Thermal profiles, crystallization behaviors and microstructure of diacylglycerol-enriched palm oil blends with diacylglycerol-enriched palm olein.

PubMed

Xu, Yayuan; Zhao, Xiaoqing; Wang, Qiang; Peng, Zhen; Dong, Cao

2016-07-01

To elucidate the possible interaction mechanisms between DAG-enriched oils, this study investigated how mixtures of DAG-enriched palm-based oils influenced the phase behavior, thermal properties, crystallization behaviors and the microstructure in binary fat blends. DAG-enriched palm oil (PO-DAGE) was blended with DAG-enriched palm olein (POL-DAGE) in various percentages (0%, 10%, 30%, 50%, 70%, 90%, 100%). Based on the observation of iso-solid diagram and phase diagram, the binary mixture of PO-DAGE/POL-DAGE showed a better compatibility in comparison with their corresponding original blends. DSC thermal profiles exhibited that the melting and crystallization properties of PO-DAGE/POL-DAGE were distinctively different from corresponding original blends. Crystallization kinetics revealed that PO-DAGE/POL-DAGE blends displayed a rather high crystallization rate and exhibited no spherulitic crystal growth. From the results of polarized light micrographs, PO-DAGE/POL-DAGE blends showed more dense structure with very small needle-like crystals than PO/POL. X-ray diffraction evaluation revealed when POL-DAGE was added in high contents to PO-DAGE, above 30%, β-polymorph dominated, and the mount of β' forms crystals was decreasing. Copyright © 2016 Elsevier Ltd. All rights reserved.

Studies of fatty acid composition, physicochemical and thermal properties, and crystallization behavior of mango kernel fats from various Thai varieties.

PubMed

Sonwai, Sopark; Ponprachanuvut, Punnee

2014-01-01

Mango kernel fat (MKF) has received attention in recent years due to the resemblance between its characteristics and those of cocoa butter (CB). In this work, fatty acid (FA) composition, physicochemical and thermal properties and crystallization behavior of MKFs obtained from four varieties of Thai mangoes: Keaw-Morakot (KM), Keaw-Sawoey (KS), Nam-Dokmai (ND) and Aok-Rong (AR), were characterized. The fat content of the mango kernels was 6.40, 5.78, 5.73 and 7.74% (dry basis) for KM, KS, ND and AR, respectively. The analysis of FA composition revealed that all four cultivars had oleic and stearic acids as the main FA components with ND and AR exhibiting highest and lowest stearic acid content, respectively. ND had the highest slip melting point and solid fat content (SFC) followed by KS, KM and AR. All fat samples exhibited high SFC at 20℃ and below. They melted slowly as the temperature increased and became complete liquids as the temperature approached 35°C. During static isothermal crystallization at 20°C, ND displayed the highest Avrami rate constant k followed by KS, KM and AR, indicating that the crystallization was fastest for ND and slowest for AR. The Avrami exponent n of all samples ranged from 0.89 to 1.73. The x-ray diffraction analysis showed that all MKFs crystallized into a mixture of pseudo-β', β', sub-β and β structures with β' being the predominant polymorph. Finally, the crystals of the kernel fats from all mango varieties exhibited spherulitic morphology.

Unique nucleation activity of inorganic fullerene-like WS2 nanoparticles in polyphenylene sulfide nanocomposites: isokinetic and isoconversional study of dynamic crystallization kinetics.

PubMed

Naffakh, Mohammed; Marco, Carlos; Gómez, Marián A; Jiménez, Ignacio

2009-05-21

The dynamic crystallization kinetics of polyphenylene sulfide (PPS) nanocomposites with inorganic fullerene WS2 nanopartices (IF-WS2) content varying from 0.05 to 8 wt % has been studied using differential scanning calorimetry (DSC). The analysis of the crystallization at different cooling rates demonstrates that the completely isokinetic description of the crystallization process is not possible. However, the isoconversional methods in combination with the JMAEK equation provide a better understanding of the kinetics of the dynamic crystallization process. The addition of IF-WS2 influences the crystallization kinetics of PPS but in ways unexpected for polymer nanocomposites. A drastic change from retardation to promotion of crystallization is observed with increasing nanoparticle content. In the same way, the results of the nucleation activity and the effective energy barrier confirmed the unique dependence of the crystallization behavior of PPS on composition. In addition, the morphological data obtained from the polarized optical microscopy (POM) and time-resolved synchrotron X-ray diffraction is consistent with results of the crystallization kinetics of PPS/IF-WS2 nanocomposites.

Structure and phase formation behavior and dielectric and magnetic properties of lead iron tantalate-lead zirconate titanate multiferroic ceramics

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

Wongmaneerung, R., E-mail: re_nok@yahoo.com; Tipakontitikul, R.; Jantaratana, P.

2016-03-15

Highlights: • The multiferroic ceramics consisted of PFT and PZT. • Crystal structure changed from cubic to mixedcubic and tetragonal with increasing PZT content. • Dielectric showed the samples underwent a typical relaxor ferroelectric behavior. • Magnetic properties showed very interesting behavior with square saturated magnetic hysteresis loops. - Abstract: Multiferroic (1 − x)Pb(Fe{sub 0.5}Ta{sub 0.5})O{sub 3}–xPb(Zr{sub 0.53}Ti{sub 0.47})O{sub 3} (or PFT–PZT) ceramics were synthesized by solid-state reaction method. The crystal structure and phase formation of the ceramics were examined by X-ray diffraction (XRD). The local structure surrounding Fe and Ti absorbing atoms was investigated by synchrotron X-ray Absorption Near-Edgemore » Structure (XANES) measurement. Dielectric properties were studied as a function of frequency and temperature using a LCR meter. A vibrating sample magnetometer (VSM) was used to determine the magnetic hysteresis loops. XRD study indicated that the crystal structure of the sample changed from pure cubic to mixed cubic and tetragonal with increasing PZT content. XANES measurements showed that the local structure surrounding Fe and Ti ions was similar. Dielectric study showed that the samples underwent a typical relaxor ferroelectric behavior while the magnetic properties showed very interesting behavior with square saturated magnetic hysteresis loops.« less

Non-Isothermal Calorimetric Studies of the Crystallization of Lithium Disilicate Glass

NASA Technical Reports Server (NTRS)

Ray, C. S.; Day, D. E.; Huang, W.; Narayan, K. Lakshmi; Cull, T. S.; Kelton, K. F.

1996-01-01

The influence of preannealing treatments on the polymorphic crystallization of lithium disilicate glasses is examined. As expected, glasses heated at different rates through the temperature range where there is significant nucleation develop widely different numbers of nuclei. This can dramatically influence the stability and transformation characteristics of the annealed glass. Non-isothermal differential scanning calorimetry (DSC) and differential thermal analysis (DTA) measurements are demonstrated to be useful to probe the nucleation behavior. The first systematic investigations of particle size effects on the non-isothermal transformation behavior are presented and discussed. Based on DTA and microscopy experiments, we show that small particles of lithium disilicate glasses crystallize primarily by surface crystallization. The relative importance of surface versus volume crystallization is examined by varying particle size, by introducing nucleating agents and by exposing glasses to atmospheres of different water content. These data are analyzed quantitatively using a numerical model developed in a second paper following in this volume.

Relationships between the morphology and thermoresponsive behavior in micro/nanostructured thermosetting matrixes containing a 4'-(hexyloxy)-4-biphenylcarbonitrile liquid crystal.

PubMed

Tercjak, Agnieszka; Mondragon, Iñaki

2008-10-07

Meso/nanostructured thermoresponsive thermosetting materials based on an epoxy resin modified with two different molecular weight amphiphilic poly(styrene- block-ethylene oxide) block copolymers (PSEO) and a low molecular weight liquid crystal, 4'-(hexyloxy)-4-biphenylcarbonitrile (HOBC), were investigated. A strong influence of the addition of PSEO on the morphology generated in HOBC--(diglicydyl ether of bisphenol A epoxy resin/ m-xylylenediamine) was detected, especially in the case of the addition of PSEO block copolymers with a higher PEO-block content and a lower molecular weight. The morphologies generated in the ternary systems also influenced the thermoresponsive behavior of the HOBC separated phase provoked by applying an external field, such as a temperature gradient and an electrical field. Thermal analysis of the investigated materials allowed for a better understanding of the relationships between generated morphology/thermo-optical properties/PSEO:HOBC ratio, and HOBC content. Controlling the relationship between the morphology and thermoresponsive behavior in micro/nanostructured thermosetting materials based on a 4'-(hexyloxy)-4-biphenylcarbonitrile liquid crystal allows the development of materials which can find application in thermo- and in some cases electroresponsive devices, with a high contrast ratio between transparent and opaque states.

Investigation on the Tribological Behavior and Wear Mechanism of Five Different Veneering Porcelains

PubMed Central

Min, Jie; Zhang, Qianqian; Qiu, Xiaoli; Zhu, Minhao; Yu, Haiyang; Gao, Shanshan

2015-01-01

Objectives The primary aim of this research was to investigate the wear behavior and wear mechanism of five different veneering porcelains. Methods Five kinds of veneering porcelains were selected in this research. The surface microhardness of all the samples was measured with a microhardness tester. Wear tests were performed on a ball-on-flat PLINT fretting wear machine, with lubrication of artificial saliva at 37°C. The friction coefficients were recorded by the testing system. The microstructure features, wear volume, and damage morphologies were recorded and analyzed with a confocal laser scanning microscope and a scanning electron microscope. The wear mechanism was then elucidated. Results The friction coefficients of the five veneering porcelains differ significantly. No significant correlation between hardness and wear volume was found for these veneering porcelains. Under lubrication of artificial saliva, the porcelain with higher leucite crystal content exhibited greater wear resistance. Additionally, leucite crystal size and distribution in glass matrix influenced wear behavior. The wear mechanisms for these porcelains were similar: abrasive wear dominates the early stage, whereas delamination was the main damage mode at the later stage. Furthermore, delamination was more prominent for porcelains with larger crystal sizes. Significance Wear compatibility between porcelain and natural teeth is important for dental restorative materials. Investigation on crystal content, size, and distribution in glass matrix can provide insight for the selection of dental porcelains in clinical settings. PMID:26368532

The effect of butter grains on physical properties of butter-like emulsions.

PubMed

Rønholt, Stine; Buldo, Patrizia; Mortensen, Kell; Andersen, Ulf; Knudsen, Jes C; Wiking, Lars

2014-01-01

Milk fat exists as globules in its natural state in milk. The potential of using globular fat to modulate the rheological properties and crystallization behavior in butter-like emulsions was studied in the present work. We conducted a comparative study of butter-like emulsions, with a fat phase consisting of 0, 10, 25, 50, or 100% anhydrous milk fat (AMF), the remaining fat being butter grains, and all samples containing 20% water, to obtain systematic variation in the ratio of globular fat. All emulsions were studied over 4wk of storage at 5°C. By combining small and large deformation rheology, we conducted a detailed characterization of the rheological behavior of butter-like emulsions. We applied differential scanning calorimetry to monitor thermal behavior, confocal laser scanning microscopy for microstructural analysis, and low-field pulsed nuclear magnetic resonance spectrometry to measure solid fat content. By combining these techniques, we determined that increasing the fraction of globular fat (by mixing with butter grains) decreases the hardness of butter-like emulsions up to an order of magnitude at d 1. However, no difference was observed in thermal behavior as a function of butter grain content, as all emulsions containing butter grains revealed 2 endothermal peaks corresponding to the high (32.7°C ± 0.6) and medium (14.6°C ± 0.1) melting fractions of fatty acids. In terms of microstructure, decreasing the amount of butter grains in the emulsions resulted in formation of a denser fat crystal network, corresponding to increased hardness. Moreover, microstructural analysis revealed that the presence of butter grains resulted in faster formation of a continuous fat crystal network compared with the 100% AMF sample, which was dominated by crystal clusters surrounded by liquid oil. During storage, hardness remained stable and no changes in thermal behavior were observed, despite an increase in solid fat content of up to 5%. After 28d of storage, we observed no difference in either microstructural or rheological properties, indicating that formation of primary bonds occurs primarily within the first day of storage. The rheological behavior of butter-like emulsions is not determined solely by hardness, but also by stiffness related to secondary bonds within the fat crystal network. The complex rheological behavior of milk fat-based emulsions is better characterized using multiple parameters. Copyright © 2014 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Non-isothermal crystallization kinetics of eucalyptus lignosulfonate/polyvinyl alcohol composite.

PubMed

Ye, De-Zhan; Zhang, Xi; Gu, Shaojin; Zhou, Yingshan; Xu, Weilin

2017-04-01

The nonisothermal crystallinization kinetic was performed on Polyvinyl alcohol (PVA) mixed with eucalyptus lignosulfonate calcuim (HLS) as the biobased thermal stabilizer, which was systematically analyzed based on Jeziorny model, Ozawa equation and the Mo method. The results indicated that the entire crystallization process took place through two main stages involving the primary and secondary crystallization processes. The Mo method described nonisothermal crystallization behavior well. Based on the results of the half time for completing crystallization, k c value in Jeziorny model, F(T) value in Mo method and crystallization activation energy, it was concluded that low loading of HLS accelerated PVA crystallization process, however, the growth rate of PVA crystallization was impeded at high content of HLS. Copyright © 2017 Elsevier B.V. All rights reserved.

Magnetic structure and phase stability of the van der Waals bonded ferromagnet Fe 3-xGeTe 2

DOE PAGES

May, Andrew F.; Calder, Stuart A.; Cantoni, Claudia; ...

2016-01-08

The magnetic structure and phase diagram of the layered ferromagnetic compound Fe 3GeTe 2 have been investigated by a combination of synthesis, x-ray and neutron diffraction, high-resolution microscopy, and magnetization measurements. Single crystals were synthesized by self-flux reactions, and single-crystal neutron diffraction finds ferromagnetic order with moments of 1.11(5)μ B/Fe aligned along the c axis at 4 K. These flux-grown crystals have a lower Curie temperature T c ≈ 150 K than crystals previously grown by vapor transport (T c = 220 K). The difference is a reduced Fe content in the flux-grown crystals, as illustrated by the behavior observedmore » in a series of polycrystalline samples. As Fe content decreases, so do the Curie temperature, magnetic anisotropy, and net magnetization. Furthermore, Hall-effect and thermoelectric measurements on flux-grown crystals suggest that multiple carrier types contribute to electrical transport in Fe 3–xGeTe 2 and structurally similar Ni 3–xGeTe 2.« less

Influence of lignin on morphology, structure and thermal behavior of polylactic acid-based biocomposites

NASA Astrophysics Data System (ADS)

Canetti, Maurizio; Cacciamani, Adriana; Bertini, Fabio

2016-05-01

Polylactic acid (PLA) is a thermoplastic biodegradable polymer that can be made from annually renewable resources. Lignin is a natural amorphous polyphenolic macromolecule inexpensive and easily available. In the present study PLA and acetylated lignin biocomposites were prepared by casting from chloroform solution. PLA can crystallize from the melt in the α and α' forms, depending on the adopted crystallization conditions. The presence of the lignin in the biocomposites can interfere with the crystal formation process. Isothermal crystallizations were performed at different temperatures, the presence of lignin causes an increase of the time of crystallization, while the overall crystallization rate and the spherulite radial growth rate decrease with enhancing the lignin content in the biocomposites.

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.

Preparation, melting behavior and thermal stability of poly(lactic acid)/poly(propylene carbonate) blends processed by vane extruder

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

Zou, Wei, E-mail: zw55624@163.com; Chen, Rongyuan; Zhang, Haichen

Poly (lactic acid) (PLA)/Poly (propylene carbonate) (PPC) blends were prepared by vane extruder which is a type of novel polymer processing extruder based on elongation force field. Scanning electron microscope (SEM), differential scanning calorimetry (DSC) and thermogravimetric (TG) were used respectively to analyze the compatibility, the melting behavior and thermal stability properties of PLA/PPC blends affected by the different content of PPC. The results showed that with the increase of the PPC content, the glass transition temperature of PLA was reduced, and the glass transition temperature of PPC was increased, which indicated that PLA and PPC had partial compatibility. Themore » cold crystallization temperature of PLA increased with the increase of the PPC content, which showed that PPC hindered the cold crystallization process of PLA. The addition of PPC had little impact on the melting process of PLA, and the melting temperature of PLA was almost kept the same value. Thermogravimetric analysis showed that the thermal stability of PPC was worse than that of PLA, the addition of PPC reduced the thermal stability of PLA.« less

The preparation and characterization of a lithium borate glass prepared by the gel technique

NASA Technical Reports Server (NTRS)

Weinberg, M. C.; Neilson, G. F.; Smith, G. L.; Dunn, B.; Moore, G. S.; Mackenzie, J. D.

1985-01-01

The preparation of an amorphous lithium borate gel by the metal organic procedure is described. In addition, a preliminary evaluation of the behavior of the gel upon heating is given. In particular the crystallization tendency of the gel is studied with the aid of DTA and X-ray diffraction, and the structural changes in the gel are monitored with the aid of IR spectroscopy. The glass produced from the lithium borate gel is compared to both the gel precursor material and a glass of similar composition prepared by conventional techniques. Specifically, the relevant water contents, crystallization behavior, and structural features are contrasted.

Non-isothermal crystallization kinetics and characterization of biodegradable poly(butylene succinate-co-neopentyl glycol succinate) copolyesters.

PubMed

Xie, Wen-Jie; Zhou, Xiao-Ming

2015-01-01

Both biodegradable aliphatic neat poly(butylene succinate) (PBS) and poly(butylene succinate-co-neopentyl glycol succinate) (P(BS-co-NPGS)) copolyesters with different 1,4-butanediol/neopentyl glycol ratios were synthesized through a two-step process of transesterification and polycondensation using stannous chloride and 4-Methylbenzenesulfonic acid as the co-catalysts. The structure, non-isothermal crystallization behavior, crystalline morphology and crystal structure of neat PBS and P(BS-co-NPGS) copolyesters were characterized by (1)H NMR, differential scanning calorimetry (DSC), polarized optical microscope (POM) and wide angle X-ray diffraction (WAXD), respectively. The Avrami equation modified by Jeziorny and Mo's method was employed to describe the non-isothermal crystallization kinetics of the neat PBS and its copolyesters. The modified Avrami equation could adequately describe the primary stage of non-isothermal crystallization kinetics of the neat PBS and its copolyesters. Mo's method provided a fairly satisfactory description of the non-isothermal crystallization of neat PBS and its copolyesters. Interestingly, the values of 1/t1/2, Zc and F(T) obtained by the modified Avrami equation and Mo's method analysis indicated that the crystallization rate increased first and then decreased with an increase of NPGS content compared that of neat PBS, whereas the crystallization mechanism almost kept unchanged. The results of tensile testing showed that the ductility of PBS was largely improved by incorporating NPGS units. The elongation at break increased remarkably with increasing NPGS content. In particular, the sample with 20% NPGS content showed around 548% elongation at break. Copyright © 2014 Elsevier B.V. All rights reserved.

Semicrystalline polyamide engineering thermoplastics based on the renewable monomer, 1,9-nonane diamine: Thermal properties and water absorption

DOE PAGES

Kugel, Alex; He, Jie; Samanta, Satyabrata; ...

2012-08-27

Here, a series of poly(1,9-nonamethylene adipamide-co-1,9-nonamethylene terephthalamide) copolymers were produced using melt polymerization and the thermal properties, crystal structure, and moisture uptake characterized. The results confirmed that the copolymers exhibit isomorphism. As expected, glass transition temperature and the apparent melting temperature increased with increasing terephthalmide content. Using the difference in the apparent melting temperature to the crystallization temperature as a measure of relative crystallization rate, it was observed that crystallization rate decreased as the terephthalamide content of the copolymer was increased from 0 to 50 mole percent but then sharply increased when increased beyond 50 mole percent. This behavior maymore » be the result of extensive inter- and intramolecular interactions in the melt associated with terephthalmide units in the polymer chain that nucleate crystallization upon cooling below the equilibrium melting temperature. Comparing the thermal properties of copolymers possessing an excess of terephthalmide units to the commodity polyamide Nylon 6,6, it is believed that these copolymers may have utility as partially renewable engineering thermoplastics.« less

Effect of Starch on Sintering Behavior for Fabricating Porous Cordierite Ceramic

NASA Astrophysics Data System (ADS)

Li, Ye; Cao, Wei; Gong, Lunlun; Zhang, Ruifang; Cheng, Xudong

2016-10-01

Porous cordierite ceramics were prepared with starch as pore-forming agent by solid-state method. The green bodies were sintered at 1,100-1,400 °C for 2 h. The characterization was focused on thermal analysis, phase evolution, sintering behavior, porosity and micro-structural changes. The results show that cordierite becomes the main crystallization phase at 1,200 °C. The shrinkage behavior shows the most obvious dependence on the sintering temperature and starch content, and it can be divided into three stages. Moreover, the open porosity increases with the increase of starch content, but the pore-forming effectivity decreases. Nevertheless, compared with the open porosity curves, the bulk density curves are more in line with the linear rule. The microphotographs show the densification process with the sintering temperature and the variation of pore connectivity with the starch content.

Ultrasonic evaluation of oxidation and reduction effects on the elastic behavior and global microstructure of YBa2Cu3O7-x

NASA Technical Reports Server (NTRS)

Roth, Don J.; Deguire, Mark R.; Dolhert, Leonard E.

1991-01-01

Ultrasonic velocity measurement techniques were used to evaluate the effects of oxidation and reduction on the elastic properties, global microstructure and oxygen content of the YBa2Cu3O(7-x) ceramic superconductor for samples ranging from 70 to 90 pct. of theoretical density. Bulk density, velocity, and elastic modulus generally increased with increasing oxygen content upon oxidation, and this behavior was reversible. Velocity image patterns were similar after oxidation and reduction treatments for a 90 pct. dense sample, although the velocity value at any given point on the sample was changed following the treatments. The unchanging pattern correlated with destructive measurements showing that the spatial pore distribution (fraction and size) was not measurably altered after the treatments. Changes in superconducting behavior, crystal structure, and grain structure were observed consistent with changes in oxygen content.

Crystallization and Martensitic Transformation Behavior of Ti-Ni-Si Alloy Ribbons Prepared via Melt Spinning.

PubMed

Park, Ju-Wan; Kim, Yeon-Wook; Nam, Tae-Hyun

2018-09-01

Ti-(50-x)Ni-xSi (at%) (x = 0.5, 1.0, 3.0, 5.0) alloy ribbons were prepared via melt spinning and their crystallization procedure and transformation behavior were investigated using differential scanning calorimtry, X-ray diffraction, and transmission electron microscopy. Ti-Ni-Si alloy ribbons with Si content less than 1.0 at% were crystalline, whereas those with Si content more than 3.0 at% were amorphous. Crystallization occurred in the sequence of amorphous →B2 → B2 → Ti5Si4 + TiNi3 → B2 + Ti5Si4 + TiNi3 + TiSi in the Ti-47.0Ni-3.0Si alloy and amorphous →R → R + Ti5Si4 + TiNi3 → R + Ti5Si4 + TiNi3 + TiSi in the Ti-45.0Ni-5.0Si alloy. The activation energy for crystallization was 189 ±8.6 kJ/mol for the Ti-47Ni-3Si alloy and 212±8.6 kJ/mol for the Ti-45Ni-5Si alloy. One-stage B2-R transformation behavior was observed in Ti-49.5Ni-0.5Si, Ti-49.0Ni-1.0Si, and Ti-47.0Ni- 3.0Si alloy ribbons after heating to various temperatures in the range of 873 K to 1073 K. In the Ti-45.0Ni-5.0Si alloy, one-stage B2-R transformation occurred after heating to 893 K, two-stage B2-R-B19' occurred after heating to 973 K, and two-stage B2-R-B19' occurred on cooling and one-stage B19'-B2 occurred on heating, after heating to 1073 K.

Low sulfur content in submarine lavas: an unreliable indicator of subaerial eruption

USGS Publications Warehouse

Davis, A.S.; Clague, D.A.; Schulz, M.S.; Hein, J.R.

1991-01-01

Low S content (<250 ppm) has been used to identify subaerially erupted Hawaiian and Icelandic lavas. Large differences in S content of submarine-erupted lavas from different tectonic settings indicate that the behavior of S is complex. Variations in S abundance in undegassed, submarine-erupted lavas can result from different source compositions, different percentages of partial melting, and crystal fractionation. Low S concentrations in highly vesicular submarine lavas suggest that partial degassing can occur despite great hydrostatic pressure. These processes need to be evaluated before using S content as an indicator of eruption depth. -Authors

Effects of B2O3 content and sintering temperature on crystallization and microstructure of CBS glass-ceramic coatings

NASA Astrophysics Data System (ADS)

Li, Pengyang; Wang, Shubin; Liu, Jianggao; Feng, Mengjie; Yang, Xinwang

2015-11-01

Borosilicate glass-ceramics precursors with varying compositional ratios in the CaO-SiO2-B2O3 (CBS) system were synthesized by sol-gel method. The precursors were calcined at 1200 °C for 2 h to form glass powders. The glass-ceramics were prepared by overlaying glass slurries on the substrates before sintering at different temperatures. The as-prepared glasses and glass-ceramics were characterized by differential scanning calorimetry and X-ray diffraction. The crystallization activation energies (Ec) were calculated using the Kissinger method from DSC results. The morphology and crystallization behavior of the glass-ceramics were monitored by scanning electron microscopy. Both glass transition and crystallization temperatures decreased, however, the metastable zone increased. The Ec values of CBS glasses and glass-ceramics were 254.1, 173.2 and 164.4 kJ/mol with increasing B2O3 content, whereas that of the calcined G3 glass was 104.9 kJ/mol. Finally, the coatings were prepared at a low temperature (700 °C). The crystals that grew on the surface of multilayer coatings demonstrated heterogeneous surface nucleation and crystallization after heat-treatment from 700 °C to 850 °C for 4 h.

Effects of crystallization on structural and dielectric properties of thin amorphous films of (1 - x)BaTiO3-xSrTiO3 (x=0-0.5, 1.0)

NASA Astrophysics Data System (ADS)

Kawano, H.; Morii, K.; Nakayama, Y.

1993-05-01

The possibilities for fabricating solid solutions of (Ba1-x,Srx)TiO3 (x≤0.5,1.0) by crystallization of amorphous films and for improving their dielectric properties by adjusting the Sr content were investigated. Thin amorphous films were prepared from powder targets consisting of mixtures of BaTiO3 and SrTiO3 by sputtering with a neutralized Ar-ion beam. The amorphous films crystallized into (Ba1-x, Srx)TiO3 solid solutions with a cubic perovskite-type structure after annealing in air at 923 K for more than 1 h. The Debye-type dielectric relaxation was observed for the amorphous films, whereas the crystallized films showed paraelectric behavior. The relative dielectric constants were of the order of 20 for the amorphous samples, but increased greatly after crystallization to about 60-200, depending on the composition; a larger increase in the dielectric constant was observed in the higher Sr content films, in the range x≤0.5, which could be correlated with an increase in the grain size of the crystallites. The crystallization processes responsible for the difference in the grain size are discussed based on the microstructural observations.

-Based Slag System

NASA Astrophysics Data System (ADS)

Jiang, Binbin; Wang, Wanlin; Sohn, Il; Wei, Juan; Zhou, Lejun; Lu, Boxun

2014-06-01

The crystallization behavior of a CaO-Al2O3-based slag system with various ZrO2 content (from 1 to 5 wt pct) and CaO/Al2O3 (C/A) ratio (from 0.8 to 1.2) has been studied by using single hot thermocouple technology (SHTT) in this article. The continuous-cooling-transformation (CCT) diagrams and time-temperature-transformation (TTT) diagrams of the above slag system were constructed for the analysis of the varying crystallization behaviors. The results suggested that Al2O3 tended to enhance the slag samples crystallization when the C/A ratio ranged from 0.8 to 1.2, and the critical cooling rate and crystallization temperature increased with the decrease of C/A ratio; meanwhile, the incubation time was also getting shorter with the reduction of C/A ratio. The addition of ZrO2 would enhance the crystallization of slag samples because of the induced heterogeneous nucleation of molten slag. However, the general crystallization was determined by the balance between molten slag viscosity and heterogeneous nucleation, such that Sample 3 (C/A = 1.0, ZrO2 = 3 pct, B2O3 = 10 pct, Li2O = 3 pct [in wt pct]) would demonstrate the strongest crystallization kinetics in a high-temperature zone. The different crystals formed during the tests were also analyzed by scanning electron microscopy (SEM) and X-ray diffraction (XRD).

Anomalous rheological behavior of long glass fiber reinforced polypropylene

NASA Astrophysics Data System (ADS)

Kim, Dong Hak; Lee, Young Sil; Son, Younggon

2012-12-01

Dynamic rheological properties of PP-based long glass fiber-reinforced thermoplastics (LFT) were investigated. Weight fractions of the glass fibers investigated in the present study ranged from 0.15 to 0.5, which are higher than those of previous studies. We observed very abnormal rheological behavior. Complex viscosity (η*) of the LFT increased with the glass fiber content up to 40 wt. %. However, the η* with a weight fraction of 0.5 is observed to be lower than that of LFT with a weight fraction of 0.4 in spite of higher glass fiber content. From various experiments, we found that this abnormal behavior is analogous to the rheological behavior of a lyotropic liquid crystalline polymer solution and concluded that the abnormal rheological behavior for the LFT is attributed to the formation of a liquid crystal- like structure at high concentrations of long glass fibers.

Retrieval of ice crystals' mass from ice water content and particle distribution measurements: a numerical optimization approach

NASA Astrophysics Data System (ADS)

Coutris, Pierre; Leroy, Delphine; Fontaine, Emmanuel; Schwarzenboeck, Alfons; Strapp, J. Walter

2016-04-01

A new method to retrieve cloud water content from in-situ measured 2D particle images from optical array probes (OAP) is presented. With the overall objective to build a statistical model of crystals' mass as a function of their size, environmental temperature and crystal microphysical history, this study presents the methodology to retrieve the mass of crystals sorted by size from 2D images using a numerical optimization approach. The methodology is validated using two datasets of in-situ measurements gathered during two airborne field campaigns held in Darwin, Australia (2014), and Cayenne, France (2015), in the frame of the High Altitude Ice Crystals (HAIC) / High Ice Water Content (HIWC) projects. During these campaigns, a Falcon F-20 research aircraft equipped with state-of-the art microphysical instrumentation sampled numerous mesoscale convective systems (MCS) in order to study dynamical and microphysical properties and processes of high ice water content areas. Experimentally, an isokinetic evaporator probe, referred to as IKP-2, provides a reference measurement of the total water content (TWC) which equals ice water content, (IWC) when (supercooled) liquid water is absent. Two optical array probes, namely 2D-S and PIP, produce 2D images of individual crystals ranging from 50 μm to 12840 μm from which particle size distributions (PSD) are derived. Mathematically, the problem is formulated as an inverse problem in which the crystals' mass is assumed constant over a size class and is computed for each size class from IWC and PSD data: PSD.m = IW C This problem is solved using numerical optimization technique in which an objective function is minimized. The objective function is defined as follows: 2 J(m)=∥P SD.m - IW C ∥ + λ.R (m) where the regularization parameter λ and the regularization function R(m) are tuned based on data characteristics. The method is implemented in two steps. First, the method is developed on synthetic crystal populations in order to evaluate the behavior of the iterative algorithm, the influence of data noise on the quality of the results, and to set up a regularization strategy. Therefore, 3D synthetic crystals have been generated and numerically processed to recreate the noise caused by 2D projections of randomly oriented 3D crystals and by the discretization of the PSD into size classes of predefined width. Subsequently, the method is applied to the experimental datasets and the comparison between the retrieved TWC (this methodology) and the measured ones (IKP-2 data) will enable the evaluation of the consistency and accuracy of the mass solution retrieved by the numerical optimization approach as well as preliminary assessment of the influence of temperature and dynamical parameters on crystals' masses.

Characterization of carbohydrate-protein matrices for nutrient delivery.

PubMed

Zhou, Yankun; Roos, Yrjö H

2011-05-01

Amorphous carbohydrates may show glass transition and crystallization as a result of thermal or water plasticization. Proteins often affect the state transitions of carbohydrates in carbohydrate-protein systems. Water sorption behavior and effects of water on glass transition and crystallization in freeze-dried lactose, trehalose, lactose-casein (3: 1), lactose-soy protein isolate (3:1), trehalose-casein (3:1), and trehalose-soy protein isolate (3:1) systems were studied. Water sorption was determined gravimetrically as a function of time, and Brunauer-Emmett-Teller (BET) and Guggenheim-Anderson-de Boer (GAB) models were fitted to the experimental data. Glass transition temperature (T(g)) and instant crystallization temperature (T(ic)) in anhydrous and water plasticized systems were measured using differential scanning calorimetry (DSC). The Gordon-Taylor equation was used to model water content dependence of the T(g) values. The critical water content and water activity (a(w)) at 24 °C were calculated and crystallization of lactose and trehalose in the systems was followed at and above 0.54 a(w). Carbohydrate-protein systems showed higher amounts of sorbed water and less rapid sugar crystallization than pure sugars. A greater sugar crystallization delay was found in carbohydrate-casein systems than in carbohydrate-soy protein isolate systems. The T(g) and T(ic) values decreased with increasing water content and a(w). However, higher T(ic) values for lactose-protein systems were found than for lactose at the same a(w). Trehalose showed lower T(ic) value than lactose at 0.44 a(w) but no instant crystallization was measured below 0.44 a(w). State diagrams for each system are useful in selecting processing parameters and storage conditions in nutrient delivery applications. © 2011 Institute of Food Technologists®

The solidification behavior of calcium oxide-aluminum oxide slags

NASA Astrophysics Data System (ADS)

Prapakorn, Kritsada

The binary CaO-Al2O3 based slag and the ternary CaO-Al2O3-MgO based slag are common slags covering and inclusions that are found in calcium treated Al-killed, continuously cast steels. However, the effect of cooling conditions and chemistry on the solidification behavior of these slags is not well characterized. To better understand this phenomena, the solidification behavior of these slags was studied by using double hot thermocouple technique. TTT and CCT diagrams of these slags were determined to quantify the solidification behavior in both dry and humid atmospheres. In this work, these slag samples were easily undercooled and the solidification behavior of these slags was found to be a strong function of cooling conditions. The crystallization tendency of these slags follows the trends suggested by the phase diagram. In CaO-Al2O3 based slags, The eutectic composition (50%CaO) give the lowest crystallization tendency due to the lowest liquidus temperature. In a eutectic CaO-Al2O3 slag sample, dissolved water in the sample increases crystallization tendency and enhances the growth. It was also found that the crystalline phase that formed during cooling in both the dry and humid conditions is the mixture between 3CaO.Al2O 3 and CaO.Al2O3 phases. In CaO-Al2O3-MgO based slags, the crystallization tendency increases with MgO content because the high MgO content leads to the high liquidus temperature. The effect of dissolved of water on the crystallization of CaO-Al2O3-MgO based slags is not as prominent as in the eutectic CaO-Al2O3 slag. Thus, the addition of MgO to CaO-Al2O3 slags was seen to minimize or eliminate the effect of humidity on the solidification of CaO-Al2O3 based slags. In this work, Uhlmann's method was used to estimate the solid-liquid interfacial energy of CaO-Al2O3 based slag for the temperature between 1100--1250°C. The result is between 0.25--0.4 Joules/m 2.

High-Intensity Ultrasound to Improve Physical and Functional Properties of Lipids.

PubMed

Wagh, Ashwini; Birkin, Peter; Martini, Silvana

2016-01-01

High-intensity ultrasound (HIU) has been used in recent years to change the crystallization behavior of edible lipids. This technique can be used in combination with other processing technologies to tailor lipids' functional properties and broaden their application for various food products. In general, sonication induces crystallization, increases crystallization rate, and generates a harder and more elastic crystalline network characterized by smaller crystals with a sharper melting profile. An important application of HIU is to improve the hardness and elasticity of shortenings that have a low content of saturated fatty acids and are free of trans-fats. This review summarizes recent research that used HIU to change the physical and functional properties of edible lipids and focuses on the importance of controlling processing variables such as sonication power level and duration and crystallization temperature.

Nanostructure and elastic modulus of single trabecula in bovine cancellous bone.

PubMed

Yamada, Satoshi; Tadano, Shigeru; Fukuda, Sakurako

2014-11-07

We aimed to investigate the elastic modulus of trabeculae using tensile tests and assess the effects of nanostructure at the hydroxyapatite (HAp) crystal scale on the elastic modulus. In the experiments, 18 trabeculae that were at least 3mm in length in the proximal epiphysis of three adult bovine femurs were used. Tensile tests were conducted using a small tensile testing device coupled with microscopy under air-dried condition. The c-axis orientation of HAp crystals and the degree of orientation were measured by X-ray diffraction. To observe the deformation behavior of HAp crystals under tensile loading, the same tensile tests were conducted in X-ray diffraction measurements. The mineral content of specimens was evaluated using energy dispersive X-ray spectrometry. The elastic modulus of a single trabecula varied from 4.5 to 23.6 GPa, and the average was 11.5 ± 5.0 GPa. The c-axis of HAp crystals was aligned with the trabecular axis and the crystals were lineally deformed under tensile loading. The ratio of the HAp crystal strain to the tissue strain (strain ratio) had a significant correlation with the elastic modulus (r=0.79; P<0.001). However, the mineral content and the degree of orientation did not vary widely and did not correlate with the elastic modulus in this study. It suggests that the strain ratio may represent the nanostructure of a single trabecula and would determine the elastic modulus as well as mineral content and orientation. Copyright © 2014 Elsevier Ltd. All rights reserved.

Crystallization mechanisms in cream during ripening and initial butter churning.

PubMed

Buldo, Patrizia; Kirkensgaard, Jacob J K; Wiking, Lars

2013-01-01

The temperature treatment of cream is the time-consuming step in butter production. A better understanding of the mechanisms leading to partial coalescence, such as fat crystallization during ripening and churning of the cream, will contribute to optimization of the production process. In this study, ripening and churning of cream were performed in a rheometer cell and the mechanisms of cream crystallization during churning of the cream, including the effect of ripening time, were investigated to understand how churning time and partial coalescence are affected. Crystallization mechanisms were studied as function of time by differential scanning calorimetry, nuclear magnetic resonance and by X-ray scattering. Microstructure formation was investigated by small deformation rheology and static light scattering. The study demonstrated that viscosity measurements can be used to detect phase inversion of the emulsion during churning of the cream in a rheometer cell. Longer ripening time (e.g., 5h vs. 0 h) resulted in larger butter grains (91 vs. 52 µm), higher viscosity (5.3 vs. 1.3 Pa · s), and solid fat content (41 vs. 13%). Both ripening and churning time had an effect on the thermal behavior of the cream. Despite the increase in solid fat content, no further changes in crystal polymorphism and in melting behavior were observed after 1h of ripening and after churning. The churning time significantly decreased after 0.5h of ripening, from 22.9 min for the cream where no ripening was applied to 16.23 min. Therefore, the crystallization state that promotes partial coalescence (i.e., aggregation of butter grains) is obtained within the first hour of cream ripening at 10 °C. The present study adds knowledge on the fundamental processes of crystallization and polymorphism of milk fat occurring during ripening and churning of cream. In addition, the dairy industry will benefit from these insights on the optimization of butter manufacturing. Copyright © 2013 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Preparation and properties of recycled HDPE/clay hybrids

Treesearch

Yong Lei; Qinglin Wu; Craig M. Clemons

2007-01-01

Hybrids based on recycled high density polyethylene (RHDPE) and organic clay were made by melt compounding. The influence of blending method, compatibilizers, and clay content on clay intercalation and exfoliation, RHDPE crystallization behavior, and the mechanical properties of RHDPE/clay hybrids were investigated. Both maleated polyethylene (MAPE) and titanate could...

Composition and Elution Behavior of Various Elements from Printed Circuit Boards, Cathode-ray Tube Glass, and Liquid-crystal Displays in Waste Consumer Electronics.

PubMed

Inaba, Kazuho; Murata, Tomoyoshi; Yamamura, Shigeki; Nagano, Masaaki; Iwasaki, Kazuhiro; Nakajima, Daisuke; Takigami, Hidetaka

2018-01-01

The contents and elution behavior of metals in consumer electronics parts were determined so as to understand their maximum environmental risk. Elements contained most in printed-circuit boards were Cu, Si, Br, Ca, Al, Sn, Pb, Sb, Ba, Fe, Ni, Ti, and Zn; in cathode-ray tube glass were Si, Pb, Ba, Sr, Zn, Zr, Ca, and Sb; in arsenic contained liquid-crystal displays were Si, Ca, Sr, Ba, As, and Fe; and in antimony contained liquid-crystal displays were Si, Ba, Ca, Sb, Sr, Fe, and Sn. The elements eluted most from printed-circuit boards were Zn, Pb, and Cu; from cathode-ray tube glass were Pb, Zn, B, Ba, and Si; and from liquid-crystal displays were B and Si, and the toxic As and Sb. The amount eluted was greatest at acidic pH. It was revealed that officially recommended 6-h-shaking with a pure water test was insufficient to understand the real environmental risk of waste electronics.

Characterization and modeling of mechanical behavior of single crystal titanium deformed by split-Hopkinson pressure bar

DOE PAGES

Morrow, B. M.; Lebensohn, R. A.; Trujillo, C. P.; ...

2016-03-28

Single crystal titanium samples were dynamically loaded using split-Hopkinson pressure bar (SHPB) and the resulting microstructures were examined. Characterization of the twins and dislocations present in the microstructure was conducted to understand the pathway for observed mechanical behavior. Electron backscatter diffraction (EBSD) was used to measure textures and quantify twinning. Microstructures were profusely twinned after loading, and twin variants and corresponding textures were different as a function of initial orientation. Focused ion beam (FIB) foils were created to analyze dislocation content using transmission electron microscopy (TEM). Large amounts of dislocations were present, indicating that plasticity was achieved through slip andmore » twinning together. Viscoplastic self-consistent (VPSC) modeling was used to confirm the complex order of operations during deformation. The activation of different mechanisms was highly dependent upon crystal orientation. For [0001] and View the MathML source[101¯1]-oriented crystals, compressive twinning was observed, followed by secondary tensile twinning. Furthermore, dislocations though prevalent in the microstructure, contributed to final texture far less than twinning.« less

Magmatic water contents determined through clinopyroxene: Examples from the Western Canary Islands, Spain

NASA Astrophysics Data System (ADS)

Weis, Franz A.; Skogby, Henrik; Troll, Valentin R.; Deegan, Frances M.; Dahren, Börje

2015-07-01

Water is a key parameter in magma genesis, magma evolution, and resulting eruption styles, because it controls the density, the viscosity, as well as the melting and crystallization behavior of a melt. The parental water content of a magma is usually measured through melt inclusions in minerals such as olivine, a method which may be hampered, however, by the lack of melt inclusions suitable for analysis, or postentrapment changes in their water content. An alternative way to reconstruct the water content of a magma is to use nominally anhydrous minerals (NAMs), such as pyroxene, which take up low concentrations of hydrogen as a function of the magma's water content. During magma degassing and eruption, however, NAMs may dehydrate. We therefore tested a method to reconstruct the water contents of dehydrated clinopyroxene phenocrysts from the Western Canary islands (n = 28) through rehydration experiments followed by infrared and Mössbauer spectroscopy. Employing currently available crystal/melt partitioning data, the results of the experiments were used to calculate parental water contents of 0.71 ± 0.07 to 1.49 ± 0.15 wt % H2O for Western Canary magmas during clinopyroxene crystallization at upper mantle conditions. This H2O range is in agreement with calculated water contents using plagioclase-liquid-hygrometry, and with previously published data for mafic lavas from the Canary Islands and comparable ocean island systems elsewhere. Utilizing NAMs in combination with hydrogen treatment can therefore serve as a proxy for pre-eruptive H2O contents, which we anticipate becoming a useful method applicable to mafic rocks where pyroxene is the main phenocryst phase.

Crystallization Behavior and Heat Transfer of Fluorine-Free Mold Fluxes with Different Na2O Concentration

NASA Astrophysics Data System (ADS)

Yang, Jian; Zhang, Jianqiang; Sasaki, Yasushi; Ostrovski, Oleg; Zhang, Chen; Cai, Dexiang; Kashiwaya, Yoshiaki

2016-08-01

In this study, the crystallization behavior and heat transfer of CaO-SiO2-Na2O-B2O3-TiO2-Al2O3-MgO-Li2O fluorine-free mold fluxes with different Na2O contents (5 to 11 mass pct) were studied using single/double hot thermocouple technique (SHTT/DHTT) and infrared emitter technique (IET), respectively. Continuous cooling transformation (CCT) and time-temperature transformation (TTT) diagrams constructed using SHTT showed that crystallization temperature increased and incubation time shortened with the increase of Na2O concentration, indicating an enhanced crystallization tendency. The crystallization process of mold fluxes in the temperature field simulating the casting condition was also investigated using DHTT. X-ray diffraction (XRD) analysis of the quenched mold fluxes showed that the dominant phase changed from CaSiO3 to Ca11Si4B2O22 with the increasing concentration of Na2O. The heat transfer examined by IET showed that the increase of Na2O concentration reduced the responding heat flux when Na2O was lower than 9 mass pct but the further increase of Na2O to 11 mass pct enhanced the heat flux. The correlation between crystallinity and heat transfer was discussed in terms of crystallization tendency and crystal morphology.

Beating the Heat - Fast Scanning Melts Silk Beta Sheet Crystals

NASA Astrophysics Data System (ADS)

Cebe, Peggy; Hu, Xiao; Kaplan, David L.; Zhuravlev, Evgeny; Wurm, Andreas; Arbeiter, Daniela; Schick, Christoph

2013-01-01

Beta-pleated-sheet crystals are among the most stable of protein secondary structures, and are responsible for the remarkable physical properties of many fibrous proteins, such as silk, or proteins forming plaques as in Alzheimer's disease. Previous thinking, and the accepted paradigm, was that beta-pleated-sheet crystals in the dry solid state were so stable they would not melt upon input of heat energy alone. Here we overturn that assumption and demonstrate that beta-pleated-sheet crystals melt directly from the solid state to become random coils, helices, and turns. We use fast scanning chip calorimetry at 2,000 K/s and report the first reversible thermal melting of protein beta-pleated-sheet crystals, exemplified by silk fibroin. The similarity between thermal melting behavior of lamellar crystals of synthetic polymers and beta-pleated-sheet crystals is confirmed. Significance for controlling beta-pleated-sheet content during thermal processing of biomaterials, as well as towards disease therapies, is envisioned based on these new findings.

Isothermal Crystallization Kinetics of Palm Oil as Influenced by Addition of a Commercial Phytosterol Ester Mixture.

PubMed

Daels, Eva; Goderis, Bart; Matton, Valerie; Foubert, Imogen

2018-04-18

In literature there is good agreement on the health-promoting effects of phytosterols. However, addition of phytosterol esters (PEs) to lipid (containing food products) may influence its crystallization behavior. This study investigated the crystallization kinetics of palm oil (PO) after addition of PEs in high concentrations (≥10%). The isothermal crystallization of the PE-PO blends was analyzed at a temperature of 20 °C and at a supercooling of 18.7 °C using differential scanning calorimetry and time-resolved synchrotron X-ray diffraction. At increasing PE concentrations, PO crystallization at an isothermal temperature of 20 °C started later and was slower and a smaller amount of crystals were formed. Furthermore, a delay in polymorphic transition from α to β' was observed. When the blends were isothermally crystallized at a supercooling of 18.7 °C, only two of these effects remained: the delay in polymorphic transition and the decrease in crystalline content.

Miscibility, Crystallization, and Rheological Behavior of Solution Casting Poly(3-hydroxybutyrate)/poly(ethylene succinate) Blends Probed by Differential Scanning Calorimetry, Rheology, and Optical Microscope Techniques

NASA Astrophysics Data System (ADS)

Sun, Wei-hua; Qiao, Xiao-ping; Cao, Qi-kun; Liu, Jie-ping

2010-02-01

The miscibility and crystallization of solution casting biodegradable poly(3-hydroxybutyrate)/poly(ethylene succinate) (PHB/PES) blends was investigated by differential scanning calorimetry, rheology, and optical microscopy. The blends showed two glass transition temperatures and a depression of melting temperature of PHB with compositions in phase diagram, which indicated that the blend was partially miscible. The morphology observation supported this result. It was found that the PHB and PES can crystallize simultaneously or upon stepwise depending on the crystallization temperatures and compositions. The spherulite growth rate of PHB increased with increasing of PES content. The influence of compositions on the spherulitic growth rate for the partially miscible polymer blends was discussed.

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

Xu, J.; Chen, T; Yang, C

Low-dimensional nanoparticles have a strong ability to induce the crystallization of polymer matrices. One-dimensional carbon nanotubes (CNTs) and two-dimensional graphene nanosheets (GNSs), both of which are both carbon-based nanoparticles, provide a good opportunity to investigate the effects of differently dimensional nanoparticles on the crystallization behavior of a polymer. For this purpose, respective nanocomposites of CNTs and GNSs with poly(L-lactide) (PLLA) as matrix were prepared by solution coagulation. Time-resolved Fourier-transform infrared spectroscopy (FTIR) and synchrotron wide-angle X-ray diffraction (WAXD) were performed to probe chain conformational changes and to determine the crystallization kinetics during the isothermal crystallization of the PLLA nanocomposites andmore » neat PLLA, especially in the early stages. Both CNTs and GNSs could serve as nucleating agents in accelerating the crystallization kinetics of PLLA; however, the ability of CNTs to induce crystallization was stronger than that of GNSs. On increasing the content of CNTs from 0.05 to 0.1 wt %, the induction period was shortened and the crystallization rate was enhanced, but the reverse situation was found for GNSs nanocomposites. In the case of neat PLLA, -CH{sub 3} interchain interactions preceded -(COC + CH{sub 3}) interchain interactions during the crystallization. Conversely, in the CNTs and GNSs nanocomposites, the conformational ordering began with -(COC + CH{sub 3}) interchain interactions, which resulted directly in a reduced induction period. Interchain interactions of this type could be explained in terms of surface-induced conformational order (SICO). Finally, the effect of the dimensionality of the nanoparticles on the crystallization behavior of PLLA is discussed.« less

Relationships between molecular structure and kinetic and thermodynamic controls in lipid systems. Part III. Crystallization and phase behavior of 1-palmitoyl-2,3-stearoyl-sn-glycerol (PSS) and tristearoylglycerol (SSS) binary system.

PubMed

Bouzidi, Laziz; Narine, Suresh S

2012-01-01

The phase behavior of 1-palmitoyl-2,3-distearoyl-sn-glycerol (PSS)/tristearoylglycerol (SSS) binary system was investigated in terms of polymorphism, crystallization and melting behavior, microstructure and solid fat content (SFC) using widely different constant cooling rates. Kinetic phase diagrams were experimentally determined from the DSC heating thermograms and analyzed using a thermodynamic model to account for non-ideality of mixing. The kinetic phase diagram presented a typical eutectic behavior with a eutectic point at the 0.5(PSS) mixture with a probable precipitation line from 0.5(PSS) to 1.0(PSS), regardless of the rate at which the sample was cooled. The eutectic temperature decreased only slightly with increasing cooling rate. PSS has a strong effect on the physical properties of the PSS-SSS mixtures. In fact, the overall phase behavior of the PSS-SSS binary system was determined, for a very large part, by the asymmetrical TAG. Moreover, PSS is a key driver of the high stability observed in crystal growth, polymorphism and phase development. Levels as low as 10% PSS, when cooled slowly, and 30% when cooled rapidly, were found to be sufficient to suppress the effect of thermal processing. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

Rheology and thermal budget of lunar basalts: an experimental study and its implications for rille formation of non-Newtonian lavas on the Moon

NASA Astrophysics Data System (ADS)

Sehlke, A.; Whittington, A. G.

2015-12-01

Sinuous lava channels are a characteristic feature observed on the Moon. Their formation is assumed to be due to a combination of mechanical and thermal erosion of the lava into the substrate during emplacement as surface channels, or due to collapsed subsurface lava tubes after the lava has evacuated. The viscosity (η) of the lava plays an important role, because it controls the volume flux of the emplaced lava that governs the mechanical and thermal erosion potential of the lava flow. Thermal properties, such as heat capacity (Cp) and latent heat of crystallization (ΔHcryst) are important parameters in order for the substrate to melt and causing thermal buffering during crystallization of the flowing lava. We experimentally studied the rheological evolution of analog lavas representing the KREEP terrain and high-Ti mare basalts during cooling and crystallization. We find that the two lavas behave very differently. High-Ti mare lava begins to crystallize around 1300 ºC with a viscosity of 8.6±0.6 Pa s and crystal content around 2 vol%. On cooling to 1169 ºC, the effective viscosity of the crystal-melt suspension is increased to only 538±33 Pa s (at a strain rate of 1 s-1) due to crystallization of 14±1 vol% blocky magnetite and acicular ulvöspinel-rich magnetite. The flow behavior of these suspensions depends on the strain rate, where flow curves below strain rates of 10 s-1show shear-thinning character, but resemble Bingham behavior at greater strain rates. In contrast, the KREEP lava crystallizes rapidly over a narrow temperature interval of ~ 30 degrees. The first crystals detected were ulvospinel-rich magnetites at 1204 ºC with ~2 vol% and a viscosity of 90±2 Pa s. On cooling to 1178 ºC, anorthite and enstatite appears, so that the crystal-melt suspension has become strongly pseudoplastic at a crystal content of 22±2 vol% with a flow index (n) of 0.63 and an effective viscosity of 1600±222 Pa s at a strain rate of 1 s-1. We are currently measuring the heat capacity of crystal-bearing glasses (representing erodible solid substrate) and the heat released during lava crystallization at different cooling rates measured by differential scanning calorimetry (DSC). The rheological and thermal properties will then be integrated into thermo-mechanical models of rille formation in non-Newtonian lavas on the lunar surface.

Compositional segregation and electrical properties characterization of [001]- and [011]-oriented co-growth Pb(In1/2Nb1/2)O3-Pb(Mg1/3Nb2/3)O3-PbTiO3 single crystal

NASA Astrophysics Data System (ADS)

Song, Kexin; Li, Zhenrong; Guo, Haisheng; Xu, Zhuo; Fan, Shiji

2018-04-01

A Pb(In1/2Nb1/2)O3-Pb(Mg1/3Nb2/3)O3-PbTiO3 relaxor ferroelectric single crystal boule of 3 in. diameter was grown using [001]- and [011]-oriented co-growth crystals as seeds by the modified Bridgman method. The as-grown crystal boule was divided into two growth regions [001] and [011]. The composition and the electrical properties of samples of the two regions were characterized in detail along the growth direction in the whole crystal boule. The PT content of [001]-grown samples increased from 27.7 to 36.8 mol. % along the growth direction, especially they are averagely higher about 0.7 mol. % than those of [011]-grown samples at the same growth position. The PMN content of [001]-grown samples decreased from 43.0 to 34.8 mol. %, which is lower than that of the corresponding [011]-grown samples. The compositional segregation behavior along [001] and [011] growth directions was discussed based on the crystal growth theories. Variations in the rhombohedral to tetragonal phase transition temperature (TRT), the piezoelectric properties, the coercive electric field and the remnant polarization of [001] samples were discussed according to changes in compositional segregation and crystal anisotropy. Under the exact same growth conditions, the [011]-grown crystal has a larger composition segregation effect than that of the [001]-grown crystal. This result provides a positive effect on analysing the nature and reducing the effect of compositional segregation.

Recent achievements on polyanion-type compounds for sodium-ion batteries: Syntheses, crystal chemistry and electrochemical performance

NASA Astrophysics Data System (ADS)

Guo, Sheng-Ping; Li, Jia-Chuang; Xu, Qian-Ting; Ma, Ze; Xue, Huai-Guo

2017-09-01

In the past several years, many efforts have been made to develop polyanion-type cathode materials for sodium ion batteries by chemists and material scientists. These materials are one of the main types of promising cathodes though the studies are still in their infancy. This paper reviews almost all the important advances of polyanion-type cathodes on their syntheses, crystal structures, morphologies, electrochemical performance and Na redox mechanisms. It specifically focuses on their crystal chemistry and electrochemical behaviors. The contents are divided into several categories according to their chemical compositions. After introduction of the synthetic methods, phosphates (ortho-, pyro- and fluoro-), silicates, sulfates, and mixed anions type cathodes are summarized and discussed successively.

Al and Mg Alloys for Aerospace Applications Using Rapid Solidification and Powder Metallurgy Processing.

DTIC Science & Technology

1986-11-14

5wt % Si was completely different from that of the alloy without silicon. The (X phase formed around the primary Mg2 Si crystals, and an irregular...content, and primary crystals in a binary Mg- 5wt % Si alloy did not exhibit this behavior. The surface of the rapidly solidified melt pools was rough and...Microhardness* of the laser treated alloys . Alloy As-cast Laser treated Mg- 5wt %Li 40.8 55.7 o, Mg- 5wt %Li- 5wt % Si 51.1 74.1 Mg-8wt%Li 42.8 71.2

The iron-nickel-phosphorus system: Effects on the distribution of trace elements during the evolution of iron meteorites

NASA Astrophysics Data System (ADS)

Corrigan, Catherine M.; Chabot, Nancy L.; McCoy, Timothy J.; McDonough, William F.; Watson, Heather C.; Saslow, Sarah A.; Ash, Richard D.

2009-05-01

To better understand the partitioning behavior of elements during the formation and evolution of iron meteorites, two sets of experiments were conducted at 1 atm in the Fe-Ni-P system. The first set examined the effect of P on solid metal/liquid metal partitioning behavior of 22 elements, while the other set explored the effect of the crystal structures of body-centered cubic (α)- and face-centered cubic (γ)-solid Fe alloys on partitioning behavior. Overall, the effect of P on the partition coefficients for the majority of the elements was minimal. As, Au, Ga, Ge, Ir, Os, Pt, Re, and Sb showed slightly increasing partition coefficients with increasing P-content of the metallic liquid. Co, Cu, Pd, and Sn showed constant partition coefficients. Rh, Ru, W, and Mo showed phosphorophile (P-loving) tendencies. Parameterization models were applied to solid metal/liquid metal results for 12 elements. As, Au, Pt, and Re failed to match previous parameterization models, requiring the determination of separate parameters for the Fe-Ni-S and Fe-Ni-P systems. Experiments with coexisting α and γ Fe alloy solids produced partitioning ratios close to unity, indicating that an α versus γ Fe alloy crystal structure has only a minor influence on the partitioning behaviors of the trace element studied. A simple relationship between an element's natural crystal structure and its α/γ partitioning ratio was not observed. If an iron meteorite crystallizes from a single metallic liquid that contains both S and P, the effect of P on the distribution of elements between the crystallizing solids and the residual liquid will be minor in comparison to the effect of S. This indicates that to a first order, fractional crystallization models of the Fe-Ni-S-P system that do not take into account P are appropriate for interpreting the evolution of iron meteorites if the effects of S are appropriately included in the effort.

Non-triglyceride components modulate the fat crystal network of palm kernel oil and coconut oil.

PubMed

Chai, Xiuhang; Meng, Zong; Jiang, Jiang; Cao, Peirang; Liang, Xinyu; Piatko, Michael; Campbell, Shawn; Lo, Seong Koon; Liu, Yuanfa

2018-03-01

PKO and CNO are composed of 97-98% triacylglycerols and 2-3% minor non-triglyceride components (FFA, DAG and MAG). Triglycerides were separated from minor components by chromatographic method. The lipid composition, thermal properties, polymorphism, isothermal crystallization behavior, nanostructure and microstructure of PKO, PKO-TAG, CNO and CNO-TAG were evaluated. Removal of minor components had no effect on lipid composition and equilibrium solid fat contents. However, presence of minor components did increase the slip melting point and promoted the onset of crystallization from DSC crystallization profiles. The thickness of the nanoscale crystals increased with no polymorphic transformation after removing the minor components. Crystallization kinetics revealed that minor components decreased crystal growth rate with higher t 1/2 . Sharp changes in the values of the Avrami constant k and exponent n were observed for all fats around 10°C. Increases in n around 10°C indicated a change from one-dimensional to multi-dimensional growth . From the results of polarized light micrographs, the transformation from the coarser crystal structure to tiny crystal structure occurred in microstructure networks at the action of minor components. Copyright © 2017 Elsevier Ltd. All rights reserved.

