Lonsdaleite has been used as an indicator of shock from cratering events, but does it exist?

NASA Astrophysics Data System (ADS)

Nemeth, P.; Garvie, L. A.; Buseck, P. R.

2013-12-01

In 1967 a new diamond polymorph was described from the Canyon Diablo iron meteorite [1] and called lonsdaleite (also referred to as hexagonal diamond. It was identified from reflections (e.g., at 0.218, 0.193, and 0.150 nm), additional to those in diamond, that were indexed in terms of a hexagonal cell [1]. Lonsdaleite was attributed to shock-induced transformation of graphite within the iron meteorite upon impact [1, 2] and has subsequently been used as an indicator of shock and meteorite impact [3, 4, 5]. Given the importance of lonsdaleite, we reinvestigated the structure of the shock-formed diamond and lonsdaleite from the Canyon Diablo meteorite with an aberration-corrected ultra-high-resolution scanning transmission electron microscope (STEM), with the view of providing further insights into the shock-forming mechanism. The STEM images allowed direct structural interpretation at 0.1-nm resolution and showed that the samples consist of single-crystal and twinned diamond, as well as graphite intimately associated at the nanoscale. A characteristic feature of the STEM images is stacking faults and twins (111, 200, 113) that interrupt the regularity of the crystal structure. Uncommon, subnanometer-sized regions occur with two- and four-layer hexagonal symmetry, though these regions merge into diamond with stacking faults. Although we did not find lonsdaleite, the defects can give rise to extra reflections like those attributed to lonsdaleite. For example, the (113) diamond twin results in a 0.216-nm spacing that matches that of the broad 0.218-nm lonsdaleite peak. Our observations from Canyon Diablo provide a new understanding of shocked diamond structures and question the existence of lonsdaleite and its inferred geologic implication, although the abundance of diamond twinning and stacking faults may be indicative of shock metamorphism. [1] Frondel, C. & Marvin, U.B. (1967) Lonsdaleite, a hexagonal polymorph of diamond. Nature 217, 587-589. [2] Lipschutz, M. & Anders, E. (1961) The record in the meteorites-IV: Origin of diamonds in iron meteorites. Geochimica et Cosmochimica Acta 24, 83-105. [3] Kennet, D. J., Kennet, J. P., West, A., Mercer, C., Que Hee, S. S., Bement, L., Bunch, T. E., Sellers, M., & Wolbach, W. S. (2009) Nanodiamonds in the Younger Dryas boundary sediment layers. Science 323, 94. [4] Le Guillou, C., Rouzaud, J.N., Remusat, L., Jambon, A., & Bourot-Denise, M. (2010) Structures, origin and evolution of various carbon phases in the ureilite Northwest Africa 4742 compared with laboratory-shocked graphite. Geochimica Et Cosmochimica Acta 74(14), 4167-4185. [5] Hough, R.M., Gilmour, I., Pillinger, C.T., Arden, J.W., Gilkes, K.W.R., Yuan, J. & Milledge, H.J. (1995) Diamond and silicon carbide in an impact melt rock from the Ries impact crater. Nature 378, 41-44.

Erbium ion implantation into diamond - measurement and modelling of the crystal structure.

PubMed

Cajzl, Jakub; Nekvindová, Pavla; Macková, Anna; Malinský, Petr; Sedmidubský, David; Hušák, Michal; Remeš, Zdeněk; Varga, Marián; Kromka, Alexander; Böttger, Roman; Oswald, Jiří

2017-02-22

Diamond is proposed as an extraordinary material usable in interdisciplinary fields, especially in optics and photonics. In this contribution we focus on the doping of diamond with erbium as an optically active centre. In the theoretical part of the study based on DFT simulations we have developed two Er-doped diamond structural models with 0 to 4 carbon vacancies in the vicinity of the Er atom and performed geometry optimizations by the calculation of cohesive energies and defect formation energies. The theoretical results showed an excellent agreement between the calculated and experimental cohesive energies for the parent diamond. The highest values of cohesive energies and the lowest values of defect formation energies were obtained for models with erbium in the substitutional carbon position with 1 or 3 vacancies in the vicinity of the erbium atom. From the geometry optimization the structural model with 1 vacancy had an octahedral symmetry whereas the model with 3 vacancies had a coordination of 10 forming a trigonal structure with a hexagonal ring. In the experimental part, erbium doped diamond crystal samples were prepared by ion implantation of Er + ions using ion implantation fluences ranging from 1 × 10 14 ions per cm 2 to 5 × 10 15 ions per cm 2 . The experimental results revealed a high degree of diamond structural damage after the ion implantation process reaching up to 69% of disordered atoms in the samples. The prepared Er-doped diamond samples annealed at the temperatures of 400, 600 and 800 °C in a vacuum revealed clear luminescence, where the 〈110〉 cut sample has approximately 6-7 times higher luminescence intensity than the 〈001〉 cut sample with the same ion implantation fluence. The reported results are the first demonstration of the Er luminescence in the single crystal diamond structure for the near-infrared spectral region.

Quenchable compressed graphite synthesized from neutron-irradiated highly oriented pyrolytic graphite in high pressure treatment at 1500 °C

NASA Astrophysics Data System (ADS)

Niwase, Keisuke; Terasawa, Mititaka; Honda, Shin-ichi; Niibe, Masahito; Hisakuni, Tomohiko; Iwata, Tadao; Higo, Yuji; Hirai, Takeshi; Shinmei, Toru; Ohfuji, Hiroaki; Irifune, Tetsuo

2018-04-01

The super hard material of "compressed graphite" (CG) has been reported to be formed under compression of graphite at room temperature. However, it returns to graphite under decompression. Neutron-irradiated graphite, on the other hand, is a unique material for the synthesis of a new carbon phase, as reported by the formation of an amorphous diamond by shock compression. Here, we investigate the change of structure of highly oriented pyrolytic graphite (HOPG) irradiated with neutrons to a fluence of 1.4 × 1024 n/m2 under static pressure. The neutron-irradiated HOPG sample was compressed to 15 GPa at room temperature and then the temperature was increased up to 1500 °C. X-ray diffraction, high-resolution transmission electron microscopy on the recovered sample clearly showed the formation of a significant amount of quenchable-CG with ordinary graphite. Formation of hexagonal and cubic diamonds was also confirmed. The effect of irradiation-induced defects on the synthesis of quenchable-CG under high pressure and high temperature treatment was discussed.

Direct conversion of h-BN into c-BN and formation of epitaxial c-BN/diamond heterostructures

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

Narayan, Jagdish, E-mail: narayan@ncsu.edu; Bhaumik, Anagh; Xu, Weizong

2016-05-14

We have created a new state of BN (named Q-BN) through rapid melting and super undercooling and quenching by using nanosecond laser pulses. Phase pure c-BN is formed either by direct quenching of super undercooled liquid or by nucleation and growth from Q-BN. Thus, a direct conversion of hexagonal boron nitride (h-BN) into phase-pure cubic boron nitride (c-BN) is achieved by nanosecond pulsed laser melting at ambient temperatures and atmospheric pressure in air. According to the P-T phase diagram, the transformation from h-BN into c-BN under equilibrium processing can occur only at high temperatures and pressures, as the hBN-cBN-Liquid triplemore » point is at 3500 K/9.5 GPa or 3700 K/7.0 GPa with a recent theoretical refinement. Using nonequilibrium nanosecond laser melting, we have created super undercooled state and shifted this triple point to as low as 2800 K and atmospheric pressure. The rapid quenching from super undercooled state leads to the formation of a new phase, named as Q-BN. We present detailed characterization of Q-BN and c-BN layers by using Raman spectroscopy, high-resolution scanning electron microscopy, electron-back-scatter diffraction, high-resolution TEM, and electron energy loss spectroscopy, and discuss the mechanism of formation of nanodots, nanoneedles, microneedles, and single-crystal c-BN on sapphire substrate. We have also deposited diamond by pulsed laser deposition of carbon on c-BN and created c-BN/diamond heterostructures, where c-BN acts as a template for epitaxial diamond growth. We discuss the mechanism of epitaxial c-BN and diamond growth on lattice matching c-BN template under pulsed laser evaporation of amorphous carbon, and the impact of this discovery on a variety of applications.« less

Atomistic insights on the nanoscale single grain scratching mechanism of silicon carbide ceramic based on molecular dynamics simulation

NASA Astrophysics Data System (ADS)

Liu, Yao; Li, Beizhi; Kong, Lingfei

2018-03-01

The precision and crack-free surface of brittle silicon carbide (SiC) ceramic was achieved in the nanoscale ductile grinding. However, the nanoscale scratching mechanism and the root causes of SiC ductile response, especially in the atomistic aspects, have not been fully understood yet. In this study, the SiC atomistic scale scratching mechanism was investigated by single diamond grain scratching simulation based on molecular dynamics. The results indicated that the ductile scratching process of SiC could be achieved in the nanoscale depth of cut through the phase transition to an amorphous structure with few hexagonal diamond structure. Furthermore, the silicon atoms in SiC could penetrate into diamond grain which may cause wear of diamond grain. It was further found out that the chip material in the front of grain flowed along the grain side surface to form the groove protrusion as the scratching speed increases. The higher scratching speed promoted more atoms to transfer into the amorphous structure and reduced the hexagonal diamond and dislocation atoms number, which resulted in higher temperature, smaller scratching force, smaller normal stress, and thinner subsurface damage thickness, due to larger speed impaction causing more bonds broken which makes the SiC more ductile.

The Game of Hex

ERIC Educational Resources Information Center

Scott, Paul

2007-01-01

In this article, the author discusses the game of Hex, including its history, strategies and problems. Like all good games, the rules are very simple. Hex is played on a diamond shaped board made up of hexagons. It can be of any size, but an 11x11 board makes for a good game. Two opposite sides of the diamond are labelled "red," the other two…

Pattern formation in three-dimensional reaction-diffusion systems

NASA Astrophysics Data System (ADS)

Callahan, T. K.; Knobloch, E.

1999-08-01

Existing group theoretic analysis of pattern formation in three dimensions [T.K. Callahan, E. Knobloch, Symmetry-breaking bifurcations on cubic lattices, Nonlinearity 10 (1997) 1179-1216] is used to make specific predictions about the formation of three-dimensional patterns in two models of the Turing instability, the Brusselator model and the Lengyel-Epstein model. Spatially periodic patterns having the periodicity of the simple cubic (SC), face-centered cubic (FCC) or body-centered cubic (BCC) lattices are considered. An efficient center manifold reduction is described and used to identify parameter regimes permitting stable lamellæ, SC, FCC, double-diamond, hexagonal prism, BCC and BCCI states. Both models possess a special wavenumber k* at which the normal form coefficients take on fixed model-independent ratios and both are described by identical bifurcation diagrams. This property is generic for two-species chemical reaction-diffusion models with a single activator and inhibitor.

Study of proton radiation effects among diamond and rectangular gate MOSFET layouts

NASA Astrophysics Data System (ADS)

Seixas, L. E., Jr.; Finco, S.; Silveira, M. A. G.; Medina, N. H.; Gimenez, S. P.

2017-01-01

This paper describes an experimental comparative study of proton ionizing radiation effects between the metal-oxide-semiconductor (MOS) Field Effect Transistors (MOSFETs) implemented with hexagonal gate shapes (diamond) and their respective counterparts designed with the classical rectangular ones, regarding the same gate areas, channel widths and geometrical ratios (W/L). The devices were manufactured by using the 350 nm bulk complementary MOS (CMOS) integrated circuits technology. The diamond MOSFET with α angles higher or equal to 90° tends to present a smaller vulnerability to the high doses ionizing radiation than those observed in the typical rectangular MOSFET counterparts.

Static high pressure studies on Nd and Sc

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

Akella, J.; Xu, J.; Smith, G.S.

1985-06-24

We have investigated the crystal structural transformations in neodymium and scandium up to 4.0 GPa pressure and at room temperature, in a diamond-anvil high pressure apparatus. Nd has a double hexagonal-close packed (dhcp) structure at ambient pressure and temperature. Then it transforms to a face-centered cubic (fcc) structure at 3.8 GPa, which further transforms to a triple hexagonal-close packed structure (thcp) at about 18.0 GPa. In scandium we observed only one transformation from the hexagonal-close packed (hcp) structure at room temperature to a tetragonal structure. This transformation occurs between 19.0 and 23.2 GPa pressure.

Discovery of Superconductivity in Hard Hexagonal ε-NbN.

PubMed

Zou, Yongtao; Qi, Xintong; Zhang, Cheng; Ma, Shuailing; Zhang, Wei; Li, Ying; Chen, Ting; Wang, Xuebing; Chen, Zhiqiang; Welch, David; Zhu, Pinwen; Liu, Bingbing; Li, Qiang; Cui, Tian; Li, Baosheng

2016-02-29

Since the discovery of superconductivity in boron-doped diamond with a critical temperature (TC) near 4 K, great interest has been attracted in hard superconductors such as transition-metal nitrides and carbides. Here we report the new discovery of superconductivity in polycrystalline hexagonal ε-NbN synthesized at high pressure and high temperature. Direct magnetization and electrical resistivity measurements demonstrate that the superconductivity in bulk polycrystalline hexagonal ε-NbN is below ∼11.6 K, which is significantly higher than that for boron-doped diamond. The nature of superconductivity in hexagonal ε-NbN and the physical mechanism for the relatively lower TC have been addressed by the weaker bonding in the Nb-N network, the co-planarity of Nb-N layer as well as its relatively weaker electron-phonon coupling, as compared with the cubic δ-NbN counterpart. Moreover, the newly discovered ε-NbN superconductor remains stable at pressures up to ∼20 GPa and is significantly harder than cubic δ-NbN; it is as hard as sapphire, ultra-incompressible and has a high shear rigidity of 201 GPa to rival hard/superhard material γ-B (∼227 GPa). This exploration opens a new class of highly desirable materials combining the outstanding mechanical/elastic properties with superconductivity, which may be particularly attractive for its technological and engineering applications in extreme environments.

Discovery of superconductivity in hard hexagonal ε-NbN

DOE PAGES

Zou, Yongtao; Li, Qiang; Qi, Xintong; ...

2016-02-29

Since the discovery of superconductivity in boron-doped diamond with a critical temperature (T C) near 4 K, great interest has been attracted in hard superconductors such as transition-metal nitrides and carbides. Here we report the new discovery of superconductivity in polycrystalline hexagonal ε-NbN synthesized at high pressure and high temperature. Direct magnetization and electrical resistivity measurements demonstrate that the superconductivity in bulk polycrystalline hexagonal ε-NbN is below ~11.6 K, which is significantly higher than that for boron-doped diamond. The nature of superconductivity in hexagonal ε-NbN and the physical mechanism for the relatively lower T C have been addressed by themore » weaker bonding in the Nb-N network, the co-planarity of Nb-N layer as well as its relatively weaker electron-phonon coupling, as compared with the cubic δ-NbN counterpart. Moreover, the newly discovered ε-NbN superconductor remains stable at pressures up to ~20 GPa and is significantly harder than cubic δ-NbN; it is as hard as sapphire, ultra-incompressible and has a high shear rigidity of 201 GPa to rival hard/superhard material γ-B (~227 GPa). Furthermore, this exploration opens a new class of highly desirable materials combining the outstanding mechanical/elastic properties with superconductivity, which may be particularly attractive for its technological and engineering applications in extreme environments.« less

Discovery of Superconductivity in Hard Hexagonal ε-NbN

PubMed Central

Zou, Yongtao; Qi, Xintong; Zhang, Cheng; Ma, Shuailing; Zhang, Wei; Li, Ying; Chen, Ting; Wang, Xuebing; Chen, Zhiqiang; Welch, David; Zhu, Pinwen; Liu, Bingbing; Li, Qiang; Cui, Tian; Li, Baosheng

2016-01-01

Since the discovery of superconductivity in boron-doped diamond with a critical temperature (TC) near 4 K, great interest has been attracted in hard superconductors such as transition-metal nitrides and carbides. Here we report the new discovery of superconductivity in polycrystalline hexagonal ε-NbN synthesized at high pressure and high temperature. Direct magnetization and electrical resistivity measurements demonstrate that the superconductivity in bulk polycrystalline hexagonal ε-NbN is below ∼11.6 K, which is significantly higher than that for boron-doped diamond. The nature of superconductivity in hexagonal ε-NbN and the physical mechanism for the relatively lower TC have been addressed by the weaker bonding in the Nb-N network, the co-planarity of Nb-N layer as well as its relatively weaker electron-phonon coupling, as compared with the cubic δ-NbN counterpart. Moreover, the newly discovered ε-NbN superconductor remains stable at pressures up to ∼20 GPa and is significantly harder than cubic δ-NbN; it is as hard as sapphire, ultra-incompressible and has a high shear rigidity of 201 GPa to rival hard/superhard material γ-B (∼227 GPa). This exploration opens a new class of highly desirable materials combining the outstanding mechanical/elastic properties with superconductivity, which may be particularly attractive for its technological and engineering applications in extreme environments. PMID:26923318

On diamond, graphitic and amorphous carbons in primitive extraterrestrial solar system materials

NASA Technical Reports Server (NTRS)

Rietmeijer, Frans J. M.

1990-01-01

Carbon is among the most abundant elements in the universe and carbon chemistry in meteorites and comets is an important key to understanding many Solar System and interstellar processes. Yet, the mineralogical properties and interrelations between various structural forms of elemental carbon remain ambiguous. Crystalline elemental carbons include rhombohedral graphite, hexagonal graphite, cubic diamond, hexagonal diamond (i.e., lonsdaleite or carbon-2H) and chaoite. Elemental carbon also occurs as amorphous carbon and poorly graphitized (or turbostratic) carbon but of all the forms of elemental carbon only graphite is stable under physical conditions that prevail in small Solar System bodies and in the interstellar medium. The recent discovery of cubic diamond in carbonaceous chondrites and hexagonal diamond in chondritic interplanetary dust particles (IDPs) have created a renewed interest in the crystalline elemental carbons that were not formed by shock processes on a parent body. Another technique, Raman spectroscopy, confirms a widespread occurrence of disordered graphite in the Allende carbonaceous chondrite and in chondritic IDPs. Elemental carbons have also been identified by their characteristic K-edge features in electron energy loss spectra (EELS). However, the spectroscopic data do not necessarily coincide with those obtained by selected area electron diffraction (SAED). In order to interpret these data in terms of rational crystalline structures, it may be useful to consider the principles underlying electron diffraction and spectroscopic analyses. Electron diffraction depends on electron scattering, on the type of atom and the distance between atoms in a crystal lattice. Spectroscopic data are a function of the type of atom and the energy of bonds between atoms. Also, SAED is a bulk sampling technique when compared to techniques such as Raman spectroscopy or EELS. Thus, it appears that combined analyses provide contradictory results and that amorphous, or short-range ordered, carbon identified by conventional TEM imaging and SAED may show evidence for sp(3) bonds in EELS spectra. It is suggested that complex, nanometer-scale, mineralogical interrelations are common to all elemental carbons irrespective of their origin. The subsequent thermal history, or energy balance, will determine the ultimate microstructure.

Low pressure growth of cubic boron nitride films

NASA Technical Reports Server (NTRS)

Ong, Tiong P. (Inventor); Shing, Yuh-Han (Inventor)

1997-01-01

A method for forming thin films of cubic boron nitride on substrates at low pressures and temperatures. A substrate is first coated with polycrystalline diamond to provide a uniform surface upon which cubic boron nitride can be deposited by chemical vapor deposition. The cubic boron nitride film is useful as a substitute for diamond coatings for a variety of applications in which diamond is not suitable. any tetragonal or hexagonal boron nitride. The cubic boron nitride produced in accordance with the preceding example is particularly well-suited for use as a coating for ultra hard tool bits and abrasives, especially those intended to use in cutting or otherwise fabricating iron.

Static high-pressure structural studies on Dy to 119 GPa

NASA Astrophysics Data System (ADS)

Patterson, Reed; Saw, Cheng K.; Akella, Jagannadham

2004-05-01

Structural phase transitions in the rare-earth metal dysprosium have been studied in a diamond anvil cell to 119 GPa by x-ray diffraction. Four transformations following the sequence hcp→Sm-type→dhcp→hR24 (hexagonal)→bcm (monoclinic) are observed at 6, 15, 43, and 73 GPa, respectively. The hexagonal to monoclinic transformation is accompanied by a 6% reduction in volume, which is attributed to delocalization of the 4f electrons, similar to that seen in Ce, Pr, and Gd.

In situ observation of shear-driven amorphization in silicon crystals.

PubMed

He, Yang; Zhong, Li; Fan, Feifei; Wang, Chongmin; Zhu, Ting; Mao, Scott X

2016-10-01

Amorphous materials are used for both structural and functional applications. An amorphous solid usually forms under driven conditions such as melt quenching, irradiation, shock loading or severe mechanical deformation. Such extreme conditions impose significant challenges on the direct observation of the amorphization process. Various experimental techniques have been used to detect how the amorphous phases form, including synchrotron X-ray diffraction, transmission electron microscopy (TEM) and Raman spectroscopy, but a dynamic, atomistic characterization has remained elusive. Here, by using in situ high-resolution TEM (HRTEM), we show the dynamic amorphization process in silicon nanocrystals during mechanical straining on the atomic scale. We find that shear-driven amorphization occurs in a dominant shear band starting with the diamond-cubic (dc) to diamond-hexagonal (dh) phase transition and then proceeds by dislocation nucleation and accumulation in the newly formed dh-Si phase. This process leads to the formation of an amorphous Si (a-Si) band, embedded with dh-Si nanodomains. The amorphization of dc-Si via an intermediate dh-Si phase is a previously unknown pathway of solid-state amorphization.

Real-Time Examination of Atomistic Mechanisms during Shock-Induced Structural Transformation in Silicon

DOE PAGES

Turneaure, Stefan J.; Sinclair, N.; Gupta, Y. M.

2016-07-20

Experimental determination of atomistic mechanisms linking crystal structures during a compression driven solid-solid phase transformation is a long standing and challenging scientific objective. Also, when using new capabilities at the Dynamic Compression Sector at the Advanced Photon Source, the structure of shocked Si at 19 GPa was identified as simple hexagonal and the lattice orientations between ambient cubic diamond and simple hexagonal structures were related. Furthermore, this approach is general and provides a powerful new method for examining atomistic mechanisms during stress-induced structural changes.

Static High Pressure Structural studies on Dy to 119 GPa

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

Patterson, J R; Saw, C K; Akella, J

2003-11-12

Structural phase transitions in the rare-earth metal Dysprosium have been studied in a Diamond Anvil Cell (DAC) to 119 GPa by x-ray diffraction. Four transformations following the sequence hcp {yields} Sm-type {yields} dhcp {yields} hR24 (hexagonal) {yields} bcm (monoclinic) are observed at 6, 15, 43, and 73 GPa respectively. The hexagonal to monoclinic transformation is accompanied by a 6% reduction in volume, which is attributed to delocalization of the 4f electrons, similar to that seen in Ce, Pr, and Gd.

Thermal stability of simple tetragonal and hexagonal diamond germanium

DOE PAGES

Huston, Larissa Q.; Johnson, Brett C.; Haberl, Bianca; ...

2017-11-07

Here, exotic phases of germanium, that form under high pressure but persist under ambient conditions, are of technological interest due to their unique optical and electrical properties. The thermal evolution and stability of two of these exotic Ge phases, the simple tetragonal (st12) and hexagonal diamond (hd) phases, are investigated in detail. These metastable phases, formed by high pressure decompression in either a diamond anvil cell or by nanoindentation, are annealed at temperatures ranging from 280 to 320 °C for st12-Ge and 200 to 550 °C for hd-Ge. In both cases, the exotic phases originated from entirely pure Ge precursormore » materials. Raman microspectroscopy is used to monitor the phase changes ex situ following annealing. Our results show that hd-Ge synthesized via a pure form of a-Ge first undergoes a subtle change in structure and then an irreversible phase transformation to dc-Ge with an activation energy of (4.3 ± 0.2) eV at higher temperatures. St12-Ge was found to transform to dc-Ge with an activation energy of (1.44 ± 0.08) eV. Taken together with results from previous studies, this study allows for intriguing comparisons with silicon and suggests promising technological applications.« less

Thermal stability of simple tetragonal and hexagonal diamond germanium

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

Huston, Larissa Q.; Johnson, Brett C.; Haberl, Bianca

Here, exotic phases of germanium, that form under high pressure but persist under ambient conditions, are of technological interest due to their unique optical and electrical properties. The thermal evolution and stability of two of these exotic Ge phases, the simple tetragonal (st12) and hexagonal diamond (hd) phases, are investigated in detail. These metastable phases, formed by high pressure decompression in either a diamond anvil cell or by nanoindentation, are annealed at temperatures ranging from 280 to 320 °C for st12-Ge and 200 to 550 °C for hd-Ge. In both cases, the exotic phases originated from entirely pure Ge precursormore » materials. Raman microspectroscopy is used to monitor the phase changes ex situ following annealing. Our results show that hd-Ge synthesized via a pure form of a-Ge first undergoes a subtle change in structure and then an irreversible phase transformation to dc-Ge with an activation energy of (4.3 ± 0.2) eV at higher temperatures. St12-Ge was found to transform to dc-Ge with an activation energy of (1.44 ± 0.08) eV. Taken together with results from previous studies, this study allows for intriguing comparisons with silicon and suggests promising technological applications.« less

Ab initio structure determination of n-diamond.

PubMed

Li, Da; Tian, Fubo; Chu, Binhua; Duan, Defang; Sha, Xiaojing; Lv, Yunzhou; Zhang, Huadi; Lu, Nan; Liu, Bingbing; Cui, Tian

2015-08-24

A systematic computational study on the crystal structure of n-diamond has been performed using first-principle methods. A novel carbon allotrope with hexagonal symmetry R32 space group has been predicted. We name it as HR-carbon. HR-carbon composed of lonsdaleite layers and unique C3 isosceles triangle rings, is stable over graphite phase above 14.2 GPa. The simulated x-ray diffraction pattern, Raman, and energy-loss near-edge spectrum can match the experimental results very well, indicating that HR-carbon is a likely candidate structure for n-diamond. HR-carbon has an incompressible atomic arrangement because of unique C3 isosceles triangle rings. The hardness and bulk modulus of HR-carbon are calculated to be 80 GPa and 427 GPa, respectively, which are comparable to those of diamond. C3 isosceles triangle rings are very important for the stability and hardness of HR-carbon.

Shear-driven phase transformation in silicon nanowires

NASA Astrophysics Data System (ADS)

Vincent, L.; Djomani, D.; Fakfakh, M.; Renard, C.; Belier, B.; Bouchier, D.; Patriarche, G.

2018-03-01

We report on an unprecedented formation of allotrope heterostructured Si nanowires by plastic deformation based on applied radial compressive stresses inside a surrounding matrix. Si nanowires with a standard diamond structure (3C) undergo a phase transformation toward the hexagonal 2H-allotrope. The transformation is thermally activated above 500 °C and is clearly driven by a shear-stress relief occurring in parallel shear bands lying on {115} planes. We have studied the influence of temperature and axial orientation of nanowires. The observations are consistent with a martensitic phase transformation, but the finding leads to clear evidence of a different mechanism of deformation-induced phase transformation in Si nanowires with respect to their bulk counterpart. Our process provides a route to study shear-driven phase transformation at the nanoscale in Si.

Shear-driven phase transformation in silicon nanowires.

PubMed

Vincent, L; Djomani, D; Fakfakh, M; Renard, C; Belier, B; Bouchier, D; Patriarche, G

2018-03-23

We report on an unprecedented formation of allotrope heterostructured Si nanowires by plastic deformation based on applied radial compressive stresses inside a surrounding matrix. Si nanowires with a standard diamond structure (3C) undergo a phase transformation toward the hexagonal 2H-allotrope. The transformation is thermally activated above 500 °C and is clearly driven by a shear-stress relief occurring in parallel shear bands lying on {115} planes. We have studied the influence of temperature and axial orientation of nanowires. The observations are consistent with a martensitic phase transformation, but the finding leads to clear evidence of a different mechanism of deformation-induced phase transformation in Si nanowires with respect to their bulk counterpart. Our process provides a route to study shear-driven phase transformation at the nanoscale in Si.

New Occurrence of Shocked Graphite Aggregates at Barringer Crater

NASA Astrophysics Data System (ADS)

Miura, Y.; Noma, Y.; Iancu, O. G.

1993-07-01

High-pressure carbon minera]s are considered to be formed by solid-solid transformation under static or impact high-pressure condition, but shocked quartz aggregates of impact craters are considered to be formed by quenched accretion of various aggregates by dynamic impact process [1-3]. The main purpose of this study is to elucidate new findings and occurrences of shocked graphite (SG) aggregates [2,3] at the Barringer meteorite crater. The graphite nodule block of Barringer Crater used in this study is collected near the rim. The sample is compared with standard graphite samples of Korea, Madagascar, and artificial impact graphites. There are four different mineral aggregates of the Barringer graphite nodule sample: (1) shocked graphite-1, (2) shocked graphite-2 and hexagonal diamond in the vein, (3) shocked quartz-1 (with kamacite) in the rim, and (4) calcite in the rim (Table 1). X-ray diffraction peaks of shocked graphite reveal low X-ray intensity, high Bragg-angle shift of X-ray diffraction peak, and multiple splitting of X-ray diffraction peaks. X-ray calculated density (rho) has been determined by X-ray diffractometer by the equation of density deviation Delta rho (%) = 100 x {(rho-rho(sub)0)/rho(sub)0}, where standard density rho(sub)0 is 2.255 g/cm^3 in Korean graphite [2,3]. The high-density value of shocked graphite grain obtained in Barringer is Delta rho = +0.6 +/- 0.1%. Shocked hexagonal diamonds (chaoite) show a high value of Delta rho = +0.6 +/- 0.9%. Analytical electron microscopy data reveal three different aggregates in the graphite nodule samples (Table 1): (1) shocked graphite-1 in the matrix, which contains uniformly Fe and Ca elements formed under gas state; (2) shocked graphite-2 in the vein, where crystallized shocked graphites and hexagonal diamonds are surrounded by kamacite-rich metals formed under gas-melt states of mixed compositions from iron meteorite and target rocks; and (3) shocked quartz-1 and kamacite in the rim, where coexisted elements are supplied from kamacite, sandstone, and limestone. The shocked quartz-1 grains with high density contain Fe and Ca elements that are different from the shocked quartz-2 of pure silica [1] formed at the final stage from the Coconino sandstone. (4) Limestone in the rim is attached from Kaibab limestone. The present shocked graphites with high density are the same as artificial fine-grained shocked graphites (Delta rho = +0.7%). Table 1, which appears here in the hard copy, shows formation stages with two shocked graphites in the Barringer Crater. Formation of shocked aggregates with chemical contamination indicate dynamic accretion processes of quenching and depression at impact. The existence of two shocked graphites indicates the two formation stages of the first gas-state and the second gas-melt states with quenching processes. The origin of carbon in the shocked graphites is considered in this study to be from Kaibab limestone. References: [1] Miura Y. (1991) Shock Waves, 1, 35-41. [2] Miura Y. (1992) Proc. Shock Waves (Japan), 2, 54-57. [3] Miura Y. et al. (1993) Symp. NIPR Antarctic Meteorite (Tokyo), in press. [4] Foote A. E. (1891) Am. J. Sci., 42, 413-417. [5] Hannemann R. E. et al. (1967) Science, 155, 995-997.

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

Han,W.Q.

Boron nitride (BN) is a synthetic binary compound located between III and V group elements in the Periodic Table. However, its properties, in terms of polymorphism and mechanical characteristics, are rather close to those of carbon compared with other III-V compounds, such as gallium nitride. BN crystallizes into a layered or a tetrahedrally linked structure, like those of graphite and diamond, respectively, depending on the conditions of its preparation, especially the pressure applied. Such correspondence between BN and carbon readily can be understood from their isoelectronic structures [1, 2]. On the other hand, in contrast to graphite, layered BN ismore » transparent and is an insulator. This material has attracted great interest because, similar to carbon, it exists in various polymorphic forms exhibiting very different properties; however, these forms do not correspond strictly to those of carbon. Crystallographically, BN is classified into four polymorphic forms: Hexagonal BN (h-BN) (Figure 1(b)); rhombohedral BN (r-BN); cubic BN (c-BN); and wurtzite BN (w-BN). BN does not occur in nature. In 1842, Balmain [3] obtained BN as a reaction product between molten boric oxide and potassium cyanide under atmospheric pressure. Thereafter, many methods for its synthesis were reported. h-BN and r-BN are formed under ambient pressure. c-BN is synthesized from h-BN under high pressure at high temperature while w-BN is prepared from h-BN under high pressure at room temperature [1]. Each BN layer consists of stacks of hexagonal plate-like units of boron and nitrogen atoms linked by SP{sup 2} hybridized orbits and held together mainly by Van der Waals force (Fig 1(b)). The hexagonal polymorph has two-layered repeating units: AA'AA'... that differ from those in graphite: ABAB... (Figure 1(a)). Within the layers of h-BN there is coincidence between the same phases of the hexagons, although the boron atoms and nitrogen atoms are alternatively located along the c-axis. The rhombohedral system consists of three-layered units: ABCABC..., whose honeycomb layers are arranged in a shifted phase, like as those of graphite. Reflecting its weak interlayer bond, the h-BN can be cleaved easily along its layers, and hence, is widely used as a lubricant material. The material is stable up to a high temperature of 2300 C before decomposition sets in [2] does not fuse a nitrogen atmosphere of 1 atm, and thus, is applicable as a refractory material. Besides having such properties, similar to those of graphite, the material is transparent, and acts as a good electric insulator, especially at high temperatures (10{sup 6} {Omega}m at 1000 C) [1]. c-BN and w-BN are tetrahedrally linked BN. The former has a cubic sphalerite-type structure, and the latter has a hexagonal wurtzite-type structure. c-BN is the second hardest known material (the hardest is diamond), the so-called white diamond. It is used mainly for grinding and cutting industrial ferrous materials because it does not react with molten iron, nickel, and related alloys at high temperatures whereas diamond does [1]. It displays the second highest thermal conductivity (6-9 W/cm.deg) after diamond. This chapter focuses principally upon information about h-BN nanomaterials, mainly BN nanotubes (BNNTs), porous BN, mono- and few-layer-BN sheets. There are good reviews book chapters about c-BN in [1, 4-6].« less

Crystalline structures of particles interacting through the harmonic-repulsive pair potential

NASA Astrophysics Data System (ADS)

Levashov, V. A.

