of < 1 ppm in urKREEP. Using these data, predict that the bulk water content of the magma ocean would have <10 ppm. In contrast, estimate water contents of 320 ppm for the bulk Moon and 1.4 wt % for urKREEP from plagioclase in ferroan anorthosites. Results and interpretation: NanoSIMS data from granitic clasts from Apollo sample 15405,78 show that alkali feldspar, a common mineral in K-enriched rocks, can have approx. 20 ppm of water, which implies magmatic water contents of approx. 1 wt % in the high-silica magmas. This estimate is 2 to 3 orders of magnitude higher than that estimated from apatite in similar rocks. However, the Cl and F contents of apatite in chemically similar rocks suggest that these melts also had high Cl/F ratios, which leads to spuriously low water estimates from the apatite. We can only estimate the minimum water content of urKREEP (+ bulk Moon) from our alkali feldspar data because of the unknown amount of degassing that led to the formation of the granites. Assuming a reasonable 10 to 100 times enrichment of water from urKREEP into the granites produces an estimate of 100-1000 ppm of water for the urKREEP reservoir. Using the modeling of and the 100-1000 ppm of water in urKREEP suggests a minimum bulk silicate Moon water content between 2 and 20 ppm. However, hydrogen loss was likely very significant in the evolution of the lunar mantle. Conclusions: Lunar granites crystallized between 4.3-3.8 Ga from relatively wet melts that degassed upon crystallization. The formation of these granites likely removed significant amounts of water from some mantle source regions, e.g. later mare basalts predicting derivation from a mantle with <10 ppm water. However, this would have been a heterogeneous pro-cess based on K distribution. Thus some, if not most of the mantle may not have been devolatilized by this process; as seen by water in volcanic glasses and melt inclusions.

Microstructured Electrolyte Membranes to Improve Fuel Cell Performance

NASA Astrophysics Data System (ADS)

Wei, Xue

Fuel cells, with the advantages of high efficiency, low greenhouse gas emission, and long lifetime are a promising technology for both portable power and stationary power sources. The development of efficient electrolyte membranes with high ionic conductivity, good mechanical durability and dense structure at low cost remains a challenge to the commercialization of fuel cells. This thesis focuses on exploring novel composite polymer membranes and ceramic electrolytes with the microstructure engineered to improve performance in direct methanol fuel cells (DMFCs) and solid oxide fuel cells (SOFCs), respectively. Polymer/particle composite membranes hold promise to meet the demands of DMFCs at lower cost. The structure of composite membranes was controlled by aligning proton conducting particles across the membrane thickness under an applied electric field. The field-induced structural changes caused the membranes to display an enhanced water uptake, proton conductivity, and methanol permeability in comparison to membranes prepared without an applied field. Although both methanol permeability and proton conductivity are enhanced by the applied field, the permeability increase is relatively lower than the proton conductivity improvement, which results in enhanced proton/methanol selectivity and improved DMFC performance. Apatite ceramics are a new class of fast ion conductors being studied as alternative SOFC electrolytes in the intermediate temperature range. An electrochemical/hydrothermal deposition method was developed to grow fully dense apatite membranes containing well-developed crystals with c-axis alignment to promote ion conductivity. Hydroxyapatite seed crystals were first deposited onto a metal substrate electrochemically. Subsequent ion substitution during the hydrothermal growth process promoted the formation of dense, fully crystalline films with microstructure optimal for ion transport. The deposition parameters were systematically investigated, such as reactant type, reagent concentration, solution pH, and reaction time. Dense apatite films were formed on palladium substrates that can serve as intermediate temperature fuel cell anodes. The novel apatite membrane structure is promising for fuel cell applications, as well as in improving the biocompatibility of orthopedic implants when coated on stainless steel or titanium substrates.

Trace element studies of silicate-rich inclusions in the Guin (UNGR) and Kodaikanal (IIE) iron meteorites

NASA Astrophysics Data System (ADS)

Kurat, Gero; Zinner, Ernst; Varela, Maria Eugenia

2007-08-01

A devitrified glass inclusion from the Guin (UNGR) iron consists of cryptocrystalline feldspars, pyroxenes, and silica and is rich in SiO2, Al2O3, and Na2O. It contains a rutile grain and is in contact with a large Cl apatite. The latter is very rich in rare earth elements (REEs) (˜80 × CI), which display a flat abundance pattern, except for Eu and Yb, which are underabundant. The devitrified glass is very poor in REEs (<0.1 × CI), except for Eu and Yb, which have positive abundance anomalies. Devitrified glass and Cl apatite are out of chemical equilibrium and their complementary REE patterns indicate a genesis via condensation under reducing conditions. Inclusion 1 in the Kodaikanal (IIE) iron consists of glass only, whereas inclusion 2 consists of clinopyroxene, which is partly overgrown by low-Ca pyroxene, and apatite embedded in devitrified glass. All minerals are euhedral or have skeletal habits indicating crystallization from the liquid precursor of the glass. Pyroxenes and the apatite are rich in trace elements, indicating crystallization from a liquid that had 10-50 × CI abundances of REEs and refractory lithophile elements (RLEs). The co-existing glass is poor in REEs (˜0.1-1 × CI) and, consequently, a liquid of such chemical composition cannot have crystallized the phenocrysts. Glasses have variable chemical compositions but are rich in SiO2, Al2O3, Na2O, and K2O as well as in HFSEs, Be, B, and Rb. The REE abundance patterns are mostly flat, except for the glass-only inclusion, which has heavy rare earth elements (HREEs) > light rare earth elements (LREEs) and deficits in Eu and Yb—an ultrarefractory pattern. The genetic models suggested so far cannot explain what is observed and, consequently, we offer a new model for silicate inclusion formation in IIE and related irons. Nebular processes and a relationship with E meteorites (Guin) or Ca-Al-rich inclusions (CAIs) (Kodaikanal) are indicated. A sequence of condensation (CaS, TiN or refractory pyroxene-rich liquids) and vapor-solid elemental exchange can be identified that took place beginning under reducing and ending at oxidizing conditions (phosphate, rutile formation, alkali and Fe2+ metasomatism, metasomatic loss of REEs from glass).

Patterns of calcium oxalate monohydrate crystallization in complex biological systems

NASA Astrophysics Data System (ADS)

Golovanova, O. A.; Korol'kov, V. V.; Kuimova, M. V.

2017-01-01

The paper presents the features of calcium oxalate crystallization in the presence of additives revealed through experimental modeling. The patterns of phase formation are shown for the Ca2+ - C2O4 2- - H2O and Ca2+ - C2O4 2- - PO4 3- - H2O systems with the components and pH of the saline varying over a wide concentrations range. The effect of additives on crystallization of calcium oxalate monohydrate was investigated. It was found that the ionic strength and magnesium ions are inhibitors, and calcium oxalate and hydroxyapatite crystals are catalysts of calcium oxalate monohydrate crystallization. The basic calcium phosphate (apatite) was found to be most thermodynamically stable, which indicates its special role in kidney stone formation since it is found in virtually all stones.

Type A-B carbonate chlorapatite synthesized at high pressure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fleet, Michael E.; Liu, Xi

2008-09-15

Sodium-bearing type A-B carbonate chlorapatites {l_brace}CCLAP; Ca{sub 10-(y+z)}Na{sub y}{open_square}{sub z}[(PO{sub 4}){sub 6-(y+2z)}(CO{sub 3}){sub y+2z}][Cl{sub 2-=} 2{sub x}(CO{sub 3}){sub x}], with x{approx}y{approx}4z{approx}0.4{r_brace} have been synthesized from carbonate-rich melts at 1350-1000 deg. C and 1.0 GPa, and investigated by single-crystal X-ray structure and FTIR spectroscopy. Typical crystal and compositional data are: a=9.5321(4) A, c=6.8448(3) A, space group P6{sub 3}/m, R=0.027, R{sub w}=0.025, x=0.37(3), y=0.57(2). Crystal-chemical features and FTIR spectra are similar to Na-bearing type A-B carbonate hydroxyapatites (CHAP) and fluorapatites (CFAP) reported recently. The molar amounts of Na and channel (type A) carbonate maintain a near 1:1 ratio in all three compositionmore » series, confirming that the Na cation and A and B carbonate ion substituents exist as a defect cluster within the apatite matrix, to facilitate charge compensation and spatial accommodation. Uptake of carbonate is significantly lower in CCLAP than in CHAP for similar conditions of crystal synthesis. - Graphical abstract: Defect cluster (blue) of A carbonate ion in apatite channel, Na{sup +} cation, and B carbonate ion replacing phosphate group, in carbonate chlorapatite synthesized at high pressure.« less

In-Situ Apatite Laser Ablation U-Th-Sm/He Dating, Methods and Challenges

NASA Astrophysics Data System (ADS)

Pickering, J. E.; Matthews, W.; Guest, B.; Hamilton, B.; Sykes, C.

2015-12-01

In-situ, laser ablation U-Th-Sm/He dating is an emerging technique in thermochronology that has been proven as a means to date zircon and monzonite1-5. In-situ U-Th-Sm/He thermochronology eliminates many of the problems and inconveniences associated with traditional, whole grain methods, including; reducing bias in grain selection based on size, shape and clarity; allowing for the use of broken grains and grains with inclusions; avoiding bad neighbour effects; and eliminating safety hazards associated with dissolution. In-situ apatite laser ablation is challenging due to low concentrations of U and Th and thus a low abundance of radiogenic He. For apatite laser ablation to be effective the ultra-high-vacuum (UHV) line must have very low and consistent background levels of He. To reduce He background, samples are mounted in a UHV stable medium. Our mounting process uses a MicroHePP (Microscope Mounted Heated Platen Press) to press samples into FEP (fluorinated ethylene propylene) bonded to an aluminum backing plate. Samples are ablated using a Resonetics 193 nm excimer laser and liberated He is measured using a quadrupole mass spectrometer on the ASI Alphachron noble gas line; collectively this system is known as the Resochron. The ablated sites are imaged using a Zygo Zescope optical profilometer and ablated pit volume measured using PitVol, a custom MatLab algorithm developed to enable precise and unbiased measurement of the ablated pit geometry. We use the well-characterized Durango apatite to demonstrate the accuracy and precision of the method. He liberated from forty-two pits, having volumes between 1700 and 9000 um3, were measured using the Resochron. The ablated sites were imaged using a Zygo Zescope optical profilometer and ablated pit volume measured using PitVol. U, Th and Sm concentrations were measured by laser ablation and the U-Th-Sm/He age calculated by standard age equation. An age of 33.8±0.31 Ma was determined and compares well with conventional U-Th/He methods, whole grain degassing and dissolution, that produced an age of 32.73±0.47 Ma for chips of the same Durango crystal. Further dating of other well characterized apatite crystals will be used to test the robustness of the method.

Petrology of Martian meteorite Northwest Africa 998

NASA Astrophysics Data System (ADS)

Treiman, Allan H.; Irving, Anthony J.

2008-05-01

Nakhlite Northwest Africa (NWA) 998 is an augite-rich cumulate igneous rock with mineral compositions and oxygen isotopic composition consistent with an origin on Mars. This 456-gram, partially fusion-crusted meteorite consists of (by volume) ˜75% augite (core composition Wo39En39Fs22), ˜9% olivine (Fo35), ˜7% plagioclase (Ab61An35) as anhedra among augite and olivine, ˜3.5% low-calcium pyroxenes (pigeonite and orthopyroxene) replacing or forming overgrowths on olivine and augite, ˜1% titanomagnetite, and other phases including potassium feldspar, apatite, pyrrhotite, chalcopyrite, ilmenite, and fine-grained mesostasis material. Minor secondary alteration materials include "iddingsite" associated with olivine (probably Martian), calcite crack fillings, and iron oxide/hydroxide staining (both probably terrestrial). Shock effects are limited to minor cataclasis and twinning in augite. In comparison to other nakhlites, NWA 998 contains more low-calcium pyroxenes and its plagioclase crystals are blockier. The large size of the intercumulus feldspars and the chemical homogeneity of the olivine imply relatively slow cooling and chemical equilibration in the late- and post-igneous history of this specimen, and mineral thermometers give subsolidus temperatures near 730 °C. Oxidation state was near that of the QFM buffer, from about QFM-2 in earliest crystallization to near QFM in late crystallization, and to about QFM + 1.5 in some magmatic inclusions. The replacement or overgrowth of olivine by pigeonite and orthopyroxene (with or without titanomagnetite), and the marginal replacement of augite by pigeonite, are interpreted to result from late-stage reactions with residual melts (consistent with experimental phase equilibrium relationships). Apatite is concentrated in planar zones separating apatite-free domains, which suggests that residual magma (rich in P and REE) was concentrated in planar (fracture?) zones and possibly migrated through them. Loss of late magma through these zones is consistent with the low bulk REE content of NWA 998 compared with the calculated REE content of its parent magma.

Oriented attachment by enantioselective facet recognition in millimeter-sized gypsum crystals.

PubMed

Viedma, Cristóbal; Cuccia, Louis A; McTaggart, Alicia; Kahr, Bart; Martin, Alexander T; McBride, J Michael; Cintas, Pedro

2016-09-22

Crystal growth by oriented attachment involves the spontaneous self-assembly of adjoining crystals with common crystallographic orientations. Herein, we report the oriented attachment of gypsum crystals on agitation to form stereoselective mesoscale aggregates.

Preliminary observations of the effect of solutal convection on crystal morphology

NASA Technical Reports Server (NTRS)

Broom, M. Beth H.; Witherow, William K.; Snyder, Robert S.; Carter, Daniel C.

1988-01-01

Studies to examine the effect of solutal convection on crystal morphology using sucrose as a model system were initiated. Aspect ratios, defined as the width of the 100-plane-oriented face over the width of the 001-plane-oriented face, were determined for oriented crystals which were grown with either the 001-oriented or the 100-oriented face perpendicular to the convective flow. The dependence of the crystal morphology on orientation is much greater for crystals grown with one face occluded than for crystals grown suspended in solution. Many factors appear to interact in a complex fashion to influence crystal morphology.

Increase of apatite dissolution rate by Scots pine roots associated or not with Burkholderia glathei PML1(12)Rp in open-system flow microcosms

NASA Astrophysics Data System (ADS)

Calvaruso, Christophe; Turpault, Marie-Pierre; Frey-Klett, Pascale; Uroz, Stéphane; Pierret, Marie-Claire; Tosheva, Zornitza; Kies, Antoine

2013-04-01

The release of nutritive elements through apatite dissolution represents the main source of phosphorus, calcium, and several micronutrients (e.g., Zn, Cu) for organisms in non-fertilized forest ecosystems. The aim of this study was to quantify, for the first time, the dissolution rate of apatite grains by tree roots that were or were not associated with a mineral weathering bacterial strain, and by various acids known to be produced by tree roots and soil bacterial strains in open-system flow microcosms. In addition, we explored whether the mobilization of trace elements (including rare earth elements) upon apatite dissolution was affected by the presence of trees and associated microorganisms. The dissolution rate of apatite by Scots pine plants that were or were not inoculated with the strain Burkholderia glathei PML1(12)Rp, and by inorganic (nitric) and organic (citric, oxalic and gluconic) acids at pH 5.5, 4.8, 3.8, 3.5, 3.0, and 2.0 was monitored in two controlled experiments: "plant-bacteria interaction" and "inorganic and organic acids". Analyses of the outlet solutions in the "plant-bacteria interaction" experiment showed that Scots pine roots and B. glathei PML1(12)Rp produced protons and organic acids such as gluconate, oxalate, acetate, and lactate. The weathering budget calculation revealed that Scots pines (with or without PML1(12)Rp) significantly increased (factor > 10) the release of Ca, P, As, Sr, Zn, U, Y, and rare earth elements such as Ce, La, Nd from apatite, compared to control abiotic treatment. Scanning electron microscopy observation confirmed traces of apatite dissolution in contact of roots. Most dissolved elements were taken up by Scots pine roots, i.e., approximately 50% of Ca, 70% of P, 30% of As, 70% of Sr, 90% of Zn, and 100% of U, Y, and rare earth elements. Interestingly, no significant additional effect due to the bacterial strain PML1(12)Rp on apatite dissolution and Scots pine nutrition and growth was observed. The "inorganic and organic acids" experiment demonstrated that the apatite dissolution efficacy of organic acids was higher than for the inorganic acid and varied in function of the acids: oxalic acid > citric acid > gluconic acid > nitric acid for pH ⩽3.5. In addition, apatite dissolution increased with increasing acidity for each acid. Only oxalic acid generated non-stoichiometric release of calcium and phosphorus from apatite in the solution at pH ⩽3.5, due to the precipitation of Ca-oxalate crystals at apatite surfaces. Comparison of the experiments revealed that the apatite dissolution rate by Scots pines supplied with nutritive solution at pH 5.5 reached 2.0 × 10-13 mol cm-2 s-1 and was equivalent to rates with nitric acid at pH 3.2, gluconic acid at pH 3.5, citric acid at pH 3.7, and oxalic acid at pH 3.8. Altogether our results highlight that, through the production of weathering agents, notably protons and organic acids, tree roots and root-associated microorganisms are able to significantly increase the release of macro- and micro-nutrients from apatite, thus maintaining high-nutrient conditions to support their growth.

Atomic substitutions in synthetic apatite; Insights from solid-state NMR spectroscopy

NASA Astrophysics Data System (ADS)

Vaughn, John S.

Apatite, Ca5(PO4)3X (where X = F, Cl, or OH), is a unique mineral group capable of atomic substitutions for cations and anions of varied size and charge. Accommodation of differing substituents requires some kind of structural adaptation, e.g. new atomic positions, vacancies, or coupled substitutions. These structural adaptations often give rise to important physicochemical properties relevant to a range of scientific disciplines. Examples include volatile trapping during apatite crystallization, substitution for large radionuclides for long-term storage of nuclear fission waste, substitution for fluoride to improve acid resistivity in dental enamel composed dominantly of hydroxylapatite, and the development of novel biomaterials with enhanced biocompatibility. Despite the importance and ubiquity of atomic substitutions in apatite materials, many of the mechanisms by which these reactions occur are poorly understood. Presence of substituents at dilute concentration and occupancy of disordered atomic positions hinder detection by bulk characterization methods such as X-ray diffraction (XRD) and infrared (IR) spectroscopy. Solid-state nuclear magnetic resonance (NMR) spectroscopy is an isotope-specific structural characterization technique that does not require ordered atomic arrangements, and is therefore well suited to investigate atomic substitutions and structural adaptations in apatite. In the present work, solid-state NMR is utilized to investigate structural adaptations in three different types of apatite materials; a series of near-binary F, Cl apatite, carbonate-hydroxylapatite compositions prepared under various synthesis conditions, and a heat-treated hydroxylapatite enriched in 17O. The results indicate that hydroxyl groups in low-H, near binary F,Cl apatite facilitate solid-solution between F and Cl via column reversals, which result in average hexagonal symmetry despite very dilute OH concentration ( 2 mol percent). In addition, 19F NMR spectra indicate that fluorine occupies a complex distribution of atomic positions, which give rise to complex 19F peak shapes owing to varied F-Ca distance. 13C NMR analysis of carbonate-hydroxylapatite indicates that AB-type carbonate hydroxylapatite can be prepared without the presence of sodium or heat treatment. Isotopic 17O enrichment of hydroxylapatite and 17O NMR analysis reveals distinct signals corresponding to phosphate and hydroxyl oxygens, and heat treatment under vacuum results in loss of hydroxyl signal due to decomposition to tricalcium phosphate, which was observed by powder X-Ray diffraction (PXRD).

Characterization of helium diffusion behavior from continuous heating experiments: Sample screening and identification of multiple 4He components

NASA Astrophysics Data System (ADS)

McDannell, K. T.; Idleman, B. D.; Zeitler, P. K.

2015-12-01

Old, slowly cooled apatites often yield overdispersed helium ages due to factors such as parent zonation, He implantation, radiation damage, crystal defects, and fluid inclusions. Careful mineral selection and many replicate analyses can mitigate the impact of some of these effects. However, this approach adds unnecessary costs in time and resources when dating well-behaved apatites and is generally ineffective at identifying the root cause of age dispersion and providing suitable age corrections for poorly behaved samples. We assess a new technique utilizing static-gas measurement during continuous heating as a means to rapidly screen apatite samples. In about the time required for a conventional total-gas analysis, this method can discriminate between samples showing the volume-diffusion behavior expected for apatite and those showing anomalous release patterns, inconsistent with their use in thermochronologic applications. This method may also have the potential to quantify and discriminate between the radiogenic and extraneous 4He fractions released by a sample. Continuously heated samples that outgas by volume diffusion during a linear heating schedule should produce a characteristic sigmoidal 4He fractional loss profile, with the exact shape and position of these profiles (in loss vs. heating time space) controlled by sample kinetics, grain size, and heating rate. Secondary factors such as sample zoning and alpha-loss distribution have a relatively minor impact on such profiles. Well-behaved examples such as the Durango standard and other apatites with good age reproducibility show the expected smooth, sigmoidal gas release with complete exhaustion by temperatures predicted for volume diffusion using typical apatite kinetics (e.g., by ~900˚C for linear heating at 20˚C/minute). In contrast, "bad actor" samples that do not replicate well show significant degrees of helium release deferred to higher temperatures. We report on screening results for a range of samples including a suite of slowly cooled Cretaceous apatites from the Hangay Dome in central Mongolia, assessing the degree to which screening using cumulative heating can reliably identify bad-actor grains, and possibly, correct their ages.

Iron and oxygen isotope signatures of the Pea Ridge and Pilot Knob magnetite-apatite deposits, southeast Missouri, USA

USGS Publications Warehouse

Childress, Tristan; Simon, Adam C.; Day, Warren C.; Lundstrom, Craig C.; Bindeman, Ilya N.

2016-01-01

New O and Fe stable isotope ratios are reported for magnetite samples from high-grade massive magnetite of the Mesoproterozoic Pea Ridge and Pilot Knob magnetite-apatite ore deposits and these results are compared with data for other iron oxide-apatite deposits to shed light on the origin of the southeast Missouri deposits. The δ18O values of magnetite from Pea Ridge (n = 12) and Pilot Knob (n = 3) range from 1.0 to 7.0 and 3.3 to 6.7‰, respectively. The δ56Fe values of magnetite from Pea Ridge (n = 10) and Pilot Knob (n = 6) are 0.03 to 0.35 and 0.06 to 0.27‰, respectively. These δ18O and the δ56Fe values suggest that magnetite crystallized from a silicate melt (typical igneous δ56Fe ranges 0.06–0.49‰) and grew in equilibrium with a magmatic-hydrothermal aqueous fluid. We propose that the δ18O and δ56Fe data for the Pea Ridge and Pilot Knob magnetite-apatite deposits are consistent with the flotation model recently proposed by Knipping et al. (2015a), which invokes flotation of a magmatic magnetite-fluid suspension and offers a plausible explanation for the igneous (i.e., up to ~15.9 wt % TiO2 in magnetite) and hydrothermal features of the deposits.

Ultrastructure of selected struvite-containing urinary calculi from dogs.

PubMed

Domingo-Neumann, R A; Ruby, A L; Ling, G V; Schiffman, P S; Johnson, D L

1996-09-01

To elucidate the ultrastructural details of struvite-containing urinary calculi from dogs. 38 specimens were selected from a collection of approximately 13,000 canine urinary calculi: 18 of these were composed entirely of struvite, and 20 consisted of struvite and calcium phosphate (apatite). Qualitative and quantitative analyses of specimens included use of plain and polarized light microscopy, x-ray diffractometry, scanning electron microscopy with backscattered electron imagery, x-ray fluorescence scans, and electron microprobe analysis. 4 textural types were recognized among struvite calculi, and 4 textural types of struvite-apatite calculi were described. Evidences of calculus dissolution were described from 4 calculi studied. The presence of small, well interconnected primary pores in struvite-containing urinary calculi from dogs appears to be a significant factor in determining the possible interaction of calculi with changes in the urine composition. The progress of dissolution from the calculus surface to the calculus interior appears to be largely affected by the primary porosity originally present between crystals forming the calculus framework. Apatite was observed to be more resistant to dissolution than struvite. The prevalence of fine concentric laminations having low porosity, and the common occurrence of apatite among struvite-containing urinary calculi from dogs may be 2 reasons why the efficacy of dietary and medicinal manipulations in dissolving urinary calculi is greater among cats than it is among dogs.

Improving bioactivity of inert bioceramics by a novel Mg-incorporated solution treatment

NASA Astrophysics Data System (ADS)

Dehestani, Mahdi; Zemlyanov, Dmitry; Adolfsson, Erik; Stanciu, Lia A.

2017-12-01

Zirconia/alumina ceramics possess outstanding mechanical properties for dental and orthopedic applications, but due to their poor surface bioactivities they exhibit a weak bone-bonding ability. This work proposes an effective 30-min solution treatment which could successfully induce formation of bone-like apatite on the surface of 3Y-TZP and a ternary composite composed of yttria-stabilized zirconia, ceria-stabilized zirconia, and alumina (35 vol% 3Y-TZP + 35 vol% 12Ce-TZP + 30 vol% Al2O3) after 3 weeks immersion in simulated body fluid (SBF). XRD was used for phase identification in the ceramic materials. The influence of solution treatment on the surface chemistry and its role on apatite formation were investigated via SEM, EDS and XPS. In vitro apatite-forming ability for the solution-treated and untreated samples of the composite and individual substrates of 3Y-TZP, 12Ce-TZP, and Al2O3 was evaluated by immersion in SBF. Apatite crystals were formed only on 3Y-TZP and composite substrates, implying that it is mainly the 3Y-TZP constituent that contributes to the bioactivity of the composite. Further, it was found from the XPS analysis that the zirconia material with higher phase stability (12Ce-TZP) produced less Zrsbnd OH functional groups on its surface after solution treatment which accounts for its weaker bioactivity compared to 3Y-TZP.

Ultrastructural studies of synthetic apatite crystals.

PubMed

Arends, J; Jongebloed, W L

1979-03-01

In this paper a survey is given of some ultrastructural properties of synthetic hydroxyapatite. The preparation method by which single crystals with a length in the range of 0.1-3.0mm and a defined purity and stoïchiometry can be produced is given. Two groups of materials are considered in detail: carbonate-rich (greater than 0.1% CO3) and low-carbonate hydroxyapatites. The experiments on carbonate-rich material, being the most interesting from a biological point of view, show that acids attack at an active site in the hexagonal basal-plane of the crystals. Later on the crystals dissolve in the center of the crystal parallel to the c-axis forming tube-like structures. The active site can be protected from dissolution if the crystals are pretreated by EHDP or MFP. A comparison with lattice defect theory shows that most likely dislocations of the "hollow-core" type are responsible for the preferential dissolution.

Thermodynamic basis for evolution of apatite in calcified tissues (Invited)

NASA Astrophysics Data System (ADS)

Navrotsky, A.; Drouet, C.; Rollin-Martinet, S.; Champion, E.; Grossin, D.

2013-12-01

Bone remodeling and tooth enamel maturation are biological processes which alter the physico-chemical features of biominerals with time. However, although the ubiquity of bone remodeling is clear, why is well crystallized bone mineral systematically replaced by immature nanocrystalline inorganic material? In enamel, a clear evolution is also seen from the first mineral formed during the secretory stage to its mature well crystalline form, which then changes little in the adult tooth. This contribution provides the thermodynamic basis underlying these biological processes. We determined the energetics of biomimetic apatites corresponding to an increasing degree of maturation. Our data point out the progressive evolution of the enthalpy (ΔHf°) and free energy (ΔGf°) of formation toward more negative values upon maturation. Entropy contributions to ΔGf° values are small compared to enthalpy contributions. ΔHf° varies from -12058.9 × 12.2 to -12771.0 × 21.4 kJ/mol for maturation times increasing from 20 min to 3 weeks, approaching the value for stoichiometric hydroxyapatite, -13431.0 × 22.7 kJ/mol. Apatite thermodynamic stability increases as its composition moved toward stoichiometry. These findings imply diminishing aqueous solubility of calcium and phosphate ions as well as decreased surface reactivity. Such thermodynamically-driven maturation is favorable for enamel maturation since this biomineral must resist external aggressions such as contact with acids. In contrast, maintaining a metastable highly reactive and soluble form of apatite is essential to the effective participation of bone as a source of calcium and phosphate for homeostasis. Therefore our data strongly suggest that, far from being trivial, the intrinsic thermodynamic properties of apatite represent a critical driving force for continuous bone remodeling, in contrast to current views favoring a purely biologically driven cycle. These thermodynamic data may prove helpful in other domains relating, for example, to apatite-based biomaterials development or in (geo)microbiology.

Characterization of early dental caries by polarized Raman spectroscopy

NASA Astrophysics Data System (ADS)

Choo-Smith, Lin-P'ing; Ko, Alex C.-T.; Hewko, Mark D.; Dong, Cecilia C.; Cleghorn, Blaine M.; Sowa, Michael G.

2006-02-01

The early approximal caries lesion in enamel is observed clinically as a white spot and is difficult to detect and/or monitor with current methods available to dentists. New methods with high sensitivity and specificity are required to enable improved early dental caries diagnosis. Using unpolarized Raman spectroscopy to examine unsectioned teeth, peak intensity changes in the phosphate (PO 4 3-) vibrations (ν II, ν 3 and ν 4) were observed between spectra of sound and carious enamel. However, there is little change in the ν I vibration with this approach. In contrast, when tooth sections were examined by unpolarized Raman spectroscopy, marked changes in the ν I peak at 959 cm -1 were noted between healthy and carious enamel. These differences suggest that sampling orientation play a role in understanding the spectral changes. Using polarized Raman spectroscopy to examine unsectioned samples, cross polarized measurements from sound enamel exhibited significant reduction of the ν I peak compared with parallel polarized measurements. A similar reduction was observed with carious enamel, however, the reduction was not as prominent. By calculating the depolarization ratio of the area under the ν I peak, sound enamel can be clearly distinguished from demineralized regions. The spectral changes observed are attributed to changes in the structure and/or orientation of the apatite crystals as a result of the acid demineralization process.

Rapid assessment of crystal orientation in semi-crystalline polymer films using rotational zone annealing and impact of orientation on mechanical properties

DOE PAGES

Ye, Changhuai; Wang, Chao; Wang, Jing; ...

2017-08-17

Crystal orientation in semi-crystalline polymers tends to enhance their performance, such as increased yield strength and modulus, along the orientation direction. Zone annealing (ZA) orients the crystal lamellae through a sharp temperature gradient that effectively directs the crystal growth, but the sweep rate (V ZA) of this gradient significantly impacts the extent of crystal orientation. Here in this work, we demonstrate rotational zone annealing (RZA) as an efficient method to elucidate the influence of V ZA on the crystal morphology of thin films in a single experiment using isotactic poly(1-butene), PB-1, as a model semi-crystalline polymer. These RZA results aremore » confirmed using standard, serial linear ZA to tune the structure from an almost unidirectional oriented morphology to weakly oriented spherulites. The overall crystallinity is only modestly changed in comparison to isothermal crystallization (maximum of 55% from ZA vs. 48% for isothermal crystallization). However, the average grain size increases and the spherulites become anisotropic from ZA. Due to these structural changes, the Young's modulus of the oriented films, both parallel and perpendicular to the spherulite orientation direction, is significantly increased by ZA. The modulus does become anisotropic after ZA due to the directionality in the crystal structure, with more than a threefold increase in the modulus parallel to the orientation direction for the highest oriented film in comparison to the modulus from isothermal crystallization. Lastly, RZA enables rapid identification of conditions to maximize orientation of crystals in thin polymer films, which could find utility in determining conditions to improve crystallinity and performance in organic electronics.« less

Rapid assessment of crystal orientation in semi-crystalline polymer films using rotational zone annealing and impact of orientation on mechanical properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ye, Changhuai; Wang, Chao; Wang, Jing

Crystal orientation in semi-crystalline polymers tends to enhance their performance, such as increased yield strength and modulus, along the orientation direction. Zone annealing (ZA) orients the crystal lamellae through a sharp temperature gradient that effectively directs the crystal growth, but the sweep rate (V ZA) of this gradient significantly impacts the extent of crystal orientation. Here in this work, we demonstrate rotational zone annealing (RZA) as an efficient method to elucidate the influence of V ZA on the crystal morphology of thin films in a single experiment using isotactic poly(1-butene), PB-1, as a model semi-crystalline polymer. These RZA results aremore » confirmed using standard, serial linear ZA to tune the structure from an almost unidirectional oriented morphology to weakly oriented spherulites. The overall crystallinity is only modestly changed in comparison to isothermal crystallization (maximum of 55% from ZA vs. 48% for isothermal crystallization). However, the average grain size increases and the spherulites become anisotropic from ZA. Due to these structural changes, the Young's modulus of the oriented films, both parallel and perpendicular to the spherulite orientation direction, is significantly increased by ZA. The modulus does become anisotropic after ZA due to the directionality in the crystal structure, with more than a threefold increase in the modulus parallel to the orientation direction for the highest oriented film in comparison to the modulus from isothermal crystallization. Lastly, RZA enables rapid identification of conditions to maximize orientation of crystals in thin polymer films, which could find utility in determining conditions to improve crystallinity and performance in organic electronics.« less

SM50 Repeat-Polypeptides Self-Assemble into Discrete Matrix Subunits and Promote Appositional Calcium Carbonate Crystal Growth during Sea Urchin Tooth Biomineralization

PubMed Central

Mao, Yelin; Satchell, Paul G.; Luan, Xianghong; Diekwisch, Thomas G.H.

2015-01-01

The two major proteins involved in vertebrate enamel formation and echinoderm sea urchin tooth biomineralization, amelogenin and SM50, are both characterized by elongated polyproline repeat domains in the center of the macromolecule. To determine the role of polyproline repeat polypeptides in basal deuterostome biomineralization, we have mapped the localization of SM50 as it relates to crystal growth, conducted self-assembly studies of SM50 repeat polypeptides, and examined their effect on calcium carbonate and apatite crystal growth. Electron micrographs of the growth zone of Strongylocentrotus purpuratus sea urchin teeth documented a series of successive events from intravesicular mineral nucleation to mineral deposition at the interface between tooth surface and odontoblast syncytium. Using immunohistochemistry, SM50 was detected within the cytoplasm of cells associated with the developing tooth mineral, at the mineral secreting front, and adjacent to initial mineral deposits, but not in muscles and ligaments. Polypeptides derived from the SM50 polyproline alternating hexa- and hepta-peptide repeat region (SM50P6P7) formed highly discrete, donut-shaped self-assembly patterns. In calcium carbonate crystal growth studies, SM50P6P7 repeat peptides triggered the growth of expansive networks of fused calcium carbonate crystals while in apatite growth studies, SM50P6P7 peptides facilitated the growth of needle-shaped and parallel arranged crystals resembling those found in developing vertebrate enamel. In comparison, SM50P6P7 surpassed the PXX24 polypeptide repeat region derived from the vertebrate enamel protein amelogenin in its ability to promote crystal nucleation and appositional crystal growth. Together, these studies establish the SM50P6P7 polyproline repeat region as a potent regulator in the protein-guided appositional crystal growth that occurs during continuous tooth mineralization and eruption. In addition, our studies highlight the role of species-specific polyproline repeat motifs in the formation of discrete self-assembled matrices and the resulting control of mineral growth. PMID:26194158

SM50 repeat-polypeptides self-assemble into discrete matrix subunits and promote appositional calcium carbonate crystal growth during sea urchin tooth biomineralization.

PubMed

Mao, Yelin; Satchell, Paul G; Luan, Xianghong; Diekwisch, Thomas G H

2016-01-01

The two major proteins involved in vertebrate enamel formation and echinoderm sea urchin tooth biomineralization, amelogenin and SM50, are both characterized by elongated polyproline repeat domains in the center of the macromolecule. To determine the role of polyproline repeat polypeptides in basal deuterostome biomineralization, we have mapped the localization of SM50 as it relates to crystal growth, conducted self-assembly studies of SM50 repeat polypeptides, and examined their effect on calcium carbonate and apatite crystal growth. Electron micrographs of the growth zone of Strongylocentrotus purpuratus sea urchin teeth documented a series of successive events from intravesicular mineral nucleation to mineral deposition at the interface between tooth surface and odontoblast syncytium. Using immunohistochemistry, SM50 was detected within the cytoplasm of cells associated with the developing tooth mineral, at the mineral secreting front, and adjacent to initial mineral deposits, but not in muscles and ligaments. Polypeptides derived from the SM50 polyproline alternating hexa- and hepta-peptide repeat region (SM50P6P7) formed highly discrete, donut-shaped self-assembly patterns. In calcium carbonate crystal growth studies, SM50P6P7 repeat peptides triggered the growth of expansive networks of fused calcium carbonate crystals while in apatite growth studies, SM50P6P7 peptides facilitated the growth of needle-shaped and parallel arranged crystals resembling those found in developing vertebrate enamel. In comparison, SM50P6P7 surpassed the PXX24 polypeptide repeat region derived from the vertebrate enamel protein amelogenin in its ability to promote crystal nucleation and appositional crystal growth. Together, these studies establish the SM50P6P7 polyproline repeat region as a potent regulator in the protein-guided appositional crystal growth that occurs during continuous tooth mineralization and eruption. In addition, our studies highlight the role of species-specific polyproline repeat motifs in the formation of discrete self-assembled matrices and the resulting control of mineral growth. Copyright © 2015 Elsevier GmbH. All rights reserved.

Radionuclide Incorporation and Long Term Performance of Apatite Waste Forms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Jianwei; Lian, Jie; Gao, Fei

2016-01-04

This project aims to combines state-of-the-art experimental and characterization techniques with atomistic simulations based on density functional theory (DFT) and molecular dynamics (MD) simulations. With an initial focus on long-lived I-129 and other radionuclides such as Cs, Sr in apatite structure, specific research objectives include the atomic scale understanding of: (1) incorporation behavior of the radionuclides and their effects on the crystal chemistry and phase stability; (2) stability and microstructure evolution of designed waste forms under coupled temperature and radiation environments; (3) incorporation and migration energetics of radionuclides and release behaviors as probed by DFT and molecular dynamics (MD) simulations;more » and (4) chemical durability as measured in dissolution experiments for long term performance evaluation and model validation.« less

Contact metamorphism, partial melting and fluid flow in the granitic footwall of the South Kawishiwi Intrusion, Duluth Complex, USA

NASA Astrophysics Data System (ADS)

Benko, Z.; Mogessie, A.; Molnar, F.; Severson, M.; Hauck, S.; Lechler, P.; Arehart, G.

2012-04-01

The footwall of the South Kawishiwi Intrusion (SKI) a part of the Mesoproterozoic (1.1 Ga) Duluth Complex consists of Archean granite-gneiss, diorite, granodiorite (Giant Range Batholith), thin condensed sequences of Paleoproterozoic shale (Virginia Fm.), as well as banded iron formation (Biwabik Iron Fm). Detailed (re)logging and petrographic analysis of granitic footwall rocks in the NM-57 drillhole from the Dunka Pit area has been performed to understand metamorphic processes, partial melting, deformation and geochemical characteristics of de-volatilization or influx of fluids. In the studied drillhole the footwall consists of foliated metagranite that is intersected by mafic (dioritic) dykes of older age than the SKI. In the proximal contact zones, in the mafic dykes, the orthopyroxene+clinopyroxene+plagioclase+quartz+Fe-Ti-oxide+hornblende±biotite porphyroblasts embedded in a plagioclase+K-feldspar+orthopyroxene+apatite matrix indicate pyroxene-hornfels facies conditions. Migmatitization is revealed by the euhedral crystal faces of plagioclase and pyroxene against anhedral quartz crystals in the in-situ leucosome and by the presence of abundant in-source plagioclase±biotite leucosome veinlets. Amphibole in the melanosome of mafic dykes was formed with breakdown of biotite and implies addition of H2O to the system during partial melting. Towards the deeper zones, the partially melted metatexite-granite can be characterized by K-feldspar+plagioclase+quartz+ortho/clinopyroxene+biotite+Fe-Ti-oxide+apatite mineral assemblage. The felsic veins with either pegmatitic or aplititic textures display sharp contact both to the granite and the mafic veins. They are characterized by K-feldspar+quartz±plagioclase±muscovite mineral assemblage. Sporadic occurrence of muscovite suggest local fluid saturated conditions. Emplacement of gabbroic rocks of the SKI generated intense shear in some zones of the granitic footwall resulting in formation of biotite-rich mylonites with lepidoblastic texture. High modal content of syn-tectonic biotite in these shear zones indicate involvement of large amount of fluids during deformation. Apatite is an omnipresent accessory mineral in all rock types, with up to 1-3% modal proportion. Crystal habit is columnar or rarely needle-like. XCl/XF and XOH/XF ratios of apatite were compared with depth in the drillhole and in relation to the host rock type. Apatite in the metagranite and in the mafic dyke is fluorine-rich (XFgranite≈1,27-1,63; XFmafic dyke≈1,51-1,83) and their XCl/XFgranite≈0,083 to 0,051 and XCl/XFmafic dyke≈0,051 to 0,044 ratios decrease towards the distal parts of the contact. Apatite in biotite-rich mylonite, as well as in the porphyroblasts of mafic dykes, is extremely depleted in chlorine- and hydroxyl-anions (XCl/XFmylonite≈0,02 and XOH/XFmylonite≈0,14), whereas apatite in felsic dykes and in the in-source leucosome are enriched in hydroxyl and chlorine relative to fluorine (XCl/XFfelsic vein≈0,21 and XOH/XFfelsic vein≈0,37). These variations suggest release of chlorine enriched fluids from the partially melted contact zones and movement and enrichments of these fluids in migration channels of partial melts. It has been for a long time accepted that fluids emerging from the metamorphosed Virginia Formation played an essential role in the formation of the Cu-Ni sulphide and PGE mineralization at the bottom of the gabbroic intrusions in the northwestern marginal zones of the Duluth Complex. Our study proves that the granitic footwall was also an important source of fluids and melts. We acknowledge the Austrian Science Found (FWF P23157-N21) to A. Mogessie for the financial support.

Shock and Microstructural Characterization of the α-ω Phase Transition in Titanium Crystals

NASA Astrophysics Data System (ADS)

Morrow, Benjamin M.; Rigg, Paulo A.; Jones, David R.; Addessio, Francis L.; Trujillo, Carl P.; Saavedra, Ramon A.; Martinez, Daniel T.; Cerreta, Ellen K.

2017-12-01

A multicrystal comprised of a small number of large crystals of high-purity titanium and a [0001] oriented high-purity single crystal titanium sample were shock loaded using gas gun plate impact experiments. Tests were performed at stresses above the α {-}ω phase transition stress (for high-purity polycrystalline specimens) to observe the behavior of oriented crystals under similar conditions. Post-mortem characterization of the shocked microstructure was conducted on the single crystal sample to measure textures, and quantify phases and twinning. The apparent activation of plastic and transformation mechanisms was dependent upon crystal orientation. Specifically, the [0001] crystal showed a higher Hugoniot elastic limit than the [10\\bar{1}0] or [3\\bar{1}\\bar{4}4] orientations. The slope of velocity as a function of time was lower in the [0001] orientation than the other orientations during plastic deformation, indicating sluggish transformation kinetics for the α to ω phase transition for the [0001] oriented crystal. Microtexture measurements of a recovered [0001] oriented single crystal revealed the presence of retained ω phase after unloading, with orientations of the constituent phase fractions indicative of the forward α → ω transition, rather than the reverse ω → α transition, suggesting that the material never achieved a state of 100% ω phase.

Advances in surfaces and osseointegration in implantology. Biomimetic surfaces

PubMed Central

Albertini, Matteo; Fernandez-Yague, Marc; Lázaro, Pedro; Herrero-Climent, Mariano; Bullon, Pedro; Gil, Francisco-Javier

2015-01-01

The present work is a revision of the processes occurring in osseointegration of titanium dental implants according to different types of surfaces -namely, polished surfaces, rough surfaces obtained from subtraction methods, as well as the new hydroxyapatite biomimetic surfaces obtained from thermochemical processes. Hydroxyapatite’s high plasma-projection temperatures have proven to prevent the formation of crystalline apatite on the titanium dental implant, but lead to the formation of amorphous calcium phosphate (i.e., with no crystal structure) instead. This layer produce some osseointegration yet the calcium phosphate layer will eventually dissolve and leave a gap between the bone and the dental implant, thus leading to osseointegration failure due to bacterial colonization. A new surface -recently obtained by thermochemical processes- produces, by crystallization, a layer of apatite with the same mineral content as human bone that is chemically bonded to the titanium surface. Osseointegration speed was tested by means of minipigs, showing bone formation after 3 to 4 weeks, with the security that a dental implant can be loaded. This surface can be an excellent candidate for immediate or early loading procedures. Key words:Dental implants, implants surfaces, osseointegration, biomimetics surfaces. PMID:25662555

Reproducibility of apatite fission-track length data and thermal history reconstruction

NASA Astrophysics Data System (ADS)

Ketcham, Richard A.; Donelick, Raymond A.; Balestrieri, Maria Laura; Zattin, Massimiliano

2009-07-01

The ability to derive detailed thermal history information from apatite fission-track analysis is predicated on the reliability of track length measurements. However, insufficient attention has been given to whether and how these measurements should be standardized. In conjunction with a fission-track workshop we conducted an experiment in which 11 volunteers measured ~ 50 track lengths on one or two samples. One mount contained Durango apatite with unannealed induced tracks, and one contained apatite from a crystalline rock containing spontaneous tracks with a broad length distribution caused by partial resetting. Results for both mounts showed scatter indicative of differences in measurement technique among the individual analysts. The effects of this variability on thermal history inversion were tested using the HeFTy computer program to model the spontaneous track measurements. A cooling-only scenario and a reheating scenario more consistent with the sample's geological history were posed. When a uniform initial length value from the literature was used, results among analysts were very inconsistent in both scenarios, although normalizing for track angle by projecting all lengths to a c-axis parallel crystallographic orientation improved some aspects of congruency. When the induced track measurement was used as the basis for thermal history inversion congruency among analysts, and agreement with inversions based on data previously collected, was significantly improved. Further improvement was obtained by using c-axis projection. Differences among inversions that persisted could be traced to differential sampling of long- and short-track populations among analysts. The results of this study, while demonstrating the robustness of apatite fission-track thermal history inversion, nevertheless point to the necessity for a standardized length calibration schema that accounts for analyst variation.

Vacuum-sintered body of a novel apatite for artificial bone

NASA Astrophysics Data System (ADS)

Tamura, Kenichi; Fujita, Tatsushi; Morisaki, Yuriko

2013-12-01

We produced regenerative artificial bone material and bone parts using vacuum-sintered bodies of a novel apatite called "Titanium medical apatite (TMA®)" for biomedical applications. TMA was formed by chemically connecting a Ti oxide molecule with the reactive [Ca10(PO4)6] group of Hydroxyapatite (HAp). The TMA powders were kneaded with distilled water, and solid cylinders of compacted TMA were made by compression molding at 10 MPa using a stainless-steel vessel. The TMA compacts were dried and then sintered in vacuum (about 10-3 Pa) or in air using a resistance heating furnace in the temperature range 1073-1773 K. TMA compacts were sintered at temperatures greater than 1073 K, thus resulting in recrystallization. The TMA compact bodies sintered in the range 1273-1773 K were converted into mixtures composed of three crystalline materials: α-TCP (tricalcium phosphate), β-TCP, and Perovskite-CaTiO3. The Perovskite crystals were stable and hard. In vacuum-sintering, the Perovskite crystals were transformed into fibers (approximately 1 µm in diameter × 8 µm in length), and the fiber distribution was uniform in various directions. We refer to the TMA vacuum-sintered bodies as a "reinforced composite material with Perovskite crystal fibers." However, in atmospheric sintering, the Perovskite crystals were of various sizes and were irregularly distributed as a result of the effect of oxygen. After sintering temperature at 1573 K, the following results were obtained: the obtained TMA vacuum-sintered bodies (1) were white, (2) had a density of approximately 2300 kg/m3 (corresponding to that of a compact bone or a tooth), and had a thermal conductivity of approximately 31.3 W/(m·K) (corresponding to those of metal or ceramic implants). Further, it was possible to cut the TMA bodies into various forms with a cutting machine. An implant made of TMA and inserted into a rabbit jaw bone was covered by new bone tissues after just one month because of the high biocompatibility of the TMA implant. TMA vacuum-sintered bodies are promising biomaterials for use as artificial bone materials to regenerate bone parts and produce bone reinforcement structures that are used for bone junctions in dental and orthopedic surgery.

Zeolites replacing plant fossils in the Denver formation, Lakewood, Colorado.

USGS Publications Warehouse

Modreski, P.J.; Verbeek, E.R.; Grout, M.A.

1984-01-01

Well-developed crystals of heulandite and stilbite, within fossil wood, occur in sedimentary rocks in Lakewood, Jefferson County. The rocks belong to the Denver formation, a locally fossiliferous deposit of fluvial claystone, siltstone, sandstone and conglomerate, containing some volcanic mudflows (andesitic) of late Cretaceous to Palaeocene age. Altered volcanic glass released Na and Ca into the ground-water and subsequently zeolites were crystallized in the open spaces between grains and within fossil plant structures. Minor pyrite, quartz (jasper), calcite and apatite also occur as replacements of fossil wood. Similar zeolite occurrences in other areas are reviewed.-R.S.M.

Control of liquid crystal molecular orientation using ultrasound vibration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Taniguchi, Satoki; Wave Electronics Research Center, Doshisha University, 1-3 Tataramiyakodani, Kyotanabe, Kyoto 610-0321; Koyama, Daisuke

2016-03-07

We propose a technique to control the orientation of nematic liquid crystals using ultrasound and investigate the optical characteristics of the oriented samples. An ultrasonic liquid crystal cell with a thickness of 5–25 μm and two ultrasonic lead zirconate titanate transducers was fabricated. By exciting the ultrasonic transducers, the flexural vibration modes were generated on the cell. An acoustic radiation force to the liquid crystal layer was generated, changing the molecular orientation and thus the light transmission. By modulating the ultrasonic driving frequency and voltage, the spatial distribution of the molecular orientation of the liquid crystals could be controlled. The distributionmore » of the transmitted light intensity depends on the thickness of the liquid crystal layer because the acoustic field in the liquid crystal layer is changed by the orientational film.« less

Functional biomimetic analogs help remineralize apatite-depleted demineralized resin-infiltrated dentin via a bottom-up approach

PubMed Central

Kim, Jongryul; Arola, Dwayne D.; Gu, Lisha; Kim, Young Kyung; Mai, Sui; Liu, Yan; Pashley, David H.; Tay, Franklin R.

2010-01-01

Natural biominerals are formed through metastable amorphous precursor phases via a bottom-up, nanoparticle-mediated mineralization mechanism. Using an acid-etched human dentin model to create a layer of completely-demineralized collagen matrix, a bio-inspired mineralization scheme has been developed based on the use of dual biomimetic analogs. These analogs help to sequester fluidic amorphous calcium phosphate nanoprecursors and function as templates for guiding homogeneous apatite nucleation within the collagen fibrils. By adopting this scheme for remineralizing adhesive resin-bonded, completely-demineralized dentin, we have been able to redeposit intrafibrillar and extrafibrillar apatites in completely-demineralized collagen matrices that are imperfectly infiltrated by resins. This study utilizes a spectrum of completely- and partially-demineralized dentin collagen matrices to further validate the necessity for using a biomimetic analog-containing medium for remineralizing resin-infiltrated partially-demineralized collagen matrices in which remnant seed crystallites are present. In control specimens in which biomimetic analogs are absent from the remineralization medium, remineralization could only be seen in partially-demineralized collagen matrices probably by epitaxial growth via a top-down crystallization approach. Conversely, in the presence of biomimetic analogs in the remineralization medium, intrafibrillar remineralization of completely-demineralized collagen matrices via a bottom-up crystallization mechanism can additionally be identified. The latter is characterized by the transition of intrafibrillar minerals from an inchoate state of continuously-braided microfibrillar electron-dense amorphous strands to discrete nanocrystals, and ultimately into larger crystalline platelets within the collagen fibrils. Biomimetic remineralization via dual biomimetic analogs has the potential to be translated into a functional delivery system for salvaging failing resin-dentin bonds. PMID:20045745

Changes in physicochemical and biological properties of porcine bone derived hydroxyapatite induced by the incorporation of fluoride

NASA Astrophysics Data System (ADS)

Qiao, Wei; Liu, Quan; Li, Zhipeng; Zhang, Hanqing; Chen, Zhuofan

2017-12-01

As the main inorganic component of xenogenic bone graft material, bone-derived biological apatite (BAp) has been widely used in implant dentistry, oral and maxillofacial surgery and orthopedics. However, BAp produced via calcination of animal bones still suffers from some drawbacks, such as insufficient mechanical strength and inadequate degradation rate, which impede its application. Fluoride is known to play important roles in both physiological and pathological processes of human hard tissues for its double effects on bones and teeth. In order to understand the effects of fluoride on the properties of BAp, as well as the mechanism behind them, porcine bone derived hydroxyapatite (PHAp) was prepared via thermal treatment, which was then fluoride incorporated at a series concentrations of sodium fluoride, and noted as 0.25-FPHAp, 0.50-FPHAp, and 0.75-FPHAp respectively. The physicochemical characteristics of the materials, including crystal morphology, crystallinity, functional groups, elemental composition, compressive strength, porosity and solubility, were then determined. The biological properties, such as protein adsorption and cell attachment, were also evaluated. It was found that the spheroid-like crystals of PHAp were changed into rod-like after fluoride substitution, resulting in a fluoride concentration-dependent increase in compressive strength, as well as a decreased porosity and solubility of the apatite. However, even though the addition of fluoride was demonstrated to enhance protein adsorption and cell attachment of the materials, the most favorable results were intriguingly achieved in FPHAp with the least fluoride content. Collectively, low level of fluoride incorporation is proposed promising for the modification of clinically used BAp based bone substitute materials, because of its being able to maintain a good balance between physicochemical and biological properties of the apatite.

Fungal degradation of calcium-, lead- and silicon-bearing minerals.

PubMed

Adeyemi, Ademola O; Gadd, Geoffrey M

2005-06-01

The aim of this study was to examine nutritional influence on the ability of selected filamentous fungi to mediate biogenic weathering of the minerals, apatite, galena and obsidian in order to provide further understanding of the roles of fungi as biogeochemical agents, particularly in relation to the cycling of metals and associated elements found in minerals. The impact of three organic acid producing fungi (Aspergillus niger, Serpula himantioides and Trametes versicolor) on apatite, galena and obsidian was examined in the absence and presence of a carbon and energy source (glucose). Manifestation of fungal weathering included corrosion of mineral surfaces, modification of the mineral substrate through transformation into secondary minerals (i.e. crystal formation) and hyphal penetration of the mineral substrate. Physicochemical interactions of fungal metabolites, e.g. H+ and organic acids, with the minerals are thought to be the primary driving forces responsible. All experimental fungi were capable of mineral surface colonization in the absence and presence of glucose but corrosion of the mineral surface and secondary mineral formation were affected by glucose availability. Only S. himantioides and T. versicolor were able to corrode apatite in the absence of glucose but none of the fungi were capable of doing so with the other minerals. In addition, crystal formation with galena was entirely dependent on the availability of glucose. Penetration of the mineral substrates by fungal hyphae occurred but this did not follow any particular pattern. Although the presence of glucose in the media appeared to influence positively the mineral penetrating abilities of the fungi, the results obtained also showed that some geochemical change(s) might occur under nutrient-limited conditions. It was, however, unclear whether the hyphae actively penetrated the minerals or were growing into pre-existing pores or cracks.

Functional biomimetic analogs help remineralize apatite-depleted demineralized resin-infiltrated dentin via a bottom-up approach.

PubMed

Kim, Jongryul; Arola, Dwayne D; Gu, Lisha; Kim, Young Kyung; Mai, Sui; Liu, Yan; Pashley, David H; Tay, Franklin R

2010-07-01

Natural biominerals are formed through metastable amorphous precursor phases via a bottom-up, nanoparticle-mediated mineralization mechanism. Using an acid-etched human dentin model to create a layer of completely demineralized collagen matrix, a bio-inspired mineralization scheme has been developed based on the use of dual biomimetic analogs. These analogs help to sequester fluidic amorphous calcium phosphate nanoprecursors and function as templates for guiding homogeneous apatite nucleation within the collagen fibrils. By adopting this scheme for remineralizing adhesive resin-bonded, completely demineralized dentin, we have been able to redeposit intrafibrillar and extrafibrillar apatites in completely demineralized collagen matrices that are imperfectly infiltrated by resins. This study utilizes a spectrum of completely and partially demineralized dentin collagen matrices to further validate the necessity for using a biomimetic analog-containing medium for remineralizing resin-infiltrated partially demineralized collagen matrices in which remnant seed crystallites are present. In control specimens in which biomimetic analogs are absent from the remineralization medium, remineralization could only be seen in partially demineralized collagen matrices, probably by epitaxial growth via a top-down crystallization approach. Conversely, in the presence of biomimetic analogs in the remineralization medium, intrafibrillar remineralization of completely demineralized collagen matrices via a bottom-up crystallization mechanism can additionally be identified. The latter is characterized by the transition of intrafibrillar minerals from an inchoate state of continuously braided microfibrillar electron-dense amorphous strands to discrete nanocrystals, and ultimately into larger crystalline platelets within the collagen fibrils. Biomimetic remineralization via dual biomimetic analogs has the potential to be translated into a functional delivery system for salvaging failing resin-dentin bonds. Copyright 2009 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Stable isotope (C, O) and monovalent cation fractionation upon synthesis of carbonate-bearing hydroxyl apatite (CHAP) via calcite transformation

NASA Astrophysics Data System (ADS)

Böttcher, Michael E.; Schmiedinger, Iris; Wacker, Ulrike; Conrad, Anika C.; Grathoff, Georg; Schmidt, Burkhard; Bahlo, Rainer; Gehlken, Peer-L.; Fiebig, Jens

2016-04-01

Carbonate-bearing hydroxyl-apatite (CHAP) is of fundamental and applied interest to the (bio)geochemical, paleontological, medical and material science communities, since it forms the basic mineral phase in human and animal teeth and bones. In addition, it is found in non-biogenic phosphate deposits. The stable isotope and foreign element composition of biogenic CHAP is widely used to estimate the formation conditions. This requires careful experimental calibration under well-defined boundary conditions. Within the DFG project EXCALIBOR, synthesis of carbonate-bearing hydroxyapatite was conducted via the transformation of synthetic calcite powder in aqueous solution as a function of time, pH, and temperature using batch-type experiments. The aqueous solution was analyzed for the carbon isotope composition of dissolved inorganic carbonate (gas irmMS), the oxygen isotope composition of water (LCRDS), and the cationic composition. The solid was characterized by powder X-ray diffraction, micro Raman and FTIR spectroscopy, SEM-EDX, elemental analysis (EA, ICP-OES) and gas irmMS. Temperature was found to significantly impact the transformation rate of calcite to CHAP. Upon complete transformation, CHAP was found to contain up to 5% dwt carbonate, depending on the solution composition (e.g., pH), both incorporated on the A and B type position of the crystal lattice. The oxygen isotope fractionation between water and CHAP decreased with increasing temperature with a tentative slope shallower than those reported in the literature for apatite, calcite or aragonite. In addition, the presence of dissolved NH4+, K+ or Na+ in aqueous solution led to partial incorporation into the CHAP lattice. How these distortions of the crystal lattice may impact stable isotope discrimination is subject of future investigations.