Understanding the rheology of two and three-phase magmas

NASA Astrophysics Data System (ADS)

Coats, R.; Cai, B.; Kendrick, J. E.; Wallace, P. A.; Hornby, A. J.; Miwa, T.; von Aulock, F. W.; Ashworth, J. D.; Godinho, J.; Atwood, R. C.; Lee, P. D.; Lavallée, Y.

2017-12-01

The rheology of magma plays a fundamental role in determining the style of a volcanic eruption, be it explosive or effusive. Understanding how magmas respond to changes in stress/ strain conditions may help to enhance eruption forecast models. The presence of crystals and bubbles in magmas alter the viscosity of suspensions and favor a non-Newtonian response. Thus, with the aim of grasping the rheological behavior of volcanic materials, uniaxial compressive tests were performed on natural and synthetic samples. A suite of variably porous (10-32 vol.%), highly crystalline ( 50 vol.%) dacite from the 1991-95 eruption of Mt Unzen, Japan, was selected as the natural material, while synthetic samples were sintered with desired porosities (<3, 20 and 30 vol.%) and TiO2 particles (0-50 vol.%). Tests were carried out at both room temperature and above the glass transition temperature (Tg) of the different materials to cover the entirety of the extrusion process. Room temperature tests were performed at constant strain rates of 10-1, 10-3, and 10-5 s-1. The response was brittle and peak stresses reached were positively correlated to strain rate and negatively correlated to porosity. At temperatures above Tg, strain rates of 10-3, 10-4, and 10-5 s-1 were imposed resulting in dominantly brittle, transitional and dominantly viscous responses, respectively. Samples with a brittle response reached higher peak stresses, and strain-to-failure values, at high temperature than at room temperature. In both materials, non-Newtonian, shear-thinning behavior was observed and while synthetic samples showed an expected increase in apparent viscosity with increasing crystal content, surprisingly natural samples did not show a correlation between apparent viscosity and porosity. We hypothesise this is due to crystal content being the governing factor for the volume fractions explored. In situ, high temperature synchrotron X-ray tomography was performed on selected crystal/pore volume fractions at Diamond Light Source. Unexpectedly, these observations suggest that fractures nucleate in crystals due to crystal interactions, before propagating through the interstitial melt. This ongoing study promises to uncover the way crystal-bearing magmas flow or fail, necessary to constrain magmatic processes and volcanic hazards.

Mutual interaction between high and low stereo-regularity components for crystallization and melting behaviors of polypropylene blend fibers

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

Kawai, Kouya; Takarada, Wataru; Kikutani, Takeshi, E-mail: kikutani.t.aa@m.titech.ac.jp

Crystallization and melting behaviors of blend fibers of two types of polypropylene (PP), i.e. high stereo-regularity/high molecular weight PP (HPP) and low stereo-regularity/low molecular weight PP (LPP), was investigated. Blend fibers consisting of various HPP/LPP compositions were prepared through the melt spinning process. Differential scanning calorimetry (DSC), temperature modulated DSC (TMDSC) and wide-angle X-ray diffraction (WAXD) analysis were applied for clarifying the crystallization and melting behaviors of individual components. In the DSC measurement of blend fibers with high LPP composition, continuous endothermic heat was detected between the melting peaks of LPP at around 40 °C and that of HPP atmore » around 160 °C. Such endothermic heat was more distinct for the blend fibers with higher LPP composition indicating that the melting of LPP in the heating process was hindered because of the presence of HPP crystals. On the other hand, heat of crystallization was detected at around 90 °C in the case of blend fibers with LPP content of 30 to 70 wt%, indicating that the crystallization of HPP component was taking place during the heating of as-spun blend fibers in the DSC measurement. Through the TMDSC analysis, re-organization of the crystalline structure through the simultaneous melting and re-crystallization was detected in the cases of HPP and blend fibers, whereas re-crystallization was not detected during the melting of LPP fibers. In the WAXD analysis during the heating of fibers, amount of a-form crystal was almost constant up to the melting in the case of single component HPP fibers, whereas there was a distinct increase of the intensity of crystalline reflections from around 100 °C, right after the melting of LPP in the case of blend fibers. These results suggested that the crystallization of HPP in the spinning process as well as during the conditioning process after spinning was hindered by the presence of LPP.« less

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

The influence of the concentration of Sr ions on the crystal and magnetic structures of Ba{sub 2} –{sub x}Sr{sub x}FeMoO{sub 6} double perovskites (x = 0–1.6)

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

Turchenko, V. A., E-mail: turchenko@jinr.ru; Kalanda, N. A.; Kovalev, L. V.

2017-01-15

The crystal and magnetic structures of a solid solution of double perovskite Ba{sub 2–} {sub x}Sr{sub x}FeMoO{sub 6} (x = 0–1.6) have been investigated by neutron diffraction. The high-resolution diffraction patterns have provided precise information about the changes in the crystal and magnetic structures with an increase in the strontium content and data on the behavior of the sample microstructure. Replacement of barium with strontium leads to a change in the lattice symmetry from cubic (x = 0, sp. gr. Fm3̄m)) to tetragonal (x = 0.4, sp. gr. I4/m). At x = 1.0, the symmetry is either tetragonal (sp. gr.more » I4/m) or orthorhombic (sp. gr. Fmmm), and at x = 1.6 the symmetry becomes again tetragonal (sp. gr. I4/m). The values of the Curie temperature and microstrain increase with an increase in the strontium content.« less

The rheology of crystal-rich magmas (Kuno Award Lecture)

NASA Astrophysics Data System (ADS)

Huber, Christian; Aldin Faroughi, Salah; Degruyter, Wim

2016-04-01

The rheology of magmas controls not only eruption dynamics but also the rate of transport of magmas through the crust and to a large extent the rate of magma differentiation and degassing. Magma bodies stalled in the upper crust are known to spend most of their lifespan above the solidus at a high crystal content (Cooper and Kent, 2014; Huber et al., 2009), where the probability of melt extraction (crystal fractionation) is the greatest (Dufek and Bachmann, 2010). In this study, we explore a new theoretical framework to study the viscosity of crystal bearing magmas. Since the seminal work of A. Einstein and W. Sutherland in the early 20th century, it has been shown theoretically and tested experimentally that a simple self-similar behavior exist between the relative viscosity of dilute (low crystal content) suspensions and the particle volume fraction. The self-similar nature of that relationship is quickly lost as we consider crystal fractions beyond a few volume percent. We propose that the relative viscosity of crystal-bearing magmas can be fully described by two state variables, the intrinsic viscosity and the crowding factor (a measure of the packing threshold in the suspension). These two state variables can be measured experimentally under different conditions, which allows us to develop closure relationships in terms of the applied shear stress and the crystal shape and size distributions. We build these closure equations from the extensive literature on the rheology of synthetic suspensions, where the nature of the particle shape and size distributions is better constrained and apply the newly developed model to published experiments on crystal-bearing magmas. We find that we recover a self-similar behavior (unique rheology curve) up to the packing threshold and show that the commonly reported break in slope between the relative viscosity and crystal volume fraction around the expected packing threshold is most likely caused by a sudden change in the state of dispersion of the magma (change in the state variables caused by either shear localization or crystal breakage). We argue that the model we propose is a first step to go beyond fitting experimental data and towards building a predictive rheology model for crystal-bearing magmas. Cooper, K.M., and Kent, A.J.R. (2014) Rapid remobilization of magmatic crystals kept in cold storage. Nature, 506(7489), 480-483. Dufek, J., and Bachmann, O. (2010) Quantum magmatism: Magmatic compositional gaps generated by melt-crystal dynamics. Geology, 38(8), 687-690. Huber, C., Bachmann, O., and Manga, M. (2009) Homogenization processes in silicic magma chambers by stirring and mushification (latent heat buffering). Earth and Planetary Science Letters, 283(1-4), 38-47.

Formation of silicon nanocrystals in silicon carbide using flash lamp annealing

NASA Astrophysics Data System (ADS)

Weiss, Charlotte; Schnabel, Manuel; Prucnal, Slawomir; Hofmann, Johannes; Reichert, Andreas; Fehrenbach, Tobias; Skorupa, Wolfgang; Janz, Stefan

2016-09-01

During the formation of Si nanocrystals (Si NC) in SixC1-x layers via solid-phase crystallization, the unintended formation of nanocrystalline SiC reduces the minority carrier lifetime and therefore the performance of SixC1-x as an absorber layer in solar cells. A significant reduction in the annealing time may suppress the crystallization of the SiC matrix while maintaining the formation of Si NC. In this study, we investigated the crystallization of stoichiometric SiC and Si-rich SiC using conventional rapid thermal annealing (RTA) and nonequilibrium millisecond range flash lamp annealing (FLA). The investigated SixC1-x films were prepared by plasma-enhanced chemical vapor deposition and annealed at temperatures from 700 °C to 1100 °C for RTA and at flash energies between 34 J/cm2 and 62 J/cm2 for FLA. Grazing incidence X-ray diffraction and Fourier transformed infrared spectroscopy were conducted to investigate hydrogen effusion, Si and SiC NC growth, and SiC crystallinity. Both the Si content and the choice of the annealing process affect the crystallization behavior. It is shown that under certain conditions, FLA can be successfully utilized for the formation of Si NC in a SiC matrix, which closely resembles Si NC in a SiC matrix achieved by RTA. The samples must have excess Si, and the flash energy should not exceed 40 J/cm2 and 47 J/cm2 for Si0.63C0.37 and Si0.77C0.23 samples, respectively. Under these conditions, FLA succeeds in producing Si NC of a given size in less crystalline SiC than RTA does. This result is discussed in terms of nucleation and crystal growth using classical crystallization theory. For FLA and RTA samples, an opposite relationship between NC size and Si content was observed and attributed either to the dependence of H effusion on Si content or to the optical absorption properties of the materials, which also depend on the Si content.

Apatite-Melt Partitioning of Volatiles in Basaltic Systems: Implications for Determining Volatile Abundances in Planetary Bodies from Apatite

NASA Technical Reports Server (NTRS)

McCubbin, F. M.

2017-01-01

Apatite [Ca5(PO4)3(F,Cl,OH)] is present in a wide range of planetary materials, and 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 [i.e., 1]. Experimental studies have investigated the apatite-melt partitioning behavior of F, Cl, and OH in basaltic systems [e.g., 2- 3], reporting that apatite-melt partitioning of volatiles is best described as exchange equilibria similar to Fe-Mg partitioning between olivine and silicate melt. However, exchange coefficients may vary as a function of temperature, pressure, melt composition, and/or oxygen fugacity. Furthermore, exchange coefficients may vary in portions of apatite compositional space where F, Cl, and OH do not mix ideally in apatite [3]. In these regions of ternary space, we anticipate that crystal chemistry could influence partitioning behavior. Consequently, we conducted experiments to investigate the effect of apatite crystal chemistry on apatite-melt partitioning of F, Cl, and OH.

Crystal structure, Raman scattering and magnetic properties of CuCr2-xZrxSe4 and CuCr2-xSnxSe4 selenospinels

NASA Astrophysics Data System (ADS)

Pinto, C.; Galdámez, A.; Barahona, P.; Moris, S.; Peña, O.

2018-06-01

Selenospinels, CuCr2-xMxSe4 (M = Zr and Sn), were synthesized via conventional solid-state reactions. The crystal structure of CuCr1.5Sn0.5Se4, CuCr1.7Sn0.3Se4, CuCr1.5Zr0.5Se4, and CuCr1.8Zr0.2Se4 were determined using single-crystal X-ray diffraction. All the phases crystallized in a cubic spinel-type structure. The chemical compositions of the single-crystals were examined using energy-dispersive X-ray analysis (EDS). Powder X-ray diffraction patterns of CuCr1.3Sn0.7Se4 and CuCr1.7Sn0.3Se4 were consistent with phases belonging to the Fd 3 bar m Space group. An analysis of the vibrational properties on the single-crystals was performed using Raman scattering measurements. The magnetic properties showed a spin glass behavior with increasing Sn content and ferromagnetic order for CuCr1.7Sn0.3Se4.

Influence of NiO on the crystallization kinetics of near stoichiometric cordierite glasses nucleated with TiO2

NASA Astrophysics Data System (ADS)

Goel, Ashutosh; Shaaban, Essam R.; Ribeiro, Manuel J.; Melo, Francisco C. L.; Ferreira, José M. F.

2007-09-01

This work presents the effect of NiO on the thermal behavior and the crystallization kinetics of glasses lying near the stoichiometric cordierite composition nucleated with TiO2. Three glasses with NiO content varying between 1 and 5 mol% have been synthesized in Pt crucibles. Activation energies for structural relaxation and viscous flow have been calculated using the data obtained from differential thermal analysis (DTA). Kinetic fragility of the glasses along with other thermal parameters has been calculated. Non-isothermal crystallization kinetic studies have been employed to study the mechanism of crystallization in all three glasses. The crystallization sequence in the glasses has been followed by x-ray diffraction analysis of the heat treated glass samples in the temperature range of 800-1200 °C. μ-cordierite has been observed to be the first crystalline phase in all the glass samples after heat treatment at 850 °C, while NiO plays an important role in determining the crystallization sequence at higher temperatures, leading to the formation of α-cordierite.

Quartz crystal microbalance with coupled spectroscopic ellipsometry-study of temperature-responsive polymer brush systems

NASA Astrophysics Data System (ADS)

Adam, Stefan; Koenig, Meike; Rodenhausen, Keith Brian; Eichhorn, Klaus-Jochen; Oertel, Ulrich; Schubert, Mathias; Stamm, Manfred; Uhlmann, Petra

2017-11-01

Using a combined setup of quartz crystal microbalance with dissipation monitoring together with spectroscopic ellipsometry, the thermo-responsive behavior of two different brush systems (poly(N-isopropyl acrylamide) and poly(2-oxazoline)s) was investigated and compared to the behavior of the free polymer in solution. Poly(2-oxazoline)s with three different hydrophilicities were prepared by changing the content of a hydrophilic comonomer. While both polymer types exhibit a sharp, discontinuous thermal transition in solution, in the brush state the transition gets broader in the case of poly(N-isopropyl acrylamide) and is transformed into a continuous transition for poly(2-oxazoline)s. The position of the transition in solution is influenced by the degree of hydrophilicity of the poly(2-oxazoline). The difference in areal mass detected by quartz crystal microbalance and by spectroscopic ellipsometry, has been attributed to the chain segment density profile of the polymer brushes. Applying this density profile information, for poly(N-isopropyl acrylamide) two different swelling stages could be identified, while for poly(2-oxazoline) the transition between a parabolic and more step-wise profile is found continuous. The different swelling characteristics were attributed to the different miscibility behavior types, with the brush state acting similar to a crosslinked system.

Electrodeposited Ni-Co films from electrolytes with different Co contents

NASA Astrophysics Data System (ADS)

Karpuz, Ali; Kockar, Hakan; Alper, Mursel; Karaagac, Oznur; Haciismailoglu, Murside

2012-02-01

The properties of electrodeposited Ni-Co films produced from electrolyte consisted of nickel sulfamate, cobalt sulfate and boric acid were investigated as a function of Co content in the films. The compositional analysis performed by an energy dispersive X-ray spectroscopy demonstrated that the Co content of the films increases as the cobalt sulfate concentration in the electrolyte increases. The anomalous codeposition behavior was observed for all concentrations. The crystal structure was analyzed using an X-ray diffraction technique. The face centered cubic (fcc) structure was observed in the films containing from 0 at.% Co to 58 at.% Co. For the higher atomic Co contents (64 at.% and 80 at.%), a mixed phase of dominantly fcc and hexagonal closed packed (hcp) structure was observed although the (10.0) and (10.1) hcp peaks had minor intensities in the patterns. Surface micrographs obtained from a scanning electron microscope revealed that the film surface has a rougher appearance as the Co content increases. Magnetic measurements showed that the saturation magnetization gradually increased with increasing Co content of the films. The coercivity, Hc can be controlled by the structural parameters such as average grain size and crystal structure. The results also indicated that the optimum film composition was 28-40 at.% Co since the lower Hc and higher magnetoresistance (MR) values with very smooth or slightly granular surfaces were achieved at this Co content. It is revealed that Co content has an important effect on structural, magnetic and MR properties of the Ni-Co films.

Complex magnetic differentiation of cobalts in Na x CoO2 with 22 K Néel temperature

NASA Astrophysics Data System (ADS)

Mukhamedshin, I. R.; Gilmutdinov, I. F.; Salosin, M. A.; Alloul, H.

2014-06-01

Single crystals of sodium cobaltates Na x CoO2 with x ≈ 0.8 were grown by the floating zone technique. Using electrochemical Na de-intercalation method we reduced the sodium content in the as-grown crystals down to pure phase with 22 K Néel temperature and x ≈ 0.77. The 59Co NMR study in the paramagnetic state of the T N = 22 K phase permitted us to evidence that at least 6 Co sites are differentiated. They could be separated by their magnetic behavior into three types: a single site with cobalt close to non-magnetic Co3+, two sites with the most magnetic cobalts in the system, and the remaining three sites displaying an intermediate behavior. This unusual magnetic differentiation calls for more detailed NMR experiments on our well characterized samples.

Time-dependent deformation of polymer network in polymer-stabilized cholesteric liquid crystals (Conference Presentation)

NASA Astrophysics Data System (ADS)

Lee, Kyung Min; Tondiglia, Vincent P.; Bunning, Timothy J.; White, Timothy J.

2017-02-01

Recently, we reported direct current (DC) field controllable electro-optic (EO) responses of negative dielectric anisotropy polymer stabilized cholesteric liquid crystals (PSCLCs). A potential mechanism is: Ions in the liquid crystal mixtures are trapped in/on the polymer network during the fast photopolymerization process, and the movement of ions by the application of the DC field distorts polymer network toward the negative electrode, inducing pitch variation through the cell thickness, i.e., pitch compression on the negative electrode side and pitch expansion on positive electrode side. As the DC voltage is directly applied to a target voltage, charged polymer network is deformed and the reflection band is tuned. Interestingly, the polymer network deforms further (red shift of reflection band) with time when constantly applied DC voltage, illustrating DC field induced time dependent deformation of polymer network (creep-like behavior). This time dependent reflection band changes in PSCLCs are investigated by varying the several factors, such as type and concentration of photoinitiators, liquid crystal monomer content, and curing condition (UV intensity and curing time). In addition, simple linear viscoelastic spring-dashpot models, such as 2-parameter Kelvin and 3-parameter linear models, are used to investigate the time-dependent viscoelastic behaviors of polymer networks in PSCLC.

The effect of porosity and gamma-gamma' eutectic content on the low cycle fatigue behavior of hydrogen-charged PWA-1480

NASA Technical Reports Server (NTRS)

Gayda, John; Dreshfield, Robert L.; Gabb, Timothy P.

1991-01-01

Single crystal superalloys such as PWA 1480 are considered for turbopump blades in the main engines of the space shuttle. As fatigue resistance in a hydrogen environment is a key issue in this application, a study of the effect of porosity and gamma-gamma' eutectic content on the fatigue life of a hydrogen-charged PWA 1480 was performed. Porosity and eutectic were linked to fatigue initiation, and therefore reduction of either of both may be one means to improve fatigue life of PWA 1480 when hydrogen is present.

Influence of dislocations and second phases on the magnetostrictive behavior of iron-gallium and other iron alloy single crystals

NASA Astrophysics Data System (ADS)

Saha, Biswadeep

Rare-earth-free Fe-Ga magnetostrictive alloys exhibit an excellent combination of large low-field magnetostriction, strength, ductility, wide operating temperature range, and low cost. Various observations in these and other alpha-Fe-based magnetostrictive alloys suggest that lattice strain modulations that are influenced by solute elements, near neighbor atomic environments around Fe atoms, coherent and incoherent precipitates, and structural defects such as dislocations likely play an important role in their magnetostrictive behavior. In the first part, the effect of dislocations on the magnetostriction of Fe-Ga single crystals was examined. The [001]- and [126]-oriented Fe-20 at.% Ga single crystal samples were deformed in a controlled way to introduce dislocation arrays with two different array geometries. Magnetostriction values showed a much lower decrease after deformation for the case of a [001]-oriented crystal, where eight different slip systems were operative and consequently eight different sets of dislocation arrays are expected. A drastic drop in magnetostriction measured along the sample axis is observed in the sample subjected to a small strain by deformation of a [126]-oriented crystal during which slip occurred on only one slip system. The nature of strain modulation introduced in this case was spatially asymmetric. The [126] deformation was accompanied by an acoustic emission during the formation of slip band. Transmission electron microscopy was carried out to examine the nature of dislocation distribution. The results show that the nature of strain modulation introduced by the dislocation arrays has a strong influence on the magnetostrictive behavior of magnetostrictive alloys. In the second part of this research, the effect of Mo addition to Fe was examined in detail. Addition of Mo to Fe increased the magnetostriction (3/2)lambda100 Fe very rapidly to 137 ppm at 10 at.% Mo, the highest value observed in these alloys. Further Mo additions decreased the magnetostriction. Magnetization data show a drastic drop in magnetization to 63 emu/gm for Fe-20 at.% Mo from 176 emu/gm for Fe-10 at.% Mo suggesting the formation large amounts of nonmagnetic second phase and reduction in total Fe content of the alloy. The drop in magnetostriction at higher Mo contents is associated with the formation of a second phase.

The competing effects of slip and twinning on the deformation of Hadfield manganese steel single and polycrystals

NASA Astrophysics Data System (ADS)

Karaman, Ibrahim

2000-10-01

Hadfield steel is well known for its high strain hardening. However, the mechanism of high strain hardening is still not completely understood. There is a striking paucity of single crystal studies that would allow a superior understanding of the fundamental deformation mechanisms by circumventing the complications associated with grain boundaries. With this need, the present study is aimed at studying Hadfield steel in single and polycrystalline forms. For this purpose, the stress-strain behavior of Hadfield steel (Fe, 12.3% Mn, 1.0 C, in wt.%) single crystals studied for selected orientations ([001], [1¯11], [1¯23], [1¯44] and [1¯5 10]), and for different interstitial contents under tension and compression in the temperature range of 113 K to 293 K. The effect of twinning, slip and stacking faults was revealed in terms of the critical stress levels, and the strain-hardening coefficients. Based on the experimental observations, a model is presented that predicts the orientation, stress direction and solid solution content effects on the critical stress for initiating twinning. Nitrogen was also added to Hadfield steel. Nitrogen was not only proven to be a more effective strengthening agent than carbon in Hadfield steel but also it served as a better trigger for twinning. Stress-strain responses of Hadfield steel were modeled using a viscoplastic self consistent approach. A unique hardening formulation was proposed in the constitutive model incorporating length scales associated with spacing between twin lamellae and grain boundaries. The responses of single crystals and polycrystals with different grain sizes were captured closely with the model. Based on simulations, it was possible to explain unequivocally the upward curvature in stress-strain curves of Hadfield steel. A similar study on the 316L stainless steel single crystals indicated that the addition of nitrogen lead austenitic stainless steel to exhibit deformation mechanisms, orientation and temperature dependence similar to Hadfield steel. Therefore, it is concluded that the mechanical behavior of fcc high strength materials, and the underlying mechanisms responsible for their behavior are universal, irrespective of the way in which the high strength levels are achieved.

Magnetic and magnetostrictive behavior of Dy 3+ doped CoFe 2O 4 single crystals grown by flux method

NASA Astrophysics Data System (ADS)

Kambale, Rahul C.; Song, K. M.; Won, C. J.; Lee, K. D.; Hur, N.

2012-02-01

We studied the effect of Dy 3+ content on the magnetic properties of cobalt ferrite single crystal. The single crystals of CoFe 1.9Dy 0.1O 4 were grown by the flux method using Na 2B 4O 7.10 H 2O (Borax) as a solvent (flux). The black and shiny single crystals were obtained as a product. The X-ray diffraction analysis at room temperature confirmed the spinel cubic structure with lattice constant a=8.42 Å of the single crystals. The compositional analysis endorses the presence of constituents Co, Fe and Dy elements after sintering at 1300 °C within the final structure. The magnetic hysteresis measurements at various temperatures viz. 10 K, 100 K, 200 K and 300 K reveal the soft ferrimagnetic nature of the single crystal than that of for pure CoFe 2O 4. The observed saturation magnetization ( Ms) and coercivity ( Hc) are found to be lower than that of pure CoFe 2O 4 single crystal. The magnetostriction ( λ) measurement was carried out along the [001] direction. The magnetic measurements lead to conclude that the present single crystals can be used for magneto-optic recording media.

Preparation of Desirable Porous Cell Structure Polylactide/Wood Flour Composite Foams Assisted by Chain Extender

PubMed Central

Wang, Youyong; Song, Yongming; Du, Jun; Xi, Zhenhao; Wang, Qingwen

2017-01-01

Polylactide (PLA)/wood flour composite foam were prepared through a batch foaming process. The effect of the chain extender on the crystallization behavior and dynamic rheological properties of the PLA/wood flour composites were investigated as well as the crystal structure and cell morphology of the composite foams. The incorporation of the chain extender enhanced the complex viscosity and storage modulus of PLA/wood flour composites, indicating the improved melt elasticity. The chain extender also led to a decreased crystallization rate and final crystallinity of PLA/wood flour composites. With an increasing chain extender content, a finer and more uniform cell structure was formed, and the expansion ratio of PLA/wood flour composite foams was much higher than without the chain extender. Compared to the unfoamed composites, the crystallinity of the foamed PLA/wood flour composites was improved and the crystal was loosely packed. However, the new crystalline form was not evident. PMID:28846604

Computer Modeling of Non-Isothermal Crystallization

NASA Technical Reports Server (NTRS)

Kelton, K. F.; Narayan, K. Lakshmi; Levine, L. E.; Cull, T. C.; Ray, C. S.

1996-01-01

A realistic computer model for simulating isothermal and non-isothermal phase transformations proceeding by homogeneous and heterogeneous nucleation and interface-limited growth is presented. A new treatment for particle size effects on the crystallization kinetics is developed and is incorporated into the numerical model. Time-dependent nucleation rates, size-dependent growth rates, and surface crystallization are also included. Model predictions are compared with experimental measurements of DSC/DTA peak parameters for the crystallization of lithium disilicate glass as a function of particle size, Pt doping levels, and water content. The quantitative agreement that is demonstrated indicates that the numerical model can be used to extract key kinetic data from easily obtained calorimetric data. The model can also be used to probe nucleation and growth behavior in regimes that are otherwise inaccessible. Based on a fit to data, an earlier prediction that the time-dependent nucleation rate in a DSC/DTA scan can rise above the steady-state value at a temperature higher than the peak in the steady-state rate is demonstrated.

Video-microscopy of NCAP films: the observation of LC droplets in real time

NASA Astrophysics Data System (ADS)

Reamey, Robert H.; Montoya, Wayne; Wong, Abraham

1992-06-01

We have used video-microscopy to observe the behavior of liquid crystal (LC) droplets within nematic droplet-polymer films (NCAP) as the droplets respond to an applied electric field. The textures observed at intermediate fields yielded information about the process of liquid crystal orientation dynamics within droplets. The nematic droplet-polymer films had low LC content (less than 1 percent) to allow the observation of individual droplets in a 2 - 6 micrometers size range. The aqueous emulsification technique was used to prepare the films as it allows the straightforward preparation of low LC content films with a controlled droplet size range. Standard electro-optical (E-O) tests were also performed on the films, allowing us to correlate single droplet behavior with that of the film as a whole. Hysteresis measured in E-O tests was visually confirmed by droplet orientation dynamics; a film which had high hysteresis in E-O tests exhibited distinctly different LC orientations within the droplet when ramped up in voltage than when ramped down in voltage. Ramping the applied voltage to well above saturation resulted in some droplets becoming `stuck'' in a new droplet structure which can be made to revert back to bipolar with high voltage pulses or with heat.

Ductility and fracture in B2 FeAl alloys. Ph.D. Thesis Final Report

NASA Technical Reports Server (NTRS)

Crimp, Martin A.

1987-01-01

The mechanical behavior of B2FeAl alloys was studied. Stoichiometric Fe-50Al exhibits totally brittle behavior while iron-rich Fe-40Al yields and displays about 3% total strain. This change in behavior results from large decreases in the yield strength with iron-rich deviations from stoichiometry while the fracture stress remains essentially constant. Single crystal studies show that these yield strength decreases are directly related to decreases in the critical resolved shear stress for a group of zone axes /111/ set of (110) planes slip. This behavior is rationalized in terms of the decrease in antiphase boundary energy with decreasing aluminum content. The addition of boron results in improvements in the mechanical behavior of alloys on the iron-rich side of stoichiometry. These improvements are increased brittle fracture stresses of near-stoichiometric alloys, and enhanced ductility of up to 6% in Fe-40Al. These effects were attributed to increased grain boundary adhesion as reflected by changes in fracture mode from intergranular to transgranular failure. The increases in yield strength, which are observed in both polycrystals and single crystals, result from the quenching in of large numbers of thermal vacancies. Hall-Petch plots show that the cooling rate effects are a direct result of changes in the Hall-Petch intercept/lattice resistance flow.

Investigations into the mechanical and physical behavior of thermoplastic elastomers

NASA Astrophysics Data System (ADS)

Wright, Kathryn Janelle

This thesis describes investigations into the physical and mechanical characteristics of two commercial thermoplastic elastomer (TPE) systems. Both systems studied exhibit elastomeric behavior similar to more traditional crosslinked elastomers; however, in these TPEs non-conventional polymer architectures and morphologies are used to produce their elastomeric behavior. The two TPEs of interest are ethylene-propylene random copolymers and dynamically vulcanized blends of ethylene-propylene-diene monomer (EPDM) and isotactic polypropylene (iPP). Very few studies have examined the mechanical behavior of these materials in terms of their composition and morphology. As such, the primary goal of this research is to both qualitatively and quantitatively understand the influence of composition and morphology on mechanical behavior. In additional very little information is available that compares their performance with that of crosslinked elastomers. As a result, the secondary goal is to qualitatively compare the mechanical responses of these TPEs with that of their more traditional counterparts. The ethylene-propylene copolymers studied have very high comonomer contents and exhibit slow crystallization kinetics. Their morphology consists of nanoscale crystallites embedded in an amorphous rubbery matrix. These crystallites act as physical crosslinks that allow for elasticity. Slow crystallization causes subsequent changes in mechanical behavior that take place over days and even weeks. Physical responses (e.g., density, crystallization kinetics, and crystal structure) of five copolymer compositions are investigated. Mechanical responses (e.g., stiffness, ductility, yielding, and reversibility) are also examined. Finally, the influence of morphology on deformation is studied using in situ analytical techniques. The EPDM/iPP blends are dynamically vulcanized which produces a complex morphology consisting of chemically crosslinked EPDM domains embedded within a semicrystalline iPP matrix. Six compositions are investigated as a function of three parameters: major volume fraction, iPP molecular weight, and EPDM cure state. The influence of these parameters on morphology and resulting mechanical behavior is examined. This work culminates in the development of a morphological model to describe the steady-state reversibility of these EPDM/iPP blends. The model is then evaluated in terms of composition and cure state.

Classification of the crystallization behavior of amorphous active pharmaceutical ingredients in aqueous environments.

PubMed

Van Eerdenbrugh, Bernard; Raina, Shweta; Hsieh, Yi-Ling; Augustijns, Patrick; Taylor, Lynne S

2014-04-01

To classify the crystallization behavior of amorphous active pharmaceutical ingredients (API) exposed to aqueous environments. A set of approximately 50 chemically and physically diverse active pharmaceutical ingredients (APIs) was selected for this study. Two experimental setups were employed to characterize the crystallization behavior of the amorphous API in an aqueous environment. For the first approach, precipitation, as evidenced by the development of turbidity, was induced using the solvent shift method, by mixing concentrated API solutions in DMSO with an aqueous buffer in a capillary. Subsequently, crystallization was monitored in situ over time using synchrotron radiation (simultaneous SAXS/WAXS beamline 12-ID-B at the Advanced Photon Source, Argonne National Laboratories, Argonne, IL). In the second approach, amorphous films were prepared by melt quenching; after adding buffer, crystallization was monitored with time using polarized light microscopy. In general, the crystallization behavior of a given compound was similar irrespective of the experimental method employed. However, the crystallization behavior among different compounds varied significantly, ranging from immediate and complete crystallization to no observable crystallization over biorelevant time scales. Comparison of the observed behavior with previous studies of crystallization tendency in non-aqueous environments revealed that the crystallization tendency of individual APIs was somewhat similar regardless of the crystallization environment. API properties, rather than the method by which amorphous materials are generated, tend to dictate crystallization behavior in aqueous media.

Measuring Solvent Content of Macromolecular Crystals Using Fluorescence Recovery after Photobleaching

NASA Astrophysics Data System (ADS)

Siewny, Matthew; Kmetko, Jan

2010-10-01

We work out a novel protocol for measuring the solvent content (the fraction of crystal volume occupied by solvent) in biological crystals by the technique of fluorescence recovery after photobleaching (FRAP). Crystals of proteins with widely varying known solvent content (lysozyme, thaumatin, catalase, and ferritin) were grown in their native solution doped with sodium fluorescein dye and hydroxylamine (to prevent dye from binding to amine groups of the proteins.) The crystals were irradiated by a broadband, high intensity light through knife slits, leaving a rectangular area of bleached dye within the crystals. Measuring the flow of dye out of the bleached area allowed us to construct a curve relating the diffusion coefficient of dye to the channel size within the crystals, by solving the diffusion equation analytically. This curve may be used to measure the solvent content of any biological crystal in its native solution and help determine the number of proteins in the crystallographic asymmetric unit cell in x-ray structure solving procedures.

Characteristics of nano-sized yttria powder synthesized by a polyvinyl alcohol solution route at low temperature.

PubMed

Lee, Sang-Jin; Jung, Choong-Hwan

2012-01-01

Nano-sized yttria (Y2O3) powders were successfully synthesized at a low temperature of 400 degrees C by a simple polymer solution route. PVA polymer, as an organic carrier, contributed to an atom-scale homogeneous precursor gel and it resulted in fully crystallized, nano-sized yttria powder with high specific surface area through the low temperature calcination. In this process, the content of PVA, calcination temperature and heating time affected the microstructure and crystallization behavior of the powders. The development of crystalline phase and the final particle size were strongly dependant on the oxidation reaction from the polymer burn-out step and the PVA content. In this paper, the PVA solution technique for the fabrication of nano-sized yttria powders is introduced. The effects of PVA content and holding time on the powder morphology and powder specific surface area are also studied. The characterization of the synthesized powders is examined by using XRD, DTA/TG, SEM, TEM and nitrogen gas adsorption. The yttria powder synthesized from the PVA content of 3:1 ratio and calcined at 400 degrees C had a crystallite size of about 20 nm or less with a high surface areas of 93.95-120.76 m2 g(-1).

The mode of emplacement of Neogene flood basalts in Eastern Iceland: The plagioclase ultraphyric basalts in the Grænavatn group

NASA Astrophysics Data System (ADS)

Óskarsson, Birgir V.; Andersen, Christina B.; Riishuus, Morten S.; Sørensen, Erik Vest; Tegner, Christian

2017-02-01

Plagioclase ultraphyric basalt lava with high fraction of solids have a mode of emplacement that is poorly understood. In this study we conduct detailed mapping of a PUB group in eastern Iceland, namely the Grænavatn group, and assess the group architecture, flow morphology and internal structure with additional constraints from petrography, petrology and crystal size distribution, to derive information on emplacement dynamics of plagioclase ultraphyric basalts. We also derive information on the plumbing system of the group with reference to the source of the macrocysts. The group is exposed in steep glacially carved fjords and can be traced for more than 70 km along strike. The flows have mixed architecture of simple and compound flows. Individual flow lobes have thicknesses in the range of 1-24 m and many reach widths and lengths exceeding 1000 m. The flows vary from rubbly to slabby pahoehoe, but are predominantly of pahoehoe type. The aspect ratio of the group and the nature of the flows indicate fissure-fed eruptions. The plagioclase macrocrysts (5-30 mm) are An-rich, exhibit bimodal size distribution and the modal proportions within the group varies from 15-40%. Clinopyroxene macrocrysts are also present ranging from 1-6%. The lowermost flow is thickest and carries the greatest crystal cargo load. The morphology of the lava flows suggests low viscous behavior, at odds with the high crystal content. The very calcic plagioclase macrocrysts (An80-85) are in disequilibrium with the groundmass and plagioclase microlaths therein (An50-70), meaning that the crystal-laden magmas quickly ascended from deeper crustal levels to the surface. The flows with highest crystal content may have maintained high temperatures by heat exchange with the primitive macrocrysts in the flows and developed non-Newtonian behavior such as shear thinning. Such conditions would have enabled the flows to advance rapidly during episodes with high effusion rates forming the simple flows, and subsequently maintained by insulated lobe-by-lobe emplacement. Occasionally surges disrupted the crust to form rubbly and slabby pahoehoe. A Herschel-Bulkley model is applied to the flows yielding effusion rates in the order of 103-104 m 3/s for the largest eruptions. Variation in crystal proportions within the group and individual flows is considered to be the result of magmas penetrating a crystal mush, followed by disaggregation and mobilization, sorting by flotation, mixing of magma batches and transportation of heterogeneous crystal-laden magmas to the surface with opportunities for staging en route.

Synergistic promotion of polar phase crystallization of PVDF by ionic liquid with PEG segment

NASA Astrophysics Data System (ADS)

Xu, Pei; Fu, Weijia; Cui, Zhaopei; Ding, Yunsheng

2018-06-01

To investigate the effect of imidazolium ionic liquid with poly(ethylene glycol) segment (IL) on the polar phase crystallization behavior of poly(vinylidene fluoride) (PVDF), a series of PVDF/IL composites were prepared using solution-cast method. The crystallization peak temperature of PVDF composites and the growth speed of samples decrease with increasing of IL. The >CF2 groups in amorphous region are retained and >CF2 groups in crystalline region are liberated by the PEG long soft segments of IL. The intensity of peaks represented as α phase reduces, moreover polar phase content increases with increasing of IL. The interaction between the >CF2 and the imidazolium cation can induce the polar phase, and the interaction between the >CF2 and PEG soft segment can strengthen polar crystalline induction. PVDF/12IL composite can form big γ spherulite circled by β phase.

Influence of carbon content on the copper-telluride phase formation and on the resistive switching behavior of carbon alloyed Cu-Te conductive bridge random access memory cells

NASA Astrophysics Data System (ADS)

Devulder, Wouter; Opsomer, Karl; Franquet, Alexis; Meersschaut, Johan; Belmonte, Attilio; Muller, Robert; De Schutter, Bob; Van Elshocht, Sven; Jurczak, Malgorzata; Goux, Ludovic; Detavernier, Christophe

2014-02-01

In this paper, we investigate the influence of the carbon content on the Cu-Te phase formation and on the resistive switching behavior in carbon alloyed Cu0.6Te0.4 based conductive bridge random access memory (CBRAM) cells. Carbon alloying of copper-tellurium inhibits the crystallization, while attractive switching behavior is preserved when using the material as Cu-supply layer in CBRAM cells. The phase formation is first investigated in a combinatorial way. With increasing carbon content, an enlargement of the temperature window in which the material stays amorphous was observed. Moreover, if crystalline phases are formed, subsequent phase transformations are inhibited. The electrical switching behavior of memory cells with different carbon contents is then investigated by implementing them in 580 μm diameter dot TiN/Cu0.6Te0.4-C/Al2O3/Si memory cells. Reliable switching behavior is observed for carbon contents up to 40 at. %, with a resistive window of more than 2 orders of magnitude, whereas for 50 at. % carbon, a higher current in the off state and only a small resistive window are present after repeated cycling. This degradation can be ascribed to the higher thermal and lower drift contribution to the reset operation due to a lower Cu affinity towards the supply layer, leading cycle-after-cycle to an increasing amount of Cu in the switching layer, which contributes to the current. The thermal diffusion of Cu into Al2O3 under annealing also gives an indication of the Cu affinity of the source layer. Time of flight secondary ion mass spectroscopy was used to investigate this migration depth in Al2O3 before and after annealing, showing a higher Cu, Te, and C migration for high carbon contents.

Acceleration of Crystal Growth of Amorphous Griseofulvin by Low-Concentration Poly(ethylene oxide): Aspects of Crystallization Kinetics and Molecular Mobility.

PubMed

Shi, Qin; Zhang, Chen; Su, Yuan; Zhang, Jie; Zhou, Dongshan; Cai, Ting

2017-07-03

This study aims to investigate the crystallization behavior and molecular dynamics of amorphous griseofulvin (GSF) in the presence of low-concentration poly(ethylene oxide) (PEO). We observe that the addition of 3% w/w PEO remarkably increases the crystal growth rate of GSF by two orders of magnitude in both the supercooled liquid and glassy states. The liquid dynamics of amorphous GSF in the presence and absence of PEO are characterized by dielectric spectroscopy. With an increase of the PEO content, the α-relaxation times of the systems decrease, indicating the increase of global molecular mobility. The couplings between molecular mobility and crystallization kinetics of GSF systems show strong time-dependences below T g . The overlapping of α-relaxation times of GSF in presence and absence of PEO as a function of T g /T suggest the "plasticization" effect of PEO additives. However, the crystallization kinetics of amorphous GSF containing low-concentration PEO do not overlap with those of pure GSF on a T g /T scale. The remarkable accelerating effect of crystal growth of amorphous GSF by low-concentration PEO can be partially attributed to the increase of global mobility. The high segmental mobility of PEO is expected to strongly affect the crystal growth rates of GSF. These findings are relevant for understanding and predicting the physical stability of amorphous pharmaceutical solid dispersions.

Hydrophilicity, pore structure and mechanical performance of CNT/PVDF materials affected by carboxyl contents in multi-walled carbon nanotubes

NASA Astrophysics Data System (ADS)

Zhang, Yanxia; Jiang, Ce; Tian, Run; Li, Guangfen

2018-01-01

Poly (vinylidene fluoride) (PVDF) membranes have been prepared by loading different type of MWCNTs-COOH as the dispersed phase via phase inversion method. The chemically functionalized MWCNTs with increasing carboxyl content were chosen for achieving a better dispersion in PVDF and altering the membrane hydrophilicity. The effect of the carboxyl content in MWCNTs on crystal structure, thermal behavior, membrane morphology, hydrophilicity, and water flux of blended membranes were investigated. Due to the addition of carbon nanotubes, various performances of the hybrid membrane had obvious changes. The most prominent was that thermal stability could be enhanced and the pore morphology was more preferable, also that the hydrophilicity were improved, further that water flux could be increased to some extent.

Kinetics of UV laser radiation defects in high performance glasses

NASA Astrophysics Data System (ADS)

Natura, U.; Feurer, T.; Ehrt, D.

2000-05-01

High purity fluoride phosphate glasses are attractive candidates as UV transmitting materials. The calculated values for the ultraviolet resonance wavelength are comparable with those of pure silica glass or fluoride single crystal CaF2. The formation of radiation-induced defect centers leads to additional absorption bands in the VUV-UV-vis range. The damage and the healing behavior by lamps and lasers are investigated in dependence on phosphate content and the content of impurities, mainly transition metals. Experiments were carried out using pulsed lasers with a duration of femto- and nanoseconds at a wavelength of 248 nm. The initial slope of the induced absorption shows a nonlinear dependence on the pulse energy density. Resonant and non-resonant two-photon mechanisms were observed. Two-photon-absorption coefficients at 248 nm for samples with different phosphate contents were measured. Models of the kinetics of the radiation-induced defects were developed. The inclusion of energy transfer was necessary to explain the difference in the damage behavior for nanosecond (248 nm, 193 nm) and femtosecond (248 nm) laser pulses.

High-pressure behavior of intermediate scapolite: compressibility, structure deformation and phase transition

NASA Astrophysics Data System (ADS)

Lotti, Paolo; Comboni, Davide; Merlini, Marco; Hanfland, Michael

2018-05-01

Scapolites are common volatile-bearing minerals in metamorphic rocks. In this study, the high-pressure behavior of an intermediate member of the scapolite solid solution series (Me47), chemical formula (Na1.86Ca1.86K0.23Fe0.01)(Al4.36Si7.64)O24[Cl0.48(CO3)0.48(SO4)0.01], has been investigated up to 17.79 GPa, by means of in situ single-crystal synchrotron X-ray diffraction. The isothermal elastic behavior of the studied scapolite has been described by a III-order Birch-Murnaghan equation of state, which provided the following refined parameters: V 0 = 1110.6(7) Å3, {K_{{V_0}}} = 70(2) GPa ({β _{{V_0}}} = 0.0143(4) GPa-1) and {K_{{V}}^' = 4.8(7). The refined bulk modulus is intermediate between those previously reported for Me17 and Me68 scapolite samples, confirming that the bulk compressibility among the solid solution increases with the Na content. A discussion on the P-induced structure deformation mechanisms of tetragonal scapolite at the atomic scale is provided, along with the implications of the reported results for the modeling of scapolite stability. In addition, a single-crystal to single-crystal phase transition, which is displacive in character, has been observed toward a triclinic polymorph at 9.87 GPa. The high-pressure triclinic polymorph was found to be stable up to the highest pressure investigated.

Nucleated Poly(L-lactic acid) with N, N‧-oxalyl bis(benzoic acid) dihydrazide

NASA Astrophysics Data System (ADS)

Tian, Liang-Liang; Cai, Yan-Hua

2018-04-01

One of the major challenges in the field of Poly(L-lactic acid) (PLLA) is the enhancement of crystallization. In the present work, the evaluation of the influence of N, N‧-oxalyl bis(benzoic acid) dihydrazide (TBOD), as a novel organic nucleating agent, on the non-isothermal crystallization, melting behavior, and thermal stability of PLLA was performed using differential scanning calorimeter and thermogravimetric analysis. Non-isothermal crystallization measurement revealed that TBOD had an excellent accelerating effect for the crystallization of PLLA in cooling, and upon the addition of 3 wt% TBOD, PLLA exhibited the highest onset crystallization temperature and the crystallization peak temperature, as well as the largest non-isothermal crystallization enthalpy. In particular, when the TBOD concentration was 1 wt% ∼ 3 wt%, the onset crystallization temperatures were higher than the theoretical ceiling temperature of crystallization, thoroughly demonstrating the powerful crystallization promoting ability of TBOD. Additionally, the non-isothermal crystallization behavior of PLLA/TBOD depended on the TBOD concentration, cooling rate as well as the final melting temperature. The melting behavior of PLLA/TBOD after non-isothermal crystallization further confirmed the effect of TBOD on the crystallization process and crystal structure of PLLA, and the appearance of the double melting peaks during melting stages was attribute to the melting-recrystallization. For melting behavior after isothermal crystallization, the crystallization temperature and crystallization time significantly affected the melting behavior of PLLA/TBOD. The addition of TBOD could not change the thermal decomposition profile of the PLLA, but the thermal stability did not regularly decrease with increasing of TBOD concentration, indicating that there might exist intermolecular interaction between PLLA and TBOD.

Effect of electron beam irradiation on thermal and crystallization behavior of PP/EPDM blend

NASA Astrophysics Data System (ADS)

Balaji, Anand Bellam; Ratnam, Chantara Thevy; Khalid, Mohammad; Walvekar, Rashmi

2017-12-01

The irradiation stability of ethylene-propylene diene terpolymer (EPDM)/ polypropylene (PP) blends is studied in an attempt to develop radiation compatible PP/EPDM blends suitable for medical applications. The PP/EPDM blends with mixing ratios of 80/20, 50/50/ 20/80 were prepared in an internal mixer at 165 °C and a rotor speed of 50 rpm followed by compression molding. The blends and the individual components were irradiated using 3.0 MeV electron beam (EB) accelerator at doses ranging from 0 to 100 kGy in air and room temperature. Later, the PP/EPDM blends were subjected to gel content, thermal stability, crystallization and dynamic mechanical properties before and after irradiation. Results revealed that the irradiation-induced crosslinking in the PP/EPDM blend increases with the increasing irradiation dose and the EPDM content in the blend. However, the thermal stability of the blends did not show any significant changes upon irradiation. The dynamic mechanical analysis shows that the EPDM rich blend has higher compatibility than PP dominant blends. A further improvement in the blend compatibility found to be achieved upon irradiation.

Devitrification and recrystallization of nanoparticle-containing glycerol and PEG-600 solutions.

PubMed

Lv, Fukou; Liu, Baolin; Li, Weijie; Jaganathan, Ganesh K

2014-02-01

Nanoparticles in solution offer unique electrical, mechanical and thermal properties due to their physical presence and interaction with the state of dispersion. This work is aimed to study the effects of hydroxyapatite (HA) nanoparticles on the devitrification and recrystallization events of two important cryoprotective solutions used in cell and tissue preservation namely glycerol (60%w/w) and PEG-600 (50%w/w). HA nanoparticles (20, 40 or 60 nm) were incorporated into solutions at the content of 0.1% or 0.5%(w/w), and were studied by differential scanning calorimeter (DSC) and cryomicroscopy. The presence of nanoparticles does not change the glass transition temperatures and melting temperatures of quenched solutions, but significantly affects the behavior of devitrification and recrystallization upon warming. Cryomicroscopic investigation showed the complex interactions among solution type, nanoparticle size and nanoparticle content, which apparently influence ice crystal growth or recrystallization in the quenched dispersions. These findings have significant implications for biomaterial cryopreservation, cryosurgery, and food manufacturing. The complexity of ice crystal growth kinetics in nanoparticle-containing dispersions remains to be poorly understood at the moment. Copyright © 2013 Elsevier Inc. All rights reserved.

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).

Structural transformation of crystallized debranched cassava starch during dual hydrothermal treatment in relation to enzyme digestibility.

PubMed

Boonna, Sureeporn; Tongta, Sunanta

2018-07-01

Structural transformation of crystallized debranched cassava starch prepared by temperature cycling (TC) treatment and then subjected to annealing (ANN), heat-moisture treatment (HMT) and dual hydrothermal treatments of ANN and HMT was investigated. The relative crystallinity, lateral crystal size, melting temperature and resistant starch (RS) content increased for all hydrothermally treated samples, but the slowly digestible starch (SDS) content decreased. The RS content followed the order: HMT → ANN > HMT > ANN → HMT > ANN > TC, respectively. The HMT → ANN sample showed a larger lateral crystal size with more homogeneity, whereas the ANN → HMT sample had a smaller lateral crystal size with a higher melting temperature. After cooking at 50% moisture, the increased RS content of samples was observed, particularly for the ANN → HMT sample. These results suggest that structural changes of crystallized debranched starch during hydrothermal treatments depend on initial crystalline characteristics and treatment sequences, influencing thermal stability, enzyme digestibility, and cooking stability. Copyright © 2018 Elsevier Ltd. All rights reserved.

Fractionation of the platinum-group elments and Re during crystallization of basalt in Kilauea Iki Lava Lake, Hawaii

USGS Publications Warehouse

Pitcher, L.; Helz, R.T.; Walker, R.J.; Piccoli, P.

2009-01-01

Kilauea Iki lava lake formed during the 1959 summit eruption of Kilauea Volcano, then crystallized and differentiated over a period of 35??years. It offers an opportunity to evaluate the fractionation behavior of trace elements in a uniquely well-documented basaltic system. A suite of 14 core samples recovered from 1967 to 1981 has been analyzed for 5 platinum-group elements (PGE: Ir, Os, Ru, Pt, Pd), plus Re. These samples have MgO ranging from 2.4 to 26.9??wt.%, with temperatures prior to quench ranging from 1140????C to ambient (110????C). Five eruption samples were also analyzed. Osmium and Ru concentrations vary by nearly four orders of magnitude (0.0006-1.40??ppb for Os and 0.0006-2.01??ppb for Ru) and are positively correlated with MgO content. These elements behaved compatibly during crystallization, mostly likely being concentrated in trace phases (alloy or sulfide) present in olivine phenocrysts or included chromite. Iridium also correlates positively with MgO, although less strongly than Os and Ru. The somewhat poorer correlation for Ir, compared with Os and Ru, may reflect variable loss of Ir as volatile IrF6 in some of the most magnesian samples. Rhenium is negatively correlated with MgO, behaving as an incompatible trace element. Its behavior in the lava lake is complicated by apparent volatile loss of Re, as suggested by a decrease in Re concentration with time of quenching for lake samples vs. eruption samples. Platinum and Pd concentrations are negatively, albeit weakly, correlated with MgO, so these elements were modestly incompatible during crystallization of the major silicate phases. Palladium contents peaked before precipitation of immiscible sulfide liquid, however, and decline sharply in the most differentiated samples. In contrast, Pt appears to have been unaffected by sulfide precipitation. Microprobe data confirm that Pd entered the sulfide liquid before Re, and that Pt is not strongly chalcophile in this system. Occasional high Pt values in both eruption and lava lake samples suggest the presence of unevenly distributed, unidentified Pt-rich trace phases in some Kilauea Iki materials. Estimated mineral (olivine + chromite)/melt D values for Os, Ir, Ru and Pt for equilibrium crystallization for samples from ~ 7 to 27??wt.% MgO are 26, 8.2, 19 and 0.55, respectively. These Os, Ir and Ru estimates are somewhat higher than previous estimates for similar systems. If fractional crystallization is instead assumed, D values are much more similar. Results confirm many prior observations in other mafic systems that olivine (together with included phases) has a major effect on absolute and relative abundances of Re and the PGE. The relatively linear correlations between these elements and MgO potentially permit accurate estimation of the concentrations of these elements in the primary melts of comparable systems, especially in instances where the MgO content of the primary melt is well constrained. ?? 2008 Elsevier B.V.

Overcoming the Fundamental Challenges in Improving the Impact Strength and Crystallinity of PLA Biocomposites: Influence of Nucleating Agent and Mold Temperature.

PubMed

Nagarajan, Vidhya; Zhang, Kunyu; Misra, Manjusri; Mohanty, Amar K

2015-06-03

Poly(lactic acid) (PLA), one of the widely studied renewable resource based biopolymers, has yet to gain a strong commercial standpoint because of certain property limitations. This work is a successful attempt in achieving PLA biocomposites that showed concurrent improvements in impact strength and heat deflection temperature (HDT). Biocomposites were fabricated from a super toughened ternary blend of PLA, poly(ether-b-amide) elastomeric copolymer and ethylene-methyl acrylate-glycidyl methacrylate and miscanthus fibers. The effects of varying the processing parameters and addition of various nucleating agents were investigated. Crystallinity was controlled by optimizing the mold temperature and cycle time of the injection process. With the addition of 1 wt % aromatic sulfonate derivative (Lak-301) as a nucleating agent at a mold temperature of 110 °C, PLA biocomposites exhibited dramatic reduction in crystallization half time to 1.3 min with crystallinity content of 42%. Mechanical and thermal properties assessment for these biocomposites revealed a 4-fold increase in impact strength compared to neat PLA. The HDT of PLA biocomposites increased to 85 °C from 55 °C compared to neat PLA. Crystallization behavior was studied in detail using differential scanning calorimetry and was supported with observations from wide-angle X-ray diffraction profiles and polarized optical microscopy. The presence of a nucleating agent did not alter the crystal structure of PLA; however, a significant difference in spherulite size, crystallization rate and content was observed. Fracture surface morphology and distribution of nucleating agent in the PLA biocomposites were investigated through scanning electron microscopy.

The Biomolecular Crystallization Database Version 4: expanded content and new features.

PubMed

Tung, Michael; Gallagher, D Travis

2009-01-01

The Biological Macromolecular Crystallization Database (BMCD) has been a publicly available resource since 1988, providing a curated archive of information on crystal growth for proteins and other biological macromolecules. The BMCD content has recently been expanded to include 14 372 crystal entries. The resource continues to be freely available at http://xpdb.nist.gov:8060/BMCD4. In addition, the software has been adapted to support the Java-based Lucene query language, enabling detailed searching over specific parameters, and explicit search of parameter ranges is offered for five numeric variables. Extensive tools have been developed for import and handling of data from the RCSB Protein Data Bank. The updated BMCD is called version 4.02 or BMCD4. BMCD4 entries have been expanded to include macromolecule sequence, enabling more elaborate analysis of relations among protein properties, crystal-growth conditions and the geometric and diffraction properties of the crystals. The BMCD version 4.02 contains greatly expanded content and enhanced search capabilities to facilitate scientific analysis and design of crystal-growth strategies.

Effect of Multiple Alloying Elements on the Glass-Forming Ability, Thermal Stability, and Crystallization Behavior of Zr-Based Alloys

NASA Astrophysics Data System (ADS)

Bazlov, A. I.; Tsarkov, A. A.; Ketov, S. V.; Suryanarayana, C.; Louzguine-Luzgin, D. V.

2018-02-01

Effect of multiple alloying elements on the glass-forming ability, thermal stability, and crystallization behavior of Zr-based glass-forming alloys were studied in the present work. We investigated the effect of complete or partial substitution of Ti and Ni with similar early and late transition metals, respectively, on the glass-forming ability and crystallization behavior of the Zr50Ti10Cu20Ni10Al10 alloy. Poor correlation was observed between different parameters indicating the glass-forming ability and the critical size of the obtained glassy samples. Importance of the width of the crystallization interval is emphasized. The kinetics of primary crystallization, i.e., the rate of nucleation and rate of growth of the nuclei of primary crystals is very different from that of the eutectic alloys. Thus, it is difficult to estimate the glass-forming ability only on the basis of the empirical parameters not taking into account the crystallization behavior and the crystallization interval.

High pressure Raman spectroscopy of H2O-CH3OH mixtures.

PubMed

Hsieh, Wen-Pin; Chien, Yu-Hsiang

2015-02-23

Complex intra-molecular interactions and the hydrogen-bonding network in H2O-volatile mixtures play critical roles in many dynamics processes in physical chemistry, biology, and Earth and planetary sciences. We used high pressure Raman spectroscopy to study the pressure evolution of vibrational frequencies and bonding behavior in H2O-CH3OH mixtures. We found that the presence of low CH3OH content in H2O increases the transition pressure where water crystallizes to ice VI, but does not significantly change the pressure where ice VI transforms to ice VII. Furthermore, the stiffening rates of C-H stretching frequencies dω/dP in CH3OH significantly decrease upon the crystallization of water, and the softening rates of the O-H stretching frequencies of ice VII are suppressed over a narrow pressure range, after which the frequencies of these modes shift with pressure in ways similar to pure CH3OH and ice VII, respectively. Such complex pressure evolution of Raman frequencies along with pronounced variations in Raman intensities of CH3OH within the sample, and the hysteresis of the water-ice VI phase transition suggest pressure-induced segregation of low content CH3OH from ice VII. These findings indicate the significant influence of volatiles on the crystallization of sub-surface ocean and thermal evolution within large icy planets and satellites.

Laboratory plant study on the melting process of asbestos waste

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

Sakai, Shinichi; Terazono, Atsushi; Takatsuki, Hiroshi

The melting process was studied as a method of changing asbestos into non-hazardous waste and recovering it as a reusable resource. In an initial effort, the thermal behaviors of asbestos waste in terms of physical and chemical structure have been studied. Then, 10 kg/h-scale laboratory plant experiments were carried out. By X-ray diffraction analysis, the thermal behaviors of sprayed-on asbestos waste revealed that chrysotile asbestos waste change in crystal structure at around 800 C, and becomes melted slag, mainly composed of magnesium silicate, at around 1,500 C. Laboratory plant experiments on the melting process of sprayed-on asbestos have shown thatmore » melted slag can be obtained. X-ray diffraction analysis of the melted slag revealed crystal structure change, and SEM analysis showed the slag to have a non-fibrous form. And more, TEM analysis proved the very high treatment efficiency of the process, that is, reduction of the asbestos content to 1/10{sup 6} as a weight basis. These analytical results indicate the effectiveness of the melting process for asbestos waste treatment.« less

Combining Pre- and Post-Nucleation Trajectories for the Synthesis of High FAU-Content Faujasite Nanocrystals from Organic-Free Sols

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

Khaleel, Maryam; Xu, Wenqian; Lesch, David A.