2017-09-01

The behavior of identical particles interacting through the harmonic-repulsive pair potential has been studied in 3D using molecular dynamics simulations at a number of different densities. We found that at many densities, as the temperature of the systems decreases, the particles crystallize into complex structures whose formation has not been anticipated in previous studies on the harmonic-repulsive pair potential. In particular, at certain densities, crystallization into the structure I a 3 ¯ d (space group #230) with 16 particles in the unit cell occupying Wyckoff special positions (16b) was observed. This crystal structure has not been observed previously in experiments or in computer simulations of single component atomic or soft matter systems. At another density, we observed a liquid which is rather stable against crystallization. Yet, we observed crystallization of this liquid into the monoclinic C2/c (space group #15) structure with 32 particles in the unit cell occupying four different non-special Wyckoff (8f) sites. In this structure particles located at different Wyckoff sites have different energies. From the perspective of the local atomic environment, the organization of particles in this structure resembles the structure of some columnar quasicrystals. At a different value of the density, we did not observe crystallization at all despite rather long molecular dynamics runs. At two other densities, we observed the formation of the β S n distorted diamond structures instead of the expected diamond structure. Possibly, we also observed the formation of the R 3 ¯ c hexagonal lattice with 24 particles per unit cell occupying non-equivalent positions.

Magnetically Orchestrated Formation of Diamond at Lower Temperatures and Pressures

NASA Astrophysics Data System (ADS)

Little, Reginald B.; Lochner, Eric; Goddard, Robert

2005-01-01

Man's curiosity and fascination with diamonds date back to ancient times. The knowledge of the many properties of diamond is recorded during Biblical times. Antoine Lavoisier determined the composition of diamond by burning in O2 to form CO2. With the then existing awareness of graphite as carbon, the race began to convert graphite to diamond. The selective chemical synthesis of diamond has been pursued by Cagniard, Hannay, Moisson and Parson. On the basis of the thermodynamically predicted equilibrium line of diamond and graphite, P W Bridgman attempted extraordinary conditions of high temperature (>2200°C) and pressure (>100,000 atm) for the allotropic conversion of graphite to diamond. H T Hall was the first to successfully form bulk diamond by realizing the kinetic restrictions to Bridgman's (thermodynamic) high pressure high temperature direct allotropic conversion. Moreover, Hall identified catalysts for the faster kinetics of diamond formation. H M Strong determined the import of the liquid catalyst during Hall's catalytic synthesis. W G Eversole discovered the slow metastable low pressure diamond formation by pyrolytic chemical vapor deposition with the molecular hydrogen etching of the rapidly forming stable graphitic carbon. J C Angus determined the import of atomic hydrogen for faster etching for faster diamond growth at low pressure. S Matsumoto has developed plasma and hot filament technology for faster hydrogen and carbon radical generations at low pressure for faster diamond formation. However the metastable low pressure chemical vapor depositions by plasma and hot filament are prone to polycrystalline films. From Bridgman to Hall to Eversole, Angus and Matsumoto, much knowledge has developed of the importance of pressure, temperature, transition metal catalyst, liquid state of metal (metal radicals atoms) and the carbon radical intermediates for diamond synthesis. Here we advance this understanding of diamond formation by demonstrating the external magnetic organization of carbon, metal and hydrogen radicals for lower temperature and pressure synthesis. Here we show that strong static external magnetic field (>15 T) enhances the formation of single crystal diamond at lower pressure and even atmospheric pressure with implications for much better, faster high quality diamond formation by magnetization of current high pressure and temperature technology.

Bottom-up construction of a superstructure in a porous uranium-organic crystal

NASA Astrophysics Data System (ADS)

Li, Peng; Vermeulen, Nicolaas A.; Malliakas, Christos D.; Gómez-Gualdrón, Diego A.; Howarth, Ashlee J.; Mehdi, B. Layla; Dohnalkova, Alice; Browning, Nigel D.; O'Keeffe, Michael; Farha, Omar K.

2017-05-01

Bottom-up construction of highly intricate structures from simple building blocks remains one of the most difficult challenges in chemistry. We report a structurally complex, mesoporous uranium-based metal-organic framework (MOF) made from simple starting components. The structure comprises 10 uranium nodes and seven tricarboxylate ligands (both crystallographically nonequivalent), resulting in a 173.3-angstrom cubic unit cell enclosing 816 uranium nodes and 816 organic linkers—the largest unit cell found to date for any nonbiological material. The cuboctahedra organize into pentagonal and hexagonal prismatic secondary structures, which then form tetrahedral and diamond quaternary topologies with unprecedented complexity. This packing results in the formation of colossal icosidodecahedral and rectified hexakaidecahedral cavities with internal diameters of 5.0 nanometers and 6.2 nanometers, respectively—ultimately giving rise to the lowest-density MOF reported to date.

Identification of Au–S complexes on Au(100)

DOE PAGES

Walen, Holly; Liu, Da -Jiang; Oh, Junepyo; ...

2016-01-25

In this study, using a combination of scanning tunneling microscopy and density functional theory (DFT) calculations, we have identified a set of related Au–S complexes that form on Au(100), when sulfur adsorbs and lifts the hexagonal surface reconstruction. The predominant complex is diamond-shaped with stoichiometry Au 4S 5. All of the complexes can be regarded as combinations of S–Au–S subunits. The complexes exist within, or at the edges of, p(2 × 2) sulfur islands that cover the unreconstructed Au regions, and are observed throughout the range of S coverage examined in this study, 0.009 to 0.12 monolayers. A qualitative modelmore » is developed which incorporates competitive formation of complexes, Au rafts, and p(2 × 2) sulfur islands, as Au atoms are released by the surface structure transformation.« less

A topological coordinate system for the diamond cubic grid.

PubMed

Čomić, Lidija; Nagy, Benedek

2016-09-01

Topological coordinate systems are used to address all cells of abstract cell complexes. In this paper, a topological coordinate system for cells in the diamond cubic grid is presented and some of its properties are detailed. Four dependent coordinates are used to address the voxels (triakis truncated tetrahedra), their faces (hexagons and triangles), their edges and the points at their corners. Boundary and co-boundary relations, as well as adjacency relations between the cells, can easily be captured by the coordinate values. Thus, this coordinate system is apt for implementation in various applications, such as visualizations, morphological and topological operations and shape analysis.

Synthesis of thin films in boron-carbon-nitrogen ternary system by microwave plasma enhanced chemical vapor deposition

NASA Astrophysics Data System (ADS)

Kukreja, Ratandeep Singh

The Boron Carbon Nitorgen (B-C-N) ternary system includes materials with exceptional properties such as wide band gap, excellent thermal conductivity, high bulk modulus, extreme hardness and transparency in the optical and UV range that find application in most fields ranging from micro-electronics, bio-sensors, and cutting tools to materials for space age technology. Interesting materials that belong to the B-C-N ternary system include Carbon nano-tubes, Boron Carbide, Boron Carbon Nitride (B-CN), hexagonal Boron Nitride ( h-BN), cubic Boron Nitride (c-BN), Diamond and beta Carbon Nitride (beta-C3N4). Synthesis of these materials requires precisely controlled and energetically favorable conditions. Chemical vapor deposition is widely used technique for deposition of thin films of ceramics, metals and metal-organic compounds. Microwave plasma enhanced chemical vapor deposition (MPECVD) is especially interesting because of its ability to deposit materials that are meta-stable under the deposition conditions, for e.g. diamond. In the present study, attempt has been made to synthesize beta-carbon nitride (beta-C3N4) and cubic-Boron Nitride (c-BN) thin films by MPECVD. Also included is the investigation of dependence of residual stress and thermal conductivity of the diamond thin films, deposited by MPECVD, on substrate pre-treatment and deposition temperature. Si incorporated CNx thin films are synthesized and characterized while attempting to deposit beta-C3N4 thin films on Si substrates using Methane (CH4), Nitrogen (N2), and Hydrogen (H2). It is shown that the composition and morphology of Si incorporated CNx thin film can be tailored by controlling the sequence of introduction of the precursor gases in the plasma chamber. Greater than 100mum size hexagonal crystals of N-Si-C are deposited when Nitrogen precursor is introduced first while agglomerates of nano-meter range graphitic needles of C-Si-N are deposited when Carbon precursor is introduced first in the deposition chamber. Hexagonal -- BN thin films are successfully deposited using Diborane (B2H6) (5% in H2), Ammonia (NH3) and H2 as precursor gases in the conventional MPECVD mode with and without the negative DC bias. The quality of h-BN in the films improved with pressure and when NH3 used as the first precursor gas in the deposition chamber. c-BN thin films are successfully deposited using Boron-Trifluoride (BF3) (10% in Argon (Ar)), N2, H2, Ar and Helium (He) gases in the electron cyclotron resonance (ECR) mode of the MPECVD system with negative DC bias. Up-to 66% c-BN in the films is achieved under deposition conditions of lower gas flow rates and higher deposition pressures than that reported in the literature for film deposited by ECR-MPECVD. It is shown that the percentage c-BN in the films correlates with the deposition pressure, BF3/H2 ratio and, negative DC bias during nucleation and growth. Diamond thin films are deposited using 60%Ar, 39% H2 and, 1%CH4 at 600°C, 700°C and 800°C substrate temperatures, measured by an IR pyrometer, on Si substrates pre-treated with 3-6nm diamond sol and 20-40mum diamond slurry. Raman spectroscopy, FTIR, X-Ray diffraction (XRD) and, photo-thermal reflectivity methods are used to characterize the thin films. Residual stresses observed for the diamond thin films deposited in this study are tensile in nature and increased with deposition temperature. Better quality diamond films with lower residual stresses are obtained for films deposited on Si substrate pre-treated with 3-6nm diamond sol. Preliminary results on thermal conductivity, k, suggest that k is directly dependent on the deposition temperature and independent of substrate pre-treatment signifying that the nano-seeding technique can be used to replace conventional surface activation technique for diamond seeding where needed.

n-Type diamond and method for producing same

DOEpatents

Anderson, Richard J.

2002-01-01

A new n-type semiconducting diamond is disclosed, which is doped with n-type dopant atoms. Such diamond is advantageously formed by chemical vapor deposition from a source gas mixture comprising a carbon source compound for the diamond, and a volatile hot wire filament for the n-type impurity species, so that the n-type impurity atoms are doped in the diamond during its formation. A corresponding chemical vapor deposition method of forming the n-type semiconducting diamond is disclosed. The n-type semiconducting diamond of the invention may be usefully employed in the formation of diamond-based transistor devices comprising pn diamond junctions, and in other microelectronic device applications.

Magnetic transition temperatures follow crystallographic symmetry in Samarium under high-pressures and low-temperatures

DOE PAGES

Vohra, Yogesh K.; Tsoi, Georgiy M.; Johnson, Craig R.

2016-12-21

Magnetic ordering temperatures in rare earth metal samarium (Sm) have been studied using an ultrasensitive electrical transport measurement technique in a designer diamond anvil cell to high-pressure up to 47 GPa and low-temperature to 10 K. The two magnetic transitions at 106 K and 14 K in the α-Sm phase, attributed to antiferromagnetic ordering on hexagonal and cubic layers respectively, collapse in to one magnetic transition near 10 GPa when Sm assumes a double hexagonal close packed (dhcp) phase. On further increase in pressure above 34 GPa, the magnetic transitions split again as Sm adopts a hexagonal-hP3 structure indicating differentmore » magnetic transition temperatures for different crystallographic sites. A model for magnetic ordering for the hexagonal-hP3 phase in samarium has been proposed based on the experimental data. The magnetic transition temperatures closely follow the crystallographic symmetry during α-Sm → dhcp → fcc/dist.fcc → hP3 structure sequence at high-pressures and low-temperatures.« less

Magnetic transition temperatures follow crystallographic symmetry in Samarium under high-pressures and low-temperatures

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

Vohra, Yogesh K.; Tsoi, Georgiy M.; Johnson, Craig R.

Magnetic ordering temperatures in rare earth metal samarium (Sm) have been studied using an ultrasensitive electrical transport measurement technique in a designer diamond anvil cell to high-pressure up to 47 GPa and low-temperature to 10 K. The two magnetic transitions at 106 K and 14 K in the α-Sm phase, attributed to antiferromagnetic ordering on hexagonal and cubic layers respectively, collapse in to one magnetic transition near 10 GPa when Sm assumes a double hexagonal close packed (dhcp) phase. On further increase in pressure above 34 GPa, the magnetic transitions split again as Sm adopts a hexagonal-hP3 structure indicating differentmore » magnetic transition temperatures for different crystallographic sites. A model for magnetic ordering for the hexagonal-hP3 phase in samarium has been proposed based on the experimental data. The magnetic transition temperatures closely follow the crystallographic symmetry during α-Sm → dhcp → fcc/dist.fcc → hP3 structure sequence at high-pressures and low-temperatures.« less

Magnetic transition temperatures follow crystallographic symmetry in samarium under high-pressures and low-temperatures

NASA Astrophysics Data System (ADS)

Johnson, Craig R.; Tsoi, Georgiy M.; Vohra, Yogesh K.

2017-02-01

Magnetic ordering temperatures in rare earth metal samarium (Sm) have been studied using an ultrasensitive electrical transport measurement technique in a designer diamond anvil cell to high-pressure up to 47 GPa and low-temperature to 10 K. The two magnetic transitions at 106 K and 14 K in the α-Sm phase, attributed to antiferromagnetic ordering on hexagonal and cubic layers respectively, collapse in to one magnetic transition near 10 GPa when Sm assumes a double hexagonal close packed (dhcp) phase. On further increase in pressure above 34 GPa, the magnetic transitions split again as Sm adopts a hexagonal-hP3 structure indicating different magnetic transition temperatures for different crystallographic sites. A model for magnetic ordering for the hexagonal-hP3 phase in samarium has been proposed based on the experimental data. The magnetic transition temperatures closely follow the crystallographic symmetry during α-Sm  →  dhcp  →  fcc/dist.fcc  →  hP3 structure sequence at high-pressures and low-temperatures.

Magnetic transition temperatures follow crystallographic symmetry in samarium under high-pressures and low-temperatures.

PubMed

Johnson, Craig R; Tsoi, Georgiy M; Vohra, Yogesh K

2017-02-15

Magnetic ordering temperatures in rare earth metal samarium (Sm) have been studied using an ultrasensitive electrical transport measurement technique in a designer diamond anvil cell to high-pressure up to 47 GPa and low-temperature to 10 K. The two magnetic transitions at 106 K and 14 K in the α-Sm phase, attributed to antiferromagnetic ordering on hexagonal and cubic layers respectively, collapse in to one magnetic transition near 10 GPa when Sm assumes a double hexagonal close packed (dhcp) phase. On further increase in pressure above 34 GPa, the magnetic transitions split again as Sm adopts a hexagonal-hP3 structure indicating different magnetic transition temperatures for different crystallographic sites. A model for magnetic ordering for the hexagonal-hP3 phase in samarium has been proposed based on the experimental data. The magnetic transition temperatures closely follow the crystallographic symmetry during α-Sm  →  dhcp  →  fcc/dist.fcc  →  hP3 structure sequence at high-pressures and low-temperatures.

Optical Design of Segmented Hexagon Array Solar Mirror

NASA Technical Reports Server (NTRS)

Huegele, Vince

2000-01-01

A segmented array of mirrors was designed for a solar concentrator test stand at MSFC for firing solar thermal propulsion engines. The 144 mirrors each have a spherical surface to approximate a parabolic concentrator when combined into the entire 18-foot diameter array. The mirror segments are aluminum hexagons that had the surface diamond turned and quartz coated. The array focuses sunlight reflected from a heliostat to a 4 inch diameter spot containing 10 kw of power at the 15-foot focal point. The derivation of the surface figure for the respective mirror elements is shown. The alignment process of the array is discussed and test results of the system's performance is given.

Novel polymer composite having diamond particles and boron nitride platelets for thermal management of electric vehicle motors

NASA Astrophysics Data System (ADS)

Nakajima, Anri; Shoji, Atsushi; Yonemori, Kei; Seo, Nobuhide

2016-02-01

Thermal conductivities of silicone matrix polymers including fillers of diamond particles and/or hexagonal boron nitride (h-BN) platelets were systematically investigated in an attempt to find a thermal interface material (TIM) having high isotropic thermal conductivity and high electrical insulating ability to enable efficient heat dissipation from the motor coil ends of electric vehicles. The TIM with mixed fillers of diamond particles and h-BN platelets had a maximum thermal conductivity of 6.1 W m-1 K-1 that was almost isotropic. This is the highest value among the thermal conductivities of TIMs with silicone matrix polymer reported to date. The mechanism behind the thermal conductivity of the TIMs was also examined from the viewpoint of the change in the number of thermally conductive networks and/or a decrease in the thermal resistivity of junctions of neighboring diamond particles through the incorporation of h-BN platelets. The TIMs developed in this study will make it possible to manage the heat of electric motors and will help to popularize electric vehicles.

Bottom-up construction of a superstructure in a porous uranium-organic crystal

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

Li, Peng; Vermeulen, Nicolaas A.; Malliakas, Christos D.

Bottom-up construction of highly intricate structures from simple building blocks remains one of the most difficult challenges in chemistry. We report a structurally complex, mesoporous uranium-based metal-organic framework (MOF) made from simple starting components. The structure comprises 10 uranium nodes and seven tricarboxylate ligands (both crystallographically nonequivalent), resulting in a 173.3-angstrom cubic unit cell enclosing 816 uranium nodes and 816 organic linkers—the largest unit cell found to date for any nonbiological material. The cuboctahedra organize into pentagonal and hexagonal prismatic secondary structures, which then form tetrahedral and diamond quaternary topologies with unprecedented complexity. This packing results in the formation ofmore » colossal icosidodecahedral and rectified hexakaidecahedral cavities with internal diameters of 5.0 nanometers and 6.2 nanometers, respectively—ultimately giving rise to the lowest-density MOF reported to date.« less

Data science implications in diamond formation and craton evolution

NASA Astrophysics Data System (ADS)

Pan, F.; Huang, F.; Fox, P. A.

2017-12-01

Diamonds are so-called "messengers" from the deep Earth. Fluid and mineral inclusions in diamonds could reflect the compositions of fluids/melts and wall-rocks in which diamond formed. Recently many diamond samples are examined to study the water content in the mantle transition zone1, the mechanism of diamond formation2 and the mantle evolution history3. However, most of the studies can only explain local activities. Therefore, an overall project of data grouping, comparison and correlation is needed, but limited progress has been made due to a lack of benchmark datasets on diamond formation and effective computing algorithms. In this study, we start by proposing the very first complete and easily-accessible dataset on mineral and fluid inclusions in diamonds. We rescue, collect and organize the data available from papers, journals and other publications resources ([2-4] and more), and then apply several state-of-the-art machine learning methods to tackle this earth science problem by clustering diamond formation process into distinct groups primarily based on the compositions, the formation temperature and pressure, the age and so on. Our ongoing work includes further data exploration and training existing models. Our preliminary results show that diamonds formed from older cratons usually have higher formation temperature. Also peridotitic diamonds take a much larger population than the ecologitic ones. More details are being discovered when we finish constructing the database and training our model. We expect the result to demonstrate the advantages of using machine learning and data science in earth science research problems. Our methodology for knowledge discovery are very general and can be broadly applied to other earth science research problems under the same framework.[1] Pearson et al, Nature (2014); [2] Tomlinson et al, EPSL (2006); [3] Weiss et al, Nature (2016); [4] Stachel and Harris, Ore Geology Reviews (2008); Weiss et al, EPSL (2013)

Effects of rapid thermal annealing on the contact of tungsten/p-diamond

NASA Astrophysics Data System (ADS)

Zhao, D.; Li, F. N.; Liu, Z. C.; Chen, X. D.; Wang, Y. F.; Shao, G. Q.; Zhu, T. F.; Zhang, M. H.; Zhang, J. W.; Wang, J. J.; Wang, W.; Wang, H. X.

2018-06-01

The electrical properties, surface morphology and interface characteristics of W/p-diamond contact before and after annealing have been investigated. It is shown that the as-fabricated W/p-diamond contact exhibited non-linear behavior. After annealing at a temperature higher than 400 °C, the W/p-diamond contact showed ohmic behaviour. The specific contact resistance of W/p-diamond was 8.2 × 10-4 Ω·cm2 after annealing at 500 °C for 3 min in a N2 ambient, which was extracted from fitting the I-V relationship of TLM. It is noted that the RMS roughness increases with the annealing temperature increasing, which could be ascribed to the formation of WOX by the reaction of W and oxygen at high temperature. The XPS measurement showed that the barrier height of the W/p-diamond is 0.45 ± 0.12 eV after annealing at 500 °C. Furthermore, the formation of defects at the W/p-diamond interface, probably created by the formation of tungsten carbide during rapid thermal annealing, should be responsible for the ohmic formation of W/p-diamond after annealing at high temperature.

Diamond formation due to a pH drop during fluid–rock interactions

DOE PAGES

Sverjensky, Dimitri A.; Huang, Fang

2015-11-03

Diamond formation has typically been attributed to redox reactions during precipitation from fluids or magmas. Either the oxidation of methane or the reduction of carbon dioxide has been suggested, based on simplistic models of deep fluids consisting of mixtures of dissolved neutral gas molecules without consideration of aqueous ions. The role of pH changes associated with water–silicate rock interactions during diamond formation is unknown. Here we show that diamonds could form due to a drop in pH during water–rock interactions. We use a recent theoretical model of deep fluids that includes ions, to show that fluid can react irreversibly withmore » eclogite at 900 °C and 5.0 GPa, generating diamond and secondary minerals due to a decrease in pH at almost constant oxygen fugacity. Overall, our results constitute a new quantitative theory of diamond formation as a consequence of the reaction of deep fluids with the rock types that they encounter during migration. Diamond can form in the deep Earth during water–rock interactions without changes in oxidation state.« less

Diamond formation due to a pH drop during fluid–rock interactions

PubMed Central

Sverjensky, Dimitri A.; Huang, Fang

2015-01-01

Diamond formation has typically been attributed to redox reactions during precipitation from fluids or magmas. Either the oxidation of methane or the reduction of carbon dioxide has been suggested, based on simplistic models of deep fluids consisting of mixtures of dissolved neutral gas molecules without consideration of aqueous ions. The role of pH changes associated with water–silicate rock interactions during diamond formation is unknown. Here we show that diamonds could form due to a drop in pH during water–rock interactions. We use a recent theoretical model of deep fluids that includes ions, to show that fluid can react irreversibly with eclogite at 900 °C and 5.0 GPa, generating diamond and secondary minerals due to a decrease in pH at almost constant oxygen fugacity. Overall, our results constitute a new quantitative theory of diamond formation as a consequence of the reaction of deep fluids with the rock types that they encounter during migration. Diamond can form in the deep Earth during water–rock interactions without changes in oxidation state. PMID:26529259

Li15Al3Si6 (Li14.6Al3.4Si6), a compound displaying a heterographite-like anionic framework.

PubMed

Spina, Laurent; Tillard, Monique; Belin, Claude

2003-02-01

The title compound, lithium aluminium silicide (15/3/6), crystallizes in the hexagonal centrosymmetric space group P6(3)/m. The three-dimensional structure of this ternary compound may be depicted as two interpenetrating lattices, namely a graphite-like Li(3)Al(3)Si(6) layer and a distorted diamond-like lithium lattice. As is commonly found for LiAl alloys, the Li and Al atoms are found to share some crystallographic sites. The diamond-like lattice is built up of Li cations, and the graphite-like anionic layer is composed of Si, Al and Li atoms in which Si and Al are covalently bonded [Si-Al = 2.4672 (4) A].

Thermal evolution of the metastable r8 and bc8 polymorphs of silicon

DOE PAGES

Haberl, Bianca; Guthrie, Malcolm; Sinogeikin, Stanislav V.; ...

2015-01-28

The kinetics of two metastable polymorphs of silicon under thermal annealing was investigated. These phases with body-centered cubic bc8 and rhombohedral r8 structures can be formed upon pressure release from metallic silicon.We study these metastable polymorphs were formed by two different methods, via point loading and in a diamond anvil cell (DAC). Upon thermal annealing different transition pathways were detected. In the point loading case, the previously reported Si-XIII formed and was confirmed as a new phase with an as-yet-unidentified structure. In the DAC case, bc8-Si transformed to the hexagonal-diamond structure at elevated pressure, consistent with previous studies at ambientmore » pressure. In contrast, r8-Si transformed directly to diamond-cubic Si at a temperature of 255⁰C. In conclusion, these data were used to construct diagrams of the metastability regimes of the polymorphs formed in a DAC and may prove useful for potential technological applications of these metastable polymorphs.« less

Thermal evolution of the metastable r8 and bc8 polymorphs of silicon

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

Haberl, Bianca; Guthrie, Malcolm; Sinogeikin, Stanislav V.

The kinetics of two metastable polymorphs of silicon under thermal annealing was investigated. These phases with body-centered cubic bc8 and rhombohedral r8 structures can be formed upon pressure release from metallic silicon.We study these metastable polymorphs were formed by two different methods, via point loading and in a diamond anvil cell (DAC). Upon thermal annealing different transition pathways were detected. In the point loading case, the previously reported Si-XIII formed and was confirmed as a new phase with an as-yet-unidentified structure. In the DAC case, bc8-Si transformed to the hexagonal-diamond structure at elevated pressure, consistent with previous studies at ambientmore » pressure. In contrast, r8-Si transformed directly to diamond-cubic Si at a temperature of 255⁰C. In conclusion, these data were used to construct diagrams of the metastability regimes of the polymorphs formed in a DAC and may prove useful for potential technological applications of these metastable polymorphs.« less

Symmetry and Structure of Cubic Semiconductor Surfaces.

PubMed

Jenkins, Stephen J

2017-11-07

A systematic stereographic approach to the description of surface symmetry and structure, applied previously to face-centered cubic, body-centered cubic, and hexagonal close-packed metals, is here extended to the surfaces of diamond-structure and zinc-blende-structure semiconductors. A variety of symmetry-structure combinations are categorized and the chiral properties of certain cases emphasized. A general condition for nonpolarity in the surfaces of zincblende materials is also noted.

Phase diagram of carbon and the factors limiting the quantity and size of natural diamonds

NASA Astrophysics Data System (ADS)

Blank, Vladimir D.; Churkin, Valentin D.; Kulnitskiy, Boris A.; Perezhogin, Igor A.; Kirichenko, Alexey N.; Denisov, Viktor N.; Erohin, Sergey V.; Sorokin, Pavel B.; Popov, Mikhail Yu

2018-03-01

Phase diagrams of carbon, and those focusing on the graphite-to-diamond transitional conditions in particular, are of great interest for fundamental and applied research. The present study introduces a number of experiments carried out to convert graphite under high-pressure conditions, showing a formation of stable phase of fullerene-type onions cross-linked by sp3-bonds in the 55-115 GPa pressure range instead of diamonds formation (even at temperature 2000-3000 K) and the already formed diamonds turn into carbon onions. Our results refute the widespread idea that diamonds can form at any pressure from 2.2 to 1000 GPa. The phase diagram built within this study allows us not only to explain the existing numerous experimental data on the formation of diamond from graphite, but also to make assumptions about the conditions of its growth in Earth’s crust.

A new phase transformation path from nanodiamond to new-diamond via an intermediate carbon onion

NASA Astrophysics Data System (ADS)

Xiao, J.; Li, J. L.; Liu, P.; Yang, G. W.

2014-11-01

The investigation of carbon allotropes such as graphite, diamond, fullerenes, nanotubes and carbon onions and mechanisms that underlie their mutual phase transformation is a long-standing problem of great fundamental importance. New diamond (n-diamond) is a novel metastable phase of carbon with a face-centered cubic structure; it is called ``new diamond'' because many reflections in its electron diffraction pattern are similar to those of diamond. However, producing n-diamond from raw carbon materials has so far been challenging due to n-diamond's higher formation energy than that of diamond. Here, we, for the first time, demonstrate a new phase transformation path from nanodiamond to n-diamond via an intermediate carbon onion in the unique process of laser ablation in water, and establish that water plays a crucial role in the formation of n-diamond. When a laser irradiates colloidal suspensions of nanodiamonds at ambient pressure and room temperature, nanodiamonds are first transformed into carbon onions serving as an intermediate phase, and sequentially carbon onions are transformed into n-diamonds driven by the laser-induced high temperature and high pressure from the carbon onion as a nanoscaled temperature and pressure cell upon the process of laser irradiation in a liquid. This phase transformation not only provides new insight into the physical mechanism involved, but also offers one suitable opportunity for breaking controllable pathways between n-diamond and carbon allotropes such as diamond and carbon onions.The investigation of carbon allotropes such as graphite, diamond, fullerenes, nanotubes and carbon onions and mechanisms that underlie their mutual phase transformation is a long-standing problem of great fundamental importance. New diamond (n-diamond) is a novel metastable phase of carbon with a face-centered cubic structure; it is called ``new diamond'' because many reflections in its electron diffraction pattern are similar to those of diamond. However, producing n-diamond from raw carbon materials has so far been challenging due to n-diamond's higher formation energy than that of diamond. Here, we, for the first time, demonstrate a new phase transformation path from nanodiamond to n-diamond via an intermediate carbon onion in the unique process of laser ablation in water, and establish that water plays a crucial role in the formation of n-diamond. When a laser irradiates colloidal suspensions of nanodiamonds at ambient pressure and room temperature, nanodiamonds are first transformed into carbon onions serving as an intermediate phase, and sequentially carbon onions are transformed into n-diamonds driven by the laser-induced high temperature and high pressure from the carbon onion as a nanoscaled temperature and pressure cell upon the process of laser irradiation in a liquid. This phase transformation not only provides new insight into the physical mechanism involved, but also offers one suitable opportunity for breaking controllable pathways between n-diamond and carbon allotropes such as diamond and carbon onions. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr05246c

Eclogitic inclusions in diamonds: Evidence of complex mantle processes over time

NASA Astrophysics Data System (ADS)

Taylor, Lawrence A.; Snyder, Gregory A.; Crozaz, Ghislaine; Sobolev, Vladimir N.; Yefimova, Emiliya S.; Sobolev, Nikolai V.

1996-08-01

The first ion-probe trace element analyses of clinopyroxene-garnet pairs both included within diamonds and from the eclogite host xenoliths are reported; these diamondiferous eclogites are from the Udachnaya and Mir kimberlite pipes, Yakutia, Russia. The major and trace element analyses of these diamond-inclusion and host-rock pairs are compared in order to determine the relative ages of the diamonds, confirm or deny genetic relationships between the diamonds and the eclogites, evaluate models of eclogite petrogenesis, and model igneous processes in the mantle before, during, and after diamond formation. The most striking aspect of the chemical compositions of the diamond inclusions is the diversity of relationships with their eclogite hosts. No single distinct pattern of variation from diamond inclusion minerals to host minerals is found for all four samples. Garnet and clinopyroxene inclusions in the diamonds from two samples (U-65/3 and U-66/3) have lower Mg#s, lower Mg, and higher Fe contents, and lower LREE than those in the host eclogite. We interpret such variations as due to metasomatism of the host eclogite after diamond formation. One sample, U-41/3 shows enrichment in diamond-inclusion MREE enrichment relative to the eclogite host and may indicate a metasomatic event prior to, or during, diamond formation. Bulanova [2] found striking differences between inclusions taken from within different portions of the very same diamond. Clinopyroxene inclusions taken from the central (early) portions of Yakutian diamonds were lower in Mg# and Mg contents (by up to 25%) than those later inclusions at the rims of diamonds. These trends are parallel to those between diamond inclusions and host eclogites determined for four of the five samples from the present study and may merely represent changing magmatic and/or P-T conditions in the mantle. Garnet trace element compositions are similar in relative proportions, but variable in abundances, between diamond inclusions and host eclogites. This is probably due to the rapid diffusion of trace elements in garnet under mantle temperatures and consequent alteration of the garnet, and not due to juvenile diamonds 'locking in' source heterogeneities (c.f., [3]). Trace element compositions of clinopyroxenes included in diamonds are generally similar to those in the host eclogite. However, one host clinopyroxene does show enrichment in the LREE compared to that in the inclusion and may be attributed to mantle metasomatism, not related to kimberlite transport. In another eclogite, M-46, the host clinopyroxene is depleted in the LREE and Fe, and enriched in the HREE and Mg, relative to the inclusion and is consistent with partial melting of the eclogite subsequent to diamond formation. Sm/Nd ratios in clinopyroxenes appear to be little affected by these processes for most samples, allowing SmNd isotopic studies to yield important information about ancient protoliths. Eclogitic mineral inclusions in Yakutian diamonds appear consanguineous with the diamonds, a contention supported by the observations of Bulanova [2]. Therefore, ReOs whole-rock and Sm/Nd clinopyroxene age determinations of the Udachnaya eclogites also yield the time of diamond formation, approximately 2.9 Ga [32,33].