Mineral chemistry of magnetite from magnetite-apatite mineralization and their host rocks: examples from Kiruna, Sweden, and El Laco, Chile

NASA Astrophysics Data System (ADS)

Broughm, Shannon G.; Hanchar, John M.; Tornos, Fernando; Westhues, Anne; Attersley, Samuel

2017-12-01

Interpretation of the mineralizing environment of magnetite-apatite deposits remains controversial with theories that include a hydrothermal or magmatic origin or a combination of those two processes. To address this controversy, we have analyzed the trace element content of magnetite from precisely known geographic locations and geologic environments from the Precambrian magnetite-apatite ore and host rocks in Kiruna, Sweden, and the Pliocene-Holocene El Laco volcano in the Atacama desert of Chile. Magnetite samples from Kiruna have low trace element concentrations with little chemical variation between the ore, host, and related intrusive rocks. Magnetite from andesite at El Laco, and dacite from the nearby Láscar volcano, has high trace element concentrations typical of magmatic magnetite. El Laco ore magnetite have low trace element concentrations and displays growth zoning in incompatible elements (Si, Ca, and Ce), compatible elements (Mg, Al, and Mn), large-ion lithophile element (Sr), and high field strength element (Y, Nb, and Th). The El Laco ore magnetite are similar in composition to magnetite that has been previously interpreted to have crystallized from hydrothermal fluids; however, there is a significant difference in the internal zoning patterns. At El Laco, each zoned element is either enriched or depleted in the same layers, suggesting the magnetite crystallized from a volatile-rich, iron-oxide melt. In general, the compositions of magnetite from these two deposits plot in very wide fields that are not restricted to the proposed fields in published discriminant diagrams. This suggests that the use of these diagrams and genetic models based on them should be used with caution.

Bone-like apatite coating on functionalized poly(etheretherketone) surface via tailored silanization layers technique.

PubMed

Zheng, Yanyan; Xiong, Chengdong; Zhang, Shenglan; Li, Xiaoyu; Zhang, Lifang

2015-10-01

Poly(etheretherketone) (PEEK) is a rigid semi-crystalline polymer with outstanding mechanical properties, bone-like stiffness and suitable biocompatibility that has attracted much interest as a biomaterial for orthopedic and dental implants. However, the bio-inert surface of PEEK limits its biomedical applications when direct osteointegration between the implants and the host tissue is desired. In this work, -PO4H2, -COOH and -OH groups were introduced on the PEEK surface by further chemical treatments of the vinyl-terminated silanization layers formed on the hydroxylation-pretreated PEEK surface. Both the surface-functionalized and pristine specimens were characterized by X-ray photoelectron spectroscopy (XPS), attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy and water contact angle measurements. When placed in 1.5 strength simulated body fluid (SBF) solution, apatite was observed to form uniformly on the functionalized PEEK surface and firmly attach to the substrate. The characterized results demonstrated that the coating was constituted by poorly crystallized bone-like apatite and the effect of surface functional groups on coating formation was also discussed in detail. In addition, in vitro biocompatibility of PEEK, in terms of pre-osteoblast cell (MC3T3-E1) attachment, spreading and proliferation, was remarkably enhanced by the bone-like apatite coating. Thus, this study provides a method to enhance the bioactivity of PEEK and expand its applications in orthopedic and dental implants. Copyright © 2015 Elsevier B.V. All rights reserved.

Effect of orientation on deformation behavior of Fe nanowires: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Sainath, G.; Srinivasan, V. S.; Choudhary, B. K.; Mathew, M. D.; Jayakumar, T.

2014-04-01

Molecular dynamics simulations have been carried out to study the effect of crystal orientation on tensile deformation behaviour of single crystal BCC Fe nanowires at 10 K. Two nanowires with an initial orientation of <100>/{100} and <110>/{111} have been chosen for this study. The simulation results show that the deformation mechanisms varied with crystal orientation. The nanowire with an initial orientation of <100>/{100} deforms predominantly by twinning mechanism, whereas the nanowire oriented in <110>/{111}, deforms by dislocation plasticity. In addition, the single crystal oriented in <110>/{111} shows higher strength and elastic modulus than <100>/{100} oriented nanowire.

Precise and accurate in situ Pb-Pb dating of apatite, monazite, and sphene by laser ablation multiple-collector ICP-MS

NASA Astrophysics Data System (ADS)

Willigers, B. J. A.; Baker, J. A.; Krogstad, E. J.; Peate, D. W.

2002-03-01

To evaluate in situ Pb dating by laser ablation multiple-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS), we analysed apatite, sphene, and monazite from Paleoproterozoic metamorphic rocks from West Greenland. Pb isotope ratios were also determined in the National Institute of Standards and Technology (NIST) 610 glass standard and were corrected for mass fractionation by reference to the measured thallium isotope ratio. The NIST 610 glass was used to monitor Pb isotope mass fractionation in the low Tl/Pb accessory minerals. Replicate analyses of the glass (1 to 2 min) yielded ratios with an external reproducibility comparable to conventional analyses of standard reference material 981 by thermal ionisation mass spectrometry (TIMS). Mineral grains were generally analysed with a 100-μm laser beam, although some monazite crystals were analysed at smaller spot sizes (10 and 25 μm). The common Pb isotope ratios required for age calculations were either measured on coexisting plagioclase by LA-MC-ICP-MS or could be ignored, as individual crystals exhibit sufficient Pb isotopic heterogeneity to perform isochron calculations on replicate analyses of single crystals. Mean mineral ages with the 204Pb ion beam measured in the multiplier were as follows: apatite, 1715 ± 23 m.y.; sphene, 1789 ± 11 m.y.; and monazite, 1783 to 1888 m.y., with relative uncertainties on individual monazite ages of <0.2% but highly reproducible age determinations on single monazite crystals (≪1%). Isochron ages calculated from several mineral analyses without assumption of common Pb also yield precise age determinations. Apatite and monazite Pb ages determined by in situ Pb isotope analysis are identical to those determined by conventional TIMS analysis of bulk mineral separates, and the analytical uncertainties of these short laser analyses with no prior mechanical or chemical separation are comparable to those obtained by TIMS. Detailed examination of the sphene in situ age data does, however, show a small discrepancy between the LA-MC-ICP-MS and TIMS ages (˜1% younger). High-resolution mass scans of the sphene during ablation clearly showed several small and as yet unidentified isobaric interferences that overlap with the 207Pb peak at the resolution conditions for measurement of isotope ratios. These might account for the age discrepancy between the LA-MC-ICP-MS and TIMS sphene ages. LA-MC-ICP-MS is a rapid, accurate, and precise method for in situ determination of Pb isotope ratios that can be used for geochronological studies in a manner similar to an ion microprobe, albeit currently at a somewhat degraded spatial resolution. Further modifications to the LA-MC-ICP-MS system, such as improved sensitivity, ion transmission, and LA methodology, may lead to this type of instrument becoming the method of choice for many types of in situ Pb isotope dating.

Multi-scale simulations of apatite-collagen composites: from molecules to materials

NASA Astrophysics Data System (ADS)

Zahn, Dirk

2017-03-01

We review scale-bridging simulation studies for the exploration of atomicto-meso scale processes that account for the unique structure and mechanic properties of apatite-protein composites. As the atomic structure and composition of such complex biocomposites only partially is known, the first part (i) of our modelling studies is dedicated to realistic crystal nucleation scenarios of inorganic-organic composites. Starting from the association of single ions, recent insights range from the mechanisms of motif formation, ripening reactions and the self-organization of nanocrystals, including their interplay with growth-controlling molecular moieties. On this basis, (ii) reliable building rules for unprejudiced scale-up models can be derived to model bulk materials. This is exemplified for (enamel-like) apatite-protein composites, encompassing up to 106 atom models to provide a realistic account of the 10 nm length scale, whilst model coarsening is used to reach μm length scales. On this basis, a series of deformation and fracture simulation studies were performed and helped to rationalize biocomposite hardness, plasticity, toughness, self-healing and fracture mechanisms. Complementing experimental work, these modelling studies provide particularly detailed insights into the relation of hierarchical composite structure and favorable mechanical properties.

Mineral ecophysiological evidence for microbial activity in banded iron formation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Dr. Yi-Liang; Konhauser, Dr, Kurt; Cole, David R

2011-01-01

The phosphorus composition of banded-iron formations (BIFs) has been used as a proxy for Precambrian seawater composition and the paleoeredox state of Earth's surface environment. However, it is unclear whether the phosphorus in BIFs originally entered the sediment as a sorbed component of the iron oxyhydroxide particles, or whether it was incorporated into the biomass of marine phytoplankton. We conducted high-resolution mineral analyses and report here the first detection of an Fe(III) acetate salt, as well as nanocrystals of apatite in association with magnetite, in the 2.48 Ga Dales Gorge Member of the Brockman Iron Formation (a BIF), Hamersley, Westernmore » Australia. The clusters of apatite are similar in size and morphology to biogenic apatite crystals resulting from biomass decay in Phanerozoic marine sediments, while the formation of an Fe(III) acetate salt and magnetite not only implies the original presence of biomass in the BIF sediments, but also that organic carbon likely served as an electron donor during bacterial Fe(III) reduction. This study is important because it suggests that phytoplankton may have played a key role in the transfer of phosphorus (and other trace elements) from the photic zone to the seafloor.« less

The influence of artificial radiation damage and thermal annealing on helium diffusion kinetics in apatite

NASA Astrophysics Data System (ADS)

Shuster, David L.; Farley, Kenneth A.

2009-01-01

Recent work [Shuster D. L., Flowers R. M. and Farley K. A. (2006) The influence of natural radiation damage on helium diffusion kinetics in apatite. Earth Planet. Sci. Lett.249(3-4), 148-161] revealing a correlation between radiogenic 4He concentration and He diffusivity in natural apatites suggests that helium migration is retarded by radiation-induced damage to the crystal structure. If so, the He diffusion kinetics of an apatite is an evolving function of time and the effective uranium concentration in a cooling sample, a fact which must be considered when interpreting apatite (U-Th)/He ages. Here we report the results of experiments designed to investigate and quantify this phenomenon by determining He diffusivities in apatites after systematically adding or removing radiation damage. Radiation damage was added to a suite of synthetic and natural apatites by exposure to between 1 and 100 h of neutron irradiation in a nuclear reactor. The samples were then irradiated with a 220 MeV proton beam and the resulting spallogenic 3He used as a diffusant in step-heating diffusion experiments. In every sample, irradiation increased the activation energy ( E a) and the frequency factor ( D o/ a2) of diffusion and yielded a higher He closure temperature ( T c) than the starting material. For example, 100 h in the reactor caused the He closure temperature to increase by as much as 36 °C. For a given neutron fluence the magnitude of increase in closure temperature scales negatively with the initial closure temperature. This is consistent with a logarithmic response in which the neutron damage is additive to the initial damage present. In detail, the irradiations introduce correlated increases in E a and ln( D o/a 2) that lie on the same array as found in natural apatites. This strongly suggests that neutron-induced damage mimics the damage produced by U and Th decay in natural apatites. To investigate the potential consequences of annealing of radiation damage, samples of Durango apatite were heated in vacuum to temperatures up to 550 °C for between 1 and 350 h. After this treatment the samples were step-heated using the remaining natural 4He as the diffusant. At temperatures above 290 °C a systematic change in T c was observed, with values becoming lower with increasing temperature and time. For example, reduction of T c from the starting value of 71 to ˜52 °C occurred in 1 h at 375 °C or 10 h at 330 °C. The observed variations in T c are strongly correlated with the fission track length reduction predicted from the initial holding time and temperature. Furthermore, like the neutron irradiated apatites, these samples plot on the same E a - ln( D o/ a2) array as natural samples, suggesting that damage annealing is simply undoing the consequences of damage accumulation in terms of He diffusivity. Taken together these data provide unequivocal evidence that at these levels, radiation damage acts to retard He diffusion in apatite, and that thermal annealing reverses the process. The data provide support for the previously described radiation damage trapping kinetic model of Shuster et al. (2006) and can be used to define a model which fully accommodates damage production and annealing.

Elastic response of (001)-oriented PWA 1480 single crystal - The influence of secondary orientation

NASA Technical Reports Server (NTRS)

Kalluri, Sreeramesh; Abdul-Azis, Ali; Mcgaw, Michael

1991-01-01

The influence of secondary orientation on the elastic response of a zone axis (001)-oriented nickel-base single-crystal superalloy, PWA 1480, was investigated under mechanical loading conditions by applying finite element techniques. Elastic stress analyses were performed with a commercially available finite element code. Secondary orientation of the single-crystal superalloy was offset with respect to the global coordinate system in increments from 0 to 90 deg and stresses developed within the single crystal were determined for each loading condition. The results indicated that the stresses were strongly influenced by the angular offset between the secondary crystal orientation and the global coordinate system. The degree of influence was found to vary with the type of loading condition (mechanical, thermal, or combined) imposed on the single-crystal superalloy.

Magnetic Control of MOF Crystal Orientation and Alignment.

PubMed

Cheng, Fei; Marshall, Ellis S; Young, Adam J; Robinson, Peter J; Bouillard, Jean-Sebastien G; Adawi, Ali M; Vermeulen, Nicolaas A; Farha, Omar K; Reithofer, Michael R; Chin, Jia Min

2017-11-07

Most metal-organic frameworks (MOFs) possess anisotropic properties, the full exploitation of which necessitates a general strategy for the controllable orientation of such MOF crystals. Current methods largely rely upon layer-by-layer MOF epitaxy or tuning of MOF crystal growth on appropriate substrates, yielding MOFs with fixed crystal orientations. Here, the dynamic magnetic alignment of different MOF crystals (NH 2 -MIL-53(Al) and NU-1000) is shown. The MOFs were magnetized by electrostatic adsorption of iron oxide nanoparticles, dispersed in curable polymer resins (Formlabs 1+ clear resin/ Sylgard 184), magnetically oriented, and fixed by resin curing. The importance of crystal orientation on MOF functionality was demonstrated whereby magnetically aligned NU-1000/Sylgard 184 composite was excited with linearly polarized 405 nm light, affording an anisotropic fluorescence response dependent on the polarization angle of the excitation beam relative to NU-1000 crystal orientation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rare earth element carriers in the Shergotty meteorite and implications for its chronology

NASA Technical Reports Server (NTRS)

Lundberg, Laura L.; Crozaz, Ghislaine; Zinner, Ernst; Mckay, Gordon

1988-01-01

This paper reports on the results of ion-probe measurements of REE concentrations in individual grains of the Shergotty meteorite. The phases analyzed included whitlockite, apatite, baddeleyite, augite, pigeonite, maskelynite, and K-rich glass; the whitlockite and apatite phases were also analyzed for U. Results indicate that whitlockite contains the bulk of the REE in Shergotty, with no evidence for distinct light-REE patterns in texturally different whitlockites. The results on the evolution of the REE abundances in the Shergotty late-stage interstitial melt, inferred from the analysis of whitlockite, are consistent with closed system crystallization. No metasomatic alteration is required to explain the REE data. It is concluded that there is no compelling reason to attribute chronological significance to the Sm-Nd array, as was done by Jagoutz and Waenke (1986).

Alignment of crystal orientations of the multi-domain photonic crystals in Parides sesostris wing scales

PubMed Central

Yoshioka, S.; Fujita, H.; Kinoshita, S.; Matsuhana, B.

2014-01-01

It is known that the wing scales of the emerald-patched cattleheart butterfly, Parides sesostris, contain gyroid-type photonic crystals, which produce a green structural colour. However, the photonic crystal is not a single crystal that spreads over the entire scale, but it is separated into many small domains with different crystal orientations. As a photonic crystal generally has band gaps at different frequencies depending on the direction of light propagation, it seems mysterious that the scale is observed to be uniformly green under an optical microscope despite the multi-domain structure. In this study, we have carefully investigated the structure of the wing scale and discovered that the crystal orientations of different domains are not perfectly random, but there is a preferred crystal orientation that is aligned along the surface normal of the scale. This finding suggests that there is an additional factor during the developmental process of the microstructure that regulates the crystal orientation. PMID:24352678

Ultrastructural properties of laser-irradiated and heat-treated dentin.

PubMed

Rohanizadeh, R; LeGeros, R Z; Fan, D; Jean, A; Daculsi, G

1999-12-01

Previous studies using scanning electron microscopy and infrared absorption spectroscopy reported that laser irradiation causes compositional changes in enamel. The purpose of this study was to evaluate the ultrastructural and compositional changes in dentin caused by irradiation with a short-pulse laser (Q-switched Nd:YAG). The irradiated and non-irradiated areas of the lased dentin samples were investigated by scanning (SEM) and transmission electron microscopy (TEM), micro-micro electron diffraction, and electron microprobe analysis of dispersive energy (EDX). Heat-treated dentin was similarly investigated. This study demonstrated that laser irradiation resulted in the recrystallization of dentin apatite and in the formation of additional calcium phosphate phases consisting of magnesium-substituted beta-tricalcium phosphate, beta-TCMP, beta-(Ca,Mg)3(PO4)2, and tetracalcium phosphate, TetCP, Ca4(PO4)O. TEM analyses of the modified and unmodified zones of the irradiated areas showed two types of crystal populations: much larger crystals from the modified zone and crystals with size and morphology similar to those of dentin apatite in the unmodified zone. The morphology of crystals in the modified zones in the irradiated dentin resembled those of dentin sintered at 800 or 950 degrees C. In the irradiated areas (modified and unmodified zones), the Ca/P ratio was lower compared with that in the non-irradiated dentin. The Mg/Ca ratio in the modified zones was higher than that in the unmodified zones and in the non-irradiated dentin. In sintered dentin, the Mg/Ca ratio increased as a function of sintering temperature. The ultrastructural and compositional changes observed in laser-irradiated dentin may be attributed to high temperature and high pressure induced by microplasma during laser irradiation. These changes may alter the solubility of the irradiated dentin, making it less susceptible to acid dissolution or to the caries process.

Peculiar Feldspar And Quartz Inclusions Within Zircons From Anorthosites, North Eastern Desert, Egypt

NASA Astrophysics Data System (ADS)

Eliwa, H. A.; Dawoud, M. I.; Khalaf, I. M.; Negendank, J. F.; Itaya, T.

2004-12-01

Zircons from three anorthosite outcrops along Wadi Dib area, north Eastern Desert of Egypt contain abundant and conspicuous inclusions of quartz, feldspar, amphibole and apatite. These anorthosites, as (50-100m thick) layers, represent the top of mafic-ultramafic intrusions exhibiting rhythmic layering visible by reputation of melanocratic and leucocratic layers. Field and microscopic studies exhibit that these anorthosites were affected by the action of residual magmatic solutions associated with the late stage crystallization of the younger granites, which modified their mineralogical composition. They are composed totally of plagioclase with subordinate amount of clinoenstatite, augite, amphibole, biotite, K-feldspar, and quartz. Accessories are magnetite, ilmenite, apatite and zircon. The abundance and the mode of occurrence of K-feldspar, quartz, and biotite with apatite and zircon among the megacrysts suggest their formation is ascribed to the interaction with the residual solutions. The microprobe data exhibit difference between feldspar and amphiboles contained herein zircons and those as anorthosite mineral constituents. The genetic relationship between zircons and their inclusions suggests later growth of zircons than inclusions and most probably at the final stage of rock modification. Zircons are magmatic and found in the interstitial feldspar and quartz among plagioclase megacrysts in aggregates or as individual grains. The microscopic and SEM images investigation exhibit that most zircons are subhedral to euhedral equant and prismatic crystals. Most zircons have same range of crystal morphologies and internal growth structures with predominance of prism /{100/} and pyramid /{101/} and occasionally prism /{110/} and pyramid /{111/}. No evidences for poly-faceted grains, inherited cores or later overgrowths were detected. CL images distinguished zircons with visible core-rim structures and others with regular and continuous growth zones contained herein various inclusions. The dark CL cores in the core-rim structured zircons are higher in U, Y and sometimes Hf relative to the CL bright rims. Microprobe data and x-ray chemical mapping of various zoned zircons suggest that U and Y with sometimes Hf have a negative correlation to the CL brightness, while Th doesn't exhibit any significant correlation.

Comparative study on inorganic composition and crystallographic properties of cortical and cancellous bone.

PubMed

Wang, Xiao-Yan; Zuo, Yi; Huang, Di; Hou, Xian-Deng; Li, Yu-Bao

2010-12-01

To comparatively investigate the inorganic composition and crystallographic properties of cortical and cancellous bone via thermal treatment under 700 °C. Thermogravimetric measurement, infrared spectrometer, X-ray diffraction, chemical analysis and X-ray photo-electron spectrometer were used to test the physical and chemical properties of cortical and cancellous bone at room temperature 250 °C, 450 °C, and 650 °C, respectively. The process of heat treatment induced an extension in the a-lattice parameter and changes of the c-lattice parameter, and an increase in the crystallinity reflecting lattice rearrangement after release of lattice carbonate and possible lattice water. The mineral content in cortical and cancellous bone was 73.2wt% and 71.5wt%, respectively. For cortical bone, the weight loss was 6.7% at the temperature from 60 °C to 250 °C, 17.4% from 250 °C to 450 °C, and 2.7% from 450 °C to 700 °C. While the weight loss for the cancellous bone was 5.8%, 19.9%, and 2.8 % at each temperature range, the Ca/P ratio of cortical bone was 1.69 which is higher than the 1.67 of stoichiometric HA due to the B-type CO₃²⁻ substitution in apatite lattice. The Ca/P ratio of cancellous bone was lower than 1.67, suggesting the presence of more calcium deficient apatite. The collagen fibers of cortical bone were arrayed more orderly than those of cancellous bone, while their mineralized fibers ollkded similar. The minerals in both cortical and cancellous bone are composed of poorly crystallized nano-size apatite crystals with lattice carbonate and possible lattice water. The process of heat treatment induces a change of the lattice parameter, resulting in lattice rearrangement after the release of lattice carbonate and lattice water and causing an increase in crystal size and crystallinity. This finding is helpful for future biomaterial design, preparation and application. Copyright © 2010 The Editorial Board of Biomedical and Environmental Sciences. Published by Elsevier B.V. All rights reserved.

Deformation Mechanism and Recrystallization Relationships in Galfenol Single Crystals: On the Origin of Goss and Cube Orientations

NASA Astrophysics Data System (ADS)

Na, Suok-Min; Smith, Malcolm; Flatau, Alison B.

2018-06-01

In this work, deformation mechanism related to recrystallization behavior in single-crystal disks of Galfenol (Fe-Ga alloy) was investigated to gain insights into the influence of crystal orientations on structural changes and selective grain growth that take place during secondary recrystallization. We started with the three kinds of single-crystal samples with (011)[100], (001)[100], and (001)[110] orientations, which were rolled and annealed to promote the formation of different grain structures and texture evolutions. The initial Goss-oriented (011)[100] crystal mostly rotated into {111}<112> orientations with twofold symmetry and shear band structures by twinning resulted in the exposure of rolled surface along {001}<110> orientation during rolling. In contrast, the Cube-oriented (001)[100] single crystal had no change in texture during rolling with the thickness reduction up to 50 pct. The {123}<111> slip systems were preferentially activated in these single crystals during deformation as well as {112}<111> slip systems that are known to play a role in primary slip of body-centered cubic (BCC) materials such as α-iron and Fe-Si alloys. After annealing, the deformed Cube-oriented single crystal had a small fraction (<10 pct) of recrystallized Goss-oriented grains. The weak Goss component remained in the shear bands of the 50 pct rolled Goss-oriented single crystal, and it appeared to be associated with coalescence of subgrains inside shear band structures during primary recrystallization. Rolling of the (001)[110] single crystal led to the formation of a tilted (001)[100] component close to the <120> orientation, associated with {123}<111> slip systems as well. This was expected to provide potential sites of nucleation for secondary recrystallization; however, no Goss- and Cube-oriented components actually developed in this sample during secondary recrystallization. Those results illustrated how the recrystallization behavior can be influenced by deformed structure and the slip systems.

Elastic response of zone axis (001)-oriented PWA 1480 single crystal: The influence of secondary orientation

NASA Technical Reports Server (NTRS)

Kalluri, Sreeramesh; Abdul-Aziz, Ali; Mcgaw, Michael A.

1991-01-01

The influence of secondary orientation on the elastic response of a zone axis (001)-oriented nickel-base single-crystal superalloy, PWA 1480, was investigated under mechanical loading conditions by applying finite element techniques. Elastic stress analyses were performed with a commercially available finite element code. Secondary orientation of the single-crystal superalloy was offset with respect to the global coordinate system in increments from 0 to 90 deg and stresses developed within the single crystal were determined for each loading condition. The results indicated that the stresses were strongly influenced by the angular offset between the secondary crystal orientation and the global coordinate system. The degree of influence was found to vary with the type of loading condition (mechanical, thermal, or combined) imposed on the single-crystal superalloy.

A taxonomy of apatite frameworks for the crystal chemical design of fuel cell electrolytes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pramana, Stevin S.; Klooster, Wim T.; Institute of Materials Research and Engineering, 3 Research Link, Singapore 117602

2008-08-15

Apatite framework taxonomy succinctly rationalises the crystallographic modifications of this structural family as a function of chemical composition. Taking the neutral apatite [La{sub 8}Sr{sub 2}][(GeO{sub 4}){sub 6}]O{sub 2} as a prototype electrolyte, this classification scheme correctly predicted that 'excess' oxygen in La{sub 9}SrGe{sub 6}O{sub 26.5} is tenanted in the framework as [La{sub 9}Sr][(GeO{sub 4}){sub 5.5}(GeO{sub 5}){sub 0.5}]O{sub 2}, rather than the presumptive tunnel location of [La{sub 9}Sr][(GeO{sub 4}){sub 6}]O{sub 2.5}. The implication of this approach is that in addition to the three known apatite genera-A{sub 10}(BO{sub 3}){sub 6}X{sub 2}, A{sub 10}(BO{sub 4}){sub 6}X{sub 2}, A{sub 10}(BO{sub 5}){sub 6}X{sub 2}-hybrid electrolytesmore » of the types A{sub 10}(BO{sub 3}/BO{sub 4}/BO{sub 5}){sub 6}X{sub 2} can be designed, with potentially superior low-temperature ion conduction, mediated by the introduction of oxygen to the framework reservoir. - Graphical abstract: Apatite framework taxonomy succinctly rationalises the crystallographic modifications of this structural family as a function of chemical composition. Neutron diffraction identified that the excess oxygen in La{sub 9}SrGe{sub 6}O{sub 26.5} is tenanted in the framework as [La{sub 9}Sr][(GeO{sub 4}){sub 5.5}(GeO{sub 5}){sub 0.5}]O{sub 2}. The implication of this approach is that in addition to the three known apatite genera-A{sub 10}(BO{sub 3}){sub 6}X{sub 2}, A{sub 10}(BO{sub 4}){sub 6}X{sub 2}, A{sub 10}(BO{sub 5}){sub 6}X{sub 2}-hybrid electrolytes of the types A{sub 10}(BO{sub 3}/BO{sub 4}/BO{sub 5}){sub 6}X{sub 2} can be designed.« less

Back contact to film silicon on metal for photovoltaic cells

DOEpatents

Branz, Howard M.; Teplin, Charles; Stradins, Pauls

2013-06-18

A crystal oriented metal back contact for solar cells is disclosed herein. In one embodiment, a photovoltaic device and methods for making the photovoltaic device are disclosed. The photovoltaic device includes a metal substrate with a crystalline orientation and a heteroepitaxial crystal silicon layer having the same crystal orientation of the metal substrate. A heteroepitaxial buffer layer having the crystal orientation of the metal substrate is positioned between the substrate and the crystal silicon layer to reduce diffusion of metal from the metal foil into the crystal silicon layer and provide chemical compatibility with the heteroepitaxial crystal silicon layer. Additionally, the buffer layer includes one or more electrically conductive pathways to electrically couple the crystal silicon layer and the metal substrate.

Phage display for the discovery of hydroxyapatite-associated peptides.

PubMed

Jin, Hyo-Eon; Chung, Woo-Jae; Lee, Seung-Wuk

2013-01-01

In nature, proteins play a critical role in the biomineralization process. Understanding how different peptide or protein sequences selectively interact with the target crystal is of great importance. Identifying such protein structures is one of the critical steps in verifying the molecular mechanisms of biomineralization. One of the promising ways to obtain such information for a particular crystal surface is to screen combinatorial peptide libraries in a high-throughput manner. Among the many combinatorial library screening procedures, phage display is a powerful method to isolate such proteins and peptides. In this chapter, we will describe our established methods to perform phage display with inorganic crystal surfaces. Specifically, we will use hydroxyapatite as a model system for discovery of apatite-associated proteins in bone or tooth biomineralization studies. This model approach can be generalized to other desired crystal surfaces using the same experimental design principles with a little modification of the procedures. © 2013 Elsevier Inc. All rights reserved.

Secondary orientation effects in a single crystal superalloy under mechanical and thermal loads

NASA Technical Reports Server (NTRS)

Kalluri, Sreeramesh; Abdul-Aziz, Ali; Mcgaw, Michael A.

1991-01-01

The nickel-base single crystal superalloy PWA 1480 is a candidate blading material for the advanced turbopump development program of the SSME. In order to improve thermal fatigue resistance of the turbine blades, the single crystal superalloy PWA 1480 is grown along the low modulus zone axes (001) crystal orientation by a directional solidification process. Since cubic single crystal materials such as PWA 1480 exhibit anisotropic elastic behavior, the stresses developed within the single crystal superalloy due to mechanical and thermal loads are likely to be affected by the exact orientation of the secondary crystallographic direction with respect to the geometry of the turbine blade. The effects of secondary crystal orientation on the elastic response of single crystal PWA 1480 superalloy were investigated.

Snow Crystal Orientation Effects on the Scattering of Passive Microwave Radiation

NASA Technical Reports Server (NTRS)

Foster, J. L.; Barton, J. S.; Chang, A. T. C.; Hall, D. K.

1999-01-01

For this study, consideration is given to the role crystal orientation plays in scattering and absorbing microwave radiation. A discrete dipole scattering model is used to measure the passive microwave radiation, at two polarizations (horizontal and vertical), scattered by snow crystals oriented in random and non random positions, having various sizes (ranging between 1 micrometers to 10,000 micrometers in radius), and shapes (including spheroids, cylinders, hexagons). The model results demonstrate that for the crystal sizes typically found in a snowpack, crystal orientation is insignificant compared to crystal size in terms of scattering microwave energy in the 8,100 gm (37 GHz) region of the spectrum. Therefore, the assumption used in radiative transfer approaches, where snow crystals are modeled as randomly oriented spheres, is adequate to account for the transfer of microwave energy emanating from the ground and passing through a snowpack.

Interdiffusion behavior between NiAlHf coating and Ni-based single crystal superalloy with different crystal orientations

NASA Astrophysics Data System (ADS)

Wang, Ruili; Gong, Xueyuan; Peng, Hui; Ma, Yue; Guo, Hongbo

2015-01-01

NiAlHf coatings were deposited onto Ni-based single crystal (SC) superalloy with different crystal orientations by electron beam physical vapor deposition (EB-PVD). The effects of the crystal orientations of the superalloy substrate on inter-diffusion behavior between the substrate and the NiAlHf coating were investigated. Substrate diffusion zone (SDZ) containing needle-like μ phases and interdiffusion zone (IDZ) mainly consisting of the ellipsoidal and rod-like μ phases were formed in the SC alloy after heat-treatment 10 h at 1100 °C. The thickness of secondary reaction zone (SRZ) formed in the SC alloy with (0 1 1) crystal orientation is about 14 μm after 50 h heat-treatment at 1100 °C, which is relatively thicker than that in the SC alloy with (0 0 1) crystal orientation, whereas the IDZ revealed similar thickness.

Spatial Instability of the Linearly Polarized Plane Wave in a Cubic Crystal

NASA Astrophysics Data System (ADS)

Kuz'mina, M. S.; Khazanov, E. A.

2016-12-01

We study theoretically the development of a small-scale spatial instability of a plane wave in a cubic crystal with [111], [001] and [101] orientations. It is shown that in the [111] oriented crystals the instability develops at lower intensities than in the [001] and [101] oriented crystals. In the latter two crystals, the instability can significantly be suppressed by choosing the optimal radiation polarization. It is found that in the case of a small B integral, the method of temporal contrast enhancement of laser pulses by generating an orthogonal polarization achieves the largest efficiency with the [101] orientation, while the [001] orientation is more preferable for B > 3.

Elaboration, Rietveld refinements and vibrational spectroscopic study of Na₁-xKxCaPb₃(PO₄)₃ lacunar apatites (0 ⩽ x ⩽ 1).

PubMed

Lahrich, S; Elmhammedi, M A; Manoun, B; Tamraoui, Y; Mirinioui, F; Azrour, M; Lazor, P

2015-06-15

Synthesis of apatites, Na1-xKxCaPb3(PO4)3 0 ⩽ x ⩽ 1, with anion vacancy were carried out using solid state reactions. The solid solution of apatite-type structure crystallize in the hexagonal system, space group P63/m (No. 176). Rietveld refinements showed that around 90% of Pb(2+) cations are located in the (6h) sites, the left amount of Pb(2+) cations are located in the (4f) sites; 27-31% of Ca(2+) cations are located in the (6h) sites, the left amount of Ca(2+) cations are located in the (4f) sites. The ninefold coordination sites (4f) are also occupied by the K(+) and Na(+) monovalent ions. The structure can be described as built up from [PO4](3-) tetrahedra and Pb(2+)/Ca(2+) of sixfold coordination cavities (6h positions), which delimit void hexagonal tunnels running along [001]. These tunnels are connected by cations of mixed sites (4f) which are half occupied by Pb(2+)/Ca(2+) and half by Na(+)/K(+) mixed cations. The assignment of the observed frequencies in the Raman and infrared spectra is discussed on the basis of a unit cell group analysis and by comparison with other apatites. Vibrational spectra of all the compositions are similar and show some linear shifts of the frequencies as a function of the composition toward lower values due the substitutions of Na(+) by K(+) with a larger radius. Copyright © 2015 Elsevier B.V. All rights reserved.

Stability and cellular responses to fluorapatite-collagen composites.

PubMed

Yoon, Byung-Ho; Kim, Hae-Won; Lee, Su-Hee; Bae, Chang-Jun; Koh, Young-Hag; Kong, Young-Min; Kim, Hyoun-Ee

2005-06-01

Fluorapatite (FA)-collagen composites were synthesized via a biomimetic coprecipitation method in order to improve the structural stability and cellular responses. Different amounts of ammonium fluoride (NH4F), acting as a fluorine source for FA, were added to the precipitation of the composites. The precipitated composites were freeze-dried and isostatically pressed in a dense body. The added fluorine was incorporated nearly fully into the apatite structure (fluoridation), and a near stoichiometric FA-collagen composite was obtained with complete fluoridation. The freeze-dried composites had a typical biomimetic network, consisting of collagen fibers and precipitates of nano-sized apatite crystals. The human osteoblast-like cells on the FA-collagen composites exhibited significantly higher proliferation and differentiation (according to alkaline phosphatase activity) than those on the hydroxyapatite-collagen composite. These enhanced osteoblastic cell responses were attributed to the fluorine release and the reduced dissolution rate.

Influence of substrate material and surface finishing on the morphology of the calcium-phosphate coating.

PubMed

Leitão, E; Barbosa, M A; de Groot, K

1997-07-01

The formation of an apatite-like layer was achieved by immersing Ti-6A1-4V, Ti-Al-2.5Fe, and 316 L stainless-steel substrata in Hank's balanced salt solution (HBSS). The layer was characterized by surface analysis techniques, namely X-ray microanalysis and X-ray diffraction, and the morphology was observed by scanning electron microscopy and atomic force microscopy. The concentrations of Ca and P were monitored as a function of time. The morphology of the precipitate layer seems to be dependent both on the type of metal substrate and its surface finish. Polished Ti-6A1-4V and Ti-Al-2.5Fe surfaces exhibit a plate precipitate morphology, whereas rougher surfaces show scattered crystal-like precipitation. The results suggest that the layer produced by immersion of polished titanium alloys in HBSS is constituted by an amorphous apatite.

The effect of NaOH concentration on the steam-hydrothermally treated bioactive microarc oxidation coatings containing Ca, P, Si and Na on pure Ti surface.

PubMed

Zhou, Rui; Wei, Daqing; Cao, Jianyun; Feng, Wei; Cheng, Su; Du, Qing; Li, Baoqiang; Wang, Yaming; Jia, Dechang; Zhou, Yu

2015-04-01

The microarc oxidation (MAO) coating covered pure Ti plates are steam-hydrothermally treated in autoclaves containing NaOH solutions with different concentrations of 0, 0.001, 0.01, 0.1 and 1mol·L(-1). Due to the composition of Ti, O, Ca, P, Si and Na elements in the MAO coating, anatase and hydroxyapatite (HA) crystals are generated from the previously amorphous MAO coating after the steam-hydrothermal treatment. Meanwhile, it is noticed that the amount of HA crystals increases but showing a decline trend in aspect ratio in morphologies with the increasing of NaOH concentration. Interestingly, the steam-hydrothermally treated MAO coatings exhibit better bonding strength with Ti substrate (up to 43.8±1.1MPa) than that of the untreated one (20.1±3.1MPa). In addition, benefiting from the corrosive attack of the dissolved NaOH in water vapor on the MAO coating, Ti-OH is also formed on the steam-hydrothermally treated MAO coating surface, which can trigger apatite nucleation. Thus, the steam-hydrothermally treated MAO coatings exhibit good apatite-inducing ability. Copyright © 2015 Elsevier B.V. All rights reserved.

A helium-based model for the effects of radiation damage annealing on helium diffusion kinetics in apatite

NASA Astrophysics Data System (ADS)

Willett, Chelsea D.; Fox, Matthew; Shuster, David L.

2017-11-01

Widely used to study surface processes and the development of topography through geologic time, (U-Th)/He thermochronometry in apatite depends on a quantitative description of the kinetics of 4He diffusion across a range of temperatures, timescales, and geologic scenarios. Empirical observations demonstrate that He diffusivity in apatite is not solely a function of temperature, but also depends on damage to the crystal structure from radioactive decay processes. Commonly-used models accounting for the influence of thermal annealing of radiation damage on He diffusivity assume the net effects evolve in proportion to the rate of fission track annealing, although the majority of radiation damage results from α-recoil. While existing models adequately quantify the net effects of damage annealing in many geologic scenarios, experimental work suggests different annealing rates for the two damage types. Here, we introduce an alpha-damage annealing model (ADAM) that is independent of fission track annealing kinetics, and directly quantifies the influence of thermal annealing on He diffusivity in apatite. We present an empirical fit to diffusion kinetics data and incorporate this fit into a model that tracks the competing effects of radiation damage accumulation and annealing on He diffusivity in apatite through geologic time. Using time-temperature paths to illustrate differences between models, we highlight the influence of damage annealing on data interpretation. In certain, but not all, geologic scenarios, the interpretation of low-temperature thermochronometric data can be strongly influenced by which model of radiation damage annealing is assumed. In particular, geologic scenarios involving 1-2 km of sedimentary burial are especially sensitive to the assumed rate of annealing and its influence on He diffusivity. In cases such as basement rocks in Grand Canyon and the Canadian Shield, (U-Th)/He ages predicted from the ADAM can differ by hundreds of Ma from those predicted by other models for a given thermal path involving extended residence between ∼40-80 °C.

Orientation of liquid crystalline blue phases on unidirectionally orienting surfaces

NASA Astrophysics Data System (ADS)

Takahashi, Misaki; Ohkawa, Takuma; Yoshida, Hiroyuki; Fukuda, Jun-ichi; Kikuchi, Hirostugu; Ozaki, Masanori

2018-03-01

Liquid crystalline cholesteric blue phases (BPs) continue to attract interest due to their fast response times and quasi-polarization-independent phase modulation capabilities. Various approaches have recently been proposed to control the crystal orientation of BPs on substrates; however, their basic orientation properties on standard, unidirectionally orienting alignment layers have not been investigated in detail. Through analysis of the azimuthal orientation of Kossel diagrams, we study the 3D crystal orientation of a BP material—with a phase sequence of cholesteric, BP I, and BP II—on unidirectionally orienting surfaces prepared using two methods: rubbing and photoalignment. BP II grown from the isotropic phase is sensitive to surface conditions, with different crystal planes orienting on the two substrates. On the other hand, strong thermal hysteresis is observed in BPs grown through a different liquid crystal phase, implying that the preceding structure determines the orientation. More specifically, the BP II-I transition is accompanied by a rotation of the crystal such that the crystal direction defined by certain low-value Miller indices transform into different directions, and within the allowed rotations, different azimuthal configurations are obtained in the same cell depending on the thermal process. Our findings demonstrate that, for the alignment control of BPs, the thermal process is as important as the properties of the alignment layer.

Crystallization, Crystal Orientation and Morphology of Poly(ethylene oxide) under 1D Defect-Free Nanoscale Confinement

NASA Astrophysics Data System (ADS)

Hsiao, Ming-Siao; Zheng, Joseph X.; van Horn, Ryan M.; Quirk, Roderic P.; Thomas, Edwin L.; Lotz, Bernard; Cheng, Stephen Z. D.

2009-03-01

One-dimensional (1-D) defect-free nanoscale confinement is created by growing single crystals of PS-b-PEO block copolymers in dilute solution. Those defect-free, 1-D confined lamellae having different PEO layer thicknesses in PS-b-PEO lamellar single crystals (or crystal mats) were used to study the polymer recrystallization and crystal orientation evolution as a function of recrystallization temperature (Trx) because the Tg^PS is larger than Tm^PEO in the PS-b-PEO single crystal. The results are summarized as follows. First, by the combination of electron diffraction and known PEO crystallography, the crystallization of PEO only takes place at Trx<-5^oC. Meanwhile a unique tilted PEO orientation is formed at Trx >-5^oC after self-seeding. The origin of the formation of tilted chains in the PEO crystal will be addressed. Second, from the analysis of 2D WAXD patterns of crystal mats, it is shown that the change in PEO c-axis orientation from homogeneous at low Trx to homeotropic at higher Trx transitions sharply, within 1^oC. The mechanism inducing this dramatic change in crystal orientation will be investigated in detail.

Towards 3D crystal orientation reconstruction using automated crystal orientation mapping transmission electron microscopy (ACOM-TEM).

PubMed

Kobler, Aaron; Kübel, Christian

2018-01-01

To relate the internal structure of a volume (crystallite and phase boundaries) to properties (electrical, magnetic, mechanical, thermal), a full 3D reconstruction in combination with in situ testing is desirable. In situ testing allows the crystallographic changes in a material to be followed by tracking and comparing the individual crystals and phases. Standard transmission electron microscopy (TEM) delivers a projection image through the 3D volume of an electron-transparent TEM sample lamella. Only with the help of a dedicated TEM tomography sample holder is an accurate 3D reconstruction of the TEM lamella currently possible. 2D crystal orientation mapping has become a standard method for crystal orientation and phase determination while 3D crystal orientation mapping have been reported only a few times. The combination of in situ testing with 3D crystal orientation mapping remains a challenge in terms of stability and accuracy. Here, we outline a method to 3D reconstruct the crystal orientation from a superimposed diffraction pattern of overlapping crystals without sample tilt. Avoiding the typically required tilt series for 3D reconstruction enables not only faster in situ tests but also opens the possibility for more stable and more accurate in situ mechanical testing. The approach laid out here should serve as an inspiration for further research and does not make a claim to be complete.

Single and multiphase inclusions in metapelitic garnets of the Rhodope Metamorphic Province, NE Greece.

PubMed

Mposkos, Evripidis; Perraki, Maria; Palikari, Sarra

2009-08-01

Single and multiphase inclusions in garnet porphyroblasts from the diamond-bearing pelitic gneisses were studied by means of combined Raman Spectroscopy and Electron Scanning Microscopy (SEM/EDX). They are either randomly distributed or with preferred orientation within the garnet host and their dimensions vary from less than 5 up to 60 microm. In the single-phase inclusions quartz, rutile, kyanite and graphite dominate. Biotite, zircon, apatite, monazite and allanite are also common. Two types of multiphase inclusions were recognized, hydrous silicate (Type I) and silicate-carbonate (Type II) ones. The carbon-bearing multiphase inclusions predominantly consist of Mg-siderite+graphite+CO(2)+muscovite+quartz formed by a high density carboniferous fluid rich in Fe, Mg, Si and less Ca, Mn, Al and K trapped in the growing garnet in a prograde stage of metamorphism at high-pressure (HP) conditions. The carbon-free multiphase inclusions predominantly consist of biotite+quartz+rutile+/-kyanite+muscovite formed through decompression-dehydration/melting reactions of pre-existing phengite. Single and multiphase inclusions are characterized by polygonal to negative crystal shape formed by dissolution-reprecipitation mechanism between the garnet host and the inclusions during the long lasting cooling period (>100 Ma) of the Kimi Complex.

Distinct crystallinity and orientations of hydroxyapatite thin films deposited on C- and A-plane sapphire substrates

NASA Astrophysics Data System (ADS)

Akazawa, Housei; Ueno, Yuko

2014-10-01

We report how the crystallinity and orientation of hydroxyapatite (HAp) films deposited on sapphire substrates depend on the crystallographic planes. Both solid-phase crystallization of amorphous HAp films and crystallization during sputter deposition at elevated temperatures were examined. The low-temperature epitaxial phase on C-plane sapphire substrates has c-axis orientated HAp crystals regardless of the crystallization route, whereas the preferred orientation switches to the (310) direction at higher temperatures. Only the symmetric stretching mode (ν1) of PO43- units appears in the Raman scattering spectra, confirming well-ordered crystalline domains. In contrast, HAp crystals grown on A-plane sapphire substrates are always oriented toward random orientations. Exhibiting all vibrational modes (ν1, ν3, and ν4) of PO43- units in the Raman scattering spectra reflects random orientation, violating the Raman selection rule. If we assume that Raman intensities of PO43- units represent the crystallinity of HAp films, crystallization terminating the surface with the C-plane is hindered by the presence of excess H2O and OH species in the film, whereas crystallization at random orientations on the A-plane sapphire is rather promoted by these species. Such contrasting behaviors between C-plane and A-plane substrates will reflect surface-plane dependent creation of crystalline seeds and eventually determine the orientation of resulting HAp films.

Strontium isotope systematics of scheelite and apatite from the Felbertal tungsten deposit, Austria - results of in-situ LA-MC-ICP-MS analysis

NASA Astrophysics Data System (ADS)

Kozlik, Michael; Gerdes, Axel; Raith, Johann G.

2016-02-01

The in-situ Sr isotopic systematics of scheelite and apatite from the Felbertal W deposit and a few regional Variscan orthogneisses ("Zentralgneise") have been determined by LA-MC-ICP-MS. The 87Sr/86Sr ratios of scheelite and apatite from the deposit are highly radiogenic and remarkably scattering. In the early magmatic-hydrothermal scheelite generations (Scheelite 1 and 2) the 87Sr/86Sr ratios range from 0.72078 to 0.76417 and from 0.70724 to 0.76832, respectively. Metamorphic Scheelite 3, formed by recrystallisation and local mobilisation of older scheelite, is characterised by even higher 87Sr/86Sr values between 0.74331 and 0.80689. Statistics allows discriminating the three scheelite generations although there is considerable overlap between Scheelite 1 and 2; they could be mixtures of the same isotopic reservoirs. The heterogeneous and scattering 87Sr/86Sr ratios of the two primary scheelite generations suggest modification of the Sr isotope system due to fluid-rock interaction and isotopic disequilibrium. Incongruent release of 87Sr from micas in the Early Palaeozoic host rocks of the Habach Complex contributed to the solute budget of the hydrothermal fluids and may explain the radiogenic Sr isotope signature of scheelite. Spatially resolved analyses revealed isotopic disequilibrium even on a sub-mm scale within zoned Scheelite 2 crystals indicating scheelite growth in an isotopic dynamical hydrothermal system. Zoned apatite from the W mineralised Early Carboniferous K1-K3 orthogneiss in the western ore field yielded 87Sr/86Sr of 0.72044-0.74514 for the cores and 0.74535-0.77937 for the rims. Values of magmatic apatite cores from the K1-K3 orthogneiss are comparable to those of primary Scheelite 1; they are too radiogenic to be magmatic. The Sr isotopic composition of apatite cores was therefore equally modified during the hydrothermal mineralisation processes, therefore supporting the single-stage genetic model in which W mineralisation is associated with the intrusion of the K1-K3 metagranitoid at Felbertal. The subsequent regional metamorphic overprint of the deposit caused redistribution of 87Sr as a consequence of metamorphic reactions involving Rb and Sr-bearing minerals. Metamorphic Scheelite 3 and apatite rims (e.g., in the K1-K3 orthogneiss) generally became more radiogenic during this process. However, local recrystallisation of primary scheelite under closed conditions (without addition of 87Sr by the metamorphic fluid) is also documented. The latter process resulted in a homogenisation of the isotope composition of Scheelite 3. Further increase in 87Sr/86Sr ratios in Scheelite 3 and apatite rims is attributed to Late Alpine (?) metamorphic recrystallisation and redistribution of 87Sr by metamorphic fluids.

The role of intracellular calcium phosphate in osteoblast-mediated bone apatite formation

PubMed Central

Boonrungsiman, Suwimon; Gentleman, Eileen; Carzaniga, Raffaella; Evans, Nicholas D.; McComb, David W.; Porter, Alexandra E.; Stevens, Molly M.

2012-01-01

Mineralization is a ubiquitous process in the animal kingdom and is fundamental to human development and health. Dysfunctional or aberrant mineralization leads to a variety of medical problems, and so an understanding of these processes is essential to their mitigation. Osteoblasts create the nano-composite structure of bone by secreting a collagenous extracellular matrix (ECM) on which apatite crystals subsequently form. However, despite their requisite function in building bone and decades of observations describing intracellular calcium phosphate, the precise role osteoblasts play in mediating bone apatite formation remains largely unknown. To better understand the relationship between intracellular and extracellular mineralization, we combined a sample-preparation method that simultaneously preserved mineral, ions, and ECM with nano-analytical electron microscopy techniques to examine osteoblasts in an in vitro model of bone formation. We identified calcium phosphate both within osteoblast mitochondrial granules and intracellular vesicles that transported material to the ECM. Moreover, we observed calcium-containing vesicles conjoining mitochondria, which also contained calcium, suggesting a storage and transport mechanism. Our observations further highlight the important relationship between intracellular calcium phosphate in osteoblasts and their role in mineralizing the ECM. These observations may have important implications in deciphering both how normal bone forms and in understanding pathological mineralization. PMID:22879397

In-Situ U-Pb Dating of Apatite by Hiroshima-SHRIMP: Contributions to Earth and Planetary Science.

PubMed

Terada, Kentaro; Sano, Yuji

2012-01-01

The Sensitive High Resolution Ion MicroProbe (SHRIMP) is the first ion microprobe dedicated to geological isotopic analyses, especially in-situ analyses related to the geochronology of zircon. Such a sophisticated ion probe, which can attain a high sensitivity at a high mass resolution, based on a double focusing high mass-resolution spectrometer, designed by Matsuda (1974), was constructed at the Australian National University. In 1996, such an instrument was installed at Hiroshima University and was the first SHRIMP to be installed in Japan. Since its installation, our focus has been on the in-situ U-Pb dating of the mineral apatite, as well as zircon, which is a more common U-bearing mineral. This provides the possibility for extending the use of in-situ U-Pb dating from determining the age of formation of volcanic, granitic, sedimentary and metamorphic minerals to the direct determination of the diagenetic age of fossils and/or the crystallization age of various meteorites, which can provide new insights into the thermal history on the Earth and/or the Solar System. In this paper, we review the methodology associated with in-situ apatite dating and our contribution to Earth and Planetary Science over the past 16 years.

In-Situ U–Pb Dating of Apatite by Hiroshima-SHRIMP: Contributions to Earth and Planetary Science

PubMed Central

Terada, Kentaro; Sano, Yuji

2012-01-01

The Sensitive High Resolution Ion MicroProbe (SHRIMP) is the first ion microprobe dedicated to geological isotopic analyses, especially in-situ analyses related to the geochronology of zircon. Such a sophisticated ion probe, which can attain a high sensitivity at a high mass resolution, based on a double focusing high mass-resolution spectrometer, designed by Matsuda (1974), was constructed at the Australian National University. In 1996, such an instrument was installed at Hiroshima University and was the first SHRIMP to be installed in Japan. Since its installation, our focus has been on the in-situ U–Pb dating of the mineral apatite, as well as zircon, which is a more common U-bearing mineral. This provides the possibility for extending the use of in-situ U–Pb dating from determining the age of formation of volcanic, granitic, sedimentary and metamorphic minerals to the direct determination of the diagenetic age of fossils and/or the crystallization age of various meteorites, which can provide new insights into the thermal history on the Earth and/or the Solar System. In this paper, we review the methodology associated with in-situ apatite dating and our contribution to Earth and Planetary Science over the past 16 years. PMID:24349912

Synthesis, bioactivity and zeta potential investigations of chlorine and fluorine substituted hydroxyapatite.

PubMed

Fahami, Abbas; Beall, Gary W; Betancourt, Tania

2016-02-01

Chlorine and fluorine substituted hydroxyapatites (HA-Cl-F) with different degrees of ion replacement were successfully prepared by the one step mechanochemical activation method. X-ray diffraction (XRD) and FT-IR spectra indicated that substitution of these anions in milled powders resulted in the formation of pure hydroxyapatite phase except for the small observed change in the lattice parameters and unit cell volumes of the resultant hydroxyapatite. Microscopic observations showed that the milled product had a cluster-like structure made up of polygonal and spherical particles with an average particle size of approximately ranged from 20±5 to 70±5nm. The zeta potential of milled samples was performed at three different pH (5, 7.4, and 9). The obtained zeta potential values were negative for all three pH values. Negative zeta potential was described to favor osseointegration, apatite nucleation, and bone regeneration. The bioactivity of samples was investigated on sintered pellets soaked in simulated body fluid (SBF) solution and apatite crystals formed on the surface of the pellets after being incubated for 14days. Zeta potential analysis and bioactivity experiment suggested that HA-Cl-F will lead to the formation of new apatite particles and therefore be a potential implant material. Copyright © 2015 Elsevier B.V. All rights reserved.

Remineralization of artificial dentinal caries lesions by biomimetically modified Mineral Trioxide Aggregate

PubMed Central

Qi, Yi-pin; Li, Nan; Niu, Li-na; Primus, Carolyn M.; Ling, Jun-Qi; Pashley, David H.; Tay, Franklin R.

2011-01-01

Fluoride-releasing restorative materials are available for remineralization of enamel and root caries. However, dentin remineralization is more difficult than enamel remineralization due to the paucity of apatite seed crystallites along the lesion surface for heterogeneous crystal growth. Extracellular matrix proteins play critical roles in controlling apatite nucleation/growth in collagenous tissues. This study examined the remineralization efficacy of mineral trioxide aggregate (MTA) in phosphate-containing simulated body fluid (SBF) by incorporating polyacrylic acid and sodium tripolyphosphate as biomimetic analogs of matrix proteins for remineralizing caries-like dentin. Artificial caries-like dentin lesions incubated in SBF were remineralized over a 6-week period using MTA or MTA containing biomimetic analogs in the absence or presence of dentin adhesive application. Lesion depths and integrated mineral loss were monitored with micro-computed tomography. Ultrastructure of baseline and remineralized lesions were examined by transmission electron microscopy. Dentin remineralization was best achieved using MTA containing biomimetic analogs regardless of whether an adhesive was applied; dentinal tubules within the remineralized dentin were occluded by apatite. It is concluded that the MTA version employed in the study may be doped with biomimetic analogs for remineralization of unbonded and bonded artificial caries-like lesions in the presence of SBF. PMID:22085925

Remineralization of artificial dentinal caries lesions by biomimetically modified mineral trioxide aggregate.

PubMed

Qi, Yi-pin; Li, Nan; Niu, Li-na; Primus, Carolyn M; Ling, Jun-Qi; Pashley, David H; Tay, Franklin R

2012-02-01

Fluoride-releasing restorative materials are available for remineralization of enamel and root caries. However, remineralization of dentin is more difficult than remineralization of enamel due to the paucity of apatite seed crystallites along the lesion surface for heterogeneous crystal growth. Extracellular matrix proteins play critical roles in controlling apatite nucleation/growth in collagenous tissues. This study examined the remineralization efficacy of mineral trioxide aggregate (MTA) in phosphate-containing simulated body fluid (SBF) by incorporating polyacrylic acid and sodium tripolyphosphate as biomimetic analogs of matrix proteins for remineralizing caries-like dentin. Artificial caries-like dentin lesions incubated in SBF were remineralized over a 6 week period using MTA alone or MTA containing biomimetic analogs in the absence or presence of dentin adhesive application. Lesion depths and integrated mineral loss were monitored with microcomputed tomography. The ultrastructure of baseline and remineralized lesions was examined by transmission electron microscopy. Dentin remineralization was best achieved using MTA containing biomimetic analogs regardless of whether an adhesive was applied; dentinal tubules within the remineralized dentin were occluded by apatite. It is concluded that the version of MTA employed in this study may be doped with biomimetic analogs for remineralization of unbonded and bonded artificial caries-like lesions in the presence of SBF. Copyright © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Mineral ecophysiological evidence for biogeochemical cycles in 2461-2495 million year old banded iron formations (BIF).

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Y; Konhauser, Dr, Kurt; Cole, David

2011-01-01

The phosphorus composition of banded-iron formations (BIFs) has been used as a proxy for Precambrian seawater composition and the paleoeredox state of Earth's surface environment. However, it is unclear whether the phosphorus in BIFs originally entered the sediment as a sorbed component of the iron oxyhydroxide particles, or whether it was incorporated into the biomass of marine phytoplankton. We conducted high-resolution mineral analyses and report here the first detection of an Fe(III) acetate salt, as well as nanocrystals of apatite in association with magnetite, in the 2.48 Ga Dales Gorge Member of the Brockman Iron Formation (a BIF), Hamersley, Westernmore » Australia. The clusters of apatite are similar in size and morphology to biogenic apatite crystals resulting from biomass decay in Phanerozoic marine sediments, while the formation of an Fe(III) acetate salt and magnetite not only implies the original presence of biomass in the BIF sediments, but also that organic carbon likely served as an electron donor during bacterial Fe(III) reduction. This study is important because it suggests that phytoplankton may have played a key role in the transfer of phosphorus (and other trace elements) from the photic zone to the seafloor.« less

An NMR Study of Biomimetic Fluorapatite – Gelatine Mesocrystals

PubMed Central

Vyalikh, Anastasia; Simon, Paul; Rosseeva, Elena; Buder, Jana; Scheler, Ulrich; Kniep, Rüdiger

2015-01-01

The mesocrystal system fluoroapatite—gelatine grown by double-diffusion is characterized by hierarchical composite structure on a mesoscale. In the present work we apply solid state NMR to characterize its structure on the molecular level and provide a link between the structural organisation on the mesoscale and atomistic computer simulations. Thus, we find that the individual nanocrystals are composed of crystalline fluorapatite domains covered by a thin boundary apatite-like layer. The latter is in contact with an amorphous layer, which fills the interparticle space. The amorphous layer is comprised of the organic matrix impregnated by isolated phosphate groups, Ca3F motifs and water molecules. Our NMR data provide clear evidence for the existence of precursor complexes in the gelatine phase, which were not involved in the formation of apatite crystals, proving hence theoretical predictions on the structural pre-treatment of gelatine by ion impregnation. The interfacial interactions, which may be described as the glue holding the composite materials together, comprise hydrogen bond interactions with the apatite PO43− groups. The reported results are in a good agreement with molecular dynamics simulations, which address the mechanisms of a growth control by collagen fibers, and with experimental observations of an amorphous cover layer in biominerals. PMID:26515127

Thermal and Structural Analysis of a Hollow Core Space Shuttle Main Engine (SSME) Turbine Blade

NASA Technical Reports Server (NTRS)

Abdul-Aziz, Ali; Kalluri, Sreeramesh; McGaw, Michael A.

1995-01-01

The influence of primary and secondary orientations on the elastic response of a hollow core, (001)-oriented nickel base single-crystal superalloy turbine blade, was investigated under combined thermal and mechanical conditions. Finite element techniques is employed through MARC finite element code to conduct the analyses on a hollow core SSME turbine blade made out of PWA 1480 single crystal material. Primary orientation of the single crystal superalloy was varied in increments of 2 deg, from 0 to 10 deg, from the (001) direction. Two secondary orientations (0 and 45 deg) were considered with respect to the global coordinate system, as the primary orientation angle was varied. The stresses developed within the single crystal blade were determined for different orientations of the blade. The influence of angular offsets such as the single crystal's primary and secondary orientations and the loading conditions on the elastic stress response of the PWA 1480 hollow blade are summarized. The influence of he primary orientation angle, when constrained between the bounds considered, was not found to be as significant as the influence of the secondary orientation angle.