The effects of synthesis conditions on the FAU/EMT content and the size of nanocrystals, formed from inorganic aluminosilicate sols, were investigated. High resolution transmission electron microscopy imaging and comparison of experimental X-ray diffraction patterns with simulations demonstrated that all materials made starting from synthesis mixtures in the composition range (1.8-33) SiO2: 1 Al2O3: (2.7-33) Na2O: (41-1000) H2O contain FAU/EMT intergrowths. Compositions with low water content increase the FAU fraction up to 0.8 but the crystal size exceeds 100 nm. Extension of the higher FAU purity to nanocrystals was achieved only by first mixing the sol at high water content compositionsmore » that favor nanocrystal formation and then - after a certain time - lowering by freeze-drying the water to levels favoring the formation of FAU. Cryogenic transmission electron microscopy and small angle X-ray scattering from representative optically clear and colloidally stable precursor sols (aged and crystallized at ambient temperature) reveal the formation of amorphous aggregates before the detection of crystals, in agreement with earlier findings and an existing model for the aggregative growth of the zeolite MFI. The presence of these amorphous aggregates coincides with the aforementioned state of sol that preserves the original trajectory towards nano-crystals after the pronounced reduction of water content by freeze-drying. If water reduction by freeze-drying is applied earlier (before the detection of amorphous aggregates), the sol follows the low water content trajectory towards larger crystals. Despite this memory effect, the sol at this stage is still agnostic towards FAU or EMT formation, the relative content of which is dominantly determined by the final water content. These findings demonstrate that it is possible to combine the effects of pre-and post-nucleation sol composition to steer crystal size and crystal structure, respectively. They confirm precursor nanoparticle evolution, while they emphasize the importance of solution phase composition at both pre- and post-nucleation stages of aggregative crystal growth.« less

Ultratight crystal packing of a 10 kDa protein

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

Trillo-Muyo, Sergio; Jasilionis, Andrius; Domagalski, Marcin J.

2013-03-01

The crystal structure of the C-terminal domain of a putative U32 peptidase from G. thermoleovorans is reported; it is one of the most tightly packed protein structures reported to date. While small organic molecules generally crystallize forming tightly packed lattices with little solvent content, proteins form air-sensitive high-solvent-content crystals. Here, the crystallization and full structure analysis of a novel recombinant 10 kDa protein corresponding to the C-terminal domain of a putative U32 peptidase are reported. The orthorhombic crystal contained only 24.5% solvent and is therefore among the most tightly packed protein lattices ever reported.

On the synthesis of AlPO4-21 molecular sieve by vapor phase transport method and its phase transformation to AlPO4-15 molecular sieve

NASA Astrophysics Data System (ADS)

Shao, Hui; Chen, Jingjing; Chen, Xia; Leng, Yixin; Zhong, Jing

2015-04-01

An experimental design was applied to the synthesis of AlPO4-21 molecular sieve (AWO structure) by vapor phase transport (VPT) method, using tetramethylguanidine (TMG) as the template. In this study, the effects of crystallization time, crystallization temperature, phosphor content, template content and water content in the synthesis gel were investigated. The materials obtained were characterized by X-ray diffraction, scanning electron microscopy and fourier transform infrared spectroscopy (FT-IR). Microstructural analysis of the crystal growth in vapor synthetic conditions revealed a revised crystal growth route from zeolite AlPO4-21 to AlPO4-15 in the presence of the TMG. Homogenous hexagonal prism AlPO4-21 crystals with size of 7 × 3 μm were synthesized at a lower temperature (120 °C), which were completely different from the typical tabular parallelogram crystallization microstructure of AlPO4-21 phase. The crystals were transformed into AlPO4-21 phase with higher crystallization temperature, longer crystallization time, higher P2O5/Al2O3 ratio and higher TMG/Al2O3 ratio.

Effects of Ultrasonic Parameters on the Crystallization Behavior of Virgin Coconut Oil.

PubMed

Wu, Linhe; Cao, Jun; Bai, Xinpeng; Chen, Haiming; Zhang, Yuxiang; Wu, Qian

2016-12-01

Crystallization behavior of virgin coconut oil (VCO) in the absence and presence of ultrasonic treatment under a temperature gradient field was investigated. The effects of ultrasonic parameters on the crystallization behavior of VCO were studied by differential scanning calorimetry, ultraviolet/visible spectrophotometry and polarized light microscopy. The thermal effect of the ultrasonic treatment was also increased at higher power levels. Therefore, the optimal power level was determined at approximately 36 W. Induction time reduced evidently and the crystallization rate was accelerated under ultrasonic treatment at crystallization temperature (T c ) above 15°C. However, no significant difference in induction time was noted at 13°C. The result of morphological studies showed that the growth mechanism of crystals was significantly changed. Meanwhile, smaller and uniform crystals were produced by the ultrasonic treatment. This study shows a novel technique to accelerate the crystallization rate and alter the growth mechanism of VCO crystals.

Optimization of single crystals of solid electrolytes with tysonite-type structure (LaF3) for conductivity at 293 K: 2. Nonstoichiometric phases R 1- y M y F3- y ( R = La-Lu, Y; M = Sr, Ba)

NASA Astrophysics Data System (ADS)

Sorokin, N. I.; Sobolev, B. P.; Krivandina, E. A.; Zhmurova, Z. I.

2015-01-01

Single crystals of fluorine-conducting solid electrolytes R 1 - y Sr y F3 - y and R 1 - y Ba y F3 - y ( R = La-Lu, Y) with a tysonite-type structure (LaF3) have been optimized for room-temperature conductivity σ293 K. The optimization is based on high-temperature measurements of σ( T) in two-component nonstoichiometric phases R 1 - y M y F3 - y ( M = Sr, Ba) as a function of the MF2 content. Optimization for thermal stability is based on studying the phase diagrams of MF2- RF3 systems ( M = Sr, Ba) and the behavior of nonstoichiometric crystals upon heating when measuring temperature dependences σ( T). Single crystals of many studied R 1 - y Sr y F3 - y and R 1 - y Ba y F3 - y phases have σ293 K values large enough to use these materials in solid-state electrochemical devices (chemical sensors, fluorine-ion batteries, accumulators, etc.) operating at room temperature.

Effects of multi-walled carbon nanotubes on rheological and physical properties of polyamide-based thermoplastic elastomers

NASA Astrophysics Data System (ADS)

Bae, Won-Sik; Kwon, Oh Joo; Kim, Byoung Chul; Chae, Dong Wook

2012-09-01

The polyamide-based thermoplastic elastomers (Pebax®) were melt compounded with multi-walled carbon nanotubes (MWNTs: 0.25˜5 wt%) and the variation of rheological and physical properties with MWNT contents was investigated. The crystallization temperature (Tc) of the nanocomposites with 0.5 wt% MWNTs was most increased by ca. 8oC, but it was decreased by further addition. In addition, the presence of MWNTs broadened the Tc peak with increasing nanotube contents. In contrast, the melting behavior was little influenced by the presence of MWNTs for all compositions. The incorporation of MWNTs increased the complex viscosity with MWNT contents and the abrupt increase was observed from 1 wt%. In addition, lower Newtonian flow region became disappearing with increasing MWNT contents, exhibiting notable shear thinning behavior from 1 wt% loading. Storage modulus was increased with MWNT contents in a similar manner to viscosity. Casson plot demonstrated a non-zero positive intercept for all the samples. In particular, the abrupt increase of yield stress was observed from 1 wt% loading. In the Cole-Cole plot, the nanocomposites gave a deviated curve from pure Pebax and the slope was decreased with increasing MWNT contents. The relaxation time calculated from viscoelastic parameters was increased with nanotube contents, but the increasing extents were reduced with increasing frequency. From 2 wt% MWNTs, the electrical conductivity was observed, indicating that the electrical percolation existed between 1.5 and 2 wt%. At 0.25 wt% loading the tensile strength was slightly increased, but it was gradually decreased by further addition. The introduction of MWNTs increased the tensile modulus with nanotube contents. In addition, ductile properties were reduced with increasing MWNT contents, resulting in low toughness.

ISDAC Microphysics

DOE Data Explorer

McFarquhar, Greg

2011-07-25

Best estimate of cloud microphysical parameters derived using data collected by the cloud microphysical probes installed on the National Research Council (NRC) of Canada Convair-580 during ISDAC. These files contain phase, liquid and ice crystal size distributions (Nw(D) and Ni(D) respectively), liquid water content (LWC), ice water content (IWC), extinction of liquid drops (bw), extinction of ice crystals (bi), effective radius of water drops (rew) and of ice crystals (rei) and median mass diameter of liquid drops (Dmml) and of ice crystals (Dmmi) at 30 second resolution.

Optical and chemical analysis of iron in Luna 20 plagioclase.

NASA Technical Reports Server (NTRS)

Bell, P. M.; Mao, H. K.

1973-01-01

Review of analytical data on the iron content of Luna 20 anorthitic plagioclase, obtained by a highly sensitive technique for measuring polarized absorption related to crystal-field splittings and by automated electron microprobe analysis of oriented single crystals. The iron content is found to range from a few hundredths to a few tenths of a weight per cent from crystal to crystal. The optical and chemical properties of the iron appear to be caused by postcrystallization migration and exsolution. Postcrystallization effects may obscure evidence of the original oxidation state and iron concentration of these crystals.

Abundant Cool Magnesium-Rich Pyroxene Crystals in Comet Hale-Bopp

NASA Technical Reports Server (NTRS)

Wooden, D. H.

1999-01-01

Modeling of the observed dust emission from Comet Hale-Bopp over a large range of heliocentric distances (2.8 AU - 0.93 AU -1.7 AU) led to the discovery of Mg-rich pyroxene crystals in the coma These pyroxene crystals are apparent in the 10 micron spectrum only when the comet is close to perihelion (r(sub h) = 1.2 AU) because they are cooler than the other silicate minerals. The pyroxene crystals are cooler than the other species because of their high Mg-content. They do not absorb as efficiently as the other silicate minerals. Given the same high Mg content of Mg/(Mg + Fe) = 0.9, radiative equilibrium computations show that pyroxene crystals are expected to be 150 K cooler than olivine crystals. The pyroxene crystals are also about 10x more abundant than the other silicate mineral species. Their high Mg content and relatively large abundance are in agreement with the preponderance of pyroxene interplanetary dust particles (IDPs) and the recent reanalysis of the PUMA-I flyby of Comet Halley. Before Hale-Bopp, only olivine crystals were detected spectroscopically in comets, probably because the pyroxene crystals are less optically active, hence significantly cooler and harder to detect in contrast to the warmer silicate species. Determining the relative abundances of silicate minerals depends on their Mg contents. If the pyroxene crystals in Comet Hale-Bopp are solar nebula condensates, then they probably had to form during the early FU Orionis epoch when the inner disk was hot enough and be transported out to the region of formation of icy planetesimals without being reheated. Reheating events appear to reincorporate Fe back into the crystals or form Fe-rich rims, which are not consistent with the high-Mg-content crystals. The condensation of Mg-rich pyroxene crystals is expected from solar nebula thermal equilibrium computations. However, their subsequent transport to the outer solar nebula unaltered has yet to be theoretically demonstrated. The discovery of Mg-rich crystals in Comet Hale-Bopp and in AGB stars opens the possibility that these crystals are relic interstellar grains. One-third of IDPs have been shown to have significant deuterium enrichments, thus indicating that they contain presolar material. By spectroscopic analogy to IDPs the Mg-rich pyroxene crystals in Comet Hale-Bopp may be presolar grains. If so, then the comet contains largely ISM silicates. ISM grains may have been the dominant source of dust in the outer early solar nebula.

Associations between crystal methamphetamine use and potentially unsafe sexual activity among gay men in Australia.

PubMed

Rawstorne, Patrick; Digiusto, Erol; Worth, Heather; Zablotska, Iryna

2007-10-01

It has been suggested that crystal methamphetamine may have disinhibiting or aphrodisiac effects, which may lead to unsafe sexual behavior and increase the risk of HIV transmission. Using data from two Australian studies, the Sydney Gay Community Periodic Survey study and the Positive Health (PH) cohort study, we examined changes over time in use of crystal, other recreational drugs, and Viagra, and in a range of sex-related behaviors. Compared to non-users, crystal users reported having more sex partners, looking for sex in more types of venues, and being more likely to engage in unprotected anal intercourse with casual partners (UAIC) and in esoteric sex. Crystal users were also more likely to be using other recreational drugs and Viagra than non-users. Crystal use remained significantly associated with UAIC after adjustment for other relevant variables in a log-binomial regression analysis (adjusted prevalence rate ratio=1.26; 95% CI: 1.19-1.34). The other variables (HIV status, number of sex partners, number of types of venue where men looked for sex, Viagra use, other drug use) were independently associated with UAIC, and did not show confounding or mediating effects on the crystal-UAIC association. Nevertheless, these data did not allow reliable attribution of higher levels of these sex-related behaviors among crystal users specifically to the effects of crystal. The prevalence of crystal use among Australian men who have sex with men (MSM) increased between 2002 and 2005 (e.g., from 26% to 39% among HIV-+ MSM). However, the prevalence of UAIC remained stable or decreased over time in various study subgroups, as did the prevalence of other sex-related behaviors, suggesting that crystal use does not necessarily drive unsafe sexual behavior. Crystal use and unsafe sexual behavior can, and should, be considered and addressed separately in health promotion and community education campaigns.

Stepwise crystallization and the layered distribution in crystallization kinetics of ultra-thin poly(ethylene terephthalate) film

NASA Astrophysics Data System (ADS)

Zuo, Biao; Xu, Jianquan; Sun, Shuzheng; Liu, Yue; Yang, Juping; Zhang, Li; Wang, Xinping

2016-06-01

Crystallization is an important property of polymeric materials. In conventional viewpoint, the transformation of disordered chains into crystals is usually a spatially homogeneous process (i.e., it occurs simultaneously throughout the sample), that is, the crystallization rate at each local position within the sample is almost the same. Here, we show that crystallization of ultra-thin poly(ethylene terephthalate) (PET) films can occur in the heterogeneous way, exhibiting a stepwise crystallization process. We found that the layered distribution of glass transition dynamics of thin film modifies the corresponding crystallization behavior, giving rise to the layered distribution of the crystallization kinetics of PET films, with an 11-nm-thick surface layer having faster crystallization rate and the underlying layer showing bulk-like behavior. The layered distribution in crystallization kinetics results in a particular stepwise crystallization behavior during heating the sample, with the two cold-crystallization temperatures separated by up to 20 K. Meanwhile, interfacial interaction is crucial for the occurrence of the heterogeneous crystallization, as the thin film crystallizes simultaneously if the interfacial interaction is relatively strong. We anticipate that this mechanism of stepwise crystallization of thin polymeric films will allow new insight into the chain organization in confined environments and permit independent manipulation of localized properties of nanomaterials.

Stepwise crystallization and the layered distribution in crystallization kinetics of ultra-thin poly(ethylene terephthalate) film

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

Zuo, Biao, E-mail: chemizuo@zstu.edu.cn, E-mail: wxinping@yahoo.com; Xu, Jianquan; Sun, Shuzheng

2016-06-21

Crystallization is an important property of polymeric materials. In conventional viewpoint, the transformation of disordered chains into crystals is usually a spatially homogeneous process (i.e., it occurs simultaneously throughout the sample), that is, the crystallization rate at each local position within the sample is almost the same. Here, we show that crystallization of ultra-thin poly(ethylene terephthalate) (PET) films can occur in the heterogeneous way, exhibiting a stepwise crystallization process. We found that the layered distribution of glass transition dynamics of thin film modifies the corresponding crystallization behavior, giving rise to the layered distribution of the crystallization kinetics of PET films,more » with an 11-nm-thick surface layer having faster crystallization rate and the underlying layer showing bulk-like behavior. The layered distribution in crystallization kinetics results in a particular stepwise crystallization behavior during heating the sample, with the two cold-crystallization temperatures separated by up to 20 K. Meanwhile, interfacial interaction is crucial for the occurrence of the heterogeneous crystallization, as the thin film crystallizes simultaneously if the interfacial interaction is relatively strong. We anticipate that this mechanism of stepwise crystallization of thin polymeric films will allow new insight into the chain organization in confined environments and permit independent manipulation of localized properties of nanomaterials.« less

Isothermal crystallization of gamma irradiated LDPE in the presence of oxygen

NASA Astrophysics Data System (ADS)

Lanfranconi, M. R.; Alvarez, V. A.; Perez, C. J.

2015-06-01

This work is focused on the study of the effect of oxygen on the isothermal crystallization process of gamma irradiated low density polyethylene (LDPE). The induction time increased with the dose indicating a retarding effect. On other hand, at the same dose, this parameter decreased with the augment in the oxygen content. The classical Avrami equation was used to analyze the crystallization kinetic of these materials. n values suggested that both, the dose and the oxygen content, did not affect the mechanism of crystals growth. An Arrhenius type equation was used for the rate constant (k). Used models correctly reproduced the experimental data. TTT diagrams of studied materials were constructed and also reflected the effects of the doses and the oxygen content.

Physics-Based Crystal Plasticity Modeling of Single Crystal Niobium

NASA Astrophysics Data System (ADS)

Maiti, Tias

Crystal plasticity models based on thermally activated dislocation kinetics has been successful in predicting the deformation behavior of crystalline materials, particularly in face-centered cubic (fcc) metals. In body-centered cubic (bcc) metals success has been limited owing to ill-defined slip planes. The flow stress of a bcc metal is strongly dependent on temperature and orientation due to the non-planar splitting of a/2 screw dislocations. As a consequence of this, bcc metals show two unique deformation characteristics: (a) thermally-activated glide of screw dislocations--the motion of screw components with their non-planar core structure at the atomistic level occurs even at low stress through the nucleation (assisted by thermal activation) and lateral propagation of dislocation kink pairs; (b) break-down of the Schmid Law, where dislocation slip is driven only by the resolved shear stress. Since the split dislocation core has to constrict for a kink pair formation (and propagation), the non-planarity of bcc screw dislocation cores entails an influence of (shear) stress components acting on planes other than the primary glide plane on their mobility. Another consequence of the asymmetric core splitting on the glide plane is a direction-sensitive slip resistance, which is termed twinning/atwinning sense of shear and should be taken into account when developing constitutive models. Modeling thermally-activated flow including the above-mentioned non-Schmid effects in bcc metals has been the subject of much work, starting in the 1980s and gaining increased interest in recent times. The majority of these works focus on single crystal deformation of commonly used metals such as Iron (Fe), Molybdenum (Mo), and Tungsten (W), while very few published studies address deformation behavior in Niobium (Nb). Most of the work on Nb revolves around fitting parameters of phenomenological descriptions, which do not capture adequately the macroscopic multi-stage hardening behavior and evolution of crystallographic texture from a physical point of view. Therefore, we aim to develop a physics-based crystal plasticity model that can capture these effects as a function of grain orientations, microstructure parameters, and temperature. To achieve this goal, first, a new dilatational constitutive model is developed for simulating the deformation of non-compact geometries (foams or geometries with free surfaces) using the spectral method. The model has been used to mimic the void-growth behavior of a biaxially loaded plate with a circular inclusion. The results show that the proposed formulation provides a much better description of void-like behavior compared to the pure elastic behavior of voids. Using the developed dilatational framework, periodic boundary conditions arising from the spectral solver has been relaxed to study the tensile deformation behavior of dogbone-shaped Nb single crystals. Second, a dislocation density-based constitutive model with storage and recovery laws derived from Discrete Dislocation Dynamics (DDD) is implemented to model multi-stage strain hardening. The influence of pre-deformed dislocation content, dislocation interaction strengths and mean free path on stage II hardening is then simulated and compared with in-situ tensile experiments.

Improvement of seawater salt quality by hydro-extraction and re-crystallization methods

NASA Astrophysics Data System (ADS)

Sumada, K.; Dewati, R.; Suprihatin

2018-01-01

Indonesia is one of the salt producing countries that use sea water as a source of raw materials, the quality of salt produced is influenced by the quality of sea water. The resulting average salt quality contains 85-90% NaCl. The Indonesian National Standard (SNI) for human salt’s consumption sodium chloride content is 94.7 % (dry base) and for industrial salt 98,5 %. In this study developed the re-crystallization without chemical and hydro-extraction method. The objective of this research to choose the best methods based on efficiency. The results showed that re-crystallization method can produce salt with NaCl content 99,21%, while hydro-extraction method content 99,34 % NaCl. The salt produced through both methods can be used as a consumption and industrial salt, Hydro-extraction method is more efficient than re-crystallization method because re-crystallization method requires heat energy.

EFFECTS OF FEATHER CRYSTALS IN THE MACROSTRUCTURE ON EARING BEHAVIOR AND ELOXAL STRUCTURE OF SHEETS OF PURE ALUMINUM (in German)

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

Zieger, H.

1961-10-01

The as-cast structure of d.c.-cast aluminum ingots sometimes shows feather-like crystals. The influence of this type of crystals on the earing behavior and on the surface markings after anodizing was investigated on Al 99.5- sheets of 2 mm thickness. Feather-like crystals gave rise to more irregular and higher earings in all cases. Hot and afterwards cold rolled sheets showed markings on the anodized surface, which were intensified by feather-like crystals in the ingot. Extruding prior to hot rolling suppressed these markings completely, but did not affect the earing behavior. (auth)

Structure, morphology and Raman and optical spectroscopic analysis of In1-xCuxP thin films grown by MOCVD technique for solar cell applications

NASA Astrophysics Data System (ADS)

Alshahrie, Ahmed; Juodkazis, S.; Al-Ghamdi, A. A.; Hafez, M.; Bronstein, L. M.

2017-10-01

Nanocrystalline In1-xCuxP thin films (0 ≤ x ≤ 0.5) have been deposited on quartz substrates by a Metal-Organic Chemical Vapor Deposition (MOCVD) technique. The effect of the copper ion content on the structural crystal lattice, morphology and optical behavior of the InP thin films was assessed using X-ray diffraction, scanning electron microscopy, atomic force microscopy, Raman spectroscopy and spectrophotometry. All films exhibited a crystalline cubic zinc blende structure, inferring the solubility of the Cu atoms in the InP crystal structure. The XRD patterns demonstrated that the inclusion of Cu atoms into the InP films forced the nanoparticles in the films to grow along the (1 1 1) direction. The AFM topography showed that the Cu ions reduce the surface roughness of deposited films. The Raman spectra of the deposited films contain the first and second order anti-stoke ΓTO, ΓLO, ΧLO + ΧTO, 2ΓTO, and ΓLO + ΓTO bands which are characteristic of the InP crystalline structure. The intensities of these bands decreased with increasing the content of the Cu atoms in the InP crystals implying the creation of a stacking fault density in the InP crystal structure. The In1-xCuxP thin films have shown high optical transparency of 90%. An increase of the optical band gap from 1.38 eV to 1.6 eV was assigned to the increase of the amount of Cu ions in the InP films. The In0.5Cu0.5P thin film exhibited remarkable optical conductivity with very low dissipation factor which makes it a promising buffer window for solar energy applications.

A finite-strain homogenization model for viscoplastic porous single crystals: II - Applications

NASA Astrophysics Data System (ADS)

Song, Dawei; Ponte Castañeda, P.

2017-10-01

In part I of this work (Song and Ponte Castañeda, 2017a), a new homogenization-based constitutive model was developed for the finite-strain, macroscopic response of porous viscoplastic single crystals. In this second part, the new model is first used to investigate the instantaneous response and the evolution of the microstructure for porous FCC single crystals for a wide range of loading conditions. The loading orientation, Lode angle and stress triaxiality are found to have significant effects on the evolution of porosity and average void shape, which play crucial roles in determining the overall hardening/softening behavior of porous single crystals. The predictions of the model are found to be in fairly good agreement with numerical simulations available from the literature for all loadings considered, especially for low triaxiality conditions. The model is then used to investigate the strong effect of crystal anisotropy on the instantaneous response and the evolution of the microstructure for porous HCP single crystals. For uniaxial tension and compression, the overall hardening/softening behavior of porous HCP crystals is found to be controlled mostly by the evolution of void shape, and not so much by the evolution of porosity. In particular, porous HCP crystals exhibit overall hardening behavior with increasing porosity, while they exhibit overall softening behavior with decreasing porosity. This interesting behavior is consistent with corresponding results for porous FCC crystals, but is found to be more significant for porous HCP crystals with large anisotropy, such as porous ice, where the non-basal slip systems are much harder than the basal systems.

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

Jones, B.; Renault, R.W.

Platy calcite crystals, which have their c axis parallel to their shortest length axis, are common components of travertine deposits found around some hot springs in the Kenya Rift Valley. They are composite crystals formed of numerous paper-thin subcrystals. Individual plates allowed to grow without obstruction develop a hexagonal motif. The Kenyan crystals typically form in hot (>75 C) waters that have a low Ca content (<10 mg/l), a high CO{sub 2} content, and a high rate of CO{sub 2} degassing. At Chemurkeu, aggregates of numerous small platy crystals collectively form lattice crystals that superficially resemble ray crystals. The wallsmore » of the lattice crystals are formed of large platy crystals that have their long and intermediate length axes aligned parallel to the plane of the long axis of the lattice crystal. Internally, the lattice crystals are formed of small platy calcite crystals arranged in a boxlike pattern that creates the appearance of a lattice when viewed in thin section. Lattice crystals are highly porous, with each pore being enclosed by platy crystals. At Lorusio, travertines are mainly formed of pseudodentrites that are constructed by numerous small platy crystals attached to a main stem which is a large platy crystal that commonly curves along its long axis. The pseudodentrites are the main construction blocks in ledges and lilypads that form in the vent pool and spring outflow channels, where the water is too hot for microbes other than hyperthermophiles. The platy calcite crystals in the Kenyan travertines are morphologically similar to platy calcite crystals that form as scale in pipes in the geothermal fields of New Zealand and hydrothermal angel wing calcite from the La Fe mine in Mexico. Comparison of the Kenyan and New Zealand crystals indicates that platy calcite crystals form from waters with a low Ca{sup 2+} content and a high CO{sub 3}/Ca ratio due to rapid rates of CO{sub 2} degassing.« less

Surface nucleation in complex rheological systems

NASA Astrophysics Data System (ADS)

Herfurth, J.; Ulrich, J.

2017-07-01

Forced nucleation induced by suitable foreign seeds is an important tool to control the production of defined crystalline products. The quality of a surface provided by seed materials represents an important variable in the production of crystallizing layers that means for the nucleation process. Parameters like shape and surface structure, size and size distribution of the seed particles as well as the ability to hold up the moisture (the solvent), can have an influence on the nucleation process of different viscous supersaturated solutions. Here the properties of different starch powders as seeds obtained from corn, potato, rice, tapioca and wheat were tested. It could be found, that the best nucleation behavior of a sugar solution could be reached with the use of corn starch as seed material. Here the surface of the crystallized sugar layer is smooth, crystallization time is short (<3 h) and the shape of the product is easily reproducible. Beneficial properties of seed materials are therefore an edged, uneven surface, small particle sizes as well as low moisture content at ambient conditions within the seed materials.

Cohesive finite element modeling of the delamination of HTPB binder and HMX crystals under tensile loading

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

Walters, David J.; Luscher, Darby J.; Yeager, John D.

Accurately modeling the mechanical behavior of the polymer binders and the degradation of interfaces between binder and crystal is important to science-based understanding of the macro-scale response of polymer bonded explosives. The paper presents a description of relatively a simple bi-crystal HMX-HTPB specimen and associated tensile loading experiment including computed tomography imaging, the pertinent constitutive theory, and details of numerical simulations used to infer the behavior of the material during the delamination process. Within this work, mechanical testing and direct numerical simulation of this relatively simple bi-crystal system enabled reasonable isolation of binder-crystal interface delamination, in which the effects ofmore » the complicated thermomechanical response of explosive crystals were minimized. Cohesive finite element modeling of the degradation and delamination of the interface between a modified HTPB binder and HMX crystals was used to reproduce observed results from tensile loading experiments on bi-crystal specimens. Several comparisons are made with experimental measurements in order to identify appropriate constitutive behavior of the binder and appropriate parameters for the cohesive traction-separation behavior of the crystal-binder interface. This research demonstrates the utility of directly modeling the delamination between binder and crystal within crystal-binder-crystal tensile specimen towards characterizing the behavior of these interfaces in a manner amenable to larger scale simulation of polycrystalline PBX materials. One critical aspect of this approach is micro computed tomography imaging conducted during the experiments, which enabled comparison of delamination patterns between the direct numerical simulation and actual specimen. In addition to optimizing the cohesive interface parameters, one important finding from this investigation is that understanding and representing the strain-hardening plasticity of HTPB binder is important within the context of using a cohesive traction-separation model for the delamination of a crystal-binder system.« less

Cohesive finite element modeling of the delamination of HTPB binder and HMX crystals under tensile loading

DOE PAGES

Walters, David J.; Luscher, Darby J.; Yeager, John D.; ...

2018-02-27

Accurately modeling the mechanical behavior of the polymer binders and the degradation of interfaces between binder and crystal is important to science-based understanding of the macro-scale response of polymer bonded explosives. The paper presents a description of relatively a simple bi-crystal HMX-HTPB specimen and associated tensile loading experiment including computed tomography imaging, the pertinent constitutive theory, and details of numerical simulations used to infer the behavior of the material during the delamination process. Within this work, mechanical testing and direct numerical simulation of this relatively simple bi-crystal system enabled reasonable isolation of binder-crystal interface delamination, in which the effects ofmore » the complicated thermomechanical response of explosive crystals were minimized. Cohesive finite element modeling of the degradation and delamination of the interface between a modified HTPB binder and HMX crystals was used to reproduce observed results from tensile loading experiments on bi-crystal specimens. Several comparisons are made with experimental measurements in order to identify appropriate constitutive behavior of the binder and appropriate parameters for the cohesive traction-separation behavior of the crystal-binder interface. This research demonstrates the utility of directly modeling the delamination between binder and crystal within crystal-binder-crystal tensile specimen towards characterizing the behavior of these interfaces in a manner amenable to larger scale simulation of polycrystalline PBX materials. One critical aspect of this approach is micro computed tomography imaging conducted during the experiments, which enabled comparison of delamination patterns between the direct numerical simulation and actual specimen. In addition to optimizing the cohesive interface parameters, one important finding from this investigation is that understanding and representing the strain-hardening plasticity of HTPB binder is important within the context of using a cohesive traction-separation model for the delamination of a crystal-binder system.« less

Melting of α'- and α-crystals of poly(lactic acid)

NASA Astrophysics Data System (ADS)

Di Lorenzo, Maria Laura; Androsch, René

2016-05-01

The influence of chain structure on thermal stability of α'-crystals of poly(lactic acid) (PLA) with high L-lactic acid content (96-100 %) is detailed in this contribution. α'-crystals of PLA grow at temperatures below 120 °C, and spontaneously transform into stable α-modification during heating. Using conventional differential scanning calorimetry (DSC) and fast scanning chip calorimetry (FSC), a wide range of scanning rates, between about 10-1 and 102 K s-1 could be tested. It was found that reorganization of disordered α'-crystals into stable α-crystals can be suppressed by fast heating. The critical heating rate needed to completely melt α'-crystals and to avoid formation of α-crystals on continuation of heating varies with the chain composition, and decreases upon increase of the D-lactic acid content in the PLA chain.

Tunable bandgap in hybrid perovskite CH{sub 3}NH{sub 3}Pb(Br{sub 3−y}X{sub y}) single crystals and photodetector applications

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

Wang, L.; Duan, R. F.; Huang, F.

We report the synthesis of CH{sub 3}NH{sub 3}Pb(Br{sub 3−y}X{sub y}) (X=Cl and I) single crystals via a stepwise temperature control approach. High-quality CH{sub 3}NH{sub 3}Pb(Br{sub 3−y}X{sub y}) crystals with a tunable bandgap from 1.92 eV to 2.53 eV have been prepared successfully in this way. And further experiments revealed the influence of halogen content and preparation temperature on the structural and optical properties of these crystals. It is observed that chlorine can lower the critical nucleation energy, which results in crystallizing at lower temperature with the chlorine content increasing, while the nucleation energy increases slowly with increasing iodine content. Moreover,more » in contrast to Frank–van der Merwe growth with low heating rate, high heating rate leads to a mass of small size single crystals and Stranski-Krastanov growth. The single crystals with tunable band gap and impressive characteristics enable us to fabricate high performance photodetectors for different wavelengths.« less

[Effect of K2O addition on the crystallization property of dental glass-ceramics].

PubMed

Liu, Xiao-Qiu; Song, Wen-Zhi; Sun, Hong-Chen; Yang, Hai-Bin; Zou, Guang-Tian; Wang, Jing-Yun; Ye, Chang-Li

2006-10-01

To evaluate the effect of K2O addition on the crystallization property of dental glass-ceramics in the Li2O-SiO2-Al2O3-P2O5-ZnO system. Different content of K2O was added into Li2O-SiO2-Al2O3-P2O5-ZnO glass system. The heat-treated system of the glass-ceramics was determined by differential thermal analyses (DTA), then the crystallization components and the microstmcture of the glass-ceramics with different content of K2O were investigated from X-ray diffraction (XRD) analyses and scanning electron microscopy (SEM). Addition of K2O helped to reduce the viscosity of the glass system and improved crystallization. More lithium disilicate crystals appeared after heated-treatment of the glass system which contained 5.3 wt% addition of K2O, and the homogeneously lath-shaped crystals were 4 gm in length. Certain content of K2O can improve the crystallization property of dental glass-ceramics in the Li2O-SiO2-Al2O3-P2O5-ZnO system.

High chloride content calcium silicate glasses.

PubMed

Chen, Xiaojing; Karpukhina, Natalia; Brauer, Delia S; Hill, Robert G

2017-03-08

Chloride is known to volatilize from silicate glass melts and until now, only a limited number of studies on oxychloride silicate glasses have been reported. In this paper we have synthesized silicate glasses that retain large amounts of CaCl 2 . The CaCl 2 has been added to the calcium metasilicate composition (CaO·SiO 2 ). Glasses were produced via a melt quench route and an average of 70% of the chloride was retained after melting. Up to 31.6 mol% CaCl 2 has been successfully incorporated into these silicate glasses without the occurrence of crystallization. 29 Si MAS-NMR spectra showed the silicon being present mainly as a Q 2 silicate species. This suggests that chloride formed Cl-Ca(n) species, rather than Si-Cl bonds. Upon increasing the CaCl 2 content, the T g reduced markedly from 782 °C to 370 °C. Glass density and glass crystallization temperature decreased linearly with an increase in the CaCl 2 content. However, both linear regressions revealed a breakpoint at a CaCl 2 content just below 20 mol%. This might be attributed to a significant change in the structure and is also correlated with the nature of the crystallizing phases formed upon heat treatment. The glasses with less than 19.2 mol% CaCl 2 crystallized to wollastonite, whilst the compositions with CaCl 2 content equal to or greater than 19.2 mol% are thought to crystallize to CaCl 2 . In practice, the crystallization of CaCl 2 could not occur until the crystallization temperature fell below the melting point of CaCl 2 . The implications of the results along with the high chloride retention are discussed.

Phase Change Characteristics of InxSb40-xTe60 Chalcogenide Alloy for Phase Change Random Access Memory

NASA Astrophysics Data System (ADS)

Yun, Jae-Jin; Lee, Won-Jong

2011-07-01

The InxSb40-xTe60 alloy was selected as a new alternative phase change material for Ge2Sb2Te5 (GST) for phase change random access memory (PRAM). The crystal structure of InxSb40-xTe60 was an α(Sb2Te3) rhombohedral (a=b=c, α=β=γ≠90°) single phase with identical lattice parameters in a wide composition range of In (0-28 at. %). The crystallization temperature and melting point of InxSb40-xTe60 were in the ranges of 149-219 °C and 608-614 °C, respectively, and similar to those of GST. The electric properties of InxSb40-xTe60 with a wide composition range of In contents showed the typical PRAM properties such as current-voltage (I-V), resistance-voltage (R-V), and switching behavior. The reset current of InxSb40-xTe60 decreased with increasing In content and the low power consumption and good retention can be realized by controlling In content. The ratio of the cell resistance and sheet resistance of amorphous InxSb40-xTe60 to those crystalline InxSb40-xTe60 were almost the same as or larger than those of GST. The cycling endurance test of InxSb40-xTe60 with a wide range of In contents showed the comparable results to GST. InxSb40-xTe60 was concluded to be a very promising phase change material for PRAM.

Study of the effect of the silver content on the structural and mechanical behavior of Ag-ZrCN coatings for orthopedic prostheses.

PubMed

Ferreri, I; Lopes, V; Calderon V, S; Tavares, C J; Cavaleiro, A; Carvalho, S

2014-09-01

With the increase of elderly population and health problems that are arising nowadays, hip joint prostheses are being widely used. However, it is estimated that 20% of hip replacement surgeries simply fails after few years, mainly due to wear fatigue. Bearing this in mind, this work reports on the development of new coatings that are able to sustain long and innocuous life inside the patient, which will confer to the usual biomaterials improved physical, mechanical and tribological properties. In particular, the development of multifunctional coatings based on Ag-ZrCN, prepared by DC reactive magnetron sputtering using two targets, Zr and a modified Zr target, in an Ar+C2H2+N2 atmosphere. Silver pellets were placed in the erosion area of the alloyed Zr target in order to obtain a silver content up to 8 at.%. The structural results obtained by x-ray diffraction show that the coatings crystallize in a NaCl crystal structure typical of ZrC1-xNx. The increase of Ag content promoted the formation of an additional a-CNx amorphous phase, besides a silver crystalline phase. Hardness is decreasing, as increasing silver content. Despite the low thicknesses, adhesion values (LC3) can be considered as good. Dynamic fatigue results suggest that these coatings system can be a real asset in terms of mechanical properties, by improving the performance of usual Stainless Steel 316 L biomaterials. Copyright © 2014 Elsevier B.V. All rights reserved.

The effect of polymer content on the non-newtonian behavior of acetaminophen suspension.

PubMed

Moghimipour, Eskandar; Kouchak, Maryam; Salimi, Anayatollah; Bahrampour, Saeed; Handali, Somayeh

2013-01-01

Acetaminophen is used as an analgesic and antipyretic agent. The aim of the study was evaluation of the effect of different polymers on rheological behavior of acetaminophen suspension. In order to achieve controlled flocculation, sodium chloride was added. Then structural vehicles such as carboxymethyl cellulose (CMC), polyvinyl pyrrolidone (PVP), tragacanth, and magnesium aluminum silicate (Veegum) were evaluated individually and in combination. Physical stability parameters such as sedimentation volume (F), redispersibility (n), and growth of crystals of the suspensions were determined. Also, the rheological properties of formulations were studied. The results of this study showed that the combination of suspending agents had the most physical stability and pseudoplastic behavior with some degree of thixotropy. Viscosity of suspensions was increased by adding NaCl 0.02%. Presence of PVP is necessary for improving rheological behavior of suspensions by NaCl. This may be related to the cross-linking between the carbonyl group in the PVP segment and Na(+) ions.

The Effect of Polymer Content on the Non-Newtonian Behavior of Acetaminophen Suspension

PubMed Central

Moghimipour, Eskandar; Kouchak, Maryam; Salimi, Anayatollah; Bahrampour, Saeed; Handali, Somayeh

2013-01-01

Acetaminophen is used as an analgesic and antipyretic agent. The aim of the study was evaluation of the effect of different polymers on rheological behavior of acetaminophen suspension. In order to achieve controlled flocculation, sodium chloride was added. Then structural vehicles such as carboxymethyl cellulose (CMC), polyvinyl pyrrolidone (PVP), tragacanth, and magnesium aluminum silicate (Veegum) were evaluated individually and in combination. Physical stability parameters such as sedimentation volume (F), redispersibility (n), and growth of crystals of the suspensions were determined. Also, the rheological properties of formulations were studied. The results of this study showed that the combination of suspending agents had the most physical stability and pseudoplastic behavior with some degree of thixotropy. Viscosity of suspensions was increased by adding NaCl 0.02%. Presence of PVP is necessary for improving rheological behavior of suspensions by NaCl. This may be related to the cross-linking between the carbonyl group in the PVP segment and Na+ ions. PMID:24109512

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

Z Xu; C Chen; Y Wang

Combined effects of graphene nanosheets (GNSs) and shear flow on the crystallization behavior of isotactic polypropylene (iPP) were investigated by in-situ synchrotron wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) techniques. For crystallization under quiescent condition (at 145 C), the half-crystallization time (t{sub 1/2}) of nanocomposites containing 0.05 and 0.1 wt % GNSs was reduced to at least 50% compared to that of neat iPP, indicating the high nucleation ability of GNSs. The crystallization rate of iPP was directly proportional to the GNS content. Under a relatively weak shear flow (at a rate of 20 s{sup -1} for 5more » s duration) and a low degree of supercooling, the neat iPP exhibited an isotropic structure due to the relaxation of row nuclei. However, visible antisotropic crystals appeared in sheared iPP/GNSs nanocomposites, indicating that GNSs induced a network structure hindering the mobility of iPP chains and allowing the survival of oriented row nuclei for a long period of time. The presence of GNSs clearly enhanced the effects of shear-induced nucleation as well as orientation of iPP crystals. Two kinds of nucleating origins coexisted in the sheared nanocomposite melt: heterogeneous nucleating sites initiated by GNSs and homogeneous nucleating sites (row nuclei) induced by shear. The difference of t{sub 1/2} of nanocomposites with and without shear was significantly larger than that of neat iPP. The presence of GNSs and shear flow exhibited a synergistic interaction on promoting crystallization kinetics of iPP, although the effect of GNS concentration was not apparent. From WAXD results of isothermal and nonisothermal crystallization of sheared iPP, it was found that the appearance of {beta}-crystals depended on the preservation of row nuclei, where the {alpha}-crystals were predominant in the iPP/GNSs nanocomposites, indicating that GNSs could directly induce {alpha}-crystals of iPP.« less

Studying of crystal growth and overall crystallization of naproxen from binary mixtures.

PubMed

Kaminska, E; Madejczyk, O; Tarnacka, M; Jurkiewicz, K; Kaminski, K; Paluch, M

2017-04-01

Broadband dielectric spectroscopy (BDS) and differential scanning calorimetry (DSC) were applied to investigate the molecular dynamics and phase transitions in binary mixtures composed of naproxen (NAP) and acetylated saccharides: maltose (acMAL) and sucrose (acSUC). Moreover, the application of BDS method and optical microscopy enabled us to study both crystallization kinetics and crystal growth of naproxen from the solid dispersions with the highest content of modified carbohydrates (1:5wt ratio). It was found that the activation barriers of crystallization estimated from dielectric measurements are completely different for both studied herein mixtures. Much higher E a (=205kJ/mol) was obtained for NAP-acMAL solid dispersion. It is probably due to simultaneous crystallization of both components of the mixture. On the other hand, lower value of E a in the case of NAP-acSUC solid dispersion (81kJ/mol) indicated, that naproxen is the only crystallizing compound. This hypothesis was confirmed by X-ray diffraction studies. We also suggested that specific intermolecular dipole-dipole interactions between active substance and excipient may be an alternative explanation for the difference between activation barrier obtained for NAP-acMAL and NAP-acSUC binary mixtures. Furthermore, optical measurements showed that the activation energy for crystal growth of naproxen increases in binary mixtures. They also revealed that both excipients: acMAL and acSUC move the temperature of the maximum of crystal growth towards lower temperatures. Interestingly, this maximum occurs for nearly the same structural relaxation time, which is a good approximation of viscosity, for all samples. Finally, it was also noticed that although naproxen crystallizes to the same polymorphic form in both systems, there are some differences in morphology of obtained crystals. Thus, the observed behavior may have a significant impact on the bioavailability and dissolution rate of API produced in that way. Copyright © 2016 Elsevier B.V. All rights reserved.

Dependence of microwave dielectric properties on crystallization behaviour of CaMgSi{sub 2}O{sub 6} glass-ceramics

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

Choi, Bo Kyeong; Jang, Sung Wook; Kim, Eung Soo, E-mail: eskim@kyonggi.ac.kr

2015-07-15

The effects of the crystallization behaviour of CaMgSi{sub 2}O{sub 6} (diopside) glass-ceramics on their microwave dielectric properties were investigated as functions of the Cr{sub 2}O{sub 3} content and heat-treatment method used (one or two steps). The crystallization behaviours of the specimens were affected by the Cr{sub 2}O{sub 3} content as well as by the heat-treatment method employed, and were evaluated using X-ray diffraction and the combined Rietveld and reference intensity ratio (RIR) method. The dielectric constants (K) of the specimens did not change significantly with an increase in the Cr{sub 2}O{sub 3} content. The quality factor (Qf) of the specimensmore » increased for Cr{sub 2}O{sub 3} contents of up to 0.5 wt% Cr{sub 2}O{sub 3}, but then decreased for higher contents. These results could be attributed to the degree of crystallization. For the same Cr{sub 2}O{sub 3} content, the specimens that underwent a two-step heat treatment showed lower K values and higher Qf values than those heat-treated in one-step. These results could be attributed to the smaller crystallite size and higher degree of crystallization in the specimens obtained from the two-step heat treatment compared with those of the specimens heat-treated in one-step method.« less

Twice as smart behavior of tert-butylthiacalix[4]arene derivative in glassy and crystalline form.

PubMed

Gataullina, K V; Ziganshin, M A; Stoikov, I I; Gubaidullin, A T; Gorbatchuk, V V

2015-06-28

A studied tert-butylthiacalix[4]arene derivative with four N-(2-acetoxyethyl)carbamoylmethoxy substituents on its lower rim in partial-cone configuration (calixarene 1) can remember its previous treatment in three essentially different ways by the formation either of a molecular glass or two metastable polymorphs after heating or the removal of an included guest molecule. Guest-induced memory is very selective with a polymorph created only after the release of a few included guests among a large series of those studied and is detected via an exothermic transition. Along with ordinary properties, like glass transition, curing and cold crystallization, the molecular glass from 1 is selective due to its ability to crystallize in solvent vapors and vapor mixtures over a well-defined concentration range. Being cooperative, this property may be used for the visual detection of ethanol content in water solution when it reaches a threshold value.

Variation in trace element content of magnetite crystallized from a fractionating sulfide liquid, Sudbury, Canada: Implications for provenance discrimination

NASA Astrophysics Data System (ADS)

Dare, Sarah A. S.; Barnes, Sarah-Jane; Beaudoin, Georges

2012-07-01

Laser ablation ICP-MS analysis has been applied to many accessory minerals in order to understand better the process by which the rock formed and for provenance discrimination. We have determined trace element concentrations of Fe-oxides in massive sulfides that form Ni-Cu-PGE deposits at the base of the Sudbury Igneous Complex in Canada. The samples represent the crystallization products of fractionating sulfide liquids and consist of early-forming Fe-rich monosulfide solution (MSS) cumulates and residual Cu-rich intermediate solid solution (ISS). This study shows that Fe-oxide geochemistry is a sensitive petrogenetic indicator for the degree of fractionation of the sulfide liquid and provides an insight into the partitioning of elements between sulfide and Fe-oxide phases. In addition, it is useful in determining the provenance of detrital Fe-oxide. In a sulfide melt, all lithophile elements (Cr, Ti, V, Al, Mn, Sc, Nb, Ga, Ge, Ta, Hf, W and Zr) are compatible into Fe-oxide. The concentrations of these elements are highest in the early-forming Fe-oxide (titanomagnetite) which crystallized with Fe-rich MSS. Upon the continual crystallization of Fe-oxide from the sulfide liquid, the lithophile elements gradually decrease so that late-forming Fe-oxide (magnetite), which crystallized from the residual Cu-rich liquid, is depleted in these elements. This behavior is in contrast with Fe-oxides that crystallized from a fractionating silicate melt, whereby the concentration of incompatible elements, such as Ti, increases rather than decreases. The behavior of the chalcophile elements in magnetite is largely controlled by the crystallization of the sulfide minerals with only Ni, Co, Zn, Mo, Sn and Pb present above detection limit in magnetite. Nickel, Mo and Co are compatible in Fe-rich MSS and thus the co-crystallizing Fe-oxide is depleted in these elements. In contrast, magnetite that crystallized later from the fractionated liquid with Cu-rich ISS is enriched in Ni, Mo and Co because Fe-rich MSS is absent. The concentrations of Sn and Pb, which are incompatible with Fe-rich MSS, are highest in magnetite that formed from the fractionated Cu-rich liquid. At subsolidus temperatures, ilmenite exsolved from titanomagnetite whereas Al-spinel exsolved from the cores of some magnetite, locally redistributing the trace elements. However, during laser ablation ICP-MS analysis of these Fe-oxides both the magnetite and its exsolution products are ablated so that the analysis represents the original magmatic composition of the Fe-oxide that crystallized from the sulfide melt.

A Systematic Review of Behavioral and Treatment Outcome Studies Among HIV-Infected Men Who Have Sex with Men Who Abuse Crystal Methamphetamine

PubMed Central

Mimiaga, Matthew J.; White, Jaclyn M.; Pinkston, Megan M.; Baden, Rachel P.; Mitty, Jennifer A.

2012-01-01

Abstract Men who have sex with men (MSM) have the highest incidence of HIV infection in the United States. One of the contributing factors to HIV spread among this group is the use of crystal methamphetamine (“meth”). The objective was to review the behavioral impact of crystal meth use in HIV-infected MSM and potential treatment options. A systematic review of MEDLINE identified studies that evaluated the clinical effects of crystal meth on the HIV-infected MSM population. Search terms included HIV, methamphetamine, MSM, antiretroviral therapy, adherence, resistance, and treatment. U.S. citations in the English language in peer-reviewed journals until December 2010 were included. The primary author reviewed eligible articles, and relevant data including study design, sample, and outcomes were entered into an electronic data table. The 61 included studies highlight that HIV-infected MSM who use crystal meth are more likely to report high-risk sexual behaviors, incident sexually transmitted infections, and serodiscordant unprotected anal intercourse, compared to HIV-infected MSM who do not use crystal meth. Medication adherence in this population is notably low, which may contribute to transmission of resistant virus. No medications have proven effective in the treatment of crystal meth addiction, and the role of behavioral therapies, such as contingency management are still in question. HIV-infected MSM who abuse crystal meth have worse HIV-related health outcomes. Behavioral interventions have shown variable results in treating crystal meth addiction, and more investigation into rehabilitation options are needed. The results presented support efforts to develop and implement novel interventions to reduce crystal meth use in HIV-infected MSM. PMID:22070609

Unusual Crystallization Behavior Close to the Glass Transition

NASA Astrophysics Data System (ADS)

Desgranges, Caroline; Delhommelle, Jerome

2018-03-01

Using molecular simulations, we shed light on the mechanism underlying crystal nucleation in metal alloys and unravel the interplay between crystal nucleation and glass transition, as the conditions of crystallization lie close to this transition. While decreasing the temperature of crystallization usually results in a lower free energy barrier, we find an unexpected reversal of behavior for glass-forming alloys as the temperature of crystallization approaches the glass transition. For this purpose, we simulate the crystallization process in two glass-forming Copper alloys, Ag6 Cu4 , which has a positive heat of mixing, and CuZr, characterized by a large negative heat of mixing. Our results allow us to identify this unusual behavior as directly correlated with a nonmonotonic temperature dependence for the formation energy of connected icosahedral structures, which are incompatible with crystalline order and impede the development of the crystal nucleus, leading to an unexpectedly larger free energy barrier at low temperature. This, in turn, promotes the formation of a predominantly closed-packed critical nucleus, with fewer defects, thereby suggesting a new way to control the structure of the crystal nucleus, which is of key importance in catalysis.

Exploring the zone of anisotropy and broken symmetries in DNA-mediated nanoparticle crystallization.

PubMed

O'Brien, Matthew N; Girard, Martin; Lin, Hai-Xin; Millan, Jaime A; Olvera de la Cruz, Monica; Lee, Byeongdu; Mirkin, Chad A

2016-09-20

In this work, we present a joint experimental and molecular dynamics simulations effort to understand and map the crystallization behavior of polyhedral nanoparticles assembled via the interaction of DNA surface ligands. In these systems, we systematically investigated the interplay between the effects of particle core (via the particle symmetry and particle size) and ligands (via the ligand length) on crystallization behavior. This investigation revealed rich phase diagrams, previously unobserved phase transitions in polyhedral crystallization behavior, and an unexpected symmetry breaking in the ligand distribution on a particle surface. To understand these results, we introduce the concept of a zone of anisotropy, or the portion of the phase space where the anisotropy of the particle is preserved in the crystallization behavior. Through comparison of the zone of anisotropy for each particle we develop a foundational roadmap to guide future investigations.

Magma Chamber of the 26.5 ka Oruanui Eruption, Taupo Volcano, New Zealand

NASA Astrophysics Data System (ADS)

Liu, Y.; Anderson, A. T.; Wilson, C. J.; Davis, A. M.

2004-12-01

We have investigated melt inclusions and their host quartz crystals from the Bishop-Tuff-sized 26.5 ka Oruanui eruption at Taupo volcano, New Zealand. Compositions (major and trace elements, H2O and CO2) of melt inclusions and cathodoluminescence (CL) images of quartz were obtained for eight individual pumices from early, middle and late depositional units. All melt inclusions are high-silica weakly peraluminous rhyolites. Melt inclusions for different eruptive phases have similar ranges of H2O contents (3.8-5.2 wt %), but late-erupted samples have higher CO2 contents (mostly > 140 ppm). A positive correlation between CO2 and compatible trace elements such as Sr suggests that crystallization and melt entrapment occurred under gas-saturated conditions. Trace elements variations in melt inclusions are consistent with fractionation of 30-40 wt % crystals (plagioclase+quartz+pyroxene+amphibole). Crystal contents in pumices, trace-element contents in melt inclusions, and CL zoning patterns of quartz show no correlation with eruptive phases, suggesting that the Oruanui magma was well mixed before eruption. Some Oruanui quartz crystals contain distinctive CL zonings with a jagged ('restitic') core mantled by a black CL zone. Trace element variations in melt inclusions in the 'restitic' cores are consistent with fractionation of Ba-bearing minerals such as sanidine and/or biotite, both of which are rare or absent in rocks erupted from Taupo volcanic center. The above evidence suggests that Oruanui rhyolite is generated by assimilation of previous intruded rocks or country rocks, differentiated by crystal fractionation, and then mixed prior to eruption. Despite the differences in trace element and volatile contents, and crystal assemblages, both Bishop Tuff and Oruanui magmas involve crystal fractionation as one of the main differentiation mechanisms during their evolution. However, there are pronounced differences in the pre-eruptive stratification of the two chambers, which may reflect the tectonic settings, eruption rates, and ages of the systems.

Crystal-rich lava dome extrusion during vesiculation: an experimental study

NASA Astrophysics Data System (ADS)

Pistone, M.; Whittington, A. G.; Andrews, B. J.; Cottrell, E.

2016-12-01

Lava dome-forming eruptions represent a common eruptive style and a major hazard on numerous active volcanoes worldwide. The influence of volatiles on the rheological mechanics of lava dome extrusion remains unclear. Here we present new experimental results on the rheology of synthesized, crystal-rich (50 to 80 vol% quartz crystals), hydrous (4.2 wt% H2O in the glass) dacites, which vesiculate from 5 to 27 vol% gas bubbles at high temperatures (483 to 797 °C) during deformation conducted in a parallel plate viscometer (constant stress at 0.64 MPa, and variable strain-rates ranging from 8.32•10-8 to 3.58•10-5 s-1). The experiments replicated lava dome deformation in volcanic conduits during vesiculation of the residual melt, instigated in the experiments by increasing temperature. During gas exsolution we find that the rheological lubrication of the system during deformation is strongly dictated by the imposed initial crystallinity. At low crystal content (< 60 vol%) strain localization within shear bands, composed of melt and gas bubbles that likely interconnect, controls the overall sample rheology. At high crystallinity (60 to 70 vol%) gas pressurization (i.e. pore pressure increase) within crystal clusters and embryonic formation of microscopic fractures drive the system to a brittle behavior. At higher crystallinity (80 vol%) gas pressurization triggers brittle fragmentation through macroscopic fractures, which sustain outgassing and determines the viscous death of the system. The contrasting behaviors at different crystallinities have direct impact on the style of volcanic eruptions. Outgassing induced by deformation and bubble coalescence reduces the system pressurization and the potential for an explosive eruption. Conversely, high crystallinity lava domes experience limited loss of exsolved gas during deformation, permitting the achievement of large overpressures prior to fragmentation, favoring likely explosive eruptions. These findings provide a dataset that might be used to constrain the physical properties of natural lava domes at active volcanoes and show how crystallinity and corresponding gas pressurization control dome growth rate and consequent eruption style.

Crystallization modifiers in lipid systems.

PubMed

Ribeiro, Ana Paula Badan; Masuchi, Monise Helen; Miyasaki, Eriksen Koji; Domingues, Maria Aliciane Fontenele; Stroppa, Valter Luís Zuliani; de Oliveira, Glazieli Marangoni; Kieckbusch, Theo Guenter

2015-07-01

Crystallization of fats is a determinant physical event affecting the structure and properties of fat-based products. The stability of these processed foods is regulated by changes in the physical state of fats and alterations in their crystallization behavior. Problems like polymorphic transitions, oil migration, fat bloom development, slow crystallization and formation of crystalline aggregates stand out. The change of the crystallization behavior of lipid systems has been a strategic issue for the processing of foods, aiming at taylor made products, reducing costs, improving quality, and increasing the applicability and stability of different industrial fats. In this connection, advances in understanding the complex mechanisms that govern fat crystallization led to the development of strategies in order to modulate the conventional processes of fat structuration, based on the use of crystallization modifiers. Different components have been evaluated, such as specific triacyglycerols, partial glycerides (monoacylglycerols and diacylglycerols), free fatty acids, phospholipids and emulsifiers. The knowledge and expertise on the influence of these specific additives or minor lipids on the crystallization behavior of fat systems represents a focus of current interest for the industrial processing of oils and fats. This article presents a comprehensive review on the use of crystallization modifiers in lipid systems, especially for palm oil, cocoa butter and general purpose fats, highlighting: i) the removal, addition or fractionation of minor lipids in fat bases; ii) the use of nucleating agents to modify the crystallization process; iii) control of crystallization in lipid bases by using emulsifiers. The addition of these components into lipid systems is discussed in relation to the phenomena of nucleation, crystal growth, morphology, thermal behavior and polymorphism, with the intention of providing the reader with a complete panorama of the associated mechanisms with crystallization of fats and oils.

Synergistic effects of nucleating agents and plasticizers on the crystallization behavior of poly(lactic acid).

PubMed

Shi, Xuetao; Zhang, Guangcheng; Phuong, Thanh Vu; Lazzeri, Andrea

2015-01-19

The synergistic effect of nucleating agents and plasticizers on the thermal and mechanical performance of PLA nanocomposites was investigated with the objective of increasing the crystallinity and balancing the stiffness and toughness of PLA mechanical properties. Calcium carbonate, halloysite nanotubes, talc and LAK (sulfates) were compared with each other as heterogeneous nucleating agents. Both the DSC isothermal and non-isothermal studies indicated that talc and LAK were the more effective nucleating agents among the selected fillers. Poly(D-lactic acid) (PDLA) acted also as a nucleating agent due to the formation of the PLA stereocomplex. The half crystallization time was reduced by the addition of talc to about 2 min from 37.5 min of pure PLA by the isothermal crystallization study. The dynamic mechanical thermal study (DMTA) indicated that nanofillers acted as both reinforcement fillers and nucleating agents in relation to the higher storage modulus. The plasticized PLA studied by DMTA indicated a decreasing glass transition temperature with the increasing of the PEG content. The addition of nanofiller increased the Young's modulus. PEG had the plasticization effect of increasing the break deformation, while sharply decreasing the stiffness and strength of PLA. The synergistic effect of nanofillers and plasticizer achieved the balance between stiffness and toughness with well-controlled crystallization.