Improvements in the Formation of Boron-Doped Diamond Coatings on Platinum Wires Using the Novel Nucleation Process (NNP)

PubMed Central

Fhaner, Mathew; Zhao, Hong; Bian, Xiaochun; Galligan, James J.; Swain, Greg M.

2010-01-01

In order to increase the initial nucleation density for the growth of boron-doped diamond on platinum wires, we employed the novel nucleation process (NNP) originally developed by Rotter et al. and discussed by others [1–3]. This pretreatment method involves (i) the initial formation of a thin carbon layer over the substrate followed by (ii) ultrasonic seeding of this “soft” carbon layer with nanoscale particles of diamond. This two-step pretreatment is followed by the deposition of boron-doped diamond by microwave plasma-assisted CVD. Both the diamond seed particles and sites on the carbon layer itself function as the initial nucleation zones for diamond growth from an H2-rich source gas mixture. We report herein on the characterization of the pre-growth carbon layer formed on Pt as well as boron-doped films grown for 2, 4 and 6 h post NNP pretreatment. Results from scanning electron microscopy, Raman spectroscopy and electrochemical studies are reported. The NNP method increases the initial nucleation density on Pt and leads to the formation of a continuous diamond film in a shorter deposition time than is typical for wires pretreated by conventional ultrasonic seeding. The results indicate that the pregrowth layer itself consists of nanoscopic domains of diamond and functions well to enhance the initial nucleation of diamond without any diamond powder seeding. PMID:21617759

Super-deep diamond genesis at Redox conditions of slab-mantle boundary

NASA Astrophysics Data System (ADS)

Gao, J.; Chen, B.; Wu, X.

2017-12-01

Diamond genesis is an intriguing issue for diamond resources and the deep carbon cycle of the Earth's interiors. Super-deep diamonds, representing only 6% of the global diamond population, often host inclusions with phase assemblages requiring a sublithospheric origin (>300 km). Being the windows for probing the deep Earth, super-deep diamonds with their distinctive micro-inclusions not only record a history of oceanic lithosphere subduction and upward transport at a depth of >250 km to even 1000 km, but indicate their genesis pertinent to mantle-carbonate melts in a Fe0-bufferred reduced condition. Our pilot experiments have evidenced the formation of diamonds from MgCO3-Fe0 system in a diamond anvil cell device at 25 GPa and 1800 K. Detailed experimental investigations of redox mechanism of MgCO3-Fe0 and CaCO3-Fe0 coupling have been conducted using multi-anvil apparatus. The conditions are set along the oceanic lithosphere subduction paths in the pressure-temperature range of 10-24 GPa and 1200-2000 K, covering the formation region of most super-deep diamonds. The clear reaction zones strongly support the redox reaction between carbonatitic slab and Fe0-bearing metals under mantle conditions. Our study has experimentally documented the possibility of super-deep diamond genesis at redox conditions of carbonateitic slab and Fe0-bearings. The kinetics of diamond formation as a function of pressure-temperature conditions are also discussed.

Diamond formation through isochemical cooling of CHO fluids vs redox buffering: examples from Marange peridotitic and Zimmi eclogitic diamonds

NASA Astrophysics Data System (ADS)

Smit, Karen V.; Stachel, Thomas; Stern, Richard A.; Shirey, Steven B.; Steele, Andrew

2017-04-01

Traditional models for diamond formation within the lithospheric mantle invoke either carbonate reduction or methane oxidation. Both these mechanisms require some oxygen exchange with the surrounding wall-rock at the site of diamond precipitation. However, peridotite does not have sufficient buffering capacity to allow for diamond formation via these traditional models and instead peridotitic diamonds may form through isochemical cooling of H2O-rich CHO fluids [1]. Marange mixed-habit diamonds from eastern Zimbabwe provide the first natural confirmation of this new diamond growth model [2]. Although Marange diamonds do not contain any silicate or sulphide inclusions, they contain Ni-N-vacancy complexes detected through photoluminescence (PL) spectroscopy that suggest the source fluids equilibrated in the Ni-rich depleted peridotitic lithosphere. Cuboid sectors also contain abundant micro-inclusions of CH4, the first direct observation of reduced CH4-rich fluids that are thought to percolate through the lithospheric mantle [2]. In fluid inclusion-free diamonds, core-to-rim trends in δ13C and N content are used to infer the speciation of the diamond-forming fluid. Core to rim trends of increasing δ13C with decreasing N content are interpreted as diamond growth from oxidized CO2- or carbonate-bearing fluids. Diamond growth from reduced species should show the opposite trends - decreasing δ13C from core to rim with decreasing N content. Within the CH4-bearing growth sectors of Marange diamonds, however, such a 'reduced' trend is not observed. Rather, δ13C increases from core to rim within a homogeneously grown zone [2]. These contradictory observations can be explained through either mixing between CH4- and CO2-rich end-members of hydrous fluids [2] or through closed system precipitation from an already mixed CH4-CO2 H2O-maximum fluid with XCO2 (CO2/[CO2+CH4]) between 0.3 and 0.7 [3]. These results demonstrate that Marange diamonds precipitated from cooling CH4-CO2-bearing hydrous fluids rather than through redox buffering. As this growth mechanism applies to both the fluid-rich cuboid and gem-like octahedral sectors of Marange diamonds, a non-redox model for diamond formation from mixed CH4-CO2 fluids is indicated for a wider range of gem-quality peridotitic diamonds. Indeed, at the redox conditions of global diamond-bearing lithospheric mantle (FMQ -2 to -4; [4]), CHO fluids are strongly water-dominated and contain both CH4 and CO2 as dominant carbon species [5]. By contrast diamond formation in eclogitic assemblages, through either redox buffering or cooling of carbon-bearing fluids, is not as well constrained. Zimmi diamonds from the West African craton have eclogitic sulphide inclusions (with low Ni and high Re/Os) and formed at 650 Ma, overlapping with the timing of subduction [6]. In one Zimmi diamond, a core to rim trend of decreasing δ13C (-23.4 to -24.5 ) and N content is indicative of formation from reduced C2H6/CH4-rich fluids, likely derived from oceanic crust recycled during Neoproterozoic subduction. Unlike mixed CH4-CO2 fluids near the water maximum, isochemical cooling or ascent of such reduced CHO fluids is not effficient at diamond precipitation. Furthermore, measurable carbon isotopic variations in diamond are not predicted in this model and therefore cannot be reconciled with the ˜1 ‰ internal variation seen. Consequently, this Zimmi eclogitic diamond likely formed through redox buffering of reduced subduction-related fluids, infiltrating into sulphide-bearing eclogite. References 1. Luth and Stachel, 2014. CMP, 168, 1083 2. Smit et al., 2016. Lithos, 265, 68-81 3. Stachel et al., in review 4. Stagno et al., 2013. Nature, 493, 84-88 5. Zhang and Duan, 2009. GCA 73, 2089-2102 6. Smit et al., 2016. Precamb Res, 286, 152-166

The uniquely high-temperature character of Cullinan diamonds: A signature of the Bushveld mantle plume?

NASA Astrophysics Data System (ADS)

Korolev, N. M.; Kopylova, M.; Bussweiler, Y.; Pearson, D. G.; Gurney, J.; Davidson, J.

2018-04-01

The mantle beneath the Cullinan kimberlite (formerly known as "Premier") is a unique occurrence of diamondiferous cratonic mantle where diamonds were generated contemporaneously and shortly following a mantle upwelling that led to the formation of a Large Igneous Province that produced the world's largest igneous intrusion - the 2056 Ma Bushveld Igneous Complex (BIC). We studied 332 diamond inclusions from 202 Cullinan diamonds to investigate mantle thermal effects imposed by the formation of the BIC. The overwhelming majority of diamonds come from three parageneses: (1) lithospheric eclogitic (69%), (2) lithospheric peridotitic (21%), and (3) sublithospheric mafic (9%). The lithospheric eclogitic paragenesis is represented by clinopyroxene, garnet, coesite and kyanite. Main minerals of the lithospheric peridotitic paragenesis are forsterite, enstatite, Cr-pyrope, Cr-augite and spinel; the sublithospheric mafic association includes majorite, CaSiO3 phases and omphacite. Diamond formation conditions were calculated using an Al-in-olivine thermometer, a garnet-clinopyroxene thermometer, as well as majorite and Raman barometers. The Cullinan diamonds may be unique on the global stage in recording a cold geotherm of 40 mW/m2 in cratonic lithosphere that was in contact with underlying convecting mantle at temperatures of 1450-1550 °C. The studied Cullinan diamonds contain a high proportion of inclusions equilibrated at temperatures exceeding the ambient 1327 °C adiabat, i.e. 54% of eclogitic diamonds and 41% of peridotitic diamonds. By contrast, ≤ 1% of peridotitic diamond inclusions globally yield equally high temperatures. We propose that the Cullinan diamond inclusions recorded transient, slow-dissipating thermal perturbations associated with the plume-related formation of the 2 Ga Bushveld igneous province. The presence of inclusions in diamond from the mantle transition zone at 300-650 km supports this view. Cullinan xenoliths indicative of the thermal state of the cratonic lithosphere at 1.2 Ga are equilibrated at the relatively low temperatures, not exceeding adiabatic. The ability of diamonds to record super-adiabatic temperatures may relate to their entrainment from the deeper, hotter parts of the upper mantle un-sampled by the kimberlite in the form of xenoliths or their equilibration in a younger lithosphere after a decay of the thermal disturbance.

Boron-doped diamond microdisc arrays: electrochemical characterisation and their use as a substrate for the production of microelectrode arrays of diverse metals (Ag, Au, Cu)via electrodeposition.

PubMed

Simm, Andrew O; Banks, Craig E; Ward-Jones, Sarah; Davies, Trevor J; Lawrence, Nathan S; Jones, Timothy G J; Jiang, Li; Compton, Richard G

2005-09-01

A novel boron-doped diamond (BDD) microelectrode array is characterised with electrochemical and atomic force microscopic techniques. The array consists of 40 micron-diameter sized BDD discs which are separated by 250 microns from their nearest neighbour in a hexagonal arrangement. The conducting discs can be electroplated to produce arrays of copper, silver or gold for analytical purposes in addition to operating as an array of BDD-microelectrodes. Proof-of-concept is shown for four separate examples; a gold plated array for arsenic detection, a copper plated array for nitrate analysis, a silver plated array for hydrogen peroxide monitoring and last, cathodic stripping voltammetry for lead at the bare BDD-array.

Heterogeneous Catalysis for Thermochemical Conversion Publications |

Science.gov Websites

pentagons is an upside-down Y shape and H2 +with a sideways Y shape with two lines at the base. A gold arrow a photo of woody biomass. In the center is a diamond shape composed of four outer triangle sections blue spheres. In the upper left is a large molecule shape made up of a hexagon of black spheres

Fabrication of microchannels in polycrystalline diamond using pre-fabricated Si substrates

NASA Astrophysics Data System (ADS)

Chandran, Maneesh; Elfimchev, Sergey; Michaelson, Shaul; Akhvlediani, Rozalia; Ternyak, Orna; Hoffman, Alon

2017-10-01

In this paper, we report on a simple, feasible method to fabricate microchannels in diamond. Polycrystalline diamond microchannels were produced by fabricating trenches in a Si wafer and subsequently depositing a thin layer of diamond onto this substrate using the hot filament vapor deposition technique. Fabrication of trenches in the Si substrate at different depths was carried out by standard photolithography, and the subsequent deposition of the diamond layer was performed by the hot filament chemical vapor deposition technique. The growth mechanism of diamond that leads to the formation of closed diamond microchannels is discussed in detail based on the Knudsen number and growth chemistry of diamond. Variations in the crystallite size, crystalline quality, and thickness of the diamond layer along the trench depths were systematically analyzed using cross-sectional scanning electron microscopy and Raman spectroscopy. Defect density and formation of non-diamond forms of carbon in the diamond layer were found to increase with the trench depth, which sets a limit of 5-45 μm trench depth (or an aspect ratio of 1-9) for the fabrication of diamond microchannels using this method under the present conditions.

Preparation of novel layer-stack hexagonal CdO micro-rods by a pre-oxidation and subsequent evaporation process

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

Peng, Kun, E-mail: kpeng@hnu.edu.cn; Hunan Province Key Laboratory for Spray Deposition Technology and Application, Hunan University, Changsha 410082; Jiang, Pan

2014-12-15

Graphical abstract: Layer-stack hexagonal cadmium oxide (CdO) micro-rods were prepared. - Highlights: • Novel hexagonal layer-stack structure CdO micro-rods were synthesized by a thermal evaporation method. • The pre-oxidation, vapor pressure and substrate nature play a key role on the formation of CdO rods. • The formation mechanism of CdO micro-rods was explained. - Abstract: Novel layer-stack hexagonal cadmium oxide (CdO) micro-rods were prepared by pre-oxidizing Cd granules and subsequent thermal oxidation under normal atmospheric pressure. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were performed to characterize the phase structure and microstructure. The pre-oxidation process, vapor pressure and substratemore » nature were the key factors for the formation of CdO micro-rods. The diameter of micro-rod and surface rough increased with increasing of thermal evaporation temperature, the length of micro-rod increased with the increasing of evaporation time. The formation of hexagonal layer-stack structure was explained by a vapor–solid mechanism.« less

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

Sverjensky, Dimitri A.; Huang, Fang

Diamond formation has typically been attributed to redox reactions during precipitation from fluids or magmas. Either the oxidation of methane or the reduction of carbon dioxide has been suggested, based on simplistic models of deep fluids consisting of mixtures of dissolved neutral gas molecules without consideration of aqueous ions. The role of pH changes associated with water–silicate rock interactions during diamond formation is unknown. Here we show that diamonds could form due to a drop in pH during water–rock interactions. We use a recent theoretical model of deep fluids that includes ions, to show that fluid can react irreversibly withmore » eclogite at 900 °C and 5.0 GPa, generating diamond and secondary minerals due to a decrease in pH at almost constant oxygen fugacity. Overall, our results constitute a new quantitative theory of diamond formation as a consequence of the reaction of deep fluids with the rock types that they encounter during migration. Diamond can form in the deep Earth during water–rock interactions without changes in oxidation state.« less

Microstructural evolution of diamond growth during HFCVD

NASA Technical Reports Server (NTRS)

Singh, J.

1994-01-01

High resolution transmission electron microscopy (HRTEM) was used to study the nucleation and growth mechanism of diamond by hot filament chemical vapor deposition (HFCVD) process. A novel technique has shown a direct evidence for the formation of the diamond-like carbon layer 8-14 nm thick in which small diamond micro-crystallites were embedded. These diamond micro-crystallites were formed as a result of transformation of diamond-like carbon into diamond. The diamond micro-crystallites present in the amorphous diamond-like carbon layer provided nucleation sites for diamond growth. Large diamond crystallites were observed to grow from these micro-crystallites. The mechanism of diamond growth will be presented based on experimental findings.

The role of the cubic structure in freezing of a supercooled water droplet on an ice substrate

NASA Astrophysics Data System (ADS)

Takahashi, T.; Kobayashi, T.

1983-12-01

The possibility of the formation of a metastable cubic (diamond) structure and its role in freezing of a supercooled water droplet on an ice substrate are discussed in terms of two-dimensional nucleation. The mode of stacking sequence of new layers formed by two-dimensional nucleation is divided into single and multi-nucleation according to the degree of supercooling and to the size of the supercooled droplet. In the case of single nucleation a frozen droplet develops into a complete hexagonal single crystal or an optically single crystal (containing discontinuous stacking faults). In the case of multi-nucleation attention is paid to the size effect and the stacking direction of the nucleus to calculate the waiting time in the nucleation. Then the frozen droplets are crystallographically divided into three categories: completely single crystals, optically single crystals (containing a small cubic structure, i.e. stacking faults) and polycrystals with a misorientation of 70.53° between the c-axes.

Nature of phase transitions in crystalline and amorphous GeTe-Sb2Te3 phase change materials.

PubMed

Kalkan, B; Sen, S; Clark, S M

2011-09-28

The thermodynamic nature of phase stabilities and transformations are investigated in crystalline and amorphous Ge(1)Sb(2)Te(4) (GST124) phase change materials as a function of pressure and temperature using high-resolution synchrotron x-ray diffraction in a diamond anvil cell. The phase transformation sequences upon compression, for cubic and hexagonal GST124 phases are found to be: cubic → amorphous → orthorhombic → bcc and hexagonal → orthorhombic → bcc. The Clapeyron slopes for melting of the hexagonal and bcc phases are negative and positive, respectively, resulting in a pressure dependent minimum in the liquidus. When taken together, the phase equilibria relations are consistent with the presence of polyamorphism in this system with the as-deposited amorphous GST phase being the low entropy low-density amorphous phase and the laser melt-quenched and high-pressure amorphized GST being the high entropy high-density amorphous phase. The metastable phase boundary between these two polyamorphic phases is expected to have a negative Clapeyron slope. © 2011 American Institute of Physics

Chromatographic study of formation conditions of rhombododecahedral diamond crystals

NASA Astrophysics Data System (ADS)

Zhimulev, E. I.; Sonin, V. M.; Chepurov, A. I.; Tomilenko, A. A.

2009-06-01

The results of chromatographic study of the formation of rhombododecahedral diamonds synthesized in the Fe-Ni-(Ti)-C system at 5.5-6.0 GPa and 1350-1450°C are presented, including crystals with rounded surfaces of the rhombododecahedron with parallel striation, which are morphological analogues of natural diamonds abundant at various kimberlite, lamproite, and placer deposits. Chromatography was performed at 150°C with mechanical breakup of diamonds. The stable release of methane when diamonds of habit {110} are crushed is established. It is concluded that the appearance of the habit rhombododecahedron may be related not only to the effect of temperature and pressure on crystal growth but also to reductive conditions of crystallization. At the same time, the appearance of significant amounts of hydrocarbons in the system probably results in stopping of the growth of faces {110} and {100} and, instead, formation of specific surfaces that are composed of microscopic accessories faced by planes {111}.

Pressure induced structural phase transition of OsB 2: First-principles calculations

NASA Astrophysics Data System (ADS)

Ren, Fengzhu; Wang, Yuanxu; Lo, V. C.

2010-04-01

Orthorhombic OsB 2 was synthesized at 1000 °C and its compressibility was measured by using the high-pressure X-ray diffraction in a Diacell diamond anvil cell from ambient pressure to 32 GPa [R.W. Cumberland, et al. (2005)]. First-principles calculations were performed to study the possibility of the phase transition of OsB 2. An analysis of the calculated enthalpy shows that orthorhombic OsB 2 can transfer to the hexagonal phase at 10.8 GPa. The calculated results with the quasi-harmonic approximation indicate that this phase transition pressure is little affected by the thermal effect. The calculated phonon band structure shows that the hexagonal P 6 3/ mmc structure (high-pressure phase) is stable for OsB 2. We expect the phase transition can be further confirmed by the experimental work.

Chemical reaction of hexagonal boron nitride and graphite nanoclusters in mechanical milling systems

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

Muramatsu, Y.; Grush, M.; Callcott, T.A.

1997-04-01

Synthesis of boron-carbon-nitride (BCN) hybrid alloys has been attempted extensively by many researchers because the BCN alloys are considered an extremely hard material called {open_quotes}super diamond,{close_quotes} and the industrial application for wear-resistant materials is promising. A mechanical alloying (MA) method of hexagonal boron nitride (h-BN) with graphite has recently been studied to explore the industrial synthesis of the BCN alloys. To develop the MA method for the BCN alloy synthesis, it is necessary to confirm the chemical reaction processes in the mechanical milling systems and to identify the reaction products. Therefore, the authors have attempted to confirm the chemical reactionmore » process of the h-BN and graphite in mechanical milling systems using x-ray absorption near edge structure (XANES) methods.« less

Theoretical model of dynamic spin polarization of nuclei coupled to paramagnetic point defects in diamond and silicon carbide

NASA Astrophysics Data System (ADS)

Ivády, Viktor; Szász, Krisztián; Falk, Abram L.; Klimov, Paul V.; Christle, David J.; Janzén, Erik; Abrikosov, Igor A.; Awschalom, David D.; Gali, Adam

2015-09-01

Dynamic nuclear spin polarization (DNP) mediated by paramagnetic point defects in semiconductors is a key resource for both initializing nuclear quantum memories and producing nuclear hyperpolarization. DNP is therefore an important process in the field of quantum-information processing, sensitivity-enhanced nuclear magnetic resonance, and nuclear-spin-based spintronics. DNP based on optical pumping of point defects has been demonstrated by using the electron spin of nitrogen-vacancy (NV) center in diamond, and more recently, by using divacancy and related defect spins in hexagonal silicon carbide (SiC). Here, we describe a general model for these optical DNP processes that allows the effects of many microscopic processes to be integrated. Applying this theory, we gain a deeper insight into dynamic nuclear spin polarization and the physics of diamond and SiC defects. Our results are in good agreement with experimental observations and provide a detailed and unified understanding. In particular, our findings show that the defect electron spin coherence times and excited state lifetimes are crucial factors in the entire DNP process.

Diamonds in dense molecular clouds - A challenge to the standard interstellar medium paradigm

NASA Technical Reports Server (NTRS)

Allamandola, L. J.; Sandford, S. A.; Tielens, A. G. G. M.; Herbst, T. M.

1993-01-01

Observations of a newly discovered infrared C-H stretching band indicate that interstellar diamond-like material appears to be characteristic of dense clouds. In sharp contrast, the spectral signature of dust in the diffuse interstellar medium is dominated by -CH2- and -CH3 groups. This dichotomy in the aliphatic organic component between the dense and diffuse media challenges standard assumptions about the processes occurring in, and interactions between, these two media. The ubiquity of this interstellar diamond-like material rules out models for meteoritic diamond formation in unusual circumstellar environments and implies that the formation of the diamond-like material is associated with common interstellar processes or stellar types.

Engineering and Localization of Quantum Emitters in Large Hexagonal Boron Nitride Layers.

PubMed

Choi, Sumin; Tran, Toan Trong; Elbadawi, Christopher; Lobo, Charlene; Wang, Xuewen; Juodkazis, Saulius; Seniutinas, Gediminas; Toth, Milos; Aharonovich, Igor

2016-11-02

Hexagonal boron nitride is a wide-band-gap van der Waals material that has recently emerged as a promising platform for quantum photonics experiments. In this work, we study the formation and localization of narrowband quantum emitters in large flakes (up to tens of micrometers wide) of hexagonal boron nitride. The emitters can be activated in as-grown hexagonal boron nitride by electron irradiation or high-temperature annealing, and the emitter formation probability can be increased by ion implantation or focused laser irradiation of the as-grown material. Interestingly, we show that the emitters are always localized at the edges of the flakes, unlike most luminescent point defects in three-dimensional materials. Our results constitute an important step on the roadmap of deploying hexagonal boron nitride in nanophotonics applications.

Natural diamond formation by self-redox of ferromagnesian carbonate

NASA Astrophysics Data System (ADS)

Chen, Ming; Shu, Jinfu; Xie, Xiande; Tan, Dayong; Mao, Ho-kwang

2018-03-01

Formation of natural diamonds requires the reduction of carbon to its bare elemental form, and pressures (P) greater than 5 GPa to cross the graphite–diamond transition boundary. In a study of shocked ferromagnesian carbonate at the Xiuyan impact crater, we found that the impact pressure–temperature (P-T) of 25–45 GPa and 800–900 °C were sufficient to decompose ankerite Ca(Fe2+,Mg)(CO3)2 to form diamond in the absence of another reductant. The carbonate self-reduced to diamond by concurrent oxidation of Fe2+ to Fe3+ to form a high-P polymorph of magnesioferrite, MgFe3+2O4. Discovery of the subsolidus carbonate self-reduction mechanism indicates that diamonds could be ubiquitously present as a dominant host for carbon in the Earth’s lower mantle.

Micro and nanocrystalline diamond formation on reticulated vitreous carbon substrate

NASA Astrophysics Data System (ADS)

Diniz, A. V.; Trava-Airoldi, V. J.; Corat, E. J.; Ferreira, N. G.

2005-10-01

High diamond nucleation and a three-dimensional growth on reticulated vitreous carbon substrate are obtained by chemical vapor deposition. Scanning electron microscopy images show continuous films covering the whole substrate including the center of 3.5 mm thick porous samples. It is evident the nanocrystalline diamond (NCD) film formation on deeper substrate regions. The grain size can vary from nano to micro scale for deposition time of 20 h. Raman spectra of sample regions closer to filaments exhibit well-defined diamond line. For central regions of sample (depth between 1.0 and 2.0 mm) Raman spectra also confirm NCD film.

Carbon isotope fractionation during diamond growth in depleted peridotite: Counterintuitive insights from modelling water-maximum CHO fluids as multi-component systems

NASA Astrophysics Data System (ADS)

Stachel, T.; Chacko, T.; Luth, R. W.

2017-09-01

Because of the inability of depleted cratonic peridotites to effectively buffer oxygen fugacities when infiltrated by CHO or carbonatitic fluids, it has been proposed recently (Luth and Stachel, 2014) that diamond formation in peridotites typically does not occur by rock-buffered redox reactions as previously thought but by an oxygen-conserving reaction in which minor coexisting CH4 and CO2 components in a water-rich fluid react to form diamond (CO2 + CH4 = 2C + 2H2O). In such fluid-buffered systems, carbon isotope fractionation during diamond precipitation occurs in the presence of two dominant fluid carbon species. Carbon isotope modelling of diamond precipitation from mixed CH4- and CO2-bearing fluids reveals unexpected fundamental differences relative to diamond crystallization from a single carbon fluid species: (1) irrespective of which carbon fluid species (CH4 or CO2) is dominant in the initial fluid, diamond formation is invariably associated with progressive minor (<1‰) enrichment of diamond in 13C as crystallization proceeds. This is in contrast to diamond precipitation by rock-buffered redox processes from a fluid containing only a single carbon species, which can result in either progressive 13C enrichment (CO2 or carbonate fluids) or 13C depletion (CH4 fluids) in the diamond. (2) Fluid speciation is the key factor controlling diamond δ13 C values; as XCO2 (XCO2 = CO2/[CO2 + CH4]) in the initial fluid increases from 0.1 to 0.9 (corresponding to an increase in fO2 of 0.8 log units), the carbon isotope composition of the first-precipitated diamond decreases by 3.7‰. The tight mode in δ13C of - 5 ± 1 ‰ for diamonds worldwide places strict constraints on the dominant range of XCO2 in water-rich fluids responsible for diamond formation. Specifically, precipitation of diamonds with δ13C values in the range -4 to -6‰ from mantle-derived fluids with an average δ13C value of -5‰ (derived from evidence not related to diamonds) requires that diamond-forming fluids were relatively reduced and had methane as the dominant carbon species (XCO2 = 0.1-0.5). Application of our model to a recently published set of in-situ carbon isotope analyses for peridotitic diamonds from Marange, Zimbabwe (Smit et al., 2016), which contain CH4 fluid inclusions, allows us to perfectly match the observed co-variations in δ13 C, δ15 N and N content and at the same time explain the previously counter-intuitive observation of progressive 13C enrichment in diamonds that appear to have grown from a fluid with methane as the dominant carbon species. Similarly, the almost complete absence in the published record of progressive 13C depletion trends within diamonds likely reflects ubiquitous precipitation from CH4- and CO2-bearing water-rich fluids, rather than diamond formation exclusively by carbonate-bearing and CH4-free oxidized fluids or melts.

A unifying picture of gas-phase formation and growth of PAH (Polycyclic Aromatic Hydrocarbons), soot, diamond and graphite

NASA Technical Reports Server (NTRS)

Frenklach, Michael

1990-01-01

A variety of seemingly different carbon formation processes -- polycyclic aromatic hydrocarbons and diamond in the interstellar medium, soot in hydrocarbon flames, graphite and diamond in plasma-assisted-chemical vapor deposition reactors -- may all have closely related underlying chemical reaction mechanisms. Two distinct mechanisms for gas-phase carbon growth are discussed. At high temperatures it proceeds via the formation of carbon clusters. At lower temperatures it follows a polymerization-type kinetic sequence of chemical reactions of acetylene addition to a radical, and reactivation of the resultant species through H-abstraction by a hydrogen atom.

Tracing the depositional history of Kalimantan diamonds by zircon provenance and diamond morphology studies

NASA Astrophysics Data System (ADS)

Kueter, Nico; Soesilo, Joko; Fedortchouk, Yana; Nestola, Fabrizio; Belluco, Lorenzo; Troch, Juliana; Wälle, Markus; Guillong, Marcel; Von Quadt, Albrecht; Driesner, Thomas

2016-11-01

Diamonds in alluvial deposits in Southeast Asia are not accompanied by indicator minerals suggesting primary kimberlite or lamproite sources. The Meratus Mountains in Southeast Borneo (Province Kalimantan Selatan, Indonesia) provide the largest known deposit of these so-called "headless" diamond deposits. Proposals for the origin of Kalimantan diamonds include the adjacent Meratus ophiolite complex, ultra-high pressure (UHP) metamorphic terranes, obducted subcontinental lithospheric mantle and undiscovered kimberlite-type sources. Here we report results from detailed sediment provenance analysis of diamond-bearing Quaternary river channel material and from representative outcrops of the oldest known formations within the Alino Group, including the diamond-bearing Campanian-Maastrichtian Manunggul Formation. Optical examination of surfaces of diamonds collected from artisanal miners in the Meratus area (247 stones) and in West Borneo (Sanggau Area, Province Kalimantan Barat; 85 stones) points toward a classical kimberlite-type source for the majority of these diamonds. Some of the diamonds host mineral inclusions suitable for deep single-crystal X-ray diffraction investigation. We determined the depth of formation of two olivines, one coesite and one peridotitic garnet inclusion. Pressure of formation estimates for the peridotitic garnet at independently derived temperatures of 930-1250 °C are between 4.8 and 6.0 GPa. Sediment provenance analysis includes petrography coupled to analyses of detrital garnet and glaucophane. The compositions of these key minerals do not indicate kimberlite-derived material. By analyzing almost 1400 zircons for trace element concentrations with laser ablation ICP-MS (LA-ICP-MS) we tested the mineral's potential as an alternative kimberlite indicator. The screening ultimately resulted in a small subset of ten zircons with a kimberlitic affinity. Subsequent U-Pb dating resulting in Cretaceous ages plus a detailed chemical reflection make a kimberlitic origin unfavorable with respect to the regional geological history. Rather, trace elemental analyses (U, Th and Eu) suggest an eclogitic source for these zircons. The age distribution of detrital zircons allows in general a better understanding of collisional events that formed the Meratus orogen and identifies various North Australian Orogens as potential Pre-Mesozoic sediment sources. Our data support a model whereby the majority of Kalimantan diamonds were emplaced within the North Australian Craton by volcanic processes. Partly re-deposited into paleo-collectors or residing in their primary host, these diamond-deposits spread passively throughout Southeast Asia by terrane migration during the Gondwana breakup. Terrane amalgamation events largely metamorphosed these diamond-bearing lithologies while destroying the indicative mineral content. Orogenic uplift finally liberated their diamond-content into new, autochthonous placer deposits.

NV centers in 3 C ,4 H , and 6 H silicon carbide: A variable platform for solid-state qubits and nanosensors

NASA Astrophysics Data System (ADS)

von Bardeleben, H. J.; Cantin, J. L.; Csóré, A.; Gali, A.; Rauls, E.; Gerstmann, U.

2016-09-01

The outstanding magneto-optical properties of the nitrogen-vacancy (NV) center in diamond have stimulated the search for similar systems. We show here that NV triplet centers can also be generated in all the main SiC polytypes. We have identified by electron paramagnetic resonance spectroscopy and first-principles calculations the axial NV- pairs in 3 C ,4 H , and 6 H SiC, showing polytype and lattice site-specific magnetic and optical properties. We demonstrate very efficient room-temperature spin polarization of the ground state upon near infrared optical excitation for the NV center in 3 C SiC and axial NV centers in the hexagonal (4 H ,6 H ) polytypes; the signals of basal pairs are much lower in intensity. Axial NV centers in hexagonal SiC polytypes and thus constitute unidirectional ensembles which may be useful in nanosensing applications.

Nanoindentation hardness and atomic force microscope imaging studies of pressure-quenched zirconium metal

NASA Astrophysics Data System (ADS)

Catledge, Shane A.; Spencer, Philemon T.; Vohra, Yogesh K.

2000-11-01

We have carried out mechanical property measurements on zirconium metal compressed in a diamond anvil cell to 19 GPa at room temperature with subsequent quenching to room pressure. The irreversible transformation from the ambient hexagonal-close-packed phase to the simple hexagonal ω phase (AlB2 structure) is confirmed by synchrotron energy dispersive x-ray diffraction followed by nanoindentation of the pressure-quenched sample. We document an 80% increase in hardness as a consequence of the pressure-induced transformation to the ω phase at room temperature. This is a large increase for a metallic phase transformation and can be attributed to the presence of sp2-hybrid bonds forming graphite-like nets in the (0001) plane of the AlB2 structure. Atomic force microscopy of the indents shows that a plastic deformation of 2 μm in depth was achieved with a force of 200 mN.

High-density fluids and the growth of monocrystalline diamonds

NASA Astrophysics Data System (ADS)

Weiss, Y.; Kiflawi, I.; Davies, N.; Navon, O.