The influence of primary and secondary orientations on the elastic response of a nickel-base single-crystal superalloy

NASA Technical Reports Server (NTRS)

Abdul-Aziz, Ali; Kalluri, Sreeramesh; Mcgaw, Michael A.

1993-01-01

The influence of primary orientation on the elastic response of a (001)-oriented nickel-base single-crystal superalloy, PWA 1480, was investigated under mechanical, thermal, and combined thermal and mechanical loading conditions using finite element techniques. Elastic stress analyses were performed using the MARC finite element code on a square plate of PWA 1480 material. Primary orientation of the single crystal superalloy was varied in increments of 2 deg, from 0 to 10 deg, from the (001) direction. Two secondary orientations (0 and 45 deg) were considered, with respect to the global coordinate system, as the primary orientation angle was varied. The stresses developed within the single crystal plate were determined for each loading condition. In this paper, the influence of the angular offset between the primary crystal orientation and the loading direction on the elastic stress response of the PWA 1480 plate is presented for different loading conditions. The influence of primary orientation angle, when constrained between the bounds considered, was not found to be as significant as the influence of the secondary orientation angle, which is not typically controlled.

Crystal orientation dependence of femtosecond laser-induced periodic surface structure on (100) silicon.

PubMed

Jiang, Lan; Han, Weina; Li, Xiaowei; Wang, Qingsong; Meng, Fantong; Lu, Yongfeng

2014-06-01

It is widely believed that laser-induced periodic surface structures (LIPSS) are independent of material crystal structures. This Letter reports an abnormal phenomenon of strong dependence of the anisotropic formation of periodic ripples on crystal orientation, when Si (100) is processed by a linearly polarized femtosecond laser (800 nm, 50 fs, 1 kHz). LIPSS formation sensitivity with a π/2 modulation is found along different crystal orientations with a quasi-cosinusoid function when the angle between the crystal orientation and polarization direction is changed from 0° to 180°. Our experiments indicate that it is much easier (or more difficult) to form ripple structures when the polarization direction is aligned with the lattice axis [011]/[011¯] (or [001]). The modulated nonlinear ionization rate along different crystal orientations, which arises from the direction dependence of the effective mass of the electron is proposed to interpret the unexpected anisotropic LIPSS formation phenomenon. Also, we demonstrate that the abnormal phenomenon can be applied to control the continuity of scanned ripple lines along different crystal orientations.

Apatite-hosted melt inclusions in Damiao massif anorthosite complex, North China

NASA Astrophysics Data System (ADS)

Wang, M.; Veksler, I. V.; Zhang, Z.

2014-12-01

Models for the nelsonite formation are currently highly contentious, with liquid immiscibility and fractional crystallization as frequently proposed formation mechanisms. The nelsonites in the Damiao massif anorthosite complex in the North China Craton and experimental evidence are revisited for the existence of silica-free CaO-FeO-Fe2O3-TiO2-P2O5 immiscible nelsonitic liquids. Our results of differential scanning calorimetry (DSC) demonstrate that nelsonite with the composition of one-third apatite and two-thirds Fe-Ti oxides by weight completely melts well above 1450 ºC, which is in good agreement with numerous experimental studies of the CaO-P2O5-FexO system in connection to metallurgy. Thus, the composition cannot be molten at temperatures relevant for crystallization of the Damiao magma. A review of experimental studies of liquid immiscibility and analyses of natural immiscible glasses show that all the liquids on the Fe- and P-rich side of the miscibility gap have at least 20 wt. % of aluminosilicate components. Main results of this study come from the analyses of apatite-hosted melt inclusions in Damiao nelsonite. The inclusions range from ~3 to 200 μm in diameter. They are ubiquitous and meet all the morphological criteria of primary melt inclusions crystallised into assemblages of daughter minerals. Almost all of them contain vermiculite and chlorite, and some contain biotite, amphibole, phlogopite and Fe-Ti oxides. Out of dozens analysed inclusions, only three have high contents of SiO2 (62.1-73.8 wt. %) and low contents of FeO (0.25-2.35 wt. %). Bulk compositions of other inclusions show large variations in SiO2 (20.79-50.16 wt. %) and FeOt (13.44-32.78 wt. %). With a few exceptions, the inclusions are very low in CaO (0.04-1.51 wt. %, and high in Al2O3 (10-21.17 wt. %). Despite the high Fe content, the compositions differ from those of the typical immiscible Fe-rich melts. It appears that the cumulus apatite crystallised from Fe-rich, hydrated silicate melt. We propose that the inclusions at Damiao record a trend of intercumulus melt evolution, which was strongly affected by separation of a hydrothermal fluid phase and the losses of alkali and Ca silicate components from the melt into the fluid.

Laser Ablation in situ (U-Th-Sm)/He and U-Pb Double-Dating of Apatite and Zircon: Techniques and Applications

NASA Astrophysics Data System (ADS)

McInnes, B.; Danišík, M.; Evans, N.; McDonald, B.; Becker, T.; Vermeesch, P.

2015-12-01

We present a new laser-based technique for rapid, quantitative and automated in situ microanalysis of U, Th, Sm, Pb and He for applications in geochronology, thermochronometry and geochemistry (Evans et al., 2015). This novel capability permits a detailed interrogation of the time-temperature history of rocks containing apatite, zircon and other accessory phases by providing both (U-Th-Sm)/He and U-Pb ages (+trace element analysis) on single crystals. In situ laser microanalysis offers several advantages over conventional bulk crystal methods in terms of safety, cost, productivity and spatial resolution. We developed and integrated a suite of analytical instruments including a 193 nm ArF excimer laser system (RESOlution M-50A-LR), a quadrupole ICP-MS (Agilent 7700s), an Alphachron helium mass spectrometry system and swappable flow-through and ultra-high vacuum analytical chambers. The analytical protocols include the following steps: mounting/polishing in PFA Teflon using methods similar to those adopted for fission track etching; laser He extraction and analysis using a 2 s ablation at 5 Hz and 2-3 J/cm2fluence; He pit volume measurement using atomic force microscopy, and U-Th-Sm-Pb (plus optional trace element) analysis using traditional laser ablation methods. The major analytical challenges for apatite include the low U, Th and He contents relative to zircon and the elevated common Pb content. On the other hand, apatite typically has less extreme and less complex zoning of parent isotopes (primarily U and Th). A freeware application has been developed for determining (U-Th-Sm)/He ages from the raw analytical data and Iolite software was used for U-Pb age and trace element determination. In situ double-dating has successfully replicated conventional U-Pb and (U-Th)/He age variations in xenocrystic zircon from the diamondiferous Ellendale lamproite pipe, Western Australia and increased zircon analytical throughput by a factor of 50 over conventional methods.Reference: Evans NJ, McInnes BIA, McDonald B, Becker T, Vermeesch P, Danisik M, Shelley M, Marillo-Sialer E and Patterson D. An in situ technique for (U-Th-Sm)/He and U-Pb double dating. J Analytical Atomic Spectrometry, 30, 1636 - 1645.

A Holistic Model That Physicochemically Links Iron Oxide - Apatite and Iron Oxide - Copper - Gold Deposits to Magmas

NASA Astrophysics Data System (ADS)

Simon, A. C.; Reich, M.; Knipping, J.; Bilenker, L.; Barra, F.; Deditius, A.; Lundstrom, C.; Bindeman, I. N.

2015-12-01

Iron oxide-apatite (IOA) and iron oxide-copper-gold deposits (IOCG) are important sources of their namesake metals and increasingly for rare earth metals in apatite. Studies of natural systems document that IOA and IOCG deposits are often spatially and temporally related with one another and coeval magmatism. However, a genetic model that accounts for observations of natural systems remains elusive, with few observational data able to distinguish among working hypotheses that invoke meteoric fluid, magmatic-hydrothermal fluid, and immiscible melts. Here, we use Fe and O isotope data and high-resolution trace element (e.g., Ti, V, Mn, Al) data of individual magnetite grains from the world-class Los Colorados (LC) IOA deposit in the Chilean Iron Belt to elucidate the origin of IOA and IOCG deposits. Values of d56Fe range from 0.08‰ to 0.26‰, which are within the global range of ~0.06‰ to 0.5‰ for magnetite formed at magmatic conditions. Values of δ18O for magnetite and actinolite are 2.04‰ and 6.08‰, respectively, consistent with magmatic values. Ti, V, Al, and Mn are enriched in magnetite cores and decrease systematically from core to rim. Plotting [Al + Mn] vs. [Ti + V] indicates that magnetite cores are consistent with magmatic and/or magmatic-hydrothermal (i.e., porphyry) magnetites. Decreasing Al, Mn, Ti, V is consistent with a cooling trend from porphyry to Kiruna to IOCG systems. The data from LC are consistent with the following new genetic model for IOA and IOCG systems: 1) magnetite cores crystallize from silicate melt; 2) these magnetite crystals are nucleation sites for aqueous fluid that exsolves and scavenges inter alia Fe, P, S, Cu, Au from silicate melt; 3) the magnetite-fluid suspension is less dense that the surrounding magma, allowing ascent; 4) as the suspension ascends, magnetite grows in equilibrium with the fluid and takes on a magmatic-hydrothermal character (i.e., lower Al, Mn, Ti, V); 5) during ascent, magnetite, apatite and actinolite are deposited to form IOA deposits; 6) the further ascending fluid transports Fe, Cu, Au and S toward the surface where metal-oxides and metal-sulfides precipitate to form IOCG deposits. This model is globally applicable and explains the observed temporal and spatial relationship between magmatism and formation of IOA and IOCG deposits.

Three-Dimensional Stress Fields and Slip Systems for Single Crystal Superalloy Notched Specimens

NASA Technical Reports Server (NTRS)

Magnan, Shannon M.; Throckmorton, David (Technical Monitor)

2002-01-01

Single crystal superalloys have become increasingly popular for turbine blade and vane applications due to their high strength, and creep and fatigue resistance at elevated temperatures. The crystallographic orientation of a single crystal material greatly affects its material properties, including elastic modulus, shear modulus, and ductility. These directional properties, along with the type of loading and temperature, dictate an anisotropic response in the yield strength, creep resistance, creep rupture ductility, fatigue resistance, etc. A significant amount of research has been conducted to determine the material properties in the <001> orientation, yet the material properties deviating from the <001> orientation have not been assessed for all cases. Based on the desired application and design criteria, a crystal orientation is selected to yield the maximum properties. Currently, single crystal manufacturing is able to control the primary crystallographic orientation within 15 of the target orientation, which is an acceptable deviation to meet both performance and cost guidelines; the secondary orientation is rarely specified. A common experiment is the standard load-controlled tensile test, in which specimens with different orientations can be loaded to observe the material response. The deformation behavior of single-crystal materials under tension and compression is known to be a function of not only material orientation, but also of varying microdeformation (i.e. dislocation) mechanisms. The underlying dislocation motion causes deformation via slip, and affects the activation of specific slip systems based on load and orientation. The slip can be analyzed by observing the visible traces left on the surface of the specimen from the slip activity within the single crystal material. The goal of this thesis was to predict the slip systems activated in three-dimensional stress fields of a notched tensile specimen, as a function of crystal orientation, using finite element analysis without addressing microstructural deformation mechanisms that govern their activation. Out of three orientations tested, the specimen with a [110] load orientation and a [001] growth direction had the lowest maximum resolved shear stress; this specimen orientation appears to be the best design candidate for a tensile application.

Shear induced orientation of edible fat and chocolate crystals

NASA Astrophysics Data System (ADS)

Mazzanti, Gianfranco; Welch, Sarah E.; Marangoni, Alejandro G.; Sirota, Eric B.; Idziak, Stefan H. J.

2003-03-01

Shear-induced orientation of fat crystallites was observed during crystallization of cocoa butter, milk fat, stripped milk fat and palm oil. This universal effect was observed in systems crystallized under high shear. The minor polar components naturally present in milk fat were found to decrease the shear-induced orientation effect in this system. The competition between Brownian and shear forces, described by the Peclet number, determines the crystallite orientation. The critical radius size, from the Gibbs-Thomson equation, provides a tool to understand the effect of shear at the onset stages of crystallization.

Fast optical switch having reduced light loss

NASA Technical Reports Server (NTRS)

Nelson, Bruce N. (Inventor); Cooper, Ronald F. (Inventor)

1992-01-01

An electrically controlled optical switch uses an electro-optic crystal of the type having at least one set of fast and slow optical axes. The crystal exhibits electric field induced birefringence such that a plane of polarization oriented along a first direction of a light beam passing through the crystal may be switched to a plane of polarization oriented along a second direction. A beam splitting polarizer means is disposed at one end of the crystal and directs a light beam passing through the crystal whose plane of polarization is oriented along the first direction differently from a light beam having a plane of polarization oriented along the second direction. The electro-optic crystal may be chosen from the crystal classes 43m, 42m, and 23. In a preferred embodiment, the electro-optic crystal is a bismuth germanium oxide crystal or a bismuth silicon oxide crystal. In another embodiment of the invention, polarization control optics are provided which transmit substantially all of the incident light to the electro-optic crystal, substantially reducing the insertion loss of the switch.

Interactions of bioactive glass materials in the oral environment

NASA Astrophysics Data System (ADS)

Efflandt, Sarah Elizabeth

The aim of this research was to investigate bioactive glass materials for their use in dental restorations. Mechanical properties such as strength, toughness and wear resistance were considered initially, but the focus of this thesis was the biological properties such as reactions with saliva and interactions with natural dental tissues. Bioactive composite materials were created by incorporating bioactive glass and alumina powders into an aqueous suspension, slip casting, and infiltrating with resin. Microstructure, mechanical properties and wear resistance were evaluated. Mechanically, the composites are comparable to natural dental tissues and current dental materials with a strength of 206 +/- 18.7 MPa and a toughness of 1.74 +/- 0.08 MPa(m)1/2. Interfacial reactions were examined using bulk bioactive glasses. Disks were prepared from a melt, placed in saliva and incubated at 37°C. Surfaces were analyzed at 2, 5, 10, 21, and 42 days using scanning electron microscopy (SEM) and microdiffraction. Results showed changes at 2 days with apatite crystallization by 10 days. These glass disks were then secured against extracted human dentin and incubated in saliva for 21 or 42 days. Results from SEM, electron microprobe analysis (EMPA) and microdiffraction showed that dentin and bioactive glasses adhered in this in vitro environment due to attraction of collagen to bioactive glasses and growth of an interfacial apatite. After investigating these bulk glass responses, particulate bioactive glasses were placed in in vitro and in vivo set-ups for evaluation. Particles immersed in biologically buffered saliva showed crystallization of apatite at 3 days. These bioactive glass particles were placed in the molars of mini-pigs and left in vivo. After 30 days the bioactive paste was evaluated using SEM, EMPA and microdiffraction analyses. Results showed that the paste gained structural integrity and had chemical changes in vivo. These sets of experiments show that bioactive glasses have many mechanical and biological characteristics desirable for use in dental materials. Hopefully, the conclusions presented here will lead to further investigations toward their use in dentistry.

Volatile Content of 4-Vesta: Evidence from Unequilibrated Eucrites

NASA Technical Reports Server (NTRS)

Sarafian, A. R.; Nielsen, S. G.; Marschall, H. R.; Gaetani, G. A.; Hauri, E. H.; Righter, K.; Berger, E. L.

2017-01-01

Eucrites are a class of basaltic meteorites that, along with the howardites and diogenites, likely derive from the asteroid 4-Vesta. This asteroid is depleted in moderately volatile elements relative to the Earth and carbonaceous chondrites. Extrapolation of this depletion trend predicts that bulk silicate 4-Vesta (BSV) contains at most 250-1000 µg/g H2O, which is approximately a factor of two lower than the H2O content of Earth. To obtain more accurate H2O and F estimates for BSV, we examined four unequilibrated antarctic meteorites, Yamato(Y)-793548, Y-82210, Y-75011, and Y-74450, by EPMA and SIMS. Pyroxenes contain MgO-rich cores and FeO-rich rims, consistent with primary magmatic zoning. Volatile concentrations generally follow patterns expected for growth zoning with lower values in the cores and higher in the rims. These features indicate that thermal metamorphism and other post-crystallization processes did not significantly perturb the volatile contents of these unequilibrated eucrite pyroxenes. We used these data to derive best estimates for the BSV H2O and F content based on experimentally determined pyroxene-melt partition coefficients and models for magma generation on Vesta. In addition, we measured D/H in the early crystallizing pyroxenes and late crystallzing apatites. We find that the D/H of pyroxene and apatite are within error of one another as well as previous measurements of apatite in equilibrated eucrites. These results imply that degassing was minimal or did not fractionate D/H. Degassing may have been limited if eucrites were shallowly emplaced sills or dykes, or the total H2O content of the magmas was too low for vapor saturation. An alternative mechanism for limited D/H fractionation is that degassing did occur, but the H2/H2O of the exsolved vapor was approximately 15:85, as predicted from experiments.

Probing the calcium and sodium local environment in bones and teeth using multinuclear solid state NMR and X-ray absorption spectroscopy.

PubMed

Laurencin, Danielle; Wong, Alan; Chrzanowski, Wojciech; Knowles, Jonathan C; Qiu, Dong; Pickup, David M; Newport, Robert J; Gan, Zhehong; Duer, Melinda J; Smith, Mark E

2010-02-07

Despite the numerous studies of bone mineral, there are still many questions regarding the exact structure and composition of the mineral phase, and how the mineral crystals become organised with respect to each other and the collagen matrix. Bone mineral is commonly formulated as hydroxyapatite, albeit with numerous substitutions, and has previously been studied by (31)P and (1)H NMR, which has given considerable insight into the complexity of the mineral structure. However, to date, there has been no report of an NMR investigation of the other major component of bone mineral, calcium, nor of common minority cations like sodium. Here, direct analysis of the local environment of calcium in two biological apatites, equine bone (HB) and bovine tooth (CT), was carried out using both (43)Ca solid state NMR and Ca K-edge X-ray absorption spectroscopy, revealing important structural information about the calcium coordination shell. The (43)Ca delta(iso) in HB and CT is found to correlate with the average Ca-O bond distance measured by Ca K-edge EXAFS, and the (43)Ca NMR linewidths show that there is a greater distribution in chemical bonding around calcium in HB and CT, compared to synthetic apatites. In the case of sodium, (23)Na MAS NMR, high resolution 3Q-MAS NMR, as well as (23)Na{(31)P} REDOR and (1)H{(23)Na} R(3)-HMQC correlation experiments give the first direct evidence that some sodium is located inside the apatite phase in HB and CT, but with a greater distribution of environments compared to a synthetic sodium substituted apatite (Na-HA).

Crystal orientation of PEO confined within the nanorod templated by AAO nanochannels.

PubMed

Liu, Chien-Liang; Chen, Hsin-Lung

2018-06-18

The orientation of poly(ethylene oxide) (PEO) crystallites developed in the nanochannels of anodic aluminum oxide (AAO) membrane has been investigated. PEO was filled homogeneously into the nanochannels in the melt state, and the crystallization confined within the PEO nanorod thus formed was allowed to take place subsequently at different temperatures. The effects of PEO molecular weight (MPEO), crystallization temperature (Tc) and AAO channel diameter (DAAO) on the crystal orientation attained in the nanorod were revealed by 2-D wide angle X-ray scattering (WAXS) patterns. In the nanochannels with DAAO = 23 nm, the crystallites formed from PEO with the lowest MPEO (= 3400 g mol-1) were found to adopt a predominantly perpendicular orientation with the crystalline stems aligning normal to the channel axis irrespective of Tc (ranging from -40 to 20 °C). Increasing MPEO or decreasing Tc tended to induce the development of the tilt orientation characterized by the tilt of the (120) plane by 45° from the channel axis. In the case of the highest MPEO (= 95 000 g mol-1) studied, both perpendicular and tilt orientations coexisted irrespective of Tc. Coexistent orientation was always observed in the channels with a larger diameter (DAAO = 89 nm) irrespective of MPEO and Tc. Compared with the previous results of the crystal orientation attained in nanotubes templated by the preferential wetting of the channel walls by PEO, the window of the perpendicular crystal orientation in the nanorod was much narrower due to its weaker confinement effect imposed on the crystal growth than that set by the nanotube.

Petrographic, geochemical and isotopic evidence of crustal assimilation processes in the Ponte Nova alkaline mafic-ultramafic massif, SE Brazil

NASA Astrophysics Data System (ADS)

Azzone, Rogério Guitarrari; Montecinos Munoz, Patricio; Enrich, Gaston Eduardo Rojas; Alves, Adriana; Ruberti, Excelso; Gomes, Celsode Barros

2016-09-01

Crustal assimilation plus crystal fractionation processes of different basanite magma batches control the evolution of the Ponte Nova cretaceous alkaline mafic-ultramafic massif in SE Brazil. This massif is composed of several intrusions, the main ones with a cumulate character. Disequilibrium features in the early-crystallized phases (e.g., corrosion and sieve textures in cores of clinopyroxene crystals, spongy-cellular-textured plagioclase crystals, gulf corrosion texture in olivine crystals) and classical hybridization textures (e.g., blade biotite and acicular apatite crystals) provide strong evidence of open-system behavior. All samples are olivine- and nepheline-normative rocks with basic-ultrabasic and potassic characters and variable incompatible element enrichments. The wide ranges of whole-rock 87Sr/86Sri and 143Nd/144Ndi ratios (0.70432-0.70641 and 0.512216-0.512555, respectively) are indicative of crustal contribution from the Precambrian basement host rocks. Plagioclase and apatite 87Sr/86Sr ratios (0.70422-0.70927) obtained for the most primitive samples of each intrusion indicate disequilibrium conditions from early- to principal-crystallization stages. Isotope mixing-model curves between the least contaminated alkaline basic magma and heterogeneous local crustal components indicate that each intrusion of the massif is differentiated from the others by varied degrees of crustal contribution. The primary mechanisms of crustal contribution to the Ponte Nova massif involve the assimilation of host rock xenoliths during the development of the chamber environment and the assimilation of partial melts from the surrounding host rocks. Thermodynamic models using the melts algorithm indicate that parental alkaline basic magmas can be strongly affected by contamination processes subsequently to their initial stages of crystallization when there is sufficient energy to assimilate partial melts of crustal host rocks. The assimilation processes are considered to be responsible for the increse in the K2O/Na2O, Ba/Sr and Rb/Sr ratios. This enrichment was associated with the relevant role of biotite breakdown in the assimilated host rock partial melts. The petrological model for the Ponte Nova massif is explained as repeated influxes of antecryst-laden basanite magmas that deposited most of their suspended crystals on the floor of the upper-crust magma chamber. Each intrusion is representative of relatively primitive olivine- and clinopyroxene-phyric basanites that had assimilated different degrees of partial melts of heterogeneous host rocks. This study reveals the relevant role of crustal assimilation processes in the magmatic evolution of nepheline-normative rocks, especially in upper-crust chamber environments.

Water in the Lunar Interior and the Apparent KREEP-Mare Dichotomy

NASA Astrophysics Data System (ADS)

McCubbin, F. M.; Nekvasil, H.

2010-12-01

Recent SIMS analysis of lunar apatite has shown that hydroxyl is structurally bound within lunar apatite from a number of different lunar lithologic types (McCubbin et al., 2010a, 2010b; Boyce et al., 2010; Greenwood et al., 2010). These studies along with previous SIMS analyses of lunar fire fountain glasses (Saal et al., 2008) confirm that there is at least some water in the lunar interior, with abundance estimates in magmatic source regions ranging from 64 ppb to 5 ppm water (McCubbin et al., 2010a). Surprisingly, apatite from rocks with KREEP-rich incompatible trace element signatures are depleted in hydroxyl in comparison to apatite from typical mare basalts. This result is counter-intuitive to the lunar magma ocean model, which predicts that incompatible constituents (e.g., water) would have been concentrated in the last dregs of liquid referred to as “urKREEP”. The mare basalts, which formed by partial melting of earlier LMO cumulates, are typically depleted in these incompatible constituents. Complicating the issue further, chlorine, another incompatible magmatic volatile element in apatite, follows the predicted trend with apatite from KREEP-rich rocks containing significant chlorine concentrations in comparison to apatite from mare basalts (McCubbin et al., 2009). The preceding results imply one of two scenarios 1) Water did not behave incompatibly during LMO crystallization and was preferentially stored within the LMO cumulate minerals 2) A secondary process such as degassing has perturbed the initial volatile contents of the urKREEP liquid or of the secondary magmas that have KREEP-rich incompatible trace element signatures. In regards to the first scenario, the mineral melt partition coefficients for water would need to have exceeded unity at the very low water concentrations of the LMO liquid. This scenario is consistent with the behavior of chlorine, as chlorine is not typically stored in nominally anhydrous phases like pyroxene or olivine, likely due to its large ionic radius. However, there is no empirical or experimental evidence to support the elevated D values for water. Regarding the second scenario, if significant degassing of the urKREEP liquid or KREEP-rich secondary magmas occurred, water would have certainly been lost preferentially to the other volatile constituents in apatite (fluorine and chlorine); however chlorine isotopes analyzed in lunar apatites are highly fractionated (Sharp et al., 2010), indicating degassing of chlorine in the absence of water. Therefore, this scenario only works if degassing on the Moon was a multi-stage and complex process where water and chlorine degassing are decoupled, which is not typically the case for terrestrial systems (Aiuppa et al., 2009, Webster and De Vivo, 2002; Webster et al., 1999). Solving this apparent KREEP-mare dichotomy regarding magmatic volatiles in the lunar interior is the next important step in figuring out the importance, relevance, and implications of water in the lunar interior. Moreover, it will lend insight into the roles of the other magmatic volatiles during the thermal and magmatic evolution of the Moon.

Thermodynamic Mixing Behavior Of F-OH Apatite Crystalline Solutions

NASA Astrophysics Data System (ADS)

Hovis, G. L.

2011-12-01

It is important to establish a thermodynamic data base for accessory minerals and mineral series that are useful in determining fluid composition during petrologic processes. As a starting point for apatite-system thermodynamics, Hovis and Harlov (2010, American Mineralogist 95, 946-952) reported enthalpies of mixing for a F-Cl apatite series. Harlov synthesized all such crystalline solutions at the GFZ-Potsdam using a slow-cooled molten-flux method. In order to expand thermodynamic characterization of the F-Cl-OH apatite system, a new study has been initiated along the F-OH apatite binary. Synthesis of this new series made use of National Institute of Standards and Technology (NIST) 2910a hydroxylapatite, a standard reference material made at NIST "by solution reaction of calcium hydroxide with phosphoric acid." Synthesis efforts at Lafayette College have been successful in producing fluorapatite through ion exchange between hydroxylapatite 2910a and fluorite. In these experiments, a thin layer of hydroxylapatite powder was placed on a polished CaF2 disc (obtained from a supplier of high-purity crystals for spectroscopy), pressed firmly against the disc, then annealed at 750 °C (1 bar) for three days. Longer annealing times did not produce further change in unit-cell dimensions of the resulting fluorapatite, but it is uncertain at this time whether this procedure produces a pure-F end member (chemical analyses to be performed in the near future). It is clear from the unit-cell dimensions, however, that the newly synthesized apatite contains a high percentage of fluorine, probably greater than 90 mol % F. Intermediate compositions for a F-OH apatite series were made by combining 2910a hydroxylapatite powder with the newly synthesized fluorapatite in various proportions, then conducting chemical homogenization experiments at 750 °C on each mixture. X-ray powder diffraction data indicated that these experiments were successful in producing chemically homogeneous intermediate series members, as doubled peaks merged into single diffraction maxima, the latter changing position systematically with bulk composition. All of the resulting F-OH apatite series members have hexagonal symmetry. The "a" unit-cell dimension behaves linearly with composition, and "c" is nearly constant across the series. Unit-cell volume also is linear with F:OH ratio, thus behaving in a thermodynamically ideal manner. Solution calorimetric experiments have been conducted in 20.0 wt % HCl at 50 °C on all series members. Enthalpies of F-OH mixing are nonexistent at F-rich compositions but have small negative values toward the hydroxylapatite end member. There is no enthalpy barrier, therefore, to complete F-OH mixing across the series, indicated as well by the ease of chemical homogenization for intermediate F:OH series members. In addition to the synthetic specimens described above, natural samples of hydroxylapatite, fluorapatite, and chlorapatite have been obtained for study from the U.S. National Museum of Natural History, as well as the American Museum of Natural History (our sincere appreciation to both museums for providing samples). Solution calorimetric results for these samples will be compared with data for the synthetic OH, F, and Cl apatite analogs noted above.

Cirrus properties deduced from CO2 lidar observations of zenith-enhanced backscatter from oriented crystals

NASA Technical Reports Server (NTRS)

Eberhard, Wynn L.

1993-01-01

Many lidar researchers have occasionally observed zenith-enhanced backscatter (ZEB) from middle and high clouds. The ZEB signature consists of strong backscatter when the lidar is pointed directly at zenith and a dramatic decline in backscatter as the zenith angle dips slightly off zenith. Mirror-like reflection from horizontal facets of oriented crystals (especially plates) is generally accepted as the cause. It was found during a 3-year observation program that approximately 50 percent of ice clouds had ZEB, regardless of cloud height. The orientation of crystals and the ZEB they cause are important to study and understand for several reasons. First, radiative transfer in clouds with oriented crystals is different than if the same particles were randomly oriented. Second, crystal growth depends partly on the orientation of the particles. Third, ZEB measurements may provide useful information about cirrus microphysical and radiative properties. Finally, the remarkable effect of ZEB on lidar signals should be understood in order to properly interpret lidar data.

Crystallographic control of surface structure on the sectoral zoning of iron in a diopside from Orford nickel mine (Quebec), Canada

NASA Astrophysics Data System (ADS)

Paquette, J.; Zangooi, A.; Thornton, K.

2004-05-01

The influence of surface structure on partitioning between mineral and melt (or solution) has been noted by other workers in a handful of minerals, including calcite, dolomite, apatite, topaz and diamond. Each one of these minerals displays at least one crystallographic face where steps present during crystal growth are not equivalent by symmetry. When this is the case, sectors grown at the edge of these steps commonly show differential incorporation of minor or trace elements. In the diopside investigated here, electron probe microanalyses performed on the as-grown (100) surface of several crystals show concentric and sectoral zoning defined by variations in Fe content. Atomic force microscopy (AFM) was used to study the surfaces of the three crystallographic forms present on the diopside crystals, with the goal of relating the compositional zoning to the surface structure of the faces. The dominant {100} faces are covered with growth hillocks consisting of four vicinal faces defined by steps parallel to [010] and [001]. The steps are often bunched into macrosteps and the resulting hillocks are visible optically. The steps along the two crystallographic directions show significant differences in straightness and smoothness that indicate non-equivalent kinetics. The wavier steps correspond to Fe-enriched areas within the {100} sectors. The {010} faces, next in morphological importance, are dominated by a single step orientation and show no differential incorporation. They display topography related to polysynthetic twinning. The {110} faces are much smaller and very few show resolvable steps. Sector zoning (i.e. diffential partitioning among non-equivalent crystallographic faces) has been described in the past from pyroxenes. Explanations have invoked either differences in surface structure among non-equivalent faces or their unequal growth rates. This particular occurrence indicates that trace element incorporation is, in fact, highly site-specific and that significant compositioinal zoning can be induced on a single face without invoking the effect of growth rate. The natural diopside crystals from the Orford nickel mine (Brompton, Quebec) show a unusual bladed habit flattened on {100} faces. Exceptional fluid chemistry during crystallization may therefore be required for the persistence of steps responsible for differential incorporation. Nevertheless, whenever this zoning is present, the trace element involved cannot be expected to reflect thermodynamic equilibrium between the solid and the fluid from which it crystallized.

Influence of heat treatments upon the mechanical properties and in vitro bioactivity of ZrO2-toughened MgO-CaO-SiO2-P2O5-CaF2 glass-ceramics.

PubMed

Li, Huan-Cai; Wang, Dian-Gang; Meng, Xiang-Guo; Chen, Chuan-Zhong

2014-09-01

Zirconia-toughened MgO-CaO-SiO2-P2O5-CaF2 glass-ceramics are prepared using sintering techniques, and a series of heat treatment procedures are designed to obtain a glass-ceramic with improved properties. The crystallization behavior, phase composition, and morphology of the glass-ceramics are characterized. The bending strength, elastic modulus, fracture toughness, and microhardness of the glass-ceramics are investigated, and the effect mechanism of heat treatments upon the mechanical properties is discussed. The bioactivity of glass-ceramics is then evaluated using the in vitro simulated body fluid (SBF) soaking test, and the mechanism whereby apatite forms on the glass-ceramic surfaces in the SBF solution is discussed. The results indicate that the main crystal phase of the G-24 sample undergoing two heat treatment procedures is Ca5(PO4)3F (fluorapatite), and those of the G-2444 sample undergoing four heat treatment procedures are Ca5(PO4)3F and β-CaSiO3 (β-wollastonite). The heat treatment procedures are found to greatly influence the mechanical properties of the glass-ceramic, and an apatite layer is induced on the glass-ceramic surface after soaking in the SBF solution.

The thickness of the crystal mush on the floor of the Bushveld magma chamber

NASA Astrophysics Data System (ADS)

Holness, Marian B.; Cawthorn, R. Grant; Roberts, James

2017-12-01

The thickness of the crystal mush on magma chamber floors can be constrained using the offset between the step-change in the median value of dihedral angles formed at the junctions between two grains of plagioclase and a grain of another phase (typically clinopyroxene, but also orthopyroxene and olivine) and the first appearance or disappearance of the liquidus phase associated with the step-change in median dihedral angle. We determined the mush thickness in the Rustenburg Layered Suite of the Bushveld Complex at clinopyroxene-in (in Lower Main Zone) and magnetite-in (in Upper Zone). We also examined an intermittent appearance of cumulus apatite in Upper Zone, using both the appearance and disappearance of cumulus apatite. In all cases, the mush thickness does not exceed 4 m. These values are consistent with field observations of a mechanically rigid mush at the bases of both magnetitite and chromitite layers overlying anorthosite. Mush thickness of the order of a few metres suggests that neither gravitationally-driven compaction nor compositional convection within the mush layer is likely to have been important processes during solidification: adcumulates in the Bushveld are most likely to have formed at the top of the mush during primary crystallisation. Similarly, it is unlikely either that migration of reactive liquids occurs through large stretches of stratigraphy, or that layering is formed by mechanisms other than primary accumulation.

Fourier transform infrared spectroscopy for analysis of kidney stones.

PubMed

Khan, Aysha Habib; Imran, Sheharbano; Talati, Jamsheer; Jafri, Lena

2018-01-01

To compare the results of a chemical method of kidney stone analysis with the results of Fourier transform infrared (FT-IR) spectroscopy. Kidney stones collected between June and October 2015 were simultaneously analyzed by chemical and FT-IR methods. Kidney stones (n=449) were collected from patients from 1 to 81 years old. Most stones were from adults, with only 11.5% from children (aged 3-16 years) and 1.5% from children aged <2 years. The male to female ratio was 4.6. In adults, the calcium oxalate stone type, calcium oxalate monohydrate (COM, n=224), was the most common crystal, followed by uric acid and calcium oxalate dihydrate (COD, n=83). In children, the most frequently occurring type was predominantly COD (n=21), followed by COM (n=11), ammonium urate (n=10), carbonate apatite (n=6), uric acid (n=4), and cystine (n=1). Core composition in 22 stones showed ammonium urate (n=2), COM (n=2), and carbonate apatite (n=1) in five stones, while uric acid crystals were detected (n=13) by FT-IR. While chemical analysis identified 3 stones as uric acid and the rest as calcium oxalate only. Agreement between the two methods was moderate, with a kappa statistic of 0.57 (95% confidence interval, 0.5-0.64). Disagreement was noted in the analysis of 77 stones. FT-IR analysis of kidney stones can overcome many limitations associated with chemical analysis.

Micro-Raman spectroscopy shows how the coating process affects the characteristics of hydroxylapatite.

PubMed

Saber-Samandari, Saeed; Alamara, Kadhim; Saber-Samandari, Samaneh; Gross, Karlis A

2013-12-01

The diversity in the structural and chemical state of apatites allows implant manufacturers to fine-tune implant properties. This requires suitable manufacturing processes and characterization tools to adjust the amorphous phase and hydroxyl content from the source hydroxylapatite. Hydroxylapatite was processed by high-velocity oxy-fuel spraying, plasma spraying and flame spraying, and primarily analyzed by Raman spectroscopy. Investigation of rounded splats, the building blocks of thermal spray coatings, allowed correlation between the visual identity of the splat surface and the Raman spectra. Splats were heat-treated to crystallize any remaining amorphous phase. The ν1 PO4 stretching peak at 950-970 cm(-1) displayed the crystalline order, but the hydroxyl peak at 3572 cm(-1) followed the degree of dehydroxylation. Hydroxyl loss was greatest for flame-sprayed particles, which create the longest residence time for the melted particle. Higher-frequency hydroxyl peaks in flame- and plasma-sprayed splats indicated a lower structural order for the recrystallized hydroxylapatite within the splats. Crystallization at 700 °C has shown potential for revealing hydroxyl ions previously trapped in amorphous calcium phosphate. This work compares Fourier transform infrared and Raman spectroscopy to measure the hydroxyl content in rapidly solidified apatites and shows that Raman spectroscopy is more suitable. Copyright © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

On the synthesis of tailored biomimetic hydroxyapatite nanoplates through a bioinspired approach in the presence of collagen or chitosan and L-arginine.

PubMed

Tsetsekou, A; Brasinika, D; Vaou, V; Chatzitheodoridis, E

2014-10-01

Controlling the structure of hydroxyapatite nanocrystals is vital for acquiring a consistent product. In an effort to synthesize crystals mimicking the morphology of natural bone's apatite, a bioinspired process was developed based on the use of a natural biomacromolecule, collagen or chitosan, in conjunction with l-arginine to direct the formation of hydroxyapatite from H3PO4 and Ca(OH)2. Different cases were investigated by employing various concentrations of the precursors and two molar ratios of Ca/P 1/1 and 10/6. The reaction was carried out at basic pH conditions and at biomimetic temperature (40°C). The resulting aqueous suspensions were characterized in terms of their rheological behavior, whereas the derived powders were fully evaluated by transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction analysis and Raman spectroscopy. The analysis showed that in all cases, the only phase detected was hydroxyapatite of a plate-like morphology very similar to that of natural apatite. The homogeneity of the morphology and the crystal size distribution depend on the precursors' final concentration with the mean size ranging from 5 nm up to 20 nm. The powder that demonstrated the best characteristics in terms of homogeneity was that produced in the presence of collagen for molar ratio of Ca/P 1/1. Copyright © 2014 Elsevier B.V. All rights reserved.

Crystallization Dynamics of Organolead Halide Perovskite by Real-Time X-ray Diffraction.

PubMed

Miyadera, Tetsuhiko; Shibata, Yosei; Koganezawa, Tomoyuki; Murakami, Takurou N; Sugita, Takeshi; Tanigaki, Nobutaka; Chikamatsu, Masayuki

2015-08-12

We analyzed the crystallization process of the CH3NH3PbI3 perovskite by observing real-time X-ray diffraction immediately after combining a PbI2 thin film with a CH3NH3I solution. A detailed analysis of the transformation kinetics demonstrated the fractal diffusion of the CH3NH3I solution into the PbI2 film. Moreover, the perovskite crystal was found to be initially oriented based on the PbI2 crystal orientation but to gradually transition to a random orientation. The fluctuating characteristics of the crystallization process of perovskites, such as fractal penetration and orientational transformation, should be controlled to allow the fabrication of high-quality perovskite crystals. The characteristic reaction dynamics observed in this study should assist in establishing reproducible fabrication processes for perovskite solar cells.

The influence of orientation on the stress rupture properties of nickel-base superalloy single crystals

NASA Technical Reports Server (NTRS)

Mackay, R. A.; Maier, R. D.

1982-01-01

Constant load creep rupture tests were performed on MAR-M247 single crystals at 724 MPa and 774 C where the effect of anisotropy is prominent. The initial orientations of the specimens as well as the final orientations of selected crystals after stress rupture testing were determined by the Laue back-reflection X-ray technique. The stress rupture lives of the MAR-M247 single crystals were found to be largely determined by the lattice rotations required to produce intersecting slip, because second-stage creep does not begin until after the onset of intersecting slip. Crystals which required large rotations to become oriented for intersecting slip exhibited the shortest stress rupture lives, whereas crystals requiring little or no rotations exhibited the lowest minimum creep rates, and consequently, the longest stress rupture lives.

Investigation of ferroelectric liquid crystal orientation in the silica microcapillaries

NASA Astrophysics Data System (ADS)

Budaszewski, D.; Domański, A. W.; Woliński, T. R.

2013-05-01

In the paper we present our recent results concerning the orientation of ferroelectric liquid crystal molecules inside silica micro capillaries. We have infiltrated the silica micro capillaries with experimental ferroelectric liquid crystal material W-260K synthesized in the Military University of Technology. The infiltrated micro capillaries were observed under the polarization microscope while both a polarizer and an analyzer were crossed. The studies on the orientation of ferroelectric liquid crystal molecules may contribute to further studies on behavior of this group of liquid crystal materials inside photonic crystal fiber. The obtained results may lead to design of a new type of fast optical fiber sensors.

Tectono-magmatic evolution of the Chihuahua-Sinaloa border region in northern Mexico: Insights from zircon-apatite U-Pb geochronology, zircon Hf isotope composition and geochemistry of granodiorite intrusions

NASA Astrophysics Data System (ADS)

Mahar, Munazzam Ali; Goodell, Philip C.; Feinstein, Michael Nicholas

2016-11-01

We present the whole-rock geochemistry, LA-ICP-MS zircon-apatite U-Pb ages and zircon Hf isotope composition of the granodioritic plutons at the southwestern boundary of Chihuahua with the states of Sinaloa and Sonora. These granodiorites are exposed in the north and south of the Rio El Fuerte in southwest Chihuahua and northern Sinaloa. The magmatism spans over a time period of 37 Ma from 90 to 53 Ma. Zircons are exclusively magmatic with strong oscillatory zoning. No inheritance of any age has been observed. Our new U-Pb dating ( 250 analyses) does not support the involvement of older basement lithologies in the generation of the granitic magmas. The U-Pb apatite ages from granodiorites in southwest Chihuahua vary from 52 to 70 Ma. These apatite ages are 1 to 20 Ma younger than the corresponding zircon U-Pb crystallization ages, suggesting variable cooling rates from very fast to 15 °C/Ma ( 800 °C to 500 °C) and shallow to moderate emplacement depths. In contrast, U-Pb apatite ages from the Sinaloa batholith are restricted from 64 to 61 Ma and are indistinguishable from the zircon U-Pb ages range from 67 to 60 Ma within the error, indicating rapid cooling and very shallow emplacement. However, one sample from El Realito showed a larger difference of 20 Ma in zircon-apatite age pair: zircon 80 ± 0.8 Ma and apatite 60.6 ± 4 Ma, suggesting a slower cooling rate of 15 °C/Ma. The weighted mean initial εHf (t) isotope composition (2σ) of granodiorites varies from + 1.8 to + 5.2. The radiogenic Hf isotope composition coupled with previous Sr-Nd isotope data demonstrates a significant shift from multiple crustal sources in the Sonoran batholithic belt to the predominant contribution of the mantle-derived magmas in the southwest Chihuahua and northern Sinaloa. Based on U-Pb ages, the absence of inheritance, typical high Th/U ratio and radiogenic Hf isotope composition, we suggest that the Late Cretaceous-Paleogene magmatic rocks in this region are not derived from melting of a felsic older crust, neither evolved North American Proterozoic basement nor Jurassic metasedimentary rocks of the Guerrero terrane. Instead, the magma was primarily derived from partial melting of mantle related sources, possibly in the subcontinental mantle wedge above the Farallon plate. Our younger U-Pb zircon-apatite ages are well correlated with the late-stage cogenetic porphyry Cu-Au mineralization at 57 to 59 Ma. If the origin of ore mineralization is related to the magma sources of host batholiths, then a minimal input from crustal melt is suggested in the genesis of Cu-Au porphyry system.

Orientation control of barium titanate films using metal oxide nanosheet layer

NASA Astrophysics Data System (ADS)

Uchida, Hiroshi; Oi, Tomotake; Noguchi, Keito; Moki, Shota; Kim, Jin Woon; Shima, Hiromi; Nishida, Ken; Kiguchi, Takanori; Akama, Akihiko; Konno, Toyohiko J.; Funakubo, Hiroshi

2016-10-01

In the present work, we aim to achieve the preferred crystal orientation of chemical solution deposition (CSD)-derived BaTiO3 films on ubiquitous Si wafers with the assistance of Ca2Nb3O10 nanosheet (ns-CN) template layers. The ns-CN on platinized Si (Pt/Si) substrates aligned the BaTiO3(100) plane to the substrate surface, because of the favorable lattice matching of the ns-CN (001) plane. The CSD process in air required a high crystallization temperature of 900 °C for the preferred crystal orientation of BaTiO3(100) because of the BaCO3 byproduct generated during the combustion reaction of the precursor gel. The processing in vacuum to remove CO2 species enhanced the crystal orientation even at the crystallization temperature of 800 °C, although it can generate oxygen vacancies (\\text{V}\\text{O}{} \\bullet \\bullet ) that cause distorted polarization behavior under an applied field higher than approximately 150 kV/cm. The relative dielectric constant (εr) of the (100)-oriented BaTiO3 film on the ns-CN-supported Pt/Si substrate (ns-CN/Pt/Si) was generally larger than that of the randomly oriented film on Pt/Si, depending on the degree of crystal orientation.

Magnetically-assembled micro/mesopixels exhibiting light intensity enhancement in the (012) planes of fish guanine crystals

NASA Astrophysics Data System (ADS)

Chikashige, T.; Iwasaka, M.

2018-05-01

In this study, a new method was investigated to form light-reflecting dots at the micrometer scale using the magnetic orientations of biogenic guanine crystals obtained from fish skin and scales. The crystal platelets, possessing average dimensions of 5 μm×20 μm×100 nm, were dispersed in water and observed during exposure to vertical magnetic fields up to 5 T. The magnetic field direction was parallel to Earth's gravity, and allowed the narrowest edges of the crystals to be observed at the micrometer scale for the first time. The magnetic orientation process was initiated under conditions where the crystal platelets in water were laid on a glass substrate or where the platelets had random orientations. In the former case, the crystal platelets followed a two-stage magnetic orientation process where, in the first step, the platelet widths were aligned in the magnetic field direction. The second step required rotation of the ˜20-μm-long plates with respect to the Earth's gravity, where application of a 5 T magnetic field enabled their orientation. Real-time images of the magnetically aligning platelets provided new evidence that the crystal platelets also emitted reflected light from a very narrow window at two crystal planes (i.e., (0 1 ¯ 2 ¯ ) and (0 1 ¯ 2 )). In the latter case with random platelet orientation, spatially-condensed light-reflecting dots appeared while the guanine crystal platelets were floating and maintaining their orientation. The technique developed for controlling light-reflecting microscale objects in an aqueous medium can be applied to produce a type of microfluidic optical tool.

Micromechanical models for the stiffness and strength of UHMWPE macrofibrils

NASA Astrophysics Data System (ADS)

Dong, Hai; Wang, Zheliang; O'Connor, Thomas C.; Azoug, Aurelie; Robbins, Mark O.; Nguyen, Thao D.

2018-07-01

Ultrahigh molecular weight polyethylene (UHMWPE) fibers have a complex hierarchical structure that at the micron-scale is composed of oriented chain crystals, lamellar crystals, and amorphous domains organized into macrofibrils. We developed a computational micromechanical modeling study of the effects of the morphological structure and constituent material properties on the deformation mechanisms, stiffness and strength of the UHMWPE macrofibrils. Specifically, we developed four representative volume elements, which differed in the arrangement and orientation of the lamellar crystals, to describe the various macrofibrillar microstructures observed in recent experiments. The stiffness and strength of the crystals were determined from molecular dynamic simulations of a pure PE crystal. A finite deformation crystal plasticity model was used to describe the crystals and an isotropic viscoplastic model was used for the amorphous phase. The results show that yielding in UHMWPE macrofibrils under axial tension is dominated by the slip in the oriented crystals, while yielding under transverse compression and shear is dominated by slips in both the oriented and lamellar crystals. The results also show that the axial modulus and strength are mainly determined by the volume fraction of the oriented crystals and are insensitive to the arrangements of the lamellar crystals when the modulus of the amorphous phase is significantly smaller than that of the crystals. In contrast, the arrangement and size of the lamellar crystals have a significant effect on the stiffness and strength under transverse compression and shear. These findings can provide a guide for new materials and processing design to improve the properties of UHMWPE fibers by controlling the macrofibrillar morphologies.

Adsorption and conformational modification of fibronectin and fibrinogen adsorbed on hydroxyapatite. A QCM-D study.

PubMed

Fernández-Montes Moraleda, Belén; San Román, Julio; Rodríguez-Lorenzo, Luís M

2016-10-01

Hydroxyapatite is a bioactive ceramic frequently used for bone engineering/replacement. One of the parameters that influence the biological response to implanted materials is the conformation of the first adsorbed protein layer. In this work, the adsorption and conformational changes of two fibroid serum proteins; fibronectin and fibrinogen adsorbed onto four different hydroxyapatite powders are studied with a Quartz Crystal Microbalance with Dissipation (QCM-D). Each of the calcined apatites adsorbs less protein than their corresponding synthesized samples. Adsorption on synthesized samples yields always an extended conformation whereas a reorganization of the layer is observed for the calcined samples. Fg acquires a "Side on" conformation in all the samples at the beginning of the experiment except for one of the synthesized samples where an "End-on" conformation is obtained during the whole experiment. The Extended conformation is the active conformation for Fn. This conformation is favored by apatites with large specific surface area (SSA) and on highly concentrated media. Apatite surface features should be considered in the selection or design of materials for bone regeneration, since it is possible to control the conformation mode of attachment of Fn and Fg by an appropriate selection of them. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 104A: 2585-2594, 2016. © 2016 Wiley Periodicals, Inc.

Fluorapatite crystal growth from modified seawater solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Van Cappellen, P.; Berner, R.A.

Seeded precipitation experiments were conducted in a pH/fluoride-stat system to study the crystal growth of fluorapatite (FAP) in carbonate-free NaCl-CaCl{sub 2}-NaF-Na{sub 2}HPO{sub 4} solutions, at seawater calcium concentration, chlorinity, and pH. With increasing supersaturation, the dependence of the growth rate on the relative supersaturation changes from parabolic to exponential. This is interpreted as reflecting a transition in the crystal growth mechanism from growth at dislocation-induced surface steps to surface nucleation-controlled growth. The analysis of the kinetic data leads to a mineral-aqueous solution interfacial tension for FAP of 289 mJ/M{sup 2}. The Arrhenius activation energy of the growth reaction in themore » temperature range 12 to 35C is 47 kJ/mol. The effect of pH on FAP growth was tested for pH values from 7 to 8.5. In this range, growth of FAP is catalyzed by hydrogen ions. The apparent growth rate constant is proportional to (a{sub H{sup +}}){sup m} where m, the rate order with respect to H{sup +}, is a non-integral number which depends on pH. At identical degrees of supersaturation, the growth rate of FAP at pH = 7 is nearly twice that at pH = 8. When corrected for bottom water temperatures, pore water pH, and the retardation of Mg{sup 2+}, the experimental growth rates predict that during burial in modern phosphatic sediments, apatite particles grow to sizes on the order of 0.1-10{mu}m. The relatively slow growth kinetics of FAP are consistent with the observed small particle sizes of marine sedimentary apatite.« less

Effect of process parameters and crystal orientation on 3D anisotropic stress during CZ and FZ growth of silicon

NASA Astrophysics Data System (ADS)

Drikis, Ivars; Plate, Matiss; Sennikovs, Juris; Virbulis, Janis

2017-09-01

Simulations of 3D anisotropic stress are carried out in <100> and <111> oriented Si crystals grown by FZ and CZ processes for different diameters, growth rates and process stages. Temperature dependent elastic constants and thermal expansion coefficients are used in the FE simulations. The von Mises stress at the triple point line is 5-11% higher in <111> crystals compared to <100> crystals. The process parameters have a larger effect on the von Mises stress than the crystal orientation. Generally, the <111> crystal has a higher azimuthal variation of stress along the triple point line ( 8%) than the <100> crystal ( 2%). The presence of a crystal ridge increases the stress beside the ridge and decreases it on the ridge compared with the round crystal.

Three-dimensional analysis of dislocation multiplication during thermal process of grown silicon with different orientations

NASA Astrophysics Data System (ADS)

Gao, B.; Nakano, S.; Harada, H.; Miyamura, Y.; Kakimoto, K.

2017-09-01

We used an advanced 3D model to study the effect of crystal orientation on the dislocation multiplication in single-crystal silicon under accurate control of the cooling history of temperature. The incorporation of the anisotropy effect of the crystal lattice into the model has been explained in detail, and an algorithm for accurate control of the temperature in the furnace has also been presented. This solver can dynamically track the history of dislocation generation for different orientations during thermal processing of single-crystal silicon. Four orientations, [001], [110], [111], and [112], have been examined, and the comparison of dislocation distributions has been provided.

Advances in Laser Microprobe (U-Th)/He Geochronology

NASA Astrophysics Data System (ADS)

van Soest, M. C.; Monteleone, B. D.; Boyce, J. W.; Hodges, K. V.

2008-12-01

The development of the laser microprobe (U-Th)/He dating method has the potential to overcome many of the limitations that affect conventional (U-Th)/He geochronology. Conventional single- or multi-crystal (U- Th)/He geochronology requires the use of pristine, inclusion-free, euhedral crystals. Furthermore, the ages that are obtained require corrections for the effects of zoning and alpha ejection based on an ensemble of assumptions before interpretation of their geological relevance is possible. With the utilization of microbeam techniques many of the limitations of conventional (U-Th)/He geochronology can either be eliminated by careful spot selection or accounted for by detailed depth profiling analyses of He, U and Th on the same crystal. Combined He, Th, and U depth profiling on the same crystal potentially even offers the ability to extract thermal histories from the analyzed grains. Boyce et al. (2006) first demonstrated the laser microprobe (U-Th)/He dating technique by successfully dating monazite crystals using UV laser ablation to liberate He and determined U and Th concentrations using a Cameca SX-Ultrachron microprobe. At Arizona State University, further development of the microprobe (U-Th)/He dating technique continues using an ArF Excimer laser connected to a GVI Helix Split Flight Tube noble gas mass spectrometer for He analysis and SIMS techniques for U and Th. The Durango apatite age standard has been successfully dated at 30.7 +/- 1.7 Ma (2SD). Work on dating zircons by laser ablation is currently underway, with initial results from Sri Lanka zircon at 437 +/- 14 Ma (2SD) confirmed by conventional (U-Th)/He analysis and in agreement with the published (U-Th)/He age of 443 +/- 9 Ma (2SD) for zircons from this region in Sri Lanka (Nasdala et al., 2004). The results presented here demonstrate the laser microprobe (U-Th)/He method as a powerful tool that allows application of (U- Th)/He dating to areas of research such as detrital apatite and zircon dating, where conventional (U-Th)/He geochronology has limited applicability. Boyce et al. (2006) GCA 70 (3031-3039), Nasdala et al. (2004) Am. Min. 89 (219-231)

Immediate erosive potential of cola drinks and orange juices.

PubMed

Jensdottir, T; Holbrook, P; Nauntofte, B; Buchwald, C; Bardow, A

2006-03-01

Little is known about the erosive potential of soft drinks within the first minutes of exposure to teeth, and about the potentially protective role of salivary proteins. We hypothesized that the erosive potential is determined primarily by pH and decreases in the presence of salivary proteins. To investigate this, we first added uncoated hydroxyapatite crystals and, second, salivary-protein-coated hydroxyapatite crystals to 20 commercially available cola drinks and orange juices simultaneously, with pH recordings every 15 sec for 3 min. The amount of apatite lost per liter of soft drink per sec was calculated from titratable acidity values to each pH obtained by crystal addition. The erosive potential within the first minutes of exposure was determined solely by the pH of the drink, and the erosive potential was ten-fold higher in cola drinks compared with juices. However, salivary proteins reduced the erosive potential of cola drinks by up to 50%.

Amelogenin Affects Brushite Crystal Morphology and Promotes Its Phase Transformation to Monetite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ren, Dongni; Ruan, Qichao; Tao, Jinhui

2016-09-07

Amelogenin protein is involved in organized apatite crystallization during enamel formation. Brushite (CaHPO4·2H2O), which is one of the precursors for hydroxyapatite in in vitro mineralization, has been used for fabrication of biomaterials for hard tissue repair. In order to explore its potential application in biomimetic material synthesis, we studied the influence of amelogenin on brushite morphology and phase transformation to monetite. Our results show that amelogenin can adsorb onto surface of brushite, leading to the formation of layered structures on the (010) face. Amelogenin promoted the phase transformation of brushite into monetite (CaHPO4) in the dry state, presumably by interactingmore » with crystalline water layers in brushite unit cell. Changes to the crystal morphology by amelogenin continued even after the phase transformation to monetite forming an organized nanotextured structure of nano-sticks resembling the bundle structure in enamel.« less

Tricalcium phosphate-Fluorapatite as bone tissue engineering: Evaluation of bioactivity and biocompatibility.

PubMed

Taktak, Rym; Elghazel, Achwek; Bouaziz, Jamel; Charfi, Slim; Keskes, Hassib

2018-05-01

Biocomposites consisting of β Tricalcium phosphate (β-TCP) with 26.52% Fluorapatite (Fap) were elaborated and characterized in order to evaluate it potential application in bone graft substitute. Bioactivity was determined with in vitro tests by immersion of samples in simulated fluid body for several periods of times. The SEM, EDS and Atomic Absorption Spectroscopy showed the deposition of apatite layer on the surface of samples showing a good bioactivity. However, after 6days of soaking, the dissolution rate of Ca 2+ and PO 4 3- decreased which due probably to the improvement of crystallization of the apatite layer. These findings agree with those observed after 6weeks postimplantation of prepared macroporous scaffolds in rabbits. All histological observations of the preliminary in vivo study in the tibia of rabbits proved the biocompatibility and the resorption of the investigated bioceramic. In contrast, the implantation period will have to be optimized by further extensive animal experiments. Copyright © 2017 Elsevier B.V. All rights reserved.

Ptychographic X-ray nanotomography quantifies mineral distributions in human dentine

NASA Astrophysics Data System (ADS)

Zanette, I.; Enders, B.; Dierolf, M.; Thibault, P.; Gradl, R.; Diaz, A.; Guizar-Sicairos, M.; Menzel, A.; Pfeiffer, F.; Zaslansky, P.

2015-03-01

Bones are bio-composites with biologically tunable mechanical properties, where a polymer matrix of nanofibrillar collagen is reinforced by apatite mineral crystals. Some bones, such as antler, form and change rapidly, while other bone tissues, such as human tooth dentine, develop slowly and maintain constant composition and architecture for entire lifetimes. When studying apatite mineral microarchitecture, mineral distributions or mineralization activity of bone-forming cells, representative samples of tissue are best studied at submicrometre resolution while minimizing sample-preparation damage. Here, we demonstrate the power of ptychographic X-ray tomography to map variations in the mineral content distribution in three dimensions and at the nanometre scale. Using this non-destructive method, we observe nanostructures surrounding hollow tracts that exist in human dentine forming dentinal tubules. We reveal unprecedented quantitative details of the ultrastructure clearly revealing the spatially varying mineralization density. Such information is essential for understanding a variety of natural and therapeutic effects for example in bone tissue healing and ageing.

Roles of bond orientational ordering in glass transition and crystallization.