Composite biodegradable biopolymer coatings of silk fibroin - Poly(3-hydroxybutyric-acid-co-3-hydroxyvaleric-acid) for biomedical applications

NASA Astrophysics Data System (ADS)

Miroiu, Floralice Marimona; Stefan, Nicolaie; Visan, Anita Ioana; Nita, Cristina; Luculescu, Catalin Romeo; Rasoga, Oana; Socol, Marcela; Zgura, Irina; Cristescu, Rodica; Craciun, Doina; Socol, Gabriel

2015-11-01

Composite silk fibroin-poly(3-hydroxybutyric-acid-co-3-hydroxyvaleric-acid) (SF-PHBV) biodegradable coatings were grown by Matrix Assisted Pulsed Laser Evaporation on titanium substrates. Their physico-chemical properties and particularly the degradation behavior in simulated body fluid at 37 °C were studied as first step of applicability in local controlled release for tissue regeneration applications. SF and PHBV, natural biopolymers with excellent biocompatibility, but different biodegradability and tensile strength properties, were combined in a composite to improve their properties as coatings for biomedical uses. FTIR analyses showed the stoichiometric transfer from targets to coatings by the presence in the spectra of the main absorption maxima characteristic of both polymers. XRD investigations confirmed the FTIR results showing differences in crystallization behavior with respect to the SF and PHBV content. Contact angle values obtained through wettability measurements indicated the MAPLE deposited coatings were highly hydrophilic; surfaces turning hydrophobic with the increase of the PHBV component. Degradation assays proved that higher PHBV contents resulted in enhanced resistance and a slower degradation rate of composite coatings in SBF. Distinct drug-release schemes could be obtained by adjusting the SF:PHBV ratio to controllably tuning the coatings degradation rate, from rapid-release formulas, where SF predominates, to prolonged sustained ones, for larger PHBV content.

Effect of zinc oxide nanoparticles on dielectric behavior of nematic liquid crystal

NASA Astrophysics Data System (ADS)

Sharma, Amit; Kumar, Pankaj; Malik, Praveen

2018-05-01

In this work, phase transition and dielectric behavior of nematic liquid crystal (NLC), E7 and zinc oxide (ZnO) nanoparticles (NPs) doped nematic liquid crystals are investigated. Effect of nano-particles dispersion is analyzed and compared with the dielectric behavior of E7 and E7-ZnO. Frequency dependent dielectric permittivity at various temperatures in nematic phase for E7 and E7-ZnO sample is also studied.

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

Liuyun, Jiang, E-mail: jlytxg@163.com; Chengdong, Xiong; Lixin, Jiang

Graphical abstract: Effect of n-HA content on the isothermal crystallization, morphology and mechanical property of n-HA/PLGA composites was studied in details. The results showed that the addition of higher content of g-n-HA was favorable to promote the crystallization better in g-n-HA/PLGA composites, but it could also cause more agglomeration in PLGA matrix, as a result of worse mechanical properties, and the addition content of 3 wt% g-n-HA to PLGA matrix was an appropriate proportion, which had the highest bending strength among these g-n-HA/PLGA composites, and it might be potential to be used in biomedical fields in future. Highlights: ► Themore » effect of n-HA content on the n-HA/PLGA composites was studied in detail. ► Isothermal crystallization, microstructure and mechanical property were studied. ► The relation between n-HA content and properties of n-HA/PLGA composite was found. ► An appropriate proportion of n-HA in n-HA/PLGA composite was obtained. - Abstract: A serials of g-n-HA/PLGA composites with surface-modified g-n-HA of 1%, 3%, 6%, 10% and 15% in weight were prepared by solution mixing. The isothermal crystallization, morphology and mechanical property of g-n-HA/PLGA composites were investigated by differential scanning calorimeter (DSC), scanning electron microscope (SEM) and electromechanical universal tester. The results showed that Avrami equation was suitable for describing the isothermal crystallization process in this system, and the crystallization rate of g-n-HA/PLGA composites containing more than 3 wt% g-n-HA was basically accord with the relational expression of T{sub 110} {sub °C} > T{sub 105°C} > T{sub 115°C} > T{sub 120°C}. Moreover, at the same Tc, crystallization rate was greatly enhanced with the increasing of g-n-HA acting as nucleate. However, the addition of higher content of g-n-HA would cause more agglomeration in PLGA matrix, so that the mechanical properties of g-n-HA/PLGA composites would gradually decrease. In conclusion, the addition of higher content of g-n-HA was favorable to promote the crystallization better in g-n-HA/PLGA composites, but it could also cause more agglomeration in PLGA matrix, result in worse mechanical properties, and the addition content of 3 wt% g-n-HA to PLGA matrix was an appropriate proportion, which had the highest bending strength among these g-n-HA/PLGA composites, and it might be potential to be used in biomedical fields in future.« less

Evaluation of crystallization behavior on the surface of nifedipine solid dispersion powder using inverse gas chromatography.

PubMed

Miyanishi, Hideo; Nemoto, Takayuki; Mizuno, Masayasu; Mimura, Hisashi; Kitamura, Satoshi; Iwao, Yasunori; Noguchi, Shuji; Itai, Shigeru

2013-02-01

To investigate crystallization behavior on the surface of amorphous solid dispersion powder using inverse gas chromatography (IGC) and to predict the physical stability at temperatures below the glass transition temperature (T (g)). Amorphous solid dispersion powder was prepared by melt-quenching of a mixture of crystalline nifedipine and polyvinylpyrrolidon (PVP) K-30. IGC was conducted by injecting undecane (probe gas) and methane (reference gas) repeatedly to the solid dispersion at temperatures below T (g). Surface crystallization was evaluated by the retention volume change of undecane based on the observation that the surface of the solid dispersion with crystallized nifedipine gives an increased retention volume. On applying the retention volume change to the Hancock-Sharp equation, surface crystallization was found to follow a two-dimensional growth of nuclei mechanism. Estimation of the crystallization rates at temperatures far below T (g) using the Avrami-Erofeev equation and Arrhenius equation showed that, to maintain its quality for at least three years, the solid dispersion should be stored at -20°C (T (g) - 65°C). IGC can be used to evaluate crystallization behavior on the surface of a solid dispersion powder, and, unlike traditional techniques, can also predict the stability of the solid dispersion based on the surface crystallization behavior.

Structural Variation of LaMnO3+δ by Oxygen Nonstoichiometry

NASA Astrophysics Data System (ADS)

Niwa, Eiki; Maeda, Hiroki; Hashimoto, Takuya; Mizusaki, Junichiro

2013-07-01

The relationship between oxygen content and crystal structure of LaMnO3+δ, which is mother phase of cathode material for solid oxide fuel cells, has been investigated by X-ray diffraction, thermogravimetry and iodometric titration. It was confirmed that LaMnO3+δ with different oxygen content can be prepared by controlling sintering temperature in static air. Crystal system of LaMnO3.17±0.02 and LaMnO3.13±0.01 at room temperature was rhombohedral with space group of Rbar {3}c, whereas crystal structure of LaMnO3.08±0.01 was orthorhombic whose space group was proposed to be Pmna (No. 53). With increase of oxygen content in LaMnO3+δ, molar volume decreased and higher crystal symmetry was obtained.

Temperature dependence of single-crystal elastic constants of flux-grown alpha-GaPO(4).

PubMed

Armand, P; Beaurain, M; Rufflé, B; Menaert, B; Papet, P

2009-06-01

The lattice parameter change with respect to temperature (T) has been measured using high-temperature powder X-ray diffraction techniques for high-temperature flux-grown GaPO(4) single crystals with the alpha-quartz structure. The lattice and the volume linear thermal expansion coefficients in the temperature range 303-1173 K were computed from the X-ray data. The percentage linear thermal expansions along the a and c axes at 1173 K are 1.5 and 0.51, respectively. The temperature dependence of the mass density rho of flux-grown GaPO(4) single crystals was evaluated using the volume thermal expansion coefficient alpha(V)(T) = 3.291 x 10(-5) - 2.786 x 10(-8) [T] + 4.598 x 10(-11)[T](2). Single-crystal high-resolution Brillouin spectroscopy measurements have been carried out at ambient pressure from 303 to 1123 K to determine the elastic constants C(IJ) of high-temperature flux-grown GaPO(4) material. The single-crystal elastic moduli were calculated using the sound velocities via the measured Brillouin frequency shifts Deltanu(B). These are, to our knowledge, the highest temperatures at which single-crystal elastic constants of alpha-GaPO(4) have been measured. Most of the room-temperature elastic constant values measured on flux-grown GaPO(4) material are higher than the ones found for hydrothermally grown GaPO(4) single crystals. The fourth-order temperature coefficients of both the Brillouin frequency shifts T(nuB)((n)) and the single-crystal elastic moduli T(C(IJ))((n)) were obtained. The first-order temperature coefficients of the C(IJ) are in excellent agreement with previous reports on low-temperature hydrothermally grown alpha-GaPO(4) single crystals, while small discrepancies in the higher-order temperature coefficients are observed. This is explained in terms of the OH content in the GaPO(4) network, which is an important parameter in the crystal thermal behavior.

Sidewall crystallization and saturation front formation in silicic magma chambers

NASA Astrophysics Data System (ADS)

Lake, E. T.

2012-12-01

The cooling and crystallization style of silicic magma bodies in the upper crust falls on a continuum between whole-chamber processes of convection, crystal settling, and cumulate formation and interface driven processes of conduction and crystallization front migration. In the former case, volatile saturation occurs uniformly chamber wide, in the latter volatile saturation occurs along an inward propagating front. Ambient thermal gradient primarily controls the propagation rate; warm (> 30 °C / km) geothermal gradients promote 1000m+ thick crystal mush zones but slow crystallization front propagation. Cold geothermal gradients support the opposite. Magma chamber geometry plays a second order role in controlling propagation rates; bodies with high surface to magma ratio and large Earth's surface parallel faces exhibit more rapid propagation and smaller mush zones. Crystallization front propagation occurs at speeds of up to 6 cm/year (rhyolitic magma, thin sill geometry, 10 °C / km geotherm), far faster than diffusion of volatiles in magma and faster than bubbles can nucleate and ascend under certain conditions. Saturation front propagation is fixed by pressure and magma crystal content; above certain modest initial water contents (4.4 wt% in a dacite) mobile magma above 10 km depth always contains a saturation front. Saturation fronts propagate down from the magma chamber roof at lower water contents (3.3 wt% in a dacite at 5 km depth), creating an upper saturated interface for most common (4 - 6 wt%) magma water contents. This upper interface promotes the production of a fluid pocket underneath the apex of the magma chamber. Magma de-densification by bubble nucleation promotes convection and homogenization in dacitic systems. If the fluid pocket grew rapidly without draining, hydro-fracturing and eruption would result. The combination of fluid escape pathways and metal scavenging would generate economic vein or porphyry deposits.

Gallium arsenide single crystal solar cell structure and method of making

NASA Technical Reports Server (NTRS)

Stirn, Richard J. (Inventor)

1983-01-01

A production method and structure for a thin-film GaAs crystal for a solar cell on a single-crystal silicon substrate (10) comprising the steps of growing a single-crystal interlayer (12) of material having a closer match in lattice and thermal expansion with single-crystal GaAs than the single-crystal silicon of the substrate, and epitaxially growing a single-crystal film (14) on the interlayer. The material of the interlayer may be germanium or graded germanium-silicon alloy, with low germanium content at the silicon substrate interface, and high germanium content at the upper surface. The surface of the interface layer (12) is annealed for recrystallization by a pulsed beam of energy (laser or electron) prior to growing the interlayer. The solar cell structure may be grown as a single-crystal n.sup.+ /p shallow homojunction film or as a p/n or n/p junction film. A Ga(Al)AS heteroface film may be grown over the GaAs film.

Crystallization behavior of polypropylene and its effect on woodfiber composite properties

Treesearch

Suzhou Yin; Timothy G. Rials; Michael P. Wolcott

1999-01-01

This paper describes an approach where polarizing optical microscopy is used to observe the crystallization process of different polypropylenes in the presence of wood fiber. The crystallization behavior was found to be related to the chemical composition of the polymer systems and the addition of maleic anhydride grafted polypropylene (MAPP) to polypropylene...

Flow-induced crystallization in isotactic polypropylene

NASA Astrophysics Data System (ADS)

Hamad, Fawzi Ghassan

Brief intervals of strong flow stretch chains in a semicrystalline polymer melt, which results in an increase in the nuclei number density and a transformation of the crystal structure. This flow-induced crystallization (FIC) phenomenon is explored in this study using highly isotactic polypropylene (iPP) samples. Using one synthesized and five commercial linear isotactic polypropylene samples, we investigate the FIC behavior by imposing shear onto these samples in a rotational rheometer. Equipped with a good temperature control and flexible shear protocol, we apply different temperature and flow conditions. The magnitude of the FIC effect varies with basic processing parameters (shear rate, specific work, crystallization temperature, and shearing temperature) and material properties (totalistic, molecular weight distribution, and particle concentration in the polymer). The scope of this study is to systematically investigate the influences of these parameters on FIC. The FIC effects that are investigated in this dissertation are: crystallization kinetics, persistence time of flow-induced nuclei, and crystal morphology. The crystallization time was measured in the rheometer by monitoring the onset of crystallization after quenching samples sheared above Tm. These samples were subsequently used to study their flow-induced nuclei persistence time and crystal morphology. The lifetime of flow-induced nuclei was determined by measuring the time required to return from FIC back to quiescent crystallization using a differential scanning calorimeter. The crystal morphology was imaged using polarized optical microscopy and atomic force microscopy. We investigated the influence of specific work on the three FIC characteristics, and found three regimes that are separated by the critical work ( Wc) and the saturation work (Wsat) thresholds. Below the critical work threshold, the morphology is composed of mostly spherulite crystals, which keep a constant volume, and a small fraction of rice grain (anisotropic) crystals. The number of rice grain crystals increases with specific work, speeding up the crystallization time of the semicrystalline polymer. At critical work, spherulite formation stops, and the morphology consists only of rice grain structures. This morphology allows the sample to crystallize at higher temperatures when cooling at 5 C/min, with the sheared sample crystallizing at 129C compared to the unsheared sample at 113C. . Shearing isotactic polypropylene at higher temperatures reduced the FIC effect after subsequent quenching. Generally speaking, shearing at higher temperatures results in slower crystallization, but surprisingly, the influence of temperature is rather weak. Flow-induced crystallization persists even when shear is applied well above the equilibrium melting temperature (187C), finally weakening above the Hoffman-Weeks temperature (210C). This is likely due to the long lifetime of flow- induced precursors (crystallize to form rice grains), which remain stable at temperatures below 210C and only start to disappear slowly in prolonged annealing at temperatures above 210C (diminishing the FIC effect). Tacticity was found to govern the maximum nuclei number density in sheared samples; samples with lower isotactic content show a stronger FIC effect. Similarly, it was found that the concentration of particulates (mainly catalyst residue) are crucially important to FIC, samples with lower amounts of particles lowering the FIC nuclei number density. Data shows that the rate at which the crystallization time changes correlates with the prominence of the high molecular weight tail. A sample with a higher molecular weight tail in its distribution exhibits a faster change in crystallization time as a function of specific work. Similarly, increasing the molecular weight of the added component in a blend induces a larger change in the FIC behavior. (Abstract shortened by ProQuest.).

Effect of Nickel Content on the Crystallization Behavior in Nanocrystalline (CO1-XNIX)88ZR7B4CU1 Soft Magnetic Alloys

DTIC Science & Technology

2012-01-01

the Ti getter. The tube was removed from the lathe and the open end of the tube was placed into a fixture with a mechanical pump attached. A...manually grinding this layer off. The ingot was then prepared for the melt-spinning process. This was done by placing a Boron Nitride tube in a lathe ...placed in a lathe and rotated. While the tube was rotated, an oxygen torch was placed on one end of the tube with the heat causing the end of the tube

Transient segregation behavior in Cd1-xZnxTe with low Zn content-A qualitative and quantitative analysis

NASA Astrophysics Data System (ADS)

Neubert, M.; Jurisch, M.

2015-06-01

The paper analyzes experimental compositional profiles in Vertical Bridgman (VB, VGF) grown (Cd,Zn)Te crystals, found in the literature. The origin of the observed axial ZnTe-distribution profiles is attributed to dendritic growth after initial nucleation from supercooled melts. The analysis was done by utilizing a boundary layer model providing a very good approximation of the experimental data. Besides the discussion of the qualitative results also a quantitative analysis of the fitted model parameters is presented as far as it is possible by the utilized model.

Utilization of High-Temperature Slags From Metallurgy Based on Crystallization Behaviors

NASA Astrophysics Data System (ADS)

Sun, Yongqi; Zhang, Zuotai

2018-05-01

Here, following the principle of modifying crystallization behaviors, including avoidance and optimization, we review recent research on the utilization of hot slags. Because of the high-temperature property (1450-1650°C), the utilization of hot slags are much different from that of other wastes. We approach this issue from two main directions, namely, material recycling and heat utilization. From the respect of material recycling, the utilization of slags mainly follows total utilization and partial utilization, whereas the heat recovery from slags follows two main paths, namely, physical granulation and chemical reaction. The effective disposal of hot slags greatly depends on clarifying the crystallization behaviors, and thus, we discuss some optical techniques and their applicable scientific insights. For the purpose of crystallization avoidance, characterizing the glass-forming ability of slags is of great significance, whereas for crystallization modification, the selection of chemical additives and control of crystallization conditions comprise the central routes.

Unravelling merging behaviors and electrostatic properties of CVD-grown monolayer MoS{sub 2} domains

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

Hao, Song; Yang, Bingchu, E-mail: bingchuyang@csu.edu.cn; Hunan Key Laboratory for Super-Microstructure and Ultrafast Process, Central South University, 932 South Lushan Road, Changsha 410012

The presence of grain boundaries is inevitable for chemical vapor deposition (CVD)-grown MoS{sub 2} domains owing to various merging behaviors, which greatly limits its potential applications in novel electronic and optoelectronic devices. It is therefore of great significance to unravel the merging behaviors of the synthesized polygon shape MoS{sub 2} domains. Here we provide systematic investigations of merging behaviors and electrostatic properties of CVD-grown polycrystalline MoS{sub 2} crystals by multiple means. Morphological results exhibit various polygon shape features, ascribed to polycrystalline crystals merged with triangle shape MoS{sub 2} single crystals. The thickness of triangle and polygon shape MoS{sub 2} crystalsmore » is identical manifested by Raman intensity and peak position mappings. Three merging behaviors are proposed to illustrate the formation mechanisms of observed various polygon shaped MoS{sub 2} crystals. The combined photoemission electron microscopy and kelvin probe force microscopy results reveal that the surface potential of perfect merged crystals is identical, which has an important implication for fabricating MoS{sub 2}-based devices.« less

Critical experiments of the self-consistent model for polycrystalline Hastelloy-X

NASA Technical Reports Server (NTRS)

Shi, Shixiang; Walker, Kevin P.; Jordan, Eric H.

1991-01-01

A viscoplastic constitutive model is presented for the estimation of the overall mechanical response of Hastelloy-X polycrystalline metals from a knowledge of single crystal behavior. The behavior of polycrystal is derived from that of single crystals using a self-consistent formulation. The single crystal behavior which has been used was developed by summing postulated slip on crystallographic slip systems. The plasticity and creep are treated coupledly using unified viscoplastic model which includes the interaction effects between rapid and slow deformation at elevated temperature. The validity of the model is directly tested by experiments on Hastelloy-X in both single crystal and polycrystalline versions.

Triacylglycerol phase and 'intermediate' seed storage physiology: a study of Cuphea carthagenensis.

PubMed

Crane, Jennifer; Kovach, David; Gardner, Candice; Walters, Christina

2006-04-01

Seeds with 'intermediate' storage physiology store poorly under cold and dry conditions. We tested whether the poor shelf life can be attributed to triacylglycerol phase changes using Cuphea carthagenensis (Jacq.) seeds. Viability remained high when seeds were stored at 25 degrees C, but was lost quickly when seeds were stored at 5 degrees C. Deterioration was fastest in seeds with high (>or=0.10 g g(-1)) and low (0.01 g g(-1)) water contents (g H(2)O g dry mass(-1)), and slowest in seeds containing 0.04 g g(-1). A 45 degrees C treatment before imbibition restored germination of dry seeds by melting crystallized triacylglycerols. Here, we show that the rate of deterioration in C. carthagenensis seeds stored at 5 degrees C correlated with the rate that triacylglycerols crystallized within the seeds. Lipid crystallization, measured using differential scanning calorimetry, occurred at 6 degrees C for this species and was fastest for seeds stored at 5 degrees C that had high and very low water contents, and slowest for seeds containing 0.04 g g(-1). Germination decreased to 50% (P50) when between 16 and 38% of the triacylglycerols crystallized; complete crystallization took from 10 to over 200 days depending on water content. Our results demonstrate interactions between water and triacylglycerols in seeds: (1) water content affects the propensity of triacylglycerols to crystallize and (2) hydration of seed containing crystallized triacylglycerols is lethal. We suggest that these interactions form the basis of the syndrome of damage experienced when seeds with intermediate storage physiologies are placed in long-term storage.

Solid-Phase and Oscillating Solution Crystallization Behavior of (+)- and (-)-N-Methylephedrine.

PubMed

Tulashie, Samuel Kofi; Polenske, Daniel; Seidel-Morgenstern, Andreas; Lorenz, Heike

2016-11-01

This work involves the study of the solid-phase and solution crystallization behavior of the N-methylephedrine enantiomers. A systematic investigation of the melt phase diagram of the enantiomeric N-methylephedrine system was performed considering polymorphism. Two monotropically related modifications of the enantiomer were found. Solubilities and the ternary solubility phase diagrams of N-methylephedrine enantiomers in 2 solvents [isopropanol:water, 1:3 (Vol) and (2R, 3R)-diethyl tartrate] were determined in the temperature ranges between 15°C and 25°C, and 25°C and 40°C, respectively. Preferential nucleation and crystallization experiments at higher supersaturation leading to an unusual oscillatory crystallization behavior as well as a successful preferential crystallization experiment at lower supersaturation are presented and discussed. Copyright © 2016. Published by Elsevier Inc.

Lignin-coated cellulose nanocrystals as promising nucleating agent for poly(lactic acid)

Treesearch

Anju Gupta; William Simmons; Gregory T. Schueneman; Eric A. Mintz

2016-01-01

We report the effect of lignin-coated cellulose nanocrystals (L-CNCs) on the crystallization behavior of poly(lactic acid) (PLA). PLA/L-CNC nanocomposites were prepared by melt mixing, and the crystallization behavior of PLA was investigated using differential scanning calorimetry. Isothermal crystallization data were analyzed using Avrami and Lauritzen–Hoffman...

Random crystal field effect on the magnetic and hysteresis behaviors of a spin-1 cylindrical nanowire

NASA Astrophysics Data System (ADS)

Zaim, N.; Zaim, A.; Kerouad, M.

2017-02-01

In this work, the magnetic behavior of the cylindrical nanowire, consisting of a ferromagnetic core of spin-1 atoms surrounded by a ferromagnetic shell of spin-1 atoms is studied in the presence of a random crystal field interaction. Based on Metropolis algorithm, the Monte Carlo simulation has been used to investigate the effects of the concentration of the random crystal field p, the crystal field D and the shell exchange interaction Js on the phase diagrams and the hysteresis behavior of the system. Some characteristic behaviors have been found, such as the first and second-order phase transitions joined by tricritical point for appropriate values of the system parameters, triple and isolated critical points can be also found. Depending on the Hamiltonian parameters, single, double and para hysteresis regions are explicitly determined.

Behavior of Aging, Micro-Void, and Self-Healing of Glass/Ceramic Materials and Its Effect on Mechanical Properties

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

Liu, Wenning N.; Sun, Xin; Khaleel, Mohammad A.

This chapter first describes tests to investigate the temporal evolution of the volume fraction of ceramic phases, the evolution of micro-damage, and the self-healing behavior of the glass ceramic sealant used in SOFCs, then a phenomenological model based on mechanical analogs is developed to describe the temperature dependent Young’s modulus of glass ceramic seal materials. It was found that after the initial sintering process, further crystallization of the glass ceramic sealant does not stop, but slows down and reduces the residual glass content while boosting the ceramic crystalline content. Under the long-term operating environment, distinct fibrous and needle-like crystals inmore » the amorphous phase disappeared, and smeared/diffused phase boundaries between the glass phase and ceramic phase were observed. Meanwhile, the micro-damage was induced by the cooling-down process from the operating temperature to the room temperature, which can potentially degrade the mechanical properties of the glass/ceramic sealant. The glass/ceramic sealant self-healed upon reheating to the SOFC operating temperature, which can restore the mechanical performance of the glass/ceramic sealant. The phenomenological model developed here includes the effects of continuing aging and devitrification on the ceramic phase volume fraction and the resulted mechanical properties of glass ceramic seal material are considered. The effects of micro-voids and self-healing are also considered using a continuum damage mechanics (CDM) model. The formulation is for glass/ceramic seal in general, and it can be further developed to account for effects of various processing parameters. This model was applied to G18, and the temperature-dependent experimental measurements were used to calibrate the modeling parameters and to validate the model prediction.« less

Anisotropic constitutive modeling for nickel-base single crystal superalloys. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Sheh, Michael Y.

1988-01-01

An anisotropic constitutive model was developed based on crystallographic slip theory for nickel base single crystal superalloys. The constitutive equations developed utilizes drag stress and back stress state variables to model the local inelastic flow. Specially designed experiments were conducted to evaluate the existence of back stress in single crystal superalloy Rene N4 at 982 C. The results suggest that: (1) the back stress is orientation dependent; and (2) the back stress state variable is required for the current model to predict material anelastic recovery behavior. The model was evaluated for its predictive capability on single crystal material behavior including orientation dependent stress-strain response, tension/compression asymmetry, strain rate sensitivity, anelastic recovery behavior, cyclic hardening and softening, stress relaxation, creep and associated crystal lattice rotation. Limitation and future development needs are discussed.

Crystallization of Na2O-SiO2 gel and glass

NASA Technical Reports Server (NTRS)

Neilson, G. F.; Weinberg, M. C.

1984-01-01

The crystallization behavior of a 19 wt pct soda silica gel and gel-derived glass was compared to that of the ordinary glass of the same composition. Both bulk and ground glass samples were utilized. X-ray diffraction measurements were made to identify the crystalline phases and gauge the extent of crystallization. It was found that the gel crystallized in a distinctive manner, while the gel glass behavior was not qualitatively different from that of the ordinary glass.

Lifetime behavior of laser diodes with highly strained InGaAs QWs and emission wavelength between 1120 nm and 1180 nm

NASA Astrophysics Data System (ADS)

Bugge, F.; Bege, R.; Blume, G.; Feise, D.; Sumpf, B.; Werner, N.; Zeimer, U.; Paschke, K.; Weyers, M.

2018-06-01

Highly strained InxGa1-xAs QWs are commonly used for laser diodes in the wavelength range beyond 1100 nm, but they suffer from strain induced formation of defects. The effect of different laser structures and different laser layouts on the aging behavior was investigated. If grown and processed under optimized conditions, laser diodes emitting at 1120 nm, 1156 nm and 1180 nm have lifetimes of several 1000 h up to more than 20,000 h in dependence on structure or indium content. Laser diodes with three different emission wavelength were mounted in a microoptical bench with a second harmonic generation crystal. From these benches laser emission in the green-yellow spectral range with more than 800 mW output power was obtained.

Effect of Ga content on luminescence and defects formation processes in Gd3(Ga,Al)5O12:Ce single crystals

NASA Astrophysics Data System (ADS)

Grigorjeva, L.; Kamada, K.; Nikl, M.; Yoshikawa, A.; Zazubovich, S.; Zolotarjovs, A.

2018-01-01

Luminescence characteristics of Ce3+ - doped Gd3GaxAl5-xO12 single crystals with different Ga contents (x = 1, 2, 3, 4, 5) are studied in the 9-500 K temperature range. The spectra of the afterglow, photoluminescence, radioluminescence, and thermally stimulated luminescence (TSL) of each crystal coincide. The increase of the Ga content results in the high-energy shift of the spectra while the radioluminescence intensity at 9 K remains practically constant up to x = 4. No Ce3+ emission is observed in case of x = 5. The total TSL intensity drastically increases, reaches the maximum value around x = 2-3, and then decreases due to the thermal quenching of the Ce3+ emission. The TSL glow curve maxima are gradually shifting to lower temperatures, and the dependence of the maxima positions and the corresponding trap depths on the Ga content is close to linear. However, the activation energy of the TSL peaks creation under irradiation of the crystals in the 4f - 5d1 absorption band of Ce3+ decreases drastically with the increasing Ga content (especially in the range of x = 1-2), and this dependence is found to be strongly nonlinear. Possible reasons of the nonlinearity are discussed.

Effect of CeO2 on TiC Morphology in Ni-Based Composite Coating

NASA Astrophysics Data System (ADS)

Cai, Yangchuan; Luo, Zhen; Chen, Yao

2018-03-01

The TiC/Ni composite coating with different content of CeO2 was fabricated on the Cr12MoV steel by laser cladding. The microstructure of cladding layers with the different content of CeO2 from the bottom to the surface is columnar crystal, cellular crystal, and equiaxed crystal. When the content of CeO2 is 0 %, the cladding layer has a coarse and nonuniform microstructure and TiC particles gathering in the cladding layer, and then the wear resistance was reduced. Appropriate rare-earth elements refined and homogenised the microstructure and enhanced the content of carbides, precipitated TiC particles and original TiC particles were spheroidised and refined, the wear resistance of the cladding layer was improved significantly. Excessive rare-earth elements polluted the grain boundaries and made the excessive burning loss of TiC particles that reduced the wear resistance of the cladding layer.

Influences of superalloy composition and Pt content on the oxidation behavior of gamma–gamma prime NiPtAl bond coatings

DOE PAGES

Haynes, James A.; Unocic, Kinga A.; Lance, Michael J.; ...

2016-09-13

Here, the effects of superalloy composition and Pt content on the high-temperature oxidation behavior of γ–γ’ NiPtAl diffusion coatings were investigated over the temperature range of 1050–1150 °C. Simple NiPtAl diffusion coatings with 7 or 12 µm electroplated Pt thickness were evaluated in 1-h cycles in dry O 2 for up to 2500 cycles on four superalloys: directionally solidified (DS) alloy 142, 1st generation single-crystal (SX) alloy 1483, and 2nd generation SX alloys X4 and N5. Coatings on high-Hf alloy 142 experienced severe internal oxidation of Hf at all temperatures. Coatings on ~5 at.% Ti alloy 1483 were protective atmore » 1050 °C, but exhibited severe scale spallation at 1100 °C, with extensive formation of Ti- and Ni-rich oxides at the gas interface. Coatings with 7-µm Pt on X 4 were extremely protective at 1100 °C, but failed rapidly at 1150 °C, which also was associated with the formation of Ti-rich oxides. Increasing the coating Pt content on X 4 improved the 1150 °C oxidation behavior. Coatings on Ti-free N 5 showed the best performance at 1150 °C, especially with 12-µm Pt. Although γ–γ’ coatings can exhibit outstanding cyclic oxidation resistance with minimal Al depletion, they appear to be sensitive to substrate composition, as well as eventual Pt depletion due to interdiffusion.« less

Microscopic approach of the crystallization of tripalmitin and tristearin by microscopy.

PubMed

Silva, Roberta Claro da; Martini Soares, Fabiana Andrea Schafer De; Maruyama, Jéssica Mayumi; Dagostinho, Natália Roque; Silva, Ylana Adami; Ract, Juliana Neves Rodrigues; Gioielli, Luiz Antonio

2016-06-01

The crystallization behavior of lipids has important implications in industrial processing of food products, whose physical characteristics depend largely on crystallized fats. The study of the crystallization behavior and polymorphism of a pure lipid system is of great scientific importance as a means of gaining an understanding of the phenomena involved, serving as basic knowledge to help guide the addition or removal of these compounds in different raw materials. The crystallization behavior and polymorphism of pure tripalmitin (PPP) and tristearin (SSS) were investigated by Polarized Light Microscopy (PLM) and Differential Scanning Calorimetry (DSC) under different crystallization conditions. The polymorphic forms (β' and β) of PPP and SSS exhibited different morphologies depending on how they were obtained, either from α form recrystallization or from isotropic melt. Crystallization in the β form was faster in SSS than in PPP, indicating that the process occurs faster in TAGs composed of longer fatty acid chains. Both β' and β polymorphic forms were obtained from α form recrystallization, albeit with predominance of the β form. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Crystallization and characterization of human chorionic gonadotropin in chemically deglycosylated and enzymatically desialylated states

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

Lustbader, J.W.; Birken, S.; Pileggi, N.F.

1989-11-28

Crystals suitable for X-ray diffraction studies at moderate resolution have been grown from two forms of human chorionic gonadotropin (hCG): HF-treated hCG and neuraminidase-treated hCG. The enzymatically desialylated form of hCG produced crystals that diffract to 2.8 {angstrom} as compared to the HF-treated hCG crystals that diffract to 3.0 {angstrom}. Although it was assumed that the high and heterogeneous carbohydrate content of the glycoprotein hormones inhibited their crystallization, this report suggests that it is the negatively charged surface sugars and neither the total carbohydrate content nor its heterogeneity which interferes with crystal formation. Chemical deglycosylation resulted in significantly increased proteinmore » degradation during crystal growth. Such peptide bond cleavages were observed to a much lesser extent in the crystals grown from neuraminidase-digested hCG. Sequence analysis of the HF-treated hCG crystals suggested that up to 45% of the molecules within the crystal had an acid-labile peptide bond cleaved. In contrast, the neuraminidase-treated hCG exhibited less than 9% of this type of cleavage. The manner in which hCG was treated prior to crystallization was found to be a very important factor in the extent of peptide bound cleavages occurring during crystal growth. HF treatment of glycoproteins may render glycoproteins more susceptible to peptide bond cleavage during crystal growth.« less

Physical-Chemical Properties of the Chiral Fungicide Fenamidone and Strategies for Enantioselective Crystallization.

PubMed

Kort, Anne-Kathleen; Lorenz, Heike; Seidel-Morgenstern, Andreas

2016-06-01

Thermodynamic and kinetic parameters are of prime importance for designing crystallization processes. In this article, Preferential Crystallization, as a special approach to carry out enantioselective crystallization, is described to resolve the enantiomers of the chiral fungicide fenamidone. In preliminary investigations the melting behavior and solid-liquid equilibria in the presence of solvents were quantified. The analyses revealed a stable solid phase behavior of fenamidone in the applied solvents. Based on the results obtained, a two-step crystallization route was designed and realized capable of providing highly pure enantiomers. An initial Preferential Crystallization of the racemate was performed prior to crystallizing the target enantiomer preferentially out of the enriched mother liquor. Chirality 28:514-520, 2016. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Comparison studies of rheological and thermal behaviors of ionic liquids and nanoparticle ionic liquids.

PubMed

Xu, Yiting; Zheng, Qiang; Song, Yihu

2015-08-14

Novel nanoparticle ionic liquids (NILs) are prepared by grafting modified nanoparticles with long-chain ionic liquids (ILs). The NIL behaves like a liquid at ambient temperature. We studied the rheological behavior of the IL and NIL over the range of 10-55 °C and found an extraordinary difference between the IL and NIL: a small content of nanosilica (7%) moderately improves the crystallinity by 7% of the poly(ethylene glycol) (PEG) segment in the IL, and it improves the dynamic moduli significantly (by 5 times at room temperature). It retards the decay temperature (by 10 °C) of the dynamic moduli during heating as well. The thermal rheological hysteresis observed during heating-cooling temperature sweeps is ascribed to the melting-recrystallization of the PEG segments. Meanwhile, the IL and NIL express accelerated crystallization behavior in comparison with the oligomeric anion. For the first time, we find that ILs and NILs are able to form nanoparticle-containing spherulites at room temperature after long time aging.

Non-Newtonian behavior of plagioclase-bearing basaltic magma: Subliquidus viscosity measurement of the 1707 basalt of Fuji volcano, Japan

NASA Astrophysics Data System (ADS)

Ishibashi, Hidemi

2009-03-01

Laboratory measurements of viscosity were done for basalt erupted in 1707 AD from Fuji volcano, Japan, using a concentric cylinder rotational viscometer at temperatures of 1297-1157 °C, 1 atm pressure, and fO 2 near the Ni-NiO buffer. On cooling, elongated plagioclase crystals with a mean length/width ratio of ca. 8.5 appeared at 1237 °C, followed by olivine at 1157 °C. At progressively lower temperatures, the total crystal volume fraction increased monotonously to ca. 0.25; viscosity increased from 38.9 to 765 Pa s at a shear strain rate of 1 s - 1 . This basalt magma behaves as a Newtonian fluid at temperatures greater than 1217 °C, but shear-thinning behavior occurs at temperatures less than 1197 °C because of the suspended plagioclase crystals. This behavior is well approximated as a power law fluid. At the onset of shear thinning, the crystal volume fraction was between 0.06 and 0.13, which is attributed to the pronounced lath-shape of plagioclase crystals. The relative viscosity increases monotonously with increase of crystal volume fraction at a constant shear strain rate, and with decrease of shear strain rate at a constant crystal volume fraction. A modified form of the Krieger-Dougherty equation is introduced herein. It enables us to describe the dependencies of relative viscosity on both the crystal volume fraction and shear strain rate, and consequently the onset of shear-thinning behavior.

Structural transitions and multiferroic properties of high Ni-doped BiFeO3

NASA Astrophysics Data System (ADS)

Betancourt-Cantera, L. G.; Bolarín-Miró, A. M.; Cortés-Escobedo, C. A.; Hernández-Cruz, L. E.; Sánchez-De Jesús, F.

2018-06-01

Nickel doped bismuth ferrite powders, BiFe1-x NixO3 (0 ≤ x ≤ 0.5), were synthesized by high-energy ball milling followed by an annealing at 700 °C. A detailed study about the substitution of Fe3+ by Ni2+ on the crystal structure and multiferroic properties is presented. The X-ray diffraction patterns reveal the formation of rhombohedral structure with small amounts of Bi2Fe4O9 as a secondary phase for x < 0.1. Also it is inferred the stabilization of a Bi25FeO40, sillenite phase, as the amount of Ni2+ substitution increases, reaching up 95.23% of sillenite for x = 0.5. The magnetic behavior indicates the frustration of the G-antiferromagnetic order typical of the un-doped BiFeO3, caused by the presence of small amounts of Ni2+ (x < 0.1) on the structure. The DC conductivity exhibited a little increment with increasing Ni content (up to x = 0.1). Although the conductivity increases, for nickel concentrations of 0.2-0.5, the bismuth ferrites doped with nickel retain their property of being an electrical insulating material. Behavior modifications of electrical conductivity, permittivity and dielectric loss versus frequency are related with crystal structure transformations, when nickel concentration is increased.

Calorimetric study of phase transitions in nanocomposites of quantum dots and a liquid crystal

NASA Astrophysics Data System (ADS)

Kalakonda, P.; Iannacchione, G. S.

2015-06-01

The complex specific heat is measured over a wide temperature range for the liquid crystal (LC) 4-cyano-4-octylbiphenyl (8CB) and cadmium sulfate quantum dots (QDs) composites as a function of QD concentration. The thermal scans were performed under near-equilibrium conditions for all samples having QDs weight percent (φw) from 0 to 3wt% over a wide range of temperature well above and below the two transitions in pure 8CB. Isotropic (I) to nematic (N) and nematic to smectic-A (SmA) phase transitions evolve in character and their transition temperatures offset by (∼2.3 to 2.6 K) lower for all composite samples as compared to that in pure 8CB. The enthalpy change associated with I-N phase transitions shows slightly different behavior on heating and cooling and it also shows crossover behavior at lower and higher QD content. The enthalpy change associated with N-SmA phase transitions is independent of QD loading and thermal treatment. Given the homogeneous and random distribution of QD in these nanocomposites, we interpret that these results as arising that the nematic phase imposes self-assembly on QDs to form one-dimensional arrays leading to QDs and induces net local disordering effect in LC media.

Internally Consistent Single-Crystal Elasticity of (Mg0.89Fe0.11)2SiO4 Wadsleyite at High Pressures and High Temperatures

NASA Astrophysics Data System (ADS)

Buchen, J.; Marquardt, H.; Kurnosov, A.; Boffa Ballaran, T.; Speziale, S.; Kawazoe, T.

2016-12-01

The transition zone in Earth's upper mantle attains a pivotal role in deep Earth dynamics. Various scenarios for the fate of subducted lithospheric slabs have been identified from seismic tomographic images while petrological observations point to potential reservoirs of volatile elements in the transition zone. Among the mineral phases expected to assemble a mantle rock at depths between 410 km and 520 km, wadsleyite stands out with a remarkable hydrogen storage capacity of several weight percent H2O, a volume fraction of about 60 % for a pyrolitic mantle composition, and the potential to cause seismic anisotropy. Interpretations of seismological observations in terms of the thermal and mineralogical state of the upper transition zone rely on the elastic properties of wadsleyite at the prevailing conditions of pressure and temperature including its elastic anisotropy. We have determined internally consistent single-crystal elastic constants for wadsleyite with a relevant composition ((Mg0.89Fe0.11)1.98H0.04SiO4, 0.25(3) wt-% H2O) up to a pressure of 16 GPa at room temperature and conducted first measurements at combined high pressures and high temperatures. Single-crystal segments were cut from oriented thin sections with a focused ion beam and complementary orientations loaded together into the same pressure chamber of resistively heated diamond anvil cells. Using this two-sample approach and a combination of Brillouin spectroscopy and single-crystal X-ray diffraction, all nine independent elastic constants can be obtained under consistent conditions of pressure and temperature. Comparison of our room temperature results with those reported for wadsleyites with different iron contents suggests a very small effect of Fe-Mg substitution on the bulk modulus while the shear modulus decreases with increasing iron content. This differential effect of iron on the elastic moduli bears the potential to be seismically distinguishable from the signatures of temperature or other chemical substituents like volatile elements. The two-sample approach is currently being extended to four crystal segments to directly quantify the effect of hydrogen incorporation on the elastic behavior of iron-bearing wadsleyite.

Novel silk fibroin films prepared by formic acid/hydroxyapatite dissolution method.

PubMed

Ming, Jinfa; Liu, Zhi; Bie, Shiyu; Zhang, Feng; Zuo, Baoqi

2014-04-01

Bombyx mori silk fibroin from the silkworm was firstly found to be soluble in formic acid/hydroxyapatite system. The rheological behavior of silk fibroin solution was significantly influenced by HAp contents in dissolved solution. At the same time, silk fibroin nanofibers were observed in dissolved solution with 103.6±20.4nm in diameter. Moreover, the structure behavior of SF films prepared by formic acid/hydroxyapatite dissolution method was examined. The secondary structure of silk fibroin films was attributed to silk II structure (β-sheet), indicating that the hydroxyapatite contents in dissolved solution were not significantly affected by the structure of silk fibroin. The X-ray diffraction results exhibited obviously hydroxyapatite crystalline nature existing in silk fibroin films; however, when the hydroxyapatite content was 5.0wt.% in dissolved solution, some hydroxyapatite crystals were converted to calcium hydrogen phosphate dehydrate in silk fibroin dissolution process. This result was also confirmed by Fourier transform infrared analysis and DSC measurement. In addition, silk fibroin films prepared by this dissolution method had higher breaking strength and extension at break. Based on these analyses, an understanding of novel SF dissolution method may provide an additional tool for designing and synthesizing advanced materials with more complex structures, which should be helpful in different fields, including biomaterial applications. Copyright © 2014 Elsevier B.V. All rights reserved.

Investigating the effects of polymer molecular weight and non-solvent content on the phase separation, surface morphology and hydrophobicity of polyvinyl chloride films

NASA Astrophysics Data System (ADS)

Khoryani, Zahra; Seyfi, Javad; Nekoei, Mehdi

2018-01-01

The main aim of this research is to study the effects of polymer molecular weight as well as non-solvent concentration on the phase separation, surface morphology and wettability of polyvinyl chloride (PVC) films. Gel permeation chromatography (GPC) results showed that the Mn of the used PVC grades is 6 × 104, 8.7 × 104 and 1.26 × 105 g/mol. It was found that a proper combination of polymer molecular weight and non-solvent content could result in superhydrophobic and self-cleaning behaviors. Scanning electron microscopy (SEM) results demonstrated that addition of ethanol causes the polymer chains to be severely aggregated at the films' surface forming strand-like structures decorated by nano-scale polymer spheres. The polymer molecular weight was found to affect the degree of porosity which is highly influential on the hydrophobicity of the films. The mechanism of phase separation process was also discussed and it was found that the instantaneous demixing is the dominant mechanism once higher contents of non-solvent were used. However, a delayed demixing mechanism was detected when the lower molecular weight PVC has been used which resulted in a pore-less and dense skin layer. Differential scanning calorimetry was also utilized to study the crystallization and glass transition behavior of samples.

Methodology Developed for Modeling the Fatigue Crack Growth Behavior of Single-Crystal, Nickel-Base Superalloys

NASA Technical Reports Server (NTRS)

1996-01-01

Because of their superior high-temperature properties, gas generator turbine airfoils made of single-crystal, nickel-base superalloys are fast becoming the standard equipment on today's advanced, high-performance aerospace engines. The increased temperature capabilities of these airfoils has allowed for a significant increase in the operating temperatures in turbine sections, resulting in superior propulsion performance and greater efficiencies. However, the previously developed methodologies for life-prediction models are based on experience with polycrystalline alloys and may not be applicable to single-crystal alloys under certain operating conditions. One of the main areas where behavior differences between single-crystal and polycrystalline alloys are readily apparent is subcritical fatigue crack growth (FCG). The NASA Lewis Research Center's work in this area enables accurate prediction of the subcritical fatigue crack growth behavior in single-crystal, nickel-based superalloys at elevated temperatures.

Synthesis, characterization and magnetic properties of MWCNTs decorated with Zn-substituted MnFe2O4 nanoparticles using waste batteries extract

NASA Astrophysics Data System (ADS)

Gabal, M. A.; Al-Harthy, E. A.; Al Angari, Y. M.; Abdel Salam, M.; Asiri, A. M.

2016-06-01

Mn1-xZnxFe2O4 (x=0.2-0.8) nano-crystals, synthesized from recycling of Zn-C batteries, were successfully self-assembled alongside multi-walled carbon nanotubes (MWCNTs) via an environmentally friend sucrose auto-combustion method. The effect of Zn-content on structural and magnetic properties were investigated and discussed. XRD revealed the formation of single-phase ferrites. DTA-TG experiment showed that the auto-combustion reaction finished at about 350 °C. TEM exhibited that the MWCNTs are well decorated with ferrite particles. Hysteresis loop measurements revealed ferromagnetic behavior, with saturation magnetization decrease by the addition of MWCNTs or increasing Zn-Content. The kinetics of methylene blue dye (MB) removal using MWCNTs/Mn0.8Zn0.2Fe2O nano-composite was investigated and discussed.

Phosphorus solubility in basaltic glass: Limitations for phosphorus immobilization in glass and glass-ceramics.

PubMed

Tarrago, M; Garcia-Valles, M; Martínez, S; Neuville, D R

2018-05-11

The composition of sewage sludge from urban wastewater treatment plants is simulated using P-doped basalts. Electron microscopy analyses show that the solubility of P in the basaltic melt is limited by the formation of a liquid-liquid immiscibility in the form of an aluminosilicate phase and a Ca-Mg-Fe-rich phosphate phase. The rheological behavior of these compositions is influenced by both phase separation and nanocrystallization. Upon a thermal treatment, the glasses will crystallize into a mixture of inosilicates and spinel-like phases at low P contents and into Ca-Mg-Fe phosphate at high P contents. Hardness measurements yield values between 5.41 and 7.66 GPa, inside the range of commercial glasses and glass-ceramics. Leaching affects mainly unstable Mg 2+ -PO 4 3- complexes. Copyright © 2018 Elsevier Ltd. All rights reserved.

Bond energy prediction of Curie temperature of lithium niobate crystals.

PubMed

Zhang, Xu; Xue, Dongfeng

2007-03-15

A general expression of the Curie temperature (Tc) and spontaneous polarization (Ps) of lithium niobate (LN) crystals is energetically proposed by employing the viewpoint of the bond energy of constituent chemical bonds within the LN crystallographic frame. The calculated Tc values of various pure and doped LN crystals are in a good agreement with those reported data. Ps values of these LN crystals can also be quantitatively estimated in this work. It is found that the Li site is a sensitive lattice position to dominate the ferroelectricity of LN crystals. This novel method provides us a good understanding of ferroelectric behaviors of LN crystals, which may be applicable to the estimation of ferroelectric behaviors of LN-type solids.

Influence of bis-thiourea nickel nitrate on the structural, optical, electrical, thermal and mechanical behavior of a KDP single crystal for NLO applications

NASA Astrophysics Data System (ADS)

Rasal, Y. B.; Shaikh, R. N.; Shirsat, M. D.; Kalainathan, S.; Hussaini, S. S.

2017-03-01

A single crystal of bis-thiourea nickel nitrate (BTNN) doped potassium dihydrogen phosphate (KDP) has been grown from solution at room temperature by a slow evaporation technique. The cell parameters of the grown crystals were determined using single crystal x-ray diffraction analysis. The different functional groups of the grown crystal were confirmed using Fourier transform infrared analysis. The improved optical parameters of the grown crystal have been evaluated in the range of 200-900 nm using UV-visible spectral analysis. The grown crystal was transparent in the entire visible region and the band gap value was found to be 4.96 eV. The influence of BTNN on the third order nonlinear optical properties of KDP crystal has been investigated by means of the Z-scan technique. The second harmonic generation (SHG) efficiency of grown crystal measured using a Nd-YAG laser is 1.98 times higher than that of pure KDP. The third order nonlinear optical susceptibility (χ 3) and nonlinear absorption coefficient (β) of BTNN doped KDP crystal is found to be 1.77  ×  10-5 esu and 5.57  ×  10-6 cm W-1 respectively. The laser damage threshold (LDT) energy for the grown crystal has been measured by using a Q-switched Nd:YAG laser source. The bis-thiourea nickel nitrate shows authoritative impact on the dielectric properties of doped crystal. The influence of bis-thiourea nickel nitrate on the mechanical behavior of KDP crystal has been investigated using Vickers microhardness intender. The thermal behavior of BTNN doped KDP crystal has been analyzed by TGA/DTA analysis.

Retrogradation of Maize Starch after High Hydrostatic Pressure Gelation: Effect of Amylose Content and Depressurization Rate.

PubMed

Yang, Zhi; Swedlund, Peter; Gu, Qinfen; Hemar, Yacine; Chaieb, Sahraoui

2016-01-01

High hydrostatic pressure (HHP) has been employed to gelatinize or physically modify starch dispersions. In this study, waxy maize starch, normal maize starch, and two high amylose content starch were processed by a HHP of the order of 600 MPa, at 25°C for 15min. The effect of HHP processing on the crystallization of maize starches with various amylose content during storage at 4°C was investigated. Crystallization kinetics of HHP treated starch gels were investigated using rheology and FTIR. The effect of crystallization on the mechanical properties of starch gel network were evaluated in terms of dynamic complex modulus (G*). The crystallization induced increase of short-range helices structures were investigated using FTIR. The pressure releasing rate does not affect the starch retrogradation behaviour. The rate and extent of retrogradation depends on the amylose content of amylose starch. The least retrogradation was observed in HHP treated waxy maize starch. The rate of retrogradation is higher for HHP treated high amylose maize starch than that of normal maize starch. A linear relationship between the extent of retrogradation (phase distribution) measured by FTIR and G* is proposed.

Retrogradation of Maize Starch after High Hydrostatic Pressure Gelation: Effect of Amylose Content and Depressurization Rate

PubMed Central

Yang, Zhi; Swedlund, Peter; Gu, Qinfen; Hemar, Yacine; Chaieb, Sahraoui

2016-01-01

High hydrostatic pressure (HHP) has been employed to gelatinize or physically modify starch dispersions. In this study, waxy maize starch, normal maize starch, and two high amylose content starch were processed by a HHP of the order of 600 MPa, at 25°C for 15min. The effect of HHP processing on the crystallization of maize starches with various amylose content during storage at 4°C was investigated. Crystallization kinetics of HHP treated starch gels were investigated using rheology and FTIR. The effect of crystallization on the mechanical properties of starch gel network were evaluated in terms of dynamic complex modulus (G*). The crystallization induced increase of short-range helices structures were investigated using FTIR. The pressure releasing rate does not affect the starch retrogradation behaviour. The rate and extent of retrogradation depends on the amylose content of amylose starch. The least retrogradation was observed in HHP treated waxy maize starch. The rate of retrogradation is higher for HHP treated high amylose maize starch than that of normal maize starch. A linear relationship between the extent of retrogradation (phase distribution) measured by FTIR and G* is proposed. PMID:27219066

Subsurface Connections and Magma Mixing as revealed by Olivine- and Pyroxene-Hosted Melt Inclusions from Cerro Negro Volcano and the Las Pilas-El Hoyo Complex, Nicaragua.

NASA Astrophysics Data System (ADS)

Venugopal, S.; Moune, S.; Williams-Jones, G.

2015-12-01

Cerro Negro, the youngest volcano in the Central American Volcanic Belt, is a polygenetic cinder cone with relatively frequent explosive basaltic eruptions. Las Pilas, on the other hand, is a much larger and older complex with milder and less frequent eruptions. Based on historical data, these two closely spaced volcanoes have shown concurrent eruptive behavior, suggesting a subsurface connection. To further investigate this link, melt inclusions, which are blebs of melt trapped in growing crystals, were the obvious choice for optimal comparison of sources and determination of pre-eruptive volatile contents and magmatic conditions. Olivine-hosted inclusions were chosen for both volcanoes and pyroxene-hosted inclusions were also sampled from Las Pilas to represent the evolved melt. Major, volatile and trace elements reveal a distinct geochemical continuum with Cerro Negro defining the primitive end member and Las Pilas representing the evolved end member. Volatile contents are high for Cerro Negro (up to 1260 ppm CO2, 4.27 wt% H2O and 1700 ppm S) suggesting that volatile exsolution is likely the trigger for Cerro Negro's explosive eruptions. Las Pilas volatile contents are lower but consistent with degassing and evolutionary trends shown by major oxides. Trace element contents are rather unique and suggest Cerro Negro magmas fractionally crystallize while Las Pilas magmas are the products of mixing. Magmatic conditions were estimated with major and volatile contents: at least 2.4 kbar and 1170 °C for Cerro Negro melts and 1.3 kbar and 1130 °C for Las Pilas melts with an overall oxygen fugacity at the NNO buffer. In combination with available literature data, this study suggests an interconnected subsurface plumbing system and thus Cerro Negro should be considered as the newest vent within the Las Pilas-El Hoyo Complex.

Mechanisms of differentiation in the Skaergaard magma chamber

NASA Astrophysics Data System (ADS)

Tegner, C.; Lesher, C. E.; Holness, M. B.; Jakobsen, J. K.; Salmonsen, L. P.; Humphreys, M. C. S.; Thy, P.

2012-04-01

The Skaergaard intrusion is a superb natural laboratory for studying mechanisms of magma chamber differentiation. The magnificent exposures and new systematic sample sets of rocks that solidified inwards from the roof, walls and floor of the chamber provide means to test the relative roles of crystal settling, diffusion, convection, liquid immiscibility and compaction in different regions of the chamber and in opposite positions relative to gravity. Examination of the melt inclusions and interstitial pockets has demonstrated that a large portion of intrusion crystallized from an emulsified magma chamber composed of immiscible silica- and iron-rich melts. The similarity of ratios of elements with opposite partitioning between the immiscible melts (e.g. P and Rb) in wall, floor and roof rocks, however, indicate that large-scale separation did not occur. Yet, on a smaller scale of metres to hundred of metres and close to the interface between the roof and floor rocks (the Sandwich Horizon), irregular layers and pods of granophyre hosted by extremely iron-rich cumulates point to some separation of the two liquid phases. Similar proportions of the primocryst (cumulus) minerals in roof, wall and floor rocks indicate that crystal settling was not an important mechanism. Likewise, the lack of fractionation of elements with different behavior indicate that diffusion and fluid-driven metasomatism played relatively minor roles. Compositional convection and/or compaction within the solidifying crystal mush boundary layer are likely the most important mechanisms. A correlation of low trapped liquid fractions (calculated from strongly incompatible elements) in floor rocks with high fractionation density (the density difference between the crystal framework and the liquid) indicate that compaction is the dominating process in expelling evolved liquid from the crystal mush layer. This is supported by high and variable trapped liquid contents in the roof rocks, where gravity-driven compaction will not work.

Sol-gel synthesis and densification of aluminoborosilicate powders. Part 2: Densification

NASA Technical Reports Server (NTRS)

Bull, Jeffrey; Selvaduray, Guna; Leiser, Daniel

1992-01-01

Aluminoborosilicate (ABS) powders, high in alumina content, were synthesized by the sol-gel process utilizing four different methods of synthesis. The effect of these methods on the densification behavior of ABS powder compacts was studied. Five regions of shrinkage in the temperature range 25-1184 C were identified. In these regions, the greatest shrinkage occurred between the gel-to-glass transition temperature (T sub g approximately equal to 835 C) and the crystallization transformation temperature (T sub t approximately equal 900 C). The dominant mechanism of densification in this range was found to be viscous sintering. ABS powders were amorphous to x-rays up to T sub t at which a multiphasic structure crystallized. No 2Al2O3.B2O3 was found in these powders as predicted in the phase diagram. Above T sub t, densification was the result of competing mechanisms including grain growth and boria fluxed viscous sintering. Apparent activation energies for densification in each region varied according to the method of synthesis.

In-Situ Microphysics from the MPACE IOP

DOE Data Explorer

McFarquhar, Greg

2008-01-15

Best estimates of the size distributions of supercooled water droplets and ice crystals for mixed-phase clouds measured during M-PACE for spiral ascents/descents over Barrow and Oliktok Point, and for ramped ascents/descents between Barrow and Oliktok Point. Our best estimates of the bulk microphysical properties such as ice water content (IWC), liquid water content (LWC), effective radius of ice crystals defined following Fu (1996) (rei), effective radius of supercooled water droplets (rew), total ice crystal number concentration (Ni), total water droplet number concentration (Nw) and total condensed water content (CWC), are also provided. The quantities were derived from the FSSP, 1DC, 2DC, HVPS and the CVI. Note HVPS data are only available after 10 Oct 2004 and some procedures have been developed to account for the missing data.

Electronic, magnetic, transport, and thermal properties of single-crystalline UF e2A l10

NASA Astrophysics Data System (ADS)

Troć, R.; Samsel-Czekała, M.; Talik, E.; Wawryk, R.; Gajek, Z.; Pasturel, M.