2014-09-01

The chemical nature and composition of the growth medium of monocrystalline (MC) diamonds is still a matter of debate, partially because carbonate-bearing high-density fluids (HDFs) that are common in fibrous diamonds have not been found in MC diamonds. Here we report the first finding of HDF microinclusions in a MC octahedral diamond from Finsch, South Africa and in the MC octahedral core of a coated diamond from Kankan, Guinea; both diamonds carry nitrogen in B-centers. Numerous microinclusions in diamond Finsch_2a_cap1 are restricted to two thin layers parallel to the (1 1 1) face, ∼20 and 200 μm from the diamond rim. Low-Mg carbonatitic HDFs are found along the inner layer while the outer layer trapped saline compositions. The major and trace element compositions of the inclusions and their infrared spectra are highly similar to those of microinclusions found in fibrous diamonds. A few isolated microinclusions of saline compositions are scattered around a sulfide inclusion in the center of the octahedral core of diamond ON-KAN-383. This evidence for the involvement of oxidized fluids in the formation of MC diamonds adds to previous reports on the antiquity of HDFs in fibrous diamonds, the presence of carbonate and halide phases in inclusions in MC diamonds and the similarity of trace element pattern of a MC diamond to those of low-Mg carbonatitic HDF in fibrous diamonds. In addition, we show that the interaction of HDFs with depleted garnets can produce sinusoidal REE patterns which are one of the primary features of lherzolitic and harzburgitic garnet inclusions in MC diamonds. Together, these observations suggest that HDFs are involved in the formation of many types of diamonds from the Archaean to the Phanerozoic. HDFs are trapped in large quantities during rapid, fibrous growth, but must also be present during the growth of many MC diamonds.

Summary of impact markers and potential impact mechanisms for the YDB impact event at 12.9 ka

NASA Astrophysics Data System (ADS)

Bunch, T. E.; Schultz, P. H.; Wittke, J. H.; West, A.; Kennett, J.; Kennett, D. J.

2009-12-01

Until the announcements of a possible impact event (Firestone et al. 2007; Kennett et al., 2009a; 2009b) at the beginning of the Younger Dryas (YD) around 12.9 ka, the KT impact layer (KTB) that resulted from the Chicxulub impact at 65 mya was the only geological boundary layer known to contain coeval peaks in various impact markers, including diamonds. Here, we compare impact markers from the KTB, YD boundary layer (YDB), and the 1908 Tunguska airburst layer (TAL). First order markers, related to impact and biomass burning, include: magnetic spherules, carbon spherules, nanodiamonds (cubic and lonsdaleite), iridium anomalies, charcoal, fullerenes (with high 3He to 4He ratio), grape-like soot, and widespread extinctions. Observations and analytical data for the YDB are consistent with all of the KTB markers, while the last three markers are unknown or inconclusive for the Tunguska layer. Selected markers for cratering events, e.g, Chicxulub, are: a visible crater, shocked minerals, impact breccia, and microtektites. None of these are known for the YD event or Tunguska. The discussion here is limited to possible origins of the impact markers and not with impact consequences (climate change, extinctions, etc.). Several origins may account for impact materials in the YDB: (1) An extraordinary accretion of micrometeorites (Pinter and Ishman, 2008). However, this is inconsistent with YDB carbon spherule compositions, including the large concentrations of nanodiamonds found embedded in those carbon spherules. (2) Oblique impact(s) into the Laurentide Ice Sheet. This model is consistent with the lack of a visible crater and apparent lack of cratering markers (above), and yet also provides for shock production of the many cubic nanodiamonds and lonsdaleite found in the YDB. (3) Impact-induced aerial burst. e.g, Boslough and Crawford (2007); Shuvalov (2008). The lack of high shock pressures in an aerial detonation does not necessarily preclude the formation of cubic and hexagonal diamonds, as shown by Maruyama et al. (1993), who made hexagonal and cubic diamonds by a CVD process from a high-temperature plasma atmosphere (13,000°C) under pressure conditions similar to those in an aerial burst. The Tunguska event is commonly accepted as the result of a near-surface aerial burst and has many similarities to the YD event. (4) Comet grazing of the atmosphere (Drobysheski, 2009), involving nearly tangential entry of a comet into the Earth’s atmosphere with partial detonation and melting followed by escape of the unexploded nucleus into space. This has the net effect of an atmosphere-penetrating aerial burst followed by global fallout of detonation products. Three of the four above scenarios are plausible.

Phase relations of Fe Ni alloys at high pressure and temperature

NASA Astrophysics Data System (ADS)

Mao, Wendy L.; Campbell, Andrew J.; Heinz, Dion L.; Shen, Guoyin

2006-04-01

Using a diamond anvil cell and double-sided laser-heating coupled with synchrotron X-ray diffraction, we determined phase relations for three compositions of Fe-rich FeNi alloys in situ at high pressure and high temperature. We studied Fe with 5, 15, and 20 wt.% Ni to 55, 62, and 72 GPa, respectively, at temperatures up to ˜3000 K. Ni stabilizes the face-centered cubic phase to lower temperatures and higher pressure, and this effect increases with increasing pressure. Extrapolation of our experimental results for Fe with 15 wt.% Ni suggests that the stable phase at inner core conditions is hexagonal close packed, although if the temperature at the inner core boundary is higher than ˜6400 K, a two phase outer region may also exist. Comparison to previous laser-heated diamond anvil cell studies demonstrates the importance of kinetics even at high temperatures.

Strength and texture of Pt compressed to 63 GPa

NASA Astrophysics Data System (ADS)

Dorfman, Susannah M.; Shieh, Sean R.; Duffy, Thomas S.

2015-02-01

Angle- and energy-dispersive X-ray diffraction experiments in a radial geometry were performed in the diamond anvil cell on polycrystalline platinum samples at pressures up to 63 GPa. Observed yield strength and texture depend on grain size. For samples with 70-300-nm particle size, the yield strength is 5-6 GPa at ˜60 GPa. Coarse-grained (˜2-μm particles) Pt has a much lower yield strength of 1-1.5 GPa at ˜60 GPa. Face-centered cubic metals Pt and Au have lower strength to shear modulus ratio than body-centered cubic or hexagonal close-packed metals. While a 300-nm particle sample exhibits the <110> texture expected of face-centered-cubic metals under compression, smaller and larger particles show a weak mixed <110> and <100> texture under compression. Differences in texture development may also occur due to deviations from uniaxial stress under compression in the diamond anvil cell.

Pathways through equilibrated states with coexisting phases for gas hydrate formation

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

Malolepsza, Edyta; Keyes, Tom

Under ambient conditions, water freezes to either hexagonal ice or a hexagonal/cubic composite ice. The presence of hydrophobic guest molecules introduces a competing pathway: gas hydrate formation, with the guests in clathrate cages. Here, the pathways of the phase transitions are sought as sequences of states with coexisting phases, using a generalized replica exchange algorithm designed to sample them in equilibrium, avoiding nonequilibrium processes. For a dilute solution of methane in water under 200 atm, initializing the simulation with the full set of replicas leads to methane trapped in hexagonal/cubic ice, while gradually adding replicas with decreasing enthalpy produces themore » initial steps of hydrate growth. Once a small amount of hydrate is formed, water rearranges to form empty cages, eventually transforming the remainder of the system to metastable β ice, a scaffolding for hydrates. It is suggested that configurations with empty cages are reaction intermediates in hydrate formation when more guest molecules are available. Furthermore, free energy profiles show that methane acts as a catalyst reducing the barrier for β ice versus hexagonal/cubic ice formation.« less

Pathways through equilibrated states with coexisting phases for gas hydrate formation

DOE PAGES

Malolepsza, Edyta; Keyes, Tom

2015-12-01

Under ambient conditions, water freezes to either hexagonal ice or a hexagonal/cubic composite ice. The presence of hydrophobic guest molecules introduces a competing pathway: gas hydrate formation, with the guests in clathrate cages. Here, the pathways of the phase transitions are sought as sequences of states with coexisting phases, using a generalized replica exchange algorithm designed to sample them in equilibrium, avoiding nonequilibrium processes. For a dilute solution of methane in water under 200 atm, initializing the simulation with the full set of replicas leads to methane trapped in hexagonal/cubic ice, while gradually adding replicas with decreasing enthalpy produces themore » initial steps of hydrate growth. Once a small amount of hydrate is formed, water rearranges to form empty cages, eventually transforming the remainder of the system to metastable β ice, a scaffolding for hydrates. It is suggested that configurations with empty cages are reaction intermediates in hydrate formation when more guest molecules are available. Furthermore, free energy profiles show that methane acts as a catalyst reducing the barrier for β ice versus hexagonal/cubic ice formation.« less

Invasion of Hydrous Fluids Predates Kimberlite Formation

NASA Astrophysics Data System (ADS)

Kopylova, M. G.; Wang, Q.; Smith, E. M.

2017-12-01

Petrological observations on diamonds and peridotite xenoliths in kimberlites point towards an influx of hydrous metasomatic fluids shortly predating kimberlite formation. Diamonds may grow at different times within the same segment of the cratonic mantle, and diamonds that form shortly before (<5-7 My) the kimberlite entrainment host the more hydrous fluid inclusions. Younger fibrous diamonds typically contain 10-25 wt.% water in fluid inclusions, while older octahedrally-grown diamonds host "dry" N2-CO2 fluids. Our recent studies of fluids in diamond now show that many different kinds of diamonds can contain fluid inclusions. Specifically, we found a new way to observe and analyze fluids in octahedrally-grown, non-fibrous diamonds by examining healed fractures. This is a new textural context for fluid inclusions that reveals a valuable physical record of infiltrating mantle fluids, that postdate diamond growth, but equilibrate within the diamond stability field at depths beyond 150 km. Another sign of the aqueous fluids influx is the formation of distinct peridotite textures shortly predating the kimberlite. Kimberlites entrain peridotite xenoliths with several types of textures: older coarse metamorphic textures and younger, sheared textures. The preserved contrast in grain sizes between porphyroclasts and neoblasts in sheared peridotites constrain the maximum duration of annealing. Experimental estimates of the annealing time vary from 7x107 sec (2 years) to 106 years (1 My) depending on olivine hydration, strain rate, pressure, temperature and, ultimately, the annealing mechanism. Kimberlite sampling of sheared peridotites from the lithosphere- asthenosphere boundary (LAB) implies their formation no earlier than 1 My prior to the kimberlite ascent. Water contents of olivine measured by FTIR spectrometry using polarized light demonstrated contrasting hydration of coarse and sheared samples. Olivine from sheared peridotite samples has the average water content of 78±3 ppm, in contrast to the less hydrated coarse peridotites (33±6 ppm). LAB hydration results in the lower viscosity of the mantle (1-4 orders of magnitude) translating into 10-104- fold increase in strain rate if stress, its duration, pressure, temperature and the deformation mechanism are assumed constant.

Enhanced Photocatalytic Activity of Diamond Thin Films Using Embedded Ag Nanoparticles.

PubMed

Li, Shuo; Bandy, Jason A; Hamers, Robert J

2018-02-14

Silver nanoparticles embedded into the diamond thin films enhance the optical absorption and the photocatalytic activity toward the solvated electron-initiated reduction of N 2 to NH 3 in water. Here, we demonstrate the formation of diamond films with embedded Ag nanoparticles <100 nm in diameter. Cross-sectional scanning electron microscopy (SEM), energy-dependent SEM, and energy-dispersive X-ray analysis demonstrate the formation of encapsulated nanoparticles. Optical absorption measurements in the visible and ultraviolet region show that the resulting films exhibit plasmonic resonances in the visible and near-ultraviolet region. Measurements of photocatalytic activity using supraband gap (λ < 225 nm) and sub-band gap (λ > 225 nm) excitation show significantly enhanced ability to convert N 2 to NH 3 . Incorporation of Ag nanoparticles induces a nearly 5-fold increase in activity using a sub-band gap excitation with λ > 225 nm. Our results suggest that internal photoemission, in which electrons are excited from Ag into diamond's conduction band, is an important process that extends the wavelength region beyond diamond's band gap. Other factors, including Ag-induced optical scattering and formation of graphitic impurities are also discussed.

Crystal grain growth at the α -uranium phase transformation in praseodymium

NASA Astrophysics Data System (ADS)

Cunningham, Nicholas C.; Velisavljevic, Nenad; Vohra, Yogesh K.

2005-01-01

Structural phase transformations under pressure are examined in praseodymium metal for the range 0-40GPa at ambient temperature. Pressure was generated with a diamond-anvil cell, and data were collected using high-resolution synchrotron x-ray diffraction and the image plate technique. The structural sequence double hexagonal close packed (dhcp)→face centered cubic (fcc)→distorted-fcc (d-fcc)→ α -uranium (α-U) is observed with increasing pressure. Rietveld refinement of all crystallographic phases provided confirmation of the hR24 structure for the d-fcc phase while the previously reported monoclinic phase between the d-fcc and the α-U phase was not confirmed. We observe dramatic crystal grain growth during the volume collapse concurrent with the symmetry-lowering transition to the α-U structure. No preferred orientation axis is observed, and the formation process for these large grains is expected to be via a nucleation and growth mechanism. An analogous effect in rare earth metal cerium suggests that the grain growth during transformation to the α-U structure is a common occurrence in f -electron metals at high pressures.

Synthesis of hexagonal wurtzite Cu{sub 2}ZnSnS{sub 4} prisms by an ultrasound-assisted microwave solvothermal method

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

Long, Fei, E-mail: long.drf@gmail.com; Chi, Shangsen; Institute of Advanced Materials and Technology, University of Science and Technology Beijing, Beijing 100083

Wurtzite Cu{sub 2}ZnSnS{sub 4} (CZTS) hexagonal prisms were synthesized by a simple ultrasound-microwave solvothermal method. The product was characterized by XRD, FESEM, EDS, TEM, Raman and UV–vis spectrometer. The hexagonal prisms were 0.5–2 μm wide and 5–12 μm long. The PVP played an important role in the formation of the CZTS hexagonal prisms. In addition, the ultrasound-assisted microwave process was helpful for synthesis of wurtzite rather than kesterite phase CZTS. A nucleation–dissolution–recrystallization mechanism was also proposed to explain the growth of the CZTS hexagonal prisms. - Graphical abstract: Wurtzite Cu{sub 2}ZnSnS{sub 4} hexagonal prisms were synthesized by ultrasound-microwave solvothermal method.more » The ultrasound-assisted microwave process and PVP were useful to the growth of CZTS. A nucleation–dissolution–recrystallization growth mechanism was also proposed. - Highlights: • Wurtzite Cu{sub 2}ZnSnS{sub 4} was prepared by ultrasound-assisted microwave solvothermal method. • The wurtzite CZTS hexagonal prisms are demonstrated a band gap of 1.49 eV. • Synergistic effect of ultrasound and microwave is helpful to prepare Wurtzite CZTS. • PVP plays an important role in the formation of the CZTS hexagonal prisms. • Nucleation–dissolution–recrystallization growth mechanism of the CZTS was proposed.« less

Diamond ages from Victor (Superior Craton): Intra-mantle cycling of volatiles (C, N, S) during supercontinent reorganisation

NASA Astrophysics Data System (ADS)

Aulbach, S.; Creaser, Robert A.; Stachel, Thomas; Heaman, Larry M.; Chinn, Ingrid L.; Kong, Julie

2018-05-01

The central Superior Craton hosts both the diamondiferous 1.1 Ga Kyle Lake and Jurassic Attawapiskat kimberlites. A major thermal event related to the Midcontinent Rift at ca. 1.1 Ga induced an elevated geothermal gradient that largely destroyed an older generation of diamonds, raising the question of when, and how, the diamond inventory beneath Attawapiskat was formed. We determined Re-Os isotope systematics of sulphides included in diamonds from Victor by isotope dilution negative thermal ionisation mass spectrometry in order to obtain insights into the age and nature of the diamond source in the context of regional tectonothermal evolution. Regression of the peridotitic inclusion data (n = 14 of 16) yields a 718 ± 49 Ma age, with an initial 187Os/188Os ratio of 0.1177 ± 0.0016, i.e. depleted at the time of formation (γOs -3.7 ± 1.3). Consequently, Re depletion model ages calculated for these samples are systematically overestimated. Given that reported 187Os/188Os in olivine from Attawapiskat xenoliths varies strongly (0.1012-0.1821), the low and nearly identical initial Os of sulphide inclusions combined with their high 187Re/188Os (median 0.34) suggest metasomatic formation from a mixed source. This was likely facilitated by percolation of amounts of melt sufficient to homogenise Os, (re)crystallise sulphide and (co)precipitate diamond; that is, the sulphide inclusions and their diamond host are synchronous if not syngenetic. The ∼720 Ma age corresponds to rifting beyond the northern craton margin during Rodinia break-up. This suggests mobilisation of volatiles (C, N, S) and Os due to attendant mantle stretching and metasomatism by initially oxidising and S-undersaturated melts, which ultimately produced lherzolitic diamonds with high N contents compared to older Kyle Lake diamonds. Thus, some rift-influenced settings are prospective with respect to diamond formation. They are also important sites of hidden, intra-lithospheric volatile redistribution that can be revealed by diamond studies. Later emplacement of the Attawapiskat kimberlites, linking the carbon cycle to the surface, was associated with renewed disturbance during passage of the Great Meteor Hotspot. Lherzolitic diamond formation from oxidising small-volume melts may be the expression of an early and deep stage of the lithospheric conditioning required for the successful eruption of kimberlites, which complements the late and shallow emplacement of volatile-rich metasomes after upward displacement of a redox freezing front.

Research Technology

NASA Image and Video Library

1998-09-16

A team of engineers at Marshall Space Flight Center (MSFC) has designed, fabricated, and tested the first solar thermal engine, a non-chemical rocket that produces lower thrust but has better thrust efficiency than the chemical combustion engines. This segmented array of mirrors is the solar concentrator test stand at MSFC for firing the thermal propulsion engines. The 144 mirrors are combined to form an 18-foot diameter array concentrator. The mirror segments are aluminum hexagons that have the reflective surface cut into it by a diamond turning machine, which is developed by MSFC Space Optics Manufacturing Technology Center.

Equation of state and phase transformations study of Nd at ultra-high pressures

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

Akella, J.; Smith, G.S.; Weir, S.

1991-10-01

Neodymium was investigated to 96.0 GPa pressure in a diamond-anvil ell at room temperature. The observed structural sequence as a function of pressure is dhcp-fcc- six layered'' structure. In the diffraction pattern hexagonal doublets; notably 102, 006 and 100, 108; appear as single reflection when the c/a ratio is 4.899. However, when cc/a approaches 4.7, the splitting is clear. So far in this study, no monoclinic phase or tetragonal phase were observed. 1 fig., 18 refs.

Proceedings of the Seventh Applied Diamond Conference/Third Frontier Carbon Technology Joint Conference (ADC/FCT 2003). Supplement 1

NASA Technical Reports Server (NTRS)

Murakawa, M. (Editor); Miyoshi, K. (Editor); Koga, Y. (Editor); Schaefer, L. (Editor); Tzeng, Y. (Editor)

2003-01-01

This document contains 2 reports which were presented at the Seventh Applied Diamond Conference/Third Frontier Carbon Technology Joint Conference. The topics discuss the formation of C-N nanofibers as well as the characterization of diamond thin films.

Formation of nanodiamond films from aqueous suspensions during spin coating

NASA Astrophysics Data System (ADS)

Lebedev-Stepanov, P. V.; Molchanov, S. P.; Vasil'ev, A. L.; Mitrokhin, V. P.; Yurasik, G. A.; Aleksenskii, A. E.; Dideikin, A. T.

2016-03-01

The formation of multifunctional ordered arrays of detonation diamond particles is studied during self-assembling in spin coating of films of evaporating microdroplets. It is shown that the most homogeneous layer of diamond particles on a crystalline silicon substrate forms at a rate of substrate rotation of 8000 min-1, whereas a relation between the distribution of particles and the radius is clearly detected at rates of about 2000 min-1. As the rate of substrate rotation increases from 2500 to 8000 min-1, the density of the coating of a silicon substrate with diamond nanoparticles decreases approximately threefold. A model is proposed to estimate the increase in the number of individual diamond "points" with the substrate rotation frequency.

Mechanochemical formation of heterogeneous diamond structures during rapid uniaxial compression in graphite

NASA Astrophysics Data System (ADS)

Kroonblawd, Matthew P.; Goldman, Nir

2018-05-01

We predict mechanochemical formation of heterogeneous diamond structures from rapid uniaxial compression in graphite using quantum molecular dynamics simulations. Ensembles of simulations reveal the formation of different diamondlike products starting from thermal graphite crystal configurations. We identify distinct classes of final products with characteristic probabilities of formation, stress states, and electrical properties and show through simulations of rapid quenching that these products are nominally stable and can be recovered at room temperature and pressure. Some of the diamond products exhibit significant disorder and partial closure of the energy gap between the highest-occupied and lowest-unoccupied molecular orbitals (i.e., the HOMO-LUMO gap). Seeding atomic vacancies in graphite significantly biases toward forming products with small HOMO-LUMO gap. We show that a strong correlation between the HOMO-LUMO gap and disorder in tetrahedral bonding configurations informs which kinds of structural defects are associated with gap closure. The rapid diffusionless transformation of graphite is found to lock vacancy defects into the final diamond structure, resulting in configurations that prevent s p3 bonding and lead to localized HOMO and LUMO states with a small gap.

Diamond formation in the deep lower mantle: a high-pressure reaction of MgCO3 and SiO2

PubMed Central

Maeda, Fumiya; Ohtani, Eiji; Kamada, Seiji; Sakamaki, Tatsuya; Hirao, Naohisa; Ohishi, Yasuo

2017-01-01

Diamond is an evidence for carbon existing in the deep Earth. Some diamonds are considered to have originated at various depth ranges from the mantle transition zone to the lower mantle. These diamonds are expected to carry significant information about the deep Earth. Here, we determined the phase relations in the MgCO3-SiO2 system up to 152 GPa and 3,100 K using a double sided laser-heated diamond anvil cell combined with in situ synchrotron X-ray diffraction. MgCO3 transforms from magnesite to the high-pressure polymorph of MgCO3, phase II, above 80 GPa. A reaction between MgCO3 phase II and SiO2 (CaCl2-type SiO2 or seifertite) to form diamond and MgSiO3 (bridgmanite or post-perovsktite) was identified in the deep lower mantle conditions. These observations suggested that the reaction of the MgCO3 phase II with SiO2 causes formation of super-deep diamond in cold slabs descending into the deep lower mantle. PMID:28084421

An Explanation for Saturn's Hexagon

NASA Astrophysics Data System (ADS)

Kohler, Susanna

2015-08-01

For over three decades, weve been gathering observations of the mysterious hexagonal cloud pattern encircling Saturns north pole. Now, researchers believe they have a model that can better explain its formation.Fascinating GeometrySaturns northern Hexagon is a cloud band circling Saturns north pole at 78 N, first observed by the Voyager flybys in 198081. This remarkable pattern has now persisted for more than a Saturn year (29.5 Earth years).Eight frames demonstrating the motion within Saturns Hexagon. Click to watch the animation! The view is from a reference frame rotating with Saturn. [NASA/JPL-Caltech/SSI/Hampton University]Observations by Voyager and, more recently, Cassini have helped to identify many key characteristics of this bizarre structure. Two interesting things weve learned are:The Hexagon is associated with an eastward zonal jet moving at more than 200 mph.The cause of the Hexagon is believed to be a jet stream, similar to the ones that we experience on Earth. The path of the jet itself appears to follow the hexagons outline.The Hexagon rotates at roughly the same rate as Saturns overall rotation.While we observe individual storms and cloud patterns moving at different speeds within the Hexagon, the vertices of the Hexagon move at almost exactly the same rotational speed as that of Saturn itself.Attempts to model the formation of the Hexagon with a jet stream have yet to fully reproduce all of the observed features and behavior. But now, a team led by Ral Morales-Juberas of the New Mexico Institute of Mining and Technology believes they have created a model that better matches what we see.Simulating a Meandering JetThe team ran a series of simulations of an eastward, Gaussian-profile jet around Saturns pole. They introduced small perturbations to the jet and demonstrated that, as a result of the perturbations, the jet can meander into a hexagonal shape. With the initial conditions of the teams model, the meandering jet is able to settle into a stable hexagonal shape that rotates with very nearly the same period as Saturns rotational period.The formation of this hexagon depends on factors such as the initial amplitude and curvature of the jet. The models treatment of the wind profile within Saturns atmosphere is another key component that allowed them to match the observed characteristics of the Hexagon, such as its shape, vorticity behavior, temperature gradient, and seasonal stability.BonusThe gif below shows part of an animation the authors produced of the jet evolution in their model. You can see a hexagon begin to develop at around 230 days into the simulation, and by about 400 days it becomes stable and non-rotating (were looking at it from a reference frame rotating with Saturn). The full animation can be viewed here. [Morales-Juberas et al., 2015]CitationR. Morales-Juberas et al.2015 ApJ 806 L18 doi:10.1088/2041-8205/806/1/L18

Formation of hexagonal and cubic ice during low-temperature growth

PubMed Central

Thürmer, Konrad; Nie, Shu

2013-01-01

From our daily life we are familiar with hexagonal ice, but at very low temperature ice can exist in a different structure––that of cubic ice. Seeking to unravel the enigmatic relationship between these two low-pressure phases, we examined their formation on a Pt(111) substrate at low temperatures with scanning tunneling microscopy and atomic force microscopy. After completion of the one-molecule-thick wetting layer, 3D clusters of hexagonal ice grow via layer nucleation. The coalescence of these clusters creates a rich scenario of domain-boundary and screw-dislocation formation. We discovered that during subsequent growth, domain boundaries are replaced by growth spirals around screw dislocations, and that the nature of these spirals determines whether ice adopts the cubic or the hexagonal structure. Initially, most of these spirals are single, i.e., they host a screw dislocation with a Burgers vector connecting neighboring molecular planes, and produce cubic ice. Films thicker than ∼20 nm, however, are dominated by double spirals. Their abundance is surprising because they require a Burgers vector spanning two molecular-layer spacings, distorting the crystal lattice to a larger extent. We propose that these double spirals grow at the expense of the initially more common single spirals for an energetic reason: they produce hexagonal ice. PMID:23818592

Three-dimensional visualization of coated vesicle formation in fibroblasts

PubMed Central

1980-01-01

Fibroblasts apparently ingest low density lipoproteins (LDL) by a selective mechanism of receptor-mediated endocytosis involving the formation of coated vesicles from the plasma membrane. However, it is not known exactly how coated vesicles collect LDL receptors and pinch off from the plasma membrane. In this report, the quick-freeze, deep- etch, rotary-replication method has been applied to fibroblasts; it displays with unusual clarity the coats that appear under the plasma membrane at the start of receptor-mediated endocytosis. These coats appear to be polygonal networks of 7-nm strands or struts arranged into 30-nm polygons, most of which are hexagons but some of which are 5- and 7-sided rings. The proportion of pentagons in each network increases as the coated area of the plasma membrane puckers up from its planar configuration (where the network is mostly hexagons) to its most sharply curved condition as a pinched-off coated vesicle. Coats around the smallest vesicles (which are icosahedrons of hexagons and pentagons) appear only slightly different from "empty coats" purified from homogenized brain, which are less symmetrical baskets containing more pentagons than hexagons. A search for structural intermediates in this coat transformation allows a test of T. Kanaseki and K. Kadota's (1969. J. Cell Biol. 42:202--220.) original idea that an internal rearrangement in this basketwork from hexagons to pentagons could "power" coated vesicle formation. The most noteworthy variations in the typical hexagonal honeycomb are focal juxtapositions of 5- and 7-sided polygons at points of partial contraction and curvature in the basketwork. These appear to precede complete contraction into individual pentagons completely surrounded by hexagons, which is the pattern that characterizes the final spherical baskets around coated vesicles. PMID:6987244

Iron Oxide Nanoparticles Employed as Seeds for the Induction of Microcrystalline Diamond Synthesis

PubMed Central

2008-01-01

Iron nanoparticles were employed to induce the synthesis of diamond on molybdenum, silicon, and quartz substrates. Diamond films were grown using conventional conditions for diamond synthesis by hot filament chemical vapor deposition, except that dispersed iron oxide nanoparticles replaced the seeding. X-ray diffraction, visible, and ultraviolet Raman Spectroscopy, energy-filtered transmission electron microscopy , electron energy-loss spectroscopy, and X-ray photoelectron spectroscopy (XPS) were employed to study the carbon bonding nature of the films and to analyze the carbon clustering around the seed nanoparticles leading to diamond synthesis. The results indicate that iron oxide nanoparticles lose the O atoms, becoming thus active C traps that induce the formation of a dense region of trigonally and tetrahedrally bonded carbon around them with the ensuing precipitation of diamond-type bonds that develop into microcrystalline diamond films under chemical vapor deposition conditions. This approach to diamond induction can be combined with dip pen nanolithography for the selective deposition of diamond and diamond patterning while avoiding surface damage associated to diamond-seeding methods.

Magnetic ordering temperatures in rare earth metal dysprosium under ultrahigh pressures

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

Samudrala, Gopi K.; Tsoi, Georgiy M.; Weir, Samuel T.

Magnetic ordering temperatures in heavy rare earth metal Dysprosium (Dy) have been studied using an ultrasensitive electrical transport measurement technique in a designer diamond anvil cell to extreme conditions of pressure to 69 GPa and temperature to 10 K. Previous studies using magnetic susceptibility measurements at high pressures were only able to track magnetic ordering temperature till 7 GPa in the hexagonal close packed ( hcp) phase of Dy. Our studies indicate that the magnetic ordering temperature shows an abrupt drop of 80 K at the hcp-Sm phase transition followed by a gradual decrease that continues till 17 GPa. Thismore » is followed by a rapid increase in the magnetic ordering temperatures in the double hexagonal close packed phase and finally leveling off in the distorted face centered cubic phase of Dy. Lastly, our studies reaffirm that 4f-shell remain localized in Dy and there is no loss of magnetic moment or 4f-shell delocalization for pressures up to 69 GPa.« less

Magnetic ordering temperatures in rare earth metal dysprosium under ultrahigh pressures

DOE PAGES

Samudrala, Gopi K.; Tsoi, Georgiy M.; Weir, Samuel T.; ...

2014-04-03

Magnetic ordering temperatures in heavy rare earth metal Dysprosium (Dy) have been studied using an ultrasensitive electrical transport measurement technique in a designer diamond anvil cell to extreme conditions of pressure to 69 GPa and temperature to 10 K. Previous studies using magnetic susceptibility measurements at high pressures were only able to track magnetic ordering temperature till 7 GPa in the hexagonal close packed ( hcp) phase of Dy. Our studies indicate that the magnetic ordering temperature shows an abrupt drop of 80 K at the hcp-Sm phase transition followed by a gradual decrease that continues till 17 GPa. Thismore » is followed by a rapid increase in the magnetic ordering temperatures in the double hexagonal close packed phase and finally leveling off in the distorted face centered cubic phase of Dy. Lastly, our studies reaffirm that 4f-shell remain localized in Dy and there is no loss of magnetic moment or 4f-shell delocalization for pressures up to 69 GPa.« less

Near-zero thermal expansion in magnetically ordered state in dysprosium at high pressures and low temperatures

NASA Astrophysics Data System (ADS)

Hope, Kevin M.; Samudrala, Gopi K.; Vohra, Yogesh K.

2017-01-01

The atomic volume of rare earth metal dysprosium (Dy) has been measured up to high pressures of 35 GPa and low temperatures between 200 and 7 K in a diamond anvil cell using angle dispersive X-ray diffraction at a synchrotron source. The hexagonal close-packed (hcp), alpha-Samarium (α-Sm), and double hexagonal close-packed (dhcp) phases are observed to be stable in Dy under high-pressure and low-temperature conditions achieved in our experiments. Dy is known to undergo magnetic ordering below 176 K at ambient pressure with magnetic ordering Néel temperature (TN) that changes rapidly with increasing pressure. Our experimental measurement shows that Dy has near-zero thermal expansion in the magnetically ordered state and normal thermal expansion in the paramagnetic state for all the three known high pressure phases (hcp, α-Sm, and dhcp) to 35 GPa. This near-zero thermal expansion behavior in Dy is observed below the magnetic ordering temperature TN at all pressures up to 35 GPa.

Formation mechanism of graphite hexagonal pyramids by argon plasma etching of graphite substrates

NASA Astrophysics Data System (ADS)

Glad, X.; de Poucques, L.; Bougdira, J.

2015-12-01

A new graphite crystal morphology has been recently reported, namely the graphite hexagonal pyramids (GHPs). They are hexagonally-shaped crystals with diameters ranging from 50 to 800 nm and a constant apex angle of 40°. These nanostructures are formed from graphite substrates (flexible graphite and highly ordered pyrolytic graphite) in low pressure helicon coupling radiofrequency argon plasma at 25 eV ion energy and, purportedly, due to a physical etching process. In this paper, the occurrence of peculiar crystals is shown, presenting two hexagonal orientations obtained on both types of samples, which confirms such a formation mechanism. Moreover, by applying a pretreatment step with different time durations of inductive coupling radiofrequency argon plasma, for which the incident ion energy decreases at 12 eV, uniform coverage of the surface can be achieved with an influence on the density and size of the GHPs.

Surface characterization and orientation interaction between diamond- like carbon layer structure and dimeric liquid crystals

NASA Astrophysics Data System (ADS)

Naradikian, H.; Petrov, M.; Katranchev, B.; Milenov, T.; Tinchev, S.