PubMed

Tanaka, Hajime

2011-07-20

It is widely believed that crystallization in three dimensions is primarily controlled by positional ordering, and not by bond orientational ordering. In other words, bond orientational ordering is usually considered to be merely a consequence of positional ordering and thus has often been ignored. This one-order-parameter (density) description may be reasonable when we consider an equilibrium liquid-solid transition, but may not be enough to describe a metastable state and the kinetics of the transition. Here we propose that bond orientational ordering can play a key role in (i) crystallization, (ii) the ordering to quasi-crystal and (iii) vitrification, which occurs under rather weak frustration against crystallization. In a metastable supercooled state before crystallization, a system generally tends to have bond orientational order at least locally as a result of a constraint of dense packing. For a system interacting with hard-core repulsions, the constraint is intrinsically of geometrical origin and thus the basic physics is the same as nematic ordering of rod-like particles upon densification. Furthermore, positional ordering is easily destroyed even by weak frustration such as polydispersity and anisotropic interactions which favour a symmetry not consistent with that of the equilibrium crystal. Thus we may say that vitrification can be achieved by disturbing and prohibiting long-range positional ordering. Even in such a situation, bond orientational ordering still survives, accompanying its critical-like fluctuations, which are the origin of dynamic heterogeneity for this case. This scenario naturally explains both the absence of positional order and the development of bond orientational order upon cooling in a supercooled state. Although our argument is speculative in nature, we emphasize that this physical picture can coherently explain crystallization, vitrification, quasi-crystallization and their relationship in a natural manner. For a strongly frustrated system, even bond orientational order can be destroyed. Even in such a case there may still appear a structural signature of dense packing, which is linked to slow dynamics.

Second harmonic generation in photonic crystal cavities in (111)-oriented GaAs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Buckley, Sonia, E-mail: bucklesm@stanford.edu; Radulaski, Marina; Vučković, Jelena

2013-11-18

We demonstrate second harmonic generation at telecommunications wavelengths in photonic crystal cavities in (111)-oriented GaAs. We fabricate 30 photonic crystal structures in both (111)- and (100)-oriented GaAs and observe an increase in generated second harmonic power in the (111) orientation, with the mean power increased by a factor of 3, although there is a large scatter in the measured values. We discuss possible reasons for this increase, in particular, the reduced two photon absorption for transverse electric modes in (111) orientation, as well as a potential increase due to improved mode overlap.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Yanyan

This thesis describes application and development of advanced solid-state nuclear magnetic resonance techniques for complex materials, in particular organic-inorganic nanocomposites and thermoelectric tellurides. The apatite-collagen interface, essential for understanding the biomineralization process in bone and engineering the interface for controlled bio-mimetic synthesis and optimized mechanical properties, is buried within the nanocomposite of bone. We used multinuclear solid-state NMR to study the composition and structure of the interface. Citrate has been identified as the main organic molecule strongly bound to the apatite surface with a density of 1/(2 nm) 2, covering 1/6 of the total surface area in bovine bone. Citratemore » provides more carboxylate groups, one of the key functional groups found to affect apatite nucleation and growth, than all the non-collagenous proteins all together in bone; thus we propose that citrate stabilizes apatite crystals at a very small thickness of ~3 nm (4 unit cells) to increase bone fracture tolerance. The hypothesis has been confirmed in vitro by adding citrate in the bio-mimetic synthesis of polymerhydroxyapatite nanocomposites. The results have shown that the size of hydroxyapatite nanocrystals decreases as increasing citrate concentration. With citrate concentrations comparable to that in body fluids, similar-sized nanocrystals as in bone have been produced. Besides the dimensions of the apatite crystals, the composition of bone also affects its biofunctional and macroscopic mechanical properties; therefore, our team also extended its effort to enhance the inorganic portion in our bio-mimetic synthesis from originally 15 wt% to current 50 wt% compared to 65 wt% in bovine bone, by using Lysine-Leucine hydroxyapatite nucleating diblock co-polypeptide, which forms a gel at very low concentration. In this thesis, various advanced solid state NMR techniques have been employed to characterize nanocomposites. Meanwhile, we have developed new methods to achieve broadband high resolution NMR and improve the accuracy of inter-nuclear distance measurements involving quadrupolar spins. Broadband high resolution NMR of spin-1/2 nuclei has been accomplished by the adaptation of the magic angle turning (MAT) method to fast magic angle spinning, termed fast MAT, by solving technical problems such as off resonance effects. Fast MAT separates chemical shift anisotropy and isotropic chemical shifts over a spectral range of ~1.8 γB 1 without significant distortions. Fast MAT 125Te NMR has been applied to study technologically important telluride materials with spectra spreading up to 190 kHz. The signal-to-noise ratio of the spectra is significantly improved by using echo-matched Gaussian filtering in offline data processing. The accuracy of the measured distances between spin-1/2 and quadrupolar nuclei with methods such as SPIDER and REAPDOR has been improved by compensating for the fast longitudinal quadrupolar relaxation on the sub-millisecond with a modified S 0 pulse sequence. Also, the T1Q effect on the spin coherence and its spinning speed dependency has been explored and documented with analytical and numerical simulations as well as experimental measurements.« less

Nanocrystalline hydroxyapatite doped with selenium oxyanions: a new material for potential biomedical applications.

PubMed

Kolmas, Joanna; Oledzka, Ewa; Sobczak, Marcin; Nałęcz-Jawecki, Grzegorz

2014-06-01

Selenium-substituted hydroxyapatites containing selenate SeO4(2-) or selenite SeO3(2-) ions were synthesized using a wet precipitation method. The selenium content was determined by atomic absorbance spectrometry. The raw, unsintered powders were also characterized using powder X-ray diffraction, middle-range FT-IR spectroscopy and transmission electron microscopy with energy-dispersive X-ray spectroscopic microanalysis. The synthesized apatites were found to be pure and nanocrystalline with a crystal size similar to that in bone mineral. The incorporation of selenium oxyanions into the crystal lattice was confirmed. The toxicity of hydroxyapatites containing selenite or selenate ions was evaluated with a protozoan assay and bacterial luminescence test. Copyright © 2014 Elsevier B.V. All rights reserved.

Orientation dependence of the stress rupture properties of Nickel-base superalloy single crystals

NASA Technical Reports Server (NTRS)

Mackay, R. A.

1981-01-01

The influence of orientation of the stress rupture behavior of Mar-M247 single crystals was studied. Stress rupture tests were performed at 724 MPa and 774 C where the effect of anisotropy is prominent. The mechanical behavior of the single crystals was rationalized on the basis of the Schmid factors for the operative slip systems and the lattice rotations which the crystals underwent during deformation. The stress rupture lives were found to be greatly influenced by the lattice rotations required to produce intersecting slip, because steady-state creep does not begin until after the onset of intersecting slip. Crystals which required large rotations to become oriented for intersecting slip exhibited a large primary creep strain, a large effective stress level at the onset of steady-state creep, and consequently a short stress rupture life. A unified analysis was attained for the stress rupture behavior of the Mar-M247 single crystals tested in this study at 774 C and that of the Mar-M200 single crystals tested in a prior study at 760 C. In this analysis, the standard 001-011-111 stereographic triangle was divided into several regions of crystallographic orientation which were rank ordered according to stress rupture life for this temperature regime. This plot indicates that those crystals having orientations within about 25 deg of the 001 exhibited significantly longer lives when their orientations were closer to the 001-011 boundary of the stereographic triangle than to the 001-111 boundary.

Orientation and Temperature Dependence of Work-Hardening Rate in Cd Single Crystals

NASA Astrophysics Data System (ADS)

Uçar, N.

1997-03-01

The orientation and temperature dependence of the work-hardening rate (WHR) has been investigated in tension in the temperature range from room temperature to 500 K in Cd single crystals. The WHR was found to decrease rapidly with increasing temperature. For 21-1-3 orientated crystals, the WHR increases firstly with increasing temperature until it passes a maximum at about 350 K.

Geochemical studies of abyssal lavas recovered by DSRV Alvin from Eastern Galapagos Rift, Inca Transform, and Ecuador Rift: 2. Phase chemistry and crystallization history

NASA Astrophysics Data System (ADS)

Perfit, Michael R.; Fornari, Daniel J.

1983-12-01

A diverse suite of lavas recovered by DSRV Alvin from the eastern Galapagos rift and Inca transform includes mid-ocean ridge tholeiitic basalts (MORB), iron- and titanium-enriched basalts (FeTi basalts), and abyssal andesites. Rock types transitional in character (ferrobasalts and basaltic andesites) were also recovered. The most mafic glassy basalts contain plagioclase, augite, and olivine as near-liquidus phases, whereas in more fractionated basalts, pigeonite replaces olivine and iron-titanium oxides crystallize. Plagioclase crystallizes after pyroxenes and iron-titanium oxides in andesites, possibly due to increased water contents or cooling rates. Apatite phenocrysts are present in some andesitic glasses. Ovoid sulfide globules are also common in many lavas. Compositional variations of phenocrysts in glassy lavas reflect changes in magma chemistry, temperature of crystallization, and cooling rate. The overall chemical variations parallel the chemical evolution of the lava suite and are similar to those in other fractionated tholeiitic complexes. Elemental partitioning between plagioclase-, pyroxene-, and olivine-glass pairs suggests that equilibration occurred at low pressure in a rather restricted temperature range. Various geothermometers indicate that the most primitive MORB began to crystallize between 1150° and 1200°C with fo2 < 10-7 atm. Coexisting iron-titanium oxides in more evolved lavas yield temperatures ˜1025°C to as low as 910°C withfo2 from 10-8 to 10-12 atm. PH 2 o could have been as high as 1 kbar during andesite crystallization. Compositions of the lavas from the Galapagos rift follow the experimentally determined (1 atm-QFM) liquid line of descent. Least squares calculations for the major elements indicate that the entire suite of lavas can be produced by fractional crystallization of successive residual liquids from a MORB parent magma. FeTi basalts represent 30-65 cumulative weight percent crystallization of plagioclase, augite, and olivine. An additional 30-50% fractionation of pyroxenes, plagioclase, titanomagnetite, and possible apatite is required to generate andesite from FeTi basalt liquids. The presence of partially resorbed mafic xenocrysts in some andesites, FeTi basalt inclusions in these xenocrysts, high-silica glass inclusions in basaltic andesites, and the transitional chemistry of basaltic andesites are evidence that some magma mixing occurred during crystal fractionation. The diversity of lava types recovered at single dive sites suggests that low-pressure fractional crystallization is a very efficient process beneath the eastern Galapagos rift and that isolated magma bodies must be present at shallow levels beneath the accretionary locus. Voluminous FeTi basalts erupted at the rift-transform intersection are genetically related to the rift lavas, but their restricted chemistry reflects different thermal and tectonic controls on their petrogenesis.

Electromigration and Thermomechanical Fatigue Behavior of Sn0.3Ag0.7Cu Solder Joints

NASA Astrophysics Data System (ADS)

Zuo, Yong; Bieler, Thomas R.; Zhou, Quan; Ma, Limin; Guo, Fu

2017-12-01

The anisotropy of Sn crystal structures greatly affects the electromigration (EM) and thermomechanical fatigue (TMF) of solder joints. The size of solder joint shrinkage in electronic systems further makes EM and TMF an inseparably coupled issue. To obtain a better understanding of failure under combined moderately high (2000 A/cm2) current density and 10-150°C/1 h thermal cycling, analysis of separate, sequential, and concurrent EM and thermal cycling (TC) was imposed on single shear lap joints, and the microstructure and crystal orientations were incrementally characterized using electron backscatter diffraction (EBSD) mapping. First, it was determined that EM did not significantly change the crystal orientation, but the formation of Cu6Sn5 depended on the crystal orientation, and this degraded subsequent TMF behavior. Secondly, TC causes changes in crystal orientation. Concurrent EM and TC led to significant changes in crystal orientation by discontinuous recrystallization, which is facilitated by Cu6Sn5 particle formation. The newly formed Cu6Sn5 often showed its c-axis close to the direction of electron flow.

Electromigration and Thermomechanical Fatigue Behavior of Sn0.3Ag0.7Cu Solder Joints

NASA Astrophysics Data System (ADS)

Zuo, Yong; Bieler, Thomas R.; Zhou, Quan; Ma, Limin; Guo, Fu

2018-03-01

The anisotropy of Sn crystal structures greatly affects the electromigration (EM) and thermomechanical fatigue (TMF) of solder joints. The size of solder joint shrinkage in electronic systems further makes EM and TMF an inseparably coupled issue. To obtain a better understanding of failure under combined moderately high (2000 A/cm2) current density and 10-150°C/1 h thermal cycling, analysis of separate, sequential, and concurrent EM and thermal cycling (TC) was imposed on single shear lap joints, and the microstructure and crystal orientations were incrementally characterized using electron backscatter diffraction (EBSD) mapping. First, it was determined that EM did not significantly change the crystal orientation, but the formation of Cu6Sn5 depended on the crystal orientation, and this degraded subsequent TMF behavior. Secondly, TC causes changes in crystal orientation. Concurrent EM and TC led to significant changes in crystal orientation by discontinuous recrystallization, which is facilitated by Cu6Sn5 particle formation. The newly formed Cu6Sn5 often showed its c-axis close to the direction of electron flow.

1100 to 1500 K Slow Plastic Compressive Behavior of NiAl-xCr Single Crystals

NASA Technical Reports Server (NTRS)

Whittenberger, J. Daniel; Darolia, Ram

2003-01-01

The compressive properties of near <001> and <111> oriented NiAl-2Cr single crystals and near <011> oriented NiAl-6Cr samples have been measured between 1100 and 1500 K. The 2Cr addition produced significant solid solution strengthening in NiAl, and the <111> and <001> single crystals possessed similar strengths. The 6Cr crystals were not stronger than the 2Cr versions. At 1100 and 1200 K plastic flow in all three Cr-modified materials was highly dependent on stress with exponents > 10. The <011> oriented 6Cr alloy exhibited a stress exponent of about 8 at 1400 and 1500 K; whereas both <001> and <111> NiAl-2Cr crystals possessed stress exponents near 3 which is indicative of a viscous dislocation glide creep mechanism. While the Cottrell-Jaswon solute drag model predicted creep rates within a factor of 3 at 1500 K for <001>-oriented NiAl-2Cr; this mechanism greatly over predicted creep rates for other orientations and at 1400 K for <001> crystals.

Crystal orientation dependence of band matching in all-B2-trilayer current-perpendicular-to-plane giant magnetoresistance pseudo spin-valves using Co{sub 2}Fe(Ge{sub 0.5}Ga{sub 0.5}) Heusler alloy and NiAl spacer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Jiamin; Hono, K., E-mail: kazuhiro.hono@nims.go.jp; Graduate School of Pure and Applied Sciences, University of Tsukuba, 1-2-1, Sengen, Tsukuba 305-0047

2015-05-07

We have experimentally investigated the crystal orientation dependence of band matching in current-perpendicular-to-plane giant magnetoresistance (CPP-GMR) pseudo-spin-valves using Co{sub 2}Fe(Ge{sub 0.5}Ga{sub 0.5}) (CFGG) Heusler alloy ferromagnetic layer and NiAl spacer. The high quality epitaxial CFGG/NiAl/CFGG all-B2-trilayers structure devices were fabricated on both MgO(001) and sapphire (112{sup ¯}0) single crystal substrates to create (001) and (110) crystal orientations. Same magneto-transport properties were observed from these two differently orientated devices indicating that there is no or little orientation dependence of band matching on MR output. We also found that all-B2-trilayer structure was free of lattice matching influence depending on the crystal orientation,more » which made it a good candidate for CPP-GMR device.« less

Morphology design of porous coordination polymer crystals by coordination modulation.

PubMed

Umemura, Ayako; Diring, Stéphane; Furukawa, Shuhei; Uehara, Hiromitsu; Tsuruoka, Takaaki; Kitagawa, Susumu

2011-10-05

The design of crystal morphology, or exposed crystal facets, has enabled the development (e.g., catalytic activities, material attributes, and oriented film formation) of porous coordination polymers (PCPs) without changing material compositions. However, because crystal growth mechanisms are not fully understood, control of crystal morphology still remains challenging. Herein, we report the morphology design of [Cu(3)(btc)(2)](n) (btc = benzene-1,3,5-tricarboxylate) by the coordination modulation method (modulator = n-dodecanoic acid or lauric acid). A morphological transition (octahedron-cuboctahedron-cube) in the [Cu(3)(btc)(2)](n) crystal was observed with an increase in concentration of the modulator. By suitably defining a coarse-grained standard unit of [Cu(3)(btc)(2)](n) as its cuboctahedron main pore and determining its attachment energy on crystal surfaces, Monte Carlo coarse-grain modeling revealed the population and orientation of carboxylates and elucidated an important role of the modulator in determining the <100>- and <111>-growth throughout the crystal growth process. This comprehension, in fact, successfully led to designed crystal morphologies with oriented growth on bare substrates. Because selective crystal orientations on the bare substrates were governed by crystal morphology, this contribution also casts a new light on the unexplored issue of the significance of morphology design of PCPs.

Structural Engineering. Loads. Design Manual 2.2.

DTIC Science & Technology

1981-11-01

cast, rolled 534 Locust 46 Bronze, 7.9 to 14% Sn 509 Maple, hard 43 Bronze, aluminum 481 Maple, white 33 Copper , cast, rolled 556 Oak, chestnut 54... Copper ore, pyrites 262 Oak, live 59 Gold, cast, hammered 1205 Oak, red, black 41 Gold, bars, stacked 1133 Oak, white 46 Gold, coin in bags 1084 Pine...Phosphate rock, apatite 200 Glass, crystal 184 Porphyry 172 Hay and straw - bales 20 Pumice, natural 40 Leather 59 Quartz, flint 165 Paper 58 Sandstone

Intra-grain Common Pb Correction and Detrital Apatite U-Pb Dating via LA-ICPMS Depth Profiling

NASA Astrophysics Data System (ADS)

Boyd, P. D.; Galster, F.; Stockli, D. F.

2017-12-01

Apatite is a common accessory phase in igneous and sedimentary rocks. While apatite is widely employed as a low-temperature thermochronometric tool, it has been increasingly utilized to constrain moderate temperature cooling histories by U-Pb dating. Apatite U-Pb is characterized by a thermal sensitivity window of 375-550°C. This unique temperature window recorded by the apatite U-Pb system, and the near-ubiquitous presence of apatite in igneous and clastic sedimentary rocks makes it a powerful tool able to illuminate mid-crustal tectono-thermal processes. However, as apatite incorporates only modest amounts of U and Th (1-10s of ppm) the significant amounts of non-radiogenic "common" Pb incorporated during its formation presents a major hurdle for apatite U-Pb dating. In bedrock samples common Pb in apatite can be corrected for by the measurement of Pb in a cogenetic mineral phase, such as feldspar, that does not incorporate U or from determination of a common Pb composition from multiple analyses in Tera-Wasserburg space. While these methods for common Pb correction in apatite can work for igneous samples, they cannot be applied to detrital apatite in sedimentary rocks with variable common Pb compositions. The obstacle of common Pb in apatite has hindered the application of detrital apatite U-Pb dating in provenance studies, despite the fact that it would be a powerful tool. This study presents a new method for the in situ correction of common Pb in apatite through the utilization of novel LA-ICP-MS depth profiling, which can recover U-Pb ratios at micron-scale spatial resolution during ablation of a grain. Due to the intra-grain U variability in apatite, a mixing line for a single grain can be generated in Tera-Wasserburg Concordia space. As a case study, apatite from a Variscan alpine granite were analyzed using both the single and multi-grain method, with both methods giving identical results. As a second case study the intra-grain method was then performed on detrital apatite from the Swiss Northern Alpine Foreland Basin, where the common Pb composition and age spectra of detrital apatite grains were elucidated. The novel intra-grain apatite method enables the correction for common Pb in detrital apatite, making it feasible to incorporate detrital apatite U-Pb dating in provenance and source-to-sink studies.

Helium Diffusion in Natural Xenotime

NASA Astrophysics Data System (ADS)

Anderson, A. J.; Hodges, K. V.; Van Soest, M. C.; Hanchar, J. M.

2017-12-01

Xenotime (nominally YPO4) occurs as an accessory mineral in felsic igneous rocks, pegmatites, and gneisses, often incorporating weight percent levels of U, Th, and REEs. Although commonly used for precise U-Pb geochronology, xenotime is seldom used for (U-Th)/He thermochronometry despite the fact that its high radionuclide content allows for the rapid accumulation of radiogenic He that could potentially allow for the precise dating of very young cooling events in active geologic settings. Xenotime's likely high concentrations of radiogenic 4He also make it a promising candidate for laser microprobe (U-Th)/He dating. Unfortunately, limited data are currently available for He diffusion in xenotime, and previous experimental studies of natural and synthetic xenotime have led to discrepant results (1). Published estimates of the (U-Th)/He closure temperature for xenotime based on these experiments range from 60˚C to 300˚C. In this contribution, we report new results for incremental step heating `bulk' 4He diffusion experiments on a fragment of a natural xenotime crystal from the Torghar district of the Khyber Agency in the Federally Administered Tribal Areas of Pakistan. Laser ablation 238U/206Pb dating of this crystal yields a crystallization age of 28.82 ± 0.13 Ma. The results of our He diffusion experiments- which display excellent linearity on an Arrhenius plot assuming a spherical geometry - indicate kinetic parameters of E 133 kJ/mol and ln(D0/a2) 10.9 s-1. Our results imply a preliminary (U-Th)/He closure temperature of 80˚C for xenotime crystals with a diffusion dimension of 220 μm. This closure temperature is much lower than that previously estimated for natural xenotime (1), and it is possible, perhaps likely, that He diffusion in natural xenotime crystals display a strong compositional dependency (1). Nevertheless, our experimental data suggest that near-end member (YPO4) xenotime has an intrinsic helium diffusivity consistent with a closure temperature comparable to that of the apatite (U-Th)/He thermochronometer. As a consequence, xenotime He chronometry may serve as a higher-precision alternative to apatite He chronometry for revealing low temperature cooling histories of rocks in which it crystallized. References: 1) Farley, 2007, Geochimica et Cosmochimica Acta, v. 71.

Two-stage magnetic orientation of uric acid crystals as gout initiators

NASA Astrophysics Data System (ADS)

Takeuchi, Y.; Miyashita, Y.; Mizukawa, Y.; Iwasaka, M.

2014-01-01

The present study focuses on the magnetic behavior of uric acid crystals, which are responsible for gout. Under a sub-Tesla (T)-level magnetic field, rotational motion of the crystals, which were caused by diamagnetic torque, was observed. We used horizontal magnetic fields with a maximum magnitude of 500 mT generated by an electromagnet to observe the magnetic orientation of the uric acid microcrystals by a microscope. The uric acid crystals showed a perpendicular magnetic field orientation with a minimum threshold of 130 mT. We speculate that the distinct diamagnetic anisotropy in the uric acid crystals resulted in their rotational responses.

The Fundamentals of Dislocation Transport of Hydrogen in BCC Iron.

DTIC Science & Technology

1984-10-01

4.2.1. Single Crystal Material 24 4.2.2. Polycrystalline Material 25 4.3. Single Crystal Orientation Determination 25 4.4. Straining Permeation Test 27...Test 45 4.6. Supersaturation Study 47 S. RESULTS AND DISCUSSION 50 5.1. Single Crystal Orientation Determination 50 5.1.1. Slip System Determination 58...Orientation 162 Determination B.1. Dislocation Line Direction Determination 162 B.2. Burgers Vector Determination 164

Understanding the oriented-attachment growth of nanocrystals from an energy point of view: a review

NASA Astrophysics Data System (ADS)

Lv, Weiqiang; He, Weidong; Wang, Xiaoning; Niu, Yinghua; Cao, Huanqi; Dickerson, James H.; Wang, Zhiguo

2014-02-01

Since Penn et al. first discovered the oriented attachment growth of crystals, the oriented attachment mechanism has now become a major research focus in the crystal field, and extensive efforts have been carried out over the past decade to systematically investigate the growth mechanism and the statistical kinetic models. However, most of the work mainly focuses on the experimental results on the oriented attachment growth. In contrast to the previous reviews, our review provides an overview of the recent theoretical advances in oriented attachment kinetics combined with experimental evidences. After a brief introduction to the van der Waals interaction and Coulombic interaction in a colloidal system, the correlation between the kinetic models of oriented attachment growth and the interactions is then our focus. The impact of in situ experimental observation techniques on the study of oriented attachment growth is examined with insightful examples. In addition, the advances in theoretical simulations mainly investigating the thermodynamic origin of these interactions at the atomic level are reviewed. This review seeks to understand the oriented attachment crystal growth from a kinetic point of view and provide a quantitative methodology to rationally design an oriented attachment system with pre-evaluated crystal growth parameters.

Linearly polarized pumped passively Q-switched Nd:YVO4 microchip laser for Ince-Gaussian laser modes with controllable orientations

NASA Astrophysics Data System (ADS)

He, Hong-Sen; Zhang, Ming-Ming; Dong, Jun; Ueda, Ken-Ichi

2016-12-01

A tilted, linearly polarized laser diode end-pumped Cr4+:YAG passively Q-switched a-cut Nd:YVO4 microchip laser for generating numerous Ince-Gaussian (IG) laser modes with controllable orientations has been demonstrated by selecting the crystalline orientation of an a-cut Nd:YVO4 crystal. The same IG laser mode with different orientations has been achieved with the same absorbed pump power in a passively Q-switched Nd:YVO4 microchip laser under linearly polarized pumping when the incident pump power and the crystalline orientation of an a-cut Nd:YVO4 crystal are both properly selected. The significant improvement of pulsed laser performance of controllable IG modes has been achieved by selecting the crystalline orientation of an a-cut Nd:YVO4 crystal. The maximum pulse energy is obtained along the a-axis of an a-cut Nd:YVO4 crystal and the highest peak power is achieved along the c-axis of an a-cut Nd:YVO4 crystal, respectively, which has potential applications on quantum computation and optical manipulation. The generation of controllable IG laser modes in microchip lasers under linearly polarized pumping provides a convenient and universal way to control IG laser mode numbers with anisotropic crystal as a gain medium.

Co-crystallization of cholesterol and calcium phosphate as related to atherosclerosis

NASA Astrophysics Data System (ADS)

Hirsch, Danielle; Azoury, Reuven; Sarig, Sara

1990-09-01

Calcification of atherosclerotic plaques occurs very frequently and aggravates the disease. In biological systems, epitaxial relationships between crystal structures may be important in nucleating the deposit of a solid phase. The biologically preferred calcium phosphate species, apatite, and cholesterol crystal have structurally compatible crystallographic faces which allow epitaxial growth of one crystal upon another. The present study describes a new approach to explore, in vitro, the crystallization processes of calcium phosphate (CaP) with cholesterol (CS) and cholestanol (CN) which are related to atherosclerosis. Aqueous solutions containing calcium and phosphate ions or CaP crystals as hydroxyapatite were added into saturated ethanolic solutions of CS or CS and 10% CN. After precipitation, crystals were collected and analyzed by nuclear magnetic resonance (NMR), infra-red (IR), X-ray, scanning electron microscope (SEM-LINK), differential scanning calorimeter (DSC) and atomic absorption. The principal result is the well-formed crystals precipitation when an aqueous solution and CaP seed crystals were added to saturated solutions of CS and 10% CN. Cholesterol-cholestanol dihydrate (CC2W) crystals precipitated in the presence of CaP seeds were compared to the CC2W crystals obtained without the mineral compound. The results of this comparison indicate a special link between crystals of CaP and CC2W, and support the epitaxial relationship between the two kinds of crystals. The potential of CC2W crystals to be precipitated by CaP seed crystals prove likewise the possible significant role of the cholestanol metabolite in the process of cholesterol crystallization and calcification in the arteries.

The melt-recrystallization behavior of highly oriented α-iPP fibers embedded in a HIPS matrix.

PubMed

Ye, Liwei; Li, Huihui; Qiu, Zhaobin; Yan, Shouke

2015-03-21

The melt-recrystallization behavior of α-iPP fibers embedded in an amorphous HIPS matrix has been studied by means of optical microscopy. The amorphous HIPS serving as a supporter of iPP fibers does not become involved in the nucleation and crystallization process of the molten highly oriented iPP fibers. It also does not provide any birefringence under the optical microscope with crossed polarizers. This enables the study of orientation-induced β-iPP crystallization through a control of the melting status of the fibers. Through melting the fibers at different temperatures above 175 °C and subsequent recrystallization, some β-iPP crystals were always produced. The content of the β-iPP crystal depends strongly on the melting temperature and melting time of the iPP fibers. It was confirmed that melting the iPP fibers at relatively lower temperature, e.g. 176 °C, less amount of β-iPP crystals were observed. The content of β-iPP crystal enhances first with increasing melting temperature and then decreases with further increase of the fiber melting temperature. The β-iPP crystallization is found to be most favorable upon melting the fibers at 178 °C for 2 min. This demonstrates the requirement of a certain chain or chain segment orientation for generating β-iPP crystallization on the one hand, while higher orientation of the iPP chains or chain segments encourages the growth of iPP crystals in the α-form on the other hand. This has been further confirmed by varying the melting time of the fiber at different temperatures, since relaxation of the iPP molecular chains at a fixed temperature is time dependent. Moreover, the complete transformation of α-iPP fibers in some local places into β-iPP crystals implies that the αβ-transition may not be required for the orientation-induced β-iPP crystallization.

Resolving the chronology of the South African landscape through joint inverse modelling of AFT and apatite (U-Th)/He data

NASA Astrophysics Data System (ADS)

Wildman, Mark; Brown, Roderick; Beucher, Romain; Persano, Cristina; Stuart, Finlay

2013-04-01

Application of Low temperature thermochronometry (LTT) is a powerful method of constraining thermal history information on samples as they pass through isotherms in the upper crust. Inverse modelling of LTT data generates thermal history information which can then be correlated with independent datasets to infer geological processes that are responsible for producing the observed thermal history held in the thermochronometry record. A critical consideration when choosing which LTT method to use are the closure temperatures associated with each system. In order to generate more complete and robust thermal histories a single sample can be analysed using multiple low temperature thermochronometers that are sensitive over different but complimentary temperature ranges. The main focus of LTT work in South Africa has been on apatite fission track (AFT) analysis which is a world renowned method of constraining thermal history information between c. 60 and 110±10°C. The general conclusions that have been drawn from the South African AFT dataset is that the present day regional topography represents an eroded remnant of an elevated interior that experienced a significant uplift event with km-scale erosion in the Cretaceous following the break-up of Gondwana [1]. The exact nature of Cretaceous uplift and erosion varies both spatially and temporally, especially in south western Africa where at least two distinct denudation events are recorded at c. 130Ma and 90 Ma [2]. There are, however, alternative views suggesting significant epeirogenic-style uplift and subsequent erosion throughout the Cenozoic [3]. A key aspect of this debate which is yet to be fully resolved is the influence of mantle dynamics on the evolution of the overlying topography. To further investigate the timing and amount of Cenozoic uplift and erosion and to what degree this can be ascribed to dynamic topography, efforts have been made to complement the existing AFT record with Apatite (U-Th)/He analysis (AHe) (e.g. [4]). AHe is ideally suited to this task as it is sensitive over a lower temperature range (c. 40-75±5°C) and can therefore provide insights into erosion on the scale of 1-3 km. Correlating AFT and AHe datasets can be difficult due to variations in U and Th zonation, crystal geometry and structural defects (e.g. radiation damage) altering the closure temperature of the AHe system and resulting in significant dispersion of ages. It is therefore essential to fully understand the major cause of age dispersion and use thermal history modelling techniques that take these factors into account. Here we present a new suite of apatite (U-Th)/He data from samples along the Orange River alongside complimentary apatite fission track data from the same samples. Two samples with a large number of analysed grains, JN2 and GGO2 (23 and 21 grains, respectively) were modelled using HelFrag [5] which takes into account dispersion in AHe ages produced through analysis fragments of larger apatite grains. These modelled histories where compared with inverse modelling using QTQt [6] to extract thermal history information for each of the samples and provide new insights into the post-Cretaceous evolution of the SW African landscape and the behaviour of complex dispersion patterns commonly observed in AHe data sets. [1] Brown, R.W., Summerfield, M.A., and Gleadow, A.J.W., 2002, Denudational history along a transect across the Drakensberg Escarpment of southern Africa derived from apatite fission track thermochronology: Journal of Geophysical Research, v. 107, p. B12, 2350. [2] Kounov, A., Viola, G., de Wit, M., and Andreoli, M.A.G., 2009, Denudation along the Atlantic passive margin: new insights from apatite fission-track analysis on the western coast of South Africa: Geological Society, London, Special Publications, v. 324, p. 287-306. [3] Partridge, T.C., and Maud, R.R., 1987, Geomorphic evolution of southern Africa since the Mesozoic: South African Journal of Geology, v. 90, p. 179-208 [4] Flowers, R.M., and Schoene, B., 2010, (U-Th)/He thermochronometry constraints on unroofing of the eastern Kaapvaal craton and significance for uplift of the southern Africa Plateau: Geology, v. 38, p. 827-830. [5] Gallagher, K., 2012, Transdimensional inverse thermal history modeling for quantitative thermochronology: Journal of Geophysical Research, v. 117, p. 16. [6] Brown, R.W., Beucher, R., Roper, S., Gallagher, K., Persano, C. and Stuart, F., 2012, How to derive robust thermal histories from 'over-dispersed' single crystal apatite (U-Th)/He ages, Geophysical Research Abstracts, Vol. 14, EGU2012-11828, 2012, EGU General Assembly 2012

Solution-processed, Self-organized Organic Single Crystal Arrays with Controlled Crystal Orientation

PubMed Central

Kumatani, Akichika; Liu, Chuan; Li, Yun; Darmawan, Peter; Takimiya, Kazuo; Minari, Takeo; Tsukagoshi, Kazuhito

2012-01-01

A facile solution process for the fabrication of organic single crystal semiconductor devices which meets the demand for low-cost and large-area fabrication of high performance electronic devices is demonstrated. In this paper, we develop a bottom-up method which enables direct formation of organic semiconductor single crystals at selected locations with desired orientations. Here oriented growth of one-dimensional organic crystals is achieved by using self-assembly of organic molecules as the driving force to align these crystals in patterned regions. Based upon the self-organized organic single crystals, we fabricate organic field effect transistor arrays which exhibit an average field-effect mobility of 1.1 cm2V−1s−1. This method can be carried out under ambient atmosphere at room temperature, thus particularly promising for production of future plastic electronics. PMID:22563523

Using the chemical analysis of magnetite to constrain various stages in the formation and genesis of the Kiruna-type chadormalu magnetite-apatite deposit, Bafq district, Central Iran

NASA Astrophysics Data System (ADS)

Heidarian, Hassan; Lentz, David; Alirezaei, Saeed; Peighambari, Sima; Hall, Douglas

2016-12-01

Textural and compositional data are presented for different types of magnetite in the Chadormalu iron deposit to discern the genesis of various styles of mineralization. Samples were chosen according to their paragenetic relations to apatite and their host setting: magnetite-apatite veins in the altered host rocks, disseminated magnetite-apatite assemblages in the marginal parts of the main ore body, and massive magnetite associated with irregular apatite veinlets from internal part of the main ore body. Scanning electron microscopy - back scatter electron (SEM-BSE) images reveal that there are three main generations of magnetite in each of the different magnetite-apatite assemblages. Primary magnetite (Mag1) features abundant porosity and a dark appearance. A second generation of magnetite (Mag2) replacing Mag1 shows a lighter appearance with both sharp and gradational contacts with the primary magnetite crystals. The two magnetite types are related to dissolution-precipitation processes due to changing physico-chemical parameters of the ore fluids. A third type of magnetite (Mag3) with a recrystallized appearance and foam-like triple junctions was mostly observed in magnetite-apatite veins in the main ore body and in veins hosted by altered rocks. Electron probe microanalyses (EPMA) were utilized to discriminate the various magnetite generations in the different magnetite-apatite assemblages. Applying published elemental discrimination diagrams shows that most primary magnetites fall into the hydrothermal- and Kiruna-type fields. Primary magnetite contains lower FeO (88.77-93.65 wt.%; average 91.5 wt.%), and higher SiO2 (0.21-2.26 wt.%; ave. 0.32 wt.%), Al2O3 (0.001-0.45 wt.%; ave. 0.053 wt.%), and CaO (0.002-0.48 wt.%; ave. 0.078 wt.%) contents, which might be related to magmatically derived fluids. Secondary magnetites have higher FeO (89.23-93.49 wt.%; ave. 92.11 wt.%), lower SiO2 (0.037-0.189 wt.%; ave. 0.072 wt.%), Al2O3 (0.004-0.072 wt.%; ave. 0.019 wt.%), and CaO (<0.034 wt.%; ave. 0.013 wt.%) possibly showing a lower contribution of magmatic fluids in the formation of Mag2. The magnetite Mag3 contains the highest FeO (91.25-93.8 wt.%; average 92.69 wt.%), low to moderate SiO2 (0.008-1.44 wt.%; ave. 0.13 wt.%), Al2O3 (<0.732 wt.%; ave. 0.059 wt.%), and CaO (<0.503 wt.%; ave. 0.072 wt.%), and appears to have formed by recrystallization of the previous two generations. The different major, minor, and trace element compositions of various magnetite generations might be due to an ore-forming fluid that was initially magmatic-hydrothermal and evolved to moderately brine-dominated meteoric fluids. The involvement of a basinal brine is supported by the occurrence of a late phase 34S-enriched pyrite in the Chadormalu deposit.

Effect of Crystal Orientation on Fatigue Failure of Single Crystal Nickel Base Turbine Blade Superalloys

NASA Technical Reports Server (NTRS)

Arakere, N. K.; Swanson, G.

2002-01-01

High cycle fatigue (HCF) induced failures in aircraft gas turbine and rocket engine turbopump blades is a pervasive problem. Single crystal nickel turbine blades are being utilized in rocket engine turbopumps and jet engines throughout industry because of their superior creep, stress rupture, melt resistance, and thermomechanical fatigue capabilities over polycrystalline alloys. Currently the most widely used single crystal turbine blade superalloys are PWA 1480/1493, PWA 1484, RENE' N-5 and CMSX-4. These alloys play an important role in commercial, military and space propulsion systems. Single crystal materials have highly orthotropic properties making the position of the crystal lattice relative to the part geometry a significant factor in the overall analysis. The failure modes of single crystal turbine blades are complicated to predict due to the material orthotropy and variations in crystal orientations. Fatigue life estimation of single crystal turbine blades represents an important aspect of durability assessment. It is therefore of practical interest to develop effective fatigue failure criteria for single crystal nickel alloys and to investigate the effects of variation of primary and secondary crystal orientation on fatigue life. A fatigue failure criterion based on the maximum shear stress amplitude /Delta(sub tau)(sub max))] on the 24 octahedral and 6 cube slip systems, is presented for single crystal nickel superalloys (FCC crystal). This criterion reduces the scatter in uniaxial LCF test data considerably for PWA 1493 at 1200 F in air. Additionally, single crystal turbine blades used in the alternate advanced high-pressure fuel turbopump (AHPFTP/AT) are modeled using a large-scale three-dimensional finite element model. This finite element model is capable of accounting for material orthotrophy and variation in primary and secondary crystal orientation. Effects of variation in crystal orientation on blade stress response are studied based on 297 finite element model runs. Fatigue lives at critical points in the blade are computed using finite element stress results and the failure criterion developed. Stress analysis results in the blade attachment region are also presented. Results presented demonstrates that control of secondary and primary crystallographic orientation has the potential to significantly increase a component S resistance to fatigue crack growth with- out adding additional weight or cost. [DOI: 10.1115/1.1413767

Inverted Apatite (U-Th)/He and Fission-track Dates from the Rae craton, Baffin Island, Canada and Implications for Apatite Radiation Damage-He Diffusivity Models

NASA Astrophysics Data System (ADS)

Ault, A. K.; Reiners, P. W.; Thomson, S. N.; Miller, G. H.

2015-12-01

Coupled apatite (U-Th)/He and fission-track (AFT) thermochronology data from the same sample can be used to decipher complex low temperature thermal histories and evaluate compatibility between these two methods. Existing apatite He damage-diffusivity models parameterize radiation damage annealing as fission-track annealing and yield inverted apatite He and AFT dates for samples with prolonged residence in the He partial retention zone. Apatite chemistry also impacts radiation damage and fission-track annealing, temperature sensitivity, and dates in both systems. We present inverted apatite He and AFT dates from the Rae craton, Baffin Island, Canada, that cannot be explained by apatite chemistry or existing damage-diffusivity and fission track models. Apatite He dates from 34 individual analyses from 6 samples range from 237 ± 44 Ma to 511 ± 25 Ma and collectively define a positive date-eU relationship. AFT dates from these same samples are 238 ± 15 Ma to 350 ± 20 Ma. These dates and associated track length data are inversely correlated and define the left segment of a boomerang diagram. Three of the six samples with 20-90 ppm eU apatite grains yield apatite He and AFT dates inverted by 300 million years. These samples have average apatite Cl chemistry of ≤0.02 wt.%, with no correlation between Cl content and Dpar. Thermal history simulations using geologic constraints, an apatite He radiation damage accumulation and annealing model, apatite He dates with the range of eU values, and AFT date and track length data, do not yield any viable time-temperature paths. Apatite He and AFT data modeled separately predict thermal histories with Paleozoic-Mesozoic peaks reheating temperatures differing by ≥15 °C. By modifying the parameter controlling damage annealing (Rmr0) from the canonical 0.83 to 0.5-0.6, forward models reproduce the apatite He date-eU correlation and AFT dates with a common thermal history. Results imply apatite radiation damage anneals at higher temperatures than fission-track damage and the impact on coupled apatite He and AFT dates is magnified for protracted cooling histories. Further experimental and field-based tests are important for refining radiation damage and fission-track annealing parameters for accurate interpretation of apatite He- and AFT-derived thermal histories.

Fracture of single crystals of the nickel-base superalloy PWA 1480E in helium at 22 C

NASA Technical Reports Server (NTRS)

Chen, P. S.; Wilcox, R. C.

1991-01-01

The fracture behavior and deformation of He-charged (at 22 C) single crystals of PWA 1480E Ni-base superalloy were investigated using SEM and TEM techniques to observe the behavior of tensile fractures in notched single crystals with seven different crystal growth orientations: 100-line, 110-line, 111-line, 013-line, 112-line, 123-line, and 223-line. To identify the cleavage plane orientation, a stereoscopic technique, combined with the use of planar gamma-prime morphologies, was applied. It was found that gamma-prime particles were orderly and closely aligned with edges along the 100-line, 010-line, and 001-line-oriented directions of the gamma matrix. Different crystal growth orientations were found not to affect the morphology of gamma-prime particles. The accumulation of dislocations around gamma/gamma-prime interfaces formed strong barriers to subsequent dislocation movement and was the primary strengthening mechanism at room temperature.

Realignment of Nanocrystal Aggregates into Single Crystals as a Result of Inherent Surface Stress

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Zhaoming; Pan, Haihua; Zhu, Genxing

2016-07-19

Assembly of nanoparticles building blocks during single crystal growth is widely observed in both natural and synthetic environments. Although this form of non-classical crystallization is generally described by oriented attachment, random aggregation of building blocks leading to single crystal products is also observed, but the mechanism of crystallographic realignment is unknown. We herein reveal that random attachment during aggregation-based growth initially produces a non-oriented growth front. Subsequent evolution of the orientation is driven by the inherent surface stress applied by the disordered surface layer and results in single crystal formation via grain boundary migration. This mechanism is corroborated by measurementsmore » of orientation rate vs external stress, demonstrating a predictive relationship between the two. These findings advance our understanding of aggregation-based growth of natural minerals by nanocrystals, and suggest an approach to material synthesis that takes advantage of stress induced co-alignment.« less

Development of a two-stage in vitro model system to investigate the mineralization mechanisms involved in idiopathic stone formation: stage 1-biomimetic Randall's plaque using decellularized porcine kidneys.

PubMed

Lovett, Archana C; Khan, Saeed R; Gower, Laurie B

2018-05-18

Idiopathic calcium oxalate (CaOx) stone formers form stones that are commonly attached to calcium phosphate (CaP) deposits in the renal tissue, known as Randall's plaques (RP). Plaques are suggested to originate in the renal tubular basement membrane, where they exhibit a morphology of concentrically laminated apatitic spherules, while in the interstitial regions, the collagen fibrils and vesicles become mineralized. We hypothesize that these minerals might form by non-classical crystallization mechanisms, such as via amorphous precursors, some of which might originate from a polymer-induced liquid-precursor (PILP) process. Thus, our goal is to identify mineralogical 'signatures' of various stone formation mechanisms. To do this for idiopathic CaOx stones, we are developing a two-stage model system of CaP-CaOx composite stones, consisting of stage (1) CaP mineralized plaque, followed by stage (2) CaOx overgrowth into a stone. For the studies presented here, decellularized porcine kidneys were mineralized with CaP using polyaspartic acid or the protein osteopontin (OPN) to induce the PILP process and create biomimetic RP. Analysis of the PILP-mineralized tissues shows features that resemble the native plaques, including mineral spherules and collagen with intrafibrillar mineral. In contrast, the classical crystallization produced large apatitic spherulites, which is a very different morphology, but one which is also found in some stones. An alternative hypothesis regarding Randall's plaque, and if or when it becomes pathological, is discussed.

Characterisation, corrosion resistance and in vitro bioactivity of manganese-doped hydroxyapatite films electrodeposited on titanium.

PubMed

Huang, Yong; Ding, Qiongqiong; Han, Shuguang; Yan, Yajing; Pang, Xiaofeng

2013-08-01

This work elucidated the corrosion resistance and in vitro bioactivity of electroplated manganese-doped hydroxyapatite (MnHAp) film on NaOH-treated titanium (Ti). The NaOH treatment process was performed on Ti surface to enhance the adhesion of the MnHAp coating on Ti. Scanning electron microscopy images showed that the MnHAp coating had needle-like apatite crystals, and the approximately 10 μm thick layer was denser than HAp. Energy-dispersive X-ray spectroscopy analysis revealed that the MnHAp crystals were Ca-deficient and the Mn/P molar ratio was 0.048. X-ray diffraction confirmed the presence of single-phase MnHAp, which was aligned vertically to the substrate. Fourier transform infrared spectroscopy indicated the presence of phosphate bands ranging from 500 to 650 and 900 to 1,100 cm(-1), and a hydroxyl band at 3,571 cm(-1), which was characteristic of HAp. Bond strength test revealed that adhesion for the MnHAp coating was more enhanced than that of the HAp coating. Potentiodynamic polarisation test showed that the MnHAp-coated surface exhibited superior corrosion resistance over the HAp single-coated surface. Bioactivity test conducted by immersing the coatings in simulated body fluid showed that MnHAp coating can rapidly induce bone-like apatite nucleation and growth. Osteoblast cellular tests revealed that the MnHAp coating was better at improving the in vitro biocompatibility of Ti than the HAp coating.

Photoactive chitosan switching on bone-like apatite deposition.

PubMed

Chiono, Valeria; Gentile, Piergiorgio; Boccafoschi, Francesca; Carmagnola, Irene; Ninov, Momchil; Georgieva, Ventsislava; Georgiev, George; Ciardelli, Gianluca

2010-02-08

The work was focused on the synthesis and characterization of the chitosan-g-fluorescein (CHFL) conjugate polymer as a biocompatible amphiphilic water-soluble photosensitizer, able to stimulate hydroxyapatite deposition upon visible light irradiation. Fluorescein (FL) grafting to chitosan (CH) chains was confirmed by UV-vis analysis of water solutions of FL and CHFL and by Fourier transform infrared spectroscopy (FTIR-ATR) analysis of CHFL and CH. Smooth CHFL cast films with 4 microm thickness were obtained by solvent casting. Continuous exposure to visible light for 7 days was found to activate the deposition of calcium phosphate crystals from a conventional simulated body fluid (SBF 1.0x) on the surface of CHFL cast films. EDX and FTIR-ATR analyses confirmed the apatite nature of the deposited calcium phosphate crystals. CHFL films preincubated in SBF (1.0x) solution under visible light irradiation and in the dark for 7 days were found to support the in vitro adhesion and proliferation of MG63 osteoblast-like cells (MTT viability test; 1-3 days culture time). On the other hand, the mineralization ability of MG63 osteoblast-like cells was significantly improved on CHFL films preincubated under visible light exposure (alkaline phosphatase activity (ALP) test for 1, 3, 7, and 14 days). The use of photoactive biocompatible conjugate polymer, such as CHFL, may lead to new therapeutic options in the field of bone/dental repair, exploiting the photoexcitation mechanism as a tool for biomineralization.

Westernmost Grand Canyon incision: Testing thermochronometric resolution

NASA Astrophysics Data System (ADS)

Fox, M.; Tripathy-Lang, A.; Shuster, D. L.; Winn, C.; Karlstrom, K.; Kelley, S.

2017-09-01

The timing of carving of Grand Canyon has been debated for over 100 years with competing endmember hypotheses advocating for either a 70 Ma ("old") or <6 Ma ("young") Grand Canyon. Several geological constraints appear to support a "young" canyon model, but thermochronometric measures of cooling history and corresponding estimates of landscape evolution have been in debate. In particular, 4He/3He thermochronometric data record the distribution of radiogenic 4He (from the 238U, 235U and 232Th decay series) within an individual apatite crystal and thus are highly sensitive to the thermal history corresponding to landscape evolution. However, there are several complicating factors that make interpreting such data challenging in geologic scenarios involving reheating. Here, we analyze new data that provide measures of the cooling of basement rocks at the base of westernmost Grand Canyon, and use these data as a testbed for exploring the resolving power and limitations of 4He/3He data in general. We explore a range of thermal histories and find that these data are most consistent with a "young" Grand Canyon. A problem with the recovered thermal history, however, is that burial temperatures are under predicted based on sedimentological evidence. A solution to this problem is to increase the resistance of alpha recoil damage to annealing, thus modifying He diffusion kinetics, allowing for higher temperatures throughout the thermal history. This limitation in quantifying radiation damage (and hence crystal retentivity) introduces non-uniqueness to interpreting time-temperature paths in rocks that resided in the apatite helium partial retention zone for long durations. Another source of non-uniqueness, is due to unknown U and Th distributions within crystals. We show that for highly zoned with a decrease in effective U of 20 ppm over the outer 80% of the radius of the crystal, the 4He/3He data could be consistent with an "old" canyon model. To reduce this non-uniqueness, we obtain U and Th zonation information for separate crystals from the same rock sample through LA-ICP-MS analysis. The observed U and Th distributions are relatively uniform and not strongly zoned, thus supporting a "young" canyon model interpretation of the 4He/3He data. Furthermore, we show that for the mapped zonation, the difference between predicted 4He/3He data for a uniform crystal and a 3D model of the crystal are minimal, highlighting that zonation is unlikely to lead us to falsely infer an "old" Grand Canyon.

Determining heterogeneous slip activity on multiple slip systems from single crystal orientation pole figures

DOE PAGES

Pagan, Darren C.; Miller, Matthew P.

2016-09-01

A new experimental method to determine heterogeneity of shear strains associated with crystallographic slip in the bulk of ductile, crystalline materials is outlined. The method quantifies the time resolved evolution of misorientation within plastically deforming crystals using single crystal orientation pole figures (SCPFs) measured in-situ with X-ray diffraction. A multiplicative decomposition of the crystal kinematics is used to interpret the distributions of lattice plane orientation observed on the SCPFs in terms of heterogeneous slip activity (shear strains) on multiple slip systems. Here, to show the method’s utility, the evolution of heterogeneous slip is quantified in a silicon single crystal plasticallymore » deformed at high temperature at multiple load steps, with slip activity in sub-volumes of the crystal analyzed simultaneously.« less

Effect of crystal orientation on the phase diagrams, dielectric and piezoelectric properties of epitaxial BaTiO{sub 3} thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Huaping, E-mail: wuhuaping@gmail.com, E-mail: hpwu@zjut.edu.cn; State Key Laboratory of Structural Analysis for Industrial Equipment, Dalian University of Technology, Dalian 116024; Ma, Xuefu

2016-01-15

The influence of crystal orientations on the phase diagrams, dielectric and piezoelectric properties of epitaxial BaTiO{sub 3} thin films has been investigated using an expanded nonlinear thermodynamic theory. The calculations reveal that crystal orientation has significant influence on the phase stability and phase transitions in the misfit strain-temperature phase diagrams. In particular, the (110) orientation leads to a lower symmetry and more complicated phase transition than the (111) orientation in BaTiO{sub 3} films. The increase of compressive strain will dramatically enhance the Curie temperature T{sub C} of (110)-oriented BaTiO{sub 3} films, which matches well with previous experimental data. The polarizationmore » components experience a great change across the boundaries of different phases at room temperature in both (110)- and (111)-oriented films, which leads to the huge dielectric and piezoelectric responses. A good agreement is found between the present thermodynamics calculation and previous first-principles calculations. Our work provides an insight into how to use crystal orientation, epitaxial strain and temperature to tune the structure and properties of ferroelectrics.« less

Influence of crystal orientation on the formation of femtosecond laser-induced periodic surface structures and lattice defects accumulation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sedao, Xxx; Garrelie, Florence, E-mail: florence.garrelie@univ-st-etienne.fr; Colombier, Jean-Philippe

2014-04-28

The influence of crystal orientation on the formation of femtosecond laser-induced periodic surface structures (LIPSS) has been investigated on a polycrystalline nickel sample. Electron Backscatter Diffraction characterization has been exploited to provide structural information within the laser spot on irradiated samples to determine the dependence of LIPSS formation and lattice defects (stacking faults, twins, dislocations) upon the crystal orientation. Significant differences are observed at low-to-medium number of laser pulses, outstandingly for (111)-oriented surface which favors lattice defects formation rather than LIPSS formation.

Ancient graphite in the Eoarchean quartz-pyroxene rocks from Akilia in southern West Greenland II: Isotopic and chemical compositions and comparison with Paleoproterozoic banded iron formations

NASA Astrophysics Data System (ADS)

Papineau, Dominic; De Gregorio, Bradley T.; Stroud, Rhonda M.; Steele, Andrew; Pecoits, Ernesto; Konhauser, Kurt; Wang, Jianhua; Fogel, Marilyn L.

2010-10-01

We present detailed petrographic surveys of apatite grains in association with carbonaceous material (CM) in two banded iron formations (BIFs) from the Paleoproterozoic of Uruguay and Michigan for comparison with similar mineral associations in the highly debated Akilia Quartz-pyroxene (Qp) rock. Petrographic and Raman spectroscopic surveys of these Paleoproterozoic BIFs show that apatite grains typically occur in bands parallel to bedding and are more often associated with CM when concentrations of organic matter are high. Carbonaceous material in the Vichadero BIF from Uruguay is generally well-crystallized graphite and occurs in concentrations around 0.01 wt% with an average δ 13C gra value of -28.6 ± 4.4‰ (1 σ). In this BIF, only about 5% of apatite grains are associated with graphite. In comparison, CM in the Bijiki BIF from Michigan is also graphitic, but occurs in concentrations around 2.4 wt% with δ 13C gra values around -24.0 ± 0.3‰ (1 σ). In the Bijiki BIF, more than 78% of apatite grains are associated with CM. Given the geologic context and high levels of CM in the Bijiki BIF, the significantly higher proportion of apatite grains associated with CM in this rock is interpreted to represent diagenetically altered biomass and shows that such diagenetic mineral associations can survive metamorphism up to the amphibolite facies. Isotope compositions of CM in muffled acidified whole-rock powders from the Akilia Qp rock have average δ 13C gra values of -17.5 ± 2.5‰ (1 σ), while δ 13C carb values in whole-rock powders average -4.0 ± 1.0‰ (1 σ). Carbon isotope compositions of graphite associated with apatite and other minerals in the Akilia Qp rock were also measured with the NanoSIMS to have similar ranges of δ 13C gra values averaging -13.8 ± 5.6‰ (1 σ). The NanoSIMS was also used to semi-quantitatively map the distributions of H, N, O, P, and S in graphite from the Akilia Qp rock, and relative abundances were found to be similar for graphite associated with apatite or with hornblende, calcite, and sulfides. These analyses revealed generally lower abundances of trace elements in the Akilia graphite compared to graphite associated with apatite from Paleoproterozoic BIFs. Graphite associated with hornblende, calcite, and sulfides in the Akilia Qp rock was fluid-deposited at high-temperature from carbon-bearing fluids, and since this graphite has similar ranges of δ 13C gra values and of trace elements compared to graphite associated with apatite, we conclude that the Akilia graphite in different mineral associations formed from the same source(s) of CM. Collectively our results do not exclude a biogenic origin of the carbon in the Akilia graphite, but because some observations can not exclude graphitization of abiogenic carbon from CO 2- and CH 4-bearing mantle fluids, there remain ambiguities with respect to the exact origin of carbon in this ancient metasedimentary rock. Accordingly, there may have been several generations of graphite formation along with possibly varying mixtures of CO 2- and CH 4-bearing fluids that may have resulted in large ranges of δ 13C gra values. The possibility of fluid-deposited graphite associated with apatite should be a focus of future investigations as this may prove to be an alternative pathway of graphitization from phosphate-bearing fluids. Correlated micro-analytical approaches tested on terrestrial rocks in this work provide insights into the origin of carbon in ancient graphite and will pave the way for the search for life on other ancient planetary surfaces.

A Crystal Plasticity Model of Fatigue of Dissimilar Magnesium Alloy Bi-Crystals

NASA Astrophysics Data System (ADS)

Knight, Simon

A crystal plasticity finite element (CPFE) model was applied to the fatigue deformation of dissimilar Mg alloy bi-crystals. The mesoscopic stress-strain and microscopic slip and twinning behaviour of the model were first validated with experimental tension and compression data of pure Mg single crystals. High-cycle fatigue (HCF) simulations up to 1000 cycles were then used to systematically examine the effect of different textures on the cyclic deformation behavior of Mg AZ31-AZ80 bi-crystals at room-temperature. Fatigue behaviour was characterized in terms of the mesoscopic average stress-strain response and the evolution of the microscopic deformation (slip/twin activity). The model captures load asymmetry, cyclic hardening/softening and ratcheting. However, the model did not capture stress concentrations at the grain boundary (GB) for the grain shapes considered. Either basal slip or tensile twinning was activated for any given orientation. When the soft AZ31 grain is oriented for basal slip almost all the shear strain is contained in that grain and has approximately ten times more accumulated shear strain than the other orientations. The results reveal there is a strong effect from orientation combinations on the cyclic deformation wherein a "hard" orientation shields a "soft" orientation from strain. When the AZ80 grain is oriented for basal slip and the AZ31 grain is oriented for tensile twinning the bi-crystal is soft, but only in one direction since twinning is a polar mechanism. Approximately half as much accumulated shear strain occurs when both grains are oriented for twinning. The slip and twinning systems quickly harden in AZ31 in the first few hundred cycles and the shear strain amplitudes quickly devolve from values between 10-6 - 10-4 to around 10-7; values which would be difficult to resolve experimentally. The results were then extended to the possible effects on the fatigue behaviour of an AZ31-AZ80 dissimilar weld idealized as an AZ31-AZ80 bi-crystal. It is predicted that the worst fatigue behaviour would occur when one grain is oriented for basal slip: AZ31 grain, results in strain localization; AZ80 grain, results in an increase in twin boundaries and irreversible deformation in an AZ31 grain.

Ultrasound liquid crystal lens

NASA Astrophysics Data System (ADS)

Shimizu, Yuki; Koyama, Daisuke; Fukui, Marina; Emoto, Akira; Nakamura, Kentaro; Matsukawa, Mami

2018-04-01

A variable-focus lens using a combination of liquid crystals and ultrasound is discussed. The lens uses a technique based on ultrasound vibration to control the molecular orientation of the liquid crystal. The lens structure is simple, with no mechanical moving parts and no transparent electrodes, which is helpful for device downsizing; the structure consists of a liquid crystal layer sandwiched between two glass substrates with a piezoelectric ring. The tens-of-kHz ultrasonic resonance flexural vibration used to excite the lens generates an acoustic radiation force on the liquid crystal layer to induce changes in the molecular orientation of the liquid crystal. The orientations of the liquid crystal molecules and the optical characteristics of the lens were investigated under ultrasound excitation. Clear optical images were observed through the lens, and the focal point could be controlled using the input voltage to the piezoelectric ring to give the lens its variable-focus action.