2015-09-01

The valence and core-level x-ray photoemission spectra (XPS), performed on an UF e2A l10 single crystal, were measured using the Al Kα radiation. The results of valence XPS show practically two separate regions of spectral intensity, one just at the Fermi level (EF) and the other one being a wide content with its maximum at about 0.8 eV below EF. These give rise to two electronic configurations of the 5 f states in the studied aluminide, itinerant and localized ones, i.e., their dual character. In such a situation the corresponding valence spectra, calculated within the local density approximation (LDA), well explain the former configuration, being responsible for a metallic behavior of the studied compound. Moreover, this behavior is confirmed clearly also by our results of magnetotransport measurements. On the other hand, the obtained magnetic susceptibility, specific heat, electrical resistivity, and thermoelectric power data support very well the local character of the 5 f2 -electron configuration of the U4 + ion in UF e2A l10 having the orthorhombic and cage-type crystal structure. Based on that configuration, the magnetic and thermal characteristics of the compound were modeled by the effective crystal field (CF) potential in the intermediate coupling scheme using initial parameters obtained by the angular overlap model (AOM). The obtained final CF parameters yielded the CF level scheme, composed of only singlets, proper for orthorhombic symmetry. Such a set of singlets reproduces in a satisfactory way both the strongly anisotropic temperature variations of the magnetic susceptibility, measured along the three main crystallographic directions, as well as the Schottky anomaly, evaluated using specific heat results of isomorphic ThF e2A l10 as a phonon reference. Also, the strongly anisotropic behavior of the Seebeck coefficient and its low temperature maxima observed for the compound studied here have been explained roughly by the CF effect.

Crystal growth, structural, thermal and mechanical behavior of l-arginine 4-nitrophenolate 4-nitrophenol dihydrate (LAPP) single crystals.

PubMed

Mahadevan, M; Ramachandran, K; Anandan, P; Arivanandhan, M; Bhagavannarayana, G; Hayakawa, Y

2014-12-10

Single crystals of l-arginine 4-nitrophenolate 4-nitrophenol dihydrate (LAPP) have been grown successfully from the solution of l-arginine and 4-nitrophenol. Slow evaporation of solvent technique was adopted to grow the bulk single crystals. Single crystal X-ray diffraction analysis confirms the grown crystal has monoclinic crystal system with space group of P21. Powder X-ray diffraction analysis shows the good crystalline nature. The crystalline perfection of the grown single crystals was analyzed by HRXRD by employing a multicrystal X-ray diffractometer. The functional groups were identified from proton NMR spectroscopic analysis. Linear and nonlinear optical properties were determined by UV-Vis spectrophotometer and Kurtz powder technique respectively. It is found that the grown crystal has no absorption in the green wavelength region and the SHG efficiency was found to be 2.66 times that of the standard KDP. The Thermal stability of the crystal was found by obtaining TG/DTA curve. The mechanical behavior of the grown crystal has been studied by Vicker's microhardness method. Copyright © 2014 Elsevier B.V. All rights reserved.

Molecular basis of crystal morphology-dependent adhesion behavior of mefenamic acid during tableting.

PubMed

Waknis, Vrushali; Chu, Elza; Schlam, Roxana; Sidorenko, Alexander; Badawy, Sherif; Yin, Shawn; Narang, Ajit S

2014-01-01

The molecular basis of crystal surface adhesion leading to sticking was investigated by exploring the correlation of crystal adhesion to oxidized iron coated atomic force microscope (AFM) tips and bulk powder sticking behavior during tableting of two morphologically different crystals of a model drug, mefenamic acid (MA), to differences in their surface functional group orientation and energy. MA was recrystallized into two morphologies (plates and needles) of the same crystalline form. Crystal adhesion to oxidized iron coated AFM tips and bulk powder sticking to tablet punches was assessed using a direct compression formulation. Surface functional group orientation and energies on crystal faces were modeled using Accelrys Material Studio software. Needle-shaped morphology showed higher sticking tendency than plates despite similar particle size. This correlated with higher crystal surface adhesion of needle-shaped morphology to oxidized iron coated AFM probe tips, and greater surface energy and exposure of polar functional groups. Higher surface exposure of polar functional groups correlates with higher tendency to stick to metal surfaces and AFM tips, indicating involvement of specific polar interactions in the adhesion behavior. In addition, an AFM method is identified to prospectively assess the risk of sticking during the early stages of drug development.

Effect of high pressure microfluidization on the crystallization behavior of palm stearin - palm olein blends.

PubMed

Han, Lijuan; Li, Lin; Li, Bing; Zhao, Lei; Liu, Guoqin; Liu, Xinqi; Wang, Xuede

2014-04-24

Moderate and high microfluidization pressures (60 and 120 MPa) and different treatment times (once and twice) were used to investigate the effect of high-pressure microfluidization (HPM) treatment on the crystallization behavior and physical properties of binary mixtures of palm stearin (PS) and palm olein (PO). The polarized light microscopy (PLM), texture analyzer, X-ray diffraction (XRD) and differential scanning calorimetry (DSC) techniques were applied to analyze the changes in crystal network structure, hardness, polymorphism and thermal property of the control and treated blends. PLM results showed that HPM caused significant reductions in maximum crystal diameter in all treated blends, and thus led to changes in the crystal network structure, and finally caused higher hardness in than the control blends. The XRD study demonstrated that HPM altered crystalline polymorphism. The HPM-treated blends showed a predominance of the more stable β' form, which is of more interest for food applications, while the control blend had more α- and β-form. This result was further confirmed by DSC observations. These changes in crystallization behavior indicated that HPM treatment was more likely to modify the crystallization processes and nucleation mechanisms.

Effects of Purification on the Crystallization of Lysozyme

NASA Technical Reports Server (NTRS)

Ewing, Felecia L.; Forsythe, Elizabeth L.; Van Der Woerd, Mark; Pusey, Marc L.

1996-01-01

We have additionally purified a commercial lysozyme preparation by cation exchange chromatography, followed by recrystallization. This material is 99.96% pure with respect to macromolecular impurities. At basic pH, the purified lysozyme gave only tetragonal crystals at 20 C. Protein used directly from the bottle, prepared by dialysis against distilled water, or which did not bind to the cation exchange column had considerably altered crystallization behavior. Lysozyme which did not bind to the cation exchange column was subsequently purified by size exclusion chromatography. This material gave predominately bundles of rod-shaped crystals with some small tetragonal crystals at lower pHs. The origin of the bundled rod habit was postulated to be a thermally dependent tetragonal- orthorhombic change in the protein structure. This was subsequently ruled out on the basis of crystallization behavior and growth rate experiments. This suggests that heterogeneous forms of lysozyme may be responsible. These results demonstrate three classes of impurities: (1) small molecules, which may be removed by dialysis; (2) macromolecules, which are removable by chromatographic techniques; and (3) heterogeneous forms of the protein, which can be removed in this case by cation exchange chromatography. Of these, heterogeneous forms of the lysozyme apparently have the greatest affect on its crystallization behavior.

Advances in food crystallization.

PubMed

Hartel, Richard W

2013-01-01

Crystals often play an important role in food product quality and shelf life. Controlling crystallization to obtain the desired crystal content, size distribution, shape, and polymorph is key to manufacturing products with desired functionality and shelf life. Technical developments in the field have improved the tools with which we study and characterize crystals in foods. These developments also help our understanding of the physico-chemical phenomena that govern crystallization and improve our ability to control it during processing and storage. In this review, some of the more important recent developments in measuring and controlling crystallization are discussed.

Effects of Cr 3+ impurity concentration on the crystallography of synthetic emerald crystals

NASA Astrophysics Data System (ADS)

Lee, Pei-Lun; Huang, Eugene; Lee, Jan-Shing; Yu, Shu-Cheng

2011-06-01

Flux method has been adopted for the synthesis of emerald crystals using PbO-V 2O 5 as a flux in order to study the crystallography of the synthetic crystals. In general, the hue of green color of emerald deepens with the addition of Cr 3+. The molar volume of the synthesized crystals was found to increase with the incorporation of Cr 2O 3 dopant. The substitution of Cr 3+ for Al 3+ in the octahedral sites of beryl results in the expansion of a-axis, while c-axis remains nearly unchanged. The maximum Cr 2O 3-content allowed in the crystal lattice of emerald has been found to be about 3.5 wt%. When the doping Cr 2O 3-content exceeds 3.5 wt%, a significant anomaly in lattice parameters starts to take place, accompanying the precipitation of an unknown phase in the emerald matrix.

Crystal nucleation in amorphous (Au/100-y/Cu/y/)77Si9Ge14 alloys

NASA Technical Reports Server (NTRS)

Thompson, C. V.; Greer, A. L.; Spaepen, F.

1983-01-01

Because, unlike most metallic glasses, melt-spun alloys of the series (Au/100-y/Cu/y/)77Si9Ge14 exhibit well separated glass transition and kinetic crystallization temperatures, crystallization can be studied in the fully relaxed amorphous phase. An isothermal calorimetric analysis of the devitrification kinetics of the amorphous alloy indicates sporadic nucleation and a constant growth rate. It is found for the cases of alloys with y values lower than 25 that the classical theory of homogeneous nucleation is consistent with observations, including transient effects. An analysis of the crystallization kinetics shows that slow crystal growth rates play an important role in glass formation in these alloys. Although the reduced glass transition temperature increases with Cu content, glass formation is more difficult at high Cu contents, perhaps because of a difference in nucleus composition.

Two-step recrystallization of water in concentrated aqueous solution of poly(ethylene glycol).

PubMed

Gemmei-Ide, Makoto; Motonaga, Tetsuya; Kasai, Ryosuke; Kitano, Hiromi

2013-02-21

Crystallization behavior of water in a concentrated aqueous solution of poly(ethylene glycol) (PEG) with a water content of 37.5 wt % was investigated by temperature variable mid-infrared (mid-IR) spectroscopy in a temperature range of 298-170 K. The mid-IR spectrum of water at 298 K showed that a large water cluster was not formed and that most of the water molecules were associated with the PEG chain. Ice formation, however, occurred as found in previous studies by differential scanning calorimetory. Ice formations were grouped into three types: crystallization at 231 K during cooling, that at 198 K during heating, and that at 210 K during heating. The latter two were just recrystallization. These ice formations were the direct transition from hydration species to ice without condensation regardless of crystallization or recrystallization. This means that the recrystallized water in the present system was not generated from low-density amorphous solid water. At a low cooling rate, nearly complete crystallization at 231 K during cooling and no recrystallization were observed. At a high cooling rate, no crystallization and two-step recrystallization at 198 and 210 K were observed. The former and latter recrystallizations were found to be generated from water associated with the PEG chains with ttg (the sequence -O-CH(2)-CH(2)-O- having a trans (t) conformation about the -C-O- bond and a gauche (g) conformation about the -C-C- bond) and random conformations, respectively. These results indicate that recrystallizable water does not have a single specific water structure.

Effects of Al(3+) doping on the structure and properties of goethite and its adsorption behavior towards phosphate.

PubMed

Li, Wei; Wang, Longjun; Liu, Fan; Liang, Xiaoliang; Feng, Xionghan; Tan, Wenfeng; Zheng, Lirong; Yin, Hui

2016-07-01

Al substitution in goethite is common in soils, and has strong influence on the structure and physicochemical properties of goethite. In this research, a series of Al-doped goethites were synthesized, and characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR) and extended X-ray absorption fine structure (EXAFS) spectroscopy. The adsorption behavior of these samples towards PO4(3-) was also investigated. Characterization results demonstrated that increasing Al content in goethite led to a reduction in crystallinity, increase in specific surface area (SSA), and morphology change from needle-like to granular. Rietveld structure refinement revealed that the lattice parameter a remained almost constant and b slightly decreased, but c was significantly reduced, and the calculated crystal density increased. EXAFS analysis demonstrated that the Fe(Al)-O distance in the structure of the doped goethites was almost the same, but the Fe-Fe(Al) distance decreased with increasing Al content. Surface analysis showed that, with increasing Al content, the content of OH groups on the mineral surface increased. The adsorption of phosphate per unit mass of Al-doped goethite increased, while adsorption per unit area decreased owing to the decrease of the relative proportion of (110) facets in the total surface area of the minerals. The results of this research facilitate better understanding of the effect of Al substitution on the structure and properties of goethite and the cycling of phosphate in the environment. Copyright © 2016. Published by Elsevier B.V.

Effect of VA and MWNT contents on the rheological and physical properties of EVA

NASA Astrophysics Data System (ADS)

Kim, Jong-Ho; Lee, Seungwon; Kim, Byoung Chul; Shin, Bong-Seob; Jeon, Jong-Young; Chae, Dong Wook

2016-02-01

Ethylene vinyl acetate (EVA) copolymers with two different VA contents (15 and 33 wt.%, denoted by EVA15 and EVA33, respectively) were melt compounded with multi-walled carbon nanotubes (MWNTs) and the effect of VA and nanotube contents on the rheological, thermal and morphological properties was investigated. The addition of nanotubes into both EVAs increased the onset temperature of crystallization and broadened the peak, but further addition from 3 wt.% slightly decreased the temperature with increasing nanotube contents. In the wide angle X-ray diffraction patterns the peak of EVA15 was little affected by the presence of nanotubes but that of EVA33 slightly shifted to higher degree and became sharper with increasing nanotube contents. Dynamic viscosity (η') increased with nanotube contents giving abrupt increase at 2 wt.% nanotubes. Loss tangent decreased with increasing nanotube contents exhibiting the plateau-like behavior over most of the frequency range from 2 wt.% nanotubes. In the Casson plot, yield stress increased with nanotube content and its increasing extent was more notable for more VA content. In the Cole-Cole plot, the presence of nanotubes from 2 wt.% gave rise to the deviation from the single master curve by decreasing the slope. The deviated extent of EVA33 became more remarkable with increasing nanotube contents than that of EVA15. The stress-strain curve showed that more improved tensile modulus and yield stress were achieved by the introduction of MWNTs for EVA 33 than for EVA15. Tensile strength of EVA33 increased with increasing nanotube contents, while that of EVA15 decreased.

Anisotropy of nickel-base superalloy single crystals

NASA Technical Reports Server (NTRS)

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

1980-01-01

The influence of orientation on the tensile and stress rupture behavior of 52 Mar-M247 single crystals was studied. Tensile tests were performed at temperatures between 23 and 1093 C; stress rupture behavior was examined between 760 and 1038 C. The mechanical behavior of the single crystals was rationalized on the basis of the Schmid factor contours for the operative slip systems and the lattice rotations which the crystals underwent during deformation. The tensile properties correlated well with the appropriate Schmid factor contours. The stress rupture lives at lower testing temperatures were greatly influenced by the lattice rotations required to produce cross slip. A unified analysis was attained for the stress rupture life data generated for the Mar-M247 single crystals at 760 and 774 C under a stress of 724 MPa and the data reported for Mar-M200 single crystals tested at 760 C under a stress of 689 MPa. Based on this analysis, the stereographic triangle was divided into several regions which were rank ordered according to stress rupture life for this temperature regime.

Optical parameters and dispersion behavior of potassium magnesium chloride sulfate single crystals doped with Co+2 ions

NASA Astrophysics Data System (ADS)

Abu El-Fadl, A.; Abd-Elsalam, A. M.

2018-05-01

Single crystals of potassium magnesium chloride sulfate (KMCS) doped with cobalt ions were grown by slow cooling method. Powder XRD study confirmed the monoclinic structure of the grown crystals. The functional group vibrations were checked through FTIR spectroscopy measurements. In optical studies, the absorbance behavior of the crystals and their optical energy gap were established by Tauc plot. The refractive index, the extinction coefficient and other optical constants were calculated for the grown crystals. The normal dispersion of the refractive index was analyzed according to single oscillator Sellmeier's model. The Urbach's rule was applied to analyze the localized states density in the forbidden gap.

Enhanced dual-frequency operation of a polymerized liquid crystal microplate by liquid crystal infiltration

NASA Astrophysics Data System (ADS)

Kumagai, Takayuki; Yoshida, Hiroyuki; Ozaki, Masanori

2017-04-01

The electric-field-induced switching behavior of a polymer microplate is investigated. A microplate fabricated with a photopolymerizable dual-frequency liquid crystal was surrounded by an unpolymerized photopolymerizable dual-frequency liquid crystal in the isotropic phase. As an electric field was applied along the plane of the microplate, the microplate switched to set its interior molecular orientation to be either parallel or perpendicular to the field, depending on the frequency. Analysis of the rotational behavior, as well as numerical calculations, showed that the surrounding unpolymerized photopolymerizable dual-frequency liquid crystal infiltrated into the microplate, which enhanced the dielectric properties of the microplate. To the best of our knowledge, this is the first report of an enhanced dual-frequency dielectric response of a polymer microplate induced by liquid crystal infiltration.

The crystallization behavior and kinetics of a barium fluorozirconate type glass

NASA Technical Reports Server (NTRS)

Neilson, G. F.; Smith, G. L.; Weinberg, M. C.

1984-01-01

An investigation of the crystallization behavior of a Zr-Ba-La-Al-F glass which is subjected to isothermal heat treatments is presented. The number and nature of the crystalline phases which form and their nucleation sites are determined at three temperatures. Also, the growth rate and volume fraction of crystals which nucleate internally in the glass, when heated at 320 C, are determined as a function of time.

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.

Crystallization Behavior of A Bulk Amorphous Mg62Cu26Y12 Alloy

NASA Astrophysics Data System (ADS)

Wu, Shyue-Sheng; Chin, Tsung-Shune; Su, Kuo-Chang

1994-07-01

The crystallization temperature, the associated activation energy and the crystallized structure of a bulk amorphous Mg62Cu26Y12 alloy with a diameter of 2.5 mm were studied. It possesses a one-step crystallization behavior. The crystallization reaction was found to be represented by: AM(MG62Cu26Y12)→Mg2Cu+MgY+CuY+Mg, ( Tx=188°C, Eac=134 kJ/mol) where AM represents the amorphous state, T x the crystallization temperature at an infinitesimal heating rate, and E ac the associated activation energy. The amount of crystalline phases were found to be Mg2Cu:MgY:CuY=76:17:7. The Mg phase is identifiable only by high resolution electron microscopy, not by X-ray diffraction. The crystallization leads to a sharp rise in electrical resistivity which is reversed to those of iron-based amorphous alloys.

Viscosity measurements of crystallizing andesite from Tungurahua volcano (Ecuador).

PubMed

Chevrel, Magdalena Oryaëlle; Cimarelli, Corrado; deBiasi, Lea; Hanson, Jonathan B; Lavallée, Yan; Arzilli, Fabio; Dingwell, Donald B

2015-03-01

Viscosity has been determined during isothermal crystallization of an andesite from Tungurahua volcano (Ecuador). Viscosity was continuously recorded using the concentric cylinder method and employing a Pt-sheathed alumina spindle at 1 bar and from 1400°C to subliquidus temperatures to track rheological changes during crystallization. The disposable spindle was not extracted from the sample but rather left in the sample during quenching thus preserving an undisturbed textural configuration of the crystals. The inspection of products quenched during the crystallization process reveals evidence for heterogeneous crystal nucleation at the spindle and near the crucible wall, as well as crystal alignment in the flow field. At the end of the crystallization, defined when viscosity is constant, plagioclase is homogeneously distributed throughout the crucible (with the single exception of experiment performed at the lowest temperature). In this experiments, the crystallization kinetics appear to be strongly affected by the stirring conditions of the viscosity determinations. A TTT (Time-Temperature-Transformation) diagram illustrating the crystallization "nose" for this andesite under stirring conditions and at ambient pressure has been constructed. We further note that at a given crystal content and distribution, the high aspect ratio of the acicular plagioclase yields a shear-thinning rheology at crystal contents as low as 13 vol %, and that the relative viscosity is higher than predicted from existing viscosity models. These viscosity experiments hold the potential for delivering insights into the relative influences of the cooling path, undercooling, and deformation on crystallization kinetics and resultant crystal morphologies, as well as their impact on magmatic viscosity.

Viscosity measurements of crystallizing andesite from Tungurahua volcano (Ecuador)

PubMed Central

Cimarelli, Corrado; deBiasi, Lea; Hanson, Jonathan B.; Lavallée, Yan; Arzilli, Fabio; Dingwell, Donald B.

2015-01-01

Abstract Viscosity has been determined during isothermal crystallization of an andesite from Tungurahua volcano (Ecuador). Viscosity was continuously recorded using the concentric cylinder method and employing a Pt‐sheathed alumina spindle at 1 bar and from 1400°C to subliquidus temperatures to track rheological changes during crystallization. The disposable spindle was not extracted from the sample but rather left in the sample during quenching thus preserving an undisturbed textural configuration of the crystals. The inspection of products quenched during the crystallization process reveals evidence for heterogeneous crystal nucleation at the spindle and near the crucible wall, as well as crystal alignment in the flow field. At the end of the crystallization, defined when viscosity is constant, plagioclase is homogeneously distributed throughout the crucible (with the single exception of experiment performed at the lowest temperature). In this experiments, the crystallization kinetics appear to be strongly affected by the stirring conditions of the viscosity determinations. A TTT (Time‐Temperature‐Transformation) diagram illustrating the crystallization “nose” for this andesite under stirring conditions and at ambient pressure has been constructed. We further note that at a given crystal content and distribution, the high aspect ratio of the acicular plagioclase yields a shear‐thinning rheology at crystal contents as low as 13 vol %, and that the relative viscosity is higher than predicted from existing viscosity models. These viscosity experiments hold the potential for delivering insights into the relative influences of the cooling path, undercooling, and deformation on crystallization kinetics and resultant crystal morphologies, as well as their impact on magmatic viscosity. PMID:27656114

Characterization of Coconut Oil Fractions Obtained from Solvent Fractionation Using Acetone.

PubMed

Sonwai, Sopark; Rungprasertphol, Poonyawee; Nantipipat, Nantinee; Tungvongcharoan, Satinee; Laiyangkoon, Nantikan

2017-09-01

This work was aimed to study the solvent fraction of coconut oil (CNO). The fatty acid and triacylglycerol compositions, solid fat content (SFC) and the crystallization properties of CNO and its solid and liquid fractions obtained from fractionation at different conditions were investigated using various techniques. CNO was dissolved in acetone (1:1 w/v) and left to crystallize isothermally at 10°C for 0.5, 1 and 2 h and at 12°C for 2, 3 and 6 h. The solid fractions contained significantly lower contents of saturated fatty acids of ≤ 10 carbon atoms but considerably higher contents of saturated fatty acids with > 12 carbon atoms with respect to those of CNO and the liquid fractions. They also contained higher contents of high-melting triacylglycerol species with carbon number ≥ 38. Because of this, the DSC crystallization onset temperatures and the crystallization peak temperatures of the solid fractions were higher than CNO and the liquid fractions. The SFC values of the solid fractions were significantly higher than CNO at all measuring temperatures before reaching 0% just below the body temperature with the fraction obtained at 12°C for 2 h exhibiting the highest SFC. On the contrary, the SFC values of the liquid fractions were lower than CNO. The crystallization duration exhibited strong influence on the solid fractions. There was no effect on the crystal polymorphic structure possibly because CNO has β'-2 as a stable polymorph. The enhanced SFC of the solid fractions would allow them to find use in food applications where a specific melting temperature is desired such as sophisticated confectionery fats, and the decreased SFC of the liquid fractions would provide them with a higher cold stability which would be useful during extended storage time.

Microstructures, mechanical behavior and strengthening mechanism of TiSiCN nanocomposite films

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

Li, Wei; Liu, Ping; Xue, Zenghui

Recently, the arguments have existed in the strengthening mechanism and microstructural model of the nanocomposite film due to lack of the convincible experimental evidences. In this investigation, the quarternary TiSiCN nanocomposite films with the different C and Si contents are synthesized by the reactive-magnetron-sputtering technique. The TiSiCN film is characterized as the nanocomposite structure with the TiN nanocrystallites surrounded by the (Si 3N 4 + C + CN x) interface phase. When the C/Si content ratio is 2:2, the TiSiCN nanocomposite film is remarkably strengthened with the maximal hardness and elastic modulus of 46.1 GPa and 425 GPa, respectively. Meanwhile,more » the (Si 3N 4 + C + CN x) interfaces exhibit as a crystallized form, which can coordinate the growth misorientations and maintain the coherently epitaxial growth between the TiN nanocrystallites and interfaces. Through the high-resolution transmission electron microscopy (HRTEM) observations, this investigation firstly provides the direct experimental evidence for the crystallized feature of the interfaces when the TiSiCN nanocomposite film is strengthened, suggesting that the strengthening effect of the TiSiCN nanocomposite film can be attributed to the coherent-interface strengthening mechanism, which is expressed as the “nc-TiN/c-Si 3N 4/c-C/c-CN x” model.« less

The Effect of 4-Octyldecyloxybenzoic Acid on Liquid-Crystalline Polyurethane Composites with Triple-Shape Memory and Self-Healing Properties

PubMed Central

Ban, Jianfeng; Zhu, Linjiang; Chen, Shaojun; Wang, Yiping

2016-01-01

To better understand shape memory materials and self-healing materials, a new series of liquid-crystalline shape memory polyurethane (LC-SMPU) composites, named SMPU-OOBAm, were successfully prepared by incorporating 4-octyldecyloxybenzoic acid (OOBA) into the PEG-based SMPU. The effect of OOBA on the structure, morphology, and properties of the material has been carefully investigated. The results demonstrate that SMPU-OOBAm has liquid crystalline properties, triple-shape memory properties, and self-healing properties. The incorporated OOBA promotes the crystallizability of both soft and hard segments of SMPU, and the crystallization rate of the hard segment of SMPU decreases when the OOBA-content increases. Additionally, the SMPU-OOBAm forms a two-phase separated structure (SMPU phase and OOBA phase), and it shows two-step modulus changes upon heating. Therefore, the SMPU-OOBAm exhibits triple-shape memory behavior, and the shape recovery ratio decreases with an increase in the OOBA content. Finally, SMPU-OOBAm exhibits self-healing properties. The new mechanism can be ascribed to the heating-induced “bleeding” of OOBA in the liquid crystalline state and the subsequent re-crystallization upon cooling. This successful combination of liquid crystalline properties, triple-shape memory properties, and self-healing properties make the SMPU-OOBAm composites ideal for many promising applications in smart optical devices, smart electronic devices, and smart sensors. PMID:28773914

Microstructures, mechanical behavior and strengthening mechanism of TiSiCN nanocomposite films

DOE PAGES

Li, Wei; Liu, Ping; Xue, Zenghui; ...

2017-05-18

Recently, the arguments have existed in the strengthening mechanism and microstructural model of the nanocomposite film due to lack of the convincible experimental evidences. In this investigation, the quarternary TiSiCN nanocomposite films with the different C and Si contents are synthesized by the reactive-magnetron-sputtering technique. The TiSiCN film is characterized as the nanocomposite structure with the TiN nanocrystallites surrounded by the (Si 3N 4 + C + CN x) interface phase. When the C/Si content ratio is 2:2, the TiSiCN nanocomposite film is remarkably strengthened with the maximal hardness and elastic modulus of 46.1 GPa and 425 GPa, respectively. Meanwhile,more » the (Si 3N 4 + C + CN x) interfaces exhibit as a crystallized form, which can coordinate the growth misorientations and maintain the coherently epitaxial growth between the TiN nanocrystallites and interfaces. Through the high-resolution transmission electron microscopy (HRTEM) observations, this investigation firstly provides the direct experimental evidence for the crystallized feature of the interfaces when the TiSiCN nanocomposite film is strengthened, suggesting that the strengthening effect of the TiSiCN nanocomposite film can be attributed to the coherent-interface strengthening mechanism, which is expressed as the “nc-TiN/c-Si 3N 4/c-C/c-CN x” model.« less

Phase behavior of binary mixture systems of saturated-unsaturated mixed-acid triacylglycerols: effects of glycerol structures and chain-chain interactions.

PubMed

Bayés-García, Laura; Calvet, Teresa; Cuevas-Diarte, Miquel Àngel; Ueno, Satoru; Sato, Kiyotaka

2015-03-26

We systematically examined the phase behavior of binary mixtures of mixed-acid triacylglycerols (TAGs) containing palmitic and oleic acid moieties 1,3-dioleoyl-2-palmitoyl-glycerol (OPO), 1,2-dipalmitoyl-3-oleoyl-rac-glycerol (PPO), and 1,2-dioleoyl-3-palmitoyl-rac-glycerol (OOP), which are widely present in natural fats and are employed in the food, pharmaceutical, and cosmetic industries. Differential scanning calorimetry and X-ray diffraction methods were applied to observe the mixing behavior of PPO/OPO, OOP/OPO, and PPO/OOP under metastable and stable conditions. The results led to three conclusions: (1) Eutectic behavior was observed in PPO/OPO. (2) Molecular compound (MC) crystals were formed in the mixtures of OOP/OPO and PPO/OOP. (3) However, the MC crystals occurred only under metastable conditions and tended to separate into component TAGs to form eutectic mixture systems after 17 months of incubation. These results were contrary to those of previous studies on 1,3-dipalmitoyl-2-oleoyl glycerol (POP)/OPO and POP/PPO in which the MC crystals were thermodynamically stable. We determined that specific molecular interactions may cause this different phase behavior (stability of POP/OPO and POP/PPO MC crystals and metastability of OOP/OPO and PPO/OOP MC crystals). All results confirm the significant effects of molecular structures of glycerol groups, interactions of fatty acid chains, and polymorphism of the component TAGs on the mixing behavior of mixed-acid TAGs.

Fluorbritholite-(Y) and yttrialite-(Y) from silexites of the Keivy alkali granites, Kola Peninsula

NASA Astrophysics Data System (ADS)

Lyalina, L. M.; Zozulya, D. R.; Savchenko, Ye. E.; Tarasov, M. P.; Selivanova, E. A.; Tarasova, E.

2014-12-01

Investigation of the morphology, anatomy, and chemical composition of fluorbritholite-(Y) and yttrialite-(Y) from silexites of the Keivy alkali granites in Kola Peninsula has shown that these minerals are the main REE concentrators in this area and that their content reaches 10-15 vol %. Britholite and yttrialite are associated with zircon, aeschynite-(Y), chevkinite-(Ce), fergusonite-(Y), thorite, monazite-(Ce), xenotime-(Y) and bastnaesite-(Ce). Three morphological types of fluorbritholite-(Y) have been identified: (I) subhedral crystals and grains, (II) anhedral grains intergrown with yttrialite-(Y), and (III) poikilitic crystals and skeletal aggregates. These morphological types of fluorbritholite-(Y) are characterized by successive (I to III type) decreases in P content down to the pure silicate fluorbritholite-(Y). Crystals of the first type are heterogenous: the P content decreases and the HREE content increases from core to rim. The total REE content increases insignificantly from types I to II and drastically decreases in fluorbritholite-(Y) of type III. The successive prevalence of HREE over LREE indicates the hydrothermal conditions of mineral crystallization. The chemical composition of yttrialite-(Y) is distinguished by the relatively high Th content and depletion in Al. The compositional trend (from core to rim) in heterogeneous grains of yttrialite-(Y) testifies that their heterogeneity was caused by metasomatic alteration of the mineral. The interrelation of fluorbritholite-(Y) and yttrialite-(Y) indicate that fluorbritholite-(Y) of types II and III were formed later than yttrialite-(Y). Evidence for fluorbritholite-(Y) and yttrialite-(Y) formation suggests the significant role of hydrothermal processes in the genesis of silexites.

Characterization of Cadmium-Zinc Telluride Crystals Grown by 'Contactless' PVT Using Synchrotron White Beam Topography

NASA Technical Reports Server (NTRS)

Palosz, W.; Gillies, D.; Grasza, K.; Chung, H.; Raghothamachar, B.; Dudley, M.

1997-01-01

Crystals of Cd(1-x)Zn(x)Te grown by Physical Vapor Transport (PVT) using self-seeding 'contactless' techniques were characterized using synchrotron radiation (reflection, transmission, and Laue back-reflection X-ray topography). Crystals of low (x = 0.04) and high (up to x approx. = 0.4) ZnTe content were investigated. Twins and defects such as dislocations, precipitates, and slip bands were identified. Extensive inhomogeneous strains present in some samples were found to be generated by interaction (sticking) with the pedestal and by composition gradients in the crystals. Large (up to about 5 mm) oval strain fields were observed around some Te precipitates. Low angle grain boundaries were found only in higher ZnTe content (x greater than or equal to 0.2) samples.

Method of casting articles of a bulk-solidifying amorphous alloy

DOEpatents

Lin, X.; Johnson, W.L.; Peker, A.

1998-08-25

A casting charge of a bulk-solidifying amorphous alloy is cast into a mold from a temperature greater than its crystallized melting temperature, and permitted to solidify to form an article. The oxygen content of the casting charge is limited to an operable level, as excessively high oxygen contents produce premature crystallization during the casting operation. During melting, the casting charge is preferably heated to a temperature above a threshold temperature to eliminate heterogeneous crystallization nucleation sites within the casting charge. The casting charge may be cast from above the threshold temperature, or it may be cooled to the casting temperature of more than the crystallized melting point but not more than the threshold temperature, optionally held at this temperature for a period of time, and thereafter cast. 8 figs.

Method of casting articles of a bulk-solidifying amorphous alloy

DOEpatents

Lin, Xianghong; Johnson, William L.; Peker, Atakan

1998-01-01

A casting charge of a bulk-solidifying amorphous alloy is cast into a mold from a temperature greater than its crystallized melting temperature, and permitted to solidify to form an article. The oxygen content of the casting charge is limited to an operable level, as excessively high oxygen contents produce premature crystallization during the casting operation. During melting, the casting charge is preferably heated to a temperature above a threshold temperature to eliminate heterogeneous crystallization nucleation sites within the casting charge. The casting charge may be cast from above the threshold temperature, or it may be cooled to the casting temperature of more than the crystallized melting point but not more than the threshold temperature, optionally held at this temperature for a period of time, and thereafter cast.

Synthesis, growth and characterization of a nonlinear optical crystal: Bis l-proline hydrogen nitrate.

PubMed

Selvaraju, K; Kirubavathi, K

2013-11-01

The single crystals of bis l-proline hydrogen nitrate (BLPHN) belonging to non-centrosymmetric space group were successfully grown by the slow evaporation solution growth technique. The BLPHN crystals of size 10×7×3mm(3) were obtained in 35days. Initially, the solubility tests were carried out for two solvents such as deionized water and mixed of deionized water-acetone. Among the two solvents, the solubility of BLPHN was found to be the highest in deionized water, so crystallization of BLPHN was done from its aqueous solution. As grown, crystals were characterized by single crystal X-ray diffraction studies and optical transmission spectral studies. Infrared spectroscopy, thermo gravimetric analysis and differential thermal analysis measurements were performed to study the molecular vibration and thermal behavior of the grown BLPHN crystals. Nonlinear optical (NLO) behavior of BLPHN crystal was studied by Kurtz and Perry powder method. Copyright © 2013 Elsevier B.V. All rights reserved.

Self-Consistency of the Lauritzen-Hoffman and Strobl Models of Polymer Crystallization Evaluated for Poly(epsilon-caprolactone) Fractions and Effect of Composition on the Phenomenon of Concurrent Crystallization in Polyethylene Blends

NASA Astrophysics Data System (ADS)

Sheth, Swapnil Suhas

Narrow molecular weight fractions of poly(epsilon-caprolactone) were successfully obtained using the successive precipitation fractionation technique with toluene/n-heptane as a solvent/nonsolvent pair. Calorimetric studies of the melting behavior of fractions that were crystallized either isothermally or under constant cooling rate conditions suggested that the isothermal crystallization of the samples should be used for a proper evaluation of the molecular weight dependence of the observed melting temperature and degree of crystallinity in PCL. The molecular weight and temperature dependence of the spherulitic growth rate of fractions was studied in the context of the Lauritzen-Hoffman two-phase model and the Strobl three-phase model of polymer crystallization. The zero-growth rate temperatures, determined from spherulitic growth rates using four different methods, are consistent with each other and increase with chain length. The concomitant increase in the apparent secondary nucleation constant was attributed to two factors. First, for longer chains there is an increase in the probability that crystalline stems belong to loose chain-folds, hence, an increase in fold surface free energy. It is speculated that the increase in loose folding and resulting decrease in crystallinity with increasing chain length are associated with the ester group registration requirement in PCL crystals. The second contribution to the apparent nucleation constant arises from chain friction associated with segmental transport across the melt/crystal interface. These factors were responsible for the much stronger chain length dependence of spherulitic growth rates at fixed undercooling observed here with PCL than previously reported for PE and PEO. In the case of PCL, the scaling exponent associated with the chain length dependence of spherulitic growth rates exceeds the upper theoretical bound of 2 predicted from the Brochard- DeGennes chain pullout model. Observation that zero-growth and equilibrium melting temperature values are identical with each other within the uncertainty of their determinations casts serious doubt on the validity of Strobl three-phase model. A novel method is proposed to determine the Porod constant necessary to extrapolate the small angle X-ray scattering intensity data to large scattering vectors. The one-dimensional correlation function determined using this Porod constant yielded the values of lamellar crystal thickness, which were similar to these estimated using the Hosemann-Bagchi Paracrystalline Lattice model. The temperature dependence of the lamellar crystal thickness was consistent with both LH and the Strobl model of polymer crystallization. However, in contrast to the predictions of Strobl's model, the value of the mesomorph-to-crystal equilibrium transition temperature was very close to the zero-growth temperature. Moreover, the lateral block sizes (obtained using wide angle X-ray diffraction) and the lamellar thicknesses were not found to be controlled by the mesomorph-to-crystal equilibrium transition temperature. Hence, we concluded that the crystallization of PCL is not mediated by a mesophase. Metallocene-catalyzed linear low-density (m-LLDPE with 3.4 mol% 1-octene) and conventional low-density (LDPE) polyethylene blends of different compositions were investigated for their melt-state miscibility and concurrent crystallization tendency. Differential scanning calorimetric studies and morphological studies using atomic force microscopy confirm that these blends are miscible in the melt-state for all compositions. LDPE chains are found to crystallize concurrently with m-LLDPE chains during cooling in the m-LLDPE crystallization temperature range. While the extent of concurrent crystallization was found to be optimal in .. .. iv blends with highest m-LLDPE content studied, strong evidence was uncovered for the existence of a saturation effect in the concurrent crystallization behavior. This observation leads us to suggest that co-crystallization, rather than mere concurrent crystallization, of LDPE with m- LLDPE can indeed take place. Matching of the respective sequence length distributions in LDPE and m-LLDPE is suggested to control the extent of co-crystallization.

Crystallization behavior of polyamide-6 microcellular nanocomposites

Treesearch

Mingjun Yuan; Lih-Sheng Turng; Shaoqin Gong; Andreas Winardi

2004-09-01

The crystallization behaviors of polyamide-6 (PA-6) and its nanocomposites undergoing the microcellular injection molding process are studied using Transmission Electron Microscopy (TEM), X-ray Diffractometer (XRD), Polarized Optical Microscopy (POM), and Differential Scanning Calorimetry (DSC). The relationships among the morphology, the mechanical property of the...

Method for enhancement of useful luminescence from vacancy defects in refractory oxides for tunable lasers

DOEpatents

Chen, Yok

1990-01-01

Refractory oxide crystals suitable for use in tunable lasers and a method for preparing the same are provided. The crystals are characterized by high quantum efficiency, high thermal stability, good crystal transparency, and a high percentage of useful luminescence. The method for preparation of the crystals involves removing substantially all the hydrogen, thermochemically reducing the crystal's oxygen content to produce oxygen (anion) vacancy defects, and subsequently irradiating the crystal with electrons to inactivate trace H.sup.- ions so that an increased amount of short lived F.sup.+ luminescence is produced when the crystal is optically excited.

Quantification of oil binding capacity of structuring fats: A novel method and its application.

PubMed

Omonov, Tolibjon S; Bouzidi, Laziz; Narine, Suresh S

2010-09-01

A robust, well-defined and reproducible method to accurately measure the oil binding capacity (OBC) of structuring fats was developed. The method was validated using two oil/fat model systems, i.e., fully hydrogenated canola oil (FHCO) in canola oil (CO) (FHCO/CO) and fully hydrogenated soybean oil (FHSO) in CO (FHSO/CO). The mixtures were crystallized from the melt down to three different temperatures (15, 25 and 35 degrees C) at constant rates of cooling and the OBC was measured after different periods of storage time. The critical concentration of hard fat at which the solid fat network is stable and effectively binds oil has been also measured for mixtures crystallized at temperatures close to room temperature, i.e., 25 degrees C. Crystal structure, melting behavior, microstructure, and solid fat content of these binary systems have been investigated in relation to the OBC of the solid fat network using X-ray diffraction (XRD), differential scanning calorimetry (DSC), polarized light microscopy (PLM), and wide-line pulsed nuclear magnetic resonance (pNMR) techniques. The two model systems exhibited similar trends in OBC over time, a behavior attributed to their similar TAG composition and polymorphism. However, relatively smaller OBC values were achieved by the CO/FHSO compared to CO/FHCO samples, largely due to differences in their solid network structure. Four successive decreasing linear segments, identifying successive mechanisms of oil migration/binding, were observed in the experimental OBC versus fat weight fraction curves. The critical concentration of hard fat, at which the solid fat network is effective in binding oil, was also determined and found to be approximately 6wt% for both systems. Copyright 2010 Elsevier Ireland Ltd. All rights reserved.

A study of the crystallization, melting, and foaming behaviors of polylactic acid in compressed CO₂.

PubMed

Zhai, Wentao; Ko, Yoorim; Zhu, Wenli; Wong, Anson; Park, Chul B

2009-12-16

The crystallization and melting behaviors of linear polylactic acid (PLA) treated by compressed CO(2) was investigated. The isothermal crystallization test indicated that while PLA exhibited very low crystallization kinetics under atmospheric pressure, CO(2) exposure significantly increased PLA's crystallization rate; a high crystallinity of 16.5% was achieved after CO(2) treatment for only 1 min at 100 degrees C and 6.89 MPa. One melting peak could be found in the DSC curve, and this exhibited a slight dependency on treatment times, temperatures, and pressures. PLA samples tended to foam during the gas release process, and a foaming window as a function of time and temperature was established. Based on the foaming window, crystallinity, and cell morphology, it was found that foaming clearly reduced the needed time for PLA's crystallization equilibrium.

Effect of Slag-Steel Reaction on the Initial Solidification of Molten Steel during Continuous Casting

NASA Astrophysics Data System (ADS)

Wang, Wanlin; Lou, Zhican; Zhang, Haihui

2018-03-01

With the mold simulator technique, the effect of slag-steel reaction on the initial shell solidification as well as the heat transfer and lubrication behavior of the infiltrated mold/shell slag film was studied in this article. The results showed that the Al2O3 content, the CaO/SiO2 ratio, and the viscosity of mold flux were increased with the progress of the slag-steel reaction during casting. The slag-steel reaction has two major effects on the initial shell solidification: one is increasing the mold heat flux and shell thickness by the decrease of slag film thickness. The other is the reduction of mold heat flux by the increase of crystal fraction in slag film. Mold flux with a lower basicity, viscosity, and crystallization temperature would result in a larger liquid slag consumption and the uneven infiltration of slag into the mold and shell gap that eventually leads to the irregular solidification of initial shell with a poor surface quality, such as slag entrapment and depressions as well as glaciation marks. Conversely, mold flux with a higher viscosity, basicity, and crystallization temperature would result in a smaller liquid slag consumption, which would cause the poor mold lubrication, the longitudinal shell surface defects, and drag marks.

Effect of Slag-Steel Reaction on the Initial Solidification of Molten Steel during Continuous Casting

NASA Astrophysics Data System (ADS)

Wang, Wanlin; Lou, Zhican; Zhang, Haihui

2018-06-01

With the mold simulator technique, the effect of slag-steel reaction on the initial shell solidification as well as the heat transfer and lubrication behavior of the infiltrated mold/shell slag film was studied in this article. The results showed that the Al2O3 content, the CaO/SiO2 ratio, and the viscosity of mold flux were increased with the progress of the slag-steel reaction during casting. The slag-steel reaction has two major effects on the initial shell solidification: one is increasing the mold heat flux and shell thickness by the decrease of slag film thickness. The other is the reduction of mold heat flux by the increase of crystal fraction in slag film. Mold flux with a lower basicity, viscosity, and crystallization temperature would result in a larger liquid slag consumption and the uneven infiltration of slag into the mold and shell gap that eventually leads to the irregular solidification of initial shell with a poor surface quality, such as slag entrapment and depressions as well as glaciation marks. Conversely, mold flux with a higher viscosity, basicity, and crystallization temperature would result in a smaller liquid slag consumption, which would cause the poor mold lubrication, the longitudinal shell surface defects, and drag marks.

Phase behavior and crystal structure of 3-(1-naphthyloxy)- and 3-(4-indolyloxy)-propane-1,2-diol, synthetic precursors of chiral drugs propranolol and pindolol

NASA Astrophysics Data System (ADS)

Bredikhin, Alexander A.; Gubaidullin, Aidar T.; Bredikhina, Zemfira A.; Fayzullin, Robert R.; Samigullina, Aida I.; Zakharychev, Dmitry V.

2013-08-01

Valuable precursors of popular chiral drugs propranolol and pindolol, 3-(1-naphthyloxy)-propane-1,2-diol 3 and 3-(4-indolyloxy)-propane-1,2-diol 4 were investigated by IR spectroscopy, DSC, and X-ray diffraction methods. Both compounds, crystallizing from enantiopure feed material, form "guaifenesin-like" crystal packing in which the classic H-bonded bilayers, framed in both sides by hydrophobic fragments of the molecules, acts as the basic crystal-forming motif. Diol 4 prone to spontaneous resolution and conserves its packing pattern crystallizing from racemate. Under the same conditions, diol 3 forms weakly stable solid racemic compound. Some reasons for such a behavior are identified and discussed.

In-Line Measurement of Water Contents in Ethanol Using a Zeolite-Coated Quartz Crystal Microbalance

PubMed Central

Kim, Byoung Chul; Yamamoto, Takuji; Kim, Young Han

2015-01-01

A quartz crystal microbalance (QCM) was utilized to measure the water content in ethanol. For the improvement of measurement sensitivity, the QCM was modified by applying zeolite particles on the surface with poly(methyl methacrylate) (PMMA) binder. The measurement performance was examined with ethanol of 1% to 5% water content in circulation. The experimental results showed that the frequency drop of the QCM was related with the water content though there was some deviation. The sensitivity of the zeolite-coated QCM was sufficient to be implemented in water content determination, and a higher ratio of silicon to aluminum in the molecular structure of the zeolite gave better performance. The coated surface was inspected by microscopy to show the distribution of zeolite particles and PMMA spread. PMID:26516859

Molecular relaxation behavior and isothermal crystallization above glass transition temperature of amorphous hesperetin.

PubMed

Shete, Ganesh; Khomane, Kailas S; Bansal, Arvind Kumar

2014-01-01

The purpose of this paper was to investigate the relaxation behavior of amorphous hesperetin (HRN), using dielectric spectroscopy, and assessment of its crystallization kinetics above glass transition temperature (Tg ). Amorphous HRN exhibited both local (β-) and global (α-) relaxations. β-Relaxation was observed below Tg , whereas α-relaxation prominently emerged above Tg . β-Relaxation was found to be of Johari-Goldstein type and was correlated with α-process by coupling model. Secondly, isothermal crystallization experiments were performed at 363 K (Tg + 16.5 K), 373 K (Tg + 26.5 K), and 383 K (Tg + 36.5 K). The kinetics of crystallization, obtained from the normalized dielectric strength, was modeled using the Avrami model. Havriliak-Negami (HN) shape parameters, αHN and αHN .βHN , were analyzed during the course of crystallization to understand the dynamics of amorphous phase during the emergence of crystallites. HN shape parameters indicated that long range (α-like) were motions affected to a greater extent than short range (β-like) motions during isothermal crystallization studies at all temperature conditions. The variable behavior of α-like motions at different isothermal crystallization temperatures was attributed to evolving crystallites with time and increase in electrical conductivity with temperature. © 2013 Wiley Periodicals, Inc. and the American Pharmacists Association.

Growth morphologies of wax in the presence of kinetic inhibitors

NASA Astrophysics Data System (ADS)

Tetervak, Alexander A.

Driven by the need to prevent crystallization of normal alkanes from diesel fuels in cold climates, the petroleum industry has developed additives to slow the growth of these crystals and alter their morphologies. Although the utility of these kinetic inhibitors has been well demonstrated in the field, few studies have directly monitored their effect at microscopic morphology, and the mechanisms by which they act remain poorly understood. Here we present a study of the effects of such additives on the crystallization of long-chain n-alkanes from solution. The additives change the growth morphology from plate-like crystals to a microcrystalline mesh. When we impose a front velocity by moving the sample through a temperature gradient, the mesh growth may form a macroscopic banded pattern and also exhibit a burst-crystallization behavior. In this study, we characterize these crystallization phenomena and also two growth models: a continuum model that demonstrates the essential behavior of the banded crystallization, and a simple qualitative cellular automata model that captures basics of the burst-crystallization process. Keywords: solidification; mesh crystallization; kinetic inhibitor; burst growth.

Constitutive modeling of superalloy single crystals with verification testing

NASA Technical Reports Server (NTRS)

Jordan, Eric; Walker, Kevin P.

1985-01-01

The goal is the development of constitutive equations to describe the elevated temperature stress-strain behavior of single crystal turbine blade alloys. The program includes both the development of a suitable model and verification of the model through elevated temperature-torsion testing. A constitutive model is derived from postulated constitutive behavior on individual crystallographic slip systems. The behavior of the entire single crystal is then arrived at by summing up the slip on all the operative crystallographic slip systems. This type of formulation has a number of important advantages, including the prediction orientation dependence and the ability to directly represent the constitutive behavior in terms which metallurgists use in describing the micromechanisms. Here, the model is briefly described, followed by the experimental set-up and some experimental findings to date.

Influence of calcium oxalate crystal accumulation on the calcium content of seeds from Medicago truncatula

USDA-ARS?s Scientific Manuscript database

Crystals of calcium oxalate often form in cells adjacent to the vascular bundles in the tissues along the xylem stream. This spatial crystal pattern suggests a role for calcium oxalate formation in regulating calcium transport and partitioning to edible organs such as seeds. To investigate this pote...

Local geometric and electronic structures and origin of magnetism in Co-doped BaTiO3 multiferroics

NASA Astrophysics Data System (ADS)

Phan, The-Long; Thang, P. D.; Ho, T. A.; Manh, T. V.; Thanh, Tran Dang; Lam, V. D.; Dang, N. T.; Yu, S. C.

2015-05-01

We have prepared polycrystalline samples BaTi1-xCoxO3 (x = 0-0.1) by solid-state reaction. X-ray diffraction and Raman-scattering studies reveal the phase separation in crystal structure as changing Co-doping content (x). The samples with x = 0-0.01 are single phase in a tetragonal structure. At higher doping contents (x > 0.01), there is the formation and development of a secondary hexagonal phase. Magnetization measurements at room temperature indicate a coexistence of paramagnetic and weak-ferromagnetic behaviors in BaTi1-xCoxO3 samples with x > 0, while pure BaTiO3 is diamagnetic. Both these properties increase with increasing x. Analyses of X-ray absorption spectra recorded from BaTi1-xCoxO3 for the Co and Ti K-edges indicate the presence of Co2+ and Co3+ ions. They locate in the Ti4+ site of the tetragonal and hexagonal BaTiO3 structures. Particularly, there is a shift of oxidation state from Co2+ to Co3+ when Co-doping content increases. We believe that the paramagnetic nature in BaTi1-xCoxO3 samples is due to isolated Co2+ and Co3+ centers. The addition of Co3+ ions enhances the paramagnetic behavior. Meanwhile, the origin of ferromagnetism is due to lattice defects, which is less influenced by the changes caused by the variation in concentration of Co2+ and Co3+ ions.

Liquid Crystalline Behavior and Related Properties of Colloidal Systems of Inorganic Oxide Nanosheets

PubMed Central

Nakato, Teruyuki; Miyamoto, Nobuyoshi

2009-01-01

Inorganic layered crystals exemplified by clay minerals can be exfoliated in solvents to form colloidal dispersions of extremely thin inorganic layers that are called nanosheets. The obtained “nanosheet colloids” form lyotropic liquid crystals because of the highly anisotropic shape of the nanosheets. This system is a rare example of liquid crystals consisting of inorganic crystalline mesogens. Nanosheet colloids of photocatalytically active semiconducting oxides can exhibit unusual photoresponses that are not observed for organic liquid crystals. This review summarizes experimental work on the phase behavior of the nanosheet colloids as well as photochemical reactions observed in the clay and semiconducting nanosheets system.

Low carrier semiconductor like behavior in Lu3Ir4Ge13 single crystal

NASA Astrophysics Data System (ADS)

Kumar, Anil; Matteppanavar, Shidaling; Thamizhavel, A.; Ramakrishnan, S.

2018-04-01

Single crystal of Lu3Ir4Ge13 crystallizing in the Yb3Rh4Sn13-type cubic crystal structure has been grown by Czochralski method in a tetra-arc furnace. In this paper we report on the crystal structure, magnetic and transport properties of Lu3Ir4Ge13. The analysis of the powder x-ray diffraction (XRD) studies revealed that Lu3Ir4Ge13 crystallizes in a cubic structure with the space group Pm-3n, no. 223. The lattice parameter was obtained from the Rietveld refinement of the room temperature XRD data which amounts to 8.904 (3) Å with low R factors. The temperature dependence of the resistivity exhibited semiconductor like behavior till 1.8 K, with a broad hump around 15 - 62 K. This hump was observed in both warming and cooling cycle with a very small hysteresis, it may be due to the existence of structural transition from high - low symmetry. The temperature dependent magnetization data shows the diamagnetic behavior with an anomaly around 70 K, which is well supported by the derivative of resistivity data.

Synthesis, Self-Assembly, and Drug-Release Properties of New Amphipathic Liquid Crystal Polycarbonates

PubMed Central

Xie, Yujiao; Liu, Xiaofeng; Hu, Zhuang; Hou, Zhipeng; Chen, Zhangpei; Hu, Jianshe; Yang, Liqun

2018-01-01

New amphiphilic liquid crystal (LC) polycarbonate block copolymers containing side-chain cholesteryl units were synthesized. Their structure, thermal stability, and LC phase behavior were characterized with Fourier transform infrared (FT-IR) spectrum, 1H NMR, gel permeation chromatographic (GPC), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), polarizing optical microscope (POM), and XRD methods. The results demonstrated that the LC copolymers showed a double molecular arrangement of a smectic A phase at room temperature. With the elevating of LC unit content in such LC copolymers, the corresponding properties including decomposition temperature (Td), glass temperature (Tg), and isotropic temperature (Ti) increased. The LC copolymers showed pH-responsive self-assembly behavior under the weakly acidic condition, and with more side-chain LC units, the self-assembly process was faster, and the formed particle size was smaller. It indicated that the self-assembly driving force was derived from the orientational ability of LC. The particle size and morphologies of self-assembled microspheres loaded with doxorubicin (DOX), together with drug release tracking, were evaluated by dynamic light scattering (DLS), SEM, and UV–vis spectroscopy. The results showed that DOX could be quickly released in a weakly acidic environment due to the pH response of the self-assembled microspheres. This would offer a new strategy for drug delivery in clinic applications. PMID:29584691

Supersaturation and crystallization: non-equilibrium dynamics of amorphous solid dispersions for oral drug delivery.

PubMed

Kawakami, Kohsaku

2017-06-01

Amorphous solid dispersions (ASDs) are one of the key formulation technologies that aid the development of poorly soluble candidates. However, their dynamic behaviors, including dissolution and crystallization processes, are still full of mystery. Further understanding of these processes should enhance their wider use. Areas covered: The first part of this review describes the current understanding of the dissolution of ASDs, where phase separation behavior is frequently involved and attempts to develop appropriate dissolution tests to achieve an in vitro-in vivo correlation are examined. The second part of this review discusses crystallization of the drug molecule with the eventual aim of establishing an accelerated testing protocol for predicting its physical stability. Expert opinion: The phase separation behavior from the supersaturated state during the dissolution test must be understood, and its relevance to the oral absorption behavior needs to be clarified. Research efforts should focus on the differences between the phase behavior in in vitro and in vivo situations. Initiation time of the crystallization was shown to be predicted only from storage and glass transition temperatures. This finding should encourage the establishment of testing protocol of the physical stability of ASDs.

Rb, Sr, Nd, and Sm concentrations in quartz

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

Rossman, G.R.; Weis, D.; Wasserburg, G.J.

1987-09-01

The concentrations of Rb, Sr, Nd and Sm in quartz crystals from Crystal Peak, Colorado; Steward Mine, California; Tomas Gonzaga, Minas Gerais, Brazil; and Coleman Mines, Arkansas, were determined by isotope dilution mass spectrometry. Concentrations ranged from: 1.17 to 177 ppb Rb; 3.26 to 1027 ppm Sr; 0.0159 to 0.48 ppm Sm; 0.127 to 2.81 ppb Nd. In the Brazilian crystal, concentrations of these elements were correlated with the amount of fluid inclusion water measured visually by turbidity and quantitatively with infrared adsorption spectroscopy. The highest Rb content was found for a crystal free of visible inclusions, indicating that smallmore » amounts of Rb can also occur in quartz itself. Rb and Sr contents are much lower in synthetic quartz grown commercially from the Arkansas quartz.« less

Investigation of Structural Re-ordering of Hydrogen Bonds in LiNbO3:Mg Crystals Around the Threshold Concentration of Magnesium

NASA Astrophysics Data System (ADS)

Sidorov, N. V.; Teplyakova, N. A.; Palatnikov, M. N.; Bobreva, L. A.

2017-09-01

Crystals of LiNbO3congr and LiNbO3:Mg (0.19-5.91 mole %) were studied by IR and Raman spectroscopy. It was found that the intensities of the bands corresponding to the stretching vibrations of the OH groups in the IR spectra of LiNbO3:Mg crystals change and components of the bands disappear with increase of the Mg content. This was explained by disappearance of the OH groups close to {Nb}_{Li}^{4+}-{V}_{Li}- defects as a result of displacement of NbLi defects by Mg cations. In the Raman spectra of the LiNbO3:Mg (5.1 mole %) compared with the congruent crystal the lines corresponding to the vibrations of oxygen atoms in the oxygen octahedra and the stretching bridge vibrations of the oxygen atoms along the polar axis become broader, and new low-intensity lines that may correspond to pseudoscalar vibrations of A2-type symmetry also appear. The broadening of the lines is due to deformation of the oxygen octahedra caused both by increase of the Mg content in the crystal structure and by change in the localization of the protons. Suppression of the photorefraction effect in the LiNbO3:Mg crystals with Mg contents above the threshold level can be explained by change in the localization of the protons in the structure and by screening of the space charge field.

Frequency and Thermal Behavior of Acoustic Absorption in ɛ-GaSe Crystals

NASA Astrophysics Data System (ADS)

Dzhafarova, S. Z.

2018-04-01

The paper presents results of measuring acoustic absorption in ɛ-GaSe crystals. The absorption of a longitudinal wave which propagates normal to the crystal layers, quadratically depends on frequency. However, it does not depend on temperature, i.e. it displays an Akhiezer behavior although its absolute value considerably exceeds the expected. The analysis of the frequency and thermal behavior of absorption of piezoelectric waves propagating along the layers, includes the deduction of contribution made by the interaction between waves and charge carriers. This analysis shows the linear dependence between the lattice absorption of these waves and the frequency. The linear frequency and weak temperature dependences of the acoustic absorption characterize the additional ultra-Akhiezer absorption in glasses. In our case, it can be caused by various polytypes forming in GaSe crystals which differ merely in a mutual arrangement of layers.

Surface crystallization behavior and physical properties of (GeTe4)85(AgI)15 chalcogenide glass

NASA Astrophysics Data System (ADS)

Zhu, Erwei; Wu, Bo; Zhao, Xuhao; Wang, Jingsong; Lin, Changgui; Wang, Xunsi; Li, Xing; Tian, Peijing

2017-11-01

Glass-ceramics embedded Te and α-GeTe particles were fabricated from (GeTe4)85(AgI)15 chalcohalide glass using an appropriate heat-treatment at fairly low temperatures ranging from 160 to 190 °C for different times. The crystallization behavior and physical properties of the obtained samples were studied in detail. The glass transition temperature of crystallized samples increases with the elongation of crystallization times. And the results of mechanical properties show that, compared with the base glass, the crystallized samples present improved thermal shock resistance and fracture toughness, and meanwhile still remain its good IR transmittance. This study could provide an initial observation of crystallization in telluride glasses, and be of good guidance to fabricate novel telluride glass-ceramics that operating in far-IR spectral region ranging from 2.5 μm to 25 μm.