2017-01-01

Diamond-like carbon (DLC) and amorphous carbon films are very promising type of semiconductor materials. Depending on the hybridization sp2/sp3 ratio, the material’s band gap varies between 0.8 and 3 eV. Moreover carbon films possess different interesting for practice properties: comparable to the Silicon, Diamond like structure has 22-time better thermal conductivity etc. Here we present one type of implementation of such type nanostructure. That is one attempt for orientation of dimeric LC by using of pre-deposited DLC layer with different ratio of sp2/sp3 hybridized carbon content. It could be expected a pronounced π1-π2interaction between s and p orbital levels on the surface and the dimeric ring of LC. We present comparison of surface anchoring strengths of both orientation inter-surfaces DLC/dimeric LC and single wall carbon nanotubes (SWCNT)/dimeric LC. The mechanism of interaction of dimeric LC and activated surfaces with DLC or SWCNT will be discussed. In both cases we have π-π interaction, which in combination with hydrogen bonding, typical for the dimeric LCs, influence the LC alignment. The Raman spectroscopy data evidenced the presence of charge transfer between contacting hexagonal rings of DLC and the C = O groups of the LC molecules.

Ultrananocrystalline diamond-coated nanoporous membranes support SK-N-SH neuroblastoma endothelial cell attachment.

PubMed

Yang, Kai-Hung; Nguyen, Alexander K; Goering, Peter L; Sumant, Anirudha V; Narayan, Roger J

2018-06-06

Ultrananocrystalline diamond (UNCD) has been demonstrated to have attractive features for biomedical applications and can be combined with nanoporous membranes for applications in drug delivery systems, biosensing, immunoisolation and single molecule analysis. In this study, free-standing nanoporous UNCD membranes with pore sizes of 100 or 400 nm were fabricated by directly depositing ultrathin UNCD films on nanoporous silicon nitride membranes and then etching away silicon nitride using reactive ion etching. Successful deposition of UNCD on the substrate with a novel process was confirmed with Raman spectroscopy, X-ray photoelectron spectroscopy, cross-section scanning electron microscopy (SEM) and transmission electron microscopy. Both sample types exhibited uniform geometry and maintained a clear hexagonal pore arrangement. Cellular attachment of SK-N-SH neuroblastoma endothelial cells was examined using confocal microscopy and SEM. Attachment of SK-N-SH cells onto UNCD membranes on both porous regions and solid surfaces was shown, indicating the potential use of UNCD membranes in biomedical applications such as biosensors and tissue engineering scaffolds.

Direct Coating of Nanocrystalline Diamond on Steel

NASA Astrophysics Data System (ADS)

Tsugawa, Kazuo; Kawaki, Shyunsuke; Ishihara, Masatou; Hasegawa, Masataka

2012-09-01

Nanocrystalline diamond films have been successfully deposited on stainless steel substrates without any substrate pretreatments to promote diamond nucleation, including the formation of interlayers. A low-temperature growth technique, 400 °C or lower, in microwave plasma chemical vapor deposition using a surface-wave plasma has cleared up problems in diamond growth on ferrous materials, such as the surface graphitization, long incubation time, substrate softening, and poor adhesion. The deposited nanocrystalline diamond films on stainless steel exhibit good adhesion and tribological properties, such as a high wear resistance, a low friction coefficient, and a low aggression strength, at room temperature in air without lubrication.

Regional patterns in the paragenesis and age of inclusions in diamond, diamond composition, and the lithospheric seismic structure of Southern Africa

NASA Astrophysics Data System (ADS)

Shirey, Steven B.; Harris, Jeffrey W.; Richardson, Stephen H.; Fouch, Matthew; James, David E.; Cartigny, Pierre; Deines, Peter; Viljoen, Fanus

2003-12-01

The Archean lithospheric mantle beneath the Kaapvaal-Zimbabwe craton of Southern Africa shows ±1% variations in seismic P-wave velocity at depths within the diamond stability field (150-250 km) that correlate regionally with differences in the composition of diamonds and their syngenetic inclusions. Seismically slower mantle trends from the mantle below Swaziland to that below southeastern Botswana, roughly following the surface outcrop pattern of the Bushveld-Molopo Farms Complex. Seismically slower mantle also is evident under the southwestern side of the Zimbabwe craton below crust metamorphosed around 2 Ga. Individual eclogitic sulfide inclusions in diamonds from the Kimberley area kimberlites, Koffiefontein, Orapa, and Jwaneng have Re-Os isotopic ages that range from circa 2.9 Ga to the Proterozoic and show little correspondence with these lithospheric variations. However, silicate inclusions in diamonds and their host diamond compositions for the above kimberlites, Finsch, Jagersfontein, Roberts Victor, Premier, Venetia, and Letlhakane do show some regional relationship to the seismic velocity of the lithosphere. Mantle lithosphere with slower P-wave velocity correlates with a greater proportion of eclogitic versus peridotitic silicate inclusions in diamond, a greater incidence of younger Sm-Nd ages of silicate inclusions, a greater proportion of diamonds with lighter C isotopic composition, and a lower percentage of low-N diamonds whereas the converse is true for diamonds from higher velocity mantle. The oldest formation ages of diamonds indicate that the mantle keels which became continental nuclei were created by middle Archean (3.2-3.3 Ga) mantle depletion events with high degrees of melting and early harzburgite formation. The predominance of sulfide inclusions that are eclogitic in the 2.9 Ga age population links late Archean (2.9 Ga) subduction-accretion events involving an oceanic lithosphere component to craton stabilization. These events resulted in a widely distributed younger Archean generation of eclogitic diamonds in the lithospheric mantle. Subsequent Proterozoic tectonic and magmatic events altered the composition of the continental lithosphere and added new lherzolitic and eclogitic diamonds to the already extensive Archean diamond suite.

A quasi-hexagonal prism-shaped carbon nitride for photoreduction of carbon dioxide under visible light.

PubMed

He, Zhiqiao; Wang, Danfen; Tang, Juntao; Song, Shuang; Chen, Jianmeng; Tao, Xinyong

2017-03-01

A quasi-hexagonal prism-shaped carbon nitride (H-C 3 N 4 ) was synthesized from urea-derived C 3 N 4 (U-C 3 N 4 ) using an alkaline hydrothermal process. U-C 3 N 4 decomposition followed by hydrogen bond rearrangement of hydrolyzed products leads to the formation of a quasi-hexagonal prism-shaped structure. The H-C 3 N 4 catalysts displayed superior activity in the photoreduction of CO 2 with H 2 O compared to U-C 3 N 4 . The enhanced photocatalytic activities can be attributed to the promotion of incompletely coordinated nitrogen atom formation in the C 3 N 4 molecules. Graphical abstract ᅟ.

Local formation of nitrogen-vacancy centers in diamond by swift heavy ions

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

Schwartz, J.; Aloni, S.; Ogletree, D. F.

2014-12-03

In this paper, we exposed nitrogen-implanted diamonds to beams of swift heavy ions (~1 GeV, ~4 MeV/u) and find that these irradiations lead directly to the formation of nitrogen vacancy (NV) centers, without thermal annealing. We compare the photoluminescence intensities of swift heavy ion activated NV - centers to those formed by irradiation with low-energy electrons and by thermal annealing. NV - yields from irradiations with swift heavy ions are 0.1 of yields from low energy electrons and 0.02 of yields from thermal annealing. We discuss possible mechanisms of NV center formation by swift heavy ions such as electronic excitationsmore » and thermal spikes. While forming NV centers with low efficiency, swift heavy ions could enable the formation of three dimensional NV - assemblies over relatively large distances of tens of micrometers. Finally and further, our results show that NV center formation is a local probe of (partial) lattice damage relaxation induced by electronic excitations from swift heavy ions in diamond.« less

Formation of the nitrogen aggregates in annealed diamond by neutron irradiation

NASA Astrophysics Data System (ADS)

Mita, Y.; Nisida, Y.; Okada, M.

2018-02-01

Neutron heavy irradiation was performed on synthetic diamonds contain nitrogen atoms in isolated substitutional form (called "type Ib diamond") and they were annealed under a pressure of 6 GPa. A large number of nitrogen B-aggregate which consists of four substitutional nitrogen atoms symmetrically surrounding a vacancy was formed within 30 m from single nitrogen atoms. Furthermore it is observed that, in these diamonds, single nitrogen atoms coexist with the B-aggregates, which is unexplainable by the simple nitrogen aggregation model.

Novel phase of carbon, ferromagnetism, and conversion into diamond

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

Narayan, Jagdish, E-mail: narayan@ncsu.edu; Bhaumik, Anagh

2015-12-07

We report the discovery of a new phase of carbon (referred to as Q-carbon) and address fundamental issues related to direct conversion of carbon into diamond at ambient temperatures and pressures in air without any need for catalyst and presence of hydrogen. The Q-carbon is formed as result of quenching from super undercooled state by using high-power nanosecond laser pulses. We discuss the equilibrium phase diagram (P vs. T) of carbon and show that by rapid quenching kinetics can shift thermodynamic graphite/diamond/liquid carbon triple point from 5000 K/12 GPa to super undercooled carbon at atmospheric pressure in air. It is shown thatmore » nanosecond laser heating of diamond-like amorphous carbon on sapphire, glass, and polymer substrates can be confined to melt carbon in a super undercooled state. By quenching the carbon from the super undercooled state, we have created a new state of carbon (Q-carbon) from which nanodiamond, microdiamond, microneedles, and single-crystal thin films are formed depending upon the nucleation and growth times allowed for diamond formation. The Q-carbon quenched from liquid is a new state of solid carbon with a higher mass density than amorphous carbon and a mixture of mostly fourfold sp{sup 3} (75%–85%) with the rest being threefold sp{sup 2} bonded carbon (with distinct entropy). It is expected to have new and improved mechanical hardness, electrical conductivity, chemical, and physical properties, including room-temperature ferromagnetism (RTFM) and enhanced field emission. Here we present interesting results on RTFM, enhanced electrical conductivity and surface potential of Q-carbon to emphasize its unique properties. The Q-carbon exhibits robust bulk ferromagnetism with estimated Curie temperature of about 500 K and saturation magnetization value of 20 emu g{sup −1}. From the Q-carbon, diamond phase is nucleated and a variety of micro- and nanostructures and large-area single-crystal diamond sheets are grown by allowing growth times as needed. Subsequent laser pulses can be used to grow nanodiamond into microdiamond and nucleate other nanostructures of diamond on the top of existing microdiamond and create novel nanostructured materials. The microstructural details provide insights into the mechanism of formation of nanodiamond, microdiamond, nanoneedles, microneedles, and single-crystal thin films. This process allows carbon-to-diamond conversion and formation of useful nanostructures and microstructures at ambient temperatures in air at atmospheric pressure on practical and heat-sensitive substrates in a controlled way without need for any catalysts and hydrogen to stabilize sp{sup 3} bonding for diamond formation.« less

Novel phase of carbon, ferromagnetism, and conversion into diamond

NASA Astrophysics Data System (ADS)

Narayan, Jagdish; Bhaumik, Anagh

2015-12-01

We report the discovery of a new phase of carbon (referred to as Q-carbon) and address fundamental issues related to direct conversion of carbon into diamond at ambient temperatures and pressures in air without any need for catalyst and presence of hydrogen. The Q-carbon is formed as result of quenching from super undercooled state by using high-power nanosecond laser pulses. We discuss the equilibrium phase diagram (P vs. T) of carbon and show that by rapid quenching kinetics can shift thermodynamic graphite/diamond/liquid carbon triple point from 5000 K/12 GPa to super undercooled carbon at atmospheric pressure in air. It is shown that nanosecond laser heating of diamond-like amorphous carbon on sapphire, glass, and polymer substrates can be confined to melt carbon in a super undercooled state. By quenching the carbon from the super undercooled state, we have created a new state of carbon (Q-carbon) from which nanodiamond, microdiamond, microneedles, and single-crystal thin films are formed depending upon the nucleation and growth times allowed for diamond formation. The Q-carbon quenched from liquid is a new state of solid carbon with a higher mass density than amorphous carbon and a mixture of mostly fourfold sp3 (75%-85%) with the rest being threefold sp2 bonded carbon (with distinct entropy). It is expected to have new and improved mechanical hardness, electrical conductivity, chemical, and physical properties, including room-temperature ferromagnetism (RTFM) and enhanced field emission. Here we present interesting results on RTFM, enhanced electrical conductivity and surface potential of Q-carbon to emphasize its unique properties. The Q-carbon exhibits robust bulk ferromagnetism with estimated Curie temperature of about 500 K and saturation magnetization value of 20 emu g-1. From the Q-carbon, diamond phase is nucleated and a variety of micro- and nanostructures and large-area single-crystal diamond sheets are grown by allowing growth times as needed. Subsequent laser pulses can be used to grow nanodiamond into microdiamond and nucleate other nanostructures of diamond on the top of existing microdiamond and create novel nanostructured materials. The microstructural details provide insights into the mechanism of formation of nanodiamond, microdiamond, nanoneedles, microneedles, and single-crystal thin films. This process allows carbon-to-diamond conversion and formation of useful nanostructures and microstructures at ambient temperatures in air at atmospheric pressure on practical and heat-sensitive substrates in a controlled way without need for any catalysts and hydrogen to stabilize sp3 bonding for diamond formation.

Positive anomaly in platinum group elements and the presence of shocked diamonds: Two question marks at the Younger Dryas

NASA Astrophysics Data System (ADS)

Claeys, P. F.; Schryvers, D.; Tian, H.; Goderis, S.

2009-12-01

Recently, a large size impact was proposed as the cause of the global changes taking place at the Younger Dryas (YD) some 12,9 kyr ago. Impact evidence was reported in a C-rich black layer of broad geographic distribution. The impact markers consist of a large anomaly in the concentration of platinum group elements (PGE) and the presence of nanodiamonds, in particular lonsdaleite, which hexagonal structure is believed to be of shock origin. The impact is proposed to have occurred on the North American continent. A crater large enough (> 150 km) to induce a mass extinction some ~12.9 ka ago, formed in a geologically well-known area, is unlikely to have escaped detection. Therefore, an alternative hypothesis is that a cometary projectile exploded fully within the atmosphere spreading PGE and shock formed diamonds, without any target rock contribution, all around the Northern hemisphere. So far, PGE measurements failed to reproduce the elevated (> ppb) concentrations reported previously at Younger Dryas sites containing the black layer. In Lommel (Belgium) where the first study detected up to 117 ppb Ir, the Ir concentration is below the detection limit of the method (NiS fire assay + ICP-MS) used (0.06 ppb). At all sites analyzed the PGE pattern is typical of that of the continental crust. In several craters (Popigai, Ries) or at the KT boundary nanodiamonds have been reported associated with shocked materials. Several types of carbon components occur in the black layer of the Lommel section such as i) flakes reaching up to 1 µm, ii) nano particles of cubic diamond, 1 to 10 nm in size and iii) larger carbon onion-ring structures, which core can act as a nanoscopic pressure cell leading to the formation of nanodiamond by self- compression. The Lommel nanodiamonds present in the Younger Dryas layer do resemble nanodiamonds found in carbon spherules of unknown origin previously reported in top soil from several localities in Belgium and Germany. The C stable isotopic signature measured in the C-rich black layer is clearly produced by organic matter of terrestrial origin (-29‰).

Microinclusions in polycrystalline diamonds: insights into processes of diamond formation

NASA Astrophysics Data System (ADS)

Jacob, D. E.; Wirth, R.; Enzmann, F.; Schwarz, J. O.; Kronz, A.

2009-04-01

Polycrystalline diamond aggregates (framesites) contain silicates of eclogitic and peridotitic affinity (e.g. Kurat and Dobosi, 2000). The minerals occur mostly in interstices and are intimately intergrown with the diamonds, indicating contemporaneous crystallization within the diamond stability field in the Earth's mantle. In addition to silicates, rarer phases such as Fe-carbide can sometimes be found in framesites that record unusually low local oxygen fugacity at the time of their formation (Jacob et al., 2004). Furthermore, while most gem-sized diamonds have old, often Archaean formation ages, some polycrystalline diamond aggregates have been shown to form directly preceding the kimberlite eruption (Jacob et al., 2000). Thus, these samples may provide a unique source of information on the nature and timing of small scale processes that lead to diamond formation and complement evidence from gem-sized diamonds. Here, we present a study of micro- and nano-inclusions in diamonds from a polycrystalline diamond aggregate (framesite) from the Orapa Mine (Botswana) and combine results from TEM/FIB analyses with high-resolution computerized micro-tomography (HR-µCT) and electron microprobe analyses to further constrain the formation of diamond in the Earth's mantle. Results In total, 14 microinclusions from fifteen FIB foils were investigated. Micro- and nano-inclusions identified by TEM were smaller than 1µm down to ca. 50nm in size, and are both monomineralic and multi-phase. The cavities are often lath-shaped and oriented parallel to each other; many show lattice dislocations in the surrounding diamond. In addition, inclusions are found along open cracks within the diamond single crystals. Mineral phases in the microinclusions comprise rutile, omphacite and a FeS phase (pyrrhotite). The multiphase inclusions most often consist of cavities that are only partly occupied (less than 50% of the total space), suggesting that the empty space was originally filled by a fluid. One multiphase inclusion was found to be still fluid-bearing, showing characteristic continuous changes in diffraction contrast due to density fluctuations caused by the electron beam. No other elements than carbon were detected during AEM of this area which suggests that the fluid consists of relatively pure C-H-O species. In addition to the fluid, this inclusion contained fine-grained FeS, a silicate phase rich in Fe, P, Mg, Al, Ca and K and a quench phase, rich in Fe, P and Si. Macroinclusions (>5µm) are magnetite, often surrounded by hematite, FeS, low-Cr garnet (Py50Alm39Grs11) and omphacite (Jd23). Garnet and cpx were found as non-touching inclusions and yield 1256°C at 5 GPa. Most of the magnetite inclusions are single crystals and some are strongly deformed with signs of recrystallization. Hematite occurs as porous aggregates of nano-granules of ca. 5-7 nm sizes. High Resolution µ-Computer Tomography (HR-µCT) shows pores in the sample and the included mineral phases as areas of differing grey-values. These are a direct function of the specific x-ray density of the specific phase and can be used to differentiate oxides and silicates. Based on the 3D tomogram, the amount of pores per total volume of the diamond plus inclusion matrix is calculated to be 0.65 vol%, while magnetite inclusions amount to 3.16 vol%. The average equivalent radius of the magnetite grains (radius of a sphere with the same volume as the grain) is 17.8 µm, while that of the pores is 12.6µm. Discussion The occurrence of omphacite, rutile and FeS as microinclusions within the diamond crystals clearly shows that these phases are cogenetic to the diamonds. However, magnetite and hematite were only encountered as large inclusions in cavities that appear to be interstitial porosity. Moreover, analysis of the equivalent radius distribution of the pores and the magnetite inclusions derived from HR-µCT shows a complete overlap of the mode, indicating that magnetite preferentially fills the porosity in the sample. Furthermore, hematite occurs exclusively along the outer rim of the magnetite crystals and textural features suggest that this phase is a late replacement product of magnetite. This shows that the magnetite-bearing cavities were not shielded from the outside by the host diamond and may indicate that magnetite itself was introduced after diamond formation or during a secondary event that may still, however, have taken place at PT conditions of the diamond stability field. The microinclusion suite described here is distinct from that found in fibrous (e.g. Klein-BenDavid et al., 2007) and in microdiamonds (Kvasnytsya et al., 2006). Carbonates, halides and phosphates, that are typical for fibrous and microdiamonds were not encountered in our study. Instead, the microinclusion suite found in the framesite consists of the typical eclogitic minerals (rutile, garnet, omphacite, sulphide) plus a C-H-O fluid. Jacob et al., 2004. Contrib. Mineral. Petrol., 146, 566-576. Jacob et al., 2000. Science, 289, 1182-1185. Klein-BenDavid et al., 2007. Amer. Mineral. 91, 353-365. Kurat and Dobosi, 2000. Mineral. Petrol. 69, 143-159. Kvasnytsya et al., 2006. Ukrainian Geologist 2, 25-36.

Morphological Features of Diamond Crystals Dissolved in Fe0.7S0.3 Melt at 4 GPa and 1400°C

NASA Astrophysics Data System (ADS)

Sonin, V. M.; Zhimulev, E. I.; Pomazanskiy, B. S.; Zemnuhov, A. L.; Chepurov, A. A.; Afanasiev, V. P.; Chepurov, A. I.

2018-01-01

An experimental study of the dissolution of natural and synthetic diamonds in a sulfur-bearing iron melt (Fe0.7S0.3) with high P-T parameters (4 GPa, 1400°C) was performed. The results demonstrated that under these conditions, octahedral crystals with flat faces and rounded tetrahexahedral diamond crystals are transformed into rounded octahedroids, which have morphological characteristics similar to those of natural diamonds from kimberlite. It was suggested that, taking into account the complex history of individual natural diamond crystals, including the dissolution stages, sulfur-bearing metal melts up to sulfide melts were not only diamond-forming media during the early evolution of the Earth, but also natural solvents of diamond in the mantle environment before the formation of kimberlitic melts.

Effect of diamond-like carbon thin film coated acrylic resin on candida albicans biofilm formation.

PubMed

Queiroz, José Renato Cavalcanti; Fissmer, Sara Fernanda; Koga-Ito, Cristiane Yumi; Salvia, Ana C R D; Massi, Marcos; Sobrinho, Argermiro Soares da Silva; Júnior, Lafayette Nogueira

2013-08-01

The purpose of this study was to evaluate the effect of diamond-like carbon thin films doped and undoped with silver nanoparticles coating poly(methyl methacrylate) (PMMA) on Candida albicans biofilm formation. The control of biofilm formation is important to prevent oral diseases in denture users. Forty-five PMMA disks were obtained, finished, cleaned in an ultrasonic bath, and divided into three groups: Gc, no surface coating (control group); Gdlc, coated with diamond-like carbon film; and Gag, coated with diamond-like carbon film doped with silver nanoparticles. The films were deposited using a reactive magnetron sputtering system (physical vapor deposition process). The specimens were characterized by optical profilometry, atomic force microscopy, and Rutherford backscattering spectroscopy analyses that determined differences in chemical composition and morphological structure. Following sterilization of the specimens by γ-ray irradiation, C. albicans (ATCC 18804) biofilms were formed by immersion in 2 ml of Sabouraud dextrose broth inoculated with a standardized fungal suspension. After 24 hours, the number of colony forming units (cfu) per specimen was counted. Data concerning biofilm formation were analyzed using ANOVA and the Tukey test (p < 0.05). C. albicans biofilm formation was significantly influenced by the films (p < 0.00001), reducing the number of cfu, while not affecting the roughness parameters (p > 0.05). The Tukey test showed no significant difference between Gdlc and Gag. Films deposited were extremely thin (∼50 nm). The silver particles presented a diameter between 60 and 120 nm and regular distribution throughout the film surface (to Gag). Diamond-like carbon films, doped or undoped with silver nanoparticles, coating the base of PMMA-based dentures could be an alternative procedure for preventing candidosis in denture users. © 2013 by the American College of Prosthodontists.

Nanodiamond finding in the hyblean shallow mantle xenoliths.

PubMed

Simakov, S K; Kouchi, A; Mel'nik, N N; Scribano, V; Kimura, Y; Hama, T; Suzuki, N; Saito, H; Yoshizawa, T

2015-06-01

Most of Earth's diamonds are connected with deep-seated mantle rocks; however, in recent years, μm-sized diamonds have been found in shallower metamorphic rocks, and the process of shallow-seated diamond formation has become a hotly debated topic. Nanodiamonds occur mainly in chondrite meteorites associated with organic matter and water. They can be synthesized in the stability field of graphite from organic compounds under hydrothermal conditions. Similar physicochemical conditions occur in serpentinite-hosted hydrothermal systems. Herein, we report the first finding of nanodiamonds, primarily of 6 and 10 nm, in Hyblean asphaltene-bearing serpentinite xenoliths (Sicily, Italy). The discovery was made by electron microscopy observations coupled with Raman spectroscopy analyses. The finding reveals new aspects of carbon speciation and diamond formation in shallow crustal settings. Nanodiamonds can grow during the hydrothermal alteration of ultramafic rocks, as well as during the lithogenesis of sediments bearing organic matter.

Synthesis and Characterization of Quenched and Crystalline Phases: Q-Carbon, Q-BN, Diamond and Phase-Pure c-BN

NASA Astrophysics Data System (ADS)

Bhaumik, Anagh; Narayan, Jagdish

2018-04-01

We report the synthesis and characterization of quenched (Q-carbon and Q-BN) and crystalline (diamond and c-BN) phases using a non-equilibrium technique. These phases are formed as a result of the melting and subsequent quenching of amorphous carbon and nanocrystalline h-BN in a super undercooled state by using high-power nanosecond laser pulses. Pulsed laser annealing also leads to the formation of nanoneedles, microneedles and single-crystal thin films of diamond and c-BN. This formation is dependent on the nucleation and growth times, which are controlled by laser energy density and thermal conductivities of substrate and as-deposited thin film. The diamond nuclei present in the Q-carbon structure ( 80% sp 3) can also be grown to larger sizes using the equilibrium hot filament chemical vapor deposition process. The texture of diamond and c-BN crystals is <111> under epitaxial growth and <110> under rapid unseeded crystallization. Our nanosecond laser processing opens up a roadmap to the fabrication of novel phases on heat-sensitive substrates.

Size-dependent reactivity of diamond nanoparticles.

PubMed

Williams, Oliver A; Hees, Jakob; Dieker, Christel; Jäger, Wolfgang; Kirste, Lutz; Nebel, Christoph E

2010-08-24

Photonic active diamond nanoparticles attract increasing attention from a wide community for applications in drug delivery and monitoring experiments as they do not bleach or blink over extended periods of time. To be utilized, the size of these diamond nanoparticles needs to be around 4 nm. Cluster formation is therefore the major problem. In this paper we introduce a new technique to modify the surface of particles with hydrogen, which prevents cluster formation in buffer solution and which is a perfect starting condition for chemical surface modifications. By annealing aggregated nanodiamond powder in hydrogen gas, the large (>100 nm) aggregates are broken down into their core ( approximately 4 nm) particles. Dispersion of these particles into water via high power ultrasound and high speed centrifugation, results in a monodisperse nanodiamond colloid, with exceptional long time stability in a wide range of pH, and with high positive zeta potential (>60 mV). The large change in zeta potential resulting from this gas treatment demonstrates that nanodiamond particle surfaces are able to react with molecular hydrogen at relatively low temperatures, a phenomenon not witnessed with larger (20 nm) diamond particles or bulk diamond surfaces.

Process of negative-muon-induced formation of an ionized acceptor center ({sub μ}A){sup –} in crystals with the diamond structure

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

Belousov, Yu. M., E-mail: theorphys@phystech.edu

The formation of an ionized acceptor center by a negative muon in crystals with the diamond structure is considered. The negative muon entering a target is captured by a nucleus, forming a muonic atom {sub μ}A coupled to a lattice. The appearing radiation-induced defect has a significant electric dipole moment because of the violation of the local symmetry of the lattice and changes the phonon spectrum of the crystal. The ionized acceptor center is formed owing to the capture of an electron interacting with the electric dipole moment of the defect and with the radiation of a deformation-induced local-mode phonon.more » Upper and lower bounds of the formation rate of the ionized acceptor center in diamond, silicon, and germanium crystals are estimated. It is shown that the kinetics of the formation of the acceptor center should be taken into account when processing μSR experimental data.« less

Structure, properties, and possible mechanisms of formation of diamond-like phases

NASA Astrophysics Data System (ADS)

Belenkov, E. A.; Greshnyakov, V. A.

2016-10-01

An analysis was performed for relations between the structural parameters and the properties of 36 carbon diamond-like phases consisting of atoms occupying crystallographically equivalent positions. It was found that the crystal lattices of these phases were in stressed states with respect to the cubic diamond lattice. The density of diamond-like phases, their sublimation energies, bulk moduli, hardnesses, and band gaps depend on the deformation parameters Def and Str. The most stable phases must be phases with minimal parameters Def and Str and also with ring parameter Rng that is most close to the corresponding parameter of cubic diamond. The structures and energy characteristics of fullerites, nanotube bundles, and graphene layers of which diamond-like phases can be obtained as a result of polymerization at high pressures have been calculated.

Local formation of nitrogen-vacancy centers in diamond by swift heavy ions

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

Schwartz, J.; Ilmenau University of Technology, Department of Microelectronics and Nanoelectric Systems, 98684 Ilmenau; Aloni, S.

2014-12-07

We exposed nitrogen-implanted diamonds to beams of swift heavy ions (∼1 GeV, ∼4 MeV/u) and find that these irradiations lead directly to the formation of nitrogen vacancy (NV) centers, without thermal annealing. We compare the photoluminescence intensities of swift heavy ion activated NV{sup −} centers to those formed by irradiation with low-energy electrons and by thermal annealing. NV{sup −} yields from irradiations with swift heavy ions are 0.1 of yields from low energy electrons and 0.02 of yields from thermal annealing. We discuss possible mechanisms of NV center formation by swift heavy ions such as electronic excitations and thermal spikes. While formingmore » NV centers with low efficiency, swift heavy ions could enable the formation of three dimensional NV{sup −} assemblies over relatively large distances of tens of micrometers. Further, our results show that NV center formation is a local probe of (partial) lattice damage relaxation induced by electronic excitations from swift heavy ions in diamond.« less

Fluorinated diamond particles bonded in a filled fluorocarbon resin matrix

DOEpatents

Taylor, G.W.; Roybal, H.E.

1983-11-14

A method of producing fluorinated diamond particles bonded in a filled fluorocarbon resin matrix. Simple hot pressing techniques permit the formation of such matrices from which diamond impregnated grinding tools and other articles of manufacture can be produced. Teflon fluorocarbon resins filled with Al/sub 2/O/sub 3/ yield grinding tools with substantially improved work-to-wear ratios over grinding wheels known in the art.

Fluorinated diamond particles bonded in a filled fluorocarbon resin matrix

DOEpatents

Taylor, Gene W.; Roybal, Herman E.

1985-01-01

A method of producing fluorinated diamond particles bonded in a filled fluorocarbon resin matrix. Simple hot pressing techniques permit the formation of such matrices from which diamond impregnated grinding tools and other articles of manufacture can be produced. Teflon fluorocarbon resins filled with Al.sub.2 O.sub.3 yield grinding tools with substantially improved work-to-wear ratios over grinding wheels known in the art.

Growth and tribological properties of diamond films on silicon and tungsten carbide substrates

NASA Astrophysics Data System (ADS)

Radhika, R.; Ramachandra Rao, M. S.

2016-11-01

Hot filament chemical vapor deposition technique was used to deposit microcrystalline diamond (MCD) and nanocrystalline diamond (NCD) films on silicon (Si) and tungsten carbide (WC-6Co) substrates. Friction coefficient of larger diamond grains deposited on WC-6Co substrate shows less value approximately 0.2 while this differs marginally on films grown on Si substrate. The study claims that for a less friction coefficient, the grain size is not necessarily smaller. However, the less friction coefficient (less than 0.1 saturated value) in MCD and NCD deposited on Si is explained by the formation of graphitized tribolayer. This layer easily forms when diamond phase is thermodynamically unstable.

Diamond Composite Films for Protective Coatings on Metals and Method of Formation

NASA Technical Reports Server (NTRS)

Ong, Tiong P. (Inventor); Shing, Yuh-Han (Inventor)

1997-01-01

Composite films consisting of diamond crystallites and hard amorphous films such as diamond-like carbon, titanium nitride, and titanium oxide are provided as protective coatings for metal substrates against extremely harsh environments. A composite layer having diamond crystallites and a hard amorphous film is affixed to a metal substrate via an interlayer including a bottom metal silicide film and a top silicon carbide film. The interlayer is formed either by depositing metal silicide and silicon carbide directly onto the metal substrate, or by first depositing an amorphous silicon film, then allowing top and bottom portions of the amorphous silicon to react during deposition of the diamond crystallites, to yield the desired interlayer structure.

Self-Assembly of a [1+1] Ionic Hexagonal Macrocycle and its Antiproliferative Activity

NASA Astrophysics Data System (ADS)

Singh, Khushwant; Gangrade, Ankit; Bhowmick, Sourav; Jana, Achintya; Mandal, Biman B.; Das, Neeladri

2018-04-01

A unique irregular hexagon was self-assembled using an organic donor clip (bearing terminal pyridyl units) and a complementary organometallic acceptor clip. The resulting metallamacrocycle was characterized by multinuclear NMR, mass spectrometry, and elemental analyses. Molecular modeling confirmed hexagonal shaped cavity for this metallamacrocycle which is a unique example of a discrete hexagonal framework self-assembled from only two building blocks. Cytotoxicity of the Pt-based acceptor tecton and the self-assembled PtII-based macrocycle was evaluated using three cancer cell lines and results were compared with cisplatin. Results confirmed a positive effect of the metallamacrocycle formation on cell growth inhibition.

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

Velten, Sven; Streubel, Robert; Farhan, Alan

We report a magnetic X-ray microscopy study of the pattern formation of circulation in arrays of magnetic vortices ordered in a hexagonal and a honeycomb lattice. In the honeycomb lattice, we observe at remanence an ordered phase of alternating circulations, whereas in the hexagonal lattice, small regions of alternating lines form. A variation in the edge-to-edge distance shows that the size of those regions scales with the magnetostatic interaction. Micromagnetic simulations reveal that the patterns result from the formation of flux closure states during the nucleation process.