Theoretical and experimental analyses to determine the effects of crystal orientation and grain size on the thermoelectric properties of oblique deposited bismuth telluride thin films

NASA Astrophysics Data System (ADS)

Morikawa, Satoshi; Satake, Yuji; Takashiri, Masayuki

2018-06-01

The effects of crystal orientation and grain size on the thermoelectric properties of Bi2Te3 thin films were investigated by conducting experimental and theoretical analyses. To vary the crystal orientation and grain size, we performed oblique deposition, followed by thermal annealing treatment. The crystal orientation decreased as the oblique angle was increased, while the grain size was not changed significantly. The thermoelectric properties were measured at room temperature. A theoretical analysis was performed using a first principles method based on density functional theory. Then the semi-classical Boltzmann transport equation was used in the relaxation time approximation, with the effect of grain size included. Furthermore, the effect of crystal orientation was included in the calculation based on a simple semi-experimental model. A maximum power factor of 11.6 µW/(cm·K2) was obtained at an oblique angle of 40°. The calculated thermoelectric properties were in very good agreement with the experimentally measured values.

Uniaxial alignment of triisopropylsilylethynyl pentacene via zone-casting technique.

PubMed

Su, Yajun; Gao, Xiang; Liu, Jiangang; Xing, Rubo; Han, Yanchun

2013-09-14

Uniaxially aligned triisopropylsilylethynyl pentacene (TIPS-pentacene) crystals over a large area were fabricated using zone-casting technique. The array of TIPS-pentacene displayed a high orientation degree with a dichroic ratio (DR) of 0.80. The crystals were arranged with c axis perpendicular to the substrate and the long axis of the ribbon corresponded to the a axis of TIPS-pentacene. The properties of the solutions and the processing parameters were shown to influence the formation of the oriented TIPS-pentacene crystalline array. Solvent with a low boiling point (such as chloroform) favoured the orientation of the ribbon-like crystals. The concentration of the solution should be appropriate, ensuring the crystallization velocity of TIPS-pentacene matching with the receding of the meniscus. Besides, we proved that the casting speed should be large enough to induce a sufficient concentration gradient. The orientation mechanism of TIPS-pentacene was attributed to a synergy of the ordered nuclei and a match between the crystallization velocity and the casting speed. Field effect transistors (FETs) based on the oriented TIPS-pentacene crystalline array showed a mobility of 0.67 cm(2) V(-1) s(-1).

Tracing Life in the Earliest Terrestrial Rock Record

NASA Astrophysics Data System (ADS)

Lepland, A.; van Zuilen, M.; Arrhenius, G.

2001-12-01

The principal method for studying the earliest traces of life in the metamorphosed, oldest (> 3.5 Ga) terrestrial rocks involves determination of isotopic composition of carbon, mainly prevailing as graphite. It is generally believed that this measure can distinguish biogenic graphite from abiogenic varieties. However, the interpretation of life from carbon isotope ratios has to be assessed within the context of specific geologic circumstances requiring (i) reliable protolith interpretation (ii) control of secondary, metasomatic processes, and (iii) understanding of different graphite producing mechanisms and related carbon isotopic systematics. We have carried out a systematic study of abundance, isotopic composition and petrographic associations of graphite in rocks from the ca. 3.8 Ga Isua Supracrustal Belt (ISB) in southern West Greenland. Our study indicates that most of the graphite in ISB occurs in carbonate-rich metasomatic rocks (metacarbonates) while sedimentary units, including banded iron formations (BIFs) and metacherts, have exceedingly low graphite concentrations. Regardless of isotopic composition of graphite in metacarbonate rocks, their secondary origin disqualifies them from providing evidence for traces of life stemming from 3.8 Ga. Recognition of the secondary origin of Isua metacarbonates thus calls for reevaluation of biologic interpretations by Schidlowski et al. (1979) and Mojzsis et al. (1996) that suggested the occurrence of 3.8 Ga biogenic graphite in these rocks. The origin of minute quantities of reduced carbon, released from sedimentary BIFs and metacherts at combustion steps > 700 C remains to be clarified. Its isotopic composition (d13C from -18 to -25%) may hint at a biogenic origin. However, such isotopically light carbon was also found in Proterozoic mafic dykes cross-cutting the metasedimentary units in the ISB. The occurrence of isotopically light, reduced carbon in biologically irrelevant dykes may indicate secondary graphite crystallization from CO2 or CH4- containing fluids that in turn may derive from bioorganic sources. If this were the case, trace amounts of isotopically light secondary graphite can also be expected in metasediments, complicating the usage of light graphite as primary biomarker. The possibility of recent organic contamination, particularly important in low graphite samples, needs also to be considered; it appears as a ubiquitous component released at combustion in the 400 to 500 deg range. - A potential use of the apatite-graphite association as a biomarker has been proposed in the study by Mojzsis et al. (1996). Close inspection of several hundred apatite crystals from Isua BIFs and metacherts did, however, not show an association between these two minerals, moreover graphite is practically absent in these metasediments. In contrast, apatite crystals in the non-sedimentary metacarbonate rocks were found commonly to have invaginations, coatings and inclusions of abundant graphite. Considering that such graphite inclusions in apatite are restricted to the secondary metasomatic carbonate rocks in the ISB this association can not be considered as a primary biomarker in the Isua Supracrustal Belt References: Mojzsis,S.J, .Arrhenius,G., McKeegan, K.D.,.Harrison, T.M.,.Nutman, A.P & C.R.L.Friend.,1996. Nature 384: 55 Schidlowski, M., Appel, P.W.U., Eichmann, R. & Junge, C.E., 1979. Geochim. Cosmochim. Acta 43: 189-190.

Low-Temperature Thermochronology Investigation in Uruguay and Southernmost Brazil: Apatite (U-Th)/He Results

NASA Astrophysics Data System (ADS)

Machado, J. P.; Bicca, M. M.

2017-12-01

Low-temperature thermochronology has successfully allowed one to reveal exhumation histories of many orogenic belts across the Earth, and lately these techniques have been applied in cratonic regions. The present study aims to constrain thermal history and exhumation of the South Atlantic Passive Margin, between Uruguay and Southernmost Brazil, a region scarce of thermochronological data. This location has become relatively stable after the Neoproterozoic Brasiliano Orogeny, being more intensely disturbed by tectonics during the Gondwana Breakup and consequent opening of the Atlantic Ocean (Jurassic - Cretaceous). Both apatite and zircon (U-Th)/He methods are being applied on basement rocks, and since those have a long cooling history, radiation damage is expected to play an important role in crystal ages. A total of 25 samples were analyzed, and preliminary apatite (U-Th)/He results reveals unweighted sample ages ranging from Permian to Lower-Cretaceous in Southernmost Brazil, with a couple of outliers with Devonian - Carboniferous ages. In Uruguay results can be grouped in two different clusters: one of samples with Jurassic to Lower-Cretaceous ages, and another of Devonian to Permian ages. This wide range of results can be assign to variations in the uranium content of the grains, due the presence of inclusions, compositional zonation or substantial radiation damage of the crystalline lattice. In most cases, ages tend to increase with crystal eU content. No clear relationship between ages and tectonic terranes has been found so far, neither between ages and elevation, since the region does not have significant topographic variations. Younger ages are commonly found closer to the coastal region, possibly in response to the rift shoulders uplift during Gondwana breakup and further exhumation and denudation at higher rates. An anomalous concentration of older ages in the southern region of the Pelotas Batholith, close to the Brazil - Uruguay border, suggests a geotectonic stable area near the margin. A NW-trend of younger ages throughout southernmost Brazilian Shield may reflect cooling triggered by the structural reactivation of Precambrian basement fabrics. Hopefully, future work will permit a better comprehension of the regional exhumation patterns during the Phanerozoic.

Bioactivity and cell proliferation in radiopaque gel-derived CaO-P2O5-SiO2-ZrO2 glass and glass-ceramic powders.

PubMed

Montazerian, Maziar; Yekta, Bijan Eftekhari; Marghussian, Vahak Kaspari; Bellani, Caroline Faria; Siqueira, Renato Luiz; Zanotto, Edgar Dutra

2015-10-01

In this study, 10 mol% ZrO2 was added to a 27CaO-5P2O5-68SiO2 (mol%) base composition synthesized via a simple sol-gel method. This composition is similar to that of a frequently investigated bioactive gel-glass. The effects of ZrO2 on the in vitro bioactivity and MG-63 cell proliferation of the glass and its derivative polycrystalline (glass-ceramic) powder were investigated. The samples were characterized using thermo-gravimetric and differential thermal analysis (TG/DTA), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM) coupled to energy dispersive X-ray spectroscopy (EDS). Release of Si, Ca, P and Zr into simulated body fluid (SBF) was determined by inductively coupled plasma (ICP). Upon heat treatment at 1000 °C, the glass powder crystallized into an apatite-wollastonite-zirconia glass-ceramic powder. Hydroxycarbonate apatite (HCA) formation on the surface of the glass and glass-ceramic particles containing ZrO2 was confirmed by FTIR and SEM. Addition of ZrO2 to the base glass composition decreased the rate of HCA formation in vitro from one day to three days, and hence, ZrO2 could be employed to control the rate of apatite formation. However, the rate of HCA formation on the glass-ceramic powder containing ZrO2 crystal was equal to that in the base glassy powder. Tests with a cultured human osteoblast-like MG-63 cells revealed that the glass and glass-ceramic materials stimulated cell proliferation, indicating that they are biocompatible and are not cytotoxic in vitro. Moreover, zirconia clearly increased osteoblast proliferation over that of the Zr-free samples. This increase is likely associated with the lower solubility of these samples and, consequently, a smaller variation in the media pH. Despite the low solubility of these materials, bioactivity was maintained, indicating that these glassy and polycrystalline powders are potential candidates for bone graft substitutes and bone cements with the special feature of radiopacity. Copyright © 2015 Elsevier B.V. All rights reserved.

Effects of carbon dioxide, Nd:YAG and carbon dioxide-Nd:YAG combination lasers at high energy densities on synthetic hydroxyaptite.

PubMed

Meurman, J H; Voegel, J C; Rauhamaa-Mäkinen, R; Gasser, P; Thomann, J M; Hemmerle, J; Luomanen, M; Paunio, I; Frank, R M

1992-01-01

The aim of this study was to determine the crystalline structure and chemical alterations of synthetic hydroxyapatite after irradiation with either CO2, Nd:YAG or CO2-Nd:YAG combination lasers at high energy densities of 500-3,230 J.cm2. Further, dissolution kinetics of the lased material were analysed and compared with those of unlased apatite. Electron microscopy showed that the lased material consisted of two kinds of crystals. From the micrographs their diameters varied from 600 to 1,200 A and from 3,000 to 6,000 A, respectively. The larger crystals showed 6.9-Angström periodic lattice fringes in the transmission electron microscope. alpha-Tricalcium phosphate (TCP) was identified by X-ray diffraction. Selective-area electron diffraction identified the large crystals to consist of tricalcium phosphate while the smaller crystals were probably hydroxyapatite. Assays of dissolution kinetics showed that at these high energy densities lased material dissolved more rapidly than unlased synthetic hydroxyapatite due to the higher solubility of TCP.

In situ synthesis of magnesium-substituted biphasic calcium phosphate and in vitro biodegradation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Tae-Wan; Lee, Hyeong-Shin; Kim, Dong-Hyun

Highlights: ► Mg–BCP were successfully prepared through in situ aqueous co-precipitation method. ► The amount of β-TCP phase was changed with the magnesium substitution level. ► The substitution of magnesium led to a decrease in the unit cell volume. ► Mg–BCP could be able to develop a new apatite phase on the surface faster than BCP. -- Abstract: In situ preparation of magnesium (Mg) substituted biphasic calcium phosphate (BCP) of hydroxyapatite (HAp)/β-tricalcium phosphate (β-TCP) were carried out through aqueous co-precipitation method. The concentrations of added magnesium were varied with the calcium in order to obtain constant (Ca + Mg)/P ratiosmore » of 1.602. X-ray diffraction (XRD) and Fourier transformed infrared (FTIR) spectroscopy were used to characterize the structure of synthesized magnesium substituted BCP powders. The results have shown that substitution of magnesium in the calcium deficient apatites revealed the formation of biphasic mixtures of different HAp/β-TCP ratios after heating at 1000 °C. The ratios of the formation of phase mixtures were dependent on the content of magnesium. After immersing in Hanks’ balanced salt solution (HBSS) for 1 week, 1 wt% magnesium substituted BCP powders were degraded and precipitation started to be formed with small granules consisting of number of flake-like crystal onto the surface of synthesized powders. On the other hand, in the case of pure BCP powders, the formation of new precipitates was detected after immersion in HBSS for 2 weeks. On the basis of these results, magnesium substituted BCP could be able to develop a new apatite phase on the surface in contact with physiological fluids faster than BCP does. In addition, the retention time to produce the new apatite phase in implantation operation for the BCP powder could be controlled by the amount of magnesium substitution.« less

The Thermal Evolution of the Southeast Baffin Island Continental Margin: An Integrated Apatite Fission Track and Apatite (U-Th)/He Study

NASA Astrophysics Data System (ADS)

Jess, S.; Stephenson, R.; Brown, R. W.

2017-12-01

The elevated continental margins of the North Atlantic continue to be a focus of considerable geological and geomorphological debate, as the timing of major tectonic events and the age of topographic relief remain controversial. The West Greenland margin, on the eastern flank of Baffin Bay, is believed by some authors to have experienced tectonic rejuvenation and uplift during the Neogene. However, the opposing flank, Baffin Island, is considered to have experienced a protracted erosional regime with little tectonic activity since the Cretaceous. This work examines the thermal evolution of the Cumberland Peninsula, SE Baffin Island, using published apatite fission track (AFT) data with the addition of 103 apatite (U-Th)/He (AHe) ages. This expansion of available thermochronological data introduces a higher resolution of thermal modelling, whilst the application of the newly developed `Broken Crystals' technique provides a greater number of thermal constraints for an area dominated by AHe age dispersion. Results of joint thermal modelling of the AFT and AHe data exhibit two significant periods of cooling across the Cumberland Peninsula: Devonian/Carboniferous to the Triassic and Late Cretaceous to present. The earliest phase of cooling is interpreted as the result of major fluvial systems present throughout the Paleozoic that flowed across the Canadian Shield to basins in the north and south. The later stage of cooling is believed to result from rift controlled fluvial systems that flowed into Baffin Bay during the Mesozoic and Cenozoic during the early stages and culmination of rifting along the Labrador-Baffin margins. Glaciation in the Late Cenozoic has likely overprinted these later river systems creating a complex fjordal distribution that has shaped the modern elevated topography. This work demonstrates how surface processes, and not tectonism, can explain the formation of elevated continental margins and that recent methodological developments in the field of low temperature thermochronology are improving our understanding of onshore passive margin development.

In Situ Immobilization of Selenium in Sediment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moore, Robert C.; Stewart, Thomas Austin

2014-09-01

This project focused on the use of a sorbent, carbonated apatite, to immobilize selenium in the environment. It is know that apatite will sorb selenium and based on the mechanism of sorption it is theorized that carbonated apatite will be more effective that pure apatite. Immobilization of selenium in the environment is through the use of a sorbent in a permeable reactive barrier (PRB). A PRB can be constructed by trenching and backfill with the sorbent or in the case of apatite as the sorbent formed in situ using the apatite forming solution of Moore (2003, 2004). There is verymore » little data on selenium sorption by carbonated apatite in the literature. Therefore, in this work, the basic sorptive properties of carbonated apatite were investigated. Carbonated apatite was synthesized by a precipitation method and characterized. Batch selenium kinetic and equilibrium experiments were performed. The results indicate the carbonated apatite contained 9.4% carbonate and uptake of selenium as selenite was rapid; 5 hours for complete uptake of selenium vs. more than 100 hours for pure hydroxyapatite reported in the literature. Additionally, the carbonated apatite exhibited significantly higher distribution coefficients in equilibrium experiments than pure apatite under similar experimental conditions. The next phase of this work will be to seek additional funds to continue the research with the goal of eventually demonstrating the technology in a field application.« less

Accurate determination of chemical shift tensor orientations of single-crystals by solid-state magic angle spinning NMR

NASA Astrophysics Data System (ADS)

Avadhut, Yamini S.; Weber, Johannes; Schmedt auf der Günne, Jörn

2017-09-01

An improved implementation of single-crystal magic-angle-spinning (MAS) NMR is presented which gives access to chemical shift tensors both in orientation (relative to the crystal axis system) and principal axis values. For mounting arbitrary crystals inside ordinary MAS rotors, a mounting tool is described which allows to relate the crystal orientation determined by diffraction techniques to the rotor coordinate system. The crystal is finally mounted into a MAS rotor equipped with a special insert which allows a defined reorientation of the single-crystal by 90°. The approach is based on the idea that the dispersive spectra, which are obtained when applying read-pulses at specific rotor-phases, not only yield the size of the eigenvalues but also encode the orientation of the different chemical shift (rank-2) tensors. For this purpose two 2D-data sets with orthogonal crystal orientation are fitted simultaneously. The presented analysis for chemical shift tensors is supported by an analytical formula which allows fast calculation of phase and amplitude of individual spinning side-bands and by a protocol which solves the problem of finding the correct reference phase of the spectrum. Different rotor-synchronized pulse-sequences are introduced for the same reason. Experiments are performed on L-alanine and O-phosphorylethanolamine and the observed errors are analyzed in detail. The experimental data are opposed to DFT-computed chemical shift tensors which have been obtained by the extended embedded ion method.

On the colour of wing scales in butterflies: iridescence and preferred orientation of single gyroid photonic crystals

PubMed Central

2017-01-01

Lycaenid butterflies from the genera Callophrys, Cyanophrys and Thecla have evolved remarkable biophotonic gyroid nanostructures within their wing scales that have only recently been replicated by nanoscale additive manufacturing. These nanostructures selectively reflect parts of the visible spectrum to give their characteristic non-iridescent, matte-green appearance, despite a distinct blue–green–yellow iridescence predicted for individual crystals from theory. It has been hypothesized that the organism must achieve its uniform appearance by growing crystals with some restrictions on the possible distribution of orientations, yet preferential orientation observed in Callophrys rubi confirms that this distribution need not be uniform. By analysing scanning electron microscope and optical images of 912 crystals in three wing scales, we find no preference for their rotational alignment in the plane of the scales. However, crystal orientation normal to the scale was highly correlated to their colour at low (conical) angles of view and illumination. This correlation enabled the use of optical images, each containing up to 104–105 crystals, for concluding the preferential alignment seen along the at the level of single scales, appears ubiquitous. By contrast, orientations were found to occur at no greater rate than that expected by chance. Above a critical cone angle, all crystals reflected bright green light indicating the dominant light scattering is due to the predicted band gap along the direction, independent of the domain orientation. Together with the natural variation in scale and wing shapes, we can readily understand the detailed mechanism of uniform colour production and iridescence suppression in these butterflies. It appears that the combination of preferential alignment normal to the wing scale, and uniform distribution within the plane is a near optimal solution for homogenizing the angular distribution of the band gap relative to the wings. Finally, the distributions of orientations, shapes, sizes and degree of order of crystals within single scales provide useful insights for understanding the mechanisms at play in the formation of these biophotonic nanostructures. PMID:28630678

Correlations of oriented ice and precipitation in marine midlatitude low clouds using collocated CloudSat, CALIOP, and MODIS observations

NASA Astrophysics Data System (ADS)

Ross, Alexa; Holz, Robert E.; Ackerman, Steven A.

2017-08-01

In April 2006, the Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) launched aboard the CALIPSO satellite and into the A-Train constellation of satellites with its transmitter pointed near nadir. This proved problematic due to specular reflection from horizontally oriented ice crystals occurring more frequently than expected. Because the specular backscatter from oriented ice crystals has large attenuated backscatter and almost no depolarization, the standard lidar inversions cannot be applied. To mitigate this issue, the CALIOP transmitter was moved to 3° off nadir in November 2007. Though problematic for global CALIOP retrievals, the sensitivity to oriented ice during the first year of observations provides a unique data set to investigate scenes of this ice crystal signature. This study focuses on the CALIOP-oriented signature that occurs in midlatitude ocean regions whose cloud tops are relatively warm and low, existing below 6 km. A significant seasonal dependence is found in the Northern Hemisphere with up to 19% of clouds below 6 km yielding specular reflection by CALIOP during the colder months. In contrast, the Southern Hemisphere lacks such seasonal dependence and sees fewer oriented ice crystals. Using collocated CloudSat observations with both CALIOP and Moderate Resolution Imaging Spectroradiometer (MODIS), we investigate the correlations of the oriented signature with MODIS cloud properties. Comparing with CloudSat precipitation retrievals, we find that the oriented signature is strongly correlated with surface precipitation with 64% of CALIOP-oriented ice crystal cases precipitating compared to 40% for nonoriented cases.

Scratching experiments on quartz crystals: Orientation effects in chipping

NASA Astrophysics Data System (ADS)

Tellier, C. R.; Benmessaouda, D.

1994-06-01

The deformation and microfracture properties of quartz crystals were studied by scratching experiments. The critical load at which microfractures are initiated was found to be orientation dependent, whereas the average width of ductile grooves and chips remained relatively insensitive to crystal orientation. In contrast, a marked anisotropy in the shape of chips was observed. This anisotropy has been interpreted in terms of microfractures propagating preferentially along slip planes. Simple geometrical conditions for the SEM (scanning electron microscopy) observation of active slip planes are proposed.

Optical-diffraction method for determining crystal orientation

DOEpatents

Sopori, B.L.

1982-05-07

Disclosed is an optical diffraction technique for characterizing the three-dimensional orientation of a crystal sample. An arbitrary surface of the crystal sample is texture etched so as to generate a pseudo-periodic diffraction grating on the surface. A laser light beam is then directed onto the etched surface, and the reflected light forms a farfield diffraction pattern in reflection. Parameters of the diffraction pattern, such as the geometry and angular dispersion of the diffracted beam are then related to grating shape of the etched surface which is in turn related to crystal orientation. This technique may be used for examining polycrystalline silicon for use in solar cells.

Control of Orientation and Morphology of Crystals Grown Under Organic Templates

NASA Astrophysics Data System (ADS)

Stripe, Benjamin

Living creatures demonstrate an extraordinary ability to both grow and control the growth of inorganic crystals. These biominerals are found almost everywhere in nature from simple plants and plankton to our own teeth and bones. A great deal of research has been focused on how living creatures are able to achieve such control over the shape, size, orientation, and arrangement of these biominerals. Many studies have been done demonstrating the effects the presence of organic molecules can have on the morphology of nucleating inorganic crystals. These studies have led to the use of ordered arrays of biological molecules as templates to select the orientation of the crystals. Such experiments have had amazing success cataloging monolayers, orientations and morphologies of crystals grown beneath them. However, despite several decades of work, the exact mechanisms by which the orientation and morphology of crystals is selected by organic templates are still not known. The present study attempts to explain the complex interactions that take place at the template surface and decide the orientations and morphologies of the crystals that nucleate there. To do this, scanning electron microscopy (SEM), grazing incidence x-ray diffraction (GID), and x-ray reflectivity have been used to probe the templates and nucleating crystals in situ. The experiments described here seek to move beyond the well-studied two-component systems. In many of these two-component systems a single template and a single type of crystal are grown, and often many claims and comparisons are made about monolayer charge, crystal surface energies, stereochemical recognition, and lattice matches. However, almost all of the claims and comparisons are between systems that are different enough that assumptions about relative charge, strain, recognition, and lattice dynamics are either unfounded or poorly supported. To bridge this gap in the comparison of these different two-component systems the studies presented here are tunable three-component systems. These experiments allow for either continuously adjusting the template by means of two miscible monolayers or adjusting the growing crystals by incorporation of secondary ions. In either case, the idea is the same: we can more accurately compare two-component systems and isolate the controlling factor in the selection of orientation and morphology of the nucleating crystals. The results of these studies have shown that there is a complex interplay of charge, lattice parameters and kinetics. Despite this, we have been able to show that well-oriented growth of single non-dendritic crystals is limited to a fairly small range of surface charges and relative growth kinetics. Within this range, variations in the growing crystals can be seen based on changes in the average lattice parameters despite there being no evidence of direct epitaxy. Theories have evolved around the idea of stereochemical matching between the template and nucleating surface. These theories correlate the template molecular tilt to the orientation relative to the nucleation plane. However, these theories are not supported by the results presented in this manuscript. The data presented in this manuscript are suggestive of far more complex interfacial interactions involving an intermediary amorphous precursor, or possible networks of hydrated or hydrogen bonded ions than has been suggested in previous studies. Excitingly, it appears to be possible to control the selection of orientation using these multicomponent systems despite the complex interactions at the surface.

Phase Transformations in a Human Tooth Tissue at the Initial Stage of Caries

PubMed Central

Prutskij, Tatiana; Ippolitov, Yury

2015-01-01

The aim of the paper is to study phase transformations in solid tissues of the human teeth during the development of fissure caries by Raman and fluorescence microspectroscopy. The study of the areas with fissure caries confirmed the assumption of the formation of a weak interaction between phosphate apatite enamel and organic acids (products of microorganisms). The experimental results obtained with by Raman microspectroscopy showed the formation of dicalcium phosphate dihydrate - CaHPO4-2H2O in the area of mural demineralization of carious fissure. A comparative analysis of structural and spectroscopic data for the intact and carious enamel shows that emergence of a more soluble phase - carbonate-substituted hydroxyapatite - is typical for the initial stage of caries. It is shown that microareas of dental hard tissues in the carious fissure due to an emerging misorientation of apatite crystals have a higher fluorescence yield than the area of the intact enamel. These areas can be easily detected even prior to a deep demineralization (white spot stage) for the case of irreversibly changed organomineral complex and intensive removal of the mineral component. PMID:25901743

Fabrication of Carbonate Apatite Block through a Dissolution-Precipitation Reaction Using Calcium Hydrogen Phosphate Dihydrate Block as a Precursor.

PubMed

Tsuru, Kanji; Yoshimoto, Ayami; Kanazawa, Masayuki; Sugiura, Yuki; Nakashima, Yasuharu; Ishikawa, Kunio

2017-03-31

Carbonate apatite (CO₃Ap) block, which is a bone replacement used to repair defects, was fabricated through a dissolution-precipitation reaction using a calcium hydrogen phosphate dihydrate (DCPD) block as a precursor. When the DCPD block was immersed in NaHCO₃ or Na₂CO₃ solution at 80 °C, DCPD converted to CO₃Ap within 3 days. β-Tricalcium phosphate was formed as an intermediate phase, and it was completely converted to CO₃Ap within 2 weeks when the DCPD block was immersed in Na₂CO₃ solution. Although the crystal structures of the DCPD and CO₃Ap blocks were different, the macroscopic structure was maintained during the compositional transformation through the dissolution-precipitation reaction. CO₃Ap block fabricated in NaHCO₃ or Na₂CO₃ solution contained 12.9 and 15.8 wt % carbonate, respectively. The diametral tensile strength of the CO₃Ap block was 2 MPa, and the porosity was approximately 57% regardless of the carbonate solution. DCPD is a useful precursor for the fabrication of CO₃Ap block.

Solvent minimization induces preferential orientation and crystal clustering in serial micro-crystallography on micro-meshes, in situ plates and on a movable crystal conveyor belt

DOE Office of Scientific and Technical Information (OSTI.GOV)

Soares, Alexei S.; Mullen, Jeffrey D.; Parekh, Ruchi M.

X-ray diffraction data were obtained at the National Synchrotron Light Source from insulin and lysozyme crystals that were densely deposited on three types of surfaces suitable for serial micro-crystallography: MiTeGen MicroMeshes™, Greiner Bio-One Ltdin situmicro-plates, and a moving kapton crystal conveyor belt that is used to deliver crystals directly into the X-ray beam. 6° wedges of data were taken from ~100 crystals mounted on each material, and these individual data sets were merged to form nine complete data sets (six from insulin crystals and three from lysozyme crystals). Insulin crystals have a parallelepiped habit with an extended flat face thatmore » preferentially aligned with the mounting surfaces, impacting the data collection strategy and the design of the serial crystallography apparatus. Lysozyme crystals had a cuboidal habit and showed no preferential orientation. Preferential orientation occluded regions of reciprocal space when the X-ray beam was incident normal to the data-collection medium surface, requiring a second pass of data collection with the apparatus inclined away from the orthogonal. In addition, crystals measuring less than 20 µm were observed to clump together into clusters of crystals. Clustering required that the X-ray beam be adjusted to match the crystal size to prevent overlapping diffraction patterns. No additional problems were encountered with the serial crystallography strategy of combining small randomly oriented wedges of data from a large number of specimens. Lastly, high-quality data able to support a realistic molecular replacement solution were readily obtained from both crystal types using all three serial crystallography strategies.« less

Solvent minimization induces preferential orientation and crystal clustering in serial micro-crystallography on micro-meshes, in situ plates and on a movable crystal conveyor belt.

PubMed

Soares, Alexei S; Mullen, Jeffrey D; Parekh, Ruchi M; McCarthy, Grace S; Roessler, Christian G; Jackimowicz, Rick; Skinner, John M; Orville, Allen M; Allaire, Marc; Sweet, Robert M

2014-11-01

X-ray diffraction data were obtained at the National Synchrotron Light Source from insulin and lysozyme crystals that were densely deposited on three types of surfaces suitable for serial micro-crystallography: MiTeGen MicroMeshes™, Greiner Bio-One Ltd in situ micro-plates, and a moving kapton crystal conveyor belt that is used to deliver crystals directly into the X-ray beam. 6° wedges of data were taken from ∼100 crystals mounted on each material, and these individual data sets were merged to form nine complete data sets (six from insulin crystals and three from lysozyme crystals). Insulin crystals have a parallelepiped habit with an extended flat face that preferentially aligned with the mounting surfaces, impacting the data collection strategy and the design of the serial crystallography apparatus. Lysozyme crystals had a cuboidal habit and showed no preferential orientation. Preferential orientation occluded regions of reciprocal space when the X-ray beam was incident normal to the data-collection medium surface, requiring a second pass of data collection with the apparatus inclined away from the orthogonal. In addition, crystals measuring less than 20 µm were observed to clump together into clusters of crystals. Clustering required that the X-ray beam be adjusted to match the crystal size to prevent overlapping diffraction patterns. No additional problems were encountered with the serial crystallography strategy of combining small randomly oriented wedges of data from a large number of specimens. High-quality data able to support a realistic molecular replacement solution were readily obtained from both crystal types using all three serial crystallography strategies.

Solvent minimization induces preferential orientation and crystal clustering in serial micro-crystallography on micro-meshes, in situ plates and on a movable crystal conveyor belt

DOE PAGES

Soares, Alexei S.; Mullen, Jeffrey D.; Parekh, Ruchi M.; ...

2014-10-09

X-ray diffraction data were obtained at the National Synchrotron Light Source from insulin and lysozyme crystals that were densely deposited on three types of surfaces suitable for serial micro-crystallography: MiTeGen MicroMeshes™, Greiner Bio-One Ltdin situmicro-plates, and a moving kapton crystal conveyor belt that is used to deliver crystals directly into the X-ray beam. 6° wedges of data were taken from ~100 crystals mounted on each material, and these individual data sets were merged to form nine complete data sets (six from insulin crystals and three from lysozyme crystals). Insulin crystals have a parallelepiped habit with an extended flat face thatmore » preferentially aligned with the mounting surfaces, impacting the data collection strategy and the design of the serial crystallography apparatus. Lysozyme crystals had a cuboidal habit and showed no preferential orientation. Preferential orientation occluded regions of reciprocal space when the X-ray beam was incident normal to the data-collection medium surface, requiring a second pass of data collection with the apparatus inclined away from the orthogonal. In addition, crystals measuring less than 20 µm were observed to clump together into clusters of crystals. Clustering required that the X-ray beam be adjusted to match the crystal size to prevent overlapping diffraction patterns. No additional problems were encountered with the serial crystallography strategy of combining small randomly oriented wedges of data from a large number of specimens. Lastly, high-quality data able to support a realistic molecular replacement solution were readily obtained from both crystal types using all three serial crystallography strategies.« less

Solvent minimization induces preferential orientation and crystal clustering in serial micro-crystallography on micro-meshes, in situ plates and on a movable crystal conveyor belt

PubMed Central

Soares, Alexei S.; Mullen, Jeffrey D.; Parekh, Ruchi M.; McCarthy, Grace S.; Roessler, Christian G.; Jackimowicz, Rick; Skinner, John M.; Orville, Allen M.; Allaire, Marc; Sweet, Robert M.

2014-01-01

X-ray diffraction data were obtained at the National Synchrotron Light Source from insulin and lysozyme crystals that were densely deposited on three types of surfaces suitable for serial micro-crystallography: MiTeGen MicroMeshes™, Greiner Bio-One Ltd in situ micro-plates, and a moving kapton crystal conveyor belt that is used to deliver crystals directly into the X-ray beam. 6° wedges of data were taken from ∼100 crystals mounted on each material, and these individual data sets were merged to form nine complete data sets (six from insulin crystals and three from lysozyme crystals). Insulin crystals have a parallelepiped habit with an extended flat face that preferentially aligned with the mounting surfaces, impacting the data collection strategy and the design of the serial crystallography apparatus. Lysozyme crystals had a cuboidal habit and showed no preferential orientation. Preferential orientation occluded regions of reciprocal space when the X-ray beam was incident normal to the data-collection medium surface, requiring a second pass of data collection with the apparatus inclined away from the orthogonal. In addition, crystals measuring less than 20 µm were observed to clump together into clusters of crystals. Clustering required that the X-ray beam be adjusted to match the crystal size to prevent overlapping diffraction patterns. No additional problems were encountered with the serial crystallography strategy of combining small randomly oriented wedges of data from a large number of specimens. High-quality data able to support a realistic molecular replacement solution were readily obtained from both crystal types using all three serial crystallography strategies. PMID:25343789

Study on preferred crystal orientations of Mg-Zr-O composite protective layer in AC-PDP

NASA Astrophysics Data System (ADS)

Bingang, G.; Chunliang, L.; Zhongxiao, S.; Liu, L.; Yufeng, F.; Xing, X.; Duowang, F.

2006-11-01

In order to study the preferred crystal orientations of Mg-Zr-O composite protective layers in PDP, Mg-Zr-O composite protective layers were deposited by Electron-beam Evaporator using (MgO+ZrO{2}) powder mixture as evaporation source material. X-ray diffractometer (XRD) was used to determine preferred crystal orientations of Mg-Zr-O composite protective layers, surface morphologies of films were analyzed by FESEM and voltage characteristics were examined in a testing macroscopic discharge cell of AC-PDP. On the basis of experimental analysis, the influence of oxide addition and deposition conditions on preferred orientations of Mg-Zr-O composite protective layers were investigated. The results showed that the preferred orientations of Mg-Zr-O films were determined by lattice distortion of MgO crystal. The deposition conditions have great effects on the preferred orientations of Mg-Zr-O films. The preferred orientations affect voltage characteristics through affecting surface morphology of Mg-Zr-O films. A small amount of Zr solution in MgO can decrease firing voltage compared with using pure MgO film. Firing voltage is closely related with the [ ZrO{2}/(MgO+ZrO{2})] ratio of evaporation source materials.

TRANSIENT AMORPHOUS CALCIUM PHOSPHATE IN FORMING ENAMEL

PubMed Central

Beniash, Elia; Metzler, Rebecca A.; Lam, Raymond S.K.; Gilbert, P.U.P.A.

2009-01-01

Enamel, the hardest tissue in the body, begins as a three-dimensional network of nanometer size mineral particles, suspended in a protein gel. This mineral network serves as a template for mature enamel formation. To further understand the mechanisms of enamel formation we characterized the forming enamel mineral at an early secretory stage using x-ray absorption near-edge structure (XANES) spectromicroscopy, transmission electron microscopy (TEM), FTIR microspectroscopy and polarized light microscopy. We show that the newly formed enamel mineral is amorphous calcium phosphate (ACP), which eventually transforms into apatitic crystals. Interestingly, the size, shape and spatial organization of these amorphous mineral particles and older crystals are essentially the same, indicating that the mineral morphology and organization in enamel is determined prior to its crystallization. Mineralization via transient amorphous phases has been previously reported in chiton teeth, mollusk shells, echinoderm spicules and spines, and recent reports strongly suggest the presence transient amorphous mineral in forming vertebrate bones. The present finding of transient ACP in murine tooth enamel suggests that this strategy might be universal. PMID:19217943

Magnetic field controlled single crystal growth and surface modification of titanium alloys exposed for biocompatibility

NASA Astrophysics Data System (ADS)

Hermann, Regina; Uhlemann, Margitta; Wendrock, Horst; Gerbeth, Gunter; Büchner, Bernd

2011-03-01

The aim of this work is growth and characterisation of Ti55Nb45 (wt%) single crystals by floating-zone single crystal growth of intermetallic compounds using two-phase radio-frequency (RF) electromagnetic heating. Thereby, the process and, in particular, the flow field in the molten zone is influenced by additional magnetic fields. The growth of massive intermetallic single crystals is very often unsuccessful due to an unfavourable solid-liquid interface geometry enclosing concave fringes. It is generally known that the crystallization process stability is enhanced if the crystallization interface is convex. For this, a tailored magnetic two-phase stirrer system has been developed, which enables a controlled influence on the melt ranging from intensive inwards to outwards flows. Since Ti is favourably light, strong and biocompatible, it is one of the few materials that naturally match the requirements for implantation in the human body. Therefore, the magnetic system was applied to crystal growth of Ti alloys. The grown crystals were oriented and cut to cubes with the desired crystallographic orientations [1 0 0] and [1 0 1] normally on a plane. The electron backscatter diffraction (EBSD) technique was applied to clearly determine crystal orientation and to localize grain boundaries. The formation of oxidic nanotubes on Ti surfaces in dependence of the grain orientation was investigated, performed electrochemically by anodic oxidation from fluoride containing electrolyte.

Empirical constraints on the effects of radiation damage on helium diffusion in zircon

NASA Astrophysics Data System (ADS)

Anderson, Alyssa J.; Hodges, Kip V.; van Soest, Matthijs C.

2017-12-01

In this study, we empirically evaluate the impact of radiation damage on zircon (U-Th)/He closure temperatures for a suite of zircon crystals from the slowly cooled McClure Mountain syenite of south-central Colorado, USA. We present new zircon, titanite, and apatite conventional (U-Th)/He dates, zircon laser ablation (U-Th)/He and U-Pb dates, and zircon Raman spectra for crystals from the syenite. Titanite and apatite (U-Th)/He dates range from 447 to 523 Ma and 88.0 to 138.9 Ma, respectively, and display no clear correlation between (U-Th)/He date and effective uranium concentration. Conventional zircon (U-Th)/He dates range from 230.3 to 474 Ma, while laser ablation zircon (U-Th)/He dates show even greater dispersion, ranging from 5.31 to 520 Ma. Dates from both zircon (U-Th)/He datasets decrease with increasing alpha dose, indicating that most of the dispersion can be attributed to radiation damage. Alpha dose values for the dated zircon crystals range from effectively zero to 2.15 × 1019 α /g, spanning the complete damage spectrum. We use an independently constrained thermal model to empirically assign a closure temperature to each dated zircon grain. If we assume that this thermal model is robust, the zircon radiation damage accumulation and annealing model of Guenthner et al. (2013) does not accurately predict closure temperatures for many of the analyzed zircon crystals. Raman maps of the zircons dated by laser ablation document complex radiation damage zoning, sometimes revealing crystalline zones in grains with alpha dose values suggestive of amorphous material. Such zoning likely resulted in heterogeneous intra-crystalline helium diffusion and may help explain some of the discrepancies between our empirical findings and the Guenthner et al. (2013) model predictions. Because U-Th zoning is a common feature in zircon, radiation damage zoning is likely to be a concern for most ancient, slowly cooled zircon (U-Th)/He datasets. Whenever possible, multiple mineral-isotopic systems should be employed to add additional, independent constraints to a sample's thermal history.

Radionuclide removal by apatite

DOE PAGES

Rigali, Mark J.; Brady, Patrick V.; Moore, Robert C.

2016-12-01

In this study, a growing body of research supports widespread future reliance on apatite for radioactive waste cleanup. Apatite is a multi-functional radionuclide sorbent that lowers dissolved radionuclide concentrations by surface sorption, ion exchange, surface precipitation, and by providing phosphate to precipitate low-solubility radionuclide-containing minerals. Natural apatites are rich in trace elements, and apatite’s stability in the geologic record suggest that radionuclides incorporated into apatite, whether in a permeable reactive barrier or a waste form, are likely to remain isolated from the biosphere for long periods of time. Here we outline the mineralogic and surface origins of apatite-radionuclide reactivity andmore » show how apatites might be used to environmental advantage in the future.« less

Deducing 2D Crystal Structure at the Solid/Liquid Interface with Atomic Resolution by Combined STM and SFG Study

NASA Astrophysics Data System (ADS)

McClelland, Arthur; Ahn, Seokhoon; Matzger, Adam J.; Chen, Zhan

2009-03-01

Supplemented by computed models, Scanning Tunneling Microscopy (STM) can provide detailed structure of 2D crystals formed at the liquid/solid interface with atomic resolution. However, some structural information such as functional group orientations in such 2D crystals needs to be tested experimentally to ensure the accuracy of the deduced structures. Due to the limited sensitivity, many other experimental techniques such as Raman and infrared spectroscopy have not been allowed to provide such structural information of 2D crystals. Here we showed that Sum Frequency Generation Vibrational Spectroscopy (SFG) can measure average orientation of functional groups in such 2D crystals, or physisorbed monolayers, providing key experimental data to aid in the modeling and interpretation of the STM images. The usefulness of combining these two techniques is demonstrated with a phthalate diesters monolayer formed at the 1-phenyloctane/ highly oriented pyrolytic graphite (HOPG) interface. The spatial orientation of the ester C=O of the monolayer was successfully determined using SFG.

Low cycle fatigue of MAR-M 200 single crystals at 760 and 870 deg C

NASA Technical Reports Server (NTRS)

Milligan, W. W.; Jayaraman, N.; Bill, R. C.

1984-01-01

Fully reversed low cycle fatigue tests were conducted on single crystals of the nickel-base superalloys Mar-M 200 at 760 C and 870 C. At 760 C, planar slip (octahedral) lead to orientation-dependent strain hardening and cyclic lives. Multiple slip crystals strain hardened the most, resulting in relatively high stress ranges and low lives. Single slip crystals strain hardened the least, resulting in relatively low stress ranges and higher lives. A preferential crack initiation site which was related to slip plane geometry was observed in single slip orientated crystals. At 870 C, the trends were quite different, and the slip character was much more homogeneous. As the tensile axis orientation deviated from 001 , the stress ranges increased and the cyclic lives decreased. Two possible mechanisms were proposed to explain the behavior: one is based on Takeuchi and Kuramoto's cube cross-slip model, and the other is based on orientation-dependent creep rates.

A look-up table based approach to characterize crystal twinning for synchrotron X-ray Laue microdiffraction scans

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Yao; Wan, Liang; Chen, Kai

An automated method has been developed to characterize the type and spatial distribution of twinning in crystal orientation maps from synchrotron X-ray Laue microdiffraction results. The method relies on a look-up table approach. Taking into account the twin axis and twin plane for plausible rotation and reflection twins, respectively, and the point group symmetry operations for a specific crystal, a look-up table listing crystal-specific rotation angle–axis pairs, which reveal the orientation relationship between the twin and the parent lattice, is generated. By comparing these theoretical twin–parent orientation relationships in the look-up table with the measured misorientations, twin boundaries are mappedmore » automatically from Laue microdiffraction raster scans with thousands of data points. Finally, taking advantage of the high orientation resolution of the Laue microdiffraction method, this automated approach is also applicable to differentiating twinning elements among multiple twinning modes in any crystal system.« less

Inheritance of Crystallographic Orientation during Lithiation/Delithiation Processes of Single-Crystal α-Fe2O3 Nanocubes in Lithium-Ion Batteries.

PubMed

Ma, Xiaowei; Zhang, Manyu; Liang, Chongyun; Li, Yuesheng; Wu, Jingjing; Che, Renchao

2015-11-04

Iron oxides are very promising anode materials based on conversion reactions for lithium-ion batteries (LIBs). During conversion processes, the crystal structure and composition of the electrode material are drastically changed. Surprisingly, in our study, inheritance of a crystallographic orientation was found during lithiation/delithiation processes of single-crystal α-Fe2O3 nanocubes by ex situ transmission electron microscopy. Single-crystal α-Fe2O3 was first transformed into numerous Fe nanograins embedded in a Li2O matrix, and then the conversion between Fe and FeO nanograins became the main reversible electrochemical reaction for energy storage. Interestingly, these Fe/FeO nanograins had almost the same crystallographic orientation, indicating that the lithiated/delithiated products can inherit the crystallographic orientation of single-crystal α-Fe2O3. This finding is important for understanding the detailed electrochemical conversion processes of iron oxides, and this feature may also exist during lithiation/delithiation processes of other transition-metal oxides.

A look-up table based approach to characterize crystal twinning for synchrotron X-ray Laue microdiffraction scans

DOE PAGES

Li, Yao; Wan, Liang; Chen, Kai

2015-04-25

An automated method has been developed to characterize the type and spatial distribution of twinning in crystal orientation maps from synchrotron X-ray Laue microdiffraction results. The method relies on a look-up table approach. Taking into account the twin axis and twin plane for plausible rotation and reflection twins, respectively, and the point group symmetry operations for a specific crystal, a look-up table listing crystal-specific rotation angle–axis pairs, which reveal the orientation relationship between the twin and the parent lattice, is generated. By comparing these theoretical twin–parent orientation relationships in the look-up table with the measured misorientations, twin boundaries are mappedmore » automatically from Laue microdiffraction raster scans with thousands of data points. Finally, taking advantage of the high orientation resolution of the Laue microdiffraction method, this automated approach is also applicable to differentiating twinning elements among multiple twinning modes in any crystal system.« less

Intermediate phases in [111]- and [001]-oriented PbMg1/3Nb2/3O3-29PbTiO3 single crystals

NASA Astrophysics Data System (ADS)

Kamzina, L. S.

2017-09-01

Phase transformations in [111]- and [001]-oriented PbMg1/3Nb2/3O3-29PbTiO3 single crystals have been studied using dielectric and optical measurements before and after applying an electric field. It is shown that the subsequence of phase transitions rhombohedral ( R)—tetragonal ( T)—cubic ( C) phases is observed in nonpolarized samples of both orientations as temperature increases. In the [111]-oriented crystal, an additional intermediate monoclinic phase (it is possible, M a ) is induced after preliminary polarization at room temperature and the R- M a - T- C phase transitions are observed on heating. In the [001]-oriented crystal, after its polarization, the monoclinic phase forms instead of the rhombohedral phase even at room temperature and the M a - T- C transitions occur on heating. The results are discussed from the point of view of the existence polar nanoregions with different local symmetries in a glasslike matrix.

Compositional Variation of Terrestrial Mantle Apatites and Implications for the Halogen and Water Budgets of the Terrestrial Mantle

NASA Astrophysics Data System (ADS)

Roden, M.; Patino Douce, A. E.; Chaumba, J. B.; Fleisher, C.; Yogodzinski, G. M.

2011-12-01

Apatite in ultramafic xenoliths from various tectonic enviroments including arc (Kamchatka), plume (Hawaii), and intraplate (Lunar Crater, Nunivak, Colorado Plateau) were analyzed by electron microprobe with the aim of characterizing the Cl and F contents, and from these measured compositions to infer the nature of fluids/melts that the apatites equilibrated with. The impetus for the study derived from the generalization of O'Reilly and Griffin (1) that mantle-derived metasomatic apatites tend to be Cl-rich and mantle-derived igneous apatites tend to be F-rich. Our work largely corroborates their generalization with Cl- and/or H2O-rich compositions characterizing the apatites from Nunivak and Kamchatka while apatites from igneous or Group II xenoliths tend to be Cl-poor and be either nearly pure fluorapatite or a mix of hydroxylapatite and fluorapatite. We attribute the Cl-rich nature of the Kamchatka apatites to formation from Cl-rich fluids generated from subducted lithosphere; however the Nunivak occurrence is far removed from subducted lithosphere and may reflect a deep seated source for Cl as also indicated by brine inclusions in diamonds, Cl-rich apatites in carbonate-bearing xenoliths and a Cl-rich signature in some plumes such as Iceland, Azores and Samoa. One curious aspect of mantle-derived apatite compositions is that xenoliths with evidence of carbonatitic metasomatism commonly have Cl-rich apatites while apatites from carbonatites are invariably Cl-poor - perhaps reflecting loss of Cl in fluids evolved from the carbonatitic magma. Apatites from Group II xenoliths at Hawaii are solid solutions between fluorapatite and hydroxylapatite and show no evidence for deep-seated Cl at Hawaii. Samples of the terrestrial mantle are almost uniformly characterized by mineral assemblages with a single Ca-rich phosphate phase but the mantles of Mars, Vesta and the Moon have two Ca-rich phosphates, apatite and volatile-poor merrillite - apatite compositions existing with merrillite are typically Cl- and F-rich in the case of Mars but F-rich in the case of the Moon and Vesta (2-4). In a single reported example of terrestrial mantle xenoliths containing apatite and and a similar volatile-poor Ca-phosphate, whitlockite, the apatite contained significant Cl and H2O but was F-rich and similar to some lunar apatites. Our thermodynamic analysis of apatite-merrillite equilibria suggests that high phosphorous chemical potentials combined with high halogen and low water fugacities are required for the coexistence of a volatile-poor Ca-phosphate with apatite, and point out the relatively unique and typically water-rich nature of the upper mantle of the Earth compared to other differentiated planetary bodies. References 1. S. O'Reilly & W. Griffin, 2000, Lithos 53: 217. 2. A. Patiño Douce et al., 2011, Chem Geol. in press 3. F. McCubbin et al. 2009, LPSC abs 2246 4. A. Sarafian et al. 2011, Meteor. Soc. Abs 5023

Tuning the functional properties of PMN-PT single crystals via doping and thermoelectrical treatments

NASA Astrophysics Data System (ADS)

Luo, Laihui; Dietze, Matthias; Solterbeck, Claus-Henning; Luo, Haosu; Es-Souni, Mohammed

2013-12-01

Single crystals based on solid solutions of lead-magnesium-niobate (PMN) and lead titanate (PT) have emerged as highly promising multifunctional systems combining piezoelectric, pyroelectric, and electro-optic properties that surpass by far those of the best known lead-zirkonium-titanate ceramics. In this paper we present new findings on how the phase transition temperature and the dielectric and ferroelectric properties can be tuned depending on crystal composition, orientation, and thermoelectrical treatment. Mn-doped and pure 0.72PbMg1/3Nb2/3O3-0.28PbTiO3 (0.72PMN-0.28PT) single crystals with ⟨111⟩ and ⟨001⟩ orientations were investigated. A special attention was devoted to field cooling (FC), i.e., cooling under electric field from different temperatures. The results illustrate different findings that were not reported before: the Curie temperature, i.e., ferroelectric-paraelectric transition temperature, is enhanced after field cooling of the Mn-doped, ⟨001⟩-oriented crystal while such a shift is not observed in the ⟨111⟩-oriented and the non-doped crystals. In addition, substantial polarization suppression occurs in the Mn-doped crystals upon FC from high temperature regardless of orientation. Based on piezoforce microscopy of the domain structure that shows suppression of domain growth following field cooling from 200 °C, we propose a mechanism for polarization suppression based on domain pinning by charged defects. The practical importance of our results lies in showing the opportunity offered by a proper choice of crystal composition and poling conditions for tuning the functional properties of PMN-PT single crystals for a specific application. This should contribute to the understanding of their properties towards advanced sensor and transducers devices.

Ascorbate-apatite composite and ascorbate-FGF-2-apatite composite layers formed on external fixation rods and their effects on cell activity in vitro.

PubMed

Wang, Xiupeng; Ito, Atsuo; Sogo, Yu; Li, Xia; Tsurushima, Hideo; Oyane, Ayako

2009-09-01

Ascorbate-apatite and ascorbate-fibroblast growth factor-2 (FGF-2)-apatite composite layers were successfully formed on anodically oxidized Ti rods clinically used for external fixation by a one-step procedure at 25 degrees C, using a metastable supersaturated calcium phosphate solution supplemented with l-ascorbic acid phosphate magnesium salt n-hydrate (AsMg) and FGF-2. The AsMg-apatite and AsMg-FGF-2-apatite composite layers were evaluated in vitro using fibroblastic NIH3T3 and osteoblastic MC3T3-E1 cells. The AsMg-FGF-2-apatite composite layer markedly enhanced the NIH3T3 cell proliferation and procollagen type capital I, Ukrainian gene expression. Without FGF-2, the AsMg-apatite composite layer whose ascorbate content was 3.64+/-1.27microgcm(-2) obviously enhanced osteoblastic proliferation and differentiation. However, the AsMg-FGF-2-apatite composite layers whose FGF-2 contents were from 0.15+/-0.03 to 0.31+/-0.04microgcm(-2) inhibited osteoblastic differentiation in vitro. Thus, the AsMg-FGF-2-apatite composite layer should be precipitated on the surface of external fixators attached to skin and soft tissue. On the other hand, the AsMg-apatite composite layer should be precipitated at the part attached to bone tissue.

Surface or internal nucleation and crystallization of glass-ceramics

NASA Astrophysics Data System (ADS)

Höland, W.; Rheinberger, V. M.; Ritzberger, C.; Apel, E.

2013-07-01

Fluoroapatite (Ca5(PO4)3F) was precipitated in glass-ceramics via internal crystallization of base glasses. The crystals grew with a needle-like morphology in the direction of the crystallographic c-axis. Two different reaction mechanisms were analyzed: precipitation via a disordered primary apatite crystals and a solid state parallel reaction to rhenanite (NaCaPO4) precipitation. In contrast to the internal nucleation used in the formation of fluoroapatite, surface crystallization was induced to precipitate a phosphate-free oxyapatite of NaY9(SiO4)6O2-type. Internal nucleation and crystallization have been shown to be a very useful tool for developing high-strength lithium disilicate (Li2Si2O5) glass-ceramics. A very controlled process was conducted to transform the lithium metasilicate glass-ceramic precursor material into the final product of the lithium disilicate glass-ceramic without the major phase of the precursor material. The combination of all these methods allowed the driving forces of the internal nucleation and crystallization mechanisms to be explained. An amorphous phosphate primary phase was discovered in the process. Nucleation started at the interface between the amorphous phosphate phase and the glass matrix. The final products of all these glass-ceramics are biomaterials for dental restoration showing special optical properties, e.g. translucence and color close to dental teeth.

Slow-release fertilizer

NASA Technical Reports Server (NTRS)

Golden, Dadigamuwage C. (Inventor); Ming, Douglas W. (Inventor)

1995-01-01

A synthetic apatite containing agronutrients and a method for making the apatite are disclosed. The apatite comprises crystalline calcium phosphate having agronutrients dispersed in the crystalline structure. The agronutrients can comprise potassium, magnesium, sulfur, iron, manganese, molybdenum, chlorine, boron, copper and zinc in amounts suited for plant growth. The apatite can optionally comprise a carbonate and/or silicon solubility control agent. The agronutrients are released slowly as the apatite dissolves.

Slow-release fertilizer

NASA Technical Reports Server (NTRS)

Ming, Douglas W. (Inventor); Golden, D. C. (Inventor)

1992-01-01

A synthetic apatite containing agronutrients and a method for making the apatite are disclosed. The apatite comprises crystalline calcium phosphate having agronutrients dispersed in the crystalline structure. The agronutrients can comprise potassium, magnesium, sulfur, iron, manganese, molybdenum, chlorine, boron, copper and zinc in amounts suited for plant growth. The apatite can optionally comprise a carbonate and/or silicon solubility control agent. The agronutrients are released slowly as the apatite dissolves.

Slow-release fertilizer

NASA Astrophysics Data System (ADS)

Ming, Douglas W.; Golden, D. C.

1992-10-01

A synthetic apatite containing agronutrients and a method for making the apatite are disclosed. The apatite comprises crystalline calcium phosphate having agronutrients dispersed in the crystalline structure. The agronutrients can comprise potassium, magnesium, sulfur, iron, manganese, molybdenum, chlorine, boron, copper and zinc in amounts suited for plant growth. The apatite can optionally comprise a carbonate and/or silicon solubility control agent. The agronutrients are released slowly as the apatite dissolves.

Crystal Orientation Controlled Photovoltaic Properties of Multilayer GaAs Nanowire Arrays.

PubMed

Han, Ning; Yang, Zai-Xing; Wang, Fengyun; Yip, SenPo; Li, Dapan; Hung, Tak Fu; Chen, Yunfa; Ho, Johnny C

2016-06-28

In recent years, despite significant progress in the synthesis, characterization, and integration of various nanowire (NW) material systems, crystal orientation controlled NW growth as well as real-time assessment of their growth-structure-property relationships still presents one of the major challenges in deploying NWs for practical large-scale applications. In this study, we propose, design, and develop a multilayer NW printing scheme for the determination of crystal orientation controlled photovoltaic properties of parallel GaAs NW arrays. By tuning the catalyst thickness and nucleation and growth temperatures in the two-step chemical vapor deposition, crystalline GaAs NWs with uniform, pure ⟨110⟩ and ⟨111⟩ orientations and other mixture ratios can be successfully prepared. Employing lift-off resists, three-layer NW parallel arrays can be easily attained for X-ray diffraction in order to evaluate their growth orientation along with the fabrication of NW parallel array based Schottky photovoltaic devices for the subsequent performance assessment. Notably, the open-circuit voltage of purely ⟨111⟩-oriented NW arrayed cells is far higher than that of ⟨110⟩-oriented NW arrayed counterparts, which can be interpreted by the different surface Fermi level pinning that exists on various NW crystal surface planes due to the different As dangling bond densities. All this indicates the profound effect of NW crystal orientation on physical and chemical properties of GaAs NWs, suggesting the careful NW design considerations for achieving optimal photovoltaic performances. The approach presented here could also serve as a versatile and powerful platform for in situ characterization of other NW materials.

The lunar apatite paradox.

PubMed

Boyce, J W; Tomlinson, S M; McCubbin, F M; Greenwood, J P; Treiman, A H

2014-04-25

Recent discoveries of water-rich lunar apatite are more consistent with the hydrous magmas of Earth than the otherwise volatile-depleted rocks of the Moon. Paradoxically, this requires H-rich minerals to form in rocks that are otherwise nearly anhydrous. We modeled existing data from the literature, finding that nominally anhydrous minerals do not sufficiently fractionate H from F and Cl to generate H-rich apatite. Hydrous apatites are explained as the products of apatite-induced low magmatic fluorine, which increases the H/F ratio in melt and apatite. Mare basalts may contain hydrogen-rich apatite, but lunar magmas were most likely poor in hydrogen, in agreement with the volatile depletion that is both observed in lunar rocks and required for canonical giant-impact models of the formation of the Moon.

Revealing the preferred interlayer orientations and stackings of two-dimensional bilayer gallium selenide crystals.

PubMed

Li, Xufan; Basile, Leonardo; Yoon, Mina; Ma, Cheng; Puretzky, Alexander A; Lee, Jaekwang; Idrobo, Juan C; Chi, Miaofang; Rouleau, Christopher M; Geohegan, David B; Xiao, Kai

2015-02-23

Characterizing and controlling the interlayer orientations and stacking orders of two-dimensional (2D) bilayer crystals and van der Waals (vdW) heterostructures is crucial to optimize their electrical and optoelectronic properties. The four polymorphs of layered gallium selenide (GaSe) crystals that result from different layer stackings provide an ideal platform to study the stacking configurations in 2D bilayer crystals. Through a controllable vapor-phase deposition method, bilayer GaSe crystals were selectively grown and their two preferred 0° or 60° interlayer rotations were investigated. The commensurate stacking configurations (AA' and AB stacking) in as-grown bilayer GaSe crystals are clearly observed at the atomic scale, and the Ga-terminated edge structure was identified using scanning transmission electron microscopy. Theoretical analysis reveals that the energies of the interlayer coupling are responsible for the preferred orientations among the bilayer GaSe crystals. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tutorial: Crystal orientations and EBSD — Or which way is up?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Britton, T.B., E-mail: b.britton@imperial.ac.uk; Jiang, J.; Guo, Y.