A Study of the Crystallization, Melting, and Foaming Behaviors of Polylactic Acid in Compressed CO2

PubMed Central

Zhai, Wentao; Ko, Yoorim; Zhu, Wenli; Wong, Anson; Park, Chul B.

2009-01-01

The crystallization and melting behaviors of linear polylactic acid (PLA) treated by compressed CO2 was investigated. The isothermal crystallization test indicated that while PLA exhibited very low crystallization kinetics under atmospheric pressure, CO2 exposure significantly increased PLA’s crystallization rate; a high crystallinity of 16.5% was achieved after CO2 treatment for only 1 min at 100 °C and 6.89 MPa. One melting peak could be found in the DSC curve, and this exhibited a slight dependency on treatment times, temperatures, and pressures. PLA samples tended to foam during the gas release process, and a foaming window as a function of time and temperature was established. Based on the foaming window, crystallinity, and cell morphology, it was found that foaming clearly reduced the needed time for PLA’s crystallization equilibrium. PMID:20054476

Enhanced photocatalytic performance of mesoporous TiO{sub 2} coated SBA-15 nanocomposites fabricated through a novel approach: supercritical deposition aided by liquid-crystal template

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

Liu, Chen; Lin, Xiao; Li, Youji, E-mail: bcclyj@163.com

2016-03-15

Highlights: • Highly uniform mesoporous TiO{sub 2} nanopartices were coated SBA-15. • MT showed smaller crystallite size, higher hydroxyl content and surface area. • MT/SBA-15 show enhanced photocatalytic activity and high reused activity. • The optimum MT loading rate and calcination temperature were obtained to be 15% and 400 °C, respectively. • Photocatalytic behaviors are discussed in terms of the Langmuir–Hinshelwood model. - Abstract: Mesoporous TiO2 coated SBA-15 (MT@S) nanocomposites were fabricated through supercritical CO{sub 2} deposition aided by liquid-crystal template. The as-prepared samples were characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, diffuse reflectance spectroscopy and so on. Themore » results reveal that MT uniformly deposited onto silica with titania incorporated in SBA-15 channels, showed smaller crystallite size, higher hydroxyl content and surface area than nonporous TiO{sub 2} coated SBA-15 (NT@S) obtained by a similar route without template. With TiO{sub 2} loading ratio of 15 wt% and calcination temperature of 400 °C, 15%MT@S-400 showed the enhanced degradation efficiency for azo dyes (methylene blue, methyl orange, and rhodamine B) and phenol in comparsion with 15%NT@S-400, due to those improved textural and physicochemical properties. Meanwhile, the reused MT@S also showed high photoactivity. Additionally, the effects of MT content and calcination temperature have been examined as operational parameters. Photocatalytic reactions followed pseudo-first-order kinetics and are discussed in terms of the Langmuir–Hinshelwood model.« less

Influence of modulation periods on the tribological behavior of Si/a-C: H multilayer film

NASA Astrophysics Data System (ADS)

Zhu, Linan; Wu, Yanxia; Zhang, Shujiao; Yu, Shengwang; Tang, Bin; Liu, Ying; Zhou, Bing; Shen, Yanyan

2018-01-01

A series of Si/a-C: H multilayer films with different modulation periods were fabricated on stainless steel and silicon substrates by radio-frequency magnetron sputtering. The influence of the modulation period on the structure, morphology, mechanical properties and tribological behaviors in different environments (air, simulated acid rain, and NaCl solution) was investigated. The results show that the content of the sp2 hybrid carbon, surface roughness and hardness of the multilayer film increased firstly and then decreased with the decreased modulation period. Furthermore, the combination of the sublayer agrees well with the formation of the SiC crystal at the interface. Interestingly, the films show quite substantially different tribological properties in various test environments. The lowest friction coefficient is 0.2 for the S1 film in air. However, the lowest friction coefficient can reach 0.13 in solution. Importantly, the tribological behavior of the multilayer film is mainly determined by its hardness, as well as surface roughness in air while it is closely related with modulation period and interface structure in solution.

Tensile behavior of laser treated Fe-Si-B metallic glass

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

Joshi, Sameehan S.; Samimi, Peyman; Ghamarian, Iman

2015-10-28

Fe-Si-B metallic glass foils were treated with a linear laser track using a continuous wave Nd-YAG laser and its effect on the overall tensile behavior was investigated. Microstructure and phase evolutions were evaluated using X-ray diffraction, resistivity measurements, and transmission electron microscopy. Crystallization fraction was estimated via the differential scanning calorimetry technique. Metallic glass foils treated with the lower laser fluences (<0.49 J/mm{sup 2}) experienced structural relaxation, whereas higher laser fluences led to crystallization within the laser treated region. The overall tensile behavior was least impacted by structural relaxation, whereas crystallization severely reduced the ultimate tensile strength of the laser treatedmore » metallic glass foils.« less

TT-Cut Torsional Quartz Crystal Resonators of Free-Free Bar-Type

NASA Astrophysics Data System (ADS)

Kawashima, Hirofumi; Nakazato, Mitsuhiro

1994-05-01

This paper describes a TT-cut torsional quartz crystal resonator of free-free bar type. An object of this paper is to clarify the frequency temperature behavior, series resistance and a quality factor for TT-cut torsional quartz crystal resonators of free-free bar-type. The analysis results are then compared with the measured data. The principal results indicate that the calculated values of frequency temperature behavior for resonators of free-free bar-type agree comparatively well with the measured ones. Similar to the torsional resonators of tuning fork-type, a torsional quartz crystal resonator of free-free bar-type is also found to have an absolute value of the second order temperature coefficient β smaller than half a value of that for a flexural mode quartz crystal resonator.

Differential effect of buffering agents on the crystallization of gemcitabine hydrochloride in frozen solutions.

PubMed

Patel, Mehulkumar; Munjal, Bhushan; Bansal, Arvind K

2014-08-25

The purpose of this study was to evaluate the differential effect of buffering agents on the crystallization of gemcitabine hydrochloride (GHCl) in frozen solutions. Four buffering agents, viz. citric acid (CA), malic acid (MA), succinic acid (SA) and tartaric acid (TA) were selected and their effect on GHCl crystallization was monitored using standard DSC and low temperature XRD. Onset of GHCl crystallization during heating run in DSC was measured to compare the differential effect of buffering agents. Glass transition temperature (Tg'), unfrozen water content in the freeze concentrate and crystallization propensity of the buffering agents was also determined for mechanistic understanding of the underlying effects. CA and MA inhibited while SA facilitated crystallization of GHCl even at 25 mM concentration. Increasing the concentration enhanced their effect. However, TA inhibited GHCl crystallization at concentrations <100mM and facilitated it at concentrations ≥100 mM. Lyophilization of GHCl with either SA or TA yielded elegant cakes, while CA and MA caused collapse. Tg' failed to explain the inhibitory effects of CA, MA and TA as all buffering agents lowered the Tg' of the system. Differential effect of buffering agents on GHCl crystallization could be explained by consideration of two opposing factors: (i) their own crystallization tendency and (ii) unfrozen water content in the freeze concentrate. In conclusion, it was established that API crystallization in frozen solution is affected by the type and concentration of the buffering agents. Copyright © 2014 Elsevier B.V. All rights reserved.

Ultrasonic characterization of pork fat crystallization during cold storage.

PubMed

Corona, Edith; García-Pérez, José V; Santacatalina, Juan V; Ventanas, Sonia; Benedito, José

2014-05-01

In this work, the feasibility of using ultrasonic velocity measurements for characterizing and differentiating the crystallization pattern in 2 pork backfats (Montanera and Cebo Iberian fats) during cold storage (0 °C, 2 °C, 5 °C, 7 °C, and 10 °C) was evaluated. The fatty acid profile, thermal behavior, and textural properties (hardness) of fat were also determined. Both fats became harder during cold storage (average hardness increase for both fats, 11.5 N, 8 N, and 1.8 N at 0, °C 2 °C, and 5 °C , respectively), showing a 2-step pattern related with the separate crystallization of the different existing triacylglycerols, which was well described using a modified Avrami equation (explained variance > 99%). Due to a greater content of saturated triacylglycerols, Cebo fat (45.1%) was harder than Montanera (41.8%). The ultrasonic velocity followed a similar 2-step pattern to hardness during cold storage, being found an average increase for both fats of 184, 161, and 150 m/s at 0 °C 2 °C, and 5 °C, respectively. Thus, ultrasonic measurements were useful both to characterize the textural changes taking place during cold storage and to differentiate between fats with different composition. The cold storage of dry-cured meat products during their distribution and retail sale exert an important effect on their textural properties and consumers' acceptance due to the crystallization of the fat fraction, which is greatly influenced by the type of fat. In this work, a nondestructive ultrasonic technique was used to identify the textural changes provoked by the crystallization during cold storage, and to differentiate between fats, which could be used for quality control purposes. © 2014 Institute of Food Technologists®

Single Crystal Membranes

NASA Technical Reports Server (NTRS)

Stormont, R. W.; Morrison, A.

1974-01-01

Single crystal a- and c-axis tubes and ribbons of sodium beta-alumina and sodium magnesium beta-alumina were grown from sodium oxide rich melts. Additional experiments grew ribbon crystals containing sodium magnesium beta, beta double prime, beta triple prime, and beta quadruple prime. A high pressure crystal growth chamber, sodium oxide rich melts, and iridium for all surfaces in contact with the melt were combined with the edge-defined, film-fed growth technique to grow the single crystal beta-alumina tubes and ribbons. The crystals were characterized using metallographic and X-ray diffraction techniques, and wet chemical analysis was used to determine the sodium, magnesium, and aluminum content of the grown crystals.

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

Kuz'micheva, G. M., E-mail: galkuz@mitht.ru; Zaharko, O.; Tyunina, E. A.

Langatate crystals of the general composition La{sub 3}(Ga{sub 0.5}Ta{sub 0.5})Ga{sub 5}O{sub 14}, grown by the Czochralski method, have been investigated by neutron diffraction (single crystals) and X-ray diffraction (ground single crystals). The crystals were grown in an atmosphere of 99% Ar + 1% O{sub 2} in the Y54{sup o} direction (rotation by 54{sup o} with respect to the y axis), without subsequent annealing (orange crystal) or with vacuum annealing (colorless crystal). It is established that colorless crystals have a higher gallium content and, therefore, a larger number of oxygen vacancies in comparison with colored crystals; this is a possible reasonmore » for their lower microhardness.« less

Effects of crystallization and dopant concentration on the emission behavior of TiO2:Eu nanophosphors

PubMed Central

2012-01-01

Uniform, spherical-shaped TiO2:Eu nanoparticles with different doping concentrations have been synthesized through controlled hydrolysis of titanium tetrabutoxide under appropriate pH and temperature in the presence of EuCl3·6H2O. Through air annealing at 500°C for 2 h, the amorphous, as-grown nanoparticles could be converted to a pure anatase phase. The morphology, structural, and optical properties of the annealed nanostructures were studied using X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy [EDS], and UV-Visible diffuse reflectance spectroscopy techniques. Optoelectronic behaviors of the nanostructures were studied using micro-Raman and photoluminescence [PL] spectroscopies at room temperature. EDS results confirmed a systematic increase of Eu content in the as-prepared samples with the increase of nominal europium content in the reaction solution. With the increasing dopant concentration, crystallinity and crystallite size of the titania particles decreased gradually. Incorporation of europium in the titania particles induced a structural deformation and a blueshift of their absorption edge. While the room-temperature PL emission of the as-grown samples is dominated by the 5D0 - 7Fj transition of Eu+3 ions, the emission intensity reduced drastically after thermal annealing due to outwards segregation of dopant ions. PMID:22214494

A scanning electron microscope study of olivine crystal surfaces

NASA Technical Reports Server (NTRS)

Olsen, E. J.; Grossman, L.

1974-01-01

SEM photographs were taken of euhedral olivine grains from the Murchison C2 chondrite and several terrestrial and lunar occurrences. In general, the crystal faces of the meteorite grains are rough and uneven, with irregular growth patterns. They are very similar to crystal faces on terrestrial olivine grains that formed by sublimation from a vapor phase. They are very different from the relatively smooth and featureless surfaces of magmatic olivine crystals that precipitated from igneous melts. Qualitatively, the surface morphology of the crystal supports the contention that many euhedral crystals of olivine in C2 meteorites condensed from a gas phase.

Remarkable features in lattice-parameter ratios of crystals. II. Monoclinic and triclinic crystals.

PubMed

de Gelder, R; Janner, A

2005-06-01

The frequency distributions of monoclinic crystals as a function of the lattice-parameter ratios resemble the corresponding ones of orthorhombic crystals: an exponential component, with more or less pronounced sharp peaks, with in general the most important peak at the ratio value 1. In addition, the distribution as a function of the monoclinic angle beta has a sharp peak at 90 degrees and decreases sensibly at larger angles. Similar behavior is observed for the three triclinic angular parameters alpha, beta and gamma, with characteristic differences between the organic and metal-organic, bio-macromolecular and inorganic crystals, respectively. The general behavior observed for the hexagonal, tetragonal, orthorhombic, monoclinic and triclinic crystals {in the first part of this series [de Gelder & Janner (2005). Acta Cryst. B61, 287-295] and in the present case} is summarized and commented. The data involved represent 366 800 crystals, with lattice parameters taken from the Cambridge Structural Database, CSD (294 400 entries), the Protein Data Bank, PDB (18 800 entries), and the Inorganic Crystal Structure Database, ICSD (53 600 entries). A new general structural principle is suggested.

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.

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.

Colloidal Material Box: In-situ Observations of Colloidal Self-Assembly and Liquid Crystal Phase Transitions in Microgravity

NASA Astrophysics Data System (ADS)

Li, WeiBin; Lan, Ding; Sun, ZhiBin; Geng, BaoMing; Wang, XiaoQing; Tian, WeiQian; Zhai, GuangJie; Wang, YuRen

2016-05-01

To study the self-assembly behavior of colloidal spheres in the solid/liquid interface and elucidate the mechanism of liquid crystal phase transition under microgravity, a Colloidal Material Box (CMB) was designed which consists of three modules: (i) colloidal evaporation experimental module, made up of a sample management unit, an injection management unit and an optical observation unit; (ii) liquid crystal phase transition experimental module, including a sample management unit and an optical observation unit; (iii) electronic control module. The following two experimental plans will be performed inside the CMB aboard the SJ-10 satellite in space. (i) Self-assembly of colloidal spheres (with and without Au shell) induced by droplet evaporation, allowing observation of the dynamic process of the colloidal spheres within the droplet and the change of the droplet outer profile during evaporation; (ii) Phase behavior of Mg2Al LDHs suspensions in microgravity. The experimental results will be the first experimental observations of depositing ordered colloidal crystals and their self-assembly behavior under microgravity, and will illustrate the influence of gravity on liquid crystal phase transition.

Phase equilibrium and preparation, crystallization and viscous sintering of glass in the alumina-silica-lanthanum phosphate system

NASA Astrophysics Data System (ADS)

He, Feng

The phase equilibrium, viscosity of melt-quenched glasses, and processing of sol-gel glasses of the alumina-silica-lanthanum phosphate system were studied. These investigations were directed towards serving the objective of synthesizing nano-structured ceramic-matrix-composites via controlled crystallization of glass precursors. The thermal stability, phase equilibrium, and liquidus temperatures of the alumina- and mullite-lanthanum phosphate systems are determined. An iridium wire heater was constructed to anneal samples up to 2200°C. Phosphorus evaporation losses were significant at high temperatures, especially over 1800°C. The tentative phase diagrams of the two quasi-binary systems were presented. The viscosity of the melt-quenched mullite-lanthanum phosphate glasses was measured by three different methods, including viscous sintering of glass powder compacts, neck formation between two Frenkel glass beads, and thermal analysis of the glass transition. Improved methodologies were developed for applying the interpretative mathematical models to the results of the sintered powder and thermal analytical experiments. Good agreement was found between all three methods for both absolute values and temperature dependence. A sol-gel process was developed as a low temperature route to producing glasses. A unique, single phase mullite gel capable of low temperature (575°C) mullitization was made from tetraethoxysilane and aluminum isopropoxide at room temperature in three days. Low temperature crystallization was attributed to the avoidance of phase segregation during gel formation and annealing. This was greatly enhanced by a combination of low temperature preheating in the amorphous state, a high heating rate during crystallization and low water content. The Al2O3 content in mullite (61-68 mol%) depended on the highest annealing temperature. Two mullite-lanthanum phosphate gels were made based upon modifying the chemical procedures used for the homogeneous single phase and heterogeneous diphasic mullite gels from same starting chemicals. Amorphous powders were obtained after optimized calcinations. Their different crystallization routes and sintering behavior were investigated and correlated with the different homogeneities of precursor gels. Structurally stable open, porous ceramics (up to 80% porosity) were produced from the single-phase gel derived powder, where gases exsolved during calcination caused foaming coincident with sintering. Translucent, dense glass ceramic was made from the calcined diphasic gel by hot-pressing.

Effect of Preparation Methods on Crystallization Behavior and Tensile Strength of Poly(vinylidene fluoride) Membranes

PubMed Central

Liu, Jie; Lu, Xiaolong; Wu, Chunrui

2013-01-01

Poly(vinylidene fluoride) (PVDF) membranes were prepared by non solvent induced phase separation (NIPS), melt spinning and the solution-cast method. The effect of preparation methods with different membrane formation mechanisms on crystallization behavior and tensile strength of PVDF membranes was investigated. Fourier transform infrared spectroscopy-attenuated total reflectance (FTIR-ATR) and X-ray diffraction (XRD) were employed to examine the crystal form of the surface layers and the overall membranes, respectively. Spherulite morphologies and thermal behavior of the membranes were studied by polarized light optical microscopy (PLO) and differential scanning calorimetry (DSC) separately. It was found that the crystallization behavior of PVDF membranes was closely related to the preparation methods. For membranes prepared by the NIPS method, the skin layers had a mixture of α and β phases, the overall membranes were predominantly α phase, and the total crystallinity was 60.0% with no spherulite. For melt spinning membranes, the surface layers also showed a mixture of α and β phases, the overall membranes were predominantly α phase. The total crystallinity was 48.7% with perfect spherulites. Whereas the crystallization behavior of solution-cast membranes was related to the evaporation temperature and the additive, when the evaporation temperature was 140 °C with a soluble additive in the dope solution, obvious spherulites appeared. The crystalline morphology of PVDF exerted a great influence on the tensile strength of the membranes, which was much higher with perfect spherulites. PMID:24957064

Thermal and tensile properties of alumina filled PET nanocomposites

NASA Astrophysics Data System (ADS)

Nikam, Pravin N.; Deshpande, Vineeta D.

2018-05-01

In the present investigation, nanocomposites of poly(ethylene terephathalate)(PET) with different content (0 to 5 wt.%) of alumina nanoparticles (n-Al2O3) were prepared by melt-extrusion technique. Morphological characterization of samples was examined by transmission electron microscopy (TEM). Morphological analysis revealed that degree of dispersion of alumina nanoparticles (ANPs) was increased at lower content (i.e. upto 2 wt.%), which observed by TEM. Thermal and tensile measurements were carried out using and differential scanning calorimetry (DSC) and universal testing machine (UTM). The thermal analysis showed that the glass transition termperature (Tg), melting temperature (Tm), crystallization temperature (Tc) of PET/alumina nanocomposites (PNCs) were higher than neat PET (PET0). The heat enthalpy (ΔHm) of crystallization for PNCs was increased compared to PET0, which indicates that degree of crystallinity of PNCs also increased compared to PET0. The half-time (t0.5) of crystallization of PNCs were decreased compared to PET0 which indicates that the incorporation of ANPs nucleate the PET molecular chains and allowing the easily crystallization during nonisothermal process. The tensile analysis revealed that the tensile elastic modulus (i.e. Young's modulus) of PNCs increased almost linearly with increasing the content of ANPs while tensile elongation at break decreased nonlinearly. The tensile strength of PNCs increased with a 1 wt.% of ANPs whereas the higher content of ANPs decreased the tensile strength.

Different magnesium release profiles from W/O/W emulsions based on crystallized oils.

PubMed

Herzi, Sameh; Essafi, Wafa

2018-01-01

Water-in-oil-in-water (W/O/W) double emulsions based on crystallized oils were prepared and the release kinetics of magnesium ions from the internal to the external aqueous phase was investigated at T=4°C, for different crystallized lipophilic matrices. All the emulsions were formulated using the same surface-active species, namely polyglycerol polyricinoleate (oil-soluble) and sodium caseinate (water-soluble). The external aqueous phase was a lactose or glucose solution at approximately the same osmotic pressure as that of the inner droplets, in order to avoid osmotic water transfer phenomena. We investigated two types of crystallized lipophilic systems: one based on blends of cocoa butter and miglyol oil, exploring a solid fat content from 0 to 90% and the other system based on milk fat fractions for which the solid fat content varies between 54 and 86%. For double emulsions based on cocoa butter/miglyol oil, the rate of magnesium release was gradually lowered by increasing the % of fat crystals i.e. cocoa butter, in agreement with a diffusion/permeation mechanism. However for double emulsions based on milk fat fractions, the rate of magnesium release was independent of the % of fat crystals and remains the one at t=0. This difference in diffusion patterns, although the solid content is of the same order, suggests a different distribution of fat crystals within the double globules: a continuous fat network acting as a physical barrier for the diffusion of magnesium for double emulsions based on cocoa butter/miglyol oil and double globule/water interfacial distribution for milk fat fractions based double emulsions, through the formation of a crystalline shell allowing an effective protection of the double globules against diffusion of magnesium to the external aqueous phase. Copyright © 2017 Elsevier Inc. All rights reserved.

Bulk Crystal Growth of Nonlinear Optical Organic Materials Using Inverted Vertical Gradient Freeze Method

NASA Technical Reports Server (NTRS)

Choi, J.; Cruz, Magda; Metzl, R.; Wang, W. S.; Aggarwal, M. D.; Penn, Benjamin G.; Frazier, Donald O.

1998-01-01

A new process for producing large bulk single crystals of benzil (C6H5COCOC6H5) is reported in this paper. Good quality crystals have been successfully grown using this approach to crystal growth. This method seems to be very promising for other thermally stable NLO organic materials also. The entire contents vycor crucible 1.5 inch in diameter and 2 inch deep was converted to single crystal. Purity of the starting growth material is also an important factor in the final quality of the grown crystals. The entire crystal can be very easily taken out of the crucible by simple maneuvering. Initial characterization of the grown crystals indicated that the crystals are as good as other crystals grown by conventional Bridgman Stockbarger technique.

Influence of seed nano-crystals on electrical properties and phase transition behaviors of Ba0.85Sr0.15Ti0.90Zr0.10O3 ceramics prepared by seed-induced method

NASA Astrophysics Data System (ADS)

Sutjarittangtham, Krit; Intatha, Uraiwan; Eitssayeam, Sukum

2015-05-01

This work studied the effects of seed nano-crystal on the electrical properties and the phase transition behaviors of Ba0.85Sr0.15Ti0.90Zr0.10O3 (BSZT) ceramics. The BSZT ceramics were prepared by the seed-induced method. The seed nano-crystal were prepared by the molten salt technique, and NaCl-KCl (1:1 by mole) eutectic mixtures were used as the flux.[1] The ceramic powders were prepared by using a conventional method which added seed nano-crystals at various ratios. Results indicated that seed nano-crystals enhanced the electrical properties of ceramics. The sample with a 20 wt. % seed nano crystals has excellent value of dielectric constant ( µ r ) of 34698 at maximum temperature. The phase transition temperature was observed at 60°C. The morphology was found that the grain size increasing significantly with an increased of seed nano crystals. The relaxor ferroelectric phase transition behavior was shown by a diffuseness parameter ( ³). An increase in the BSZT-seed showed a decreased in ³ value from 1.61 to 1.44. Thus the ferroelectric of the BSZT ceramics can be confirmed by hysteresis loop.[Figure not available: see fulltext.

Tiny crystals give away the where and when of magma ascent

NASA Astrophysics Data System (ADS)

Ruth, D. C. S.; Costa Rodriguez, F.; Bouvet de Maisonneuve, C.; Franco, L.; Cortes, J. A.; Calder, E.

2016-12-01

Open vent volcanoes exhibit passive degassing and can transition to explosive behavior, with limited or no warning. Melt inclusion chemistry and volatile contents have been used to infer the inner dynamics of magma storage, recharge, degassing, and eruption triggering mechanisms. However, the interpretation of melt inclusion chemistry is ambiguous because it cannot constrain the residence times of the host crystals, which could have various sources and growth histories. To resolve this issue we combine diffusion chronometry and melt inclusion entrapment pressures from olivine crystals sourced from the 2008 eruption of Llaima volcano (Chile). Olivine crystals (core Fo70-84, rim Fo77-84) are dominantly reverse zoned, although normal zoned and complex zoned crystals are observed. These data reflect mixing between the mafic injecting magma and the crystal-rich resident magma. Fe/Mg diffusion timescales range between 16 and 1375 days. The diffusion data show a non-uniform distribution with no discernible peaks, indicating that magma injection is likely progressive, rather than punctuated. Entrapment pressures range between 8 and 151 MPa, overlapping with an inferred crystal-rich region. Longer timescales correspond to higher pressures, strongly suggesting a link between magma residence time and ascent from depth. To our knowledge, this relationship has not been previously demonstrated. We infer that mafic magma intruded at depths of 5 km below the edifice and mingled with a pre-existing crystal-mush 3 yr before the eruption. Magma migration and mingling continued and stalled at 2.5 km depth about a year prior to the eruption. Precursory activity such as volcano-tectonic and long period seismicity, and a series of minor explosions overlap with the diffusion times 6 months before the eruption. Similar diffusion timescales have been reported for eruptions at other open vent volcanoes. Our study provides the first temporal and spatial constraints on magma storage and ascent before an eruption. Furthermore at Llaima, and potentially open vent systems, the progressive nature of magma injection suggests that additional processes (e.g. variable ascent rates, changing viscosity, etc.) are needed to trigger an eruption.

Solid-state properties and crystallization behavior of PHA-739521 polymorphs.

PubMed

Sun, Changquan Calvin

2006-08-17

PHA-739521 is an experimental compound that exhibits polymorphism. The two anhydrous crystal forms, I and II, are characterized using powder X-ray diffractometry, thermal analyses, moisture sorption gravimetry. Both Forms I and II are non-hygroscopic and are stable to compaction pressure. The melting temperature is about 152 degrees C for Form I and 168 degrees C for Form II. Forms I and II are enantiotropically related where Form I is more stable below a transition temperature of approximately 70 degrees C. Crystallization behavior of this compound from solutions and during heating is also studied. Information obtained is used to design an appropriate crystallization process to successfully manufacture desired polymorph at large scale.

Refractory oxide hosts for a high power, broadly tunable laser with high quantum efficiency and method of making same

DOEpatents

Chen, Yok; Gonzalez, Roberto

1986-01-01

Refractory oxide crystals having high-quantum efficiency and high thermal stability for use as broadly tunable laser host materials. The crystals are formed by removing hydrogen from a single crystal of the oxide material to a level below about 10.sup.12 protons per cm.sup.3 and subsequently thermochemically reducing the oxygen content of the crystal to form sufficient oxygen anion vacancies so that short-lived F.sup.+ luminescence is produced when the crystal is optically excited.

Refractory oxide hosts for a high power, broadly tunable laser with high quantum efficiency and method of making same

DOEpatents

Chen, Yok; Gonzalez, R.

1985-07-03

Refractory oxide crystals having high-quantum efficiency and high thermal stability for use as broadly tunable laser host materials. The crystals are formed by removing hydrogen from a single crystal of the oxide material to a level below about 10/sup 12/ protons per cm/sup 3/ and subsequently thermochemically reducing the oxygen content of the crystal to form sufficient oxygen anion vacancies so that short-lived F/sup +/ luminescence is produced when the crystal is optically excited.

Effect of praseodymium on the electrical resistance of YВа2Сu3О7-δ single crystals

NASA Astrophysics Data System (ADS)

Vovk, R. V.; Vovk, N. R.; Khadzhai, G. Ya.; Goulatis, I. L.; Chroneos, A.

2014-07-01

The electrical resistivity in the ab-plane of the Y1-yPryВа2Сu3О7-δ single crystals with high degree of perfection in the interval of Тc - 300 K was investigated. The increasing of praseodymium content leads to the reduction of the critical temperature (Tc) from 92 to 30 K. The experimental results can be approximated by the expression, taking into account the scattering of electrons by phonons, defects, the fluctuation conductivity in the 3D Aslamazov-Larkin model, as well as the transition to a "semiconductor" type behavior of the resistivity at the high praseodymium concentrations. The concentration dependences of all fitting parameters indicate a structural transition in the region 0.35≤у≤0.43. In particular, the Debye temperature changes in this range from 350 to 550 K, and the transverse coherence length passes through a maximum ξС(0)≈5 Å. The concentration dependence of the critical temperature testifies the d-pairing of the BCS model.

Electrical transport property, thermal stability and oxidation resistance of single crystalline β-Zn4Sb3 prepared using the Bi-Sn mixed-flux method

NASA Astrophysics Data System (ADS)

Deng, Shuping; Li, Decong; Chen, Zhong; Tang, Yu; Shen, Lanxian; Deng, Shukang

2017-12-01

Single crystal samples β-Zn4Sb3 have been prepared by using Bi-Sn mixed-flux method. The obtained crystals exhibit p-type conduction behavior with carrier concentration varying from 4.40 × 1019 to 18.12 × 1019 cm-3 as carrier mobility changes from 25.8 to 61.5 cm2 V-1 s-1 at room temperature. Electrical transport properties of the samples were optimized by Bi-Sn co-doped, which brought by Bi-Sn mixed-flux. And the maximal power factor of 1.45 × 10-3 W m-1 K-2 is achieved at 510 K for the sample with Bi flux content x = 0.5. Consequently, the oxidation resistance of the sample was determined by exploring the effects of heat treatment in air on electrical transport properties and thermal stability, which the single crystalline β-Zn4Sb3 still possess an excellent oxidation resistance and thermal stability after the heat treatment process.

Antiferroelectricity in lanthanum doped zirconia without metallic capping layers and post-deposition/-metallization anneals

NASA Astrophysics Data System (ADS)

Wang, Zheng; Gaskell, Anthony Arthur; Dopita, Milan; Kriegner, Dominik; Tasneem, Nujhat; Mack, Jerry; Mukherjee, Niloy; Karim, Zia; Khan, Asif Islam

2018-05-01

We report the effects of lanthanum doping/alloying on antiferroelectric (AFE) properties of ZrO2. Starting with pure ZrO2, an increase in La doping leads to the narrowing of the AFE double hysteresis loops and an increase in the critical voltage/electric field for AFE → ferroelectric transition. At higher La contents, the polarization-voltage characteristics of doped/alloyed ZrO2 resemble that of a non-linear dielectric without any discernible AFE-type hysteresis. X-ray diffraction based analysis indicates that the increased La content while preserving the non-polar, parent AFE, tetragonal P42/nmc phase leads to a decrease in tetragonality and the (nano-)crystallite size and an increase in the unit cell volume. Furthermore, antiferroelectric behavior is obtained in the as-deposited thin films without requiring any capping metallic layers and post-deposition/-metallization anneals due to which our specific atomic layer deposition system configuration crystallizes and stabilizes the AFE tetragonal phase during growth.

Lead zirconate titanate (PZT)-based thin film capacitors for embedded passive applications

NASA Astrophysics Data System (ADS)

Kim, Taeyun

Investigations on the key processing parameters and properties relationship for lead zirconate titanate (PZT, 52/48) based thin film capacitors for embedded passive capacitor application were performed using electroless Ni coated Cu foils as substrates. Undoped and Ca-doped PZT (52/48) thin film capacitors were prepared on electroless Ni coated Cu foil by chemical solution deposition. For PZT (52/48) thin film capacitors on electroless Ni coated Cu foil, voltage independent (zero tunability) capacitance behavior was observed. Dielectric constant reduced to more than half of the identical capacitor processed on Pt/SiO2/Si. Dielectric properties of the capacitors were mostly dependent on the crystallization temperature. Capacitance densities of almost 350 nF/cm2 and 0.02˜0.03 of loss tangent were routinely measured for capacitors crystallized at 575˜600°C. Leakage current showed dependence on film thickness and crystallization temperature. From a two-capacitor model, the existence of a low permittivity interface layer (permittivity ˜30) was suggested. For Ca-doped PZT (52/48) thin film capacitors prepared on Pt, typical ferroelectric and dielectric properties were measured up to 5 mol% Ca doping. When Ca-doped PZT (52/48) thin film capacitors were prepared on electroless Ni coated Cu foil, phase stability was influenced by Ca doping and phosphorous content. Dielectric properties showed dependence on the crystallization temperature and phosphorous content. Capacitance density of ˜400 nF/cm2 was achieved, which is an improvement by more than 30% compared to undoped composition. Ca doping also reduced the temperature coefficient of capacitance (TCC) less than 10%, all of them were consistent in satisfying the requirements of embedded passive capacitor. Leakage current density was not affected significantly by doping. To tailor the dielectric and reliability properties, ZrO2 was selected as buffer layer between PZT and electroless Ni. Only RF magnetron sputtering process could yield stable ZrO2 layers on electroless Ni coated Cu foil. Other processes resulted in secondary phase formation, which supports the reaction between PZT capacitor and electroless Ni might be dominated by phosphorous component. (Abstract shortened by UMI.)

Final Report - Crystal Settling, Redox, and High Temperature Properties of ORP HLW and LAW Glasses, VSL-09R1510-1, Rev. 0, dated 6/18/09

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

Kruger, Albert A.; Wang, C.; Gan, H.

2013-11-13

The radioactive tank waste treatment programs at the U. S. Department of Energy (DOE) have featured joule heated ceramic melter technology for the vitrification of high level waste (HLW). The Hanford Tank Waste Treatment and Immobilization Plant (WTP) employs this same basic technology not only for the vitrification of HLW streams but also for the vitrification of Low Activity Waste (LAW) streams. Because of the much greater throughput rates required of the WTP as compared to the vitrification facilities at the West Valley Demonstration Project (WVDP) or the Defense Waste Processing Facility (DWPF), the WTP employs advanced joule heated meltersmore » with forced mixing of the glass pool (bubblers) to improve heat and mass transport and increase melting rates. However, for both HLW and LAW treatment, the ability to increase waste loadings offers the potential to significantly reduce the amount of glass that must be produced and disposed and, therefore, the overall project costs. This report presents the results from a study to investigate several glass property issues related to WTP HLW and LAW vitrification: crystal formation and settling in selected HLW glasses; redox behavior of vanadium and chromium in selected LAW glasses; and key high temperature thermal properties of representative HLW and LAW glasses. The work was conducted according to Test Plans that were prepared for the HLW and LAW scope, respectively. One part of this work thus addresses some of the possible detrimental effects due to considerably higher crystal content in waste glass melts and, in particular, the impact of high crystal contents on the flow property of the glass melt and the settling rate of representative crystalline phases in an environment similar to that of an idling glass melter. Characterization of vanadium redox shifts in representative WTP LAW glasses is the second focal point of this work. The third part of this work focused on key high temperature thermal properties of representative WTP HLW and LAW glasses over a wide range of temperatures, from the melter operating temperature to the glass transition.« less

Effects of Co contents on the microstructures and properties of the electrodeposited NiCo–Zr composite coatings

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

Cai, Fei; Jiang, Chuanhai, E-mail: chuanhaijiang1963@163.com; Zhao, Yuantao

2015-05-15

Highlights: • The novel NiCo–Zr coatings were prepared by electro-deposition. • Surface morphology, crystal structure, grain size and microstrain were examined. • Texture, residual stress and corrosion resistance were investigated. • Addition of Co increased the hardness and corrosion resistance of the coatings. - Abstract: In this study, the NiCo–Zr composite coatings were prepared from the electrolytes with different Co{sup 2+} concentrations by electrodeposition method. The effects of Co contents on the crystal structure, surface morphology, grain size, microstrain and residual stress were examined by X-ray diffractometer (XRD), field emission scanning electron microscopy (FESEM), Energy dispersive X-ray spectroscopy (EDX) andmore » atomic force microscope (AFM). The corrosion resistance of the composite coatings was also examined by the potentiodynamic polarization and electrochemical impedance (EIS) measurements. The results revealed that the crystal structures of the coatings were dependent on the Co contents and addition of Co content of 58 wt% resulted in the formation of hexagonal (hcp) Co. The increasing Co contents in the NiCo–Zr composite coatings resulted in the smoother and more compact surface, decreased the grain size and increased the microstrain. The micro-hardness and residual stress also increased with increasing Co contents. The addition of Co increased the corrosion resistance of the NiCo–Zr composite coatings compared with the Ni–Zr coating while the corrosion resistance of the NiCo–Zr composite coatings decreased as the Co contents increased.« less

Laboratory Investigation of Direct Measurement of Ice Water Content, Ice Surface Area, and Effective Radius of Ice Crystals Using a Laser-Diffraction Instrument

NASA Technical Reports Server (NTRS)

Gerber, H.; DeMott, P. J.; Rogers, D. C.

1995-01-01

The aircraft microphysics probe, PVM-100A, was tested in the Colorado State University dynamic cloud chamber to establish its ability to measure ice water content (IWC), PSA, and Re in ice clouds. Its response was compared to other means of measuring those ice-cloud parameters that included using FSSP-100 and 230-X 1-D optical probes for ice-crystal concentrations, a film-loop microscope for ice-crystal habits and dimensions, and an in-situ microscope for determining ice-crystal orientation. Intercomparisons were made in ice clouds containing ice crystals ranging in size from about 10 microns to 150 microns diameter, and ice crystals with plate, columnar, dendritic, and spherical shapes. It was not possible to determine conclusively that the PVM accurately measures IWC, PSA, and Re of ice crystals, because heat from the PVM evaporated in part the crystals in its vicinity in the chamber thus affecting its measurements. Similarities in the operating principle of the FSSP and PVM, and a comparison between Re measured by both instruments, suggest, however, that the PVM can make those measurements. The resolution limit of the PVM for IWC measurements was found to be on the order of 0.001 g/cubic m. Algorithms for correcting IWC measured by FSSP and PVM were developed.

Fe-Al alloy single-crystal thin film preparation for basic magnetic measurements

NASA Astrophysics Data System (ADS)

Abe, Tatsuya; Kawai, Tetsuroh; Futamoto, Masaaki; Ohtake, Mitsuru; Inaba, Nobuyuki

2018-04-01

Fe100-xAlx (x = 0, 4, 10, 20, 30 at. %) alloy films of 40 nm thickness are prepared on MgO(001) single-crystal substrates by varying substrate temperature from room temperature to 600 °C. Single-crystal films of (001) orientation with bcc-based disordered A2 structure are obtained for the Al content range of x = 0 - 20 at. %. An ordered phase of DO3 structure is observed in Fe70Al30 films prepared at temperatures higher than 200 °C, whereas (001) oriented single-crystal films of A2 structure are obtained when prepared at room temperature. The film surface profile does not depend much on the film composition, while the surface roughness increases with increasing substrate temperature. Island-like crystals are observed for films prepared at 600°C for all compositions. Difference in lattice spacing measured parallel and perpendicular to the substrate is noted for the single-crystal thin films and it increases with increasing Al content. The lattice strain in single-crystal film is caused possibly to accommodate the lattice mismatch with the MgO substrate. The (001)-oriented single-crystal films with A2 structure show four-fold symmetries in in-plane magnetic anisotropy with the easy magnetization axis A2[100] and the hard magnetization axis A2[110], whereas the films with DO3 ordered structure show almost isotropic magnetic properties.

Phase behavior of binary and polydisperse suspensions of compressible microgels controlled by selective particle deswelling

NASA Astrophysics Data System (ADS)

Scotti, A.; Gasser, U.; Herman, E. S.; Han, Jun; Menzel, A.; Lyon, L. A.; Fernandez-Nieves, A.

2017-09-01

We investigate the phase behavior of suspensions of poly(N -isopropylacrylamide) (pNIPAM) microgels with either bimodal or polydisperse size distribution. We observe a shift of the fluid-crystal transition to higher concentrations depending on the polydispersity or the fraction of large particles in suspension. Crystallization is observed up to polydispersities as high as 18.5%, and up to a number fraction of large particles of 29% in bidisperse suspensions. The crystal structure is random hexagonal close-packed as in monodisperse pNIPAM microgel suspensions. We explain our experimental results by considering the effect of bound counterions. Above a critical particle concentration, these cause deswelling of the largest microgels, which are the softest, changing the size distribution of the suspension and enabling crystal formation in conditions where incompressible particles would not crystallize.

Unique isothermal crystallization behavior of novel polyphenylene sulfide/inorganic fullerene-like WS2 nanocomposites.

PubMed

Naffakh, Mohammed; Marco, Carlos; Gómez, Marián A; Jiménez, Ignacio

2008-11-27

The isothermal crystallization of polyphenylene sulfide (PPS) nanocomposites with inorganic fullerene-like tungsten disulfide nanoparticles (IF-WS2) has been studied from a thermal and morphological point of view, using differential scanning calorimetry (DSC), scanning electron microscopy (SEM), polarized optical microscopy (POM) and time-resolved synchrotron X-ray diffraction. All the analyses revealed that the incorporation of the IF-WS2 altered significantly the crystallization behavior of PPS, in a way strongly dependent with the nanocomposite composition. The addition of IF-WS2 in 0.1 wt % proportion retarded the crystallization of PPS by increasing its fold surface free energy in a 10%. However, addition of the nanoparticles in excess of 1 wt % results in a promotion of the crystallization rate with reduction of the fold surface free energy to half the value of pure PPS.

The Effects of Job Search Behavior and Vocational Self-Concept Crystallization on Job Acquisition: Is There an Interaction?

ERIC Educational Resources Information Center

Quint, Ellen Deutsch; Kopelman, Richard E.

1995-01-01

Predicted job acquisition success would be positively related to the level of job search behavior; the degree of vocational self-concept crystallization; and most strongly, the combined effects (interaction) of the two. Data from two samples supported the first prediction, but not the latter two. (JBJ)

Effect of method of crystallization on the IV-III and IV-II polymorphic transitions of ammonium nitrate.

PubMed

Vargeese, Anuj A; Joshi, Satyawati S; Krishnamurthy, V N

2009-01-15

A study has been undertaken on the effect of crystallization method on the IV<-->III transition of ammonium nitrate (AN). AN is crystallized in three different ways, viz. recrystallization, evaporative crystallization and melt crystallization. When the samples were crystallized from saturated aqueous solution, ideal crystals were formed, which behaved differently from the crystals formed from the other methods. The DTA examination of the crystals showed that the crystals have different transition behaviour. The moisture uptake of the samples determined were found to have influenced by the mode of crystallization. The samples were further analyzed by powder X-ray diffraction (XRD) and scanning electron microscopy (SEM). The present study showed that the parameters like thermal history, number of previous transformations and moisture content have a very negligible influence on the IV<-->III transition of AN as compared to the method of crystallization.

Counit Inclusion in Hydrogenated Polynorbornene Copolymer Crystals

NASA Astrophysics Data System (ADS)

Burns, Adam; Showak, Michael; Stella, Andrew; Register, Richard

2014-03-01

Crystallization in poly(A-co-B) random copolymers, where homopolymer A is crystalline but B is not, is dictated by the degree to which crystals of A can include B units. Typically, B units are strongly excluded from the A crystals, drastically reducing the degree of crystallinity wc and crystal thickness tc even at modest comonomer contents. However, in some cases, B units can be incorporated into the crystals as defects, significantly diminishing the counits' impact on wc and tc. The extent and consequences of counit inclusion have been investigated in hydrogenated polynorbornene (hPN) with alkylnorbornene counits, synthesized by living ring-opening metathesis polymerization followed by hydrogenation. In the case of 5-hexylnorbornene (HxN) counits, a steep decline in wc and tc with counit content is found, indicative of strong exclusion. In contrast, when the counits are 5-methylnorbornene (MeN), extensive inclusion of MeN units into the crystals is observed. hP(N-co-MeN) copolymers maintain appreciable crystallinity above 30 mol% MeN, and the dependence of the melting point Tm on tc tracks that of the hPN homopolymer. Four times as much MeN as HxN (molar basis) is required to produce a comparable drop in wc. Therefore, copolymerization with MeN can be used to tune Tm without drastically reducing wc. Additionally, hPN exhibits a polymorphic transition to a rotationally disordered (RD) crystal at temperature Tcc

Growth of High Purity Oxygen-Free Silicon by Cold Crucible Techniques.

DTIC Science & Technology

1982-06-01

Liquid Metals (A Review). High Temp.-High Pressures 2(6), 583-586, 1970. 1971 Knights, C.F. and Perkins, R. Levitation Melting of Uranium Mono- Carbide . J...content - typically I PPM or less. c) The crystals grown exhibited a high level of carbon contamination (2-30 PPM ) which we believe, is caused by the...grown from melts confined in the cold crucible exhibit an unusually low oxygen content - typically 1 PPM or less. c.) The crystals grown exhibited a

Crystallization and identification of the glycosylated moieties of two isoforms of the main allergen Hev b 2 and preliminary X-ray analysis of two polymorphs of isoform II

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

Fuentes-Silva, D.; Mendoza-Hernández, G.; Stojanoff, V.

2007-09-01

Crystallization of important glycoenzymes involved in IgE-mediated latex allergy. Latex from Hevea brasiliensis contains several allergenic proteins that are involved in type I allergy. One of them is Hev b 2, which is a β-1,3-glucanase enzyme that exists in different isoforms with variable glycosylation content. Two glucanase isoforms were isolated from trees of the GV-42 clone by gel filtration, affinity and ion-exchange chromatography. Isoform I had a carbohydrate content of about 20%, with N-linked N-acetyl-glucosamine, N-acetyl-galactosamine, fucose and galactose residues as the main sugars, while isoform II showed 6% carbohydrate content constisting of N-acetyl-glucosamine, fucose, mannose and xylose. Both isoformsmore » were crystallized by the hanging-drop vapour-diffusion method. Isoform I crystals were grown using 0.2 M trisodium citrate dihydrate, 0.1 M Na HEPES pH 7.5 and 20%(v/v) 2-propanol, but these crystals were not appropriate for data collection. Isoform II crystals were obtained under two conditions and X-ray diffraction data were collected from both. In the first condition (0.2 M trisodium citrate, 0.1 M sodium cacodylate pH 6.5, 30% 2-propanol), crystals belonging to the tetragonal space group P4{sub 1} with unit-cell parameters a = b = 150.17, c = 77.41 Å were obtained. In the second condition [0.2 M ammonium acetate, 0.1 M trisodium citrate dihydrate pH 5.6, 30%(w/v) polyethylene glycol 4000] the isoform II crystals belonged to the monoclinic space group P2{sub 1}, with unit-cell parameters a = 85.08, b = 89.67, c = 101.80 Å, β = 113.6°. Preliminary analysis suggests that there are four molecules of isoform II in both asymmetric units.« less

Crystal residence times from trace element zoning in plagioclase reveal changes in magma transfer dynamics at Mt. Etna during the last 400 years

NASA Astrophysics Data System (ADS)

Viccaro, Marco; Barca, Donatella; Bohrson, Wendy A.; D'Oriano, Claudia; Giuffrida, Marisa; Nicotra, Eugenio; Pitcher, Bradley W.

2016-04-01

Trace element zoning in plagioclase of selected alkaline lavas from the historic (1607-1892 AD) and recent (1983-2013 AD) activity of Mt. Etna volcano has been used to explore the possible role that volcano-tectonics exert on magma transfer dynamics. The observed textural characteristics of crystals include near-equilibrium textures (i.e., oscillatory zoning) and textures with variable extent of disequilibrium (patchy zoning, coarse sieve textures and dissolved cores). Historic crystals exhibit lower K concentrations at lower anorthite contents, a feature in agreement with the general more potassic character of the recent lavas if compared to the historic products. Historic plagioclases have statistically higher Ba and lower Sr concentrations than the recent crystals, which result in different Sr/Ba ratios for the two suites of plagioclase. Variations in the anorthite content along core-to-rim profiles obtained on crystals with different types of textures for both the historic and recent eruptive periods were evaluated particularly versus Sr/Ba. At comparable average An contents, crystals characterized by oscillatory zoning, which are representative of near-equilibrium crystallization from the magma, display distinct Sr/Ba ratios. We suggest that these features are primarily related to recharge of a new, geochemically-distinct magma into the storage and transport system of the volcano. In addition to distinct trace element and textural characteristics of plagioclase, Sr diffusion modeling for plagioclase suggests that residence times are generally shorter for crystals found in recently erupted lavas (25-77 years, average 43 years) compared to those of the historic products (43-163 years, average 99 years). Shorter residences times correlate with gradual increases in eruption volume and eruption frequency rates through time. We attribute these features to an increasing influence, since the 17th century, of extensional tectonic structures within the upper 10 km of the Etnean crust, which have promoted shorter residence times and higher eruption frequency.

Relaxor properties of barium titanate crystals grown by Remeika method

NASA Astrophysics Data System (ADS)

Roth, Michel; Tiagunov, Jenia; Dul'kin, Evgeniy; Mojaev, Evgeny

2017-06-01

Barium titanate (BaTiO3, BT) crystals have been grown by the Remeika method using both the regular KF and mixed KF-NaF (0.6-0.4) solvents. Typical acute angle "butterfly wing" BT crystals have been obtained, and they were characterized using x-ray diffraction, scanning electron microscopy (including energy dispersive spectroscopy), conventional dielectric and acoustic emission methods. A typical wing has a triangular plate shape which is up to 0.5 mm thick with a 10-15 mm2 area. The plate has a (001) habit and an atomically smooth outer surface. Both K+ and F- solvent ions are incorporated as dopants into the crystal lattice during growth substituting for Ba2+ and O2- ions respectively. The dopants' distribution is found to be inhomogeneous, their content being almost an order of magnitude higher (up to 2 mol%) at out surface of the plate relatively to the bulk. A few μm thick surface layer is formed where a multidomain ferroelectric net is confined between two≤1 μm thick dopant-rich surfaces. The layer as a whole possess relaxor ferroelectric properties, which is apparent from the appearance of additional broad maxima, Tm, in the temperature dependence of the dielectric permittivity around the ferroelectric phase transition. Intense acoustic emission responses detected at temperatures corresponding to the Tm values allow to observe the Tm shift to lower temperatures at higher frequencies, or dispersion, typical for relaxor ferroelectrics. The outer surface of the BT wing can thus serve as a relaxor thin film for various electronic application, such as capacitors, or as a substrate for BT-based multiferroic structure. Crystals grown from KF-NaF fluxes contain sodium atoms as an additional impurity, but the crystal yield is much smaller, and while the ferroelectric transition peak is diffuse it does not show any sign of dispersion typical for relaxor behavior.

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.

NMR signal analysis to attribute the components to the solid/liquid phases present in mixes and ice creams.

PubMed

Mariette, François; Lucas, Tiphaine

2005-03-09

The NMR relaxation signals from complex products such as ice cream are hard to interpret because of the multiexponential behavior of the relaxation signal and the difficulty of attributing the NMR relaxation components to specific molecule fractions. An attribution of the NMR relaxation parameters is proposed, however, based on an approach that combines quantitative analysis of the spin-spin and spin-lattice relaxation times and the signal intensities with characterization of the ice cream components. We have been able to show that NMR can be used to describe the crystallized and liquid phases separately. The first component of the spin-spin and spin-lattice relaxation describes the behavior of the protons of the crystallized fat in the mix. The amount of fat crystals can then be estimated. In the case of ice cream, only the spin-lattice relaxation signal from the crystallized fraction is relevant. However, it enables the ice protons and the protons of the crystallized fat to be distinguished. The spin-lattice relaxation time can be used to describe the mobility of the protons in the different crystallized phases and also to quantify the amount of ice crystals and fat crystals in the ice cream. The NMR relaxation of the liquid phase of the mix has a biexponential behavior. A first component is attributable to the liquid fraction of the fat and to the sugars, while a second component is attributable to the aqueous phase. Overall, the study shows that despite the complexity of the NMR signal from ice cream, a number of relevant parameters can be extracted to study the influence of the formulation and of the process stages on the ice fraction, the crystallized fat fraction, and the liquid aqueous fraction.

Effect of Nb addition on microstructure and corrosion resistance of novel stainless steels fabricated by direct laser metal deposition

NASA Astrophysics Data System (ADS)

Wu, S. Q.; Zhang, C. H.; Zhang, S.; Wang, Q.; Liu, Y.; Abdullah, Adil O.

2018-03-01

The study demonstrated the successful fabrication of novel stainless steels by direct laser metal deposition with the aim of investigating the impact of niobium content (Nb = 0, 0.25, 0.75, 1.25 wt%) on their microstructure and electrochemical properties. The microstructure and phase evolution of the as-built stainless steels were studied using scanning electron microscope (SEM) and electron back-scatter diffraction (EBSD). Corrosion behavior of the samples was evaluated using electrochemical workstation in 3.5 wt% NaCl. Experimental results have shown that the crystal structure of as-built stainless steels was BCC with a small trace of dispersive carbides and FCC phase. Grain refinement was observed with increasing niobium content. Large-angle boundaries were obtained in different Nb-containing samples with distribution from 50° to 60°. An increase in niobium content extremely improved the corrosion resistance of as-built stainless steels and the as-built samples with 1.25 wt% exhibited the best corrosion resistance among the tested samples as indicated by its lowest corrosion rate, which was an order of magnitude lower than that of Nb-free samples.

Structural and magnetic properties of FexNi100-x alloys synthesized using Al as a reducing metal

NASA Astrophysics Data System (ADS)

Srakaew, N.; Jantaratana, P.; Nipakul, P.; Sirisathitkul, C.

2017-08-01

Iron-nickel (Fe-Ni) alloys comprising nine different compositions were rapidly synthesized from the redox reaction using aluminum foils as the reducing metal. Compared with conventional chemical syntheses, this simple approach is relatively safe and allows control over the alloy morphology and magnetic behavior as a function of the alloy composition with minimal oxidation. For alloys having low (10%-30%) Fe content the single face-centered cubic (FCC) FeNi3 phase was formed with nanorods aligned in the (1 1 1) crystalline direction on the cluster surface. This highly anisotropic morphology gradually disappeared as the Fe content was raised to 40%-70% with the alloy structure possessing a mixture of FCC FeNi3 and body-centered cubic (BCC) Fe7Ni3. The FCC phase was entirely replaced by the BCC structure upon further increase the Fe content to 80%-90%. The substitution of Ni by Fe in the crystals and the dominance of the BCC phase over the FCC structure gave rise to enhanced magnetization. By contrast, the coercive field decreased as a function of increasing Fe because of the reduction in shape anisotropy and the rise of saturation magnetization.

Correlating Single Crystal Structure, Nanomechanical, and Bulk Compaction Behavior of Febuxostat Polymorphs.

PubMed

Yadav, Jayprakash A; Khomane, Kailas S; Modi, Sameer R; Ugale, Bharat; Yadav, Ram Naresh; Nagaraja, C M; Kumar, Navin; Bansal, Arvind K

2017-03-06

Febuxostat exhibits unprecedented solid forms with a total of 40 polymorphs and pseudopolymorphs reported. Polymorphs differ in molecular arrangement and conformation, intermolecular interactions, and various physicochemical properties, including mechanical properties. Febuxostat Form Q (FXT Q) and Form H1 (FXT H1) were investigated for crystal structure, nanomechanical parameters, and bulk deformation behavior. FXT Q showed greater compressibility, densification, and plastic deformation as compared to FXT H1 at a given compaction pressure. Lower mechanical hardness of FXT Q (0.214 GPa) as compared to FXT H1 (0.310 GPa) was found to be consistent with greater compressibility and lower mean yield pressure (38 MPa) of FXT Q. Superior compaction behavior of FXT Q was attributed to the presence of active slip systems in crystals which offered greater plastic deformation. By virtue of greater compressibility and densification, FXT Q showed higher tabletability over FXT H1. Significant correlation was found with anticipation that the preferred orientation of molecular planes into a crystal lattice translated nanomechanical parameters to a bulk compaction process. Moreover, prediction of compactibility of materials based on true density or molecular packing should be carefully evaluated, as slip-planes may cause deviation in the structure-property relationship. This study supported how molecular level crystal structure confers a bridge between particle level nanomechanical parameters and bulk level deformation behavior.

Measurable characteristics of lysozyme crystal growth

NASA Technical Reports Server (NTRS)

Gorti, Sridhar; Forsythe, Elizabeth L.; Pusey, Marc L.

2005-01-01

The behavior of protein crystal growth is estimated from measurements performed at both the microscopic and molecular levels. In the absence of solutal flow, it was determined that a model that balances the macromolecular flux toward the crystal surface with the flux of the crystal surface well characterizes crystal growth observed using microscopic methods. Namely, it was determined that the model provides accurate estimates for the crystal-growth velocities upon evaluation of crystal-growth measurements obtained in time. Growth velocities thus determined as a function of solution supersaturation were further interpreted using established deterministic models. From analyses of crystal-growth velocities, it was found that the mode of crystal growth varies with respect to increasing solution supersaturation, possibly owing to kinetic roughening. To verify further the hypothesis of kinetic roughening, crystal growth at the molecular level was examined using atomic force microscopy (AFM). From the AFM measurements, it was found that the magnitude of surface-height fluctuations, h(x), increases with increasing solution supersaturation. In contrast, the estimated characteristic length, xi, decreases rapidly upon increasing solution supersaturation. It was conjectured that the magnitude of both h(x) and xi could possibly determine the mode of crystal growth. Although the data precede any exact theory, the non-critical divergence of h(x) and xi with respect to increasing solution supersaturation was nevertheless preliminarily established. Moreover, approximate models to account for behavior of both h(x) and xi are also presented.

A study on ice crystal formation behavior at intracellular freezing of plant cells using a high-speed camera.

PubMed

Ninagawa, Takako; Eguchi, Akemi; Kawamura, Yukio; Konishi, Tadashi; Narumi, Akira

2016-08-01

Intracellular ice crystal formation (IIF) causes several problems to cryopreservation, and it is the key to developing improved cryopreservation techniques that can ensure the long-term preservation of living tissues. Therefore, the ability to capture clear intracellular freezing images is important for understanding both the occurrence and the IIF behavior. The authors developed a new cryomicroscopic system that was equipped with a high-speed camera for this study and successfully used this to capture clearer images of the IIF process in the epidermal tissues of strawberry geranium (Saxifraga stolonifera Curtis) leaves. This system was then used to examine patterns in the location and formation of intracellular ice crystals and to evaluate the degree of cell deformation because of ice crystals inside the cell and the growing rate and grain size of intracellular ice crystals at various cooling rates. The results showed that an increase in cooling rate influenced the formation pattern of intracellular ice crystals but had less of an effect on their location. Moreover, it reduced the degree of supercooling at the onset of intracellular freezing and the degree of cell deformation; the characteristic grain size of intracellular ice crystals was also reduced, but the growing rate of intracellular ice crystals was increased. Thus, the high-speed camera images could expose these changes in IIF behaviors with an increase in the cooling rate, and these are believed to have been caused by an increase in the degree of supercooling. Copyright © 2016 Elsevier Inc. All rights reserved.

Crystallization tendency of active pharmaceutical ingredients following rapid solvent evaporation--classification and comparison with crystallization tendency from undercooled melts.