Enhancement of oxidation resistance via a self-healing boron carbide coating on diamond particles

PubMed Central

Sun, Youhong; Meng, Qingnan; Qian, Ming; Liu, Baochang; Gao, Ke; Ma, Yinlong; Wen, Mao; Zheng, Weitao

2016-01-01

A boron carbide coating was applied to diamond particles by heating the particles in a powder mixture consisting of H3BO3, B and Mg. The composition, bond state and coverage fraction of the boron carbide coating on the diamond particles were investigated. The boron carbide coating prefers to grow on the diamond (100) surface than on the diamond (111) surface. A stoichiometric B4C coating completely covered the diamond particle after maintaining the raw mixture at 1200 °C for 2 h. The contribution of the boron carbide coating to the oxidation resistance enhancement of the diamond particles was investigated. During annealing of the coated diamond in air, the priory formed B2O3, which exhibits a self-healing property, as an oxygen barrier layer, which protected the diamond from oxidation. The formation temperature of B2O3 is dependent on the amorphous boron carbide content. The coating on the diamond provided effective protection of the diamond against oxidation by heating in air at 1000 °C for 1 h. Furthermore, the presence of the boron carbide coating also contributed to the maintenance of the static compressive strength during the annealing of diamond in air. PMID:26831205

Enhancement of oxidation resistance via a self-healing boron carbide coating on diamond particles.

PubMed

Sun, Youhong; Meng, Qingnan; Qian, Ming; Liu, Baochang; Gao, Ke; Ma, Yinlong; Wen, Mao; Zheng, Weitao

2016-02-02

A boron carbide coating was applied to diamond particles by heating the particles in a powder mixture consisting of H3BO3, B and Mg. The composition, bond state and coverage fraction of the boron carbide coating on the diamond particles were investigated. The boron carbide coating prefers to grow on the diamond (100) surface than on the diamond (111) surface. A stoichiometric B4C coating completely covered the diamond particle after maintaining the raw mixture at 1200 °C for 2 h. The contribution of the boron carbide coating to the oxidation resistance enhancement of the diamond particles was investigated. During annealing of the coated diamond in air, the priory formed B2O3, which exhibits a self-healing property, as an oxygen barrier layer, which protected the diamond from oxidation. The formation temperature of B2O3 is dependent on the amorphous boron carbide content. The coating on the diamond provided effective protection of the diamond against oxidation by heating in air at 1000 °C for 1 h. Furthermore, the presence of the boron carbide coating also contributed to the maintenance of the static compressive strength during the annealing of diamond in air.

Direct observation of inversion capacitance in p-type diamond MOS capacitors with an electron injection layer

NASA Astrophysics Data System (ADS)

Matsumoto, Tsubasa; Kato, Hiromitsu; Makino, Toshiharu; Ogura, Masahiko; Takeuchi, Daisuke; Yamasaki, Satoshi; Imura, Masataka; Ueda, Akihiro; Inokuma, Takao; Tokuda, Norio

2018-04-01

The electrical properties of Al2O3/p-type diamond (111) MOS capacitors were studied with the goal of furthering diamond-based semiconductor research. To confirm the formation of an inversion layer in the p-type diamond body, an n-type layer for use as a minority carrier injection layer was selectively deposited onto p-type diamond. To form the diamond MOS capacitors, Al2O3 was deposited onto OH-terminated diamond using atomic layer deposition. The MOS capacitor showed clear inversion capacitance at 10 Hz. The minority carrier injection from the n-type layer reached the inversion n-channel diamond MOS field-effect transistor (MOSFET). Using the high-low frequency capacitance method, the interface state density, D it, within an energy range of 0.1-0.5 eV from the valence band edge energy, E v, was estimated at (4-9) × 1012 cm-2 eV-1. However, the high D it near E v remains an obstacle to improving the field effect mobility for the inversion p-channel diamond MOSFET.

Quantifying the distribution of nanodiamonds in pre-Younger Dryas to recent age deposits along Bull Creek, Oklahoma Panhandle, USA

NASA Astrophysics Data System (ADS)

Bement, Leland C.; Madden, Andrew S.; Carter, Brian J.; Simms, Alexander R.; Swindle, Andrew L.; Alexander, Hanna M.; Fine, Scott; Benamara, Mourad

2014-02-01

High levels of nanodiamonds (nds) have been used to support the transformative hypothesis that an extraterrestrial (ET) event (comet explosion) triggered Younger Dryas changes in temperature, flora and fauna assemblages, and human adaptations [Firestone RB, et al. (2007) Proc Natl Acad Sci USA 104(41):16016-16021]. We evaluate this hypothesis by establishing the distribution of nds within the Bull Creek drainage of the Beaver River basin in the Oklahoma panhandle. The earlier report of an abundance spike of nds in the Bull Creek I Younger Dryas boundary soil is confirmed, although no pure cubic diamonds were identified. The lack of hexagonal nds suggests Bull Creek I is not near any impact site. Potential hexagonal nds at Bull Creek were found to be more consistent with graphene/graphane. An additional nd spike is found in deposits of late Holocene through the modern age, indicating nds are not unique to the Younger Dryas boundary. Nd distributions do not correlate with depositional environment, pedogenesis, climate perturbations, periods of surface stability, or cultural activity.

Space Science

NASA Image and Video Library

1999-04-20

NASA's Space Optics Manufacturing Technology Center has been working to expand our view of the universe via sophisticated new telescopes. The Optics Center's goal is to develop low-cost, advanced space optics technologies for the NASA program in the 21st century, including the long-term goal of imaging Earth-like planets in distant solar systems. A segmented array of mirrors was designed by the Space Optics Manufacturing Technology Center for the solar concentrator test stand at the Marshall Space Flight Center (MSFC) for powering solar thermal propulsion engines. Each hexagon mirror has a spherical surface to approximate a parabolic concentrator when combined into the entire 18-foot diameter array. The aluminum mirrors were polished with a diamond turning machine that creates a glass-like reflective finish on metal. The precision fabrication machinery at the Space Optics Manufacturing Technology Center at MSFC can polish specialized optical elements to a world class quality of smoothness. This image shows optics physicist, Vince Huegele, examining one of the 144-segment hexagonal mirrors of the 18-foot diameter array at the MSFC solar concentrator test stand.

Space Science

NASA Image and Video Library

1999-04-20

NASA's Space Optics Manufacturing Technology Center has been working to expand our view of the universe via sophisticated new telescopes. The Optics Center's goal is to develop low-cost, advanced space optics technologies for the NASA program in the 21st century, including the long-term goal of imaging Earth-like planets in distant solar systems. A segmented array of mirrors was designed by the Space Optics Manufacturing Technology Center for solar the concentrator test stand at the Marshall Space Flight Center (MSFC) for powering solar thermal propulsion engines. Each hexagon mirror has a spherical surface to approximate a parabolic concentrator when combined into the entire 18-foot diameter array. The aluminum mirrors were polished with a diamond turning machine, that creates a glass-like reflective finish on metal. The precision fabrication machinery at the Space Optics Manufacturing Technology Center at MSFC can polish specialized optical elements to a world class quality of smoothness. This image shows optics physicist, Vince Huegele, examining one of the 144-segment hexagonal mirrors of the 18-foot diameter array at the MSFC solar concentrator test stand.

Near-zero thermal expansion in magnetically ordered state in dysprosium at high pressures and low temperatures

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

Hope, Kevin M.; Samudrala, Gopi K.; Vohra, Yogesh K.

The atomic volume of rare earth metal Dysprosium (Dy) has been measured up to high pressures of 35 GPa and low temperatures between 200 K and 7 K in a diamond anvil cell using angle dispersive x-ray diffraction at a synchrotron source. The hexagonal close-packed (hcp), alpha-Samarium (α-Sm), and double hexagonal close packed (dhcp) phases are observed to be stable in Dy under high-pressure and low-temperature conditions achieved in our experiments. Dy is known to undergo magnetic ordering below 176 K at ambient pressure with magnetic ordering Néel temperature (T N) that changes rapidly with increasing pressure. Our experimental measurementmore » shows that Dy has near-zero thermal expansion in the magnetically ordered state and normal thermal expansion in the paramagnetic state for all the three known high pressure phases (hcp, α-Sm, and dhcp) to 35 GPa. This near-zero thermal expansion behavior in Dy is observed below the magnetic ordering temperature T N at all pressures up to 35 GPa.« less

Preload evaluation of different screws in external hexagon joint.

PubMed

Assunção, Wirley Gonçalves; Delben, Juliana Aparecida; Tabata, Lucas Fernando; Barão, Valentim Adelino Ricardo; Gomes, Erica Alves; Garcia, Idelmo Rangel

2012-02-01

This study compared the maintenance of tightening torque in different retention screw types of implant-supported crowns. Twelve metallic crowns in UCLA abutments cast with cobalt-chromium alloy were attached to external hexagon osseointegrated implants with different retention screws: group A: titanium alloy retention screw; group B: gold alloy retention screw with gold coating; group C: titanium alloy retention screw with diamond-like carbon film coating; and group D: titanium alloy retention screw with aluminum titanium nitride coating. Three detorque measurements were obtained after torque insertion in each replica. Data were evaluated by analysis of variance (ANOVA), Tukey's test (P < 0.05), and t test (P < 0.05). Detorque value reduced in all groups (P < 0.05). Group A retained the highest percentage of torque in comparison with the other groups (P < 0.05). Groups B and D retained the lowest percentage of torque without statistically significant difference between them (P > 0.05). All screw types exhibited reduction in the detorque value. The titanium screw maintained the highest percentage of torque whereas the gold-coated screw and the titanium screw with aluminum titanium nitride coating retained the lowest percentage.

Near-zero thermal expansion in magnetically ordered state in dysprosium at high pressures and low temperatures

DOE PAGES

Hope, Kevin M.; Samudrala, Gopi K.; Vohra, Yogesh K.

2017-01-01

The atomic volume of rare earth metal Dysprosium (Dy) has been measured up to high pressures of 35 GPa and low temperatures between 200 K and 7 K in a diamond anvil cell using angle dispersive x-ray diffraction at a synchrotron source. The hexagonal close-packed (hcp), alpha-Samarium (α-Sm), and double hexagonal close packed (dhcp) phases are observed to be stable in Dy under high-pressure and low-temperature conditions achieved in our experiments. Dy is known to undergo magnetic ordering below 176 K at ambient pressure with magnetic ordering Néel temperature (T N) that changes rapidly with increasing pressure. Our experimental measurementmore » shows that Dy has near-zero thermal expansion in the magnetically ordered state and normal thermal expansion in the paramagnetic state for all the three known high pressure phases (hcp, α-Sm, and dhcp) to 35 GPa. This near-zero thermal expansion behavior in Dy is observed below the magnetic ordering temperature T N at all pressures up to 35 GPa.« less

Radiation-induced diamond crystallization: Origin of carbonados and its implications on meteorite nano-diamonds

USGS Publications Warehouse

Ozima, M.; Tatsumoto, M.

1997-01-01

Ten carbonados from Central Africa were studied for U-Th-Pb systematics. To extract U, Th, and Pb from the samples, we developed a cold combustion technique wherein diamond was burnt in liquid oxygen. The technique gave low blanks; 25-50 pg for Pb, 3 pg for U, and 5 pg for Th. After very thorough acid treatments of the carbonados with hot HNO3, HF, and HCl over one week, most of U, Th, and Pb were removed from the samples. Lead in the acid-leached diamonds was highly radiogenic (206Pb/204Pb up to 470). However, the amounts of U and Th in the acid-leached diamonds are too low to account for the radiogenic Pb even if we assume 4.5 Ga for the age of the diamonds. Therefore, we conclude that the radiogenic Pb was implanted into the diamonds from surroundings by means of recoil energy of radioactive decays of U and Th. From the radiogenic lead isotopic composition, we estimate a minimum age of 2.6 Ga and a maximum age of 3.8 Ga for the formation of the carbonados. The above findings of the implantation of recoiled radiogenic Pb into carbonados is consistent with the process of radiation-induced crystallization which was proposed for carbonado by Kaminsky (1987). We show from some theoretical considerations that when highly energetic particles, such as those emitted from radioactive decay of U and Th, interact with carbonaceous materials, they give rise to cascades of atomic disturbance (over regions of about a few nanometer), and the disturbed atoms are likely to recrystallize to form micro-diamonds because of increasing surface energy due to small size. The radiation-induced diamond formation mechanism may be relevant to the origin of nano-diamonds in primitive meteorites. Copyright ?? 1997 Elsevier Science Ltd.

A fast, parallel algorithm for distant-dependent calculation of crystal properties

NASA Astrophysics Data System (ADS)

Stein, Matthew

2017-12-01

A fast, parallel algorithm for distant-dependent calculation and simulation of crystal properties is presented along with speedup results and methods of application. An illustrative example is used to compute the Lennard-Jones lattice constants up to 32 significant figures for 4 ≤ p ≤ 30 in the simple cubic, face-centered cubic, body-centered cubic, hexagonal-close-pack, and diamond lattices. In most cases, the known precision of these constants is more than doubled, and in some cases, corrected from previously published figures. The tools and strategies to make this computation possible are detailed along with application to other potentials, including those that model defects.

Boron nitride - Composition, optical properties, and mechanical behavior

NASA Technical Reports Server (NTRS)

Pouch, John J.; Alterovitz, Samuel A.; Miyoshi, Kazuhisa; Warner, Joseph D.

1987-01-01

A low energy ion beam deposition technique was used to grow boron nitride films on quartz, germanium, silicon, gallium arsenide, and indium phosphate. The film structure was amorphous with evidence of a hexagonal phase. The peak boron concentration was 82 at. percent. The carbon and oxygen impurities were in the 5 to 8 at. percent range. Boron-nitrogen and boron-boron bonds were revealed by X-ray photoelectron spectroscopy. The index of refraction varied from 1.65 to 1.67 for films deposited on III-V compound semiconductors. The coefficient of friction for boron nitride in sliding contact with diamond was less than 0.1. The substrate was silicon.

Boron nitride: Composition, optical properties and mechanical behavior

NASA Technical Reports Server (NTRS)

Pouch, John J.; Alterovitz, Samuel A.; Miyoshi, Kazuhisa; Warner, Joseph D.

1987-01-01

A low energy ion beam deposition technique was used to grow boron nitride films on quartz, germanium, silicon, gallium arsenide, and indium phosphate. The film structure was amorphous with evidence of a hexagonal phase. The peak boron concentration was 82 at %. The carbon and oxygen impurities were in the 5 to 8 at % range. Boron-nitrogen and boron-boron bonds were revealed by X-ray photoelectron spectroscopy. The index of refraction varied from 1.65 to 1.67 for films deposited on III-V compound semiconductors. The coefficient of friction for boron nitride in sliding contact with diamond was less than 0.1. The substrate was silicon.

Bulk superhard B-C-N nanocomposite compact and method for preparing thereof

DOEpatents

Zhao, Yusheng; He, Duanwei

2004-07-06

Bulk, superhard, B-C-N nanocomposite compact and method for preparing thereof. The bulk, superhard, nanocomposite compact is a well-sintered compact and includes nanocrystalline grains of at least one high-pressure phase of B-C-N surrounded by amorphous diamond-like carbon grain boundaries. The bulk compact has a Vicker's hardness of about 41-68 GPa. It is prepared by ball milling a mixture of graphite and hexagonal boron nitride, encapsulating the ball-milled mixture, and sintering the encapsulated ball-milled mixture at a pressure of about 5-25 GPa and at a temperature of about 1000-2500 K.

Parasol cell mosaics are unlikely to drive the formation of structured orientation maps in primary visual cortex.

PubMed

Hore, Victoria R A; Troy, John B; Eglen, Stephen J

2012-11-01

The receptive fields of on- and off-center parasol cell mosaics independently tile the retina to ensure efficient sampling of visual space. A recent theoretical model represented the on- and off-center mosaics by noisy hexagonal lattices of slightly different density. When the two lattices are overlaid, long-range Moiré interference patterns are generated. These Moiré interference patterns have been suggested to drive the formation of highly structured orientation maps in visual cortex. Here, we show that noisy hexagonal lattices do not capture the spatial statistics of parasol cell mosaics. An alternative model based upon local exclusion zones, termed as the pairwise interaction point process (PIPP) model, generates patterns that are statistically indistinguishable from parasol cell mosaics. A key difference between the PIPP model and the hexagonal lattice model is that the PIPP model does not generate Moiré interference patterns, and hence stimulated orientation maps do not show any hexagonal structure. Finally, we estimate the spatial extent of spatial correlations in parasol cell mosaics to be only 200-350 μm, far less than that required to generate Moiré interference. We conclude that parasol cell mosaics are too disordered to drive the formation of highly structured orientation maps in visual cortex.

The nature and origin of interstellar diamond

NASA Technical Reports Server (NTRS)

Blake, David F.; Freund, Friedemann; Shipp, Ruth; Krishnan, Kannan F. M.; Echer, Charles J.

1988-01-01

The C-delta component of the Allende meteorite is a microscopic diamond some of whose properties seem in conflict with those expected of diamond. High spatial resolution analytical data are presented here which may help explain such results. Surface and interfacial carbon atoms in the component, which may comprise as much as 25 percent of the total, impart an 'amorphous' character to some spectral data. These data support the proposed high-pressure conversion of amorphous carbon and graphite into diamonds due to grain-grain collisions in the ISM, although a low-pressure mechanism of formation cannot be ruled out.

Role of fluid in the mechanism of formation of volcaniclastic and coherent kimberlite facies: a diamond perspective

NASA Astrophysics Data System (ADS)

Fedortchouk, Yana; Chinn, Ingrid

2016-04-01

Dissolution features on diamonds recovered from kimberlites vary depending on the dissolution conditions and can be used as a reliable proxy for volatiles and their role in kimberlite emplacement. Volatiles determine the mechanism of magma emplacement; variation in volatile content and CO2/CO2+H2O ratio may affect the geology of kimberlite bodies and formation of coherent vs. volcaniclastic kimberlite facies. Here we examine the evolution of a kimberlite system during ascent using the resorption morphology of its diamond population. We use 655 macro-diamonds from a complex kimberlite pipe in the Orapa kimberlite field (Botswana) to examine the role of volatiles in the formation of the three facies comprising this pipe: two coherent kimberlite facies (CKA and CKB) and one massive volcaniclastic facies (MVK). The diamonds come from three drillholes through each of the studied kimberlite facies. Separate diamond samples derived from 2 - 13 m intervals were combined into 40 m depth intervals for statistical purposes. Four independent morphological methods allowed us to reliably discriminate products of resorption in kimberlite magma from resorption in the mantle, and use the former in our study. We found that the proportion of diamonds with kimberlitic resorption is the lowest in CKA - 22%, medium in MVK - 50%, and highest in CKB - 73%, and it increases with depth in each of the drillholes. Each kimberlite facies shows its own style of kimberlite-induced resorption on rounded tetrahexahedron (THH) diamonds: glossy surfaces in MVK, rough corroded surfaces in CKB, and combination of glossy surfaces with chains of circular pits in CKA, where these pits represent the initial stages of development of corrosive features observed on CKB diamonds. Based on the results of our previous experimental studies we propose that resorption of MVK diamonds is a product of interaction with COH fluid, resorption of CKB diamonds is a product of interaction with a volatile-undersaturated melt (possibly carbonatitic), and CKA diamonds show an overprint of melt-controlled resorption over a fluid-controlled resorption. We propose an early separation of the fluid phase during the ascent of this kimberlite magma, segregation of this fluid and rise towards the top of the magma column. Over-pressurisation caused by the expansion of this fluid worked as a driving force for the magma ascent acceleration. The magma column has separated into two parts: (1) the bubble-rich magma towards the top, explosive emplacement of which formed the MVK facies, followed by the "tailing" bubble-poor magma quietly arriving to form the CKA facies, and (2) magma that lost volatiles to the upwardly escaping bubbles, in which a slower ascent caused more intensive diamond resorption and delayed emplacement, forming the CKB facie. It is possible that formation, buoyancy, and growth of fluid bubbles controls the ascent of the kimberlite magma, where emplacement of bubble-rich magma forms volcaniclastic kimberlite facies, while fast rise of the bubbles through the magma column separates the fluid-rich phase that moves up preparing the conduit in the surrounding rocks and forms an explosive pipe at the surface, from a volatile-depleted magma, which slowly rises and fills the pipe with CK kimberlite facies.

KSC-01pp1551

NASA Image and Video Library

2001-08-31

JOHNSON SPACE CENTER, HOUSTON, TEXAS -- EXPEDITION FOUR INSIGNIA -- The International Space Station (ISS) Expedition Four crew patch has an overall diamond shape, showing the "diamond in the rough" configuration of the Station during expedition four. The red hexagonal shape with stylized American and Russian flags represents the cross-sectional view of the S0 truss segment, which the crew will attach to the U.S. Lab Destiny. The persistent Sun shining on the Earth and Station represents the constant challenges that the crew and ground support team will face every day while operating the International Space Station, while shedding new light through daily research. The green portion of the Earth represents the fourth color in the visible spectrum and the black void of space represents humankind's constant quest to explore the unknown. The NASA insignia design for Shuttle flights ts is reserved for use by the astronauts and for other official use as the NASA Administrator may authorize. Public availability has been approved only in the forms of illustrations by the various news media. When and if there is any change in this policy, which we do not anticipate, it will be publicly announced

Expedition 4 crew insignia

NASA Image and Video Library

2001-08-01

ISS004-S-001 (August 2001) --- The International Space Station (ISS) Expedition 4 crew patch has an overall diamond shape, showing the “diamond in the rough” configuration of the Station during expedition 4. The red hexagonal shape with stylized American and Russian flags represents the cross-sectional view of the S0 truss segment, which the crew will attach to the U.S. Lab Destiny. The persistent Sun shining on the Earth and Station represents the constant challenges that the crew and ground support team will face every day while operating the International Space Station, while shedding new light through daily research. The green portion of the Earth represents the fourth color in the visible spectrum and the black void of space represents humankind’s constant quest to explore the unknown. The NASA insignia design for Shuttle flights is reserved for use by the astronauts and for other official use as the NASA Administrator may authorize. Public availability has been approved only in the forms of illustrations by the various news media. When and if there is any change in this policy, which is not anticipated, the change will be publicly announced.

Carbon stardust: From soot to diamonds

NASA Technical Reports Server (NTRS)

Tielens, Alexander G. G. M.

1990-01-01

The formation of carbon dust in the outflow from stars and the subsequent evolution of this so called stardust in the interstellar medium is reviewed. The chemical and physical processes that play a role in carbon stardust formation are very similar to those occurring in sooting flames. Based upon extensive laboratory studies of the latter, the structure and physical and chemical properties of carbon soot are reviewed and possible chemical pathways towards carbon stardust are discussed. Grain-grain collisions behind strong interstellar shocks provide the high pressures required to transform graphite and amorphous carbon grains into diamond. This process is examined and the properties of shock-synthesized diamonds are reviewed. Finally, the interrelationship between carbon stardust and carbonaceous meteorites is briefly discussed.

Control over self-assembly of diblock copolymers on hexagonal and square templates for high area density circuit boards.

PubMed

Feng, Jie; Cavicchi, Kevin A; Heinz, Hendrik

2011-12-27

Self-assembled diblock copolymer melts on patterned substrates can induce a smaller characteristic domain spacing compared to predefined lithographic patterns and enable the manufacture of circuit boards with a high area density of computing and storage units. Monte Carlo simulation using coarse-grain models of polystyrene-b-polydimethylsiloxane shows that the generation of high-density hexagonal and square patterns is controlled by the ratio N(D) of the surface area per post and the surface area per spherical domain of neat block copolymer. N(D) represents the preferred number of block copolymer domains per post. Selected integer numbers support the formation of ordered structures on hexagonal (1, 3, 4, 7, 9) and square (1, 2, 5, 7) templates. On square templates, only smaller numbers of block copolymer domains per post support the formation of ordered arrays with significant stabilization energies relative to hexagonal morphology. Deviation from suitable integer numbers N(D) increases the likelihood of transitional morphologies between square and hexagonal. Upon increasing the spacing of posts on the substrate, square arrays, nested square arrays, and disordered hexagonal morphologies with multiple coordination numbers were identified, accompanied by a decrease in stabilization energy. Control over the main design parameter N(D) may allow an up to 7-fold increase in density of spherical block copolymer domains per surface area in comparison to the density of square posts and provide access to a wide range of high-density nanostructures to pattern electronic devices.

Triphasic Tooling with Small Oriented Diamond Tip for Turning and Smoothing Lightweight Mirrors

NASA Technical Reports Server (NTRS)

Voronov, O. A.; Tompa, G. S.; Kear, B. H.; Veress, V.

2004-01-01

We are developing a new method for the growth of small diamond crystals at very high temperatures and pressures directly from a carbon melt. A prototype "Supercell" has been developed for this purpose. This system is capable of high rate crystal growth in relatively large working volumes. The resulting high quality diamond crystals will be incorporated into a triphasic diamond/titanium carbide/titanium composite tool, with an oriented diamond crystal at its tip. High pressure is needed to prevent degradation of diamond at high temperature, and to ensure the formation of a crack & composite structure. After grinding and polishing, the composite material will be joined to a steel holder, thus forming a diamond-tipped tool for turning and smoothing of a mirror surface. A properly oriented single-crystal diamond cuts and smoothes much better than a conventional polycrystalline diamond crystal. This is because the hardness depends on crystallographic orientation-the difference corresponds to 60-100 GPa on the Knoop scale. Our goal is to achieve surface roughness of about 1 nm, which will be accomplished by precision cutting and smoothing. The hardness of the functionally-graded diamond/titanium carbide/titanium composite tool varies from 100 GPa at its tip to 15 GPa at its base. Previous work has shown that the mass of machined material using an oriented-diamond tool is much larger than that for a standard diamond-metal composite tool.

Microstructural Evolution of Nanocrystalline Diamond Films Due to CH4/Ar/H2 Plasma Post-Treatment Process.

PubMed

Lin, Sheng-Chang; Yeh, Chien-Jui; Manoharan, Divinah; Leou, Keh-Chyang; Lin, I-Nan

2015-10-07

Plasma post-treatment process was observed to markedly enhance the electron field emission (EFE) properties of ultrananocrystalline diamond (UNCD) films. TEM examinations reveal that the prime factor which improves the EFE properties of these films is the coalescence of ultrasmall diamond grains (∼5 nm) forming large diamond grains about hundreds of nanometers accompanied by the formation of nanographitic clusters along the grain boundaries due to the plasma post-treatment process. OES studies reveal the presence of large proportion of atomic hydrogen and C2 (or CH) species, which are the main ingredients that altered the granular structure of the UNCD films. In the post-treatment process, the plasma interacts with the diamond films by a diffusion process. The recrystallization of diamond grains started at the surface region of the material, and the interaction zone increased with the post-treatment period. The entire diamond film can be converted into a nanocrystalline granular structure when post-treated for a sufficient length of time.

Deformation-related spectroscopic features in natural Type Ib-IaA diamonds from Zimmi (West African craton)

NASA Astrophysics Data System (ADS)

Smit, Karen V.; D'Haenens-Johansson, Ulrika F. S.; Howell, Daniel; Loudin, Lorne C.; Wang, Wuyi

2018-06-01

Zimmi diamonds (Sierra Leone) have 500 million year mantle residency times whose origin is best explained by rapid tectonic exhumation to shallower depths in the mantle, associated with continental collision but prior to kimberlite eruption. Here we present spectroscopic data for a new suite of Zimmi sulphide-bearing diamonds that allow us to evaluate the link between their spectroscopic features and their unusual geological history. Cathodoluminesence (CL) imaging of these diamonds revealed irregular patterns with abundant deformation lamellae, associated with the diamonds' tectonic exhumation. Vacancies formed during deformation were subsequently naturally annealed to form vacancy clusters, NV0/- centres and H3 (NVN0). The brownish-yellow to greenish-yellow colours observed in Zimmi Ib-IaA diamonds result from visible absorption by a combination of isolated substitutional nitrogen ( {N}S^0 ) and deformation-related vacancy clusters. Colour-forming centres and other spectroscopic features can all be attributed to the unique geological history of Zimmi Ib-IaA diamonds and their rapid exhumation after formation.

Pyramidal dislocation induced strain relaxation in hexagonal structured InGaN/AlGaN/GaN multilayer

NASA Astrophysics Data System (ADS)

Yan, P. F.; Du, K.; Sui, M. L.

2012-10-01

Due to the special dislocation slip systems in hexagonal lattice, dislocation dominated deformations in hexagonal structured multilayers are significantly different from that in cubic structured systems. In this work, we have studied the strain relaxation mechanism in hexagonal structured InGaN/AlGaN/GaN multilayers with transmission electron microscopy. Due to lattice mismatch, the strain relaxation was found initiated with the formation of pyramidal dislocations. Such dislocations locally lie at only one preferential slip direction in the hexagonal lattice. This preferential slip causes a shear stress along the basal planes and consequently leads to dissociation of pyramidal dislocations and operation of the basal plane slip system. The compressive InGaN layers and "weak" AlGaN/InGaN interfaces stimulate the dissociation of pyramidal dislocations at the interfaces. These results enhance the understanding of interactions between dislocations and layer interfaces and shed new lights on deformation mechanism in hexagonal-lattice multilayers.

Structure and Growth of Hexagonal Boron Nitride on Ir(111).

PubMed

Farwick Zum Hagen, Ferdinand H; Zimmermann, Domenik M; Silva, Caio C; Schlueter, Christoph; Atodiresei, Nicolae; Jolie, Wouter; Martínez-Galera, Antonio J; Dombrowski, Daniela; Schröder, Ulrike A; Will, Moritz; Lazić, Predrag; Caciuc, Vasile; Blügel, Stefan; Lee, Tien-Lin; Michely, Thomas; Busse, Carsten

2016-12-27

Using the X-ray standing wave method, scanning tunneling microscopy, low energy electron diffraction, and density functional theory, we precisely determine the lateral and vertical structure of hexagonal boron nitride on Ir(111). The moiré superstructure leads to a periodic arrangement of strongly chemisorbed valleys in an otherwise rather flat, weakly physisorbed plane. The best commensurate approximation of the moiré unit cell is (12 × 12) boron nitride cells resting on (11 × 11) substrate cells, which is at variance with several earlier studies. We uncover the existence of two fundamentally different mechanisms of layer formation for hexagonal boron nitride, namely, nucleation and growth as opposed to network formation without nucleation. The different pathways are linked to different distributions of rotational domains, and the latter enables selection of a single orientation only.

Investigation of nucleation and growth processes of diamond films by atomic force microscopy

NASA Technical Reports Server (NTRS)

George, M. A.; Burger, A.; Collins, W. E.; Davidson, J. L.; Barnes, A. V.; Tolk, N. H.

1994-01-01

The nucleation and growth of plasma-enhanced chemical-vapor deposited polycrystalline diamond films were studied using atomic force microscopy (AFM). AFM images were obtained for (1) nucleated diamond films produced from depositions that were terminated during the initial stages of growth, (2) the silicon substrate-diamond film interface side of diamond films (1-4 micrometers thick) removed from the original surface of the substrate, and (3) the cross-sectional fracture surface of the film, including the Si/diamond interface. Pronounced tip effects were observed for early-stage diamond nucleation attributed to tip convolution in the AFM images. AFM images of the film's cross section and interface, however, were not highly affected by tip convolution, and the images indicate that the surface of the silicon substrate is initially covered by a small grained polycrystalline-like film and the formation of this precursor film is followed by nucleation of the diamond film on top of this layer. X-ray photoelectron spectroscopy spectra indicate that some silicon carbide is present in the precursor layer.

Twinning of cubic diamond explains reported nanodiamond polymorphs

NASA Astrophysics Data System (ADS)

Németh, Péter; Garvie, Laurence A. J.; Buseck, Peter R.

2015-12-01

The unusual physical properties and formation conditions attributed to h-, i-, m-, and n-nanodiamond polymorphs has resulted in their receiving much attention in the materials and planetary science literature. Their identification is based on diffraction features that are absent in ordinary cubic (c-) diamond (space group: Fd-3m). We show, using ultra-high-resolution transmission electron microscope (HRTEM) images of natural and synthetic nanodiamonds, that the diffraction features attributed to the reported polymorphs are consistent with c-diamond containing abundant defects. Combinations of {113} reflection and <011> rotation twins produce HRTEM images and d-spacings that match those attributed to h-, i-, and m-diamond. The diagnostic features of n-diamond in TEM images can arise from thickness effects of c-diamonds. Our data and interpretations strongly suggest that the reported nanodiamond polymorphs are in fact twinned c-diamond. We also report a new type of twin (<11> rotational), which can give rise to grains with dodecagonal symmetry. Our results show that twins are widespread in diamond nanocrystals. A high density of twins could strongly influence their applications.

Vortex circulation patterns in planar microdisk arrays

DOE PAGES

Velten, Sven; Streubel, Robert; Farhan, Alan; ...

2017-06-26

We report a magnetic X-ray microscopy study of the pattern formation of circulation in arrays of magnetic vortices ordered in a hexagonal and a honeycomb lattice. In the honeycomb lattice, we observe at remanence an ordered phase of alternating circulations, whereas in the hexagonal lattice, small regions of alternating lines form. A variation in the edge-to-edge distance shows that the size of those regions scales with the magnetostatic interaction. Micromagnetic simulations reveal that the patterns result from the formation of flux closure states during the nucleation process.