2016-07-15

Electron backscatter diffraction (EBSD) is an automated technique that can measure the orientation of crystals in a sample very rapidly. There are many sophisticated software packages that present measured data. Unfortunately, due to crystal symmetry and differences in the set-up of microscope and EBSD software, there may be accuracy issues when linking the crystal orientation to a particular microstructural feature. In this paper we outline a series of conventions used to describe crystal orientations and coordinate systems. These conventions have been used to successfully demonstrate that a consistent frame of reference is used in the sample, unit cell, pole figuremore » and diffraction pattern frames of reference. We establish a coordinate system rooted in measurement of the diffraction pattern and subsequently link this to all other coordinate systems. A fundamental outcome of this analysis is to note that the beamshift coordinate system needs to be precisely defined for consistent 3D microstructure analysis. This is supported through a series of case studies examining particular features of the microscope settings and/or unambiguous crystallographic features. These case studies can be generated easily in most laboratories and represent an opportunity to demonstrate confidence in use of recorded orientation data. Finally, we include a simple software tool, written in both MATLAB® and Python, which the reader can use to compare consistency with their own microscope set-up and which may act as a springboard for further offline analysis. - Highlights: • Presentation of conventions used to describe crystal orientations • Three case studies that outline how conventions are consistent • Demonstrates a pathway for calibration and validation of EBSD based orientation measurements • EBSD computer code supplied for validation by the reader.« less

3-D microstructure of olivine in complex geological materials reconstructed by correlative X-ray μ-CT and EBSD analyses.

PubMed

Kahl, W-A; Dilissen, N; Hidas, K; Garrido, C J; López-Sánchez-Vizcaíno, V; Román-Alpiste, M J

2017-11-01

We reconstruct the 3-D microstructure of centimetre-sized olivine crystals in rocks from the Almirez ultramafic massif (SE Spain) using combined X-ray micro computed tomography (μ-CT) and electron backscatter diffraction (EBSD). The semidestructive sample treatment involves geographically oriented drill pressing of rocks and preparation of oriented thin sections for EBSD from the μ-CT scanned cores. The μ-CT results show that the mean intercept length (MIL) analyses provide reliable information on the shape preferred orientation (SPO) of texturally different olivine groups. We show that statistical interpretation of crystal preferred orientation (CPO) and SPO of olivine becomes feasible because the highest densities of the distribution of main olivine crystal axes from EBSD are aligned with the three axes of the 3-D ellipsoid calculated from the MIL analyses from μ-CT. From EBSD data we distinguish multiple CPO groups and by locating the thin sections within the μ-CT volume, we assign SPO to the corresponding olivine crystal aggregates, which confirm the results of statistical comparison. We demonstrate that the limitations of both methods (i.e. no crystal orientation data in μ-CT and no spatial information in EBSD) can be overcome, and the 3-D orientation of the crystallographic axes of olivines from different orientation groups can be successfully correlated with the crystal shapes of representative olivine grains. Through this approach one can establish the link among geological structures, macrostructure, fabric and 3-D SPO-CPO relationship at the hand specimen scale even in complex, coarse-grained geomaterials. © 2017 The Authors Journal of Microscopy © 2017 Royal Microscopical Society.

SSME single-crystal turbine blade dynamics

NASA Technical Reports Server (NTRS)

Moss, Larry A.

1988-01-01

A study was performrd to determine the dynamic characteristics of the Space Shuttle Main Engine high pressure fuel turbopump (HPFTP) blades made of single crystal (SC) material. The first and second stage drive turbine blades of HPFTP were examined. The nonrotating natural frequencies were determined experimentally and analytically. The experimental results of the SC second stage blade were used to verify the analytical procedures. The study examined the SC first stage blade natural frequencies with respect to crystal orientation at typical operating conditions. The SC blade dynamic response was predicted to be less than the directionally solidified base. Crystal axis orientation optimization indicated that the third mode interference will exist in any SC orientation.

SSME single crystal turbine blade dynamics

NASA Technical Reports Server (NTRS)

Moss, Larry A.; Smith, Todd E.

1987-01-01

A study was performed to determine the dynamic characteristics of the Space Shuttle main engine high pressure fuel turbopump (HPFTP) blades made of single crystal (SC) material. The first and second stage drive turbine blades of HPFTP were examined. The nonrotating natural frequencies were determined experimentally and analytically. The experimental results of the SC second stage blade were used to verify the analytical procedures. The analytical study examined the SC first stage blade natural frequencies with respect to crystal orientation at typical operating conditions. The SC blade dynamic response was predicted to be less than the directionally solidified blade. Crystal axis orientation optimization indicated the third mode interference will exist in any SC orientation.

AN INVESTIGATION OF THE MINERAL IN DUCTILE AND BRITTLE CORTICAL MOUSE BONE

PubMed Central

Rodriguez-Florez, Naiara; Garcia-Tunon, Esther; Mukadam, Quresh; Saiz, Eduardo; Oldknow, Karla J.; Farquharson, Colin; Millán, José Luis; Boyde, Alan; Shefelbine, Sandra J.

2015-01-01

Bone is a strong and tough material composed of apatite mineral, organic matter and water. Changes in composition and organization of these building blocks affect bone’s mechanical integrity. Skeletal disorders often affect bone’s mineral phase, either by variations in the collagen or directly altering mineralization. The aim of the current study was to explore the differences in the mineral of brittle and ductile cortical bone at the mineral (nm) and tissue (µm) levels using two mouse phenotypes. Osteogenesis imperfecta murine (oim−/−) mice were used to model brittle bone; PHOSPHO1 mutants (Phospho1−/−) had ductile bone. They were compared to their respective wild-type controls. Femora were defatted and ground to powder to measure average mineral crystal size using X-ray diffraction (XRD), and to monitor the bulk mineral to matrix ratio via thermogravimetric analysis (TGA). XRD scans were run after TGA for phase identification, to assess the fractions of hydroxyapatite and β-tricalcium phosphate. Tibiae were embedded to measure elastic properties with nanoindentation and the extent of mineralization with backscattered electron microscopy (qbSEM). Interestingly, the mineral of brittle oim−/− and ductile Phospho1−/− bones had many similar characteristics. Both pathology models had smaller apatite crystals, lower mineral to matrix ratio, and showed more thermal conversion to β-tricalcium phosphate than their wild-types, indicating deviations from stoichiometric hydroxyapatite in the original mineral. The degree of mineralization of the bone matrix was different for each strain: oim−/− were hypermineralized, while Phospho1−/− were hypomineralized. However, alterations in the mineral were associated with reduced tissue elastic moduli in both pathologies. Results revealed that despite having extremely different whole bone mechanics, the mineral of oim−/− and Phospho1−/− has several similar trends at smaller length scales. This indicates that alterations from normal crystal size, composition, and structure will reduce the mechanical integrity of bone. PMID:25418329

An investigation of the mineral in ductile and brittle cortical mouse bone.

PubMed

Rodriguez-Florez, Naiara; Garcia-Tunon, Esther; Mukadam, Quresh; Saiz, Eduardo; Oldknow, Karla J; Farquharson, Colin; Millán, José Luis; Boyde, Alan; Shefelbine, Sandra J

2015-05-01

Bone is a strong and tough material composed of apatite mineral, organic matter, and water. Changes in composition and organization of these building blocks affect bone's mechanical integrity. Skeletal disorders often affect bone's mineral phase, either by variations in the collagen or directly altering mineralization. The aim of the current study was to explore the differences in the mineral of brittle and ductile cortical bone at the mineral (nm) and tissue (µm) levels using two mouse phenotypes. Osteogenesis imperfecta model, oim(-/-) , mice have a defect in the collagen, which leads to brittle bone; PHOSPHO1 mutants, Phospho1(-/-) , have ductile bone resulting from altered mineralization. Oim(-/-) and Phospho1(-/-) were compared with their respective wild-type controls. Femora were defatted and ground to powder to measure average mineral crystal size using X-ray diffraction (XRD) and to monitor the bulk mineral to matrix ratio via thermogravimetric analysis (TGA). XRD scans were run after TGA for phase identification to assess the fractions of hydroxyapatite and β-tricalcium phosphate. Tibiae were embedded to measure elastic properties with nanoindentation and the extent of mineralization with backscattered electron microscopy (BSE SEM). Results revealed that although both pathology models had extremely different whole-bone mechanics, they both had smaller apatite crystals, lower bulk mineral to matrix ratio, and showed more thermal conversion to β-tricalcium phosphate than their wild types, indicating deviations from stoichiometric hydroxyapatite in the original mineral. In contrast, the degree of mineralization of bone matrix was different for each strain: brittle oim(-/-) were hypermineralized, whereas ductile Phospho1(-/-) were hypomineralized. Despite differences in the mineralization, nanoscale alterations in the mineral were associated with reduced tissue elastic moduli in both pathologies. Results indicated that alterations from normal crystal size, composition, and structure are correlated with reduced mechanical integrity of bone. © 2014 American Society for Bone and Mineral Research.

Understanding the evolution of S- and I-type granitic plutons through analysis of apatite.

NASA Astrophysics Data System (ADS)

Hess, B. L.; Fiege, A.; Tailby, N.

2017-12-01

The major and trace element composition of apatites from the Lachlan fold belt (LFB) S- and I-type granitoids (Australia) and the Central French Massif (CFM) S-type leucogranites (France) were analyzed to investigate their compositional and redox variation. Apatite is a common accessory mineral in magmatic systems that can incorporate a variety of trace elements, including the polyvalent elements sulfur (S), iron (Fe), and manganese (Mn). It was recently discovered that apatite can incorporate three oxidation states of S (S6+, S4+, S2-) into its structure as a function of oxygen fugacity [1]. However, the oxidation states of Mn and Fe in apatite are essentially unknown (2+ and/or 3+). In this study, we collected many electron probe line transects across apatites in several different host phases from a variety of S- and I-type plutons. The F-H-Cl contents of the S- and I-type LFB samples were similar ( 2.9 wt% F, 0.4 wt% Cl, 0.5 wt% OH). The CFM S-types contained virtually no Cl and ranged from near-endmember OH-apatite to near-endmember F-apatite. The apatites of all studied the S- and I-type plutons are characterized by similar ranges of Fe content (<1.5 wt% Fe), while Mn reaches much higher concentrations in the S-type when compared to I-type apatites (<6.5 wt% Mn). The S content of the apatites varies significantly, from <50 ppm S in the LFB S-types, up to 2,000 ppm S in the LFB I-types, and reaching 1,650 ppm S in the CFM S-types. The elevated S contents in the LFB I-type and CFM S-type apatites allowed us to measure the S oxidation states by using X-ray absorption near-edge structure (XANES) spectroscopy. The spectra show variability in S oxidation states ranging from mostly sulfate down to nearly equal S6+/S2- ratios, indicating redox variations during apatite formation. The S-type Mn + Fe content plots in a 1:1 ratio against calcium (Ca) in atoms per formula unit, while the I-type apatites have too low Mn and Fe to show a clear trend. Thus, divalent Mn and Fe probably replace Ca2+ in the S-types' apatite structure, while the incorporation of trivalent Mn or Fe in apatite is rather unlikely. We suggest that Mn and Fe contents in apatite may become a useful tracer of melt evolution once the distributions coefficients are experimentally calibrated. [1] Konecke et al. (2017), Am Mineral

ACTIVE MEDIA: BaY2F8 single crystals doped with rare-earth ions as promising up-conversion media for UV and VUV lasers

NASA Astrophysics Data System (ADS)

Pushkar', A. A.; Uvarova, T. V.; Molchanov, V. N.

2008-04-01

BaY2F8 crystals are studied as promising active media for UV and VUV lasers. The up-conversion pumping of rare-earth activators is proposed to solve problems related to the solarisation of the medium and the selection of pump sources. The technology of growing oriented BaY2F8 single crystals is developed and the influence of the crystal orientation on the growth rate and quality of single crystals is determined.

Apatite Formation: Why It May Not Work as Planned, and How to Conclusively Identify Apatite Compounds

PubMed Central

2013-01-01

Calcium phosphate apatites are inorganic compounds encountered in many different mineralized tissues. Bone mineral, for example, is constituted of nanocrystalline nonstoichiometric apatite, and the production of “analogs” through a variety of methods is frequently reported. In another context, the ability of solid surfaces to favor the nucleation and growth of “bone-like” apatite upon immersion in supersaturated fluids such as SFB is commonly used as one evaluation index of the “bioactivity” of such surfaces. Yet, the compounds or deposits obtained are not always thoroughly characterized, and their apatitic nature is sometimes not firmly assessed by appropriate physicochemical analyses. Of particular importance are the “actual” conditions in which the precipitation takes place. The precipitation of a white solid does not automatically indicate the formation of a “bone-like carbonate apatite layer” as is sometimes too hastily concluded: “all that glitters is not gold.” The identification of an apatite phase should be carefully demonstrated by appropriate characterization, preferably using complementary techniques. This review considers the fundamentals of calcium phosphate apatite characterization discussing several techniques: electron microscopy/EDX, XRD, FTIR/Raman spectroscopies, chemical analyses, and solid state NMR. It also underlines frequent problems that should be kept in mind when making “bone-like apatites.” PMID:23984373

Genesis of iron-apatite ores in Posht-e-Badam Block (Central Iran) using REE geochemistry

NASA Astrophysics Data System (ADS)

Mokhtari, Mir Ali Asghar; Zadeh, Ghader Hossein; Emami, Mohamad Hashem

2013-06-01

Rare earth elements in apatites of different ore types show characteristic patterns which are related to different modes of formation of the ores. Most of the apatite-bearing iron ores are associated with alkaline magmas with LREE/HREE fractionation varying from moderate to steep. Iron-apatite deposits in Posht-e-Badam Block (Central Iran) have a high concentration of REE (more than 1000 ppm up to 2.5%), and show a strong LREE/HREE ratio with a pronounced negative Eu anomaly. This REE pattern is typical of magmatic apatite and quiet distinct from sedimentary apatites (phosphorites) which have a low REE contents and Ce negative anomalies. On the other hand, they are comparable to the REE patterns of apatites in Kiruna-type iron ores in different parts of the world. The REE patterns of apatites, iron-apatite ores and iron ores are similar and only have different REE contents. This similarity indicates a genetic relation for these rocks. Most of the iron-apatite deposits in Central Iran have similar REE patterns too, which in turn show a genetic relation for all of these deposits. This similarity indicates a similar origin and processes in their genesis. There are some small intrusions around some of the iron-apatite deposits that are petrographically identified as syenite and gabbro. These intrusions also have REE patterns similar to that of iron-apatite ores. This demonstrates a genetic relation between these intrusions and iron-apatite ores. The REE patterns of apatites in different deposits of Posht-e-Badam Block iron-apatite ores show an affinity to alkaline to sub-alkaline magmas and rifting environment. The alkaline host rocks of Central Iran iron-apatite ores are clearly related to an extensional setting where rifting was important (SSE-NNW fault lines). A probable source for this large scale ore forming processes is relatively low partial melting of mantle rocks. The ores have originated by magmatic differentiation as a late phase in the volcanic cycle forming sub-surface injections or surface flows. These ores have formed during magmatism as immiscible liquids (silicate and Fe-P-rich magmatic liquids) which separated from strongly differentiated magmas aided by a large volatile and alkali element content. Separation of an iron oxide melt and the ensuing hydrothermal processes dominated by alkali metasomatism were both involved to different degrees in the formation of Posht-e-Badam Block iron-apatite deposits. We proposed that the separation of an iron oxide melt and the ensuing hydrothermal processes dominated by alkali metasomatism were both involved to different degrees in the formation of Posht-e-Badam Block iron-apatite deposits.

Orientation distribution of sheared isotactic polypropylene plates through thickness in the presence of sodium benzoate

NASA Astrophysics Data System (ADS)

Zhu, Peng-wei; Phillips, Andrew; Tung, Jason; Edward, Graham

2005-05-01

The orientation distribution of sheared isotactic polypropylene (iPP) containing different amount of sodium benzoate (SB) has been investigated through the gradient of shear flow field using microbeam of synchrotron wide-angle x-ray techniques. The degree of the overall orientation of α-phase crystal is found to increase with increasing concentration of SB. Compared with the sheared iPP in the absence of SB, the orientation of α-phase crystal is found to distribute over a broader range of shear flow field in the presence of SB. The overall orientation of α-phase crystal is explained in terms of a parent-daughter model or lamella-branched shish-kebab structure. As the concentration of SB increases, the contribution from the c-axis orientation of parent lamellae decreases in the flow direction. The contribution from the a*-axis orientation of daughter lamellae is developed to be dominant in the flow direction when the concentration of SB exceeds a critical value.

Revealing the preferred interlayer orientations and stackings of two-dimensional bilayer gallium selenide crystals

DOE PAGES

Li, Xufan; Basile Carrasco, Leonardo A.; Yoon, Mina; ...

2015-01-21

Characterizing and controlling the interlayer orientations and stacking order of bilayer two-dimensional (2D) crystals and van der Waals (vdW) heterostructure is crucial to optimize their electrical and optoelectronic properties. The four polymorphs of layered gallium selenide (GaSe) that result from different layer stacking provide an ideal platform to study the stacking configurations in bilayer 2D crystals. Here, through a controllable vapor-phase deposition method we selectively grow bilayer GaSe crystals and investigate their two preferred 0° or 60° interlayer rotations. The commensurate stacking configurations (AA' and AB-stacking) in as-grown 2D bilayer GaSe crystals are clearly observed at the atomic scale andmore » the Ga-terminated edge structure are identified for the first time by using atomic-resolution scanning transmission electron microscopy (STEM). Theoretical analysis of the interlayer coupling energetics vs. interlayer rotation angle reveals that the experimentally-observed orientations are energetically preferred among the bilayer GaSe crystal polytypes. Here, the combined experimental and theoretical characterization of the GaSe bilayers afforded by these growth studies provide a pathway to reveal the atomistic relationships in interlayer orientations responsible for the electronic and optical properties of bilayer 2D crystals and vdW heterostructures.« less

Hydrogen induced fracture characteristics of single crystal nickel-based superalloys

NASA Technical Reports Server (NTRS)

Chen, Po-Shou; Wilcox, Roy C.

1990-01-01

A stereoscopic method for use with x ray energy dispersive spectroscopy of rough surfaces was adapted and applied to the fracture surfaces single crystals of PWA 1480E to permit rapid orientation determinations of small cleavage planes. The method uses a mathematical treatment of stereo pair photomicrographs to measure the angle between the electron beam and the surface normal. One reference crystal orientation corresponding to the electron beam direction (crystal growth direction) is required to perform this trace analysis. The microstructure of PWA 1480E was characterized before fracture analysis was performed. The fracture behavior of single crystals of the PWA 1480E nickel-based superalloy was studied. The hydrogen-induced fracture behavior of single crystals of the PWA 1480E nickel-based superalloy was also studied. In order to understand the temperature dependence of hydrogen-induced embrittlement, notched single crystals with three different crystal growth orientations near zone axes (100), (110), and (111) were tensile tested at 871 C (1600 F) in both helium and hydrogen atmospheres at 34 MPa. Results and conclusions are given.

Impact of spherical nanoparticles on nematic order parameters

NASA Astrophysics Data System (ADS)

Kyrou, C.; Kralj, S.; Panagopoulou, M.; Raptis, Y.; Nounesis, G.; Lelidis, I.

2018-04-01

We study experimentally the impact of spherical nanoparticles on the orientational order parameters of a host nematic liquid crystal. We use spherical core-shell quantum dots that are surface functionalized to promote homeotropic anchoring on their interface with the liquid crystal host. We show experimentally that the orientational order may be strongly affected by the presence of spherical nanoparticles even at low concentrations. The orientational order of the composite system is probed by means of polarized micro-Raman spectroscopy and by optical birefringence measurements as function of temperature and concentration. Our data show that the orientational order depends on the concentration in a nonlinear way, and the existence of a crossover concentration χc≈0.004 pw . It separates two different regimes exhibiting pure-liquid crystal like (χ <χc ) and distorted-nematic ordering (χ >χc ), respectively. In the latter phase the degree of ordering is lower with respect to the pure-liquid crystal nematic phase.

Removal of lead by apatite and its stability in the presence of organic acids.

PubMed

Katoh, Masahiko; Makimura, Akihiko; Sato, Takeshi

2016-12-01

In this study, lead sorption and desorption tests were conducted with apatite and organic acids (i.e. citric, malic, and formic acids) to understand lead removal by apatite in the presence of an organic acid and lead dissolution from the lead- and organic-acid-sorbed apatite by such organic acid exposure. The lead sorption test showed that the amount of lead removed by apatite in the presence of organic acid varied depending on the type of acid used. The molar amounts of calcium dissolved from apatite in the presence and absence of organic acid were exactly the same as those of lead removed even under different pH conditions as well as different organic acid concentrations, indicating that the varying amount of lead removal in the presence of different organic acids resulted from the magnitude of the dissolution of apatite and the precipitation of lead phosphate minerals. The percentages of lead dissolved from the organic-acid-sorbed and non-organic-acid-sorbed apatite by all the organic acid extractions were equal and higher than those by water extraction. In particular, the highest extractions were observed in the non-organic-acid-sorbed apatite by citric and malic acids. These results suggest that to immobilize lead by the use of apatite in the presence of organic acids, much more apatite must be added than in the absence of organic acid, and that measures must be taken to ensure that the immobilized lead is not dissolved.

Fish debris record the hydrothermal activity in the Atlantis II deep sediments (Red Sea)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oudin, E.; Cocherie, A.

1988-01-01

The REE and U, Th, Zr, Hf, Sc have been analyzed in samples from Atlantis II and Shaban/Jean Charcot Deeps in the Red Sea. The high Zr/Hf ratio in some sediments indicates the presence of fish debris or of finely crystallized apatite. The positive ..sigma..REE vs P/sub 2/O/sub 5/ and ..sigma..REE vs Zr/Hf correlations show that fish debris and finely crystallized apatite are the main REE sink in Atlantis II Deep sediments as in other marine environments. The hydrothermal sediments and the fish debris concentrates have similar REE patterns, characterized by a LREE enrichment and a large positive Eu anomaly.more » This REE pattern is also observed in E.P.R. hydrothermal solutions. Fish debris from marine environments acquire their REE content and signature mostly from sea water during early diagenesis. The hydrothermal REE signature of Atlantis II Deep fish debris indicate that they probably record the REE signature of their hydrothermal sedimentation and diagenetic environment. The different REE signatures of the Shaban/Jean Charcot and Atlantis II Deep hydrothermal sediments suggest a sea water-dominated brine in the Shaban/Jean Charcot Deep as opposed to the predominantly hydrothermal brine in Atlantis II Deep. Atlantis II Deep fish debris are also characterized by their high U but low Th contents. Their low Th contents probably reflect the low Th content of the various possible sources (sea water, brine, sediments). Their U contents are probably controlled by the redox conditions of sedimentation.« less

Triphasic Tooling with Small Oriented Diamond Tip for Turning and Smoothing Lightweight Mirrors

NASA Technical Reports Server (NTRS)

Voronov, O. A.; Tompa, G. S.; Kear, B. H.; Veress, V.

2004-01-01

We are developing a new method for the growth of small diamond crystals at very high temperatures and pressures directly from a carbon melt. A prototype "Supercell" has been developed for this purpose. This system is capable of high rate crystal growth in relatively large working volumes. The resulting high quality diamond crystals will be incorporated into a triphasic diamond/titanium carbide/titanium composite tool, with an oriented diamond crystal at its tip. High pressure is needed to prevent degradation of diamond at high temperature, and to ensure the formation of a crack & composite structure. After grinding and polishing, the composite material will be joined to a steel holder, thus forming a diamond-tipped tool for turning and smoothing of a mirror surface. A properly oriented single-crystal diamond cuts and smoothes much better than a conventional polycrystalline diamond crystal. This is because the hardness depends on crystallographic orientation-the difference corresponds to 60-100 GPa on the Knoop scale. Our goal is to achieve surface roughness of about 1 nm, which will be accomplished by precision cutting and smoothing. The hardness of the functionally-graded diamond/titanium carbide/titanium composite tool varies from 100 GPa at its tip to 15 GPa at its base. Previous work has shown that the mass of machined material using an oriented-diamond tool is much larger than that for a standard diamond-metal composite tool.

Synthetic lead bromapatite: X-ray structure at ambient pressure and compressibility up to about 20 GPa

NASA Astrophysics Data System (ADS)

Liu, Xi; Fleet, Michael E.; Shieh, Sean R.; He, Qiang

2011-05-01

Lead bromapatite [Pb10(PO4)6Br2] has been synthesized via solid-state reaction at pressures up to 1.0 GPa, and its structure determined by single-crystal X-ray diffraction at ambient temperature and pressure. The large bromide anion is accommodated in the c-axis channel by lateral displacements of structural elements, particularly of Pb2 cations and PO4 tetrahedra. The compressibility of bromapatite was also investigated up to about 20.7 GPa at ambient temperature, using a diamond-anvil cell and synchrotron X-ray radiation. The compressibility of lead bromapatite is significantly different from that of lead fluorapatite. The pressure-volume data of lead bromapatite ( P < 10 GPa) fitted to the third-order Birch-Murnaghan equation yield an isothermal bulk modulus ( K T ) of 49.8(16) GPa and first pressure derivative ( KT^' } ) of 10.1(10). If KT^' } is fixed at 4, the derived K T is 60.8(11) GPa. The relative difference of the bulk moduli of these two lead apatites is thus about 12%, which is about two times the relative difference of the bulk moduli (~5%) of the calcium apatites fluorapatite [Ca10(PO4)6F2], chlorapatite [Ca10(PO4)6Cl2] and hydroxylapatite [Ca10(PO4)6(OH)2]. Another interesting feature apparently related to the replacement of F by Br in lead apatite is the switch in the principle axes of the strain ellipsoid: the c-axis is less compressible than the a-axis in lead bromapatite but more compressible in lead fluorapatite.

Adsorption and bioactivity studies of albumin onto hydroxyapatite surface.

PubMed

Mavropoulos, Elena; Costa, Andréa M; Costa, Lilian T; Achete, Carlos A; Mello, Alexandre; Granjeiro, José M; Rossi, Alexandre M

2011-03-01

Bovine serum albumin (BSA) may have an inhibitory or promoter effect on hydroxyapatite (HA) nucleation when apatite is precipitated in a medium containing the protein. In this study we evaluated the influence of BSA on the precipitation of calcium phosphate phases (CP) from simulated body fluid (SBF) when the protein was previously bounded to HA surface. The kinetics of BSA immobilization onto hydroxyapatite surface was performed in different buffers and protein concentrations in order to adjust experimental conditions in which BSA was tightly linked to HA surface for long periods in SBF solution. It was shown that for BSA concentration higher than 0.1mg/mL the adsorption to HA surface followed Langmuir-Freundlich mechanisms, which confirmed the existence of cooperative protein-protein interactions on HA surface. Fourier Transformed Infrared Attenuated Total Reflectance Microscopy (FTIRM-ATR) evidenced changes in BSA conformational state in favor of less-ordered structure. Analyses from high resolution grazing incident X-ray diffraction using synchrotron radiation (GIXRD), Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM) showed that a poorly crystalline calcium phosphate was precipitated on the surface of HA discs coated with BSA, after the immersion in SBF for 4 days. The new bioactive layer had morphological characteristics similar to the one formed on the HA surface without protein. It was identified as a carbonated apatite with preferential crystal growth along apatite 002 direction. The GIXRD results also revealed that BSA layer bound to the surface inhibited the HA dissolution leading to a reduction on the formation of new calcium phosphate phase. 2010 Elsevier B.V. All rights reserved.

Rare earth elements in apatite: Uptake from H{sub 2}O-bearing phosphate-fluoride melts and the role of volatile components

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fleet, M.E.; Pan, Yuanming

The partitioning of rare earth elements (REEs) between fluorapatite (FAp) and H{sub 2}O- bearing phosphate-fluoride melts has been studied at about 700 and 800{degrees}C and 0.10-0.15 GPa. REE uptake patterns, i.e., plots of D(REE:FAp/melt), are convex upwards and peak near Nd for single-REE substituted FAp at minor (0.03-0.25 wt% REE{sub 2}O{sub 3}) abundances, and binary (LREE + HREE)-substituted FAp, and hexa-REE-substituted FAp at minor to major (0.25-7.8 wt% REE{sub 2}O{sub 3}) abundances. Partition coefficients for minor abundances of REE and depolymerized phosphate melts are about 5, 8, and 1 for La, Nd, and Lu, respectively and broadly comparable to thosemore » for early fluorapatite in the fractionation of melts of basaltic composition. The Ca2 site exerts marked control on the selectivity of apatite for REE because it preferentially incorporates LREE and its effective size varies with substitution of the A-site volatile anion component (F, Cl, OH). Using simple crystal-chemical arguments, melt(or fluid)-normalized REE patterns are predicted to peak near Nd for fluorapatite and be more LREE-enriched for chlorapatite. These predictions are consistent with data from natural rocks and laboratory experiments. The wide variation in D(REE:apatite/melt) in nature (from <1 for whitlockite-bearing lunar rocks to about 100 for evolved alkalic rocks) is attributed largely to the influence of the volatile components. 49 refs., 8 figs., 3 tabs.« less

Ultrafast shock-induced orientation of polycrystalline films: Applications to high explosives

NASA Astrophysics Data System (ADS)

Franken, Jens; Hambir, Selezion A.; Dlott, Dana D.

1999-02-01

Tiny laser-driven shock waves of ˜5 GPa pressure (nanoshocks) are used to study fast mechanical processes occurring in a thin layer of polycrystalline insensitive energetic material, (3-nitro-1,2,4-triazol-5-one) (NTO). Ultrafast coherent Raman spectroscopy of shocked NTO shows the existence of three distinct mechanical processes. Very fast (˜600 ps) changes in intensity and the appearance of new transitions are associated with the uniaxial nature of compression by the shock front. Frequency shifting and broadening processes which track the ˜2 ns duration nanoshock are associated with transient changes in density and temperature. A novel slower process (5-10 ns) starts as the shock begins to unload, and continues for several nanoseconds after the shock is over, resulting in changes of widths and intensities of several vibrational transitions. By comparing ultrafast spectra to static Raman spectra of single NTO crystals in various orientations, it is concluded that this process involves shock-induced partial orientation of the crystals in the NTO layer. The NTO crystals are oriented faster than the time scale for initiating chemical reactions. The sensitivity of explosive crystals to shock initiation may depend dramatically on the orientation of the crystal relative to the direction of shock propagation, so the implications of fast shock-induced orientation for energetic materials initiation are discussed briefly.

Double Stokes-Mueller polarimetry in KTP (Potassium Titanyl Phosphate) crystal

NASA Astrophysics Data System (ADS)

Shaji, Chitra; S B, Sruthil Lal; Sharan, Alok

2017-04-01

Ultra-structural properties of material are being probed by Double Stokes-Mueller polarimetry (DSMP) technique. It makes use of higher dimensions of Stokes vector (9 X 1) and Mueller matrix (4 X9) to characterize the nonlinear optical properties of a material. Second harmonic generation (SHG) at 532nm using 1064nm as fundamental cw beam from Nd: YAG laser in type II phase matched KTP (Potassium Titanyl Phosphate) crystal is studied using DSMP. The experimental measurements for determining double Mueller matrix are carried out in the ``Polarization In Polarization Out'' (PIPO) arrangement. Nine input polarization states are incident on the sample and the linear Stokes vector of the emerging light from the sample is measured. The KTP crystal is oriented such that the SHG signal efficiency at the incident horizontal and vertical polarizations is high as compared to diagonal polarization states. The susceptibility tensor components and the phase difference between them at this orientation are determined from the double Mueller matrix elements. These determined values give information regarding the crystal axis orientations. To our knowledge, this is the first report of the use of DSMP technique to determine the crystal orientations of a biaxial crystal.

On the colour of wing scales in butterflies: iridescence and preferred orientation of single gyroid photonic crystals.

PubMed

Corkery, Robert W; Tyrode, Eric C

2017-08-06

Lycaenid butterflies from the genera Callophrys , Cyanophrys and Thecla have evolved remarkable biophotonic gyroid nanostructures within their wing scales that have only recently been replicated by nanoscale additive manufacturing. These nanostructures selectively reflect parts of the visible spectrum to give their characteristic non-iridescent, matte-green appearance, despite a distinct blue-green-yellow iridescence predicted for individual crystals from theory. It has been hypothesized that the organism must achieve its uniform appearance by growing crystals with some restrictions on the possible distribution of orientations, yet preferential orientation observed in Callophrys rubi confirms that this distribution need not be uniform. By analysing scanning electron microscope and optical images of 912 crystals in three wing scales, we find no preference for their rotational alignment in the plane of the scales. However, crystal orientation normal to the scale was highly correlated to their colour at low (conical) angles of view and illumination. This correlation enabled the use of optical images, each containing up to 10 4 -10 5 crystals, for concluding the preferential alignment seen along the [Formula: see text] at the level of single scales, appears ubiquitous. By contrast, [Formula: see text] orientations were found to occur at no greater rate than that expected by chance. Above a critical cone angle, all crystals reflected bright green light indicating the dominant light scattering is due to the predicted band gap along the [Formula: see text] direction, independent of the domain orientation. Together with the natural variation in scale and wing shapes, we can readily understand the detailed mechanism of uniform colour production and iridescence suppression in these butterflies. It appears that the combination of preferential alignment normal to the wing scale, and uniform distribution within the plane is a near optimal solution for homogenizing the angular distribution of the [Formula: see text] band gap relative to the wings. Finally, the distributions of orientations, shapes, sizes and degree of order of crystals within single scales provide useful insights for understanding the mechanisms at play in the formation of these biophotonic nanostructures.

Chemical composition, crystal size and lattice structural changes after incorporation of strontium into biomimetic apatite.

PubMed

Li, Z Y; Lam, W M; Yang, C; Xu, B; Ni, G X; Abbah, S A; Cheung, K M C; Luk, K D K; Lu, W W

2007-03-01

Recently, strontium (Sr) as ranelate compound has become increasingly popular in the treatment of osteoporosis. However, the lattice structure of bone crystal after Sr incorporation is yet to be extensively reported. In this study, we synthesized strontium-substituted hydroxyapatite (Sr-HA) with different Sr content (0.3%, 1.5% and 15% Sr-HA in mole ratio) to simulate bone crystals incorporated with Sr. The changes in chemical composition and lattice structure of apetite after synthetic incorporation of Sr were evaluated to gain insight into bone crystal changes after incorporation of Sr. X-ray diffraction (XRD) patterns revealed that 0.3% and 1.5% Sr-HA exhibited single phase spectrum, which was similar to that of HA. However, 15% Sr-HA induced the incorporation of HPO4(2-) and more CO3(2-), the crystallinity reduced dramatically. Transmission electron microscopy (TEM) images showed that the crystal length and width of 0.3% and 1.5% Sr-HA increased slightly. Meanwhile, the length and width distribution were broadened and the aspect ratio decreased from 10.68+/-4.00 to 7.28+/-2.80. The crystal size and crystallinity of 15% Sr-HA dropped rapidly, which may suggest that the fundamental crystal structure is changed. The findings from this work indicate that current clinical dosage which usually results in Sr incorporation of below 1.5% may not change chemical composition and lattice structure of bone, while it will broaden the bone crystal size distribution and strengthen the bone.

Matrix metalloproteinase-20 mediates dental enamel biomineralization by preventing protein occlusion inside apatite crystals

PubMed Central

Prajapati, Saumya; Tao, Jinhui; Ruan, Qichao; De Yoreo, James J.; Moradian-Oldak, Janet

2015-01-01

Reconstruction of enamel-like materials is a central topic of research in dentistry and material sciences. The importance of precise proteolytic mechanisms in amelogenesis to form a hard tissue with more than 95% mineral content has already been reported. A mutation in the Matrix Metalloproteinase-20 (MMP-20) gene results in hypomineralized enamel that is thin, disorganized and breaks from the underlying dentin. We hypothesized that the absence of MMP-20 during amelogenesis results in the occlusion of amelogenin in the enamel hydroxyapatite crystals. We used spectroscopy and electron microscopy techniques to qualitatively and quantitatively analyze occluded proteins within the isolated enamel crystals from MMP-20 null and Wild type (WT) mice. Our results showed that the isolated enamel crystals of MMP-20 null mice had more organic macromolecules occluded inside them than enamel crystals from the WT. The crystal lattice arrangements of MMP-20 null enamel crystals analyzed by High Resolution Transmission Electron Microscopy (HRTEM) were found to be significantly different from those of the WT. Raman studies indicated that the crystallinity of the MMP-20 null enamel crystals was lower than that of the WT. In conclusion, we present a novel functional mechanism of MMP-20, specifically prevention of unwanted organic material entrapped in the forming enamel crystals, which occurs as the result of precise amelogenin cleavage. MMP-20 action guides the growth morphology of the forming hydroxyapatite crystals and enhances their crystallinity. Elucidating such molecular mechanisms can be applied in the design of novel biomaterials for future clinical applications in dental restoration or repair. PMID:26513418

Matrix metalloproteinase-20 mediates dental enamel biomineralization by preventing protein occlusion inside apatite crystals.

PubMed

Prajapati, Saumya; Tao, Jinhui; Ruan, Qichao; De Yoreo, James J; Moradian-Oldak, Janet

2016-01-01

Reconstruction of enamel-like materials is a central topic of research in dentistry and material sciences. The importance of precise proteolytic mechanisms in amelogenesis to form a hard tissue with more than 95% mineral content has already been reported. A mutation in the Matrix Metalloproteinase-20 (MMP-20) gene results in hypomineralized enamel that is thin, disorganized and breaks from the underlying dentin. We hypothesized that the absence of MMP-20 during amelogenesis results in the occlusion of amelogenin in the enamel hydroxyapatite crystals. We used spectroscopy and electron microscopy techniques to qualitatively and quantitatively analyze occluded proteins within the isolated enamel crystals from MMP-20 null and Wild type (WT) mice. Our results showed that the isolated enamel crystals of MMP-20 null mice had more organic macromolecules occluded inside them than enamel crystals from the WT. The crystal lattice arrangements of MMP-20 null enamel crystals analyzed by High Resolution Transmission Electron Microscopy (HRTEM) were found to be significantly different from those of the WT. Raman studies indicated that the crystallinity of the MMP-20 null enamel crystals was lower than that of the WT. In conclusion, we present a novel functional mechanism of MMP-20, specifically prevention of unwanted organic material entrapped in the forming enamel crystals, which occurs as the result of precise amelogenin cleavage. MMP-20 action guides the growth morphology of the forming hydroxyapatite crystals and enhances their crystallinity. Elucidating such molecular mechanisms can be applied in the design of novel biomaterials for future clinical applications in dental restoration or repair. Copyright © 2015 Elsevier Ltd. All rights reserved.

Aragonite pseudomorphs in high-pressure marbles of Syros, Greece

NASA Astrophysics Data System (ADS)

Brady, John B.; Markley, Michelle J.; Schumacher, John C.; Cheney, John T.; Bianciardi, Grace A.

2004-01-01

Numerous rod-shaped calcite crystals occur in the blueschist to eclogite facies marbles of Syros, Greece. The rods show a shape-preferred orientation, and the long axes of the rods are oriented at a large angle to foliation. The crystals also have a crystallographic-preferred orientation: calcite c-axes are oriented parallel to the long axes of the rods. Based on their chemical composition, shape, and occurrence in high-pressure marbles, these calcite crystals are interpreted as topotactic pseudomorphs after aragonite that developed a crystallographic-preferred orientation during peak metamorphism. This interpretation is consistent with deformation of aragonite by dislocation creep, which has been observed in laboratory experiments but has not been previously reported on the basis of field evidence. Subsequent to the high-pressure deformation of the aragonite marbles, the aragonite recrystallized statically into coarse rod-shaped crystals, maintaining the crystallographic orientation developed during deformation. During later exhumation, aragonite reverted to calcite, and the marbles experienced little further deformation, at least in the pseudomorph-rich layers. Some shearing of pseudomorph-bearing marble layers did occur and is indicated by twinning of calcite and by a variable inclination of the pseudomorphs relative to foliation.

Modification of electrochemically deposited apatite using supercritical water.

PubMed

Ban, S; Hasegawa, J

2001-12-01

Supercritical water was used as a modification method of electrochemically deposited apatite on pure titanium. The apatites were coated on a commercially pure titanium plate using a hydrothermal-electrochemical method. A constant direct current at 12.5 mA/cm2 was loaded for 1 hr at 25, 60, 100, 150 and 200 degrees C in an electrolyte containing calcium and phosphate ions. The deposited apatite on the titanium substrate was stored in supercritical water at 450 degrees C under 45 MPa for 8 hr. With this treatment, the crystallinity of the apatites increased, sharp edges of the deposited apatites were rounded off, and the bonding strength of the titanium substrate to the deposited apatites significantly increased. On the other hand, weight loss in 0.01 N HCl decreased and the weight gain rate in a simulated body fluid also decreased with this treatment. It is suggested that the modification using supercritical water improved the mechanical strength of the deposited apatite, but worsened its bioactivity.

Effect of Crystal Orientation on Analysis of Single-Crystal, Nickel-Based Turbine Blade Superalloys

NASA Technical Reports Server (NTRS)

Swanson, G. R.; Arakere, N. K.

2000-01-01

High-cycle fatigue-induced failures in turbine and turbopump blades is a pervasive problem. Single-crystal nickel turbine blades are used because of their superior creep, stress rupture, melt resistance, and thermomechanical fatigue capabilities. Single-crystal materials have highly orthotropic properties making the position of the crystal lattice relative to the part geometry a significant and complicating factor. A fatigue failure criterion based on the maximum shear stress amplitude on the 24 octahedral and 6 cube slip systems is presented for single-crystal nickel superalloys (FCC crystal). This criterion greatly reduces the scatter in uniaxial fatigue data for PWA 1493 at 1,200 F in air. Additionally, single-crystal turbine blades used in the Space Shuttle main engine high pressure fuel turbopump/alternate turbopump are modeled using a three-dimensional finite element (FE) model. This model accounts for material orthotrophy and crystal orientation. Fatigue life of the blade tip is computed using FE stress results and the failure criterion that was developed. Stress analysis results in the blade attachment region are also presented. Results demonstrate that control of crystallographic orientation has the potential to significantly increase a component's resistance to fatigue crack growth without adding additional weight or cost.

Fabrication of oriented crystals as force measurement tips via focused ion beam and microlithography methods

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Zhigang; Chun, Jaehun; Chatterjee, Sayandev

Detailed knowledge of the forces between nanocrystals is very crucial for understanding many generic (e.g., random aggregation/assembly and rheology) and specific (e.g., oriented attachment) phenomena at macroscopic length scales, especially considering the additional complexities involved in nanocrystals such as crystal orientation and corresponding orientation-dependent physicochemical properties. Because there are a limited number of methods to directly measure the forces, little is known about the forces that drive the various emergent phenomena. Here we report on two methods of preparing crystals as force measurement tips used in an atomic force microscope (AFM): the focused ion beam method and microlithography method. Themore » desired crystals are fabricated using these two methods and are fixed to the AFM probe using platinum deposition, ultraviolet epoxy, or resin, which allows for the orientation-dependent force measurements. These two methods can be used to attach virtually any solid particles (from the size of a few hundreds of nanometers to millimeters). We demonstrate the force measurements between aqueous media under different conditions such as pH.« less

Crystallization Behavior of Poly(ethylene oxide) in Vertically Aligned Carbon Nanotube Array.

PubMed

Sheng, Jiadong; Zhou, Shenglin; Yang, Zhaohui; Zhang, Xiaohua

2018-03-27

We investigate the effect of the presence of vertically aligned multiwalled carbon nanotubes (CNTs) on the orientation of poly(ethylene oxide) (PEO) lamellae and PEO crystallinity. The high alignment of carbon nanotubes acting as templates probably governs the orientation of PEO lamellae. This templating effect might result in the lamella planes of PEO crystals oriented along a direction parallel to the long axis of the nanotubes. The presence of aligned carbon nanotubes also gives rise to the decreases in PEO crystallinity, crystallization temperature, and melting temperature due to the perturbation of carbon nanotubes to the crystallization of PEO. These effects have significant implications for controlling the orientation of PEO lamellae and decreasing the crystallinity of PEO and thickness of PEO lamellae, which have significant impacts on ion transport in PEO/CNT composite and the capacitive performance of PEO/CNT composite. Both the decreased PEO crystallinity and the orientation of PEO lamellae along the long axes of vertically aligned CNTs give rise to the decrease in the charge transfer resistance, which is associated with the improvements in the ion transport and capacitive performance of PEO/CNT composite.

Dense Membranes for Anode Supported all Perovskite IT-SOFCs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rambabu Bobba

2006-09-14

During this first year of the project, a post doctoral fellow (Dr. Hrudananda Jena), and two graduate students (Mr. Vinay B. V. Sivareddy, Aswin Somuru), were supported through this project funds. Also, partial support was provided to three undergraduate students (Jonthan Dooley, India Snowden, Jeremy Gilmore) majoring in Chemistry, Physics, and Engineering disciplines. Various wet chemical methods of synthesis have been attempted to prepare perovskite oxide powders with a hope to improve and engineer its properties to meet the requirements of Intermediate Temperature Solid Oxide Fuel Cell (IT-SOFCs) components. Various compounds were synthesized, characterized by XRD, TEM, SEM, XPS, electronmore » microprobe and their electrical transport properties were measured by EIS at elevated temperatures and compared. Sonochemical technique (power of ultra sonic probe 750 watt) combined with hydrothermal treatment of precursors for the preparation of calcium hydroxy apatites (Ca-HAp) was used for the first time. Ca-HAp was substituted with Sr and Mg (50% replacement of Ca in Ca-HAp) to study the effect of substitution on Ca-HAp. Calcium hydroxy apatite is a bioceramic and has potential applications as artificial bone, enamel materials. In this study we tried to investigate its use as proton conductors in PC-SOFC. The properties like electrical conductivity, crystal structure, compositions of CaHAp were studied and compared with the natural bone material. The comparison found to be excellent indicating the efficiency of the preparation techniques. The typical value of conductivity measured is 0.091 x 10{sup -6} Scm{sup -1} at 25 C and 19.26 x 10{sup -6} Scm{sup -1} at 850 C with an applied frequency of 100 kHz. The conductivity increases on increasing frequency and temperature and reaches 0.05mS/cm at 500 C. The crystal structure and phase stability of perovskites as well as apatites were investigated with respect to substitution of various iso-valent and alivalent ions to determine the % of solubility in the crystal lattice of perovskite, apatites. Various electrode and electrolyte material compositions were prepared and characterized by XRD, SEM, XPS and electron microprobe. The material compositions were selected based on their thermo-physical properties to achieve compatibility with each other in ideal fuel cell operating conditions. The series of electrode materials investigated are LaGa{sub 1-x}M{sub x}O{sub 3} (M = Mn, Mg, x = 0.1), LaCr{sub 1-x}M{sub x}O{sub 3} (M = Mn, Mg, Co, x=0.1), LaNi{sub 1-x}Fe{sub x}O{sub 3} (0 < x < 0.6) and Gd{sub 1-x}M{sub x}CoO{sub 3} (M=Ca, x=0.1). Attempts were made to prepare proton-conducting perovskites of SrCe{sub 1-x} M{sub x}O{sub 3} (M= Dy, Eu, Er, Tb, x=0.1) by using sonochemical and hydrothermal technique followed by microwave sintering processes. These compositions were prepared characterized by XRD, TEM, SEM and electrical conductivity of the pellets was measured. The interest of low temperature proton conducting electrolyte is to replace the well known oxide ion conducting solid electrolyte in SOFCs, thereby reducing the operating temperature of SOFC to lower temperature (i.e 400-600 C) and named it as PC-SOFC (proton conducting-solid oxide fuel cell).« less

Solidification rate influence on orientation and mechanical properties of MAR-M-246+Hf

NASA Technical Reports Server (NTRS)

Hamilton, D.

1983-01-01

The influence of solidification rates on the orientation and mechanical properties of MAR-M-246+Hf was studied. The preferred orientation was found to be (001) for single crystals, with all samples with 45 degrees of (001). Tensile tests were performed at room temperature. The anisotropy of directionally solidified MAR-M-246+Hf was demonstrated by gage section deformation. Dendrite arm spacing and crystal growth were found to depend on solidification rates and source material conditions. The greatest strength occurred at lower solidification rates. Some single crystals were grown by control of growth rates without seeding.

Terahertz spectroscopic analysis of crystal orientation in polymers

NASA Astrophysics Data System (ADS)

Azeyanagi, Chisato; Kaneko, Takuya; Ohki, Yoshimichi

2018-05-01

Terahertz time-domain spectroscopy (THz-TDS) is attracting keen attention as a new spectroscopic tool for characterizing various materials. In this research, the possibility of analyzing the crystal orientation in a crystalline polymer by THz-TDS is investigated by measuring angle-resolved THz absorption spectra for sheets of poly(ethylene terephthalate), poly(ethylene naphthalate), and poly(phenylene sulfide). The resultant angle dependence of the absorption intensity of each polymer is similar to that of the crystal orientation examined using pole figures of X-ray diffraction. More specifically, THz-TDS can indicate the alignment of molecules in polymers.

Elasticity of smectic liquid crystals with in-plane orientational order and dispiration asymmetry

NASA Astrophysics Data System (ADS)

Alageshan, Jaya Kumar; Chakrabarti, Buddhapriya; Hatwalne, Yashodhan

2017-02-01

The Nelson-Peliti formulation of the elasticity theory of isolated fluid membranes with orientational order emphasizes the interplay between geometry, topology, and thermal fluctuations. Fluid layers of lamellar liquid crystals such as smectic-C , hexatic smectics, and smectic-C* are endowed with in-plane orientational order. We extend the Nelson-Peliti formulation so as to bring these smectics within its ambit. Using the elasticity theory of smectics-C*, we show that positive and negative dispirations (topological defects in Smectic-C* liquid crystals) with strengths of equal magnitude have disparate energies—a result that is amenable to experimental tests.

Development of chemically vapor deposited rhenium emitters of (0001) preferred crystal orientation

NASA Technical Reports Server (NTRS)

Yang, L.; Hudson, R. G.

1973-01-01

Rhenium thermionic emitters were prepared by the pyrolysis of rhenium chlorides formed by the chlorination of rhenium pellets. The impurity contents, microstructures, degrees of (0001) preferred crystal orientation, and vacuum electron work functions of these emitters were determined as a function of deposition parameters, such as substrate temperature, rhenium pellet temperature and chlorine flow rate. A correlation between vacuum electron work function and degree of (0001) preferred crystal orientation was established. Conditions for depositing porosity-free rhenium emitters of high vacuum electron work functions were defined. Finally, three cylindrical rhenium emitters were prepared under the optimum deposition conditions.

The Crystallization Clinic-A TA Orientation Exercise

NASA Astrophysics Data System (ADS)

Kandel, Marjorie

1999-01-01

Our orientation exercise for TAs in the organic laboratories is a Crystallization Clinic, and the main feature is a contest. Each TA has a different unknown solid to recrystallize. The products are judged by the students in the organic lab courses. Beauty of the crystals is the single criterion. The contest serves to refresh the TAs' technique and to give them empathy with the beginning students.

The Finero phlogopite-peridotite massif: an example of subduction-related metasomatism

NASA Astrophysics Data System (ADS)

Zanetti, Alberto; Mazzucchelli, Maurizio; Rivalenti, Giorgio; Vannucci, Riccardo

The Finero peridotite massif is a harzburgite that suffered a dramatic metasomatic enrichment resulting in the pervasive presence of amphibole and phlogopite and in the sporadic occurrence of apatite and carbonate (dolomite)-bearing domains. Pyroxenite (websterite) dykes also contain phlogopite and amphibole, but are rare. Peridotite bulk-rock composition retained highly depleted major element characteristics, but was enriched in K, Rb, Ba, Sr, LREE (light rare earth elements) (LaN/YbN=8-17) and depleted in Nb. It has high radiogenic Sr (87Sr/86Sr(270)=0.7055-0.7093), low radiogenic Nd (ɛNd(270)=-1 to -3) and EMII-like Pb isotopes. Two pyroxenite - peridotite sections examined in detail show the virtual absence of major and trace element gradients in the mineral phases. In both rock types, pyroxenes and olivines have the most unfertile major element composition observed in Ivrea peridotites, spinels are the richest in Cr, and amphibole is pargasite. Clinopyroxenes exhibit LREE-enriched patterns (LaN/YbN 16), negative Ti and Zr and generally positive Sr anomaly. Amphibole has similar characteristics, except a weak negative Sr anomaly, but incompatible element concentration 1.9 (Sr) to 7.9 (Ti) times higher than that of coexisting clinopyroxene. Marked geochemical gradients occur toward apatite and carbonate-bearing domains which are randomly distributed in both the sections examined. In these regions, pyroxenes and amphibole (edenite) arelower in mg## and higher in Na2O, and spinels and phlogopite are richer in Cr2O3. Both the mineral assemblage and the incompatible trace element characteristics of the mineral phases recall the typical signatures of ``carbonatite'' metasomatism (HFSE depletion, Sr, LILE and LREE enrichment). Clinopyroxene has higher REE and Sr concentrations than amphibole (amph/cpxDREE,Sr=0.7-0.9) and lower Ti and Zr concentrations. It is proposed that the petrographic and geochemical features observed at Finero are consistent with a subduction environment. The lack of chemical gradients between pyroxenite and peridotite is explained by a model where melts derived from an eclogite-facies slab infiltrate the overhanging harzburgitic mantle wedge and, because of the special thermal structure of subduction zones, become heated to the temperature of the peridotite. If the resulting temperature is above that of the incipient melting of the hydrous peridotite system, the slab-derived melt equilibrates with the harzburgite and a crystal mush consisting of harzburgite and a silica saturated, hydrous melt is formed. During cooling, the crystal mush crystallizes producing the observed sequence of mineral phases and their observed chemical characteristics. In this context pyroxenites are regions of higher concentration of the melt in equilibrium with the harzburgite and not passage-ways through which exotic melts percolated. Only negligible chemical gradients can appear as an effect of the crystallization process, which also accounts for the high amphibole/clinopyroxene incompatible trace element ratios. The major element refractory composition is explained by an initially high peridotite/melt ratio. The apatite, carbonate-bearing domains are the result of the presence of some CO2 in the slab-derived melt. The CO2/H2O ratio in the peridotite mush increased by crystallization of hydrous phases (amphibole and phlogopite) locally resulting in the unmixing of a late carbonate fluid. The proposed scenario is consistent with subduction of probably Variscan age and with the occurrence of modal metasomatism before peridotite incorporation in the crust.

Octacalcium phosphate: osteoconductivity and crystal chemistry.

PubMed

Suzuki, O

2010-09-01

Octacalcium phosphate (OCP), which is structurally similar to hydroxyapatite (HA), is a possible precursor of bone apatite crystals. Although disagreement remains as to whether OCP comprises the initial mineral crystals in the early stage of bone mineralization, the results of recent biomaterial studies using synthetic OCP indicate the potential role of OCP as a bone substitute material, owing to its highly osteoconductive and biodegradable characteristics. OCP tends to convert to HA not only in an in vitro environment, but also as an implant in bone defects. Several lines of evidence from both in vivo and in vitro studies suggest that the conversion process could be involved in the stimulatory capacity of OCP for osteoblastic differentiation and osteoclast formation. However, the osteoconductivity of OCP cannot always be secured if an OCP with distinct crystal characteristics is used, because the stoichiometry and microstructure of OCP crystals greatly affect bone-regenerative properties. Osteoconductivity and stimulatory capabilities may be caused by the chemical characteristics of OCP, which allows the release or exchange of calcium and phosphate ions with the surrounding of this salt, and its tendency to grow towards specific crystal faces, which could be a variable of the synthesis condition. This paper reviews the effect of calcium phosphates on osteoblastic activity and bone regeneration, with a special emphasis on OCP, since OCP seems to be performing better than other calcium phosphates in vivo. 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Single crystal to polycrystal neutron transmission simulation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dessieux, Luc Lucius; Stoica, Alexandru Dan; Bingham, Philip R.

A collection of routines for calculation of the total cross section that determines the attenuation of neutrons by crystalline solids is presented. The total cross section is calculated semi-empirically as a function of crystal structure, neutron energy, temperature, and crystal orientation. The semi-empirical formula includes the contribution of parasitic Bragg scattering to the total cross section using both the crystal’s mosaic spread value and its orientation with respect to the neutron beam direction as parameters. These routines allow users to enter a distribution of crystal orientations for calculation of total cross sections of user defined powder or pseudo powder distributions,more » which enables simulation of non-uniformities such as texture and strain. In conclusion, the spectra for neutron transmission simulations in the neutron thermal energy range (2 meV–100 meV) are presented for single crystal and polycrystal samples and compared to measurements.« less

Insights Into the Solution Crystallization of Oriented Alq3 and Znq2 Microprisms and Nanorods.

PubMed

Boulet, Joel; Mohammadpour, Arash; Shankar, Karthik

2015-09-01

Optimized solution-based methods to grow high quality micro- and nanocrystals of organic semi-conductors with defined size, shape and orientation are important to a variety of optoelectronic applications. In this context, we report the growth of single crystal micro- and nanostructures of the organic semiconductors Tris(8-hydroxyquinoline)aluminum (Alq3) and bis(8-hydroxyquinoline)zinc (Znq2) terminating in flat crystal planes using a combination of evaporative and antisolvent crystallization. By controlling substrate-specific nucleation and optimizing the conditions of growth, we generate vertically-oriented hexagonal prism arrays of Alq3, and vertical half-disks and sharp-edged rectangular prisms of Znq2. The effect of process variables such as ambient vapour pressure, choice of anti-solvent and temperature on the morphology and crystal habit of the nanostructures were studied and the results of varying them catalogued to gain a better understanding of the mechanism of growth.

Single crystal to polycrystal neutron transmission simulation

DOE PAGES

Dessieux, Luc Lucius; Stoica, Alexandru Dan; Bingham, Philip R.

2018-02-02

A collection of routines for calculation of the total cross section that determines the attenuation of neutrons by crystalline solids is presented. The total cross section is calculated semi-empirically as a function of crystal structure, neutron energy, temperature, and crystal orientation. The semi-empirical formula includes the contribution of parasitic Bragg scattering to the total cross section using both the crystal’s mosaic spread value and its orientation with respect to the neutron beam direction as parameters. These routines allow users to enter a distribution of crystal orientations for calculation of total cross sections of user defined powder or pseudo powder distributions,more » which enables simulation of non-uniformities such as texture and strain. In conclusion, the spectra for neutron transmission simulations in the neutron thermal energy range (2 meV–100 meV) are presented for single crystal and polycrystal samples and compared to measurements.« less

Effects of withdrawal rate and starter block size on crystal orientation of a single crystal Ni-based superalloy

NASA Astrophysics Data System (ADS)

Rezaei, M.; Kermanpur, A.; Sadeghi, F.

2018-03-01

Fabrication of single crystal (SC) Ni-based gas turbine blades with a minimum crystal misorientation has always been a challenge in gas turbine industry, due to its significant influence on high temperature mechanical properties. This paper reports an experimental investigation and numerical simulation of the SC solidification process of a Ni-based superalloy to study effects of withdrawal rate and starter block size on crystal orientation. The results show that the crystal misorientation of the sample with 40 mm starter block height is decreased with increasing withdrawal rate up to about 9 mm/min, beyond which the amount of misorientation is increased. It was found that the withdrawal rate, height of the starter block and temperature gradient are completely inter-dependent and indeed achieving a SC specimen with a minimum misorientation needs careful optimization of these process parameters. The height of starter block was found to have higher impact on crystal orientation compared to the withdrawal rate. A suitable withdrawal rate regime along with a sufficient starter block height was proposed to produce SC parts with the lowest misorientation.