PubMed

Van Eerdenbrugh, Bernard; Baird, Jared A; Taylor, Lynne S

2010-09-01

In this study, the crystallization behavior of a variety of compounds was studied following rapid solvent evaporation using spin coating. Initial screening to determine model compound suitability was performed using a structurally diverse set of 51 compounds in three different solvent systems [dichloromethane (DCM), a 1:1 (w/w) dichloromethane/ethanol mixture (MIX), and ethanol (EtOH)]. Of this starting set of 153 drug-solvent combinations, 93 (40 compounds) were selected for further evaluation based on solubility, chemical solution stability, and processability criteria. These systems were spin coated and their crystallization was monitored using polarized light microscopy (7 days, dry conditions). The crystallization behavior of the samples could be classified as rapid (Class I: 39 cases), intermediate (Class II: 23 cases), or slow (Class III: 31 cases). The solvent system employed influenced the classification outcome for only four of the compounds. The various compounds showed very diverse crystallization behavior. Upon comparison of classification results with those of a previous study, where cooling from the melt was used as a preparation technique, a good similarity was found whereby 68% of the cases were identically classified. Multivariate analysis was performed using a set of relevant physicochemical compound characteristics. It was found that a number of these parameters tended to differ between the different classes. These could be further interpreted in terms of the nature of the crystallization process. Additional multivariate analysis on the separate classes of compounds indicated some potential in predicting the crystallization tendency of a given compound.

Crystallization kinetic of Sb-V2O5-TeO2 glasses investigated by DSC and their elastic moduli and Poisson's ratio

NASA Astrophysics Data System (ADS)

Souri, Dariush

2015-01-01

Ternary tellurate glasses of the form xSb-(60-x)V2O5-40TeO2 (0≤x≤15 in mol%) were prepared by using the usual melt quenching method. Differential scanning calorimetry (DSC) at different heating rates (φ) was used to thermal analyze and to gain more insight in to the thermal stability, glass forming tendency and so calorimetric behavior of the present glasses. The glass transition temperature (Tg), the temperature corresponding to the onset of crystallization (Tx) and also the crystallization temperature (TCr) were obtained at different heating rates, to estimate the key kinetic parameter of activation energy of crystallization (ΔE) by using different empirical formulas. Also some other thermal parameters such as thermal stability and glass forming tendency were determined. It was found that Tg, Tx and TCr increase with increase in Sb content and also with increase in heating rate. Moreover, Makishima-Makenzie's theory was employed to evaluate the Poisson's ratio and elastic moduli, indicating a strong relation between elastic properties and the structure of glass. From the mechanical and thermal data and also the values of oxygen molar volume ( V O *), it was founded that the glass systems can be divided in to "two compositional regions"; so, results indicate that glasses with 10≤x≤15 (especially for x=12) are more thermal stable and strong glasses, which make them as more useful and promising materials in technological advantages and device manufacturing.

Effect of niobium content on the microstructure and thermal properties of fluorapatite glass-ceramics.

PubMed

Denry, I L; Holloway, J A; Nakkula, R J; Walters, J D

2005-10-01

Niobium oxide has been shown to improve biocompatibility and promote bioactivity. The purpose of this study was to evaluate the effect of niobium oxide additions on the microstructure and thermal properties of fluorapatite glass-ceramics for biomedical applications. Four glass-ceramic compositions with increasing amounts of niobium oxide from 0 to 5 wt % were prepared. The glass compositions were melted at 1,525 degrees C for 3 h, quenched, ground, melted again at 1,525 degrees C for 3 h and furnace cooled. The coefficient of thermal expansion was measured by dilatometry. The crystallization behavior was evaluated by differential thermal analysis. The nature of the crystalline phases was investigated by X-ray diffraction. The microstructure was studied by SEM. In addition, the cytotoxicity of the ceramics was evaluated according to the ASTM standard F895--84. The results from X-ray diffraction analyses showed that fluorapatite was the major crystalline phase in all glass-ceramics. Differential thermal analyses revealed that fluorapatite crystallization occurred between 800 and 934 degrees C depending on the composition. The coefficient of thermal expansion varied from 7.6 to 9.4 x 10(-6)/ degrees C. The microstructure after heat treatment at 975 degrees C for 30 min consisted of submicroscopic fluorapatite crystals (200--300 nm) for all niobium-containing glass-ceramics, whereas the niobium-free glass-ceramic contained needle-shaped fluorapatite crystals, 2 microm in length. None of the glass-ceramics tested exhibited any cytotoxic activity as tested by ASTM standard F895--84. (c) 2005 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2005.

Effects of emulsifier addition on the crystallization and melting behavior of palm olein and coconut oil.

PubMed

Maruyama, Jessica Mayumi; Soares, Fabiana Andreia Schafer De Martini; D'Agostinho, Natalia Roque; Gonçalves, Maria Inês Almeida; Gioielli, Luiz Antonio; da Silva, Roberta Claro

2014-03-12

Two commercial emulsifiers (EM1 and EM2), containing predominantly monoacylglycerols (MAGs), were added in proportiond of 1.0 and 3.0% (w/w) to coconut oil and palm olein. EM1 consisted of approximately 90% MAGs, whereas EM2 consisted of approximately 50% MAGs. The crystallization behavior of these systems was evaluated by differential scanning calorimetry (DSC) and microscopy under polarized light. On the basis of DSC results, it was clear that the addition of EM2 accelerated the crystallization of coconut oil and delayed the crystallization of palm olein. In both oils EM2 addition led to the formation of smaller spherulites, and these effects improved the possibilities for using these fats as ingredients. In coconut oil the spherulites were maintained even at higher temperatures (20 °C). The addition of EM1 to coconut oil changed the crystallization pattern. In palm olein, the addition of 3.0% (w/w) of this emulsifier altered the pattern of crystallization of this fat.

Humidity control and hydrophilic glue coating applied to mounted protein crystals improves X-ray diffraction experiments

PubMed Central

Baba, Seiki; Hoshino, Takeshi; Ito, Len; Kumasaka, Takashi

2013-01-01

Protein crystals are fragile, and it is sometimes difficult to find conditions suitable for handling and cryocooling the crystals before conducting X-ray diffraction experiments. To overcome this issue, a protein crystal-mounting method has been developed that involves a water-soluble polymer and controlled humid air that can adjust the moisture content of a mounted crystal. By coating crystals with polymer glue and exposing them to controlled humid air, the crystals were stable at room temperature and were cryocooled under optimized humidity. Moreover, the glue-coated crystals reproducibly showed gradual transformations of their lattice constants in response to a change in humidity; thus, using this method, a series of isomorphous crystals can be prepared. This technique is valuable when working on fragile protein crystals, including membrane proteins, and will also be useful for multi-crystal data collection. PMID:23999307

Anatomy of a metabentonite: nucleation and growth of illite crystals and their colescence into mixed-layer illite/smectite

USGS Publications Warehouse

Eberl, D.D.; Blum, A.E.; Serravezza, M.

2011-01-01

The illite layer content of mixed-layer illite/smectite (I/S) in a 2.5 m thick, zoned, metabentonite bed from Montana decreases regularly from the edges to the center of the bed. Traditional X-ray diffraction (XRD) pattern modeling using Markovian statistics indicated that this zonation results from a mixing in different proportions of smectite-rich R0 I/S and illite-rich R1 I/S, with each phase having a relatively constant illite layer content. However, a new method for modeling XRD patterns of I/S indicates that R0 and R1 I/S in these samples are not separate phases (in the mineralogical sense of the word), but that the samples are composed of illite crystals that have continuous distributions of crystal thicknesses, and of 1 nm thick smectite crystals. The shapes of these distributions indicate that the crystals were formed by simultaneous nucleation and growth. XRD patterns for R0 and R1 I/S arise by interparticle diffraction from a random stacking of the crystals, with swelling interlayers formed at interfaces between crystals from water or glycol that is sorbed on crystal surfaces. It is the thickness distributions of smectite and illite crystals (also termed fundamental particles, or Nadeau particles), rather than XRD patterns for mixed-layer I/S, that are the more reliable indicators of geologic history, because such distributions are composed of well-defined crystals that are not affected by differences in surface sorption and particle arrangements, and because their thickness distribution shapes conform to the predictions of crystal growth theory, which describes their genesis.

Second All-Union Seminar on Hydromechanics and Heat-Mass Transfer in Weightlessness. Abstracts of reports: Table of contents

NASA Technical Reports Server (NTRS)

Gershuni, G. Z.; Zhukhovitskiy, Y. M.

1984-01-01

Abstracts of reports are given which were presented at the Second All Union Seminar on Hydromechanics and Heat-Mass Transfer in Weightlessness. Topics inlcude: (1) features of crystallization of semiconductor materials under conditions of microacceleration; (2) experimental results of crystallization of solid solutions of CDTE-HGTE under conditions of weightlessness; (3) impurities in crystals cultivated under conditions of weightlessness; and (4) a numerical investigation of the distribution of impurities during guided crystallization of a melt.

Second All-Union Seminar on Hydromechanics and Heat-Mass Transfer in Weightlessness. Abstracts of reports: Table of contents

NASA Astrophysics Data System (ADS)

Gershuni, G. Z.; Zhukhovitskiy, Y. M.

1984-01-01

s of reports are given which were presented at the Second All Union Seminar on Hydromechanics and Heat-Mass Transfer in Weightlessness. Topics inlcude: (1) features of crystallization of semiconductor materials under conditions of microacceleration; (2) experimental results of crystallization of solid solutions of CDTE-HGTE under conditions of weightlessness; (3) impurities in crystals cultivated under conditions of weightlessness; and (4) a numerical investigation of the distribution of impurities during guided crystallization of a melt.

Preferred growth orientation and microsegregation behaviors of eutectic in a nickel-based single-crystal superalloy

PubMed Central

Ma, Dexin; Bührig-Polaczek, Andreas

2015-01-01

A nickel-based single-crystal superalloy was employed to investigate the preferred growth orientation behavior of the (γ + γ′) eutectic and the effect of these orientations on the segregation behavior. A novel solidification model for the eutectic island was proposed. At the beginning of the eutectic island’s crystallization, the core directly formed from the liquid by the eutectic reaction, and then preferably grew along [100] direction. The crystallization of the eutectic along [110] always lagged behind that in [100] direction. The eutectic growth in [100] direction terminated on impinging the edge of the dendrites or another eutectic island. The end of the eutectic island’s solidification terminates due to the encroachment of the eutectic liquid/solid interface at the dendrites or another eutectic island in [110] direction. The distribution of the alloying elements depended on the crystalline axis. The degree of the alloying elements’ segregation was lower along [100] than [110] direction with increasing distance from the eutectic island’s center. PMID:27877773

Computational and theoretical studies of globular proteins

NASA Astrophysics Data System (ADS)

Pagan, Daniel L.

Protein crystallization is often achieved in experiment through a trial and error approach. To date, there exists a dearth of theoretical understanding of the initial conditions necessary to promote crystallization. While a better understanding of crystallization will help to create good crystals suitable for structure analysis, it will also allow us to prevent the onset of certain diseases. The core of this thesis is to model and, ultimately, understand the phase behavior of protein particles in solution. Toward this goal, we calculate the fluid-fluid coexistence curve in the vicinity of the metastable critical point of the modified Lennard-Jones potential, where it has been shown that nucleation is increased by many orders of magnitude. We use finite-size scaling techniques and grand canonical Monte Carlo simulation methods. This has allowed us to pinpoint the critical point and subcritical region with high accuracy in spite of the critical fluctuations that hinder sampling using other Monte Carlo techniques. We also attempt to model the phase behavior of the gamma-crystallins, mutations of which have been linked to genetic cataracts. The complete phase behavior of the square well potential at the ranges of attraction lambda = 1.15 and lambda = 1.25 is calculated and compared with that of the gammaII-crystallin. The role of solvent is also important in the crystallization process and affects the phase behavior of proteins in solution. We study a model that accounts for the contribution of the solvent free-energy to the free-energy of globular proteins. This model allows us to model phase behavior that includes solvent.

Crystallization kinetics and thermal resistance of bamboo fiber reinforced biodegradable polymer composites

NASA Astrophysics Data System (ADS)

Thumsorn, S.; Srisawat, N.; On, J. Wong; Pivsa-Art, S.; Hamada, H.

2014-05-01

Bamboo fiber reinforced biodegradable polymer composites were prepared in this study. Biodegradable poly(butylene succinate) (PBS) was blended with bamboo fiber in a twin screw extruder with varied bamboo content from 20-0wt%. PBS/bamboo fiber composites were fabricated by compression molding process. The effect of bamboo fiber contents on properties of the composites was investigated. Non-isothermal crystallization kinetic study of the composites was investigated based on Avrami equation. The kinetic parameters indicated that bamboo fiber acted as heterogeneous nucleation and enhanced crystallinity of the composites. Bamboo fiber was well dispersed on PBS matrix and good adhered with the matrix. Tensile strength of the composites slightly deceased with adding bamboo fiber. However, tensile modulus and impact strength of the composites increased when increasing bamboo fiber contents. It can be noted that bamboo fiber promoted crystallization and crystallinity of PBS in the composites. Therefore, the composites were better in impact load transferring than neat PBS, which exhibited improving on impact performance of the composites.

Influence of triethanolamine on the hydration product of portlandite in cement paste and the mechanism

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

Yan-Rong, Zhang; School of Civil Engineering, Beijing Key Laboratory of Track Engineering, Beijing Jiaotong University, Beijing 100044; Xiang-Ming, Kong

The influences of triethanolamine (TEA) on the portlandite in hardened cement pastes (HCPs) were systematically investigated. Results show that the addition of TEA in cement pastes leads to a visible reduction of Ca(OH){sub 2} (CH) content and considerably alters the morphology of CH crystals from large and parallel-stacked lamellar shape to smaller and distorted actinomorphic one. For the first time, the CH micro-crystals and even non-crystalline CH in HCPs were observed in the presence of TEA. Due to integration of CH micro-crystals in C–S–H phase, remarkable higher Ca/Si ratio of C–S–H phase was found. The formation of TEA-Ca{sup 2+} complexmore » via the interaction between Ca{sup 2+} and the oxygen atoms in TEA molecule was evidenced by the results of NMR and UV. It is believed that TEA can be introduced into the crystallization process of portlandite and thus significantly alters the morphology of CH crystals and even the content of the crystalline CH phase.« less

Three-dimensional behavior of ice crystals and biological cells during freezing of cell suspensions.

PubMed

Ishiguro, H; Koike, K

1998-09-11

Behavior of ice crystals and human red blood cells during extracellular-freezing was investigated in three-dimensions using a confocal laser scanning microscope(CLSM), which noninvasively produces tomograms of biological materials. Physiological saline and physiological saline with 2.4 M glycerol were used for suspension. Various cooling rates for directional solidification were used for distinctive morphology of the ice crystals. Addition of acridine orange as a fluorescent dye into the cell suspension enabled ice crystal, cells and unfrozen solution to be distinguished by different colors. The results indicate that the microscopic structure is three-dimensional for flat, cellular, and dendritic solid-liquid interfaces and that a CLSM is very effective in studying three-dimensional structure during the freezing of cell suspensions.

Comparative analysis of thermal behavior, isothermal crystallization kinetics and polymorphism of palm oil fractions.

PubMed

Zhang, Xia; Li, Lin; Xie, He; Liang, Zhili; Su, Jianyu; Liu, Guoqin; Li, Bing

2013-01-15

Thermal behavior of palm stearin (PS) and palm olein (PO) was explored by monitoring peak temperature transitions by differential scanning calorimetry (DSC). The fatty acid composition (FAC), isothermal crystallization kinetics studied by pulsed Nuclear Magnetic Resonance (pNMR) and isothermal microstructure were also compared. The results indicated that the fatty acid composition had an important influence on the crystallization process. PS and PO both exhibited more multiple endotherms than exotherms which showed irregular peak shapes. An increasing in cooling rate, generally, was associated with an increase in peak size. Application of the Avaimi equation to isothermal crystallization of PS and PO revealed different nucleation and growth mechanisms based on the Avrami exponents. PS quickly reached the end of crystallization because of more saturated triacylglycerol (TAG). The Avrami index of PS were the same as PO under the same isothermal condition at lower temperatrue, indicating that the crystallization mechanism of the two samples based on super-cooling state were the same. According to the polarized light microscope (PLM) images, crystal morphology of PS and PO was different. With the temperature increased, the structure of crystal network of both PS and PO gradually loosened.

The effect of UV exposure and heat treatment on crystallization behavior of photosensitive glasses

NASA Astrophysics Data System (ADS)

Kıbrıslı, Orhan; Ersundu, Ali Erçin

2018-05-01

In this study, photosensitive glasses in the Na2O-ZnO-Al2O3-SiO2 system with photosensitizing agents (cerium, silver, tin, antimony) and halogenides (NaF and KBr) were synthesized through a conventional melt-quenching technique. The crystallization mechanism was investigated for solely heat-treated and UV-exposed + heat-treated samples using differential thermal analysis (DTA), X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS) and scanning electron microscopy (SEM) techniques to understand the effect of UV exposure on crystallization behavior of photosensitive glasses. Accordingly, non-isothermal DTA measurements were performed at different heating rates to determine crystallization peak, T p, and onset, T c, temperatures. For solely heat-treated samples, the kinetic parameters such as the Avrami constant, n, and morphology index, m, were calculated as 1 from the Ozawa method indicating surface crystallization and the value of crystallization activation energy was calculated as 944 kJ/mol using modified Kissinger method. On the contrary, bulk crystallization was found to be predominant for UV exposed + heat-treated samples revealing that UV exposure is the primary cause of bulk crystallization in photosensitive glasses.

Crystal Chemistry and Conductivity Studies in the System La 0.5+ x+ yLi 0.5-3 xTi 1-3 yCr 3 yO 3

NASA Astrophysics Data System (ADS)

Martínez-Sarrión, M. L.; Mestres, L.; Morales, M.; Herraiz, M.

2000-12-01

The stoichiometry polymorphism and electrical behavior of solid solutions La0.5+x+yLi0.5-3xTi1-3yCr3yO3 with perovskite-type structure were studied. Data are given in the form of a solid solutions triangle, phase diagrams, XRD patterns for the three polymorphs, A, β, and C, composition dependence of their lattice parameters, and ionic and electronic conductivity plots. Microstructure and composition were studied by SEM/EDS and electron probe microanalysis. These compounds are mixed conductors. Ionic conductivity decreased when the amount of lithium diminished and electronic conductivity increased with chromium content.

Sintering and crystallization behavior of CaMgSi{sub 2}O{sub 6}-NaFeSi{sub 2}O{sub 6} based glass-ceramics

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

Goel, Ashutosh; Kansal, Ishu; Dipartimento di Ingegneria dei Materiali e dell'Ambiente, Facolta di Ingegneria, Universita di Modena e Reggio Emilia, 41100 Modena

2009-11-01

We report on the synthesis, sintering, and crystallization behaviors of a glass with a composition corresponding to 90 mol % CaMgSi{sub 2}O{sub 6}-10 mol % NaFeSi{sub 2}O{sub 6}. The investigated glass composition crystallized superficially immediately after casting of the melt and needs a high cooling rate (rapid quenching) in order to produce an amorphous glass. Differential thermal analysis and hot-stage microscopy were employed to investigate the glass forming ability, sintering behavior, relative nucleation rate, and crystallization behavior of the glass composition. The crystalline phase assemblage in the glass-ceramics was studied under nonisothermal heating conditions in the temperature range of 850-950more » deg. C in both air and N{sub 2} atmosphere. X-ray diffraction studies adjoined with the Rietveld-reference intensity ratio method were employed to quantify the amount of crystalline phases, while electron microscopy was used to shed some light on the microstructure of the resultant glass-ceramics. Well sintered glass-ceramics with diopside as the primary crystalline phase were obtained where the amount of diopside varied with the heating conditions.« less

Thermal, mechanical, optical and dielectric properties of piperazinium hydrogen phosphite monohydrate NLO single crystal

NASA Astrophysics Data System (ADS)

Rajkumar, R.; Praveen Kumar, P.

2018-05-01

Optical transparent crystal of piperazinium hydrogen phosphite monohydrate (PHPM) was grown by slow evaporation method. The grown crystal was characterized by single crystal X-ray diffraction analysis and the crystal belongs to monoclinic system. The functional groups present in PHPM crystal were confirmed by FTIR analysis. UV-Visible spectrum shows that the PHPM crystal is transparent in the visible region. The mechanical behavior of PHPM crystal was characterized by Vickers hardness test. Thermal stability of PHPM crystal was analyzed by thermogravimetric analysis. Dielectric studies were also carried out for the grown crystal. The third-order nonlinear parameters such as nonlinear refractive index and nonlinear absorption coefficient have been calculated using Z scan technique.

Refinement of the crystal structures of biomimetic weddellites produced by microscopic fungus Aspergillus niger

NASA Astrophysics Data System (ADS)

Rusakov, A. V.; Frank-Kamenetskaya, O. V.; Gurzhiy, V. V.; Zelenskaya, M. S.; Izatulina, A. R.; Sazanova, K. V.

2014-05-01

The single-crystal structures of four biomimetic weddellites CaC2O4 · (2 + x)H2O with different contents of zeolitic water ( x = 0.10-0.24 formula units) produced by the microscopic fungus Aspergillus niger were refined from X-ray diffraction data ( R = 0.029-0.038). The effect of zeolitic water content on the structural stability of weddellite was analyzed. The parameter a was shown to increase with increasing x due to the increase in the distance between water molecules along this direction. The water content and structural parameters of the synthesized weddellites are similar to those of weddellites from biofilms and kidney stones.

Enzymatically Controlled Vacancies in Nanoparticle Crystals

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

Barnaby, Stacey N.; Ross, Michael B.; Thaner, Ryan V.

In atomic systems, the mixing of metals results in distinct phase behavior that depends on the identity and bonding characteristics of the atoms. In nanoscale systems, the use of oligonucleotides as programmable “bonds” that link nanoparticle “atoms” into superlattices allows for the decoupling of atom identity and bonding. While much research in atomic systems is dedicated to understanding different phase behavior of mixed metals, it is not well understood on the nanoscale how changes in the nanoscale “bond” affect the phase behavior of nanoparticle crystals. In this work, the identity of the atom is kept the same but the chemicalmore » nature of the bond is altered, which is not possible in atomic systems, through the use of DNA and RNA bonding elements. These building blocks assemble into single crystal nanoparticle superlattices with mixed DNA and RNA bonding elements throughout. The nanoparticle crystals can be dynamically changed through the selective and enzymatic hydrolysis of the RNA bonding elements, resulting in superlattices that retain their crystalline structure and habit, while incorporating up to 35% random vacancies generated from the nanoparticles removed. Therefore, the bonding elements of nanoparticle crystals can be enzymatically and selectively addressed without affecting the nature of the atom.« less

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.

Adsorption behavior of acetone solvent at the HMX crystal faces: A molecular dynamics study.

PubMed

Liu, Yingzhe; Yu, Tao; Lai, Weipeng; Ma, Yiding; Kang, Ying; Ge, Zhongxue

2017-06-01

Molecular dynamics simulations have been performed to understand the adsorption behavior of acetone (AC) solvent at the three surfaces of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctan (HMX) crystal, i.e. (011), (110), and (020) faces. The simulation results show that the structural features and electrostatic potentials of crystal faces are determined by the HMX molecular packing, inducing distinct mass density distribution, dipole orientation, and diffusion of solvent molecules in the interfacial regions. The solvent adsorption is mainly governed by the van der Waals forces, and the crystal-solvent interaction energies among three systems are ranked as (020)≈(110)>(011). The adsorption sites for solvent incorporation at the crystal surface were found and visualized with the aid of occupancy analysis. A uniform arrangement of adsorption sites is observed at the rough (020) surface as a result of ordered adsorption motif. Copyright © 2017 Elsevier Inc. All rights reserved.

Geochemistry, thermometry and isotope ratios on the same zircon crystals: the tandem use of quadrupole LA-ICPMS and CA-TIMS

NASA Astrophysics Data System (ADS)

Olin, P. H.; Schmitz, M. D.; Crowley, J. L.

2011-12-01

Current trends in igneous petrology include the extraction of diverse geochemical information from smaller sample targets by ever more efficient and cost effective means. Igneous zircons are repositories of several types of petrogenetic information, such as magmatic crystallization ages obtained using U-Pb geochronology, magmatic temperatures using Ti-in-zircon geothermometry, and magmatic differentiation and/or mixing trends using trace element contents. Here we demonstrate a tandem quadrupole LA-ICPMS and CA-TIMS approach on single zircon crystals and within domains in single crystals, which extracts all of these data from a single laser spot analysis and then guides the acquisition of CA-TIMS ages at precisions relevant to magmatic histories. We present data from zircon-bearing intrusive and extrusive rocks spanning the compositional spectrum, and highlight results from silicic volcanic rocks with different affinities. The utility of our approach is illustrated in zircons from the Temora diorite, a commonly used standard material which we analysed using 25-μm ablation spots placed on dozens of grains which had been previously annealed and chemically abraded prior to mounting in epoxy. Our LA-ICPMS results illustrate a 3- to 5-fold variation in trace element concentrations and trace element ratios over >150 degrees of cooling as estimated from Ti-in-zircon thermometry. Some geochemical parameters (e.g., Nb/Ta variations and Eu anomalies) are consistent with crystal fractionation during progressive crystallization, while others are bimodal (e.g., Hf and U contents), suggesting the mixing of crystal/magma batches prior to final solidification. LA-ICPMS U-Pb spot ages reproduce the accepted CA-TIMS age within 2% precision and accuracy, while our CA-TIMS results on the same grains constrain the development of the observed geochemical variability to within 100 ka. Other zircon standard materials to be presented include Plesovich syenite, FC1 gabbro, and R33 diorite. Analyses of zircons from selected western Snake River Plain silicic volcanic units further demonstrate the capability of our approach. These units are targeted with the overarching goal of better understanding magmatism in the region and to identify geochemical fingerprints to better distinguish among and to correlate between units. Several rhyolites distributed along the northern margin of the plain have LA-ICPMS ages of ca. 11 Ma, within error of each other and their CA-TIMS ages, and reveal differences in temperatures of crystallization and trace element contents and ratios. Individual units have crystallization temperatures that span 100 degrees or more, and show correlations with whole-rock major and trace element contents and ratios. In many cases, zircon geochemical parameters such as REE and Y contents, and Nb/Ta and Th/U ratios allow units proximal to each other to be distinguished from one another while also providing fingerprints to correlate to distal units on the south side of the plain or elsewhere in the province.

Crystal growth and magneto-transport behavior of PdS1-δ

NASA Astrophysics Data System (ADS)

Cao, Lin; Lv, Yang-Yang; Chen, Si-Si; Li, Xiao; Zhou, Jian; Yao, Shu-Hua; Chen, Y. B.; Lu, Minghui; Chen, Yan-Feng

2018-04-01

PdS is theoretically proposed to novel topological material with eight-band fermions. Here, PdS1-δ crystals were successfully grown from KI as solvent by modified flux method. The single crystalline quality and compositional homogeneity of grown PdS1-δ are characterized by X-ray diffraction and energy dispersion spectroscopy. Temperature dependent electrical transport property of PdS1-δ demonstrates a semiconductor-like behavior. Analysis of temperature-dependent resistance indicates that there is variable-range-hopping behavior at low temperature. The clear negative MR of PdS1-δ single crystals is measured at the low temperature (<30 K), which may be ascribed to the interaction between conducting carriers and localized moments. however, the magneto-transport results have not shown the clues of topological feature of PdS.

Non-destructive thermo-mechanical behavior assessment of glass-ceramics for dental applications

NASA Astrophysics Data System (ADS)

Kordatos, E. Z.; Abdulkadhim, Z.; Feteira, A. M.

2017-05-01

Every year millions of people seek dental treatment to either repair damaged, unaesthetic and dysfunctional teeth or replace missing natural teeth. Several dental materials have been developed to meet the stringent requirements in terms of mechanical properties, aesthetics and chemical durability in the oral environment. Glass-ceramics exhibit a suitable combination of these properties for dental restorations. This research is focused on the assessment of the thermomechanical behavior of bio-ceramics and particularly lithium aluminosilicate glass-ceramics (LAS glass-ceramics). Specifically, methodologies based on Infrared Thermography (IRT) have been applied in order the structure - property relationship to be evaluated. Non-crystallized, partially crystallized and fully crystallized glass-ceramic samples have been non-destructively assessed in order their thermo-mechanical behavior to be associated with their micro-structural features.

Electrical and magnetic properties of La0.67Ba0.33Mn1- x (Me) x O3 perovskite manganites: case of manganese substituted by trivalent (Me = Cr) and tetravalent (Me = Ti) elements

NASA Astrophysics Data System (ADS)

Oumezzine, Marwène; Peña, Octavio; Kallel, Sami; Kallel, Nabil; Guizouarn, Thierry; Gouttefangeas, Francis; Oumezzine, Mohamed

2014-03-01

The effects of non-magnetic Ti4+ substitution on the structural, electrical and magnetic properties of La0.67Ba0.33Mn1- x Ti x O3 (0≤ x≤0.1) are investigated and compared to those existing in La0.67Ba0.33Mn1- x Cr x O3 (magnetic Cr3+). The structural refinement by the Rietveld method revealed that Ti-doped samples crystallize in the cubic lattice with space group , while samples with Cr crystallize in the hexagonal setting of the rhombohedral space group for identical contents of dopant. The most relevant structural features are an increase of the lattice parameters, of the cell volume and of the inter-ionic distances with increasing Ti doping level. Both series of samples show a decrease of the paramagnetic-ferromagnetic transition temperature when the amount of chromium or titanium increases. Transport measurements show that when increasing the metal doping, the resistivity increases whereas the metallic behavior of the parent compound La0.67Ba0.33MnO3 is destroyed. For a substitution higher than 5 at.% of Ti and 10 at.% of Cr, the samples exhibit a semiconducting behavior in the whole range of temperature, for which the electronic transport can be explained by variable range hopping and/or small polaron hopping models.

Identification of Zn-vacancy-hydrogen complexes in ZnO single crystals: A challenge to positron annihilation spectroscopy

NASA Astrophysics Data System (ADS)

Brauer, G.; Anwand, W.; Grambole, D.; Grenzer, J.; Skorupa, W.; Čížek, J.; Kuriplach, J.; Procházka, I.; Ling, C. C.; So, C. K.; Schulz, D.; Klimm, D.

2009-03-01

A systematic study of various, nominally undoped ZnO single crystals, either hydrothermally grown (HTG) or melt grown (MG), has been performed. The crystal quality has been assessed by x-ray diffraction, and a comprehensive estimation of the detailed impurity and hydrogen contents by inductively coupled plasma mass spectrometry and nuclear reaction analysis, respectively, has been made also. High precision positron lifetime experiments show that a single positron lifetime is observed in all crystals investigated, which clusters at 180-182 ps and 165-167 ps for HTG and MG crystals, respectively. Furthermore, hydrogen is detected in all crystals in a bound state with a high concentration (at least 0.3at.% ), whereas the concentrations of other impurities are very small. From ab initio calculations it is suggested that the existence of Zn-vacancy-hydrogen complexes is the most natural explanation for the given experimental facts at present. Furthermore, the distribution of H at a metal/ZnO interface of a MG crystal, and the H content of a HTG crystal upon annealing and time afterward has been monitored, as this is most probably related to the properties of electrical contacts made at ZnO and the instability in p -type conductivity observed at ZnO nanorods in literature. All experimental findings and presented theoretical considerations support the conclusion that various types of Zn-vacancy-hydrogen complexes exist in ZnO and need to be taken into account in future studies, especially for HTG materials.

A pilot trial of integrated behavioral activation and sexual risk reduction counseling for HIV-uninfected men who have sex with men abusing crystal methamphetamine.

PubMed

Mimiaga, Matthew J; Reisner, Sari L; Pantalone, David W; O'Cleirigh, Conall; Mayer, Kenneth H; Safren, Steven A

2012-11-01

Crystal methamphetamine use is a major driver behind high-risk sexual behavior among men who have sex with men (MSM). Prior work suggests a cycle of continued crystal methamphetamine use and high-risk sex due to loss of the ability to enjoy other activities, which appears to be a side effect of this drug. Behavioral activation (BA) is a treatment for depression that involves learning to reengage in life's activities. We evaluated a novel intervention for crystal methamphetamine abuse and high-risk sex in MSM, incorporating 10 sessions of BA with integrated HIV risk reduction counseling (RR). Forty-four subjects were screened, of whom 21 met initial entry criteria. A total of 19 participants enrolled; 16 completed an open-phase study of the intervention. Behavioral assessments were conducted at baseline, 3 months postbaseline, and 6 months postbaseline. Linear mixed effects regression models were fit to assess change over time. Mean unprotected anal intercourse (UAI) episodes decreased significantly from baseline to acute postintervention (β=-4.86; 95% confidence interval [CI]=-7.48, -2.24; p=0.0015) and from baseline to 6 months postbaseline (β=-5.07; 95% CI=-7.85, -2.29; p=0.0017; test of fixed effects χ(2)=16.59; df=2,13; p=0.0002). On average, there was a significant decrease over time in the number of crystal methamphetamine episodes in the past 3 months (χ(2)=22.43; df=2,15; p<0.0001), and the number of days of crystal methamphetamine use in the past 30 days (χ(2)=9.21; df=2,15; p=0.010). Statistically significant reductions in depressive symptoms and poly-substance use were also maintained. Adding behavioral activation to risk reduction counseling for MSM with problematic crystal methamphetamine use may augment the potency of a risk reduction intervention for this population. Due to the small sample size and time intensive intervention, future testing in a randomized design is necessary to determine efficacy, with subsequent effectiveness testing.

A Pilot Trial of Integrated Behavioral Activation and Sexual Risk Reduction Counseling for HIV-Uninfected Men Who Have Sex with Men Abusing Crystal Methamphetamine

PubMed Central

Reisner, Sari L.; Pantalone, David W.; O'Cleirigh, Conall; Mayer, Kenneth H.; Safren, Steven A.

2012-01-01

Abstract Crystal methamphetamine use is a major driver behind high-risk sexual behavior among men who have sex with men (MSM). Prior work suggests a cycle of continued crystal methamphetamine use and high-risk sex due to loss of the ability to enjoy other activities, which appears to be a side effect of this drug. Behavioral activation (BA) is a treatment for depression that involves learning to reengage in life's activities. We evaluated a novel intervention for crystal methamphetamine abuse and high-risk sex in MSM, incorporating 10 sessions of BA with integrated HIV risk reduction counseling (RR). Forty-four subjects were screened, of whom 21 met initial entry criteria. A total of 19 participants enrolled; 16 completed an open-phase study of the intervention. Behavioral assessments were conducted at baseline, 3 months postbaseline, and 6 months postbaseline. Linear mixed effects regression models were fit to assess change over time. Mean unprotected anal intercourse (UAI) episodes decreased significantly from baseline to acute postintervention (β=−4.86; 95% confidence interval [CI]=−7.48, −2.24; p=0.0015) and from baseline to 6 months postbaseline (β=−5.07; 95% CI=−7.85, −2.29; p=0.0017; test of fixed effects χ2=16.59; df=2,13; p=0.0002). On average, there was a significant decrease over time in the number of crystal methamphetamine episodes in the past 3 months (χ2=22.43; df=2,15; p<0.0001), and the number of days of crystal methamphetamine use in the past 30 days (χ2=9.21; df=2,15; p=0.010). Statistically significant reductions in depressive symptoms and poly-substance use were also maintained. Adding behavioral activation to risk reduction counseling for MSM with problematic crystal methamphetamine use may augment the potency of a risk reduction intervention for this population. Due to the small sample size and time intensive intervention, future testing in a randomized design is necessary to determine efficacy, with subsequent effectiveness testing. PMID:23030605

Relationship between the line of density anomaly and the lines of melting, crystallization, cavitation, and liquid spinodal in coarse-grained water models

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

Lu, Jibao; Molinero, Valeria, E-mail: Valeria.Molinero@utah.edu; Chakravarty, Charusita

2016-06-21

Liquid water has several anomalous properties, including a non-monotonous dependence of density with temperature and an increase of thermodynamic response functions upon supercooling. Four thermodynamic scenarios have been proposed to explain the anomalies of water, but it is not yet possible to decide between them from experiments because of the crystallization and cavitation of metastable liquid water. Molecular simulations provide a versatile tool to study the anomalies and phase behavior of water, assess their agreement with the phenomenology of water under conditions accessible to experiments, and provide insight into the behavior of water in regions that are challenging to probemore » in the laboratory. Here we investigate the behavior of the computationally efficient monatomic water models mW and mTIP4P/2005{sup REM}, with the aim of unraveling the relationships between the lines of density extrema in the p-T plane, and the lines of melting, liquid-vapor spinodal and non-equilibrium crystallization and cavitation. We focus particularly on the conditions for which the line of density maxima (LDM) in the liquid emerges and disappears as the pressure is increased. We find that these models present a retracing LDM, same as previously found for atomistic water models and models of other tetrahedral liquids. The low-pressure end of the LDM occurs near the pressure of maximum of the melting line, a feature that seems to be general to models that produce tetrahedrally coordinated crystals. We find that the mW water model qualitatively reproduces several key properties of real water: (i) the LDM is terminated by cavitation at low pressures and by crystallization of ice I{sub h} at high pressures, (ii) the LDM meets the crystallization line close to the crossover in crystallization from ice I{sub h} to a non-tetrahedral four-coordinated crystal, and (iii) the density of the liquid at the crossover in crystallization from ice I{sub h} to a four-coordinated non-tetrahedral crystal coincides with the locus of maximum in diffusivity as a function of pressure. The similarities in equilibrium and non-equilibrium phase behavior between the mW model and real water provide support to the quest to find a compressibility extremum, and determine whether it presents a maximum, in the doubly metastable region.« less

Relationship between the line of density anomaly and the lines of melting, crystallization, cavitation, and liquid spinodal in coarse-grained water models.

PubMed

Lu, Jibao; Chakravarty, Charusita; Molinero, Valeria

2016-06-21

Liquid water has several anomalous properties, including a non-monotonous dependence of density with temperature and an increase of thermodynamic response functions upon supercooling. Four thermodynamic scenarios have been proposed to explain the anomalies of water, but it is not yet possible to decide between them from experiments because of the crystallization and cavitation of metastable liquid water. Molecular simulations provide a versatile tool to study the anomalies and phase behavior of water, assess their agreement with the phenomenology of water under conditions accessible to experiments, and provide insight into the behavior of water in regions that are challenging to probe in the laboratory. Here we investigate the behavior of the computationally efficient monatomic water models mW and mTIP4P/2005(REM), with the aim of unraveling the relationships between the lines of density extrema in the p-T plane, and the lines of melting, liquid-vapor spinodal and non-equilibrium crystallization and cavitation. We focus particularly on the conditions for which the line of density maxima (LDM) in the liquid emerges and disappears as the pressure is increased. We find that these models present a retracing LDM, same as previously found for atomistic water models and models of other tetrahedral liquids. The low-pressure end of the LDM occurs near the pressure of maximum of the melting line, a feature that seems to be general to models that produce tetrahedrally coordinated crystals. We find that the mW water model qualitatively reproduces several key properties of real water: (i) the LDM is terminated by cavitation at low pressures and by crystallization of ice Ih at high pressures, (ii) the LDM meets the crystallization line close to the crossover in crystallization from ice Ih to a non-tetrahedral four-coordinated crystal, and (iii) the density of the liquid at the crossover in crystallization from ice Ih to a four-coordinated non-tetrahedral crystal coincides with the locus of maximum in diffusivity as a function of pressure. The similarities in equilibrium and non-equilibrium phase behavior between the mW model and real water provide support to the quest to find a compressibility extremum, and determine whether it presents a maximum, in the doubly metastable region.

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

A thermodynamic framework for the study of crystallization in polymers

NASA Astrophysics Data System (ADS)

Rao, I. J.; Rajagopal, K. R.

In this paper, we present a new thermodynamic framework within the context of continuum mechanics, to predict the behavior of crystallizing polymers. The constitutive models that are developed within this thermodynamic setting are able to describe the main features of the crystallization process. The model is capable of capturing the transition from a fluid like behavior to a solid like behavior in a rational manner without appealing to any adhoc transition criterion. The anisotropy of the crystalline phase is built into the model and the specific anisotropy of the crystalline phase depends on the deformation in the melt. These features are incorporated into a recent framework that associates different natural configurations and material symmetries with distinct microstructural features within the body that arise during the process under consideration. Specific models are generated by choosing particular forms for the internal energy, entropy and the rate of dissipation. Equations governing the evolution of the natural configurations and the rate of crystallization are obtained by maximizing the rate of dissipation, subject to appropriate constraints. The initiation criterion, marking the onset of crystallization, arises naturally in this setting in terms of the thermodynamic functions. The model generated within such a framework is used to simulate bi-axial extension of a polymer film that is undergoing crystallization. The predictions of the theory that has been proposed are consistent with the experimental results (see [28] and [7]).

Investigation the influences of B2O3 and R2O on the structure and crystallization behaviors of CaO-Al2O3 based F-free mold flux

NASA Astrophysics Data System (ADS)

Li, Jiangling; Kong, Bowen; Gao, Xiangyu; Liu, Qingcai; Shu, Qifeng; Chou, Kuochih

2018-04-01

The influences of B2O3 and R2O on the structure and crystallization of CaO-Al2O3 based F-free mold flux were investigated by Raman Spectroscopy and Differential Scanning Calorimetry Technique, respectively, for developing a new type of F-free mold flux. The results of structural investigations showed that B3+ is mainly in the form of [BO3]. And [BO3] appears to form BIII-O-Al linkage which will produce a positive effect on forming [AlO4] network. The number of bridging oxygen and the degree of polymerization of [AlO4] network structure for CaO-Al2O3 system were also increased with the increasing of B2O3. On the contrary, with the addition of R2O into CaO-Al2O3-B2O3 system, the number of bridging oxygen and the degree of polymerization of [AlO4] network were decreased. DSC results showed that the crystallization process became more sluggish with the increase of B2O3, which indicated that the crystallization ability was weakened. While the quenched mold fluxes crystallized more rapidly when introducing R2O. In other word, the crystallization rates of CaO-Al2O3 based slags were accelerated by the introduction of R2O. The liquidus temperature and crystallization temperature were decreased with the increasing amount of B2O3 or by addition of R2O into CaO-Al2O3 system. Only one kind of crystal was precipitated in 8% B2O3 and %R2O-containing samples, which was CaAl2O4 identified by SEM-EDS. When the content of B2O3 increased from 8% to 16%, Ca3B2O6 is clearly observed, demonstrating that the crystallization ability of Ca3B2O6 is enhanced by the increasing concentration of B2O3 in mold flux. The Ca/Al ratio of the generated calcium aluminate has been altered from 1:2 to 1:4 with the increasing of B2O3. The size of CaAl2O4 crystal is gradually increased with the addition of R2O. The crystallization ability of CaAl2O4 is promoted by R2O.

Supramolecular Polymer Network-Mediated Self-Assembly of Semicrystalline Polymers with Excellent Crystalline Performance.

PubMed

Cheng, Chih-Chia; Chuang, Wei-Tsung; Lee, Duu-Jong; Xin, Zhong; Chiu, Chih-Wei

2017-03-01

A novel application of supramolecular interactions within semicrystalline polymers, capable of self-assembling into supramolecular polymer networks via self-complementary multiple hydrogen-bonded complexes, is demonstrated for efficient construction of highly controlled self-organizing hierarchical structures to offer a direct, efficient nucleation pathway resulting in superior crystallization performance. Herein, a novel functionalized poly(ε-caprolactone) containing self-complementary sextuple hydrogen-bonded uracil-diamidopyridine (U-DPy) moieties is successfully developed and demonstrated excellent thermal and viscoelastic properties as well as high dynamic structural stability in the bulk state due to physical cross-linking created by reversible sextuple hydrogen bonding between U-DPy units. Due to the ability to vary the extent of the reversible network by tuning the U-DPy content, this newly developed material can be readily adjusted to obtain the desired crystalline products with specific characteristics. Importantly, incorporating only 0.1% U-DPy resulted in a polymer with a high crystallization rate constant, short crystallization half-time, and much more rapid crystallization kinetics than pristine PCL, indicating a low content of U-DPy moieties provides highly efficient nucleation sites that manipulate the nucleation and growth processes of polymer crystals to promote crystallization and chain alignment in bulk. This new system is suggested as a potential new route to substantially improve the performance of polymer crystallization. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nonlinear modeling of crystal system transition of black phosphorus using continuum-DFT model.

PubMed

Setoodeh, A R; Farahmand, H

2018-01-24

In this paper, the nonlinear behavior of black phosphorus crystals is investigated in tandem with dispersion-corrected density functional theory (DFT-D) analysis under uniaxial loadings. From the identified anisotropic behavior of black phosphorus due to its morphological anisotropy, a hyperelastic anisotropic (HA) model named continuum-DFT is established to predict the nonlinear behavior of the material. In this respect, uniaxial Cauchy stresses are employed on both the DFT-D and HA models along the zig-zag and armchair directions. Simultaneously, the transition of the crystal system is recognized at about 4.5 GPa of the applied uniaxial tensile stress along the zig-zag direction on the DFT-D simulation in the nonlinear region. In order to develop the nonlinear continuum model, unknown constants are surveyed with the optimized least square technique. In this regard, the continuum model is obtained to reproduce the Cauchy stress-stretch and density of strain-stretch results of the DFT-D simulation. Consequently, the modified HA model is introduced to characterize the nonlinear behavior of black phosphorus along the zig-zag direction. More importantly, the specific transition of the crystal system is successfully predicted in the new modified continuum-DFT model. The results reveal that the multiscale continuum-DFT model is well defined to replicate the nonlinear behavior of black phosphorus along the zig-zag and armchair directions.

A dislocation density based micromechanical constitutive model for Sn-Ag-Cu solder alloys

NASA Astrophysics Data System (ADS)

Liu, Lu; Yao, Yao; Zeng, Tao; Keer, Leon M.

2017-10-01

Based on the dislocation density hardening law, a micromechanical model considering the effects of precipitates is developed for Sn-Ag-Cu solder alloys. According to the microstructure of the Sn-3.0Ag-0.5Cu thin films, intermetallic compounds (IMCs) are assumed as sphere particles embedded in the polycrystalline β-Sn matrix. The mechanical behavior of polycrystalline β-Sn matrix is determined by the elastic-plastic self-consistent method. The existence of IMCs not only impedes the motion of dislocations but also increases the overall stiffness. Thus, a dislocation density based hardening law considering non-shearable precipitates is adopted locally for single β-Sn crystal, and the Mori-Tanaka scheme is applied to describe the overall viscoplastic behavior of solder alloys. The proposed model is incorporated into finite element analysis and the corresponding numerical implementation method is presented. The model can describe the mechanical behavior of Sn-3.0Ag-0.5Cu and Sn-1.0Ag-0.5Cu alloys under high strain rates at a wide range of temperatures. Furthermore, the overall Young’s modulus changes due to different contents of IMCs is predicted and compared with experimental data. Results show that the proposed model can describe both elastic and inelastic behavior of solder alloys with reasonable accuracy.

Crystallization and initial X-ray diffraction studies of scaffolding protein (gp7) of bacteriophage ϕ29

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

Badasso, Mohammed O., E-mail: badas001@umn.edu; Anderson, Dwight L.; Department of Oral Science, University of Minnesota, Minneapolis, MN 55455

2005-04-01

ϕ29 bacteriophage scaffolding protein (gp7) has been overproduced in E. coli, purified, crystallized and characterized by X-ray diffraction. Two distinct crystal forms were obtained and a diffraction data set was collected to 1.8 Å resolution. The Bacillus subtilis bacteriophage ϕ29 scaffolding protein (gp7) has been crystallized by the hanging-drop vapour-diffusion method at 293 K. Two new distinct crystal forms that both differed from a previously crystallized and solved scaffolding protein were grown under the same conditions. Form I belongs to the primitive tetragonal space group P4{sub 1}2{sub 1}2, with unit-cell parameters a = b = 77.13, c = 37.12 Å.more » Form II crystals exhibit an orthorhombic crystal form, with space group C222 and unit-cell parameters a = 107.50, b = 107. 80, c = 37.34 Å. Complete data sets have been collected to 1.78 and 1.80 Å for forms I and II, respectively, at 100 K using Cu Kα X-rays from a rotating-anode generator. Calculation of a V{sub M} value of 2.46 Å{sup 3} Da{sup −1} for form I suggests the presence of one molecule in the asymmetric unit, corresponding to a solvent content of 50.90%, whereas form II has a V{sub M} of 4.80 Å{sup 3} Da{sup −1} with a solvent content of 48.76% and two molecules in the asymmetric unit. The structures of both crystal forms are being determined by the molecular-replacement method using the coordinates of the published crystal structure of gp7.« less

Validation of a Compact Isokinetic Total Water Content Probe for Wind Tunnel Characterization at NASA Glenn Icing Research Tunnel and at NRC Ice Crystal Tunnel

NASA Technical Reports Server (NTRS)

Davison, Craig R.; Landreville, Charles; Ratvasky, Thomas P.

2017-01-01

A new compact isokinetic probe to measure total water content in a wind tunnel environment has been developed. The probe has been previously tested under altitude conditions. This paper presents a comprehensive validation of the probe under a range of liquid water conditions at sea level in the NASA Glenn Icing Research Tunnel and with ice crystals at sea level at the NRC wind tunnel. The compact isokinetic probe is compared to tunnel calibrations and other probes.

Managing the spatial properties and photon correlations in squeezed non-classical twisted light

NASA Astrophysics Data System (ADS)

Zakharov, R. V.; Tikhonova, O. V.

2018-05-01

Spatial photon correlations and mode content of the squeezed vacuum light generated in a system of two separated nonlinear crystals is investigated. The contribution of both the polar and azimuthal modes with non-zero orbital angular momentum is analyzed. The control and engineering of the spatial properties and degree of entanglement of the non-classical squeezed light by changing the distance between crystals and pump parameters is demonstrated. Methods for amplification of certain spatial modes and managing the output mode content and intensity profile of quantum twisted light are suggested.

Loss of halogens from crystallized and glassy silicic volcanic rocks

USGS Publications Warehouse

Noble, D.C.; Smith, V.C.; Peck, L.C.

1967-01-01

One hundred and sixty-four F and Cl analyses of silicic welded tuffs and lavas and glass separates are presented. Comparison of the F and Cl contents of crystallized rocks with those of nonhydrated glass and hydrated glassy rocks from the same rock units shows that most of the halogens originally present were lost on crystallization. An average of about half of the F and four-fifths of the Cl originally present was lost. Analyses of hydrated natural glasses and of glassy rocks indicate that in some cases significant amounts of halogens may be removed from or added to hydrated glass through prolonged contact with ground water. The data show that the original halogen contents of the groundmass of a silicic volcanic rock can be reliably determined only from nonhydrated glass. ?? 1967.

Polarization and switching properties of holographic polymer-dispersed liquid-crystal gratings. I. Theoretical model

NASA Astrophysics Data System (ADS)

Sutherland, Richard L.

2002-12-01

Polarization properties and electro-optical switching behavior of holographic polymer-dispersed liquid-crystal (HPDLC) reflection and transmission gratings are studied. A theoretical model is developed that combines anisotropic coupled-wave theory with an elongated liquid-crystal-droplet switching model and includes the effects of a statistical orientational distribution of droplet-symmetry axes. Angle- and polarization-dependent switching behaviors of HPDLC gratings are elucidated, and the effects on dynamic range are described. A new type of electro-optical switching not seen in ordinary polymer-dispersed liquid crystals, to the best of the author's knowledge, is presented and given a physical interpretation. The model provides valuable insight to the physics of these gratings and can be applied to the design of HPDLC holographic optical elements.

Thermoelectric Behavior of PbSe Single Crystals

DOE PAGES

Kogo, Gilbert; Pradhan, Aswini K.; Roy, Utpal N.

2016-12-05

The electrical conductivity and Seebeck coefficient of PbSe single crystals grown by the Bridgman technique display metallic behavior. The Seebeck coefficient increases linearly with increasing temperature and showed positive Seebeck values, typically valid for a p-type PbSe crystal. The electronic thermal conductivity decreases with increase in temperature. The power factor increases gradually with temperature until the maximum value of 6.51 × 10 -3 W/mK2 at 260 K, other values are 5.95 × 10 -3 W/mK 2 at 300 K, and 5.40 × 10 -3 W/mK 2 at 320 K. Our results demonstrate that as-grown PbSe crystal is generically p-type duemore » to excess in Pb and can be a potential candidate for thermoelectric power generation.« less

Gradient Plasticity Model and its Implementation into MARMOT

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

Barker, Erin I.; Li, Dongsheng; Zbib, Hussein M.

2013-08-01

The influence of strain gradient on deformation behavior of nuclear structural materials, such as boby centered cubic (bcc) iron alloys has been investigated. We have developed and implemented a dislocation based strain gradient crystal plasticity material model. A mesoscale crystal plasticity model for inelastic deformation of metallic material, bcc steel, has been developed and implemented numerically. Continuum Dislocation Dynamics (CDD) with a novel constitutive law based on dislocation density evolution mechanisms was developed to investigate the deformation behaviors of single crystals, as well as polycrystalline materials by coupling CDD and crystal plasticity (CP). The dislocation density evolution law in thismore » model is mechanism-based, with parameters measured from experiments or simulated with lower-length scale models, not an empirical law with parameters back-fitted from the flow curves.« less

Enhanced magnetic hysteresis in Ni-Mn-Ga single crystal and its influence on magnetic shape memory effect

NASA Astrophysics Data System (ADS)

Heczko, O.; Drahokoupil, J.; Straka, L.

2015-05-01

Enhanced magnetic hysteresis due to boron doping in combination with magnetic shape memory effect in Ni-Mn-Ga single crystal results in new interesting functionality of magnetic shape memory (MSM) alloys such as mechanical demagnetization. In Ni50.0Mn28.5Ga21.5 single crystal, the boron doping increased magnetic coercivity from few Oe to 270 Oe while not affecting the transformation behavior and 10 M martensite structure. However, the magnetic field needed for MSM effect also increased in doped sample. The magnetic behavior is compared to undoped single crystal of similar composition. The evidence from the X-ray diffraction, magnetic domain structure, magnetization loops, and temperature evolution of the magnetic coercivity points out that the enhanced hysteresis is caused by stress-induced anisotropy.

Low-resolution structure of Drosophila translin

PubMed Central

Kumar, Vinay; Gupta, Gagan D.

2012-01-01

Crystals of native Drosophila melanogaster translin diffracted to 7 Å resolution. Reductive methylation of the protein improved crystal quality. The native and methylated proteins showed similar profiles in size-exclusion chromatography analyses but the methylated protein displayed reduced DNA-binding activity. Crystals of the methylated protein diffracted to 4.2 Å resolution at BM14 of the ESRF synchrotron. Crystals with 49% solvent content belonged to monoclinic space group P21 with eight protomers in the asymmetric unit. Only 2% of low-resolution structures with similar low percentage solvent content were found in the PDB. The crystal structure, solved by molecular replacement method, refined to Rwork (Rfree) of 0.24 (0.29) with excellent stereochemistry. The crystal structure clearly shows that drosophila protein exists as an octamer, and not as a decamer as expected from gel-filtration elution profiles. The similar octameric quaternary fold in translin orthologs and in translin–TRAX complexes suggests an up-down dimer as the basic structural subunit of translin-like proteins. The drosophila oligomer displays asymmetric assembly and increased radius of gyration that accounts for the observed differences between the elution profiles of human and drosophila proteins on gel-filtration columns. This study demonstrates clearly that low-resolution X-ray structure can be useful in understanding complex biological oligomers. PMID:23650579

Nanostructured crystals of fluorite phases Sr1 - x R x F2 + x ( R = Y, La-Lu) and their ordering: Part III. A study of the refractive indices

NASA Astrophysics Data System (ADS)

Glushkova, T. M.; Karimov, D. N.; Krivandina, E. A.; Zhmurova, Z. I.; Sobolev, B. P.

2009-07-01

The refractive indices n of Sr1 - x R x F2 + x crystals ( R = Y, La-Lu; 0 ≤ x ≤ 0.5) have been measured at wavelengths of 0.436, 0.546, and 0.589 μm. It is established that n increases when there is an increase in the RF3 content x according to a weakly quadratic law for each R. For the isoconcentration series of Sr0.9 R 0.1F2.1 crystals, the change in n in the series of rare earth elements has a pronounced nonlinear character, which reflects the nonmonotonous change in the properties of compounds in the R series. It is shown that the method of molecular refraction additivity can be used to calculate n for Sr1 - x R x F2 + x crystals. By varying the RF3 content in them, one can obtain optical media with a gradually varied refractive index n in the range 1.44-1.55, thus filling the gap in the n values between high ones for RF3 crystals and low ones for crystals of alkaline earth fluorides MF2.

Phase determinations and crystal growth of Pb 2KNb 5O 15 (PKN)

NASA Astrophysics Data System (ADS)

Kramer, W. E.; Roland, G. W.

1982-07-01

Two problems must be addressed before good quality crystals of Pb 2KNb 5O 15 (PKN) can be grown: first, the compound does not melt congruently and therefore growth must be slow to avoid inclusions in the crystal; and second, cracking of crystals occurs during cooling due to anisotropic behavior of the thermal expansion coefficients at the Curie temperature. Extremely slow cooling in a uniform temperature gradient is necessary to get good quality, uncracked crystals.

Polymer stabilized liquid crystals: Topology-mediated electro-optical behavior and applications

NASA Astrophysics Data System (ADS)

Weng, Libo

There has been a wide range of liquid crystal polymer composites that vary in polymer concentration from as little as 3 wt.% (polymer stabilized liquid crystal) to as high as 60 wt.% (polymer dispersed liquid crystals). In this dissertation, an approach of surface polymerization based on a low reactive monomer concentration about 1 wt.% is studied in various liquid crystal operation modes. The first part of dissertation describes the development of a vertical alignment (VA) mode with surface polymer stabilization, and the effects of structure-performance relationship of reactive monomers (RMs) and polymerization conditions on the electro-optical behaviors of the liquid crystal device has been explored. The polymer topography plays an important role in modifying and enhancing the electro-optical performance of stabilized liquid crystal alignment. The enabling surface-pinned polymer stabilized vertical alignment (PSVA) approach has led to the development of high-performance and fast-switching displays with controllable pretilt angle, increase in surface anchoring energy, high optical contrast and fast response time. The second part of the dissertation explores a PSVA mode with in-plane switching (IPS) and its application for high-efficiency and fast-switching phase gratings. The diffraction patterns and the electro-optical behaviors including diffraction efficiency and response time are characterized. The diffraction grating mechanism and performance have been validated by computer simulation. Finally, the advantages of surface polymerization approach such as good optical contrast and fast response time have been applied to the fringe-field switching (FFS) system. The concentration of reactive monomer on the electro-optical behavior of the FFS cells is optimized. The outstanding electro-optical results and mechanism of increase in surface anchoring strength are corroborated by the director field simulation. The density and topology of nanoscale polymer protrusions are analyzed and confirmed by morphological study. The developed high-performance polymer-stabilized fringe-field-switching (PS-FFS) could open new types of device applications.

Mathematical model to analyze the dissolution behavior of metastable crystals or amorphous drug accompanied with a solid-liquid interface reaction.