Theoretical Study of Diamond-Like Carbons and Nucleation of Diamond

NASA Astrophysics Data System (ADS)

Lee, Choon-Heung

Different forms of amorphous carbon and hydrocarbons with varying elastic and optical properties, hardness, density and hydrogen content exist depending on the preparation technique. The structure can vary from graphitic to diamond -like, i.e., from mainly threefold coordinated to mainly four-fold coordinated. In order to study the properties of such materials, microscopic models must be developed. These studies include the modelling of crosslinked defective graphite, diamond nucleation along the graphite edges, and diamond-like carbons. Tamor's proposed structure for diamondlike carbon consists of crosslinked graphitic regions. We studied a concrete realization of this model in which the cross -links are produced by shortening the interplanar bond lengths. The model study was accomplished with a pure rhombohedral graphite cell. For this study we used a semi-empirical potential based on Tersoff's environment-dependent potential which contains angular terms. It is enhanced by a long-range potential which describes the interplanar interactions. We found a configuration corresponding to a local minimum. More general features such as the randomness of the distribution of cross-links are needed for a realistic model. A model study of diamond/graphite interfaces was motivated by recent observations by Li and Angus. They observed a significant enhancement of diamond nucleation on the graphite edge planes with the preferential orientation relationship: {0001} _{g} | {111 }_{d}, < 1120 >_{g} | < 101>_{d}. Two possible interface structures were studied using the Tersoff potential. We found that the models have comparable low interface energies even if they contain some dangling bonds. Moreover, lower interface energies were found when the dangling bonds of the non-bonded diamond layer were satisfied with hydrogen. We have proposed a growth mechanism based on this study. Finally, we constructed realistic models of dense amorphous carbon. The WWW (introduced earlier for a-Si by Wooten, Winer and Weaire) model was the starting structure. The effects of clustering of the threefold coordinated atoms in pairs, chains, or graphitic (planar hexagonal clusters) were studied. The resulting models were relaxed using the Tersoff potential. Their electronic structures were studied using an empirical tight-binding scheme with parameters adjusted to reproduce the diamond and graphite band-structures. The models were found to have densities of ~ 3 g/cm^3 and bulk moduli of ~3.1 Mbar. Localized dangling bonds and pi - pi^* states were found within the wide gap of the WWW model consistent with optical gaps of the order of 0.5-2 eV. Hydrogen atoms were introduced to remove some of the dangling bonds. The models were found to account for the essential features of ion-beam deposited amorphous carbon and hydrogenated amorphous carbon.

High-pressure behaviour of Cr-Fe-Mg-Al spinels: applications to diamond geobarometry

NASA Astrophysics Data System (ADS)

Periotto, Benedetta; Bruschini, Enrico; Nestola, Fabrizio; Lenaz, Davide; Princivalle, Francesco; Andreozzi, Giovanni B.; Bosi, Ferdinando

2014-05-01

Spinels belonging to the chromite - magnesiochromite - hercynite (FeCr2O4-MgCr2O4-FeAl2O4) system are among the most common inclusions found in diamonds (Stachel and Harris 2008). In particular, although FeCr2O4 and MgCr2O4 components sum to between 85 and 88% of spinels found in diamonds, hercynite FeAl2O4 plays a not negligible role in determining their thermo-elastic properties with concentrations reaching 7-9 % (other minor end-members like MgAl2O4, MgFe2O4 and Fe2O3 rarely reach 2-3% in total, see Lenaz et al. 2009). Recent studies were focused on the determination of the diamond formation pressure by the so-called "elastic method" (see for example Nestola et al. 2011 and references therein). It was demonstrated that accurate and precise thermo-elastic parameters are fundamental to minimize the uncertainty of formation pressure. In this work we have determined the equations of state at room temperature of three synthetic spinel end-members chromite - magnesiochromite - hercynite and one natural spinel crystal extracted from a diamond (from Udachnaya mine, Siberia, Russia) by single-crystal X-ray diffraction in situ at high-pressure. A diamond-anvil cell was mounted on a STADI IV diffractometer equipped with a point detector and motorized by SINGLE software (Angel and Finger 2011). The natural crystal was investigated to test (and possibly validate) the "empirical prediction model", capable to provide bulk modulus and its first pressure derivative only knowing the composition of the spinels found in diamonds. Such prediction model could be used to obtain pressure of formation for the diamond-spinel pair through the elastic method. Details and results will be discussed. The research was funded by the ERC Starting Grant to FN (grant agreement n° 307322). References Angel R.J., Finger L.W. (2011) SINGLE A program to control single-crystal diffractometers. Journal of Applied Crystallography, 44, 247-251. Lenaz D., Logvinova A.M., Princivalle F., Sobolev N. (2009) Structural parameters of chromite included in diamond and kimberlites from Siberia: a new tool for discriminating source. American Mineralogist, 94, 1067-1070. Nestola F., Nimis P., Ziberna L., Longo M., Marzoli A., Harris J.W., Manghnani M.H., Fedortchouk Y. (2011) First crystal-structure determination of olivine in diamond: composition and implications for provenance in the Earth's mantle. Earth and Planetary Science Letters, 305, 249-255. Stachel, T., and Harris, J.W. (2008) The origin of cratonic diamonds - constraints from mineral inclusions. Ore Geology Reviews, 34, 5-32.

Nature of diamonds in Yakutian eclogites: views from eclogite tomography and mineral inclusions in diamonds

NASA Astrophysics Data System (ADS)

Anand, Mahesh; Taylor, Lawrence A.; Misra, Kula C.; Carlson, William D.; Sobolev, Nikolai V.

2004-09-01

We have performed dissections of two diamondiferous eclogites (UX-1 and U33/1) from the Udachnaya kimberlite, Yakutia in order to understand the nature of diamond formation and the relationship between the diamonds, their mineral inclusions, and host eclogite minerals. Diamonds were carefully recovered from each xenolith, based upon high-resolution X-ray tomography images and three-dimensional models. The nature and physical properties of minerals, in direct contact with diamonds, were investigated at the time of diamond extraction. Polished sections of the eclogites were made, containing the mould areas of the diamonds, to further investigate the chemical compositions of the host minerals and the phases that were in contact with diamonds. Major- and minor-element compositions of silicate and sulfide mineral inclusions in diamonds show variations among each other, and from those in the host eclogites. Oxygen isotope compositions of one garnet and five clinopyroxene inclusions in diamonds from another Udachnaya eclogite (U51) span the entire range recorded for eclogite xenoliths from Udachnaya. In addition, the reported compositions of almost all clinopyroxene inclusions in U51 diamonds exhibit positive Eu anomaly. This feature, together with the oxygen isotopic characteristics, is consistent with the well-established hypothesis of subduction origin for Udachnaya eclogite xenoliths. It is intuitive to expect that all eclogite xenoliths in a particular kimberlite should have common heritage, at least with respect to their included diamonds. However, the variation in the composition of multiple inclusions within diamonds, and among diamonds, from the same eclogite indicates the involvement of complex processes in diamond genesis, at least in the eclogite xenoliths from Yakutia that we have studied.

Energetics and formation mechanism of borders between hexagonal boron nitride and graphene

NASA Astrophysics Data System (ADS)

Sawahata, Hisaki; Yamanaka, Ayaka; Maruyama, Mina; Okada, Susumu

2018-06-01

We studied the energetics of two-dimensional heterostructures consisting of hexagonal boron nitride (h-BN) and graphene with respect to the border structure and heterobond species using density functional theory. A BC heterobond is energetically preferable at the border between h-BN and graphene. We also found that the polarization at the zigzag border increases the total energy of the heterostructures. Competition between the bond formation energy and the polarization energy leads to chiral borders at which BC heterobonds are dominant. By taking the formation process of the heterostructures into account, the zigzag border with BC heterobonds is found to be preferentially synthesized from graphene edges under hydrogen-rich conditions.

Possible significance of cubic water-ice, H2O-Ic, in the atmospheric water cycle of Mars

NASA Technical Reports Server (NTRS)

Gooding, James L.

1988-01-01

The possible formation and potential significance of the cubic ice polymorph on Mars is discussed. When water-ice crystallizes on Earth, the ambient conditions of temperature and pressure result in the formation of the hexagonal ice polymorph; however, on Mars, the much lower termperature and pressures may permit the crystallization of the cubic polymorph. Cubic ice has two properties of possible importance on Mars: it is an excellant nucleator of other volatiles (such as CO2), and it undergoes an exothermic transition to hexagonal ice at temperatures above 170 K. These properties may have significant implications for both martian cloud formation and the development of the seasonal polar caps.

Effects of low-energy electron irradiation on formation of nitrogen–vacancy centers in single-crystal diamond

DOE PAGES

Schwartz, J.; Aloni, S.; Ogletree, D. F.; ...

2012-04-20

Exposure to beams of low-energy electrons (2-30 keV) in a scanning electron microscope locally induces formation of NV-centers without thermal annealing in diamonds that have been implanted with nitrogen ions. In this study, we find that non-thermal, electron-beam-induced NV-formation is about four times less efficient than thermal annealing. But NV-center formation in a consecutive thermal annealing step (800°C) following exposure to low-energy electrons increases by a factor of up to 1.8 compared to thermal annealing alone. Finally, these observations point to reconstruction of nitrogen-vacancy complexes induced by electronic excitations from low-energy electrons as an NV-center formation mechanism and identify localmore » electronic excitations as a means for spatially controlled room-temperature NV-center formation.« less

Grain-size-dependent diamond-nondiamond composite films: characterization and field-emission properties.

PubMed

Pradhan, Debabrata; Lin, I Nan

2009-07-01

Diamond films with grain sizes in the range of 5-1000 nm and grain boundaries containing nondiamond carbon are deposited on a silicon substrate by varying the deposition parameters. The overall morphologies of the as-deposited diamond-nondiamond composite films are examined by scanning electron microscopy and atomic force microscopy, which show a decrease in the surface roughness with a decrease in the diamond grain size. Although the Raman spectra show predominately nondiamond carbon features in the diamond films with smaller grain sizes, glancing-angle X-ray diffraction spectra show the absence of graphitic carbon features and the presence of very small amorphous carbon diffraction features. The CH4 percentage (%) in Ar and H2 plasma during deposition plays a crucial role in the formation of diamond films with different grain sizes and nondiamond carbon contents, which, in turn, determines the field-emission behavior of the corresponding diamond films. The smaller the grain size of the diamond, the lower is the turn-on field for electron emission. A lower turn-on field is obtained from the diamond films deposited with 2-5% CH4 than from the films deposited with either 1% or 7.5% CH4 in the Ar medium. A current density greater than 1 mA/cm2 (at 50 V/microm) is obtained from diamond films deposited with a higher percentage of CH4. A model is suggested for the field-emission mechanism from the diamond-nondiamond composite films with different diamond grain sizes and nondiamond contents.

Correlated carbon and oxygen isotope signatures in eclogitic diamonds with coesite inclusions: A SIMS investigation of diamonds from Guaniamo, Argyle and Orapa mines

NASA Astrophysics Data System (ADS)

Schulze, D. J.; Page, Z.; Harte, B.; Valley, J.; Channer, D.; Jaques, L.

2006-12-01

Using ion microprobes and secondary-ion mass spectrometry we have analyzed the carbon and oxygen isotopic composition of eclogite-suite diamonds and their coesite inclusions, respectively, from three suites of diamonds of Proterozoic age. Extremely high (for the mantle) oxygen isotope values (delta 18O of +10.2 to +16.9 per mil VSMOW) are preserved in coesites included in eclogitic diamonds from Guaniamo, Venezuela (Schulze et al., Nature, 2003), providing compelling evidence for an origin of their eclogite hosts by subduction of sea water altered ocean floor basalts. In situ SIMS analyses of their host diamonds yield carbon isotope values (delta 13C) of -12 to -18 per mil PDB. SIMS analyses of coesite inclusions from Argyle, Australia diamonds previously analyzed by combustion methods for d13C composition (Jaques et al., Proc. 4th Kimb. Conf, 1989), also yield anomalously high d18O values (+6.8 to +16.0 per mil VSMOW), that correlate with the anomalously low carbon isotope values (-10.3 to -14.1 per mil PDB). One coesite-bearing diamond from Orapa, Botswana analyzed in situ by SIMS has a d18O value of the coesite of +8.5 per mil VSMOW and a d13C value of the adjacent diamond host of -9.0 per mil PDB. A second Orapa stone has a SIMS carbon isotope compositional range of d13C = -14 to -16 per mil PDB, but the coesite is too small for ion probe analysis. At each of these localities, carbon isotope values of coesite-bearing diamonds that are lower than typical of mantle carbon are correlated with oxygen isotope compositions of included coesites that are substantially above the common mantle oxygen isotope range. Such results are not in accord with diamond genesis models involving formation of eclogitic diamonds from igneous melts undergoing fractionation in the mantle or by crystallization from primordial inhomogeneities in Earth's mantle. By analogy with the oxygen isotope compositions of altered ocean floor basalts and Alpine (subduction zone) eclogites they are, however, consistent with a subduction origin for these eclogite assemblages from altered ocean floor basaltic protoliths, and thus the simplest explanation for the source of the low carbon isotope values of these diamonds is formation from biogenic carbon accumulated on or near the ocean floor and subducted to the depths of eclogite and diamond stability with the altered basalts. Significantly these results, which were not predicted from studies of diamond-bearing eclogites, apply to the mantle beneath three different continental crustal blocks of both Proterozoic (Guaniamo and Argyle) and Archean/Proterozoic (Orapa) age.

[Study of the interaction of alpha-tocopherol with phospholipids, fatty acids, and their oxygenated derivatives by (31)P-NMR spectroscopy].

PubMed

Chudinova, V V; Zakharova, E I; Alekseev, S M; Chupin, V V; Evstigneeva, R P

1993-02-01

Interaction of alpha-tocopherol with phospholipids, oleic, ricinoleic acids and linoleic acid hydroperoxides was investigated by means of 31P NMR spectroscopy on a model artificial membranes containing egg phosphatidylcholine and lysophosphatidylcholine. alpha-Tocopherol was shown to support the bilayer organization of lysophospholipids, whereas its introduction into the lecithin-water system stimulated the hexagonal phase formation. Free fatty acids exhibited a synergism to alpha-tocopherol, the effect of the hexagonal phase formation being at most increased by oxygenated acids--ricinoleic acid and linoleic acid hydroperoxides. In accordance with the experimental data, a conclusion about modifying and structuring action of alpha-tocopherol was made. Origin of the alpha-tocopherol's modulating effect on the membrane structure and a possible role of hexagonal phase forming upon its action in the course of peroxidation of lipids was discussed.

Novel high pressure hexagonal OsB2 by mechanochemistry

NASA Astrophysics Data System (ADS)

Xie, Zhilin; Graule, Moritz; Orlovskaya, Nina; Andrew Payzant, E.; Cullen, David A.; Blair, Richard G.

2014-07-01

Hexagonal OsB2, a theoretically predicted high-pressure phase, has been synthesized for the first time by a mechanochemical method, i.e., high energy ball milling. X-ray diffraction indicated that formation of hexagonal OsB2 begins after 2.5 h of milling, and the reaction reaches equilibrium after 18 h of milling. Rietveld refinement of the powder data indicated that hexagonal OsB2 crystallizes in the P63/mmc space group (No. 194) with lattice parameters of a=2.916 Å and c=7.376 Å. Transmission electron microscopy confirmed the appearance of the hexagonal OsB2 phase after high energy ball milling. in situ X-ray diffraction experiments showed that the phase is stable from -225 °C to 1050 °C. The hexagonal OsB2 powder was annealed at 1050 °C for 6 days in vacuo to improve crystallinity and remove strain induced during the mechanochemical synthesis. The structure partially converted to the orthorhombic phase (20 wt%) after fast current assisted sintering of hexagonal OsB2 at 1500 °C for 5 min. Mechanochemical approaches to the synthesis of hard boride materials allow new phases to be produced that cannot be prepared using conventional methods.

Mineral inclusions and geochemical characteristics of microdiamonds from the DO27, A154, A21, A418, DO18, DD17 and Ranch Lake kimberlites at Lac de Gras, Slave Craton, Canada

NASA Astrophysics Data System (ADS)

Davies, Rondi M.; Griffin, William L.; O'Reilly, Suzanne Y.; Doyle, Buddy J.

2004-09-01

A mineral inclusion, carbon isotope, nitrogen content, nitrogen aggregation state and morphological study of 576 microdiamonds from the DO27, A154, A21, A418, DO18, DD17 and Ranch Lake kimberlites at Lac de Gras, Slave Craton, was conducted. Mineral inclusion data show the diamonds are largely eclogitic (64%), followed by peridotitic (25%) and ultradeep (11%). The paragenetic abundances are similar to macrodiamonds from the DO27 kimberlite (Davies, R.M., Griffin, W.L., O'Reilly, S.Y., 1999. Diamonds from the deep: pipe DO27, Slave craton, Canada. In: Gurney, J.J., Gurney, J.L., Pascoe, M.D., Richardson, S.H. (Eds.), The J. B. Dawson Vol., Proc. 7th Internat. Kimberlite Conf., Red Roof Designs, Cape Town, pp. 148-155) but differ to diamonds from nearby kimberlites at Ekati (e.g., Lithos (2004); Tappert, R., Stachel, T., Harris, J.W., Brey, G.P., 2004. Mineral Inclusions in Diamonds from the Panda Kimberlite, S. P., Canada. 8th International Kimberlite Conference, extended abstracts) and Snap Lake to the south (Dokl. Earth Sci. 380 (7) (2001) 806), that are dominated by peridotitic stones. Eclogitic diamonds with variable inclusion compositions and temperatures of formation (1040-1300 °C) crystallised at variable lithospheric depths sometimes in changing chemical environments. A large range to very 13C-depleted C-isotope compositions ( δ13C=-35.8‰ to -2.2‰) and an NMORB bulk composition, calculated from trace elements in garnet and clinopyroxene inclusions, are consistent with an origin from subducted oceanic crust and sediments. Carbon isotopes in the peridotitic diamonds have mantle compositions ( δ13C mode -4.0‰). Mineral inclusion compositions are largely harzburgitic. Variable temperatures of formation (garnet TNi=800-1300 °C) suggest the peridotitic diamonds originate from the shallow ultra-depleted and deeper less depleted layers of the central Slave lithosphere. Carbon isotopes ( δ13C av.=-5.1‰) and mineral inclusions in the ultradeep diamonds suggest they formed in peridotitic mantle (˜670 km). The diamonds may have been entrained in a plume and subcreted to the base of the central Slave lithosphere. Poorly aggregated nitrogen (IaA without platelets) in a large number of eclogitic (67%) and peridotitic (32%) diamonds, with similar nitrogen contents, indicates the diamonds were stored in the mantle at low temperatures (1060-<1100 °C) following crystallisation in the Archean. Type IaA diamonds have largely cubo-octahedral growth forms, and Type II and Type IaAB diamonds, with higher nitrogen aggregation states, mostly have octahedral morphologies. However, no correlation between these groups and their mineral inclusion compositions, C-isotopes, and N-contents rules out the possibility of unique source origins and suggests eclogitic and peridotitic diamonds experienced variable mantle thermal states. Variation in mineral inclusion chemistries in single diamonds, possible overgrowths of 13C-depleted eclogitic diamond on diamonds with peridotitic and ultradeep inclusions, and Type I ultradeep diamond with low N-aggregation is consistent with diamond growth over time in changing chemical environments.

Preparation of bulk superhard B-C-N nanocomposite compact

DOEpatents

Zhao, Yusheng [Los Alamos, NM; He, Duanwei [Sichuan, CN

2011-05-10

Bulk, superhard, B--C--N nanocomposite compacts were prepared by ball milling a mixture of graphite and hexagonal boron nitride, encapsulating the ball-milled mixture at a pressure in a range of from about 15 GPa to about 25 GPa, and sintering the pressurized encapsulated ball-milled mixture at a temperature in a range of from about 1800-2500 K. The product bulk, superhard, nanocomposite compacts were well sintered compacts with nanocrystalline grains of at least one high-pressure phase of B--C--N surrounded by amorphous diamond-like carbon grain boundaries. The bulk compacts had a measured Vicker's hardness in a range of from about 41 GPa to about 68 GPa.

X-ray topographic study of diamonds: implications for the genetic nature of inclusions in diamond

NASA Astrophysics Data System (ADS)

Agrosì, Giovanna; Nestola, Fabrizio; Tempesta, Gioacchino; Bruno, Marco; Scandale, Eugenio; Harris, Jeff W.

2014-05-01

In recent years, several studies have focused on the growth conditions of the diamonds through the analysis of the mineral inclusions trapped in them (Howell, 2012 and references therein). Nevertheless, to obtain rigorous information about chemical and physical conditions of diamond formation, it is crucial to determine if the crystallization of the inclusions occurred before (protogenetic nature), during (syngenetic nature) or after (epigenetic nature) the growth of diamond (Wiggers de Vries et al., 2011). X-ray topography (XRDT) can be a helpful tool to verify the genetic nature of inclusions in diamond. This technique characterizes the extended defects and reconstructs the growth history of the samples (Agrosì et al., 2013 and references therein) and, consequently contributes to elucidation of the relationship between the inclusions and the host-diamond. With this aim a diamond from the Udachnaya kimberlite, Siberia, was investigated. The diamond crystal was the one previously studied by Nestola et al. (2011) who performed in-situ crystal structure refinement of the inclusions to obtain data about the formation pressure. The inclusions were iso-oriented olivines that did not show evident cracks and subsequently could not be considered epigenetic. Optical observations revealed an anomalous birefringence in the adjacent diamond and the inclusions had typical "diamond-imposed cubo-octahedral" shape for the largest olivine. The diffraction contrast study shows that the diamond exhibits significant deformation fields related to plastic post growth deformation. The crystallographic direction of strains was established applying the extinction criterion. Section topographs were taken to minimize the overlapping of the strain field associate with the different defects and revealed that no dislocations nucleated from the olivine inclusions. Generally, when a solid inclusion has been incorporated in the growing crystal, the associated volume distortion can be minimized by means the nucleation of dislocations and/or twinning (Agrosì et al., 2013). In our case, the specific and significant features - the olivine inclusions showing a "diamond imposed cubo-octahedral shape" and no dislocation nucleation - that characterize this sample will be discussed in detail. References: F Nestola, P Nimis, L Ziberna, M Longo, A Marzoli, JW Harris, MH Manghnani (2011): Earth and Planetary Science Letters 305 (1), 249-255. Howell, D. (2012): Eur. J. Mineral., 24, 575-585. Wiggers de Vries D.F., Drury M.R., de Winter D.A. M., Bulanova G P., Pearson D. G., Davies G. R. (2011): Contrib. Mineral. Petrol. 161, 565-579. Agrosì G., Tempesta G., Scandale E., Harris J.W. (2013): Eur. J. Mineral, 25 (4), 551-559.

Fabrication and characterization of a co-planar detector in diamond for low energy single ion implantation

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

Abraham, John Bishoy Sam; Pacheco, Jose L.; Aguirre, Brandon Adrian

2016-08-09

We demonstrate low energy single ion detection using a co-planar detector fabricated on a diamond substrate and characterized by ion beam induced charge collection. Histograms are taken with low fluence ion pulses illustrating quantized ion detection down to a single ion with a signal-to-noise ratio of approximately 10. We anticipate that this detection technique can serve as a basis to optimize the yield of single color centers in diamond. In conclusion, the ability to count ions into a diamond substrate is expected to reduce the uncertainty in the yield of color center formation by removing Poisson statistics from the implantationmore » process.« less

Structural analysis of ion-implanted chemical-vapor-deposited diamond by transmission electron microscope

NASA Astrophysics Data System (ADS)

Jiang, N.; Deguchi, M.; Wang, C. L.; Won, J. H.; Jeon, H. M.; Mori, Y.; Hatta, A.; Kitabatake, M.; Ito, T.; Hirao, T.; Sasaki, T.; Hiraki, A.

1997-04-01

A transmission electron microscope (TEM) study of ion-implanted chemical-vapor-deposited (CVD) diamond is presented. CVD diamond used for transmission electron microscope observation was directly deposited onto Mo TEM grids. As-deposited specimens were irradiated by C (100 keV) ions at room temperature with a wide range of implantation doses (10 12-10 17/cm 2). Transmission electron diffraction (TED) patterns indicate that there exists a critical dose ( Dc) for the onset of amorphization of CVD diamond as a result of ion induced damage and the value of critical dose is confirmed to be about 3 × 10 15/cm 2. The ion-induced transformation process is clearly revealed by high resolution electron microscope (HREM) images. For a higher dose implantation (7 × 10 15/cm 2) a large amount of diamond phase is transformed into amorphous carbon and many tiny misoriented diamond blocks are found to be left in the amorphous solid. The average size of these misoriented diamond blocks is only about 1-2 nm. Further bombardment (10 17/cm 2) almost kills all of the diamond phase within the irradiated volume and moreover leads to local formation of micropolycrystalline graphite.

Long-term culture of pluripotent stem-cell-derived human neurons on diamond--A substrate for neurodegeneration research and therapy.

PubMed

Nistor, Paul A; May, Paul W; Tamagnini, Francesco; Randall, Andrew D; Caldwell, Maeve A

2015-08-01

Brain Computer Interfaces (BCI) currently represent a field of intense research aimed both at understanding neural circuit physiology and at providing functional therapy for traumatic or degenerative neurological conditions. Due to its chemical inertness, biocompatibility and stability, diamond is currently being actively investigated as a potential substrate material for culturing cells and for use as the electrically active component of a neural sensor. Here we provide a protocol for the differentiation of mature, electrically active neurons on microcrystalline synthetic thin-film diamond substrates starting from undifferentiated pluripotent stem cells. Furthermore, we investigate the optimal characteristics of the diamond microstructure for long-term neuronal sustainability. We also analyze the effect of boron as a dopant for such a culture. We found that the diamond crystalline structure has a significant influence on the neuronal culture unlike the boron doping. Specifically, small diamond microcrystals promote higher neurite density formation. We find that boron incorporated into the diamond does not influence the neurite density and has no deleterious effect on cell survival. Copyright © 2015 The Authors. Published by Elsevier Ltd.. All rights reserved.

Thermally induced alkylation of diamond.

PubMed

Hoeb, Marco; Auernhammer, Marianne; Schoell, Sebastian J; Brandt, Martin S; Garrido, Jose A; Stutzmann, Martin; Sharp, Ian D

2010-12-21

We present an approach for the thermally activated formation of alkene-derived self-assembled monolayers on oxygen-terminated single and polycrystalline diamond surfaces. Chemical modification of the oxygen and hydrogen plasma-treated samples was achieved by heating in 1-octadecene. The resulting layers were characterized using X-ray photoelectron spectroscopy, thermal desorption spectroscopy, atomic force microscopy, Fourier transform infrared spectroscopy, and water contact angle measurements. This investigation reveals that alkenes selectively attach to the oxygen-terminated sites via covalent C-O-C bonds. The hydrophilic oxygen-terminated diamond is rendered strongly hydrophobic following this reaction. The nature of the process limits the organic layer growth to a single monolayer, and FTIR measurements reveal that such monolayers are dense and well ordered. In contrast, hydrogen-terminated diamond sites remain unaffected by this process. This method is thus complementary to the UV-initiated reaction of alkenes with diamond, which exhibits the opposite reactivity contrast. Thermal alkylation increases the range of available diamond functionalization strategies and provides a means of straightforwardly forming single organic layers in order to engineer the surface properties of diamond.

Topological Quantum Information Processing Mediated Via Hybrid Topological Insulator Structures

DTIC Science & Technology

2013-11-13

manipulation, entanglement and detection ofMajorana fermions in diamond-topological insulator - superconductor heterojunctions. Furthennore, we propose to...the formation, manipulation, entanglement and detection of Majorana fermions in diamond-topological insulator - superconductor heterojunctions...Interactions between Superconductors and Topological Insulators Recent advances have revealed a new type of information processing, topological quantum

Bases of the Mantle-Carbonatite Conception of Diamond Genesis

NASA Astrophysics Data System (ADS)

Litvin, Yuriy; Spivak, Anna; Kuzyura, Anastasia

2016-04-01

In the mantle-carbonatite conception of diamond genesis, the results of physic-chemical experiments are coordinated with the data of analytic mineralogy of primary inclusions in natural diamonds. Generalization of the solutions of principal genetic problems constitutes the bases of the conception. The solutions are following: (1) it is grounded that diamond-parental melts of the upper mantle have peridotite/eclogite - carbonatite - carbon compositions, of the transition zone - (wadsleite↔ringwoodite) - majorite - stishovite - carbonatite - carbon compositions, and of the lower mantle - periclase/wustite - bridgmanite - Ca-perovskite -stishovite - carbonatite - carbon compositions; (2) a construction of generalized diagrams for the diamond-parental media, which reveal changeable compositions of the growth melts of diamonds and associated phases, their genetic relations to the mantle substance, and classification connections of the primary inclusions in natural diamonds; (3) experimental equilibrium phase diagrams of syngenesis of diamonds and primary inclusions, which characterize the nucleation and growth conditions of diamonds and a capture of paragenetic and xenogenetic minerals by the growing diamonds; (4) a determination of the phase diagrams of diamonds and inclusions syngenesis under the regime of fractional crystallization, which discover the regularities of ultrabasic-basic evolution and paragenesis transitions in the diamond-forming systems of the upper and lower mantle. The evidence of the physic-chemically united mode of diamond genesis at the mantle depths with different mineralogy is obtained. References. Litvin Yu.A. (2007). High-pressure mineralogy of diamond genesis. In: Advances in High-Pressure Mineralogy (edited by Eiji Ohtani), Geological Society of America Special paper 421, 83-103. Litvin Yu.A. (2012). Experimental study of physic-chemical conditions of natural diamond formation on an example of the eclogite-carbonatite-sulphide-diamond system. Geology of Ore Deposits. 54(6), 523-539. Litvin Yu.A., Spivak A.V., Solopova N.A., Dubrovinsky L.S. (2014). On origin of lower-mantle diamonds and their primary inclusions. Physics of the Earth and Planetary Interiors, 228 (The Liebermann Volume), 176-185. http://dx.doi.org/10.1016/j/pepi/2013.12.007

Dense plasma chemistry of hydrocarbons at conditions relevant to planetary interiors and inertial confinement fusion

NASA Astrophysics Data System (ADS)

Kraus, Dominik

2017-10-01

Carbon-hydrogen demixing and subsequent diamond precipitation has been predicted to strongly participate in shaping the internal structure and evolution of icy giant planets like Neptune and Uranus. The very same dense plasma chemistry is also a potential concern for CH plastic ablator materials in inertial confinement fusion (ICF) experiments where similar conditions are present during the first compression stage of the imploding capsule. Here, carbon-hydrogen demixing may enhance the hydrodynamic instabilities occurring in the following compression stages. First experiments applying dynamic compression and ultrafast in situ X-ray diffraction at SLAC's Linac Coherent Light Source demonstrated diamond formation from polystyrene (CH) at 150 GPa and 5000 K. Very recent experiments have now investigated the influence of oxygen, which is highly abundant in icy giant planets on the phase separation process. Compressing PET (C5H4O2) and PMMA(C5H8O2), we find again diamond formation at pressures above 150 GPa and temperatures of several thousand kelvins, showing no strong effect due to the presence of oxygen. Thus, diamond precipitation deep inside icy giant planets seems very likely. Moreover, small-angle X-ray scattering (SAXS) was added to the platform, which determines an upper limit for the diamond particle size, while the width of the diffraction features provides a lower limit. We find that diamond particles of several nanometers in size are formed on a nanosecond timescale. Finally, spectrally resolved X-ray scattering is used to scale amorphous diffraction signals and allows for determining the amount of carbon-hydrogen demixing inside the compressed samples even if no crystalline diamond is formed. This whole set of diagnostics provides unprecedented insights into the nanosecond kinetics of dense plasma chemistry.

Fabrication of Hierarchical Layer-by-Layer Assembled Diamond-based Core-Shell Nanocomposites as Highly Efficient Dye Absorbents for Wastewater Treatment

NASA Astrophysics Data System (ADS)

Zhao, Xinna; Ma, Kai; Jiao, Tifeng; Xing, Ruirui; Ma, Xilong; Hu, Jie; Huang, Hao; Zhang, Lexin; Yan, Xuehai

2017-03-01

The effective chemical modification and self-assembly of diamond-based hierarchical composite materials are of key importance for a broad range of diamond applications. Herein, we report the preparation of novel core-shell diamond-based nanocomposites for dye adsorption toward wastewater treatment through a layer-by-layer (LbL) assembled strategy. The synthesis of the reported composites began with the carboxyl functionalization of microdiamond by the chemical modification of diamond@graphene oxide composite through the oxidation of diamond@graphite. The carboxyl-terminated microdiamond was then alternatively immersed in the aqueous solution of amine-containing polyethylenimine and carboxyl-containing poly acrylic acid, which led to the formation of adsorption layer on diamond surface. Alternating (self-limiting) immersions in the solutions of the amine-containing and carboxyl-containing polymers were continued until the desired number of shell layers were formed around the microdiamond. The obtained core-shell nanocomposites were successfully synthesized and characterized by morphological and spectral techniques, demonstrating higher surface areas and mesoporous structures for good dye adsorption capacities than nonporous solid diamond particles. The LbL-assembled core-shell nanocomposites thus obtained demonstrated great adsorption capacity by using two model dyes as pollutants for wastewater treatment. Therefore, the present work on LbL-assembled diamond-based composites provides new alternatives for developing diamond hybrids as well as nanomaterials towards wastewater treatment applications.

High-temperature molecular dynamics simulation of aragonite.