Radar Differential Phase Signatures of Ice Orientation for the Prediction of Lightning Initiation and Cessation

NASA Technical Reports Server (NTRS)

Carey, L.D.; Petersen, W.A.; Deierling, W.

2009-01-01

The majority of lightning-related casualties typically occur during thunderstorm initiation (e.g., first flash) or dissipation (e.g., last flash). The physics of electrification and lightning production during thunderstorm initiation is fairly well understood. As such, the literature includes a number of studies presenting various radar techniques (using reflectivity and, if available, other dual-polarimetric parameters) for the anticipation of initial electrification and first lightning flash. These radar techniques have shown considerable skill at forecasting first flash. On the other hand, electrical processes and lightning production during thunderstorm dissipation are not nearly as well understood and few, if any, successful techniques have been developed to anticipate the last flash and subsequent cessation of lightning. One promising approach involves the use of dual-polarimetric radar variables to infer the presence of oriented ice crystals in lightning producing storms. In the absence of strong vertical electric fields, ice crystals fall with their largest (semi-major) axis in the horizontal associated with gravitational and aerodynamic forces. In thunderstorms, strong vertical electric fields (100-200 kV m(sup -1)) have been shown to orient small (less than 2 mm) ice crystals such that their semi-major axis is vertical (or nearly vertical). After a lightning flash, the electric field is typically relaxed and prior radar research suggests that ice crystals rapidly resume their preferred horizontal orientation. In active thunderstorms, the vertical electric field quickly recovers and the ice crystals repeat this cycle of orientation for each nearby flash. This change in ice crystal orientation from primarily horizontal to vertical during the development of strong vertical electric fields prior to a lightning flash forms the physical basis for anticipating lightning initiation and, potentially, cessation. Research has shown that radar reflectivity (Z) and other co-polar back-scattering radar measurements like differential reflectivity (Z(sub dr)) typically measured by operational dual-polarimetric radars are not sensitive to these changes in ice crystal orientation. However, prior research has demonstrated that oriented ice crystals cause significant propagation effects that can be routinely measured by most dual-polarimetric radars from X-band (3 cm) to S-band (10 cm) wavelengths using the differential propagation phase shift (often just called differential phase, phi(sub dp)) or its range derivative, the specific differential phase (K(sub dp)). Advantages of the differential phase include independence from absolute or relative power calibration, attenuation, differential attenuation and relative insensitivity to ground clutter and partial beam occultation effects (as long as the signal remains above noise). In research mode, these sorts of techniques have been used to anticipate initial cloud electrification, lightning initiation, and cessation. In this study, we develop a simplified model of ice crystal size, shape, orientation, dielectric, and associated radar scattering and propagation effects in order to simulate various idealized scenarios of ice crystals responding to a hypothetical electric field and their dual-polarimetric radar signatures leading up to lightning initiation and particularly cessation. The sensitivity of the K(sub dp) ice orientation signature to various ice properties and radar wavelength will be explored. Since K(sub dp) is proportional to frequency in the Rayleigh- Gans scattering regime, the ice orientation signatures should be more obvious at higher (lower) frequencies (wavelengths). As a result, simulations at radar wavelengths from 10 cm down to 1 cm (Ka-band) will be conducted. Resonance effects will be considered using the T-matrix method. Since most K(sub dp) Vbased observations have been shown at S-band, we will present ice orientation signatures from C-band (UAH/NASA ARMOR) and X-bd (UAH MAX) dual-polarimetric radars located in Northern Alabama. Issues related to optimal radar scanning for the detection of oriented ice will be discussed. Preliminary suggestions on how these differential phase signatures of oriented ice could contribute to lightning initiation and cessation algorithms will be presented.

Electro-optical tunable birefringent filter

DOEpatents

Levinton, Fred M [Princeton, NJ

2012-01-31

An electrically tunable Lyot type filter is a Lyot that include one or more filter elements. Each filter element may have a planar, solid crystal comprised of a material that exhibits birefringence and is electro-optically active. Transparent electrodes may be coated on each face of the crystal. An input linear light polarizer may be located on one side of the crystal and oriented at 45 degrees to the optical axis of the birefringent crystal. An output linear light polarizer may be located on the other side of the crystal and oriented at -45 degrees with respect to the optical axis of the birefringent crystal. When an electric voltage is applied between the electrodes, the retardation of the crystal changes and so does the spectral transmission of the optical filter.

U-Pb Ages of Lunar Apatites

NASA Technical Reports Server (NTRS)

Vaughan, J.; Nemchin, A. A.; Pidgeon, R. T.; Meyer, Charles

2006-01-01

Apatite is one of the minerals that is rarely utilized in U-Pb geochronology, compared to some other U-rich accessory phases. Relatively low U concentration, commonly high proportion of common Pb and low closure temperature of U-Pb system of apatite inhibit its application as geochronological tool when other minerals such as zircon are widely available. However, zircon appear to be restricted to certain type of lunar rocks, carrying so called KREEP signature, whereas apatite (and whitlockite) is a common accessory mineral in the lunar samples. Therefore, utilizing apatite for lunar chronology may increase the pool of rocks that are available for U-Pb dating. The low stability of U-Pb systematics of apatite may also result in the resetting of the system during meteoritic bombardment, in which case apatite may provide an additional tool for the study of the impact history of the Moon. In order to investigate these possibilities, we have analysed apatites and zircons from two breccia samples collected during the Apollo 14 mission. Both samples were collected within the Fra Mauro formation, which is interpreted as a material ejected during the impact that formed the Imbrium Basin.

Quasi van der Waals epitaxy of copper thin film on single-crystal graphene monolayer buffer

NASA Astrophysics Data System (ADS)

Lu, Zonghuan; Sun, Xin; Washington, Morris A.; Lu, Toh-Ming

2018-03-01

Quasi van der Waals epitaxial growth of face-centered cubic Cu (~100 nm) thin films on single-crystal monolayer graphene is demonstrated using thermal evaporation at an elevated substrate temperature of 250 °C. The single-crystal graphene was transferred to amorphous (glass) and crystalline (quartz) SiO2 substrates for epitaxy study. Raman analysis showed that the thermal evaporation method had minimal damage to the graphene lattice during the Cu deposition. X-ray diffraction and electron backscatter diffraction analyses revealed that both Cu films are single-crystal with (1 1 1) out-of-plane orientation and in-plane Σ3 twin domains of 60° rotation. The crystallinity of the SiO2 substrates has a negligible effect on the Cu crystal orientation during the epitaxial growth, implying the strong screening effect of graphene. We also demonstrate the epitaxial growth of polycrystalline Cu on a commercial polycrystalline monolayer graphene consisting of two orientation domains offset 30° to each other. It confirms that the crystal orientation of the epitaxial Cu film follows that of graphene, i.e. the Cu film consists of two orientation domains offset 30° to each other when deposited on polycrystalline graphene. Finally, on the contrary to the report in the literature, we show that the direct current and radio frequency flip sputtering method causes significant damage to the graphene lattice during the Cu deposition process, and therefore neither is a suitable method for Cu epitaxial growth on graphene.

Bioactivity of Sodium Free Fluoride Containing Glasses and Glass-Ceramics

PubMed Central

Chen, Xiaojing; Chen, Xiaohui; Brauer, Delia S.; Wilson, Rory M.; Hill, Robert G.; Karpukhina, Natalia

2014-01-01

The bioactivity of a series of fluoride-containing sodium-free calcium and strontium phosphosilicate glasses has been tested in vitro. Glasses with high fluoride content were partially crystallised to apatite and other fluoride-containing phases. The bioactivity study was carried out in Tris and SBF buffers, and apatite formation was monitored by XRD, FTIR and solid state NMR. Ion release in solutions has been measured using ICP-OES and fluoride-ion selective electrode. The results show that glasses with low amounts of fluoride that were initially amorphous degraded rapidly in Tris buffer and formed apatite as early as 3 h after immersion. The apatite was identified as fluorapatite by 19F MAS-NMR after 6 h of immersion. Glass degradation and apatite formation was significantly slower in SBF solution compared to Tris. On immersion of the partially crystallised glasses, the fraction of apatite increased at 3 h compared to the amount of apatite prior to the treatment. Thus, partial crystallisation of the glasses has not affected bioactivity significantly. Fast dissolution of the amorphous phase was also indicated. There was no difference in kinetics between Tris and SBF studies when the glass was partially crystallised to apatite before immersion. Two different mechanisms of apatite formation for amorphous or partially crystallised glasses are discussed. PMID:28788139

Pressure sensor using liquid crystals

NASA Technical Reports Server (NTRS)

Parmar, Devendra S. (Inventor); Holmes, Harlan K. (Inventor)

1994-01-01

A pressure sensor includes a liquid crystal positioned between transparent, electrically conductive films (18 and 20), that are biased by a voltage (V) which induces an electric field (E) that causes the liquid crystal to assume a first state of orientation. Application of pressure (P) to a flexible, transparent film (24) causes the conductive film (20) to move closer to or farther from the conductive film (18), thereby causing a change in the electric field (E'(P)) which causes the liquid crystal to assume a second state of orientation. Polarized light (P.sub.1) is directed into the liquid crystal and transmitted or reflected to an analyzer (A or 30). Changes in the state of orientation of the liquid crystal induced by applied pressure (P) result in a different light intensity being detected at the analyzer (A or 30) as a function of the applied pressure (P). In particular embodiments, the liquid crystal is present as droplets (10) in a polymer matrix (12) or in cells (14) in a polymeric or dielectric grid (16) material in the form of a layer (13) between the electrically conductive films (18 and 20). The liquid crystal fills the open wells in the polymer matrix (12) or grid (16) only partially.

Effects of doping impurity and growth orientation on dislocation generation in GaAs crystals grown from the melt: A qualitative finite-element study

NASA Astrophysics Data System (ADS)

Zhu, X. A.; Tsai, C. T.

2000-09-01

Dislocations in gallium arsenide (GaAs) crystals are generated by excessive thermal stresses induced during the crystal growth process. The presence of dislocations has adverse effects on the performance and reliability of the GaAs-based devices. It is well known that dislocation density can be significantly reduced by doping impurity atoms into a GaAs crystal during its growth process. A viscoplastic constitutive equation that couples the microscopic dislocation density with the macroscopic plastic deformation is employed in a crystallographic finite element model for calculating the dislocation density generated in the GaAs crystal during its growth process. The dislocation density is considered as an internal state variable and the drag stress caused by doping impurity is included in this constitutive equation. A GaAs crystal grown by the vertical Bridgman process is adopted as an example to study the influences of doping impurity and growth orientation on dislocation generation. The calculated results show that doping impurity can significantly reduce the dislocation density generated in the crystal. The level of reduction is also influenced by the growth orientation during the crystal growth process.

Orientation Dependence of Functional Properties in Heterophase Single Crystals of the Ti36.5Ni51.0Hf12.5 and Ti48.5Ni51.5 Alloys

NASA Astrophysics Data System (ADS)

Panchenko, E. Yu.; Chumlyakov, Yu. I.; Surikov, N. Yu.; Tagiltsev, A. I.; Vetoshkina, N. G.; Osipovich, K. S.; Maier, H.; Sehitoglu, H.

2016-03-01

The features of orientation dependence of stress-induced thermoelastic B2-( R)- B19'-martensitic transformations in single crystals of the Ti48.5Ni51.5 and Ni51.0Ti36.5Hf12.5 (at.%) alloys, which contain disperse particles of the Ti3Ni4 and H-phase, respectively, are revealed along with those of their shape-memory effects (SME) and superelasticity (SE). It is experimentally demonstrated that irrespective of the crystal structure of disperse particles measuring more than 100 nm, for their volume fraction f > 16% there is a weaker orientation dependence of the reversible strain in the cases of manifestation of SME and SE. In the orientations of Class I, wherein martensitic detwinning introduces a considerable contribution into transformation strain, the values of SME |ɛ SME | and SE |ɛ SE | decrease by over a factor of two compared to the theoretical lattice strain value |ɛ tr0 | for a B2- B19'-transformation and the experimental values of reversible strain for quenched TiNi crystals. In the orientations of Class 2, wherein detwinning of the martensite is suppressed as is the case in quenched single-phase single crystals, the reversible strain is maintained close to its theoretical value |ɛ tr0 |. Micromechanical models of interaction between the martensite and the disperse particles are proposed, which account for the weaker orientation dependence of |ɛ SME | and |ɛ SE | due to suppression of detwinning of the B19'-martensite crystals by the particles and a transition from a single-variant evolution of the stress-induced martensitic transformations to a multiple-variant evolution of transformations in the cases of increased size of the particles and their larger volume fractions.

Developing bioactive composite scaffolds for bone tissue engineering

NASA Astrophysics Data System (ADS)

Chen, Yun

Poly(L-lactic acid) (PLLA) films were fabricated using the method of dissolving and evaporation. PLLA scaffold was prepared by solid-liquid phase separation of polymer solutions and subsequent sublimation of solvent. Bonelike apatite coating was formed on PLLA films, PLLA scaffolds and poly(glycolic acid) (PGA) scaffolds in 24 hours through an accelerated biomimetic process. The ion concentrations in the simulated body fluid (SBF) were nearly 5 times of those in human blood plasma. The apatite formed was characterized using scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR). The apatite formed in 5SBF was similar in morphology and composition to that formed in the classical biomimetic process employing SBF or 1.5SBF, and similar to that of natural bone. This indicated that the biomimetic apatite coating process could be accelerated by using concentrated simulated body fluid at 37°C. Besides saving time, the accelerated biomimetic process is particularly significant to biodegradable polymers. Some polymers which degrade too fast to be coated with apatite by a classical biomimetic process, for example PGA, could be coated with bone-like apatite in an accelerated biomimetic process. Collagen and apatite were co-precipitated as a composite coating on poly(L-lactic acid) (PLLA) in an accelerated biomimetic process. The incubation solution contained collagen (1g/L) and simulated body fluid (SBF) with 5 times inorganic ionic concentrations as human blood plasma. The coating formed on PLLA films and scaffolds after 24 hours incubation was characterized using EDX, XRD, FTIR, and SEM. It was shown that the coating contained carbonated bone-like apatite and collagen, the primary constituents of natural bone. SEM showed a complex composite coating of submicron bone-like apatite particulates combined with collagen fibrils. This work provided an efficient process to obtain bone-like apatite/collagen composite coating. Saos-2 osteoblast-like cells were used to evaluate the cellular behaviors on these biomimetic coatings. Cell morphologies on the surfaces of PLLA films and scaffolds, PLLA films and scaffolds with apatite coating, and PLLA films and scaffolds with apatite/collagen composite coating were studied by SEM. Cell viability was assessed by the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrasodium bromide (MTT) assay. In addition, differentiated cell function was assessed by measuring alkaline phosphatase activity. These results suggested that the apatite coating and apatite/collagen composite coating fabricated through the accelerated biomimetic processes could improve the interactions between osteoblasts and PLLA. The composite coating was more effective than apatite coating in improving such interactions. PLLA scaffolds coated with submicron collagen fibrils and submicron apatite paticulates are expected to be one of the promising 3D substrates for bone tissue engineering. To facilitate coating into scaffolds, the flowing condition was introduced into the accelerated biomimetic process. The apatite formed in the different sites in the scaffold was characterized using SEM. It was found that the accelerated biomimetic process performed in the flowing condition yielded more uniform spatial distribution of apatite particles than that in the regular shaking condition. This work provides a novel condition for obtaining uniform spatial distribution of bone-like apatite within the scaffolds in a timely manner, which is expected to facilitate uniform distribution of attached cells within the scaffoldsin vitro and in vivo.

Shock wave-induced phase transition in RDX single crystals.

PubMed

Patterson, James E; Dreger, Zbigniew A; Gupta, Yogendra M

2007-09-20

The real-time, molecular-level response of oriented single crystals of hexahydro-1,3,5-trinitro-s-triazine (RDX) to shock compression was examined using Raman spectroscopy. Single crystals of [111], [210], or [100] orientation were shocked under stepwise loading to peak stresses from 3.0 to 5.5 GPa. Two types of measurements were performed: (i) high-resolution Raman spectroscopy to probe the material at peak stress and (ii) time-resolved Raman spectroscopy to monitor the evolution of molecular changes as the shock wave reverberated through the material. The frequency shift of the CH stretching modes under shock loading appeared to be similar for all three crystal orientations below 3.5 GPa. Significant spectral changes were observed in crystals shocked above 4.5 GPa. These changes were similar to those observed in static pressure measurements, indicating the occurrence of the alpha-gamma phase transition in shocked RDX crystals. No apparent orientation dependence in the molecular response of RDX to shock compression up to 5.5 GPa was observed. The phase transition had an incubation time of approximately 100 ns when RDX was shocked to 5.5 GPa peak stress. The observation of the alpha-gamma phase transition under shock wave loading is briefly discussed in connection with the onset of chemical decomposition in shocked RDX.

Minor and trace element geochemistry of volcanic rocks dredged from the Galapagos spreading center: role of crystal fractionation and mantle heterogeneity.

USGS Publications Warehouse

Clague, D.A.; Frey, F.A.; Thompson, G.; Rindge, S.

1981-01-01

A wide range of rock types (abyssal tholeiite, Fe-Ti-rich basalt, andesite, and rhyodacite) were dredged from near 95oW and 85oW on the Galapagos spreading center. Computer modeling of major element compositions has shown that these rocks could be derived from common parental magmas by successive degrees of fractional crystallization. However, the P2O5/K2O ratio implies distinct mantle source compositions for the two areas. These source regions also have different rare earth element (REE) abundance patterns. The sequence of fractionated lavas differs for the two areas and indicates earlier fractionation of apatite and titanomagnetite in the lavas from 95oW. The mantle source regions for these two areas are interpreted to be depleted in incompatible (and volatile?) elements, although the source region beneath 95oW is less severely depleted in La and K. -Authors

Fabrication, characterization and cell cultures on a novel composite chitosan-nano-hydroxyapatite scaffold.

PubMed

Palazzo, B; Gallo, A; Casillo, A; Nitti, P; Ambrosio, L; Piconi, C

2011-01-01

This paper deals with the characterizations made during the development of a nano-HAp loaded chitosan scaffold, obtained by the freeze-drying technique combined with a novel in situ crystal growth method. The nano-composites were characterized by a highly porous and interconnected structure. The XRD patterns and calculated domain sizes of the HAp nano-crystals nucleated on the chitosan scaffolds are very similar to the ones recorded for deproteinated bone apatite. Both osteoblasts (MG63) and mesenchimal cells (hMSC) were showing good proliferation and adhesion onto the scaffolds. The presence of extensive filopodia and excellent spreading in and around the interconnected porous structure, indicated a strong cellular adhesion and growth. Moreover a good hMSC osteogenic differentiation has been verified. The observations related to well-developed structure morphology, physicochemical properties and high cytocompatibility suggest that the obtained chitosan-nHA porous scaffolds are potential candidate materials for bone regeneration.

Light rare earth element systematics as a tool for investigating the petrogenesis of phoscorite-carbonatite associations, as exemplified by the Phalaborwa Complex, South Africa

NASA Astrophysics Data System (ADS)

Milani, Lorenzo; Bolhar, Robert; Frei, Dirk; Harlov, Daniel E.; Samuel, Vinod O.

2017-12-01

In-situ trace element analyses of fluorapatite, calcite, dolomite, olivine, and phlogopite have been undertaken on representative phoscorite and carbonatite rocks of the Palaeoproterozoic Phalaborwa Complex. Textural and compositional characterization reveals uniformity of fluorapatite and calcite among most of the intrusions, and seems to favor a common genetic origin for the phoscorite-carbonatite association. Representing major repositories for rare earth elements (REE), fluorapatite and calcite exhibit tightly correlated light REE (LREE) abundances, suggesting that partitioning of LREE into these rock forming minerals was principally controlled by simple igneous differentiation. However, light rare earth element distribution in apatite and calcite cannot be adequately explained by equilibrium and fractional crystallization and instead favors a complex crystallization history involving mixing of compositionally distinct magma batches, in agreement with previously reported mineral isotope variability that requires open-system behaviour.

Reconstruction of the 3-D Shape and Crystal Preferred Orientation of Olivine: A Combined X-ray µ-CT and EBSD-SEM approach

NASA Astrophysics Data System (ADS)

Kahl, Wolf-Achim; Hidas, Károly; Dilissen, Nicole; Garrido, Carlos J.; López-Sánchez Vizcaíno, Vicente; Jesús Román-Alpiste, Manuel

2017-04-01

The complete reconstruction of the microstructure of rocks requires, among others, a full description of the shape preferred orientation (SPO) and crystal preferred orientation (CPO) of the constituent mineral phases. New advances in instrumental analyses, particularly electron backscatter diffraction (EBSD) coupled to focused ion beam-scanning electron microscope (FIB-SEM), allows a complete characterization of SPO and CPO in rocks at the micron scale [1-2]. Unfortunately, the large grain size of many crystalline rocks, such as peridotite, prevents a representative characterization of the CPO and SPO of their constituent minerals by this technique. Here, we present a new approach combining X-ray micro computed tomography (µ-CT) and EBSD to reconstruct the geographically oriented, 3-D SPO and CPO of cm- to mm-sized olivine crystals in two contrasting fabric types of chlorite harzburgites (Almírez ultramafic massif, SE Spain). The semi-destructive sample treatment involves drilling of geographically oriented micro drills in the field and preparation of oriented thin sections from µ-CT scanned cores. This allows for establishing the link among geological structures, macrostructure, fabric, and 3-D SPO-CPO at the thin section scale. Based on EBSD analyses, different CPO groups of olivine crystals can be discriminated in the thin sections and allocated to 3-D SPO in the µ-CT volume data. This approach overcomes the limitations of both methods (i.e., no crystal orientation data in µ-CT and no spatial information in EBSD), hence 3-D orientation of the crystallographic axes of olivines from different orientation groups could be correlated with the crystal shapes of olivine grains. This combined µ-CT and EBSD technique enables the correlation of both SPO and CPO and representative grain size, and is capable to characterize the 3-D microstructure of olivine-bearing rocks at the hand specimen scale. REFERENCES 1. Zaefferer, S., Wright, S.I., Raabe, D., 2008. Three-Dimensional orientation microscopy in a focused ion beam-scanning electron microscope: A new dimension of microstructure characterization. Metallurgical and Materials Transactions A 39, 374-389. 2. Burnett, T.L., Kelley, R., Winiarski, B., Contreras, L., Daly, M., Gholinia, A., Burke, M.G., Withers, P.J., 2016. Large volume serial section tomography by Xe Plasma FIB dual beam microscopy. Ultramicroscopy 161, 119-129.

Differentiation of grain orientation with corrosive and colour etching on a granular bainitic steel.

PubMed

Reisinger, S; Ressel, G; Eck, S; Marsoner, S

2017-08-01

This study presents a detailed verification of the etching methods with Nital and Klemm on a granular bainitic steel. It is shown that both methods allow the identification of the crystal orientation, whereas Klemm etching enables also a quantification of the apparent phases, as also retained austenite can be distinguished from the other bainitic microstructures. A combination of atom probe tomography with electron-back-scattered-diffraction showed that both etching methods emphasize the bainitic {100} crystal orientation. However, a cross-section produced by focused ion beam evidenced that Klemm etching leads to the formation of a topography of the different oriented bainitic crystals that directly affects the thickness and therefore the apparent colour of the deposited layer formed during etching. Copyright © 2017 Elsevier Ltd. All rights reserved.

Critical CuI buffer layer surface density for organic molecular crystal orientation change

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ahn, Kwangseok; Kim, Jong Beom; Lee, Dong Ryeol, E-mail: drlee@ssu.ac.kr

We have determined the critical surface density of the CuI buffer layer inserted to change the preferred orientation of copper phthalocyanine (CuPc) crystals grown on the buffer layer. X-ray reflectivity measurements were performed to obtain the density profiles of the buffer layers and out-of-plane and 2D grazing-incidence X-ray diffraction measurements were performed to determine the preferred orientations of the molecular crystals. Remarkably, it was found that the preferred orientation of the CuPc film is completely changed from edge-on (1 0 0) to face-on (1 1 −2) by a CuI buffer layer with a very low surface density, so low thatmore » a large proportion of the substrate surface is bare.« less

Synthesis of fluorine substituted hydroxyapatite nanopowders and application of the central composite design for determination of its antimicrobial effects

NASA Astrophysics Data System (ADS)

Stanić, Vojislav; Dimitrijević, Suzana; Antonović, Dušan G.; Jokić, Bojan M.; Zec, Slavica P.; Tanasković, Sladjana T.; Raičević, Slavica

2014-01-01

Synthetic biomaterials based on fluorine substituted hydroxyapatite are potentially attractive for orthopedic and dental implant applications. The new synthesis of fluorine substituted hydroxyapatite samples were done by neutralization, which consists of adding the solution of HF and H3PO4 in suspension of Ca(OH)2. Characterization studies from XRD, SEM and FTIR spectra showed that crystals are obtained with apatite structure and those particles of all samples are nano size, with an average length of 80 nm and about 15-25 nm in diameter. The central composite design was used in order to determine the optimal conditions for the antimicrobial activity of the synthesized samples. In order to evaluate the influence of operating parameters on the percent of viable cell reduction of Streptococcus mutans, three independent variables were chosen: exposure time, pH of saline and floride concentration in apatite samples. The experimental and predicted antimicrobial activities were in close agreement. Antimicrobial activity of the samples increases with the increase of fluoride concentration and the decreased pH of saline. The maximum antimicrobial activity was achieved at the initial pH of 4.

Identifying compositional and structural changes in spongy and subchondral bone from the hip joints of patients with osteoarthritis using Raman spectroscopy.

PubMed

Buchwald, Tomasz; Niciejewski, Krzysztof; Kozielski, Marek; Szybowicz, Mirosław; Siatkowski, Marcin; Krauss, Hanna

2012-01-01

Raman microspectroscopy was used to examine the biochemical composition and molecular structure of extracellular matrix in spongy and subchondral bone collected from patients with clinical and radiological evidence of idiopathic osteoarthritis of the hip and from patients who underwent a femoral neck fracture, as a result of trauma, without previous clinical and radiological evidence of osteoarthritis. The objectives of the study were to determine the levels of mineralization, carbonate accumulation and collagen quality in bone tissue. The subchondral bone from osteoarthritis patients in comparison with control subject is less mineralized due to a decrease in the hydroxyapatite concentration. However, the extent of carbonate accumulation in the apatite crystal lattice increases, most likely due to deficient mineralization. The alpha helix to random coil band area ratio reveals that collagen matrix in subchondral bone is more ordered in osteoarthritis disease. The hydroxyapatite to collagen, carbonate apatite to hydroxyapatite and alpha helix to random coil band area ratios are not significantly changed in the differently loaded sites of femoral head. The significant differences also are not visible in mineral and organic constituents' content in spongy bone beneath the subchondral bone in osteoarthritis disease.

Identifying compositional and structural changes in spongy and subchondral bone from the hip joints of patients with osteoarthritis using Raman spectroscopy

NASA Astrophysics Data System (ADS)

Buchwald, Tomasz; Niciejewski, Krzysztof; Kozielski, Marek; Szybowicz, Mirosław; Siatkowski, Marcin; Krauss, Hanna

2012-01-01

Raman microspectroscopy was used to examine the biochemical composition and molecular structure of extracellular matrix in spongy and subchondral bone collected from patients with clinical and radiological evidence of idiopathic osteoarthritis of the hip and from patients who underwent a femoral neck fracture, as a result of trauma, without previous clinical and radiological evidence of osteoarthritis. The objectives of the study were to determine the levels of mineralization, carbonate accumulation and collagen quality in bone tissue. The subchondral bone from osteoarthritis patients in comparison with control subject is less mineralized due to a decrease in the hydroxyapatite concentration. However, the extent of carbonate accumulation in the apatite crystal lattice increases, most likely due to deficient mineralization. The alpha helix to random coil band area ratio reveals that collagen matrix in subchondral bone is more ordered in osteoarthritis disease. The hydroxyapatite to collagen, carbonate apatite to hydroxyapatite and alpha helix to random coil band area ratios are not significantly changed in the differently loaded sites of femoral head. The significant differences also are not visible in mineral and organic constituents' content in spongy bone beneath the subchondral bone in osteoarthritis disease.

Sulphur bacteria mediated formation of Palaeoproterozoic phosphorites

NASA Astrophysics Data System (ADS)

Joosu, Lauri; Lepland, Aivo; Kirsimäe, Kalle

2014-05-01

Modern phosphorite formation is typically associated with high productivity in upwelling areas where apatite (Ca-phosphate) precipitation is mediated by sulphur oxidising bacteria [1]. They inhabit the oxic/anoxic interface within the upper few centimetres of sediment column, accumulating phosphate in their cells under oxic conditions and releasing it rapidly when conditions become anoxic. Sulphur bacteria are known to live in close association with a consortium of anaerobic methane oxidising archaea and syntrophic sulphate-reducing bacteria. Paleoproterozoic, c. 2.0 Ga Zaonega Formation in Karelia, Russia contains several P-rich intervals in the upper part of 1500 m thick succession of organic-rich sedimentary rocks interlayered with mafic tuffs and lavas. Apatite in these P-rich intervals forms impure laminae, lenses and round-oval nodules which diameters typically range from 300 to 1000 μm. Individual apatite particles in P-rich laminae and nodules commonly occur as cylinders that are 1-8 μm long and have diameters of 0.5-4 μm. Cross-sections of best preserved cylindrical apatite particles reveal a thin outer rim whereas the internal parts consist of small anhedral elongated crystallites, intergrown with carbonaceous material. During recrystallization the outer rim thickens towards interior and cylinders may attain hexagonal crystal habit, but their size and shape remains largely unchanged [2]. The sizes of Zaonega nodules are similar to giant sulphide-oxidising bacteria known from modern and ancient settings [3, 4]. Individual apatite cylinders and aggregates have shapes and sizes similar to the methanotrophic archaea that inhabit microbial mats in modern seep/vent areas where they operate in close associations with sulphur-oxidising microbial communities [5]. Seep/vent influence during the Zaonega phosphogenesis is indicated by variable, though positive Eu anomaly, expected in magmatically active sedimentary environment experiencing several lava flows. Moreover, P-rich intervals in the Zaonega Formation are found in organic-rich sediments exhibiting strongly negative δ13Corg values (-37 to -34 per mil) which is interpreted to reflect the methanotrophic biomass. We conclude that modern-style phosphogenesis, mediated by sulphide-oxidising bacteria living in consortium with methanotrophs, was established at least 2 Ga ago. [1] Schulz and Schulz (2005) Science 307, 416-418 [2] Lepland, Joosu, Kirsimäe, Prave, Romashkin, Črne, Martin, Fallick, Somelar, Üpraus, Mänd, Roberts, van Zuilen, Wirth, Schreiber (2014) Nature geoscience 7, 20-24 [3] Bailey, Joye, Kalanetra, Flood, and Corsetti (2007) Nature 445, 198-201 [4] Schulz, Brinkhoff, Ferdelman, Marine, Teske and Jorgensen (1999) Science 284, 493-495 [5] Knittel, Losekann, Boetius, Kort and Amann (2005) Applied and Environmental Microbiology 71, 467-479.

Thermodynamic Properties of Sulfatian Apatite: Constraints on the Behavior of Sulfur in Calc-Alkaline Magmas

NASA Astrophysics Data System (ADS)

Core, D.; Essene, E. J.; Luhr, J. F.; Kesler, S. E.

2004-12-01

The Gibbs free energy of hydroxyellestadite [Ca10(SiO4)3(SO4)3(OH)2] was estimated using mineral equilibria applied to analyzed assemblages from the experimental charges of Luhr (1990). The apatite analyses of Peng et al. (1997) were used in conjunction with new analyses of the oxides and silicates in this study. An ideal mixing model was employed for apatite combined with mixing models from MELTS (Ghiorso & Sack, 1994) and Gibbs free energy data from Robie & Hemingway (1995) for the other crystalline phases. The resultant equation of the Gibbs free energy vs. T for hydroxyellestadite is as follows: DG°T(elem) = [2.817(T - 273) - 11831]/1000 kJ/mol, T in K. The calculated entropy for hydroxyellestadite is 1944 J/mol.K at 1073 K and 2151 J/mol.K at 1227 K. Independent estimates of the entropy of hydroxyellestadite obtained with the method of Robinson & Haas (1983) are within 5% of these values. The thermodynamic data on hydroxyellestadite were used to calculate the locus of the reactions: 2Ca10(SiO4)3(SO4)3(OH)2 + 7S2 + 21O2 = 20CaSO4 + 6SiO2 + 2H2O 6Ca10(SiO4)3(SO4)3(OH)2 + 102SiO2 + 20Fe3O4 = 60CaFeSi2O6 + 6H2O + 9S2 + 37O2 2Ca10(SiO4)3(SO4)3(OH)2 + 10Mg2Si2O6 + 14SiO2 = 20CaMgSi2O6 + 2H2O + 3S2 + 9O2 in fO2-fS2 space at fixed P-T. Application of these equilibria to apatite zoned in sulfate from oxidized granitoids reflects a drop in fS2 by more than 1 log unit during its growth. The zoning is interpreted to represent the removal of a magmatic vapor phase during crystallization of these plutons. Removal of sulfur from magmas by hydrothermal fluids is important to the ore-forming process and to the production of acid sulfate aerosols during eruption of oxidized magmas. Preservation of sulfatian apatite may yield data on the sulfidation states of ancient flood basalts such as the Deccan Traps of India and the Parana basalts of Brazil to address the environmental impact of these giant eruptions.

Elemental distribution analysis of urinary crystals.

PubMed

Fazil Marickar, Y M; Lekshmi, P R; Varma, Luxmi; Koshy, Peter

2009-10-01

Various crystals are seen in human urine. Some of them, particularly calcium oxalate dihydrate, are seen normally. Pathological crystals indicate crystal formation initiating urinary stones. Unfortunately, many of the relevant crystals are not recognized in light microscopic analysis of the urinary deposit performed in most of the clinical laboratories. Many crystals are not clearly identifiable under the ordinary light microscopy. The objective of the present study was to perform scanning electron microscopic (SEM) assessment of various urinary deposits and confirm the identity by elemental distribution analysis (EDAX). 50 samples of urinary deposits were collected from urinary stone clinic. Deposits containing significant crystalluria (more than 10 per HPF) were collected under liquid paraffin in special containers and taken up for SEM studies. The deposited crystals were retrieved with appropriate Pasteur pipettes, and placed on micropore filter paper discs. The fluid was absorbed by thicker layers of filter paper underneath and discs were fixed to brass studs. They were then gold sputtered to 100 A and examined under SEM (Jeol JSM 35C microscope). When crystals were seen, their morphology was recorded by taking photographs at different angles. At appropriate magnification, EDAX probe was pointed to the crystals under study and the wave patterns analyzed. Components of the crystals were recognized by utilizing the data. All the samples analyzed contained significant number of crystals. All samples contained more than one type of crystal. The commonest crystals encountered included calcium oxalate monohydrate (whewellite 22%), calcium oxalate dihydrate (weddellite 32%), uric acid (10%), calcium phosphates, namely, apatite (4%), brushite (6%), struvite (6%) and octocalcium phosphate (2%). The morphological appearances of urinary crystals described were correlated with the wavelengths obtained through elemental distribution analysis. Various urinary crystals that are not reported under light microscopy could be recognized by SEM-EDAX combination. EDAX is a significant tool for recognizing unknown crystals not identified by ordinary light microscopy or SEM alone.

Magma hybridization in the Western Tatra Mts. granitoid intrusion (S-Poland, Western Carpathians).

PubMed

Burda, Jolanta; Gawęda, Aleksandra; Klötzli, Urs

In the Variscan Western Tatra granites hybridization phenomena such as mixing and mingling can be observed at the contact of mafic precursors of dioritic composition and more felsic granitic host rocks. The textural evidence of hybridization include: plagioclase-K-feldspar-sphene ocelli, hornblende- and biotite-rimmed quartz ocelli, plagioclase with Ca-rich spike zonation, inversely zoned K-feldspar crystals, mafic clots, poikilitic plagioclase and quartz crystals, mixed apatite morphologies, zoned K-feldspar phenocrysts. The apparent pressure range of the magma hybridization event was calculated at 6.1 kbar to 4.6 kbar, while the temperature, calculated by independent methods, is in the range of 810°C-770°C. U-Pb age data of the hybrid rocks were obtained by in-situ LA-MC-ICP-MS analysis of zircon. The oscillatory zoned zircon crystals yield a concordia age of 368 ± 8 Ma (MSWD = 1.1), interpreted as the age of magma hybridization and timing of formation of the magmatic precursors. It is the oldest Variscan magmatic event in that part of the Tatra Mountains.

Gold in Accessory Zircon (the Kozhim Massif, Subpolar Urals)

NASA Astrophysics Data System (ADS)

Denisova, Yuliya; Pystin, Aleksandr

2017-12-01

The crystals of zircon due to their resistance to external impact of various processes can reveal information about the environment of their formation and the inclusions observed of them. Zircon contains different mineral inclusions: biotite, plagioclase, quartz, apatite, etc. However, there is no information about gold inclusions in the zircons from granites of the Sudpolar Urals. The study results of the inclusions of gold in accessory zircon of the Kozhim granitic massif are presented in this paper. The studied mineral is a dark-brown translucent short-prismatic crystal containing the inclusion of gold and the allocations of quartz. According to studies, the inclusion of gold formed during the growth of zircon and it is the gold covered with a thin film of oxide gold. It was confirmed that the crystallization of the studied zircon occurred at a temperature of 800°C and above on the stage of formation of granites of Kozhim massif. The assumption is made about the additional temperature in the course of which was caused by decreasing of temperature up to 700° C and below during postmagmatic stage.

Bioactive Glasses with Low Ca/P Ratio and Enhanced Bioactivity

PubMed Central

Araújo, Marco; Miola, Marta; Baldi, Giovanni; Perez, Javier; Verné, Enrica

2016-01-01

Three new silica-based glass formulations with low molar Ca/P ratio (2–3) have been synthesized. The thermal properties, the crystalline phases induced by thermal treatments and the sintering ability of each glass formulation have been investigated by simultaneous differential scanning calorimetry-thermogravimetric analysis (DSC-TG), X-ray diffraction (XRD) and hot stage microscopy (HSM). The glasses exhibited a good sintering behavior, with two samples achieving shrinkage of 85%–95% prior to crystallization. The bioactivity of the glasses in simulated body fluid (SBF) has been investigated by performing XRD and Fourier transform infrared spectroscopy (FTIR) on the samples prior and after immersion. The glasses with lower MgO contents were able to form a fully crystallized apatite layer after three days of immersion in simulated body fluid (SBF), while for the glass exhibiting a higher MgO content in its composition, the crystallization of the Ca–P layer was achieved after seven days. The conjugation of these properties opens new insights on the synthesis of highly bioactive and mechanically strong prosthetic materials. PMID:28773350

[Comparative studies on the material performances of natural bone-like apatite from different bone sources].

PubMed

Fan, Xiaoxia; Ren, Haohao; Chen, Shutian; Wang, Guangni; Deng, Tianyu; Chen, Xingtao; Yan, Yonggang

2014-04-01

The compressive strength of the original bone tissue was tested, based on the raw human thigh bone, bovine bone, pig bone and goat bone. The four different bone-like apatites were prepared by calcining the raw bones at 800 degrees C for 8 hours to remove organic components. The comparison of composition and structure of bone-like apatite from different bone sources was carried out with a composition and structure test. The results indicated that the compressive strength of goat bone was similar to that of human thigh bone, reached (135.00 +/- 7.84) MPa; Infrared spectrum (IR), X-ray diffraction (XRD) analysis results showed that the bone-like apatite from goat bone was much closer to the structure and phase composition of bone-like apatite of human bones. Inductively Coupled Plasma (ICP) test results showed that the content of trace elements of bone-like apatite from goat bone was closer to that of apatite of human bone. Energy Dispersive Spectrometer (EDS) results showed that the Ca/P value of bone-like apatite from goat bone was also close to that of human bone, ranged to 1.73 +/- 0.033. Scanning electron microscopy (SEM) patterns indicated that the macrographs of the apatite from human bone and that of goat bone were much similar to each other. Considering all the results above, it could be concluded that the goat bone-like apatite is much similar to that of human bone. It can be used as a potential natural bioceramic material in terms of material properties.

The effect of oxygen plasma pretreatment and incubation in modified simulated body fluids on the formation of bone-like apatite on poly(lactide-co-glycolide) (70/30).

PubMed

Qu, Xue; Cui, Wenjin; Yang, Fei; Min, Changchun; Shen, Hong; Bei, Jianzhong; Wang, Shenguo

2007-01-01

In this study, biodegradable poly(lactide-co-glycolide) (PLGA) (70/30) films and scaffolds were first treated with oxygen plasma and then incubated in a modified simulated body fluid 1.5SBF0 to prepare a bone-like apatite layer. The formation of the apatite and its influence on osteoblast-like cells growth were investigated. It was found that the bone-like apatite formability of PLGA(70/30) was enhanced by plasma pretreatment. The changes of surface chemistry and surface topography induced by oxygen plasma treatment were both effective for apatite formation. The apatite formability increased with increasing plasma-treating time. Under a treating condition of 20 W for 30 min, oxygen plasma treatment could penetrate into the inner scaffold. After 6 days incubation, the apatite formed in plasma-treated scaffold was better distributed than in untreated scaffold, and the weight and mechanical strength of the plasma-treated scaffold were both enhanced. Compared with PLGA(70/30), the apatite layer formed on oxygen plasma-treated PLGA(70/30) surface enhanced adhesion and proliferation of OCT-1 osteoblast-like cell, but had no significant effect on cell's ALP activity at day 7. A prolonged investigation is being in process to further verify the bone-like apatite effects on osteogenic differentiation.

Plastic strain arrangement in copper single crystals in sliding

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chumaevskii, Andrey V., E-mail: tch7av@gmail.com; Lychagin, Dmitry V., E-mail: dvl-tomsk@mail.ru; Tarasov, Sergei Yu., E-mail: tsy@ispms.tsc.ru

2014-11-14

Deformation of tribologically loaded contact zone is one of the wear mechanisms in spite of the fact that no mass loss may occur during this process. Generation of optimal crystallographic orientations of the grains in a polycrystalline materials (texturing) may cause hardening and reducing the deformation wear. To reveal the orientation dependence of an individual gain and simplify the task we use copper single crystals with the orientations of the compression axis along [111] and [110]. The plastic deformation was investigated by means of optical, scanning electron microscopy and EBSD techniques. It was established that at least four different zonesmore » were generated in the course of sliding test, such as non-deformed base metal, plastic deformation layer sliding, crystalline lattice reorientation layer and subsurface grain structure layer. The maximum plastic strain penetration depth was observed on [110]-single crystals. The minimum stability of [111]-crystals with respect to rotation deformation mode as well as activation of shear in the sliding contact plane provide for rotation deformation localization below the worn surface. The high-rate accumulation of misorientations and less strain penetration depth was observed on [111]-crystals as compared to those of [110]-oriented ones.« less

A new method to evaluate the quality of single crystal Cu by an X-ray diffraction butterfly pattern method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu Zhenming; Guo Zhenqi; Li Jianguo

2004-12-15

A new method for the evaluation of the quality of an Ohno continuous cast (OCC) Cu single crystal by X-ray diffraction (XRD) butterfly pattern was brought forward. Experimental results show that the growth direction of single crystal Cu is inclined from both sides of the single crystal Cu rod to the axis and is axially symmetric. The degree of deviation from the [100] orientation from the crystal axis is less than 5 deg. with a casting speed 10-40 mm/min. The orientation of single crystal Cu does not have a fixed direction but is in a regular range. Moreover, the orientationmore » of stray grains in the single crystal Cu is random from continuous casting.« less

Mechanism of calcite co-orientation in the sea urchin tooth.

PubMed

Killian, Christopher E; Metzler, Rebecca A; Gong, Y U T; Olson, Ian C; Aizenberg, Joanna; Politi, Yael; Wilt, Fred H; Scholl, Andreas; Young, Anthony; Doran, Andrew; Kunz, Martin; Tamura, Nobumichi; Coppersmith, Susan N; Gilbert, P U P A

2009-12-30

Sea urchin teeth are remarkable and complex calcite structures, continuously growing at the forming end and self-sharpening at the mature grinding tip. The calcite (CaCO(3)) crystals of tooth components, plates, fibers, and a high-Mg polycrystalline matrix, have highly co-oriented crystallographic axes. This ability to co-orient calcite in a mineralized structure is shared by all echinoderms. However, the physico-chemical mechanism by which calcite crystals become co-oriented in echinoderms remains enigmatic. Here, we show differences in calcite c-axis orientations in the tooth of the purple sea urchin ( Strongylocentrotus purpuratus ), using high-resolution X-ray photoelectron emission spectromicroscopy (X-PEEM) and microbeam X-ray diffraction (muXRD). All plates share one crystal orientation, propagated through pillar bridges, while fibers and polycrystalline matrix share another orientation. Furthermore, in the forming end of the tooth, we observe that CaCO(3) is present as amorphous calcium carbonate (ACC). We demonstrate that co-orientation of the nanoparticles in the polycrystalline matrix occurs via solid-state secondary nucleation, propagating out from the previously formed fibers and plates, into the amorphous precursor nanoparticles. Because amorphous precursors were observed in diverse biominerals, solid-state secondary nucleation is likely to be a general mechanism for the co-orientation of biomineral components in organisms from different phyla.

Chitosan reinforced apatite-wollastonite coating by electrophoretic deposition on titanium implants.

PubMed

Sharma, Smriti; Soni, Vivek P; Bellare, Jayesh R

2009-07-01

A novel bioactive porous apatite-wollastonite/chitosan composite coating was prepared by electrophoretic deposition. The influence of synthesis parameters like pH of suspension and current density was studied and optimized. X-ray diffraction confirmed crystalline phase of apatite-wollastonite in powder as well as composite coating with coat crystallinity of 65%. Scanning electron microscope showed that the porosity had interconnections with good homogeneity between the phases. The addition of chitosan increased the adhesive strength of the composite coating. Young's modulus of the coating was found to be 9.23 GPa. One of our key findings was sheet-like apatite growth unlike ball-like growth found in bioceramics. Role of chitosan was studied in apatite growth mechanism in simulated body fluid. In presence of chitosan, dense negatively charged surface with homogenous nucleation was the primary factor for sheet-like evolution of apatite layer. The results suggest that incorporation of chitosan with apatite-wollastonite in composite coating could provide excellent in vitro bioactivity with enhanced mechanical properties.

The evolution of machining-induced surface of single-crystal FCC copper via nanoindentation

NASA Astrophysics Data System (ADS)

Zhang, Lin; Huang, Hu; Zhao, Hongwei; Ma, Zhichao; Yang, Yihan; Hu, Xiaoli

2013-05-01

The physical properties of the machining-induced new surface depend on the performance of the initial defect surface and deformed layer in the subsurface of the bulk material. In this paper, three-dimensional molecular dynamics simulations of nanoindentation are preformed on the single-point diamond turning surface of single-crystal copper comparing with that of pristine single-crystal face-centered cubic copper. The simulation results indicate that the nucleation of dislocations in the nanoindentation test on the machining-induced surface and pristine single-crystal copper is different. The dislocation embryos are gradually developed from the sites of homogeneous random nucleation around the indenter in the pristine single-crystal specimen, while the dislocation embryos derived from the vacancy-related defects are distributed in the damage layer of the subsurface beneath the machining-induced surface. The results show that the hardness of the machining-induced surface is softer than that of pristine single-crystal copper. Then, the nanocutting simulations are performed along different crystal orientations on the same crystal surface. It is shown that the crystal orientation directly influences the dislocation formation and distribution of the machining-induced surface. The crystal orientation of nanocutting is further verified to affect both residual defect generations and their propagation directions which are important in assessing the change of mechanical properties, such as hardness and Young's modulus, after nanocutting process.

The Chlorine Isotopic Composition Of Lunar UrKREEP

NASA Technical Reports Server (NTRS)

Barnes, J. J.; Tartese, R.; Anand, M.; McCubbin, F. M.; Neal, C. R.; Franchi, I. A.

2016-01-01

Since the long standing paradigm of an anhydrous Moon was challenged there has been a renewed focus on investigating volatiles in a variety of lunar samples. Numerous studies have examined the abundances and isotopic compositions of volatiles in lunar apatite, Ca5(PO4)3(F,Cl,OH). In particular, apatite has been used as a tool for assessing the sources of H2O in the lunar interior. However, current models for the Moon's formation have yet to fully account for its thermal evolution in the presence of H2O and other volatiles. For ex-ample, in the context of the lunar magma ocean (LMO) model, it is anticipated that chlorine (and other volatiles) should have been concentrated in the late-stage LMO residual melts (i.e., the dregs enriched in incompatible elements such as K, REEs (Rare Earth Elements), and P, collectively called KREEP, and in its primitive form - urKREEP, given its incompatibility in mafic minerals like olivine and pyroxene, which were the dominant phases that crystallized early in the cumulate pile of the LMO. When compared to chondritic meteorites and terrestrial rocks, lunar samples have exotic chlorine isotope compositions, which are difficult to explain in light of the abundance and isotopic composition of other volatile species, especially H, and the current estimates for chlorine and H2O in the bulk silicate Moon (BSM). In order to better understand the processes involved in giving rise to the heavy chlorine isotope compositions of lunar samples, we have performed a comprehensive in situ high precision study of chlorine isotopes in lunar apatite from a suite of Apollo samples covering a range of geochemical characteristics and petrologic types.

Lead apatites: structural variations among Pb 5( BO 4) 3 Cl with B = P (pyromorphite), As (mimetite) and V (vanadinite)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Antao, Sytle M.; Dhaliwal, Inayat

The crystal structure of four Pb apatite samples, Pb 5(BO 4) 3Cl, was refined with synchrotron high-resolution powder X-ray diffraction data, Rietveld refinements, space groupP6 3/mandZ= 2. For this isotypic series,B= P 5+ is pyromorphite,B= As 5+is mimetite andB= V 5+is vanadinite. The ionic radius for As 5+(0.355 Å) is similar to that of V 5+(0.335 Å), and this is twice as large as that for P 5+(0.170 Å). However, thecunit-cell parameter for mimetite is surprisingly different from that of vanadinite, although their unit-cell volumes,V, are almost equal to each other. No explanation was available for this peculiarc-axis value for mimetite. Structural parameters such as averagemore » $$\\langle$$B—O$$\\rangle$$ [4], $$\\langle$$Pb1—O 9$$\\rangle$$ [9] and $$\\langle$$Pb2—O 6Cl 2$$\\rangle$$ [8] distances increase linearly withV (the coordination numbers for the cations are given in square brackets). Mimetite has a short Pb2—O1 distance, so the O1 oxygen atom interacts with the 6s 2lone-pair electrons of the Pb 2+ cation that causes the Cl—Cl distance (=c/2) to increase to the largest value in the series because of repulsion, which causes thec-axis to increase anomalously. Although Pb apatite minerals occur naturally in ore deposits, they are also formed as scaly deposits in lead water pipes that give rise to lead in tap water, as was found recently in Flint, Michigan, USA. It is important to identify Pb-containing phases in water-pipe deposits.« less

The interaction between cations and anionic groups inducing SHG enhancement in a series of apatite-like crystals: A first-principles study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jing, Qun; University of Chinese Academy of Sciences, Beijing 100049; Department of Physics, School of Science, Shihezi University, Shihezi 832000

2014-11-15

It is an interesting topic to reveal the origin of the SHG intensity enhancement after substitution from alkali and alkali-earth metal atoms to cadmium in a series of apatite-like borates KSr{sub 4}(BO{sub 3}){sub 3}, Ca{sub 5}(BO{sub 3}){sub 3}F, Cd{sub 5}(BO{sub 3}){sub 3}F. Combined with the first-principles method, SHG-density method and real-space atom-cutting method, the electronic structure, the optical properties and the contribution of respective ion and ion groups have been investigated. Second harmonic generation (SHG) responses are mainly attributed to BO{sub 3} groups with π conjugated configuration and their alignment framework. The contributions of A site are more important inmore » CaBOF and CdBOF compounds than in KSrBO. It is also demonstrated that the strong covalent interactions between the boron–oxygen groups and the cadmium atoms contribute the enhancement of SHG responses after substitution from alkali and alkali-earth metal atoms. - graphical abstract: Combined with the first-principles method, SHG-density method and real-space atom-cutting method, the enhancement of SHG response are attributed to the interaction between cadmium and BO{sub 3} groups. - Highlights: • SHG response on a series of apatite-like borates was studied by a SHG-density method. • SHG responses are mainly attributed to BO{sub 3} groups and their alignment framework. • The contributions of A site are more important in CaBOF and CdBOF than in KSrBO. • Covalent interaction between BO and Cd is responsible for SHG of CdBOF.« less

Purification, Crystallization, and Preliminary X-ray Analysis of Native Canavalin

NASA Technical Reports Server (NTRS)

Pusey, Marc; Dowell, Jennifer; Ng, Joseph; Gavira, Jose A.

2003-01-01

The protein canavalin is a 7S vicilin, from the Jack Bean, Canavalis ensfomis. Canavalin is described as a seed storage protein, an energy source for a developing seed, as no other known activity or function has been found. The protein was first isolated and crystallized by Sumner and Howell (J. Biol. Chem. 113, 607-610, 1936). Canavalin spontaneously crystallizes after proteolytic cleavage at neutral pH, which removes residues 1-46, 224-245, and 325-330 and produces peptides of approximately 25, 13, and 12 kDa. Preliminary gel filtration experiments indicated the presence of nucleic acid with the uncleaved protein. We developed a dual column procedure, ion exchange followed by hydroxy apatite chromatography, that effectively removes the nucleic acid and yields an essentially pure uncut canavalin preparation with an OD 280/260 ratio of approximately 1.9-2.0. Standard crystallization screens using this material gave a number of positive results having a common requirement for alcohols and Mg(2+) ion, with crystals typically appearing within a day or less. Optimization experiments to date have shown that we can obtain crystals from pH 6.5 to pH 8.2, using MPD from 5 to 20% and 0.05 to 0.2M Mg(2+) (sulfate or acetate). The crystals are of space group P2(sub 1)2(sub 1)2(sub 1), unit cell dimensions, and a complete data set to 1.5 Angstroms, resolution has now been collected at a synchrotron source. Most importantly, the crystals are not twinned, a persistent problem with the most commonly obtained rhombohedral form of proteolytically cleaved canavalin.

Effect of Crystal Orientation on Fatigue Failure of Single Crystal Nickel Base Turbine Blade Superalloys

NASA Technical Reports Server (NTRS)

Arakere, Nagaraj K.; Swanson, Gregory R.

2000-01-01

High Cycle Fatigue (HCF) induced failures in aircraft gas-turbine engines is a pervasive problem affecting a wide range of components and materials. HCF is currently the primary cause of component failures in gas turbine aircraft engines. Turbine blades in high performance aircraft and rocket engines are increasingly being made of single crystal nickel superalloys. Single-crystal Nickel-base superalloys were developed to provide superior creep, stress rupture, melt resistance and thermomechanical fatigue capabilities over polycrystalline alloys previously used in the production of turbine blades and vanes. Currently the most widely used single crystal turbine blade superalloys are PWA 1480/1493 and PWA 1484. These alloys play an important role in commercial, military and space propulsion systems. PWA1493, identical to PWA1480, but with tighter chemical constituent control, is used in the NASA SSME (Space Shuttle Main Engine) alternate turbopump, a liquid hydrogen fueled rocket engine. Objectives for this paper are motivated by the need for developing failure criteria and fatigue life evaluation procedures for high temperature single crystal components, using available fatigue data and finite element modeling of turbine blades. Using the FE (finite element) stress analysis results and the fatigue life relations developed, the effect of variation of primary and secondary crystal orientations on life is determined, at critical blade locations. The most advantageous crystal orientation for a given blade design is determined. Results presented demonstrates that control of secondary and primary crystallographic orientation has the potential to optimize blade design by increasing its resistance to fatigue crack growth without adding additional weight or cost.

Micro-structural evolution and biomineralization behavior of carbon nanofiber/bioactive glass composites induced by precursor aging time.

PubMed

Jia, Xiaolong; Tang, Tianhong; Cheng, Dan; Zhang, Cuihua; Zhang, Ran; Cai, Qing; Yang, Xiaoping

2015-12-01

Bioactive glass (BG)-containing carbon nanofibers (CNFs) are promising orthopaedic biomaterials. Herein, CNF composites were produced from electrospinning of polyacrylonitrile (PAN)/BG sol-gel precursor solution, followed by carbonization. Choosing 58S-type BG (mol%: 58.0% SiO2-26.3% CaO-15.7% P2O5) as the model, micro-structural evolution of CNF/BG composites was systematically evaluated in relating to aging times of BG precursor solution. With aging time prolonging, BG precursors underwent morphological changes from small sol clusters with loosely and randomly branched structure to highly crosslinked Si-network structure, showing continuous increase in solution viscosity. BG precursor solution with low viscosity could mix well with PAN solution, resulting in CNF composite with homogeneously distributed BG component. Whereas, BG precursor gel with densely crosslinked Si-network structure led to uneven distribution of BG component along final CNFs due to its significant phase separation from PAN component. Meanwhile, BG nanoparticles in CNFs demonstrated micro-structural evolution that they transited from weak to strong crystal state along with longer aging time. Biomineralization in simulated body fluid and in vitro osteoblasts proliferation were then applied to determine the bioactivity of CNF/BG composites. CNF/BG composites prepared from shorter aging time could induce both faster apatite deposition and cell proliferation rate. It was suggested weakly crystallized BG nanoparticles along CNFs dissolved fast and was able to provide numerous nucleation sites for apatite deposition, which also favored the proliferation of osteoblasts cells. Aging time could thus be a useful tool to regulate the biological features of CNF/BG composites. Copyright © 2015 Elsevier B.V. All rights reserved.

Geological constraints on detecting the earliest life on Earth: a perspective from the Early Archaean (older than 3.7 Gyr) of southwest Greenland

PubMed Central

Fedo, Christopher M; Whitehouse, Martin J; Kamber, Balz S

2006-01-01

At greater than 3.7 Gyr, Earth's oldest known supracrustal rocks, comprised dominantly of mafic igneous with less common sedimentary units including banded iron formation (BIF), are exposed in southwest Greenland. Regionally, they were intruded by younger tonalites, and then both were intensely dynamothermally metamorphosed to granulite facies (the highest pressures and temperatures generally encountered in the Earth's crust during metamorphism) in the Archaean and subsequently at lower grades until about 1500 Myr ago. Claims for the first preserved life on Earth have been based on the occurrence of greater than 3.8 Gyr isotopically light C occurring as graphite inclusions within apatite crystals from a 5 m thick purported BIF on the island of Akilia. Detailed geologic mapping and observations there indicate that the banding, first claimed to be depositional, is clearly deformational in origin. Furthermore, the mineralogy of the supposed BIF, being dominated by pyroxene, amphibole and quartz, is unlike well-known BIF from the Isua Greenstone Belt (IGB), but resembles enclosing mafic and ultramafic igneous rocks modified by metasomatism and repeated metamorphic recrystallization. This scenario parsimoniously links the geology, whole-rock geochemistry, 2.7 Gyr single crystal zircon ages in the unit, an approximately 1500 Myr age for apatites that lack any graphite, non-MIF sulphur isotopes in the unit and an inconclusive Fe isotope signature. Although both putative body fossils and carbon-12 enriched isotopes in graphite described at Isua are better explained by abiotic processes, more fruitful targets for examining the earliest stages in the emergence of life remain within greater than 3.7 Gyr IGB, which preserves BIF and other rocks that unambiguously formed at Earth's surface. PMID:16754603

A Geochemical Study of Postshield Volcanism and the Generation of Trachyte on West Maui, HI

NASA Astrophysics Data System (ADS)

Trenkler, M. L.; Cousens, B.