PubMed

Hirai, Daiki; Iwao, Yasunori; Kimura, Shin-Ichiro; Noguchi, Shuji; Itai, Shigeru

2017-04-30

Metastable crystals and the amorphous state of poorly water-soluble drugs in solid dispersions (SDs), are subject to a solid-liquid interface reaction upon exposure to a solvent. The dissolution behavior during the solid-liquid interface reaction often shows that the concentration of drugs is supersaturated, with a high initial drug concentration compared with the solubility of stable crystals but finally approaching the latter solubility with time. However, a method for measuring the precipitation rate of stable crystals and/or the potential solubility of metastable crystals or amorphous drugs has not been established. In this study, a novel mathematical model that can represent the dissolution behavior of the solid-liquid interface reaction for metastable crystals or amorphous drug was developed and its validity was evaluated. The theory for this model was based on the Noyes-Whitney equation and assumes that the precipitation of stable crystals at the solid-liquid interface occurs through a first-order reaction. Moreover, two models were developed, one assuming that the surface area of the drug remains constant because of the presence of excess drug in the bulk and the other that the surface area changes in time-dependency because of agglomeration of the drug. SDs of Ibuprofen (IB)/polyvinylpyrrolidone (PVP) were prepared and their dissolution behaviors under non-sink conditions were fitted by the models to evaluate improvements in solubility. The model assuming time-dependent surface area showed good agreement with experimental values. Furthermore, by applying the model to the dissolution profile, parameters such as the precipitation rate and the potential solubility of the amorphous drug were successfully calculated. In addition, it was shown that the improvement in solubility with supersaturation was able to be evaluated quantitatively using this model. Therefore, this mathematical model would be a useful tool to quantitatively determine the supersaturation concentration of a metastable drug from solid dispersions. Copyright © 2017 Elsevier B.V. All rights reserved.

Determination of the moisture content in the fluoride oxide fluxes of electroslag remelting

NASA Astrophysics Data System (ADS)

Vdovin, K. N.; Feoktistov, N. A.; Pivovarova, K. G.; Deryabin, D. A.

2016-12-01

ANF-32 flux has been studied with regard to the moisture content both after storage and upon operation. A simple and reliable procedure for the determination of the moisture content in ESR fluxes is proposed, and recommendations are given on monitoring the moisture content in calcined fluxes. The main sources of crystallization water of hydration are hydrogen sources.

The Effect of Hydrogen Annealing and Sulfur Content on the Oxidation Resistance of PWA 1480

NASA Technical Reports Server (NTRS)

Smialek, James L.

1997-01-01

For many decades the dramatic effect of trace amounts of reactive elements on alumina and chromia scale adhesion has been recognized and widely studied. Although various theories have been used to account for such behavior, the connection between scale adhesion and sulfur segregation was initially reported by Smeggil et al. This study found strong surface segregation of sulfur from very low levels in the bulk which could then be curtailed by the addition of reactive elements. It was assumed that the reactive elements, which are strong sulfide formers, acted by getting sulfur in the bulk thus precluding sulfur segregation and weakening of the oxide-metal bond. Subsequent studies confirmed that adhesion could be produced by reducing the sulfur impurity level, without reactive elements. The understanding of this phenomenon has been applied to modern single crystal superalloys, where the addition of Y, although very effective, is problematic. Also problematic is definition of the level of sulfur that is acceptable and below which no further adhesion benefit is reached. Published works have indicated a broad transition defined by various materials and oxidation tests. The present study describes the oxidation behavior of one superalloy (PWA 1480) as a function of various sulfur contents produced by hydrogen annealing for various temperatures, times, and sample thicknesses. The purpose is to define more precisely a criterion for adhesion based on total sulfur reservoir and segregation potential.

Giant magnetoresistance (GMR) behavior of electrodeposited NiFe/Cu multilayers: Dependence of non-magnetic and magnetic layer thicknesses

NASA Astrophysics Data System (ADS)

Kuru, Hilal; Kockar, Hakan; Alper, Mursel

2017-12-01

Giant magnetoresistance (GMR) behavior in electrodeposited NiFe/Cu multilayers was investigated as a function of non-magnetic (Cu) and ferromagnetic (NiFe) layer thicknesses, respectively. Prior to the GMR analysis, structural and magnetic analyses of the multilayers were also studied. The elemental analysis of the multilayers indicated that the Cu and Ni content in the multilayers increase with increasing Cu and NiFe layer thickness, respectively. The structural studies by X-ray diffraction revealed that all multilayers have face centred cubic structure with preferred (1 1 0) crystal orientation as their substrates. The magnetic properties studied with the vibrating sample magnetometer showed that the magnetizations of the samples are significantly affected by the layer thicknesses. Saturation magnetisation, Ms increases from 45 to 225 emu/cm3 with increasing NiFe layer thickness. The increase in the Ni content of the multilayers with a small Fe content causes an increase in the Ms. And, the coercivities ranging from 2 to 24 Oe are between the soft and hard magnetic properties. Also, the magnetic easy axis of the multilayers was found to be in the film plane. Magnetoresistance measurements showed that all multilayers exhibited the GMR behavior. The GMR magnitude increases with increasing Cu layer thickness and reaches its maximum value of 10% at the Cu layer thickness of 1 nm, then it decreases. And similarly, the GMR magnitude increases and reaches highest value of pure GMR (10%) for the NiFe layer thickness of 3 nm, and beyond this point GMR decreases with increasing NiFe layer thickness. Some small component of the anisotropic magnetoresistance was also observed at thin Cu and thick NiFe layer thicknesses. It is seen that the highest GMR values up to 10% were obtained in electrodeposited NiFe/Cu multilayers up to now. The structural, magnetic and magnetoresistance properties of the NiFe/Cu were reported via the variations of the thicknesses of Cu and NiFe layers with stressing the role of layer thicknesses on the high GMR behavior.

Thermally induced crystallization kinetics of uncrosslinked and unfilled synthetic cis-1,4-polyisoprene rubber monitored by shear rheological tests

NASA Astrophysics Data System (ADS)

Yang, Wei; Hong, Daesun; Kim, Hyungsu; Kim, Byungsoo; Chang, Wenji V.

2016-11-01

This study demonstrates the unique capability of a shear rotational rheometer for studying the thermally induced crystallization (TIC) of uncrosslinked and unfilled cis-1,4-polyisoprene rubber (IR). At temperatures below -15°C, a crystallization phenomenon (TIC) occurred in a quasi-unstrained IR specimen. Such a distinguished phenomenon was determined from the steady and sharp changes of both tanδ and the modulus. The changing ratio of those parameters with time characterizes the crystallization rate, on which the effects of the compressive force magnitude, testing repeat, and temperature are studied. The crystallization rate was shown to depend less on the magnitude of normal force, but depended largely on the specimen's previous testing history. A specimen not fully recovered from the previous crystallized memory showed a faster rate than before. More cooling to -25°C increased the crystallization rate, but the slow crystallization helped increase the final crystallinity. The crystallization rate was further interpreted by the Avrami equation to propose the crystal structure, whose morphological feature was shown in agreement with the reported TEM and X-ray results. However, our study found a thermo-mechanically aged specimen showed a very different rheological behavior at the late stage of crystallization suggesting the crystalline metamorphosis. But this unexpected behavior turned out to be unrecoverable indicating a property failure due to material aging more plausibly. All these findings were successfully monitored by the rheometer. It is expected the well-organized rheometric measurements can sufficiently supplement some instrumental limitations of the traditional crystallization monitoring analyzers on soft materials.

Reinjury risk of nano-calcium oxalate monohydrate and calcium oxalate dihydrate crystals on injured renal epithelial cells: aggravation of crystal adhesion and aggregation

PubMed Central

Gan, Qiong-Zhi; Sun, Xin-Yuan; Bhadja, Poonam; Yao, Xiu-Qiong; Ouyang, Jian-Ming

2016-01-01

Background Renal epithelial cell injury facilitates crystal adhesion to cell surface and serves as a key step in renal stone formation. However, the effects of cell injury on the adhesion of nano-calcium oxalate crystals and the nano-crystal-induced reinjury risk of injured cells remain unclear. Methods African green monkey renal epithelial (Vero) cells were injured with H2O2 to establish a cell injury model. Cell viability, superoxide dismutase (SOD) activity, malonaldehyde (MDA) content, propidium iodide staining, hematoxylin–eosin staining, reactive oxygen species production, and mitochondrial membrane potential (Δψm) were determined to examine cell injury during adhesion. Changes in the surface structure of H2O2-injured cells were assessed through atomic force microscopy. The altered expression of hyaluronan during adhesion was examined through laser scanning confocal microscopy. The adhesion of nano-calcium oxalate monohydrate (COM) and calcium oxalate dihydrate (COD) crystals to Vero cells was observed through scanning electron microscopy. Nano-COM and COD binding was quantitatively determined through inductively coupled plasma emission spectrometry. Results The expression of hyaluronan on the cell surface was increased during wound healing because of Vero cell injury. The structure and function of the cell membrane were also altered by cell injury; thus, nano-crystal adhesion occurred. The ability of nano-COM to adhere to the injured Vero cells was higher than that of nano-COD crystals. The cell viability, SOD activity, and Δψm decreased when nano-crystals attached to the cell surface. By contrast, the MDA content, reactive oxygen species production, and cell death rate increased. Conclusion Cell injury contributes to crystal adhesion to Vero cell surface. The attached nano-COM and COD crystals can aggravate Vero cell injury. As a consequence, crystal adhesion and aggregation are enhanced. These findings provide further insights into kidney stone formation. PMID:27382277

Particle engineering using sonocrystallization: salbutamol sulphate for pulmonary delivery.

PubMed

Dhumal, Ravindra S; Biradar, Shailesh V; Paradkar, Anant R; York, Peter

2009-02-23

The aim of present work was to produce fine elongated crystals of salbutamol sulphate (SS) by sonocrystallization for pulmonary delivery and compare with micronized and spray dried SS (SDSS) for in vitro aerosolization behavior. Application of ultrasound during anti-solvent crystallization resulted in fine elongated crystals (sonocrystallized SS; SCSS) compared to aggregates of large irregular crystals obtained without sonication. Higher sonication amplitude, time, concentration and lower processing temperatures favored formation of smaller crystals with narrow particle size distribution (PSD). SCSS was separated from dispersion by spray drying in the form of loose aggregates (SD-SCSS). The fine particle fraction (FPF) of formulations with coarse lactose carrier in cascade impactor increased from 16.66% for micronized SS to 31.12% for SDSS (obtained by spray drying aqueous SS solution) and 44.21% for SD-SCSS, due to reduced cohesive/adhesive forces and aerodynamic size by virtue of elongated shape of crystals. SD-SCSS was stable without any change in crystallinity and aerodynamic behavior for 3 months at 40 degrees C/75% RH, but amorphous SDSS showed recrystallization with poor aerosolization performance on storage. Sonocrystallization, a rapid and simple technique is reported for production of SS crystals suitable for inhalation delivery.

Trends in the precipitation and crystallization behavior of supersaturated aqueous solutions of poorly water-soluble drugs assessed using synchrotron radiation.

PubMed

Raina, Shweta A; Van Eerdenbrugh, Bernard; Alonzo, David E; Mo, Huaping; Zhang, Geoff G Z; Gao, Yi; Taylor, Lynne S

2015-06-01

Amorphous materials are high-energy solids that can potentially enhance the bioavailability of poorly soluble compounds. A major impediment to their widespread use as a formulation platform is the tendency of amorphous materials to crystallize. The aim of this study was to evaluate the relative crystallization tendency of six structural analogues belonging to the dihydropyridine class, in an aqueous environment in the absence and presence of polymers, using wide-angle X-ray scattering synchrotron radiation and polarized light microscopy. The crystallization behavior of precipitates generated from supersaturated solutions of the active pharmaceutical ingredients was found to be highly variable ranging from immediate to several hours in the absence of polymers. Polymers with intermediate hydrophilicity/hydrophobicity were found to substantially delay crystallization, whereas strongly hydrophilic or hydrophobic polymers were largely ineffective. Nuclear magnetic resonance spectroscopy experiments supported the supposition that polymers need to have affinity for both the drug-rich precipitate and the aqueous phase in order to be effective crystallization inhibitors. This study highlights the variability in the crystallization tendency of different compounds and provides insight into the mechanism of inhibition by polymeric additives. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

Mutual Influence of Mannitol and Trehalose on Crystallization Behavior in Frozen Solutions.

PubMed

Jena, Sampreeti; Suryanarayanan, Raj; Aksan, Alptekin

2016-06-01

Phase separation of trehalose during freeze-drying could render it ineffective as a lyoprotectant. The bulking agent, mannitol, on the other hand, should crystallize readily upon freezing. It is therefore imperative to understand the mutual interaction of these sugars during freezing to ensure preservation of the API during freeze-drying. We investigated the effect of mannitol to trehalose ratio (R) on the crystallization behavior of both solutes using Differential Scanning Calorimetry, X-Ray Crystallography and FTIR Spectrosopy during controlled freezing and annealing. When R = 1, crystallization of both mannitol (as hemihydrate) and trehalose (as α-anhydrate) were observed. When R ≥ 1, extent of mannitol crystallization was directly proportional to the value of R. When R < 1, trehalose completely suppressed mannitol crystallization. At R > 1, the freeze concentrate was heterogeneous and characterized by two glass transitions - the lower temperature transition (Tg") attributed to systems containing "extra" unfrozen water. When heated above Tg", crystallization of mannitol and the associated unfrozen water resulted in Tg' (glass transition temperature of the freeze-concentrate). R and not the total solute concentration, dictates the composition of the freeze concentrate as well as the physical stability of the excipients.

Predicting the crystallization propensity of carboxylic acid buffers in frozen systems--relevance to freeze-drying.

PubMed

Sundaramurthi, Prakash; Suryanarayanan, Raj

2011-04-01

Selective crystallization of buffer components in frozen solutions is known to cause pronounced pH shifts. Our objective was to study the crystallization behavior and the consequent pH shift in frozen aqueous carboxylic acid buffers. Aqueous carboxylic acid buffers were cooled to -25°C and the pH of the solution was measured as a function of temperature. The thermal behavior of solutions during freezing and thawing was investigated by differential scanning calorimetry. The crystallized phases in frozen solution were identified by X-ray diffractometry. The malate buffer system was robust with no evidence of buffer component crystallization and hence negligible pH shift. In the citrate and tartarate systems, at initial pH

Impacts of compression on crystallization behavior of freeze-dried amorphous sucrose.

PubMed

Imamura, Koreyoshi; Nomura, Mayo; Tanaka, Kazuhiro; Kataoka, Nobuhide; Oshitani, Jun; Imanaka, Hiroyuki; Nakanishi, Kazuhiro

2010-03-01

An amorphous matrix comprised of sugar molecules is used as excipient and stabilizing agent for labile ingredients in the pharmaceutical industry. The amorphous sugar matrix is often compressed into a tablet form to reduce the volume and improve handling. Herein, the effect of compression on the crystallization behavior of an amorphous sucrose matrix was investigated. Amorphous sucrose samples were prepared by freeze-drying and compressed under different conditions, followed by analyses by differential scanning calorimetry, isothermal crystallization tests, X-ray powder diffractometry, Fourier transform infrared spectroscopy (FTIR), and gas pycnometry. The compressed sample had a lower crystallization temperature and a shorter induction period for isothermal crystallization, indicating that compression facilitates the formation of the critical nucleus of a sucrose crystal. Based on FTIR and molecular dynamics simulation results, the conformational distortion of sucrose molecules due to the compression appears to contribute to the increase in the free energy of the system, which leads to the facilitation of critical nucleus formation. An isothermal crystallization test indicated an increase in the growth rate of sucrose crystals by the compression. This can be attributed to the transformation of the microstructure from porous to nonporous, as the result of compression. 2009 Wiley-Liss, Inc. and the American Pharmacists Association

Understanding the glass-forming ability of active pharmaceutical ingredients for designing supersaturating dosage forms.

PubMed

Kawakami, Kohsaku; Usui, Toshinori; Hattori, Mitsunari

2012-09-01

Amorphous solid dispersions have great potential for enhancing oral absorption of poorly soluble drugs. Crystallization behavior during storage and after exposure to aqueous media must be examined in detail for designing stable and effective amorphous formulations, and it is significantly affected by the intrinsic properties of an amorphous drug. Many attempts have been made to correlate various thermodynamic parameters of pharmaceutical glasses with their crystallization behavior; however, variations in model drugs that could be used for such investigation has been limited because the amorphous characteristics of drugs possessing a high crystallization tendency are difficult to evaluate. In this study, high-speed differential scanning calorimetry, which could inhibit their crystallization using high cooling rates up to 2000°C/s, was employed for assessing such drugs. The thermodynamic parameters of the glasses, including glass transition temperature (T(g)) and fragility, were obtained to show that their crystallization tendency cannot be explained simply by the parameters, although there have been general thought that fragility may be correlated with crystallization tendency. Also investigated was correlation between the thermodynamic parameters and crystallization tendency upon contact with water, which influences in vivo efficacy of amorphous formulations. T(g) was correlated well with the crystallization tendency upon contact with water. Copyright © 2012 Wiley Periodicals, Inc.

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.

ROBUST hot wire probe efficiency for total water content measurements in glaciated conditions

NASA Astrophysics Data System (ADS)

Leroy, Delphine; Lilie, Lyle; Weber, Marc; Schwarzenboeck, Alfons; Strapp, J. Walter

2017-04-01

During the two High Altitude Ice Crystals (HAIC, Dezitter et al. 2013)/High Ice Water Content (HIWC, Strapp et al., 2016a) international flight campaigns that investigated deep convection in the tropics, the French Falcon 20 research aircraft was equipped with two different devices measuring the Total Water Content (TWC): - the IKP-2 (Isokinetic Probe, Davison et al. 2008, 2016), - and the hot wire ROBUST probe (Strapp et al. 2008; Grandin et al. 2014). The IKP-2 probe is an evaporator that has been specifically designed to measure high ice water content (Strapp et al. 2016b) with a collection efficiency near unity. It has undergone extensive performance assessment in liquid and glaciated conditions in several wind tunnels. The Robust probe was initially developed by Science Engineering Associates to estimate high ice water content in a high speed wind tunnel, in harsh conditions where other hot-wires had been observed to suffer failures. It was known at the outset that, like other hot-wire TWC probes, it would measure only a quasi-constant fraction of the true ice water content. Early wind tunnel and flight experience with the ROBUST probe revealed that this fraction was the order of 40% for ice crystals. During the HAIC/HIWC campaigns (Leroy et al. 2016, 2017), supercooled liquid water conditions were documented according to a detailed analysis of a Rosemount Ice detector (RICE) and a Cloud Droplet Probe (CDP) measurements, and were found to be rare. Thus, the HAIC/HIWC dataset represents a unique opportunity to study in more detail the ROBUST efficiency in glaciated conditions, using the IKP-2 values as a comparative reference. Comparison of IKP-2 and ROBUST measurements will show that the ROBUST behavior differs between low (below 1.5 g/m3) and high (above 2 g/m3) ice content conditions and is also sensitive to temperature. The sensitivity of the ROBUST collection efficiency to ice particles size could also be explored as optical imaging probes were part of the airborne instrument package but no clear trend has been highlighted for the moment. References : Davison, C., J. MacLeod, J. Strapp, and D. Buttsworth, 2008: Isokinetic Total Water Content Probe in a Naturally Aspirating Configuration: Initial Aerodynamic Design and Testing. 46th AIAA Aerospace Sciences Meeting and Exhibit, American Institute of Aeronautics and Astronautics http://arc.aiaa.org/doi/abs/10.2514/6.2008-435 (Accessed February 9, 2015). Davison, C. R., J. W. Strapp, L. E. Lilie, T. P. Ratvasky, and C. Dumont, 2016: Isokinetic TWC Evaporator Probe: Calculations and Systemic Error Analysis. American Institute of Aeronautics and Astronautics http://arc.aiaa.org/doi/10.2514/6.2016-4060 (Accessed July 29, 2016). Dezitter, F., A. Grandin, J.-L. Brenguier, F. Hervy, H. Schlager, P. Villedieu, and G. Zalamansky, 2013: HAIC - High Altitude Ice Crystals. 5th AIAA Atmospheric and Space Environments Conference, American Institute of Aeronautics and Astronautics http://arc.aiaa.org/doi/abs/10.2514/6.2013-2674 (Accessed February 9, 2015). Grandin, A., J.-M. Merle, M. Weber, J. Strapp, A. Protat, and P. King, 2014: AIRBUS Flight Tests in High Total Water Content Regions. American Institute of Aeronautics and Astronautics http://arc.aiaa.org/doi/abs/10.2514/6.2014-2753 (Accessed March 8, 2016). Leroy, D., and Coauthors, 2016: HAIC/HIWC field campaigns - Specific findings on ice crystals characteristics in high ice water content cloud regions. American Institute of Aeronautics and Astronautics http://arc.aiaa.org/doi/10.2514/6.2016-4056 (Accessed January 10, 2017). Leroy, D., and Coauthors, 2017: Ice Crystal Sizes in High Ice Water Content Clouds. Part II: Statistics of Mass Diameter Percentiles in Tropical Convection Observed during the HAIC/HIWC Project. J. Atmospheric Ocean. Technol., 34, 117-136, doi:10.1175/JTECH-D-15-0246.1. Strapp, J. W., J. MacLeod, and L. Lilie, 2008: Calibration of ice water content in a wind tunnel/engine test cell facility. 15th Intl. Conf. on Cloud and Precipitation http://cabernet.atmosfcu.unam.mx/ICCP-2008/abstracts/Program_on_line/Poster_13/StrappEtAl-extended.pdf (Accessed April 25, 2016). Strapp, J. W., L. E. Lilie, T. P. Ratvasky, C. R. Davison, and C. Dumont, 2016b: Isokinetic TWC Evaporator Probe: Development of the IKP2 and Performance Testing for the HAIC-HIWC Darwin 2014 and Cayenne Field Campaigns. American Institute of Aeronautics and Astronautics http://arc.aiaa.org/doi/10.2514/6.2016-4059 (Accessed July 29, 2016). Strapp, J. W., G. A. Isaac. A. Korolev, T. Ratvasky, R. Potts, P. May, A. Protat, P. Minnis, A. Ackerman, A. Fridlind, J. Haggerty, and J. Riley, 2016a: The High Ice Water Content (HIWC) Study of deep convective clouds: Science and technical plan. FAA Rep. DOT/FAA/TC-14/31, available at http://www.tc.faa.gov/its/worldpac/techrpt/tc14-31.pdf. 105 pgs.

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.

The crystallization behavior of amorphous Ge2Sb2Te5 films induced by a multi-pulsed nanosecond laser

NASA Astrophysics Data System (ADS)

Fan, T.; Liu, F. R.; Li, W. Q.; Guo, J. C.; Wang, Y. H.; Sun, N. X.; Liu, F.

2017-09-01

In this paper, accumulated crystallization of amorphous Ge2Sb2Te5 (a-GST) films induced by a multi-pulsed nanosecond (ns) excimer laser was investigated by x-ray diffraction (XRD), atomic force microscopy, field-emission scanning electron microscopy, x-ray photoelectron spectroscopy (XPS) and a spectrophotometer. XRD analyses revealed that detectable crystallization was firstly observed in the preferred orientation (200), followed by the orientations (220) and (111) after two pulses. Optical contrast, determined by crystallinity as well as surface roughness, was found to retain a linear relation within the first three pulses. A layered growth mechanism from the top surface to the interior of a-GST films was used to explain the crystallization behavior induced by the multi-pulse ns laser. XPS analyses for bond rearrangement and electronic structure further suggested that the crystallization process was performed by generating new bonds of Ge-Te and Sb-Te after laser irradiations. This paper presents the potential of multi-level devices and tunable thermal emitters based on controllable crystallization of phase-change materials.

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.

On the Grand Challenges in Physical Petrology: the Multiphase Crossroads

NASA Astrophysics Data System (ADS)

Bergantz, G. W.

2014-12-01

Rapid progress in experimental, micro-analytical and textural analysis at the crystal scale has produced an unprecedented record of magmatic processes. However an obstacle to further progress is the lack of understanding of how mass, energy and momentum flux associated with crystal-rich, open-system events produces identifiable outcomes. Hence developing a physically-based understanding of magmatic systems linking micro-scale petrological observations with a physical template operating at the macro-scale presents a so-called "Grand Challenge." The essence of this challenge is that magmatic systems have characteristic length and feedback scales between those accessible by classical continuum and discrete methods. It has become increasingly obvious that the old-school continuum methods have limited resolution and power of explanation for multiphase (real) magma dynamics. This is, in part, because in crystal-rich systems the deformation is non-affine, and so the concept of constitutive behavior is less applicable and likely not even relevant, especially if one is interested in the emergent character of micro-scale processes. One expression of this is the cottage industry of proposing viscosity laws for magmas, which serves as "blunt force" de facto corrections for what is intrinsically multiphase behavior. Even in more fluid-rich systems many of these laws are not suitable for use in the very transport theories they aim to support. The alternative approach is the discrete method, where multiphase interactions are explicitly resolved. This is a daunting prospect given the numbers of crystals in magmas. But perhaps all crystals don't need to be modeled. I will demonstrate how discrete methods can recover critical state behavior, resolve crystal migration, the onset of visco-elastic behavior such as melt-present shear bands which sets the large-scale mixing volumes, some of the general morpho-dynamics that underlies purported rheological models, and transient controls on the emergence and dissipation of distinct thermodynamic states. As simulations with 106 - 107 crystals are now possible both the local, micro-scale crystal processes as well as the larger scale processes controlled by particle-particle-fluid interactions, can be simultaneously resolved.

The modeling, simulation, and control of transport phenomena in a thermally destabilizing Bridgman crystal growth system

NASA Astrophysics Data System (ADS)

Sonda, Paul Julio

This thesis presents a comprehensive examination of the modeling, simulation, and control of axisymmetric flows occurring in a vertical Bridgman crystal growth system with the melt underlying the crystal. The significant complexity and duration of the manufacturing process make experimental optimization a prohibitive task. Numerical simulation has emerged as a powerful tool in understanding the processing issues still prevalent in industry. A first-principles model is developed to better understand the transport phenomena within a representative vertical Bridgman system. The set of conservation equations for momentum, energy, and species concentration are discretized using the Galerkin finite element method and simulated using accurate time-marching schemes. Simulation results detail the occurrence of fascinating nonlinear dynamics, in the form of stable, time-varying behavior for sufficiently large melt regimes and multiple steady flow states. This discovery of time-periodic flows for high intensity flows is qualitatively consistent with experimental observations. Transient simulations demonstrate that process operating conditions have a marked effect on the hydrodynamic behavior within the melt, which consequently affects the dopant concentration profile within the crystal. The existence of nonlinear dynamical behavior within this system motivates the need for feedback control algorithms which can provide superior crystal quality. This work studies the feasibility of using crucible rotation to control flows in the vertical Bridgman system. Simulations show that crucible rotation acts to suppress the axisymmetric flows. However, for the case when the melt lies below the crystal, crucible rotation also acts to accelerate the onset of time-periodic behavior. This result is attributed to coupling between the centrifugal force and the intense, buoyancy-driven flows. Proportional, proportional-integral, and input-output linearizing controllers are applied to vertical Bridgman systems in stabilizing (crystal below the melt) and destabilizing (melt below the crystal) configurations. The spatially-averaged, axisymmetric kinetic energy is the controlled output. The flows are controlled via rotation of the crucible containing the molten material. Simulation results show that feedback controllers using crucible rotation effectively attenuate flow oscillations in a stabilizing configuration with time-varying disturbance. Crucible rotation is not an optimal choice for suppressing inherent flow oscillations in the destabilizing configuration.

Effect of silver-doping on the crystal structure, morphology and photocatalytic activity of TiO2 nanofibers

NASA Astrophysics Data System (ADS)

Barakat, N. A. M.; Kim, H. Y.

2012-09-01

In this study, effect of sliver-doping on the crystal structure, the nanofibrous morphology and the photocatalytic activity of titanium oxide nanofibers have been investigated. Silver-doped TiO2 nanofibers having different silver contents were prepared by calcination of electrospun nanofiber mats consisting of silver nitrate, titanium isopropoxide and poly(vinyl acetate) at 600 °C. The results affirmed formation of silver-doped TiO2 nanofibers composed of anatase and rutile when the silver nitrate content in the original electrospun solution was more than 3 wt%. The rutile phase content was directly proportional with the AgNO3 concentration in the electrospun solution. Negative impact of the silver-doping on the nanofibrous morphology was observed as increase the silver content caused to decrease the aspect ratio, i.e. producing nanorods rather nanofibers. However, silver-doping leads to modify the surface roughness. Study of the photocatalytic degradation of methylene blue dye clarified that increase the silver content strongly enhances the dye oxidation process.

Global low-energy weak solution and large-time behavior for the compressible flow of liquid crystals

NASA Astrophysics Data System (ADS)

Wu, Guochun; Tan, Zhong

2018-06-01

In this paper, we consider the weak solution of the simplified Ericksen-Leslie system modeling compressible nematic liquid crystal flows in R3. When the initial data are of small energy and initial density is positive and essentially bounded, we prove the existence of a global weak solution in R3. The large-time behavior of a global weak solution is also established.

Intrinsic behavior of face-centered-cubic supra-crystals of nanocrystals self-organized on mesoscopic scale

NASA Astrophysics Data System (ADS)

Pileni, M. P.

2005-12-01

We describe intrinsic behavior due to the high ordering of nanocrystals at the mesoscopic scale. The first example shows well-defined columns in the formation of cobalt nanocrystals when an applied magnetic field is applied during the evaporation process. Collective breathing properties between nanocrystals are demonstrated. In both cases, these features are observed when the nanocrystals are highly ordered in fcc supra-crystals.

Synthesis, growth, structural and optical studies of a novel organic Piperazine (bis) p-toluenesulfonate single crystal.

PubMed

Rekha, P; Peramaiyan, G; NizamMohideen, M; Kumar, R Mohan; Kanagadurai, R

2015-03-15

A novel organic single crystal of Piperazinium (bis) p-toluenesulfonate (PPTS) was grown by a slow evaporation solution growth technique. The structure of the grown crystal was determined using single crystal X-ray diffraction analysis. The PPTS crystal belongs to the triclinic crystal system with space group of P1¯. The presence of functional groups was confirmed by FTIR spectral analysis. The optical transmittance range and cut-off wavelength were identified by UV-vis-NIR spectral studies. The luminescent properties of PPTS crystal were investigated. The thermal behavior of PPTS crystal was studied by TG-DT analyses. Copyright © 2014 Elsevier B.V. All rights reserved.

Observations of Glide and Decomposition of a<101> Dislocations at High Temperatures in Ni-Al Single Crystals Deformed along the Hard Orientation

NASA Technical Reports Server (NTRS)

Srinivasan, R.; Daw, M. S.; Noebe, R. D.; Mills, M. J.

2003-01-01

Ni-44at.% Al and Ni-50at.% single crystals were tested in compression in the hard (001) orientations. The dislocation processes and deformation behavior were studied as a function of temperature, strain and strain rate. A slip transition in NiAl occurs from alpha(111) slip to non-alphaaaaaaaaaaa9111) slip at intermediate temperatures. In Ni-50at.% Al single crystal, only alpha(010) dislocations are observed above the slip transition temperature. In contrast, alpha(101)(101) glide has been observed to control deformation beyond the slip transition temperature in Ni-44at.%Al. alpha(101) dislocations are observed primarily along both (111) directions in the glide plane. High-resolution transmission electron microscopy observations show that the core of the alpha(101) dislocations along these directions is decomposed into two alpha(010) dislocations, separated by a distance of approximately 2nm. The temperature window of stability for these alpha(101) dislocations depends upon the strain rate. At a strain rate of 1.4 x 10(exp -4)/s, lpha(101) dislocations are observed between 800 and 1000K. Complete decomposition of a alpha(101) dislocations into alpha(010) dislocations occurs beyond 1000K, leading to alpha(010) climb as the deformation mode at higher temperature. At lower strain rates, decomposition of a alpha(101) dislocations has been observed to occur along the edge orientation at temperatures below 1000K. Embedded-atom method calculations and experimental results indicate that alpha(101) dislocation have a large Peieris stress at low temperature. Based on the present microstructural observations and a survey of the literature with respect to vacancy content and diffusion in NiAl, a model is proposed for alpha(101)(101) glide in Ni-44at.%Al, and for the observed yield strength versus temperature behavior of Ni-Al alloys at intermediate and high temperatures.

Microstructure, mechanical, and in vitro properties of mica glass-ceramics with varying fluorine content.

PubMed

Molla, Atiar Rahaman; Basu, Bikramjit

2009-04-01

The design and development of glass ceramic materials provide us the unique opportunity to study the microstructure development with changes in either base glass composition or heat treatment conditions as well as to understand processing-microstructure-property (mechanical/biological) relationship. In the present work, it is demonstrated how various crystal morphology can develop when F(-) content in base glass (K(2)O-B(2)O(3)-Al(2)O(3)-SiO(2)-MgO-F) is varied in the range of 1.08-3.85% and when all are heat treated at varying temperatures of 1000-1120 degrees C. For some selected heat treatment temperature, the heat treatment time is also varied over 4-24 h. It was established that with increase in fluoride content in the glass composition, the crystal volume fraction of the glass-ceramic decreases. Using 1.08% fluoride, more than 80% crystal volume fraction could be achieved in the K(2)O-B(2)O(3)-Al(2)O(3)-SiO(2)-MgO-F system. It was observed that with lower fluoride content glass-ceramic, if heated at 1040 degrees C for 12 h, an oriented microstructure with 'envelop like' crystals can develop. For glass ceramics with higher fluorine content (2.83% or 3.85%), hexagonal-shaped crystals are formed. Importantly, high hardness of around 8 GPa has been measured in glass ceramics with maximum amount of crystals. The three-point flexural strength and elastic modulus of the glass-ceramic (heat treated at 1040 degrees C for 24 h) was 80 MPa and 69 GPa of the sample containing 3.85% fluorine, whereas, similar properties obtained for the sample containing 1.08% F(-) was 94 MPa and 57 GPa, respectively. Further, in vitro dissolution study of the all three glass-ceramic composition in artificial saliva (AS) revealed that leached fluoride ion concentration was 0.44 ppm, when the samples were immersed in AS for 8 weeks. This was much lower than the WHO recommended safety limits of 1.5 ppm. Among all the investigated glass-ceramic samples, the glass ceramic with 3.85% F(-) content in base glass (heat treated at 1040 degrees C for 12 h), exhibits the adherence of Ca-P layer, which consists of spherical particles of 2-3 mum. Other ions, such as Mg(+2) and K(+1) ion concentrations in the solution were found to be 8 and 315 ppm after 8 weeks of leaching, respectively. The leaching of all metal ions is recorded to decrease with time, probably due to time-dependent kinetic modification of sample surface. Summarizing, the present study illustrates that it is possible to obtain a good combination of crystallization, mechanical and in vitro dissolution properties with the careful selection of base glass composition and heat treatment conditions.

Influence of surfactant on the thermal behavior of marigold oil emulsions with liquid crystal phases.

PubMed

dos Santos, Orlando David Henrique; da Rocha-Filho, Pedro Alves

2007-05-01

Vegetable oils have been largely consumed owing to the interest of pharmaceutical and cosmetic industries in using natural raw materials. The production of stable emulsions with vegetable oils challenges formulators due to its variability in composition and fatty acids constitution within batches produced. In the present work, it was studied that the influence of the size of carbon chain and the number of ethylene oxide moieties of the surfactant on the thermal behavior of eight emulsions prepared with marigold oil stabilized by liquid crystal phases. Differential scanning calorimetry (DSC) was used to determine the thermal behavior of the emulsions. The ratio of bound water was calculated, being between 29.0 and 42.0%, confirming the extension of the liquid-crystalline net in the external phase. Changing the lipophilic surfactant from Ceteth-2 to Steareth-2, there was an increase in the temperature of phase transition of the liquid crystal influencing the system stability. Calorimetric study is very useful in understanding the performance of liquid crystals with the increase of temperature and to estimate emulsions stability.

Critical behavior of the spin-1 and spin-3/2 Baxter-Wu model in a crystal field.

PubMed

Dias, D A; Xavier, J C; Plascak, J A

2017-01-01

The phase diagram and the critical behavior of the spin-1 and the spin-3/2 two-dimensional Baxter-Wu model in a crystal field are studied by conventional finite-size scaling and conformal invariance theory. The phase diagram of this model, for the spin-1 case, is qualitatively the same as those of the diluted 4-states Potts model and the spin-1 Blume-Capel model. However, for the present case, instead of a tricritical point one has a pentacritical point for a finite value of the crystal field, in disagreement with previous work based on finite-size calculations. On the other hand, for the spin-3/2 case, the phase diagram is much richer and can present, besides a pentacritical point, an additional multicritical end point. Our results also support that the universality class of the critical behavior of the spin-1 and spin-3/2 Baxter-Wu model in a crystal field is the same as the pure Baxter-Wu model, even at the multicritical points.

Evaluation of the exchange interaction and crystal fields in a prototype Dy2 SMM

NASA Astrophysics Data System (ADS)

Zhang, Qing; Sarachik, Myriam; Baker, Michael; Chen, Yizhang; Kent, Andrew; Pineda, Eufemio; McInnes, Eric

In order to gain an understanding of the INS and magnetization data obtained for Dy2, the simplest member of a newly synthesized family of dysprosium-based molecular magnets, we report on calculations of the magnetic behavior of a Dy2 cluster with the formula [hqH2][Dy2(hq)4(NO3)3].MeOH. The molecular complex contains one high symmetry Dy(III) ion and one low symmetry Dy(III) ion. Our calculations suggest that exchange coupling between the two ions controls the behavior of the magnetization at low temperature, while the crystal field of the low symmetry Dy(III) ion controls the behavior at higher temperature. A point charge electrostatic model, based on crystallographic coordinates, provides a starting point for the determination of the crystal field. Parameters in these calculations are adjusted to provide best fits to inelastic neutron scattering data (INS) and low temperature magnetometry: the INS measurements access crystal field energies and low temperature magnetization probes the Dy-Dy exchange interaction. Work supported by ARO W911NF-13-1-1025 (CCNY) and NSF-DMR-1309202 (NYU).

Effect of milling on particle shape and surface energy heterogeneity of needle-shaped crystals.

PubMed

Ho, Raimundo; Naderi, Majid; Heng, Jerry Y Y; Williams, Daryl R; Thielmann, Frank; Bouza, Peter; Keith, Adam R; Thiele, Greg; Burnett, Daniel J

2012-10-01

Milling and micronization of particles are routinely employed in the pharmaceutical industry to obtain small particles with desired particle size characteristics. The aim of this study is to demonstrate that particle shape is an important factor affecting the fracture mechanism in milling. Needle-shaped crystals of the β polymorph of D-mannitol were prepared from recrystallization in water. A portion of the recrystallized materials was ball-milled. Unmilled and milled sieved fractions of recrystallized D-mannitol were analyzed by dynamic image analysis (DIA) and inverse gas chromatography (IGC) at finite concentration to explain the breakage/fracture behavior. In the process of ball-milling, D-mannitol preferentially fractured along their shortest axis, exposing (011) plane with increased hydrophilicity and increased bounding rectangular aspect ratio. This is in contrary to attachment energy modeling which predicts a fracture mechanism across the (010) plane with increased hydrophobicity, and small change in particle shape. Crystal size, and more importantly, crystal shape and facet-specific mechanical properties, can dictate the fracture/cleavage behavior of organic crystalline materials. Thorough understanding of the crystal slip systems, combining attachment energy prediction with particle shape and surface characterization using DIA and IGC, are important in understanding fracture behavior of organic crystalline solids in milling and micronization.

Understanding the crystallization behavior of as-deposited Ti-Sb-Te alloys through real-time radial distribution functions.

PubMed

Zhu, Min; Xia, Mengjiao; Song, Zhitang; Cheng, Yan; Wu, Liangcai; Rao, Feng; Song, Sannian; Wang, Miao; Lu, Yegang; Feng, Songlin

2015-06-07

Phase change materials, successfully used in optical data-storage and non-volatile electronic memory, are well-known for their ultrafast crystallization speed. However, the fundamental understanding of their crystallization behavior, especially the nucleation process, is limited by present experimental techniques. Here, real-time radial distribution functions (RDFs), derived from the selected area electron diffractions, are employed as structural probes to comprehensively study both nucleation and subsequent growth stages of Ti-doped Sb2Te3 (TST) materials in the electron-irradiation crystallization process. It can be found that the incorporation of Ti atoms in Sb2Te3 forms wrong bonds such as Ti-Te, Ti-Sb, breaks the originally ordered atomic arrangement and diminishes the initial nucleus size of the as-deposited films, which results in better thermal stability. But these nuclei hardly grow until their sizes exceed a critical value, and then a rapid growth period starts. This means that an extended nucleation time is required to form the supercritical nuclei of TST alloys with higher concentration. Also, the increasing formation of four-membered rings, which served as nucleation sites, after doping excessive Ti is responsible for the change of the crystallization behavior from growth-dominated to nucleation-dominated.

Influence of the selenium content on thermo-mechanical and optical properties of Ge-Ga-Sb-S chalcogenide glasses

NASA Astrophysics Data System (ADS)

Ye, Bin; Dai, Shixun; Wang, Rongping; Tao, Guangming; Zhang, Peiqing; Wang, Xunsi; Shen, Xiang

2016-07-01

A number of Ge17Ga4Sb10S69-xSex (x = 0, 15, 30, 45, 60, and 69) chalcogenide glasses have been synthesized by a melt-quenching method to investigate the effect of the Se content on thermo-mechanical and optical properties of these glasses. While it was found that the glass transition temperature (Tg) decreases from 261 to 174 °C with increasing Se contents, crystallization temperature (Tc) peak only be observed in glasses with Se content of x = 45. It was evident from the measurements of structural and physical properties that changes of the glass network bring an apparent impact on the glass properties. Also, the substitution of Se for S in Ge-Ga-Sb glasses can significantly improve the thermal stability against crystallization and broaden the infrared transmission region.

[Physicochemical properties of suplatast tosilate racemate and enantiomers].

PubMed

Ushio, T; Endo, K; Yamamoto, K

1996-11-01

The physicochemical properties of the enantiomer and racemates of suplatast tosilate (ST) were investigated by means of infrared spectroscopy, solid-state 13C CP/MAS NMR spectroscopy, thermal analysis, and X-ray diffraction analysis, and by measuring the solubility and hygroscopy. The infrared and NMR spectra and X-ray diffraction pattern of the enantiomer were distinctly different from those of the racemate. The melting point of the enantiomer was lower than that of the racemate by 5 degrees C, while the solubility of the enantiomer was 1.3 times higher than that of the racemate. The hygroscopic rate of the enantiomer was greater than that of the racemate. These results suggested that ST was classified into a racemic compound crystal. Furthermore, by comparing the relative peak intensity ratios on X-ray diffraction patterns of the crystals with various optical purities prepared by recrystallization, it was found that a mixture of racemic compound crystals and either of racemic mixture crystals or racemic solid solutions was obtained by recrystallization of ST in the content of 0 to 64%ee, while the recrystallization of ST in the content of more than 64%ee led to the formation of racemic mixture crystals or racemic solid solutions.

Confined crystallization, crystalline phase deformation and their effects on the properties of crystalline polymers

NASA Astrophysics Data System (ADS)

Wang, Haopeng

With the recent advances in processing and catalyst technology, novel morphologies have been created in crystalline polymers and they are expected to substantially impact the properties. To reveal the structure-property relationships of some of these novel polymeric systems becomes the primary focus of this work. In the first part, using an innovative layer-multiplying coextrusion process to obtain assemblies with thousands of polymer nanolayers, dominating "in-plane" lamellar crystals were created when the confined poly(ethylene oxide) (PEO) layers were made progressively thinner. When the thickness was confined to 25 nanometers, the PEO crystallized as single, high-aspect-ratio lamellae that resembled single crystals. This crystallization habit imparted more than two orders of magnitude reduction in the gas permeability. The dramatic decrease in gas permeability was attributed to the reduced diffusion coefficient, because of the increase in gas diffusion path length through the in-plane lamellae. The temperature dependence of lamellar orientation and the crystallization kinetics in the confined nanolayers were also investigated. The novel olefinic block copolymer (OBC) studied in the second part consisted of long crystallizable sequences with low comonomer content alternating with rubbery amorphous blocks with high comonomer content. The crystallizable blocks formed lamellae that organized into space-filling spherulites even when the fraction of crystallizable block was so low that the crystallinity was only 7%. These unusual spherulites were highly elastic and recovered from strains as high as 300%. These "elastic spherulites" imparted higher strain recovery and temperature resistance than the conventional random copolymers that depend on isolated, fringed micellar-like crystals to provide the junctions for the elastomeric network. In the third part, positron annihilation lifetime spectroscopy (PALS) was used to obtain the temperature dependence of the free volume hole size in propylene/ethylene copolymers over a range in comonomer content. Above the glass transition temperature (Tg), the reduced free volume hole size and the densification of the amorphous phase were attributed to constraint imposed on rubbery amorphous chain segments by attached chain segments in crystals. However constant free volume fraction was found at Tg, across the crystallinity range of the copolymers, in agreement with the iso-free volume concept of glass transition.

Follow up on the crystal growth experiments of the LDEF

NASA Technical Reports Server (NTRS)

Nielsen, K. F.; Lind, M. D.

1993-01-01

The results of the 4 solution growth experiments on the LDEF have been published elsewhere. Both the crystals of CaCO3, which were large and well shaped, and the much smaller TTF-TCNQ crystals showed unusual morphological behavior. The follow up on these experiments was begun in 1981, when ESA initiated a 'Concept Definition Study' on a large, 150 kg, Solution Growth Facility (SGF) to be included in the payload of EURECA-1, the European Retrievable Carrier. This carrier was a continuation of the European Spacelab and at that time planned for launch in 1987. The long delay of the LDEF retrieval and of subsequent missions brought about reflections both on the concept of crystal growth in space and on the choice of crystallization materials that had been made for the LDEF. Already before the LDEF retrieval, research on TTF-TCNQ had been stopped, and a planned growth experiment with TTF-TCNQ on the SGF/EURECA had been cancelled. The target of the SGF investigation is now more fundamental in nature. None of the crystals to be grown here are, like TTF-TCNQ, in particular demand by science or industry, and the crystals only serve the purpose of model crystals. The real purpose of the investigation is to study the growth behavior. One of the experiments, the Soret Coefficient Measurement experiment is not growing crystals at all, but has it as its sole purpose to obtain accurate information on thermal diffusion, a process of importance in crystal growth from solution.

Impact of polymers on the crystallization and phase transition kinetics of amorphous nifedipine during dissolution in aqueous media.

PubMed

Raina, Shweta A; Alonzo, David E; Zhang, Geoff G Z; Gao, Yi; Taylor, Lynne S

2014-10-06

The commercial and clinical success of amorphous solid dispersions (ASD) in overcoming the low bioavailability of poorly soluble molecules has generated momentum among pharmaceutical scientists to advance the fundamental understanding of these complex systems. A major limitation of these formulations stems from the propensity of amorphous solids to crystallize upon exposure to aqueous media. This study was specifically focused on developing analytical techniques to evaluate the impact of polymers on the crystallization behavior during dissolution, which is critical in designing effective amorphous formulations. In the study, the crystallization and polymorphic conversions of a model compound, nifedipine, were explored in the absence and presence of polyvinylpyrrolidone (PVP), hydroxypropylmethyl cellulose (HPMC), and HPMC-acetate succinate (HPMC-AS). A combination of analytical approaches including Raman spectroscopy, polarized light microscopy, and chemometric techniques such as multivariate curve resolution (MCR) were used to evaluate the kinetics of crystallization and polymorphic transitions as well as to identify the primary route of crystallization, i.e., whether crystallization took place in the dissolving solid matrix or from the supersaturated solutions generated during dissolution. Pure amorphous nifedipine, when exposed to aqueous media, was found to crystallize rapidly from the amorphous matrix, even when polymers were present in the dissolution medium. Matrix crystallization was avoided when amorphous solid dispersions were prepared, however, crystallization from the solution phase was rapid. MCR was found to be an excellent data processing technique to deconvolute the complex phase transition behavior of nifedipine.

Optimizing the Hot-Corrosion Resistance-of-Novel gamma-Ni+gamma-prime-Ni3A1-Based Alloys and Coatings

DTIC Science & Technology

2006-07-01

TBC benefit Substrale limit 1 1 0 0 ---------- .- -.. . . . . . . --- I single crystal S1000 conventlonally cest allos . .- alloy. E directionally...usually heat treated or processed) forms. Developments in casting technologies made it possible to produce directionally-solidified and single - crystal ...advanced single - crystal superalloys with improved strength meant reductions in chromium and silicon contents. The scale growth and spallation rates can be

Multiple plagioclase crystal populations identified by crystal size distribution and in situ chemical data: Implications for timescales of magma chamber processes associated with the 1915 eruption of Lassen Peak, CA

USGS Publications Warehouse

Salisbury, M.J.; Bohrson, W.A.; Clynne, M.A.; Ramos, F.C.; Hoskin, P.

2008-01-01

Products of the 1915 Lassen Peak eruption reveal evidence for a magma recharge-magma mixing event that may have catalyzed the eruption and from which four compositional members were identified: light dacite, black dacite, andesitic inclusion, and dark andesite. Crystal size distribution, textural, and in situ chemical (major and trace element and Sr isotope) data for plagioclase from these compositional products define three crystal populations that have distinct origins: phenocrysts (long axis > 0??5 mm) that typically have core An contents between 34 and 36 mol %, microphenocrysts (long axis between 0??1 and 0??5 mm) that have core An contents of 66-69, and microlites (long axis < 0??1 mm) with variable An core contents from 64 to 52. Phenocrysts are interpreted to form in an isolated dacitic magma chamber that experienced slow cooling. Based on textural, compositional, and isotopic data for the magma represented by the dacitic component, magma recharge was not an important process until just prior to the 1915 eruption. Average residence times for phenocrysts are in the range of centuries to millennia. Microphenocrysts formed in a hybrid layer that resulted from mixing between end-member reservoir dacite and recharge magma of basaltic andesite composition. High thermal contrast between the two end-member magmas led to relatively high degrees of undercooling, which resulted in faster crystal growth rates and acicular and swallowtail crystal habits. Some plagioclase phenocrysts from the dacitic chamber were incorporated into the hybrid layer and underwent dissolution-precipitation, seen in both crystal textures and rim compositions. Average microphenocryst residence times are of the order of months. Microlites may have formed in response to decompression and/ or syn-eruptive degassing as magma ascended from the chamber through the volcanic conduit. Chemical distinctions in plagioclase microlite An contents reveal that melt of the dark andesite was more mafic than the melt of the other three compositions. We suggest that mixing of an intruding basaltic andesite and reservoir dacite before magma began ascending in the conduit allowed formation of a compositionally distinct microlite population. Melt in the other three products was more evolved because it had undergone differentiation during the months following initial mixing; as a consequence, melt and microlites among these three products have similar compositions. The results of this study highlight the integrated use of crystal size distribution, textural, and in situ chemical data in identifying distinct crystal populations and linking these populations to the thermal and chemical characteristics of complex magma bodies. ?? The Author 2008. Published by Oxford University Press. All rights reserved.

Neutralization of Hydroxide Ion in Melt-Grown NaCl Crystals

NASA Technical Reports Server (NTRS)

Otterson, Dumas A.

1961-01-01

Many recent studies of solid-state phenomena, particularly in the area of crystal imperfections, have involved the use of melt-grown NaCl single crystals. Quite often trace impurities in these materials have had a prominent effect on these phenomena. Trace amounts of hydroxide ion have been found in melt-grown NaCl crystals. This paper describes a nondestructive method of neutralizing the hydroxide ion in such crystals. Crystals of similar hydroxide content are maintained at an elevated temperature below the melting point of NaCl in a flowing atmosphere containing. dry hydrogen chloride. Heat treatment is continued until an analysis of the test specimens shows no excess hydroxide ion. A colorimetric method previously described4 is used for this analysis.

Crystallization of baria-titania-silica glasses

NASA Technical Reports Server (NTRS)

Ray, Chandra S.; Day, Delbert E.

1986-01-01

The critical cooling rate for glass formation, Rc, and the crystallization kinetics of the compositions (1/2)(100-x)BaO-(1/2)(100-x)TiO2-(x)SiO2 with x = 20, 25, 30, 33.3, and 40 mol pct were studied using a thermal image furnace. Crystallization was studied under nonisothermal conditions, and the data were analyzed using the Johnson-Mehl-Avrami equation. The Rc and activation energy for crystallization both decrease with increasing silica content. Fresnoite, Ba2TiSi2O8, crystallized from all of the glasses when they were reheated. The infrared absorption spectra of the glasses and crystals show that they both contain (Si2O7) and square pyramidal (TiO5) groups.

Tennantite-tetrahedrite series from the Madan Pb-Zn deposits, Central Rhodopes, Bulgaria

NASA Astrophysics Data System (ADS)

Vassileva, Rossitsa D.; Atanassova, Radostina; Kouzmanov, Kalin

2014-08-01

Minerals from the tennantite-tetrahedrite series (fahlores) are found as single euhedral crystals and crustiform aggregates in hydrothermal veins of the Gradishte and Petrovitsa Pb-Zn deposits of the Madan ore field, southern Bulgaria. Unusually large compositional variations and fine oscillatory crystal zoning were investigated with electron microprobe analysis. The Gradishte samples correspond dominantly to tennantite, while Petrovitsa crystals have exclusively tetrahedrite composition. Fahlore compositions at Madan correspond to zincian varieties (1.6-1.95 apfu), with low Fe-content (<0.45 apfu). Minor silver is characteristic only for the Petrovitsa samples, reaching a maximum of 0.30 apfu. The (Cu+Ag) content of the Petrovitsa tennantites and the Cu content of the Gradishte tetrahedrites systematically exceed 10 apfu resulting in compensation of the excess Cu in the structure by Fe3+. Textural characteristics, mineral relationships and available fluid inclusion and stable isotope data suggest that fahlores precipitated in the late stages of mineralization at Madan, at temperature interval of 300-200 °C from oxidizing fluids with mixed (magmatic-meteoric) signatures.

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

Baba, Seiki; Hoshino, Takeshi; Ito, Len

A new crystal-mounting method has been developed that involves a combination of controlled humid air and polymer glue for crystal coating. This method is particularly useful when applied to fragile protein crystals that are known to be sensitive to subtle changes in their physicochemical environment. Protein crystals are fragile, and it is sometimes difficult to find conditions suitable for handling and cryocooling the crystals before conducting X-ray diffraction experiments. To overcome this issue, a protein crystal-mounting method has been developed that involves a water-soluble polymer and controlled humid air that can adjust the moisture content of a mounted crystal. Bymore » coating crystals with polymer glue and exposing them to controlled humid air, the crystals were stable at room temperature and were cryocooled under optimized humidity. Moreover, the glue-coated crystals reproducibly showed gradual transformations of their lattice constants in response to a change in humidity; thus, using this method, a series of isomorphous crystals can be prepared. This technique is valuable when working on fragile protein crystals, including membrane proteins, and will also be useful for multi-crystal data collection.« less

Mafic-crystal distributions, viscosities, and lava structures of some Hawaiian lava flows

NASA Astrophysics Data System (ADS)

Rowland, Scott K.; Walker, George P. L.

1988-09-01

The distribution patterns of mafic phenocrysts in some Hawaiian basalt flows are consistent with simple in situ gravitational settling. We use the patterns to estimate the crystal settling velocity and hence viscosity of the lava, which in turn can be correlated with surface structures. Numerical modeling generates theoretical crystal concentration profiles through lava flow units of different thicknesses for differing settling velocities. By fitting these curves to field data, crystal-settling rates through the lavas can be estimated, from which the viscosities of the flows can be determined using Stokes' Law. Lavas in which the crystal settling velocity was relatively high (on the order of 5 × 10 -4 cm/sec) show great variations in phenocryst content, both from top to bottom of the same flow unit, and from one flow unit to another. Such lava is invariably pahoehoe, flow units of which are usually less than 1 m thick. Lavas in which the crystal-settling velocity was low show a small but measurable variation in phenocryst content. These lavas are part of a progression from a rough pahoehoe to toothpaste lava to a'a. Toothpaste lava is characterized by spiny texture as well as the ability to retain surface grooves during solidification, and flow units are usually thicker than 1 m. In the thickest of Hawaiian a'a flows, those of the distal type, no systematic crystal variations are observed, and high viscosity coupled with a finite yield strength prevented crystal settling. The amount of crystal settling in pahoehoe indicates that the viscosity ranged from 600 to 6000 Pa s. The limited amount of settling in toothpaste lava indicates a viscosity greater than this value, approaching 12,000 Pa s. We infer that distal-type a'a had a higher viscosity still and also possessed a yield strength.

Synthesis, structural, optical, thermal and dielectric studies on new organic nonlinear optical crystal by solution growth technique.

PubMed

Prakash, M; Geetha, D; Lydia Caroline, M

2013-04-15

Single crystals of L-phenylalanine-benzoic acid (LPBA) were successfully grown from aqueous solution by solvent evaporation technique. Purity of the crystals was increased by the method of recrystallization. The XRD analysis confirms that the crystal belongs to the monoclinic system with noncentrosymmetric space group P21. The chemical structure of compound was established by FT-NMR technique. The presence of functional groups was estimated qualitatively by Fourier transform infrared analysis (FT-IR). Ultraviolet-visible spectral analyses showed that the crystal has low UV cut-off at 254 nm combined with very good transparency of 90% in a wide range. The optical band gap was estimated to be 6.91 eV. Thermal behavior has been studied with TGA/DTA analyses. The existence of second harmonic generation (SHG) efficiency was found to be 0.56 times the value of KDP. The dielectric behavior of the sample was also studied for the first time. Copyright © 2013 Elsevier B.V. All rights reserved.

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.

Anisotropic surface physicochemical properties of spodumene and albite crystals: Implications for flotation separation

NASA Astrophysics Data System (ADS)

Xu, Longhua; Peng, Tiefeng; Tian, Jia; Lu, Zhongyuan; Hu, Yuehua; Sun, Wei

2017-12-01

Aluminosilicate minerals (e.g., spodumene, albite) have complex crystal structures and similar surface chemistries, but they have poor selectivity compared to traditional fatty acid collectors, making flotation separation difficult. Previous research has mainly considered the mineral crystal structure as a whole. In contrast, the surface characteristics at the atomic level and the effects of different crystal interfaces on the flotation behavior have rarely been investigated. This study focuses on investigating the surface anisotropy quantitatively, including the chemical bond characteristics, surface energies, and broken bond densities, using density functional theory and classical theoretical calculations. In addition, the anisotropy of the surface wettability and adsorption characteristics were examined using contact angle, zeta potential, and Fourier-transform infrared measurements. Finally, these surface anisotropies with different flotation behaviors were investigated and interpreted using molecular dynamics simulations, scanning electron microscopy, and X-ray photoelectron spectroscopy. This systematic research offers new ideas concerning the selective grinding and stage flotation of aluminosilicate minerals based on the crystal characteristics.

Mn Impurity in Bulk GaAs Crystals

NASA Astrophysics Data System (ADS)

Pawłowski, M.; Piersa, M.; Wołoś, A.; Palczewska, M.; Strzelecka, G.; Hruban, A.; Gosk, J.; Kamińska, M.; Twardowski, A.

2006-11-01

Magnetic and electron transport properties of GaAs:Mn crystals grown by Czochralski method were studied. Electron spin resonance showed the presence of Mn acceptor A in two charge states: singly ionized A- in the form of Mn2+(d5), and neutral A0 in the form of Mn2+(d5) plus a bound hole (h). It was possible to determine the relative concentration of both types of centers from intensity of the corresponding electron spin resonance lines. Magnetization measured as a function of magnetic field (up to 6 T) in the temperature range of 2-300 K revealed overall paramagnetic behavior of the samples. Effective spin was found to be about 1.5 value, which was consistent with the presence of two types of Mn configurations. In most of the studied samples the dominance of Mn2+(d5)+h configuration was established and it increased after annealing of native donors. The total value of Mn content was obtained from fitting of magnetization curves with the use of parameters obtained from electron spin resonance. In electron transport, two mechanisms of conductivity were observed: valence band transport dominated above 70 K, and hopping conductivity within Mn impurity band at lower temperatures. From the analysis of the hopping conductivity and using the obtained values of the total Mn content, the effective radius of Mn acceptor in GaAs was estimated as a = 11 ± 3 Å.