2016-12-01

The West Maui Volcano provides a complete evolutionary history of a fully developed Hawaiian volcano described by three main phases: (1) the tholeiitic shield-building stage of the Wailuku Basalts; (2) the postshield alkalic stage Honolua Volcanics; and (3) the rejuvenated stage Lahaina Volcanics of silica-undersaturated rocks. On West Maui, the postshield Honolua Volcanics erupted highly differentiated rocks (benmoreite to trachyte), with little to no intermediate alkalic rocks, upon cessation of tholeiitic shield building. Utilizing K-Ar dated samples, we present 35 new major and trace element analyses of shield, postshield, and rejuvenated stage lavas on West Maui in an attempt to identify the mechanisms present during evolution from basalt to trachyte over a defined temporal and spatial range. Wailuku basalts are dominated by olivine fractionation, whereas decreasing Sc and CaO/Al2O3 with increasing degree of differentiation indicate Honolua benmoreites and trachytes heavily fractionated clinopyroxene. Major element trends are consistent with crystallization of titano-magnetite, potassium feldspar, and minor apatite. Trace element patterns of the Honolua Volcanics are uniform with strong enrichments in LILE and the LREEs indicating fractionation and lower degrees of partial melting compared to Wailuku basalts. The HREEs are enriched relative to shield basalts with Gd/Yb values of 2.0-2.8 as a result of high degrees of fractionation and the presence of crystalizing apatite. Major and trace element trends follow the evolution of the postshield Hawi Volcanics of Kohala, where alkalic basalts differentiate up to trachyte. Compared to shield lavas, the Honolua Volcanics represent a drastic decrease in magma supply rates, infrequent eruptions, and magma residence times long enough to produce highly differentiated magmas with no significant mafic magma input.

Quartz c-axis orientation patterns in fracture cement as a measure of fracture opening rate and a validation tool for fracture pattern models

DOE PAGES

Ukar, Estibalitz; Laubach, Stephen E.; Marrett, Randall

2016-03-09

Here, we evaluate a published model for crystal growth patterns in quartz cement in sandstone fractures by comparing crystal fracture-spanning predictions to quartz c-axis orientation distributions measured by electron backscatter diffraction (EBSD) of spanning quartz deposits. Samples from eight subvertical opening-mode fractures in four sandstone formations, the Jurassic– Cretaceous Nikanassin Formation, northwestern Alberta Foothills (Canada), Cretaceous Mesaverde Group (USA; Cozzette Sandstone Member of the Iles Formation), Piceance Basin, Colorado (USA), and upper Jurassic–lower Cretaceous Cotton Valley Group (Taylor sandstone) and overlying Travis Peak Formation, east Texas, have similar quartzose composition and grain size but contain fractures with different temperature historiesmore » and opening rates based on fluid inclusion assemblages and burial history. Spherical statistical analysis shows that, in agreement with model predictions, bridging crystals have a preferred orientation with c-axis orientations at a high angle to fracture walls. The second form of validation is for spanning potential that depends on the size of cut substrate grains. Using measured cut substrate grain sizes and c-axis orientations of spanning bridges, we calculated the required orientation for the smallest cut grain to span the maximum gap size and the required orientation of the crystal with the least spanning potential to form overgrowths that span across maximum measured gap sizes. We find that within a 10° error all spanning crystals conform to model predictions. Using crystals with the lowest spanning potential based on crystallographic orientation (c-axis parallel to fracture wall) and a temperature range for fracture opening measured from fluid inclusion assemblages, we calculate maximum fracture opening rates that allow crystals to span. These rates are comparable to those derived independently from fracture temperature histories based on burial history and multiple sequential fluid inclusion assemblages. Results support the R. Lander and S. Laubach model, which predicts that for quartz deposited synchronously with fracture opening, spanning potential, or likelihood of quartz deposits that are thick enough to span between fracture walls, depends on temperature history, fracture opening rate, size of opening increments, and size, mineralogy, and crystallographic orientation of substrates in the fracture wall (transected grains). Results suggest that EBSD maps, which can be more rapidly acquired than measurement of tens to hundreds of fluid inclusion assemblages, can provide a useful measure of relative opening rates within populations of quartz-filled fractures formed under sedimentary basin conditions. Such data are useful for evaluating fracture pattern development models.« less

Quartz c-axis orientation patterns in fracture cement as a measure of fracture opening rate and a validation tool for fracture pattern models

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ukar, Estibalitz; Laubach, Stephen E.; Marrett, Randall

Here, we evaluate a published model for crystal growth patterns in quartz cement in sandstone fractures by comparing crystal fracture-spanning predictions to quartz c-axis orientation distributions measured by electron backscatter diffraction (EBSD) of spanning quartz deposits. Samples from eight subvertical opening-mode fractures in four sandstone formations, the Jurassic– Cretaceous Nikanassin Formation, northwestern Alberta Foothills (Canada), Cretaceous Mesaverde Group (USA; Cozzette Sandstone Member of the Iles Formation), Piceance Basin, Colorado (USA), and upper Jurassic–lower Cretaceous Cotton Valley Group (Taylor sandstone) and overlying Travis Peak Formation, east Texas, have similar quartzose composition and grain size but contain fractures with different temperature historiesmore » and opening rates based on fluid inclusion assemblages and burial history. Spherical statistical analysis shows that, in agreement with model predictions, bridging crystals have a preferred orientation with c-axis orientations at a high angle to fracture walls. The second form of validation is for spanning potential that depends on the size of cut substrate grains. Using measured cut substrate grain sizes and c-axis orientations of spanning bridges, we calculated the required orientation for the smallest cut grain to span the maximum gap size and the required orientation of the crystal with the least spanning potential to form overgrowths that span across maximum measured gap sizes. We find that within a 10° error all spanning crystals conform to model predictions. Using crystals with the lowest spanning potential based on crystallographic orientation (c-axis parallel to fracture wall) and a temperature range for fracture opening measured from fluid inclusion assemblages, we calculate maximum fracture opening rates that allow crystals to span. These rates are comparable to those derived independently from fracture temperature histories based on burial history and multiple sequential fluid inclusion assemblages. Results support the R. Lander and S. Laubach model, which predicts that for quartz deposited synchronously with fracture opening, spanning potential, or likelihood of quartz deposits that are thick enough to span between fracture walls, depends on temperature history, fracture opening rate, size of opening increments, and size, mineralogy, and crystallographic orientation of substrates in the fracture wall (transected grains). Results suggest that EBSD maps, which can be more rapidly acquired than measurement of tens to hundreds of fluid inclusion assemblages, can provide a useful measure of relative opening rates within populations of quartz-filled fractures formed under sedimentary basin conditions. Such data are useful for evaluating fracture pattern development models.« less

ID ICPMS Lu-Hf Geochronology of Apatite from Iron-Oxide Apatite (IOA) Deposits, Northern Chilean Iron Belt.

NASA Astrophysics Data System (ADS)

Zhang, C.; Vervoort, J. D.; Barra, F.; Palma, G.

2017-12-01

Determining the age of mineralization of ore deposits is important for understanding the mechanisms and timing of ore formation. In many cases, however, conventional dateable mineral phases (e.g., zircon, monazite) are lacking in the ore mineral assemblages. For example, Iron Oxide Apatite (IOA) and Iron Oxide Gold Copper Gold (IOCG) deposits have the remaining fundamental question as to whether they have formed by hydrothermal or magmatic processes, or some combination of the two. In these deposits, the mineralization of iron oxide is often accompanied by the growth of apatites, which typically have REE concentrations of tens to several thousand ppm and which makes them potentially amenable to dating by the Lu-Hf isochron method. These apatites, however, also have very low concentrations of Hf, which makes determination of precise Hf isotope compositions challenging. In this study, we attempted to date these deposits using the apatite Lu-Hf isochron method, using procedures modified from that of Münker et al., 2001 and Barfod et al., 2003 and report the first Lu-Hf ages for apatites from Carmen, Fresia, and Mariela IOA deposits in northern Chilean Iron Belt. The concentration of Hf in analyzed apatite is 0.001 ppm. To ensure at least 0.5ng of Hf is collected for MS analysis, 0.5g apatite was dissolved for each sample. A single stage of Ln-spec resin chromatographic columns was used to separate Hf from REEs as multi stages of separation columns would decrease the Hf yield considerably. Using these procedures, we determined a Lu-Hf apatite age for the Carmen deposit of 130.0±1.7 Ma, which is in accordance with a previously published U-Pb apatite age of 131.0±1.0 Ma (Gelcich et al., 2005). The apatites from Fresia and Mariela yield Lu-Hf ages of 132.8±5.3 Ma and 117.3±0.4 Ma respectively. The lower points on the isochrons are either a low Lu/Hf phase (actinolite, magnetite) or bulk earth ratios. These are some of the first Lu-Hf ages of directly dating apatite in the ore mineralization, and show the potential in apatite Lu-Hf geochronology. However, further work needs to be done on the chemical procedure to improve the Hf yield and lower the interferences in order to make this a more routine technique of dating ore deposits.

Flow-induced birefringence measurement system using dual-crystal transverse electro-optic modulator for microgravity fluid physics applications

NASA Technical Reports Server (NTRS)

Mackey, Jeffrey R.

1999-01-01

We have developed a new instrument that can measure fast transient birefringence and polymer chain orientation angle in complex fluids. The instrument uses a dual-crystal transverse electro-optic modulator with the second crystal's modulation voltage applied 180 deg out of phase from that of the first crystal. In this manner, the second crystal compensates for the intrinsic static birefringence of the first crystal, and it doubles the modulation depth. By incorporating a transverse electro-optic modulator with two lithium-niobate (LiNbO3) crystals oriented orthogonal to each other with a custom-designed optical system, we have produced a very small robust instrument capable of fast transient retardation measurements. By measuring the sample thickness or optical path length through the sample, we can calculate the transient birefringence. This system can also measure dichroism. We have compared the calibration results and retardation and orientation angle measurements of this instrument with those of a photoelastic modulator (PEM) based system using a quarter wave plate and a high-precision 1/16-wave plate to simulate a birefringent sample. Transient birefringence measurements on the order of 10(exp -9) can be measured using either modulator.

A double Fe-Ti oxide and Fe-sulphide liquid immiscibility in the Itsindro Gabbro Complex, Madagascar

NASA Astrophysics Data System (ADS)

Augé, Thierry; Bailly, Laurent; Roig, Jean-Yves

2017-11-01

The petrology and mineralogy of the Itsindro complex in south-central Madagascar has been investigated through samples obtained from the 320.7 m-deep Lanjanina borehole. The section consists of a 254 m-thick pyroxenite unit with interbedded gabbro layers that overlies a gabbro unit and is itself overlain by a 19 m-thick granite unit. Most of the structures are sub-horizontal. A weak magmatic layering is locally observed but at the scale of the core, the intrusion does not appear to be a layered complex. Pyroxenite and gabbro show a systematic disseminated mineralization consisting of Fe-Ti-P oxides and Fe-(Cu-Ni) sulphides that takes the form of ilmenite-titanomagnetite ± apatite and pyrrhotite ± chalcopyrite ± pentlandite. In the upper zone, from 90 to 72 m, sub-massive centimetre-to decimetre-sized layers of oxides and sulphides comprise a total of 16 m of sub-massive sulphide (the main mineralized zone). In this mineralized zone the oxide/sulphide ratio is close to 1/1. The sulphide is strongly dominated by pyrrhotite, which may locally contain inclusions of molybdenite crystals with the Re sulphide rheniite (ReS2). Oxides are generally euhedral, included in or attached to the Fe-sulphide, and also locally form sub-massive centimetre-sized bands. Apatite as a cumulus phase is ubiquitous. Locally it may account for 30% of the ore-rich samples and some samples consist of apatite-Fe-Ti oxides-Fe-Cu-Ni sulphides with virtually no silicate. Apatite is the main REE carrier but the total REE content remains low (<90 ppm). Mineral compositions and whole rock geochemistry indicate that the rocks are highly differentiated, and in spite of a relatively limited thickness, the differentiation process is observed. Two zones can be distinguished: from the bottom to 162.8 m we see a decrease in the Mg number of olivine and pyroxene, and a drop in TiO2 and Al2O3 for the latter. A reverse trend is then observed within the pyroxenite unit from the 162.8 m level upwards. The main mineralized zone is located in the upper part of this unit, about 70 m above this discontinuity. The highly differentiated Fe-Ti-P facies of the Lanjanina series in the Itsindro Gabbro Complex have been interpreted as corresponding to the Fe-Ti-P rich, Si-poor member remaining after an immiscible segregation of an evolved mafic magma. The granite dykes and the overlying granite unit represent the second, Si-rich member of the immiscibility process. The presence of large amounts of sulphide is attributed to sulphur contamination of the Fe-Ti-rich liquid. Fe-Ti oxides will tend to crystallize on the sulphide droplets and the accumulation of dense Fe-sulphides (liquid) and associated Fe-Ti oxides (solid) will result in this complex and unusual association taking the form of a net texture.

Directed self-assembly of liquid crystalline blue-phases into ideal single-crystals

NASA Astrophysics Data System (ADS)

Martínez-González, Jose A.; Li, Xiao; Sadati, Monirosadat; Zhou, Ye; Zhang, Rui; Nealey, Paul F.; de Pablo, Juan J.

2017-06-01

Chiral nematic liquid crystals are known to form blue phases--liquid states of matter that exhibit ordered cubic arrangements of topological defects. Blue-phase specimens, however, are generally polycrystalline, consisting of randomly oriented domains that limit their performance in applications. A strategy that relies on nano-patterned substrates is presented here for preparation of stable, macroscopic single-crystal blue-phase materials. Different template designs are conceived to exert control over different planes of the blue-phase lattice orientation with respect to the underlying substrate. Experiments are then used to demonstrate that it is indeed possible to create stable single-crystal blue-phase domains with the desired orientation over large regions. These results provide a potential avenue to fully exploit the electro-optical properties of blue phases, which have been hindered by the existence of grain boundaries.

Fluorapatite crystal growth from modified seawater solutions

NASA Astrophysics Data System (ADS)

Van Cappellen, Philippe; Berner, Robert A.

Seeded precipitation experiments were conducted in a pH/fluoride-stat system to study the crystal growth of fluorapatite ( FAP ) in carbonate-free NaCl-CaCl 2-NaF-Na 2HPO 4 solutions, at seawater calcium concentration, chlorinity, and pH. With increasing supersaturation, the dependence of the growth rate on the relative supersaturation changes from parabolic to exponential. This is interpreted as reflecting a transition in the crystal growth mechanism from growth at dislocation-induced surface steps to surface nucleation-controlled growth. The analysis of the kinetic data leads to a mineral-aqueous solution interfacial tension for FAP of 289 mJ/m 2. The Arrhenius activation energy of the growth reaction in the temperature range 12 to 35°C is 47 kJ/mol. The inhibition of FAP growth by Mg 2+ ions was investigated over a range of total dissolved Mg of 0 to 60 mM. At dissolved magnesium concentrations typical of marine pore waters (40-60 mM), the rate of FAP growth is 15 to 20 times slower than in the absence of Mg 2+, for the same degree of supersaturation, at 25 °C and pH = 8. The inhibitory effect can be explained by the blocking of growth sites at the surface of FAP crystals by adsorbed Mg 2+ ions. A simple Langmuir adsorption model for the retardation effect of Mg 2+ is supported by the results. The effect of pH on FAP growth was tested for pH values from 7 to 8.5. In this range, growth of FAP is catalyzed by hydrogen ions. The apparent growth rate constant is proportional to ( aH+) m where m, the rate order with respect to H +, is a non-integral number which depends on pH. At identical degrees of supersaturation, the growth rate of FAP at pH = 7 is nearly twice that at pH = 8. When corrected for bottom water temperatures, pore water pH, and the retardation of Mg 2+, the experimental growth rates predict that during burial in modern phosphatic sediments, apatite particles grow to sizes on the order of 0.1-10 μrn. The relatively slow growth kinetics of FAP are consistent with the observed small particle sizes of marine sedimentary apatite.

Peculiar orientational disorder in 4-bromo-4'-nitrobiphenyl (BNBP) and 4-bromo-4'-cyanobiphenyl (BCNBP) leading to bipolar crystals.

PubMed

Burgener, Matthias; Aboulfadl, Hanane; Labat, Gaël Charles; Bonin, Michel; Sommer, Martin; Sankolli, Ravish; Wübbenhorst, Michael; Hulliger, Jürg

2016-05-01

180° orientational disorder of molecular building blocks can lead to a peculiar spatial distribution of polar properties in molecular crystals. Here we present two examples [4-bromo-4'-nitrobiphenyl (BNBP) and 4-bromo-4'-cyanobiphenyl (BCNBP)] which develop into a bipolar final growth state. This means orientational disorder taking place at the crystal/nutrient interface produces domains of opposite average polarity for as-grown crystals. The spatial inhomogeneous distribution of polarity was investigated by scanning pyroelectric microscopy (SPEM), phase-sensitive second harmonic microscopy (PS-SHM) and selected volume X-ray diffraction (SVXD). As a result, the acceptor groups (NO2 or CN) are predominantly present at crystal surfaces. However, the stochastic process of polarity formation can be influenced by adding a symmetrical biphenyl to a growing system. For this case, Monte Carlo simulations predict an inverted net polarity compared with the growth of pure BNBP and BCNBP. SPEM results clearly demonstrate that 4,4'-dibromobiphenyl (DBBP) can invert the polarity for both crystals. Phenomena reported in this paper belong to the most striking processes seen for molecular crystals, demonstrated by a stochastic process giving rise to symmetry breaking. We encounter here further examples supporting the general thesis that monodomain polar molecular crystals for fundamental reasons cannot exist.

UV photofunctionalization promotes nano-biomimetic apatite deposition on titanium

PubMed Central

Saita, Makiko; Ikeda, Takayuki; Yamada, Masahiro; Kimoto, Katsuhiko; Lee, Masaichi Chang-Il; Ogawa, Takahiro

2016-01-01

Background Although biomimetic apatite coating is a promising way to provide titanium with osteoconductivity, the efficiency and quality of deposition is often poor. Most titanium implants have microscale surface morphology, and an addition of nanoscale features while preserving the micromorphology may provide further biological benefit. Here, we examined the effect of ultraviolet (UV) light treatment of titanium, or photofunctionalization, on the efficacy of biomimetic apatite deposition on titanium and its biological capability. Methods and results Micro-roughed titanium disks were prepared by acid-etching with sulfuric acid. Micro-roughened disks with or without photofunctionalization (20-minute exposure to UV light) were immersed in simulated body fluid (SBF) for 1 or 5 days. Photofunctionalized titanium disks were superhydrophilic and did not form surface air bubbles when immersed in SBF, whereas non-photofunctionalized disks were hydrophobic and largely covered with air bubbles during immersion. An apatite-related signal was observed by X-ray diffraction on photofunctionalized titanium after 1 day of SBF immersion, which was equivalent to the one observed after 5 days of immersion of control titanium. Scanning electron microscopy revealed nodular apatite deposition in the valleys and at the inclines of micro-roughened structures without affecting the existing micro-configuration. Micro-roughened titanium and apatite-deposited titanium surfaces had similar roughness values. The attachment, spreading, settling, proliferation, and alkaline phosphate activity of bone marrow-derived osteoblasts were promoted on apatite-coated titanium with photofunctionalization. Conclusion UV-photofunctionalization of titanium enabled faster deposition of nanoscale biomimetic apatite, resulting in the improved biological capability compared to the similarly prepared apatite-deposited titanium without photofunctionalization. Photofunctionalization-assisted biomimetic apatite deposition may be a novel method to effectively enhance micro-roughened titanium surfaces without altering their microscale morphology. PMID:26834469

Postmagmatic magnetite-apatite assemblage in mafic intrusions: a case study of dolerite at Olympic Dam, South Australia

NASA Astrophysics Data System (ADS)

Apukhtina, Olga B.; Kamenetsky, Vadim S.; Ehrig, Kathy; Kamenetsky, Maya B.; McPhie, Jocelyn; Maas, Roland; Meffre, Sebastien; Goemann, Karsten; Rodemann, Thomas; Cook, Nigel J.; Ciobanu, Cristiana L.

2016-01-01

An assemblage of magnetite and apatite is common worldwide in different ore deposit types, including disparate members of the iron-oxide copper-gold (IOCG) clan. The Kiruna-type iron oxide-apatite deposits, a subtype of the IOCG family, are recognized as economic targets as well. A wide range of competing genetic models exists for magnetite-apatite deposits, including magmatic, magmatic-hydrothermal, hydrothermal(-metasomatic), and sedimentary(-exhalative). The sources and mechanisms of transport and deposition of Fe and P remain highly debatable. This study reports petrographic and geochemical features of the magnetite-apatite-rich vein assemblages in the dolerite dykes of the Gairdner Dyke Swarm (~0.82 Ga) that intruded the Roxby Downs Granite (~0.59 Ga), the host of the supergiant Olympic Dam IOCG deposit. These symmetrical, only few mm narrow veins are prevalent in such dykes and comprise besides usually colloform magnetite and prismatic apatite also further minerals (e.g., calcite, quartz). The genetic relationships between the veins and host dolerite are implied based on alteration in the immediate vicinity (~4 mm) of the veins. In particular, Ti-magnetite-ilmenite is partially to completely transformed to titanite and magmatic apatite disappears. We conclude that the mafic dykes were a local source of Fe and P re-concentrated in the magnetite-apatite veins. Uranium-Pb ages for vein apatite and titanite associated with the vein in this case study suggest that alteration of the dolerite and healing of the fractures occurred shortly after dyke emplacement. We propose that in this particular case the origin of the magnetite-apatite assemblage is clearly related to hydrothermal alteration of the host mafic magmatic rocks.

A Sequential Leach Method and Pb Isotope Approach to Studying Apatite Weathering in Granitoid Soils at Hubbard Brook Experimental Forest, NH, USA

NASA Astrophysics Data System (ADS)

Nezat, C. A.; Blum, J. D.

2005-12-01

Easily dissolved minerals such as calcite and apatite can be important in controlling stream and ground water chemistry even though these minerals are only present in trace amounts in granitoid rocks. Because of its solubility, apatite, a calcium phosphate mineral, may be a significant source of essential nutrients (especially phosphorous) for vegetation, and has been shown to strongly influence stream and soil water composition (e.g, calcium, strontium and rare earth elements). There are additional sources of Ca (e.g., feldspars, hornblende) and P (e.g., organic matter or bound to Fe and Al oxides) in granitoid soils. In order to distinguish the chemical constituents of apatite from other pools in the bulk soil, we selectively dissolved apatite with a dilute acid leach, and measured Pb isotopic ratios of apatite, feldspar, and leachates. We tested the leaching procedure on mineral separates and verified that a dilute nitric solution primarily dissolves apatite. Silicates were dissolved in subsequent steps by successively stronger acids. We then applied this method to bulk soils collected from several soil pits across a small watershed at the Hubbard Brook Experimental Forest (HBEF), New Hampshire, USA, to determine the spatial distribution of Ca and P pools, and determine the depth of apatite depletion in the soil. We also measured Pb isotope ratios in the soil leachates to distinguish among the various sources of Pb (e.g., apatite, feldspars and anthropogenic sources). We found that Pb in the dilute nitric leach of the HBEF organic soils is dominated by anthropogenic sources and that Pb from apatite becomes increasingly important with depth.

Immobilization of uranium in contaminated soil by natural apatite addition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mrdakovic Popic, Jelena; Stojanovic, Mirjana; Milosevic, Sinisa

2007-07-01

Available in abstract form only. Full text of publication follows: The goal of this study was to evaluate the effectiveness of Serbian natural mineral apatite as soil additive for reducing the migration of uranium from contaminated sediments. In laboratory study we investigated the sorption properties of domestic apatite upon different experimental conditions, such as pH, adsorbent mass, reaction period, concentration of P{sub 2}O{sub 5} in apatite, solid/liquid ratio. In second part of study, we did the quantification of uranium in soil samples, taken from uranium mine site 'Kalna', by sequential extraction method. The same procedure was, also, used for uraniummore » determination in contaminated soil samples after apatite addition, in order to determine the changes in U distribution in soil fraction. The obtained results showed the significant level of immobilization (96.7%) upon certain conditions. Increase of %P{sub 2}O{sub 5} in apatite and process of mechano-chemical activation led to increase of immobilization capacity from 17.50% till 91.64%. The best results for uranium binding were obtained at pH 5.5 and reaction period 60 days (98.04%) The sequential extraction showed the presence of uranium (48.2%) in potentially available soil fractions, but with the apatite addition uranium content in these fractions decreased (30.64%), what is considering environmental aspect significant fact. In situ immobilization of radionuclide using inexpensive sequestering agents, such as apatite, is very adequate for big contaminated areas of soil with low level of contamination. This investigation study on natural apatite from deposit 'Lisina' Serbia was the first one of this type in our country. Key words: apatite, uranium, immobilization, soil, contamination. (authors)« less

Crystallization behavior of amorphous indium-gallium-zinc-oxide films and its effects on thin-film transistor performance

NASA Astrophysics Data System (ADS)

Suko, Ayaka; Jia, JunJun; Nakamura, Shin-ichi; Kawashima, Emi; Utsuno, Futoshi; Yano, Koki; Shigesato, Yuzo

2016-03-01

Amorphous indium-gallium-zinc oxide (a-IGZO) films were deposited by DC magnetron sputtering and post-annealed in air at 300-1000 °C for 1 h to investigate the crystallization behavior in detail. X-ray diffraction, electron beam diffraction, and high-resolution electron microscopy revealed that the IGZO films showed an amorphous structure after post-annealing at 300 °C. At 600 °C, the films started to crystallize from the surface with c-axis preferred orientation. At 700-1000 °C, the films totally crystallized into polycrystalline structures, wherein the grains showed c-axis preferred orientation close to the surface and random orientation inside the films. The current-gate voltage (Id-Vg) characteristics of the IGZO thin-film transistor (TFT) showed that the threshold voltage (Vth) and subthreshold swing decreased markedly after the post-annealing at 300 °C. The TFT using the totally crystallized films also showed the decrease in Vth, whereas the field-effect mobility decreased considerably.

The effect of aluminium on mechanical properties and deformation mechanisms of hadfield steel single crystals

NASA Astrophysics Data System (ADS)

Zakharova, E. G.; Kireeva, I. V.; Chumlyakov, Y. I.; Shul'Mina, A. A.; Sehitoglu, H.; Karaman, I.

2004-06-01

On single crystals of Hadfield steel (Fe-13Mn-1.3C, Fe-13Mn-2.7Al-1.3C, wt.%) the systematical investigations of deformation mechanisms - slip and twinning, stages of plastic flow, strain hardening coefficient depending on orientation of tensile axis have been carried out by methods of optical and electron microscopy, x-ray analysis. Is has been shown that the combination of low stacking fault energy (γ{SF}=0.03J/m^2) with high concentration of carbon atoms in aluminium-free steel results in development of the mechanical twinning at room temperature in all crystal orientations. The new type of twinning with formation of extrinsic stacking fault has been found out in [001] single crystals. Experimentally it has been established that alloying with aluminium leads to increase of stacking fault energy of Hadfield steel and suppresses twinning in all orientations of crystals at preservation of high values of strain-hardening coefficients θ.

Depth profiling of high energy nitrogen ions implanted in the <1 0 0>, <1 1 0> and randomly oriented silicon crystals

NASA Astrophysics Data System (ADS)

Erić, M.; Petrović, S.; Kokkoris, M.; Lagoyannis, A.; Paneta, V.; Harissopulos, S.; Telečki, I.

2012-03-01

This work reports on the experimentally obtained depth profiles of 4 MeV 14N2+ ions implanted in the <1 0 0>, <1 1 0> and randomly oriented silicon crystals. The ion fluence was 1017 particles/cm2. The nitrogen depth profiling has been performed using the Nuclear Reaction Analysis (NRA) method, via the study of 14N(d,α0)12C and 14N(d,α1)12C nuclear reactions, and with the implementation of SRIM 2010 and SIMNRA computer simulation codes. For the randomly oriented silicon crystal, change of the density of silicon matrix and the nitrogen "bubble" formation have been proposed as the explanation for the difference between the experimental and simulated nitrogen depth profiles. During the implantation, the RBS/C spectra were measured on the nitrogen implanted and on the virgin crystal spots. These spectra provide information on the amorphization of the silicon crystals induced by the ion implantation.

Nanoindentation of HMX and Idoxuridine to Determine Mechanical Similarity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burch, Alexandra; Yeager, John; Bahr, David

Assessing the mechanical behavior (elastic properties, plastic properties, and fracture phenomena) of molecular crystals is often complicated by the difficulty in preparing samples. Pharmaceuticals and energetic materials in particular are often used in composite structures or tablets, where the individual grains can strongly impact the solid behavior. Nanoindentation is a convenient method to experimentally assess these properties, and it is used here to demonstrate the similarity in the mechanical properties of two distinct systems: individual crystals of the explosive cyclotetramethylene tetranitramine (HMX) and the pharmaceutical idoxuridine were tested in their as-precipitated state, and the effective average modulus and hardness (whichmore » can be orientation dependent) were determined. Both exhibit a hardness of 1.0 GPa, with an effective reduced modulus of 25 and 23 GPa for the HMX and idoxuridine, respectively. They also exhibit similar yield point behavior. This indicates idoxuridine may be a suitable mechanical surrogate (or “mock”) for HMX. While the methodology to assess elastic and plastic properties was relatively insensitive to specific crystal orientation (i.e., a uniform distribution in properties was observed for all random crystals tested), the indentation-induced fracture properties appear to be much more sensitive to tip-crystal orientation, and an unloading slope analysis is used to demonstrate the need for further refinement in relating toughness to orientation in these materials with relatively complex slip systems and crystal structures. View Full-Text« less

Nanoindentation of HMX and Idoxuridine to Determine Mechanical Similarity

DOE PAGES

Burch, Alexandra; Yeager, John; Bahr, David

2017-11-01

Assessing the mechanical behavior (elastic properties, plastic properties, and fracture phenomena) of molecular crystals is often complicated by the difficulty in preparing samples. Pharmaceuticals and energetic materials in particular are often used in composite structures or tablets, where the individual grains can strongly impact the solid behavior. Nanoindentation is a convenient method to experimentally assess these properties, and it is used here to demonstrate the similarity in the mechanical properties of two distinct systems: individual crystals of the explosive cyclotetramethylene tetranitramine (HMX) and the pharmaceutical idoxuridine were tested in their as-precipitated state, and the effective average modulus and hardness (whichmore » can be orientation dependent) were determined. Both exhibit a hardness of 1.0 GPa, with an effective reduced modulus of 25 and 23 GPa for the HMX and idoxuridine, respectively. They also exhibit similar yield point behavior. This indicates idoxuridine may be a suitable mechanical surrogate (or “mock”) for HMX. While the methodology to assess elastic and plastic properties was relatively insensitive to specific crystal orientation (i.e., a uniform distribution in properties was observed for all random crystals tested), the indentation-induced fracture properties appear to be much more sensitive to tip-crystal orientation, and an unloading slope analysis is used to demonstrate the need for further refinement in relating toughness to orientation in these materials with relatively complex slip systems and crystal structures. View Full-Text« less

Nanoconfinement: an effective way to enhance PVDF piezoelectric properties.

PubMed

Cauda, Valentina; Stassi, Stefano; Bejtka, Katarzyna; Canavese, Giancarlo

2013-07-10

The dimensional confinement and oriented crystallization are both key factors in determining the piezoelectric properties of a polymeric nanostructured material. Here we prepare arrays of one-dimensional polymeric nanowires showing piezoelectric features by template-wetting two distinct polymers into anodic porous alumina (APA) membranes. In particular, poly(vinylidene fluoride), PVDF, and its copolymer poly(vinylidene fluoride-trifluoroethylene), PVTF, are obtained in commercially available APA, showing a final diameter of about 200 nm and several micrometers in length, reflecting the templating matrix features. We show that the crystallization of both polymers into a ferroelectric phase is directed by the nanotemplate confinement. Interestingly, the PVDF nanowires mainly crystallize into the β-phase in the nanoporous matrix, whereas the reference thin film of PVDF crystallizes in the α nonpolar phase. In the case of the PVTF nanowires, needle-like crystals oriented perpendicularly to the APA channel walls are observed, giving insight on the molecular orientation of the polymer within the nanowire structure. A remarkable piezoelectric behavior of both 1-D polymeric nanowires is observed, upon recording ferroelectric polarization, hysteresis, and displacement loops. In particular, an outstanding piezoelectric effect is observed for the PVDF nanowires with respect to the polymeric thin film, considering that no poling was carried out. Current versus voltage (I-V) characteristics showed a consistent switching behavior of the ferroelectric polar domains, thus revealing the importance of the confined and oriented crystallization of the polymer in monodimensional nanoarchitectures.

Characterization of monoclinic crystals in tablets by pattern-fitting procedure using X-ray powder diffraction data.

PubMed

Yamamura, Shigeo; Momose, Yasunori

2003-06-18

The purpose of this study is to characterize the monoclinic crystals in tablets by using X-ray powder diffraction data and to evaluate the deformation feature of crystals during compression. The monoclinic crystals of acetaminophen and benzoic acid were used as the samples. The observed X-ray diffraction intensities were fitted to the analytic expression, and the fitting parameters, such as the lattice parameters, the peak-width parameters, the preferred orientation parameter and peak asymmetric parameter were optimized by a non-linear least-squares procedure. The Gauss and March distribution functions were used to correct the preferred orientation of crystallites in the tablet. The March function performed better in correcting the modification of diffraction intensity by preferred orientation of crystallites, suggesting that the crystallites in the tablets had fiber texture with axial orientation. Although a broadening of diffraction peaks was observed in acetaminophen tablets with an increase of compression pressure, little broadening was observed in the benzoic tablets. These results suggest that "acetaminophen is a material consolidating by fragmentation of crystalline particles and benzoic acid is a material consolidating by plastic deformation then occurred rearrangement of molecules during compression". A pattern-fitting procedure is the superior method for characterizing the crystalline drugs of monoclinic crystals in the tablets, as well as orthorhombic isoniazid and mannitol crystals reported in the previous paper.

Energy-selective Neutron Imaging for Three-dimensional Non-destructive Probing of Crystalline Structures

NASA Astrophysics Data System (ADS)

Peetermans, S.; Bopp, M.; Vontobel, P.; Lehmann, E. H.

Common neutron imaging uses the full polychromatic neutron beam spectrum to reveal the material distribution in a non-destructive way. Performing it with a reduced energy band, i.e. energy-selective neutron imaging, allows access to local variation in sample crystallographic properties. Two sample categories can be discerned with different energy responses. Polycrystalline materials have an energy-dependent cross-section featuring Bragg edges. Energy-selective neutron imaging can be used to distinguish be- tween crystallographic phases, increase material sensitivity or penetration, improve quantification etc. An example of the latter is shown by the examination of copper discs prior to machining them into linear accelerator cavity structures. The cross-section of single crystals features distinct Bragg peaks. Based on their pattern, one can determine the orientation of the crystal, as in a Laue pattern, but with the tremendous advantage that the operation can be performed for each pixel, yielding crystal orientation maps at high spatial resolution. A wholly different method to investigate such samples is also introduced: neutron diffraction imaging. It is based on projections formed by neutrons diffracted from the crystal lattice out of the direct beam. The position of these projections on the detector gives information on the crystal orientation. The projection itself can be used to reconstruct the crystal shape. A three-dimensional mapping of local Bragg reflectivity or a grain orientation mapping can thus be obtained.

Monitoring structural transformations in crystals. 7. 1-Chloroanthracene and its photodimer.

PubMed

Turowska-Tyrk, Ilona; Grześniak, Karolina

2004-02-01

Crystals of the 1-chloroanthracene photodimer, viz. trans-bi(1-chloro-9,10-dihydro-9,10-anthracenediyl), C(28)H(18)Cl(2), were obtained from the solid-state [4+4]-photodimerization of the monomer, C(14)H(9)Cl, followed by recrystallization. The symmetry of the product molecules is defined by the orientation of the reactant molecules in the crystal. The mutual orientation parameters calculated for adjacent monomers explain the reactivity of the compound. The molecules in the crystal of the monomer and the recrystallized photodimer pack differently and the photodimer has crystallographically imposed inversion symmetry.

Self-powdering and nonlinear optical domain structures in ferroelastic β‧-Gd2(MoO4)3 crystals formed in glass

NASA Astrophysics Data System (ADS)

Tsukada, Y.; Honma, T.; Komatsu, T.

2009-08-01

Ferroelastic β'-Gd 2(MoO 4) 3, (GMO), crystals are formed through the crystallization of 21.25Gd 2O 3-63.75MoO 3-15B 2O 3 glass (mol%), and two scientific curious phenomena are observed. (1) GMO crystals formed in the crystallization break into small pieces with a triangular prism or pyramid shape having a length of 50-500 μm spontaneously during the crystallizations in the inside of an electric furnace, not during the cooling in air after the crystallization. This phenomenon is called "self-powdering phenomenon during crystallization" in this paper. (2) Each self-powdered GMO crystal grain shows a periodic domain structure with different refractive indices, and a spatially periodic second harmonic generation (SHG) depending on the domain structure is observed. It is proposed from polarized micro-Raman scattering spectra and the azimuthal dependence of second harmonic intensities that GMO crystals are oriented in each crystal grain and the orientation of (MoO 4) 2- tetrahedra in GMO crystals changes periodically due to spontaneous strains in ferroelastic GMO crystals.

Retraction of cold drawn polyethylene: the influence of lamellar thickeness and density

NASA Technical Reports Server (NTRS)

Falender, J. R.; Hansen, D.

1971-01-01

The role of crystal morphology in the retraction of oriented, linear polyethylene was studied utilizing samples crystallized under conditions controlled to vary, separately, lamellar crystal thickness and density. Samples were oriented in a simple shear deformation to a strain of 4.0 prior to measuring retraction tendency in creep and relaxation type tests. Characterizations of specimens were made using wide and small angle X-ray techniques. The specific morphological variations were chosen to test the hypothesis that a long range elastic restoring force can originate in conjunction with deformation of lamellar crystals and the consequent increase in lamellar crystal surface area and surface free energy. The results support this hypothesis.

Retraction of cold-drawn polyethylene - Influence of lamellar thickness and density.

NASA Technical Reports Server (NTRS)

Falender, J. R.; Hansen, D.

1972-01-01

The role of crystal morphology in the retraction of oriented linear polyethylene was studied utilizing samples crystallized under conditions controlled to vary, separately, lamellar crystal thickness and density. Samples were oriented in a simple shear deformation to a strain of 4.0 prior to measuring retraction tendency in creep- and relaxation-type tests. Characterizations of specimens were made using wide- and small-angle x-ray techniques. The specific morphological variations were chosen to test the hypothesis that a long-range elastic restoring force can originate in conjunction with deformation of lamellar crystals and the consequent increase in lamellar crystal surface area and surface free energy. The results support this hypothesis.

Influence of polarized PZT on the crystal growth of calcium phosphate

NASA Astrophysics Data System (ADS)

Sun, Xiaodan; Ma, Chunlai; Wang, Yude; Li, Hengde

2002-01-01

The effects of polarization on the crystallization of calcium phosphate are studied in this work. Crystals of calcium phosphate from saturated solution of hydroxyapatite (HA, Ca 10(PO 4) 6(OH) 2) were deposited on the surfaces of ferroelectric ceramics lead zirconate titanium (Pb(Ti,Zr)O 3, PZT). The results of the experiment demonstrated the acceleration effects of polarized PZT on the crystal growth of calcium phosphate. Furthermore, it is indicated that polarization also influenced the orientation of the deposited crystals due to the growth of a layer of (0 0 2) oriented octacalcium phosphate (OCP, Ca 8H 2(PO 4) 6·5H 2O) on the negatively charged surfaces of PZT.

Field-controlled structures in ferromagnetic cholesteric liquid crystals.

PubMed

Medle Rupnik, Peter; Lisjak, Darja; Čopič, Martin; Čopar, Simon; Mertelj, Alenka

2017-10-01

One of the advantages of anisotropic soft materials is that their structures and, consequently, their properties can be controlled by moderate external fields. Whereas the control of materials with uniform orientational order is straightforward, manipulation of systems with complex orientational order is challenging. We show that a variety of structures of an interesting liquid material, which combine chiral orientational order with ferromagnetic one, can be controlled by a combination of small magnetic and electric fields. In the suspensions of magnetic nanoplatelets in chiral nematic liquid crystals, the platelet's magnetic moments orient along the orientation of the liquid crystal and, consequently, the material exhibits linear response to small magnetic fields. In the absence of external fields, orientations of the liquid crystal and magnetization have wound structure, which can be either homogeneously helical, disordered, or ordered in complex patterns, depending on the boundary condition at the surfaces and the history of the sample. We demonstrate that by using different combinations of small magnetic and electric fields, it is possible to control reversibly the formation of the structures in a layer of the material. In such a way, different periodic structures can be explored and some of them may be suitable for photonic applications. The material is also a convenient model system to study chiral magnetic structures, because it is a unique liquid analog of a solid helimagnet.

Switching plastic crystals of colloidal rods with electric fields

PubMed Central

Liu, Bing; Besseling, Thijs H.; Hermes, Michiel; Demirörs, Ahmet F.; Imhof, Arnout; van Blaaderen, Alfons

2014-01-01

When a crystal melts into a liquid both long-ranged positional and orientational order are lost, and long-time translational and rotational self-diffusion appear. Sometimes, these properties do not change at once, but in stages, allowing states of matter such as liquid crystals or plastic crystals with unique combinations of properties. Plastic crystals/glasses are characterized by long-ranged positional order/frozen-in-disorder but short-ranged orientational order, which is dynamic. Here we show by quantitative three-dimensional studies that charged rod-like colloidal particles form three-dimensional plastic crystals and glasses if their repulsions extend significantly beyond their length. These plastic phases can be reversibly switched to full crystals by an electric field. These new phases provide insight into the role of rotations in phase behaviour and could be useful for photonic applications. PMID:24446033

Switching plastic crystals of colloidal rods with electric fields

NASA Astrophysics Data System (ADS)

Liu, Bing; Besseling, Thijs H.; Hermes, Michiel; Demirörs, Ahmet F.; Imhof, Arnout; van Blaaderen, Alfons

2014-01-01

When a crystal melts into a liquid both long-ranged positional and orientational order are lost, and long-time translational and rotational self-diffusion appear. Sometimes, these properties do not change at once, but in stages, allowing states of matter such as liquid crystals or plastic crystals with unique combinations of properties. Plastic crystals/glasses are characterized by long-ranged positional order/frozen-in-disorder but short-ranged orientational order, which is dynamic. Here we show by quantitative three-dimensional studies that charged rod-like colloidal particles form three-dimensional plastic crystals and glasses if their repulsions extend significantly beyond their length. These plastic phases can be reversibly switched to full crystals by an electric field. These new phases provide insight into the role of rotations in phase behaviour and could be useful for photonic applications.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Killian, Christopher; Metzler, Rebecca; Gong, Y. U. T.

Sea urchin teeth are remarkable and complex calcite structures, continuously growing at the forming end and self-sharpening at the mature grinding tip. The calcite (CaCO{sub 3}) crystals of tooth components, plates, fibers, and a high-Mg polycrystalline matrix, have highly co-oriented crystallographic axes. This ability to co-orient calcite in a mineralized structure is shared by all echinoderms. However, the physico-chemical mechanism by which calcite crystals become co-oriented in echinoderms remains enigmatic. Here, we show differences in calcite c-axis orientations in the tooth of the purple sea urchin (Strongylocentrotus purpuratus), using high-resolution X-ray photoelectron emission spectromicroscopy (X-PEEM) and microbeam X-ray diffraction ({mu}XRD).more » All plates share one crystal orientation, propagated through pillar bridges, while fibers and polycrystalline matrix share another orientation. Furthermore, in the forming end of the tooth, we observe that CaCO{sub 3} is present as amorphous calcium carbonate (ACC). We demonstrate that co-orientation of the nanoparticles in the polycrystalline matrix occurs via solid-state secondary nucleation, propagating out from the previously formed fibers and plates, into the amorphous precursor nanoparticles. Because amorphous precursors were observed in diverse biominerals, solid-state secondary nucleation is likely to be a general mechanism for the co-orientation of biomineral components in organisms from different phyla.« less

BENTHIC COMMUNITY RESPONSE TO SEDIMENT AMENDMENTS

EPA Science Inventory

The amendments apatite, organoclay, acetate, chitin, and geotextile reactive mats containing apatite and apatite + organoclay are currently under examination for remediation of contaminated sediments. The objective of this research is to evaluate toxicity to several estuarine an...

Inhibition of precipitation of carbonate apatite by trisodium citrate analysed in base of the formation of chemical complexes in growth solution

NASA Astrophysics Data System (ADS)

Prywer, Jolanta; Olszynski, Marcin; Mielniczek-Brzóska, Ewa

2015-11-01

Effect of trisodium citrate on the precipitation of carbonate apatite is studied. The experimental series are performed in the solution of artificial urine. The investigations are related to infectious urinary stones formation as carbonate apatite is one of the main components of this kind of stones. To mimic a real infection in urinary tract the aqueous ammonia solution was added to the solution of artificial urine. The spectrophotometric results demonstrate that trisodium citrate increases induction time with respect to carbonate apatite formation and decreases the efficiency of carbonate apatite precipitation. The inhibitory effect of trisodium citrate on the precipitation of carbonate apatite is explained in base of chemical speciation analysis. Such an analysis demonstrates that the inhibitory effect is mainly related with the fact that trisodium citrate binds Ca2+ ions and causes the formation of CaCit- and Ca10(PO4)6CO3 complexes. Trisodium citrate binds Ca2+ ions in the range of pH from 6 to 9.5 for which carbonate apatite is favored to be formed.

Fabrication of hydroxyapatite block from gypsum block based on (NH4)2HPO4 treatment.

PubMed

Suzuki, Yumiko; Matsuya, Shigeki; Udoh, Koh-ichi; Nakagawa, Masaharu; Tsukiyama, Yoshihiro; Koyano, Kiyoshi; Ishikawa, Kunio

2005-12-01

The aim of this study was to evaluate the feasibility of fabricating low-crystalline, porous apatite block using set gypsum as a precursor based on the fact that apatite is thermodynamically more stable than gypsum. When the set gypsum was immersed in 1 mol/L diammonium hydrogen phosphate aqueous solution at 100 degrees C, it transformed to low-crystalline porous apatite retaining its original shape. The transformation reaction caused a release of sulfate ions due to an ion exchange with phosphate ions, thus leading to a decrease in the pH of the solution. Then, due to decreased pH, dicalcium phosphate anhydrous--which has similar thermodynamic stability at lower pH--was also produced as a by-product. Apatite formed in the present method was low-crystalline, porous B-type carbonate apatite that contained approximately 0.5 wt% CO3, even though no carbonate sources--except carbon dioxide from air--were added to the reaction system. We concluded therefore that this is a useful bone filler fabrication method since B-type carbonate apatite is the biological apatite contained in bone.

Fundamental piezo-Hall coefficients of single crystal p-type 3C-SiC for arbitrary crystallographic orientation

NASA Astrophysics Data System (ADS)

Qamar, Afzaal; Dao, Dzung Viet; Phan, Hoang-Phuong; Dinh, Toan; Dimitrijev, Sima

2016-08-01

Piezo-Hall effect in a single crystal p-type 3C-SiC, grown by LPCVD process, has been characterized for various crystallographic orientations. The quantified values of the piezo-Hall effect in heavily doped p-type 3C-SiC(100) and 3C-SiC(111) for different crystallographic orientations were used to obtain the fundamental piezo-Hall coefficients, P 12 = ( 5.3 ± 0.4 ) × 10 - 11 Pa - 1 , P 11 = ( - 2.6 ± 0.6 ) × 10 - 11 Pa - 1 , and P 44 = ( 11.42 ± 0.6 ) × 10 - 11 Pa - 1 . Unlike the piezoresistive effect, the piezo-Hall effect for (100) and (111) planes is found to be independent of the angle of rotation of the device within the crystal plane. The values of fundamental piezo-Hall coefficients obtained in this study can be used to predict the piezo-Hall coefficients in any crystal orientation which is very important for designing of 3C-SiC Hall sensors to minimize the piezo-Hall effect for stable magnetic field sensitivity.

Positron Interactions with Oriented Polymers and with Chiral Quartz Crystals

NASA Astrophysics Data System (ADS)

Wu, Fei

Positron annihilation in various materials has been applied to characterize microstructure for decades. In this work, PALS was used to study material nanostructure, with a focus on the size and density of free volume and hole relaxation properties in polycarbonate (PC) and polymethylmethacrylate (PMMA); fundamental studies of polarized positron interaction with chiral crystals were also studied. Free volume relaxation in PC and PMMA with different levels of simple shear orientation was studied by PALS. Effects of applied pressure on the free volume recovery were evaluated. Combining the bulk- and pressure-dependent PALS analyses, the removal of applied pressure led to free-volume relaxation in all samples studied. The alignment of the polymer chains and free-volume holes imposes molecular restrictions on the molecular mobility of both PC and PMMA in their glassy states. Results indicated that the relaxation of the free volume holes at temperatures below glass transition is mostly reversible. Longitudinally polarized positron particles were used to reveal asymmetric interactions in chiral quartz crystals. Experimental results showed a significant intensity difference in free positronium annihilation for left handed (LH) and right handed (RH) chiral quartz crystals. Doppler broadening energy spectra (DBES) of z-cut LH or RH quartz disks at different angles were also measured by an "S parameter" to probe the observed difference. It was found that obtained annihilation energy difference of DBES was in agreement with the result of positron annihilation in bulk chiral crystals. PALS was used to compare different orientations and confirm asymmetric interactions in natural versus synthetic quartz LH and RH crystals in z and non-z orientations. Significant lifetime and intensity differences in free positronium annihilation for LH and RH quartz crystals were observed. The trend was found to be same in the related crystallographic orientations of the LH or RH crystals; the direction of incident positrons, z or non-z, did not affect the observed differences in lifetime and intensity trends. The results confirmed the existence of differential interactions of positronium with the asymmetric lattice structures of LH and RH quartz crystals.

An evolving magmatic-hydrothermal system in the formation of the Mesozoic Meishan magnetite-apatite deposit in the Ningwu volcanic basin, eastern China

NASA Astrophysics Data System (ADS)

Liu, Wen-Hao; Jiang, Man-Rong; Zhang, Xiao-Jun; Xia, Yan; Algeo, Thomas J.; Li, Huan

2018-06-01

The Meishan iron deposit contains 338 Mt of iron-ore reserves at 39% Fe and represents the largest magnetite-apatite deposit in the Ningwu Basin of eastern China. Controversy has long existed about whether this deposit had a hydrothermal or iron-oxide melt origin. Iron mineralization is genetically related to plutons that are composed of gabbro-diorite, which were emplaced at 130 ± 1 Ma. These rocks have SiO2 contents of 51.72-54.60 wt%, Na2O contents of 3.47-4.04 wt%, K2O contents of 2.02-2.69 wt%, and K2O/Na2O ratios of 0.51-0.73. These rocks are enriched in LILEs and LREEs and depleted in Nb, Ta, and Ti, which indicates that the magma originated through partial melting of an enriched lithospheric mantle source in a subduction environment. A pattern of decreasing initial Sr isotopic ratios and increasing εNd(t) values with time in Early Cretaceous magmatic rocks of the Ningwu Basin may indicate incorporation of increasing proportions of asthenospheric mantle material into the source magma, which is consistent with the processes of lithospheric thinning and asthenospheric upwelling in eastern China related to Mesozoic subduction of the Paleo-Pacific Plate. Two stages of magnetite are found in the gabbro-diorite: (1) early-crystallized magnetite as euhedral-subhedral crystals in larger clinopyroxene crystals, and (2) later-crystallized magnetite and accompanying ilmenite grains in the voids between plagioclase and clinopyroxene crystals. The formation of magnetite before clinopyroxene, combined with the results of Fe-Ti oxide geothermometry and analysis of magnetite V content, indicates that the oxygen fugacity of the source magma was greater than ΔFMQ +2.2 at an early stage (>640 °C) but decreased to ΔFMQ -2.66 as abundant magnetite crystallized at a later stage (∼489 °C). The early crystallization of magnetite at a high oxygen fugacity does not support a Fenner evolution trend for the primitive magma and diminishes the likelihood of liquid immiscibility, which could have generated an iron-rich melt, and is thus inconsistent with an iron-oxide melt origin for the Meishan iron deposit. The δ34S values of pyrite (6.6-15.1‰) and anhydrite (15.6-16.9‰) in the deposit and the occurrence of evaporites under the volcanic rocks likely indicate that the iron ores and alteration rocks of the Meishan deposit were formed by the circulation of fluids of evaporitic origin driven by heat from the hypabyssal gabbro-diorite intrusives. In the late magmatic stage, oxygen fugacity decreased to a reducing range, triggering the reduction of sulfate to reduced sulfur and leading to local gold and pyrite mineralization.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, Jie; Viengkham, Malathong; Bertozzi, Carolyn R.

The controlled integration of organic and inorganic components confers natural bone with superior mechanical properties. Bone biogenesis is thought to occur by templated mineralization of hard apatite crystals by an elastic protein scaffold, a process we sought to emulate with synthetic biomimetic hydrogel polymers. Crosslinked polymethacrylamide and polymethacrylate hydrogels were functionalized with mineral-binding ligands and used to template the formation of hydroxyapatite. Strong adhesion between the organic and inorganic materials was achieved for hydrogels functionalized with either carboxylate or hydroxy ligands. The mineral-nucleating potential of hydroxyl groups identified here broadens the design parameters for synthetic bone-like composites and suggests amore » potential role for hydroxylated collagen proteins in bone mineralization.« less

Yb:FAP and related materials, laser gain medium comprising same, and laser systems using same

DOE Office of Scientific and Technical Information (OSTI.GOV)

Krupke, William F.; Payne, Stephen A.; Chase, Lloyd L.

An ytterbium doped laser material remarkably superior to all others, including Yb:YAG, comprises Ytterbium doped apatite (Yb:Ca.sub.5 (PO.sub.4).sub.3 F) or Yb:FAP, or ytterbium doped crystals that are structurally related to FAP. The new laser material is used in laser systems pumped by diode pump sources having an output near 0.905 microns or 0.98 microns, such as InGaAs and AlInGaAs, or other narrowband pump sources near 0.905 microns or 0.98 microns. The laser systems are operated in either the conventional or ground state depletion mode.

Yb:FAP and related materials, laser gain medium comprising same, and laser systems using same

DOE Office of Scientific and Technical Information (OSTI.GOV)

Krupke, W.F.; Payne, S.A.; Chase, L.L.

An ytterbium doped laser material remarkably superior to all others, including Yb:YAG, comprises ytterbium doped apatite (Yb:Ca[sub 5](PO[sub 4])[sub 3]F) or Yb:FAP, or ytterbium doped crystals that are structurally related to FAP. The new laser material is used in laser systems pumped by diode pump sources having an output near 0.905 microns or 0.98 microns, such as InGaAs and AlInGaAs, or other narrowband pump sources near 0.905 microns or 0.98 microns. The laser systems are operated in either the conventional or ground state depletion mode. 9 figures.

Yb:FAP and related materials, laser gain medium comprising same, and laser systems using same

DOEpatents

Krupke, W.F.; Payne, S.A.; Chase, L.L.; Smith, L.K.

1994-01-18

An ytterbium doped laser material remarkably superior to all others, including Yb:YAG, comprises ytterbium doped apatite (Yb:Ca[sub 5](PO[sub 4])[sub 3]F) or Yb:FAP, or ytterbium doped crystals that are structurally related to FAP. The new laser material is used in laser systems pumped by diode pump sources having an output near 0.905 microns or 0.98 microns, such as InGaAs and AlInGaAs, or other narrowband pump sources near 0.905 microns or 0.98 microns. The laser systems are operated in either the conventional or ground state depletion mode. 9 figures.

Yb:FAP and related materials, laser gain medium comprising same, and laser systems using same

DOE Office of Scientific and Technical Information (OSTI.GOV)

Krupke, W.F.; Payne, S.A.; Chase, L.L.

An ytterbium doped laser material remarkably superior to all others, including Yb:YAG, comprises ytterbium doped apatite (Yb:Ca{sub 5}(PO{sub 4}){sub 3}F) or Yb:FAP, or ytterbium doped crystals structurally related to FAP. The new laser material is used in laser systems pumped by diode pump sources having an output near 0.905 microns or 0.98 microns, such as InGaAs and AlInGaAs, or other narrowband pump sources near 0.905 microns or 0.98 microns. The laser systems are operated in either the conventional or ground state depletion mode.

Voltage‐Controlled Switching of Strong Light–Matter Interactions using Liquid Crystals

PubMed Central

Hertzog, Manuel; Rudquist, Per; Hutchison, James A.; George, Jino; Ebbesen, Thomas W.

2017-01-01

Abstract We experimentally demonstrate a fine control over the coupling strength of vibrational light–matter hybrid states by controlling the orientation of a nematic liquid crystal. Through an external voltage, the liquid crystal is seamlessly switched between two orthogonal directions. Using these features, for the first time, we demonstrate electrical switching and increased Rabi splitting through transition dipole moment alignment. The C−Nstr vibration on the liquid crystal molecule is coupled to a cavity mode, and FT‐IR is used to probe the formed vibropolaritonic states. A switching ratio of the Rabi splitting of 1.78 is demonstrated between the parallel and the perpendicular orientation. Furthermore, the orientational order increases the Rabi splitting by 41 % as compared to an isotropic liquid. Finally, by examining the influence of molecular alignment on the Rabi splitting, the scalar product used in theoretical modeling between light and matter in the strong coupling regime is verified. PMID:29155469

Directed Self-Assembly of Liquid Crystalline Blue-Phases into Ideal Single-Crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Martinez-Gonzalez, Jose A.; Li, Xiao; Sadati, Monirosadat

Chiral nematic liquid crystals are known to form blue phases—liquid states of matter that exhibit ordered cubic arrangements of topological defects. Blue-phase specimens, however, are generally polycrystalline, consisting of randomly oriented domains that limit their performance in applications. A strategy that relies on nano-patterned substrates is presented here for preparation of stable, macroscopic single-crystal blue-phase materials. Different template designs are conceived to exert control over different planes of the blue-phase lattice orientation with respect to the underlying substrate. Experiments are then used to demonstrate that it is indeed possible to create stable single-crystal blue-phase domains with the desired orientation overmore » large regions. Lastly, these results provide a potential avenue to fully exploit the electro-optical properties of blue phases, which have been hindered by the existence of grain boundaries.« less

Variation of relative intensities between surface and bulk plasmon losses due to crystal orientations for aluminium in low energy electron reflection loss spectroscopy

NASA Astrophysics Data System (ADS)

Ichinokawa, T.; Le Gressus, C.; Mogami, A.; Pellerin, F.; Massignon, D.

The contrast change of secondary electron images due to the crystal orientations is observed by the ultra high vacuum scanning electron microscope (UHV-SEM) for crystal grains of clean surface of polycrystalline Al in the primary energy Ep of 200 eV to 5 KeV. The low energy electron loss spectra are measured by the cylindrical mirror analyzer. The relative intensity ratio between surface and bulk plasmon loss spectra was dependent on the crystal orientations. The SEM images taken by the surface and bulk plasmon signals at Ep = 230 eV show the inverse contrast depending on the grains. The inversion of the relative intensities between the surface and bulk plasmon losses is explained qualitatively by taking into account of variation of the penetration depth of the incident beam caused by the electron channeling.

Variation of relative intensities between surface and bulk plasmon losses due to crystal orientations for aluminium in low energy electron reflection loss spectroscopy

NASA Astrophysics Data System (ADS)

Ichinokawa, T.; Le Gressus, C.; Mogami, A.; Pellerin, F.; Massignon, D.

1981-10-01

The contrast change of secondary electron images due to the crystal orientations is observed by the ultra high vacuum scanning electron microscope (UHV-SEM) for crystal grains of clean surface of polycrystalline Al in the primary energy Ep of 200 eV to 5 keV. The low energy electron loss spectra are measured by the cylindrical mirror analyzer. The relative intensity ratio between surface and bulk plasmon loss spectra was dependent on the crystal orientations. The SEM images taken by the surface and bulk plasmon signals at Ep = 230 eV show the inverse contrast depending on the grains. The inversion of the relative intensities between the surface and bulk plasmon losses is explained qualitatively by taking into account of variation of the penetration depth of the incident beam caused by the electron channeling.