PubMed

Miyake, Akira; Kawano, Jun

2010-06-09

For molecular dynamics simulations using aragonite structure as the initial state, a new phase of space group P6₃22 (hexagonal aragonite) appeared at temperatures above 510 K at a pressure of 1 atm. It was a first-order phase transition which occurs metastably within the stable region of calcite and the dT/dP slope of the phase boundary between orthorhombic and hexagonal aragonite was about 1.25 × 10³ K GPa⁻¹. In the hexagonal aragonite structure, CO₃ groups were rotated by 30° around the c axis and move up and down along the c axis from their position in aragonite, and Ca ions were six-coordinated as they are in calcite. The CaO₆ octahedron of hexagonal aragonite was strongly distorted, whereas in the calcite structure it is an almost ideal octahedron. The transition between hexagonal and orthorhombic aragonite involves only small movements of CO₃ groups. Therefore, it is possible that hexagonal aragonite plays an important part in the metastable formation of aragonite within the stability field of calcite and in the development of sector trilling in aragonite.

Cubic and orthorhombic structures of aluminum hydride Al H3 predicted by a first-principles study

NASA Astrophysics Data System (ADS)

Ke, Xuezhi; Kuwabara, Akihide; Tanaka, Isao

2005-05-01

The most stable structure of aluminum hydride AlH3 is believed to be a hexagonal symmetry. However, using the density functional theory, we have identified two more stable structures for the AlH3 with the cubic and orthorhombic symmetries. Based on the quasiharmonic approximation, the cubic and orthorhombic AlH3 are almost degenerate when the zero-point energies are included. The geometric and electronic structures, the phonon, and the thermodynamic properties for the hexagonal, cubic, and orthorhombic AlH3 have been studied by means of density functional theory and direct ab initio force constant approach. The calculated electronic structures, phonon density of states, and thermodynamic functions [including S(T) and H(T)-H(0) ] for the three hydrides are similar. The results show that these three hydrides have negative enthalpies of formation, but positive free energies of formation. This conclusion is the same as that made by Wolverton for the hexagonal AlH3 [Phys. Rev. B 69, 144109 (2004)]. The thermodynamic properties indicate that the orthorhombic and cubic AlH3 should be more difficult to dissociate than the hexagonal AlH3 .

Shape transformation of bimetallic Au–Pd core–shell nanocubes to multilayered Au–Pd–Au core–shell hexagonal platelets

DOE PAGES

Bhattarai, Nabraj; Prozorov, Tanya

2015-11-05

Transformation of metallic or bimetallic (BM) nanoparticles (NPs) from one shape to another desired shape is of importance to nanoscience and nanotechnology, where new morphologies of NPs lead to enhancement of their exploitable properties. In this report, we present the shape transformation of Au octahedral NPs to Au–Pd core–shell nanocubes, followed by their transformation to nanostars and finally to multilayered Au–Pd–Au core–shell hexagonal platelets in the presence of T30 DNA. The weaker binding affinity of T30 DNA directs the growth to favor the formation of lower energy {111} facets, changing the morphology from nanocubes to nanostar. The nanostars, exhibiting unusualmore » intermediate morphologies, are comprised two sets of shell layers and have Au core, Pd intermediate shell, and Au outer shell. Similarly, the hexagonal platelets, which also have Au core and inner Pd shell, are encased in an external gold shell. As a result, the formation of multilayered Au–Pd–Au core–shell hexagonal platelets from Au–Pd core–shell nanocubes via the multilayered nanostars is monitored using scanning/transmission electron microscopy analysis.« less

Two-dimensional inorganic-organic perovskite hexagonal nanosheets: growth and mechanism

NASA Astrophysics Data System (ADS)

Shakya, Suman; Prakash, G. Vijaya

2015-03-01

In this era of novel technological materials, inorganic-organic (IO) materials has emerged as new class of materials for their application in photonic materials, miniaturized sensors, optoelectronic devices, non-linear optical apparatus by exploiting the properties of both constituents in a single entity. Here we present the formation and growth mechanism of two dimensional Inorganic-organic (IO) perovskite structures from anisotropically grown PbO hexagonal nanosheets, in three steps: Fabrication of hexagonal PbO nanosheets by the versatile bottom-up electrochemical deposition technique, iodinization of PbO into PbI2, followed by conversion of PbI2 into IO hybrid by the intercalation of organic moiety. A systematic and detailed structural study reveals that PbO nanosheet formation is more likely to result from an oriented attachment mechanism, in which the sheets formed by the reduction in surface area that happens during aggregation of small nanoparticle that each has a net dipole moment, which tends to form a self-assembled structure. Intercalation of organic moiety into the PbI2 layers yielded a selfassembled quantum-wells system of one of the IO hybrid, i.e. (C6H9C2H4NH3)2PbI4 (CHPI), sustaining the hexagonal shape.

Shape transformation of bimetallic Au–Pd core–shell nanocubes to multilayered Au–Pd–Au core–shell hexagonal platelets

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

Bhattarai, Nabraj; Prozorov, Tanya

Transformation of metallic or bimetallic (BM) nanoparticles (NPs) from one shape to another desired shape is of importance to nanoscience and nanotechnology, where new morphologies of NPs lead to enhancement of their exploitable properties. In this report, we present the shape transformation of Au octahedral NPs to Au–Pd core–shell nanocubes, followed by their transformation to nanostars and finally to multilayered Au–Pd–Au core–shell hexagonal platelets in the presence of T30 DNA. The weaker binding affinity of T30 DNA directs the growth to favor the formation of lower energy {111} facets, changing the morphology from nanocubes to nanostar. The nanostars, exhibiting unusualmore » intermediate morphologies, are comprised two sets of shell layers and have Au core, Pd intermediate shell, and Au outer shell. Similarly, the hexagonal platelets, which also have Au core and inner Pd shell, are encased in an external gold shell. As a result, the formation of multilayered Au–Pd–Au core–shell hexagonal platelets from Au–Pd core–shell nanocubes via the multilayered nanostars is monitored using scanning/transmission electron microscopy analysis.« less

Effect of temperature on the magnetic properties of nano-sized M-type barium hexagonal ferrites

NASA Astrophysics Data System (ADS)

Tchouank Tekou Carol, T.; Sharma, Jyoti; Mohammed, J.; Kumar, Sachin; Srivastava, A. K.

2017-07-01

The application of M-type hexagonal ferrites in electronic devices is increasing with technological advancement. This is due to the possibility of improving the physical and magnetic properties to suit the desired application. Enhanced magnetic properties make hexagonal ferrites suitable for hyper frequency and radar absorbing application. In this paper, we investigated the effect of heat-treatment temperature on the structural and magnetic properties of M-type barium hexagonal ferrites with chemical composition Ba1-xAlxFe12-yMnyO19 (x=0.6 and y=0.3) synthesized by sol-gel auto-combustion method and sintered at 750°C, 850°C, 950°C and 1050°C. Characterisations of the prepared samples were done using Fourier transform-infrared (FT-IR), and vibrating sample magnetometer (VSM). The formation of M-type hexaferrite has been confirmed from XRD. The presence of two prominent peaks between 400 cm-1 and 600 cm-1 in the spectra of Fourier transform-infrared spectroscopy (FT-IR) also shows the formation of ferrite phase. Saturation magnetisation (MS), remnant magnetisation (Mr), coercivity (Hc) and squareness ratio (SR) were calculated from the M-H loop obtained from vibrating sample magnetometer (VSM).

Analysis of synthetic diamond single crystals by X-ray topography and double-crystal diffractometry

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

Prokhorov, I. A., E-mail: igor.prokhorov@mail.ru; Ralchenko, V. G.; Bolshakov, A. P.

2013-12-15

Structural features of diamond single crystals synthesized under high pressure and homoepitaxial films grown by chemical vapor deposition (CVD) have been analyzed by double-crystal X-ray diffractometry and topography. The conditions of a diffraction analysis of diamond crystals using Ge monochromators have been optimized. The main structural defects (dislocations, stacking faults, growth striations, second-phase inclusions, etc.) formed during crystal growth have been revealed. The nitrogen concentration in high-pressure/high-temperature (HPHT) diamond substrates is estimated based on X-ray diffraction data. The formation of dislocation bundles at the film-substrate interface in the epitaxial structures has been revealed by plane-wave topography; these dislocations are likelymore » due to the relaxation of elastic macroscopic stresses caused by the lattice mismatch between the substrate and film. The critical thicknesses of plastic relaxation onset in CVD diamond films are calculated. The experimental techniques for studying the real diamond structure in optimizing crystal-growth technology are proven to be highly efficient.« less

Signatures of Phonon and Defect-Assisted Tunneling in Planar Metal-Hexagonal Boron Nitride-Graphene Junctions.

PubMed

Chandni, U; Watanabe, K; Taniguchi, T; Eisenstein, J P

2016-12-14

Electron tunneling spectroscopy measurements on van der Waals heterostructures consisting of metal and graphene (or graphite) electrodes separated by atomically thin hexagonal boron nitride tunnel barriers are reported. The tunneling conductance, dI/dV, at low voltages is relatively weak, with a strong enhancement reproducibly observed to occur at around |V| ≈ 50 mV. While the weak tunneling at low energies is attributed to the absence of substantial overlap, in momentum space, of the metal and graphene Fermi surfaces, the enhancement at higher energies signals the onset of inelastic processes in which phonons in the heterostructure provide the momentum necessary to link the Fermi surfaces. Pronounced peaks in the second derivative of the tunnel current, d 2 I/dV 2 , are observed at voltages where known phonon modes in the tunnel junction have a high density of states. In addition, features in the tunneling conductance attributed to single electron charging of nanometer-scale defects in the boron nitride are also observed in these devices. The small electronic density of states of graphene allows the charging spectra of these defect states to be electrostatically tuned, leading to "Coulomb diamonds" in the tunneling conductance.

High resolution structural characterisation of laser-induced defect clusters inside diamond

NASA Astrophysics Data System (ADS)

Salter, Patrick S.; Booth, Martin J.; Courvoisier, Arnaud; Moran, David A. J.; MacLaren, Donald A.

2017-08-01

Laser writing with ultrashort pulses provides a potential route for the manufacture of three-dimensional wires, waveguides, and defects within diamond. We present a transmission electron microscopy study of the intrinsic structure of the laser modifications and reveal a complex distribution of defects. Electron energy loss spectroscopy indicates that the majority of the irradiated region remains as sp3 bonded diamond. Electrically conductive paths are attributed to the formation of multiple nano-scale, sp2-bonded graphitic wires and a network of strain-relieving micro-cracks.

Diamond and moissanite in ophiolitic mantle rocks and podiform chromitites: A deep carbon source?

NASA Astrophysics Data System (ADS)

Yang, J.; Xu, X.; Wiedenbeck, M.; Trumbull, R. B.; Robinson, P. T.

2010-12-01

Diamonds are known from a variety of occurreces, mainly from mantle-derived kimberlites, meteorite impact craters, and continental deep subduction and collision zones. Recently, an unusual mineral group was discovered in the Luobusa ophiolitic chromitites from the Yarlung Zangbu suture, Tibet, which probably originated from a depth of over 300 km in the mantle. Minerals of deep origin include coesite apparently pseudomorphing stishovite, and diamond as individual grains or inclusions in OsIr alloy. To determine if such UHP and unusual minerals occur elsewhere, we collected about 1.5 t of chromitite from two orebodies in an ultramafic body in the Polar Urals. Thus far, more than 60 different mineral species have been separated from these ores. The most exciting discovery is the common occurrence of diamond, a typical UHP mineral in the Luobusa chromitites. These minerals are very similar in composition and structure to those reported from the Luobusa chromitites. So far diamond and/or moissanite have been discovered from many different ophiolitic ultramafic rocks, including in-situ grains in polished chromitite fragments. These discoveries demonstrate that the Luobusa ophiolite is not a unique diamond-bearing massif. Secondary ion mass spectrometric (SIMS) analysis shows that the ophiolite-hosted diamond has a distinctive 13C-depleted isotopic composition (δ13C from -18 to -28‰, n=70), compatible to the ophiolite-hosted moissanite (δ13C from -18 to -35‰, n=36), both are much lighter than the main carbon reservoir in the upper mantle (δ13C near -5‰). The compiled data from moissanite from kimberlites and other mantle settings share the characteristic of strongly 13C-depleted isotopic composition. This suggests that diamond and moissanite originates from a separate carbon reservoir in the mantle or that its formation involved strong isotopic fractionation. Subduction of biogenic carbonaceous material could potentially satisfy both the unusual isotopic and redox constraints on diamond and moissanite formation, but this material would need to stay chemically isolated from the upper mantle until it reached the high-T stability field of diamond and moissanite. The origin of diamond and moissanite in the mantle is still unsolved, but all evidence from the upper mantle indicates that they cannot have formed there, except under special and local redox conditions. We suggest, alternatively, that diamond and moissanite may have formed in the lower mantle, where the existence of 13C-depleted carbon is strongly suspected.

Understanding ultrafine nanodiamond formation using nanostructured explosives

PubMed Central

Pichot, Vincent; Risse, Benedikt; Schnell, Fabien; Mory, Julien; Spitzer, Denis

2013-01-01

The detonation process is able to build new materials with a bottom-up approach. Diamond, the hardest material on earth, can be synthesized in this way. This unconventional synthesis route is possible due to the presence of carbon inside the high-explosive molecules: firing high-explosive mixtures with a negative oxygen balance in a non-oxidative environment leads to the formation of nanodiamond particles. Trinitrotoluene (TNT) and hexogen (RDX) are the explosives primarily used to synthesize nanodiamonds. Here we show that the use of nanostructured explosive charges leads to the formation of smaller detonation nanodiamonds, and it also provides new understanding of nanodiamond formation-mechanisms. The discontinuity of the explosive at the nanoscale level plays the key role in modifying the diamond particle size, and therefore varying the size with microstructured charges is impossible. PMID:23831716

Simultaneous measurement of pressure evolution of crystal structure and superconductivity in FeSe[subscript 0.92] using designer diamonds

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

Uhoya, Walter; Tsoi, Georgiy; Vohra, Yogesh

Simultaneous high-pressure X-ray diffraction and electrical resistance measurements have been carried out on a PbO-type {alpha}-FeSe{sub 0.92} compound to a pressure of 44 GPa and temperatures down to 4 K using designer diamond anvils at synchrotron source. A ambient temperature, a structural phase transition from a tetragonal (P4/nmm) phase to an orthorhombic (Pbnm) phase is observed at 11 GPa and the Pbnm phase persists up to 74 GPa. The superconducting transition temperature (T{sub c}) increases rapidly with pressure reaching a maximum of {approx}28 K at {approx}6 GPa and decreases at higher pressures, disappearing completely at 14.6 GPa. Simultaneous pressure-dependent X-raymore » diffraction and resistance measurements at low temperatures show superconductivity only in a low-pressure orthorhombic (Cmma) phase of the {alpha}-FeSe{sub 0.92}. Upon increasing pressure at 10 K near T{sub c}, crystalline phases change from a mixture of orthorhombic (Cmma) and hexagonal (P63/mmc) phases to a high-pressure orthorhombic (Pbnm) phase near 6.4 GPa where T{sub c} is maximum.« less

Measurements of sound velocity in iron-nickel alloys by femtosecond laser pulses in a diamond anvil cell

NASA Astrophysics Data System (ADS)

Wakamatsu, Tatsuya; Ohta, Kenji; Yagi, Takashi; Hirose, Kei; Ohishi, Yasuo

2018-01-01

By comparing the seismic wave velocity profile in the Earth with laboratory data of the sound velocity of iron alloys, we can infer the chemical composition of materials in the Earth's core. The sound velocity of pure iron (Fe) has been sufficiently measured using various techniques, while experimental study on the sound velocity of iron-nickel (Fe-Ni) alloys is limited. Here, we measured longitudinal wave velocities of hexagonal-close-packed (hcp) structured Fe up to 29 GPa, Fe-5 wt% Ni, and Fe-15 wt% Ni up to 64 GPa via a combination of the femtosecond pulse laser pump-probe technique and a diamond anvil cell at room temperature condition. We found that the effect of Ni on the sound velocity of an Fe-based alloy is weaker than that determined by previous experimental study. In addition, we obtained the parameters of Birch's law to be V P = 1146(57)ρ - 3638(567) for Fe-5 wt% Ni and V P = 1141(45)ρ- 3808(446) for Fe-15 wt% Ni, respectively, where V P is longitudinal wave velocity (m/s) and ρ is density (g/cm3).

Measurements of sound velocity in iron-nickel alloys by femtosecond laser pulses in a diamond anvil cell

NASA Astrophysics Data System (ADS)

Wakamatsu, Tatsuya; Ohta, Kenji; Yagi, Takashi; Hirose, Kei; Ohishi, Yasuo

2018-06-01

By comparing the seismic wave velocity profile in the Earth with laboratory data of the sound velocity of iron alloys, we can infer the chemical composition of materials in the Earth's core. The sound velocity of pure iron (Fe) has been sufficiently measured using various techniques, while experimental study on the sound velocity of iron-nickel (Fe-Ni) alloys is limited. Here, we measured longitudinal wave velocities of hexagonal-close-packed (hcp) structured Fe up to 29 GPa, Fe-5 wt% Ni, and Fe-15 wt% Ni up to 64 GPa via a combination of the femtosecond pulse laser pump-probe technique and a diamond anvil cell at room temperature condition. We found that the effect of Ni on the sound velocity of an Fe-based alloy is weaker than that determined by previous experimental study. In addition, we obtained the parameters of Birch's law to be V P = 1146(57) ρ - 3638(567) for Fe-5 wt% Ni and V P = 1141(45) ρ- 3808(446) for Fe-15 wt% Ni, respectively, where V P is longitudinal wave velocity (m/s) and ρ is density (g/cm3).

Structural defects in natural plastically deformed diamonds: Evidence from EPR spectroscopy

NASA Astrophysics Data System (ADS)

Mineeva, R. M.; Titkov, S. V.; Speransky, A. V.

2009-06-01

Structural defects formed as a result of plastic deformation in natural diamond crystals have been studied by EPR spectroscopy. The spectra of brown, pink-brown, black-brown, pink-purple, and gray plastically deformed diamonds of type Ia from deposits in Yakutia and the Urals were recorded. The results of EPR spectroscopy allowed us to identify various deformation centers in the structure of natural diamonds and to show that nitrogen centers were transformed under epigenetic mechanical loading. Abundant A centers, consisting of two isomorphic nitrogen atoms located in neighboring structural sites, were destroyed as a result of this process to form a series of N1, N4, W7, M2, and M3 nitrogen centers. Such centers are characterized by an anisotropic spatial distribution and a positive charge, related to the mechanism of their formation. In addition, N2 centers (probably, deformation-produced dislocations decorated by nitrogen) were formed in all plastically deformed diamonds and W10 and W35 centers (the models have not been finally ascertained) were formed in some of them. It has been established that diamonds with various types of deformation-induced color contain characteristic associations of these deformation centers. The diversity of associations of deformation centers indicates appreciable variations in conditions of disintegration of deep-seated rocks, transfer of diamonds to the Earth’s surface, and formation of kimberlitic deposits. Depending on the conditions of mechanical loading, the diamond crystals were plastically deformed by either dislocation gliding or mechanical twinning. Characteristic features of plastic deformation by dislocation gliding are the substantial prevalence of the N2 centers over other deformation centers and the occurrence of the high-spin W10 and W35 centers. The attributes of less frequent plastic deformation by mechanical twinning are unusual localization of the M2 centers and, in some cases, the N1 centers in microtwinned lamellae. Numerous data on models of deformation centers in natural diamonds, including the M2 and M3 centers, which were observed in the studied collection for the first time, are discussed.

Use of natural diamonds to monitor 14C AMS instrument backgrounds

NASA Astrophysics Data System (ADS)

Taylor, R. E.; Southon, John

2007-06-01

To examine one component of the instrument-based background in the University of California Keck Carbon Cycle AMS spectrometer, we have obtained measurements on a set of natural diamonds pressed into sample holders. Natural diamond samples (N = 14) from different sources within rock formations with geological ages greatly in excess of 100 Ma yielded a range of currents (∼110-250 μA 12C- where filamentous graphite typically yields ∼150 μA 12C-) and apparent 14C ages (64.9 ± 0.4 ka BP [0.00031 ± 0.00002 fm] to 80.0 ± 1.1 ka BP [0.00005 ± 0.00001 fm]). Six fragments cut from a single diamond exhibited essentially identical 14C values - 69.3 ± 0.5 ka-70.6 ± 0.5 ka BP. The oldest 14C age equivalents were measured on natural diamonds which exhibited the highest current yields.

"Fullerene-like" Raman bands in UHP metamorphic diamonds: Metastable intermediate phases for diamond formation

NASA Astrophysics Data System (ADS)

Harada, Y.; Igarashi, M.; Hashiguchi, Y.; Ogasawara, Y.

2011-12-01

Mysterious Raman bands at 1430-1480 cm-1 suggesting carbon (or carbon-bearing) species have been discovered in UHP metamorphic microdiamonds entirely enclosed in dolomite marble from Kokchetav Massif (Igarashi et al., 2011). Such Raman bands first discovered at some domains in a T-type (see Ishida et al., 2003) diamond in dolomite marble in 2005, but we have not reported this because of the possibility of misidentification by contamination. Later, similar bands were also found in the rim and the core of S-type and R-type. The relative intensities of these Raman bands to diamond (at 1332 cm-1) were 10-40 % in average (max. 90-110 %) and FWHMs are broad (25-45 cm-1). The possibility of the appearance of these Raman bands was low. As we used ordinary polished thin sections (thickness: 25 μm) and the organic materials used in thin section making have Raman bands at ca. 1450 cm-1, we carefully examined observed Raman spectra and the positions of the source materials of these bands to exclude the possibility of contaminations. Examined microdiamond grains are entirely enclosed in the host garnet, and no crack was observed in the host. We conducted 2D Raman mappings at different depths with 2 μm intervals. The result showed that the domains having these Raman bands were located within diamond grains and limited area (1-3 μm). These bands were never detected from outside diamond grains (e.g., host garnet). Thus, the unknown Raman bands at 1430-1480 cm-1 were attributed to some materials inside microdiamonds entirely included in the host garnet. The possibility of contamination was denied. Recently, we found similar Raman bands in the microdiamonds in garnet in Grt-Bt gneiss. Examined microdiamonds are entirely enclosed in garnet grain and no extra phase observed near laser spots in these microdiamond grains under an optical microscope. The Raman bands at 1430-1480 cm-1 were found from 4 microdiamond grains. The peak positions and FWHMs of these bands were as follows: (a) 1433, 31 (b) 1456, 35 (b) 1458, 41 (c) 1461, 31 (e) 1462 cm-1, 44 cm-1. Their intensities to the host diamond were 10-20 % in average. The mappings at different depths also showed very limited source space inside microdiamond grains. Although it is difficult to identify the source materials only by Raman spectroscopy, we considered that the Raman bands could be attributed to some carbon or carbon-bearing species which were relicts as metastable intermediate phases for microdiamond formation under UHP. Fullerenes are speculated as possible carbon materials for those bands. The band at 1470 cm-1 is similar to Ag (2) band of C60 fullerene. The large FWHM and the variation of peak positions at 1430-1480 cm-1 may be caused by aggregations of several species of fullerenes. If our speculation is correct, metamorphic diamond could have the possibility of preservation of intermediate carbon phases in diamond because the duration for diamond growth was much shorter than kimberlitic diamonds. We should pay attentions to such extra materials inside diamonds in order to clarify the real image of the diamond formation.

Is Absence of Evidence of UHPM Evidence of Absence: Did Conditions on Earth Before the Ediacaran Period Allow Formation of UHP Rocks but Only Rarely Their Exhumation?

NASA Astrophysics Data System (ADS)

Brown, M.

2008-12-01

UHPM provides petrologic evidence of transport of continental lithosphere to asthenospheric depth and return of some of these materials to crustal depth. The rock record registers UHPM since the Ediacaran Period, and studies of inclusion assemblages in zircon have increased the evidence of UHPM in Phanerozoic orogens and enabled an assessment of the real estate involved. Plots of apparent thermal gradient vs. age of metamorphism and P vs. age of metamorphism reveal two dramatic changes in inferred thermal environment and inferred depth of metamorphism from which continental lithosphere has been recovered during Earth evolution. First, from the Mesoarchean Era to the Neoproterozoic Era, sutures in subduction-to- collision orogens are marked by eclogite and high-pressure granulite metamorphism (characterized by apparent thermal gradients of 750-350 C/GPa). The P of metamorphism in sutures jumped from <1 GPa during the Eoarchean-Paleoarchean up to 2 GPa during the Paleoproterozoic. Second, from the Cryogenian- Ediacaran to the present, many sutures in subduction-to-collision orogens, and sometimes intracratonic sutures in the overriding plate, are marked by UHPM (characterized by apparent thermal gradients of <350 C/GPa) with P of metamorphism >2.7GPa. Given this pattern of secular change to colder apparent thermal gradients in sutures, the recent discovery of diamonds in zircons of crustal paragenesis in Neoarchean sedimentary rocks is surprising. Maybe UHPM has been possible since the Neoarchean but the evidence was rarely exhumed or if exhumed maybe the evidence was rarely preserved? The Appalachian/Caledonian-Variscide-Altaid and the Cimmerian-Himalayan-Alpine orogenic systems were formed by successive closure of short-lived oceans by transfer and suturing of ribbon-continent terranes derived from the Gondwanan side. Subduction of young ocean lithosphere followed by choking of the subduction channel by arc or terrane collision limited transport of water to the mantle wedge, and suppressed development of small-scale convection, arc magmatism and backarc formation. This allowed the retro- continental margin to remain strong, which favored efficient exhumation of UHPM rocks (Warren et al., 2008, EPSL). How should we interpret the presence of diamonds in detrital zircons (age range 3,050-4,260 Ma) from the Narryer terrane? Menneken et al. (2007, Nature) argue that the age range indicates repeated conditions for diamond formation (or recycling of ancient diamond) and that diamonds imply thick continental lithosphere and crust-mantle interactions since 4,260 Ma! This implies thermal environments and tectonics in the Hadean and Archean Eons similar to the Phanerozoic Eon. However, these ancient zircons originally crystallized from low-T melts (Watson and Harrison, 2006, Science) and the 'age' of the diamonds is only constrained to be > the age of deposition and <3,050 Ma. Williams (2007, Science) suggests that C was introduced as graphite precipitated from COH fluid in fractures/imperfections in zircon prior to deep burial to form diamond during a single event. COH fluid was involved in the formation of diamonds from Phanerozoic UHPM localities, so the hypothesis is viable if an appropriate tectonic model can be developed. I will present a model for the formation and exhumation of an overriding plate source terrane for the diamond-bearing detrital zircons that is consistent with periodic changes in the tectonic regime of Earth (Brown, 2006, Geology), and the geology and likely tectonic setting of the Narryer Terrane-Yilgarn Craton during the Neoarchean. Finally, I will speculate about UMPM during the Proterozoic and exhumation vs. relamination (Hacker et al., Eos, 2007).

Synthesis of Diamond Nanoplatelets/Carbon Nanowalls on Graphite Substrate by MPCVD

NASA Astrophysics Data System (ADS)

Zhang, Wei; Lyu, Jilei; Lin, Xiaoqi; Zhu, Jinfeng; Man, Weidong; Jiang, Nan

2015-07-01

The films composed of carbon nanowalls and diamond nanoplatelets, respectively, can be simultaneously formed on graphite substrate by controlling the hydrogen etching rate during microwave plasma chemical vapor deposition. To modulate the etching rate, two kinds of substrate design were used: a bare graphite plate and a graphite groove covered with a single crystal diamond sheet. After deposition at 1200°C for 3 hours, we find that dense diamond nanoplatelets were grown on the bare graphite, whereas carbon nanowalls were formed on the grooved surface, indicating that not only reaction temperature but also etching behavior is a key factor for nanostructure formation. supported by the Public Welfare Technology Application Projects of Zhejiang Province, China (No. 2013C33G3220012)

Field electron emission enhancement in lithium implanted and annealed nitrogen-incorporated nanocrystalline diamond films

NASA Astrophysics Data System (ADS)

Sankaran, K. J.; Srinivasu, K.; Yeh, C. J.; Thomas, J. P.; Drijkoningen, S.; Pobedinskas, P.; Sundaravel, B.; Leou, K. C.; Leung, K. T.; Van Bael, M. K.; Schreck, M.; Lin, I. N.; Haenen, K.

2017-06-01

The field electron emission (FEE) properties of nitrogen-incorporated nanocrystalline diamond films were enhanced due to Li-ion implantation/annealing processes. Li-ion implantation mainly induced the formation of electron trap centers inside diamond grains, whereas post-annealing healed the defects and converted the a-C phase into nanographite, forming conduction channels for effective transport of electrons. This resulted in a high electrical conductivity of 11.0 S/cm and enhanced FEE performance with a low turn-on field of 10.6 V/μm, a high current density of 25.5 mA/cm2 (at 23.2 V/μm), and a high lifetime stability of 1,090 min for nitrogen incorporated nanocrystalline diamond films.

Two-dimensional hexagonally oriented CdCl2.H2O nanorod assembly: formation and replication.

PubMed

Deng, Zhaoxiang; Mao, Chengde

2004-09-14

This paper reports a simple bottom-up method that can controllably fabricate 2D hexagonally oriented and randomly distributed CdCl(2).H(2)O nanorods on mica surfaces. The as-formed nanorod assemblies have been successfully replicated into various matrixes, including gold, poly(dimethylsiloxane), and polyurethane. Thus, this method is compatible with soft-lithography towards further applications.

In-Situ Chemical Analyses of Mineral Inclusions in Diamonds in Kimberlitic Eclogites From Yakutia

NASA Astrophysics Data System (ADS)

ANAND, M.; MISRA, K. C.; TAYLOR, L. A.; SOBOLEV, N. V.

2001-12-01

Mineral inclusions in diamonds (DIs) are stated to provide P-T-X-t information regarding the formation of the diamonds and the nature of the upper mantle. In an endeavor to further understand the importance of diamonds and their DIs in relation to their host rocks, we have investigated several diamondiferous eclogites from Yakutia, first by HRXC tomography (Taylor et al., 2001, this meeting) and then by dissection of the eclogites into their individual minerals. The mineralogy of the host eclogite is presented by Misra et al. (2001, this meeting). Two of the diamondiferous eclogite xenoliths, although weighing but 66 g and 42 g, contain 74 and 47 macro-diamonds, resp. Based on HRXCT imaging, appropriate sections were selected in the eclogite to extract diamonds with minimum loss of material. In the majority of cases, diamonds occur as perfect octahedron with well developed crystal faces. In some cases, however, diamonds occur as macles (twinned xls). The size range of the diamonds is 1-6 mm. Optical examination reveals the sulfides as the most common DIs in these diamonds, followed by clinopyroxenes and garnets. Each diamond was cut and polished along relatively soft directions parallel to either (001) or (110) faces so as to expose DIs for in-situ analyses. Examination by cathodoluminescence (CL) on an EMP demonstrated that the majority of the diamonds have minute, optically invisible, cracks from the DIs to the surfaces of the diamonds - i.e., the possibility of an open system. These diamonds show complicated growth histories and contain DIs that are in some cases, found to be associated with secondary alteration. In addition, the DIs in each diamond, examined in-situ are of different composition from the host and different from DIs in other diamonds, a relationship reported earlier (Taylor et al., 2000, Int'l Geol Rev). These observations raise serious doubts about the significance of DIs and the pristinity and syngenesis of DIs removed by the typical diamond~crushing procedure. Therefore, extreme caution must be taken when interpreting any of the P-T-X-t conditions of diamond growth, based on DIs.

A large planetary body inferred from diamond inclusions in a ureilite meteorite.

PubMed

Nabiei, Farhang; Badro, James; Dennenwaldt, Teresa; Oveisi, Emad; Cantoni, Marco; Hébert, Cécile; El Goresy, Ahmed; Barrat, Jean-Alix; Gillet, Philippe

2018-04-17

Planetary formation models show that terrestrial planets are formed by the accretion of tens of Moon- to Mars-sized planetary embryos through energetic giant impacts. However, relics of these large proto-planets are yet to be found. Ureilites are one of the main families of achondritic meteorites and their parent body is believed to have been catastrophically disrupted by an impact during the first 10 million years of the solar system. Here we studied a section of the Almahata Sitta ureilite using transmission electron microscopy, where large diamonds were formed at high pressure inside the parent body. We discovered chromite, phosphate, and (Fe,Ni)-sulfide inclusions embedded in diamond. The composition and morphology of the inclusions can only be explained if the formation pressure was higher than 20 GPa. Such pressures suggest that the ureilite parent body was a Mercury- to Mars-sized planetary embryo.

The use of CVD diamond burs for ultraconservative cavity preparations: a report of two cases.

PubMed

Carvalho, Carlos Augusto R; Fagundes, Ticiane C; Barata, Terezinha J E; Trava-Airoldi, Vladimir Jesus; Navarro, Maria Fidela L

2007-01-01

During the past decades, scientific developments in cutting instruments have changed the conventional techniques used to remove caries lesions. Ultrasound emerged as an alternative for caries removal since the 1950s. However, the conventional technology for diamond powder aggregation with nickel metallic binders could not withstand ultrasonic power. Around 5 years ago, an alternative approach using chemical vapor deposition (CVD) resulted in synthetic diamond technology. CVD diamond burs are obtained with high adherence of the diamond as a unique stone on the metallic surface with excellent abrading performance. This technology allows for diamond deposition with coalescent granulation in different formats of substrates. When connected to an ultrasonic handpiece, CVD diamond burs become an option for cavity preparation, maximizing preservation of tooth structure. Potential advantages such as reduced noise, minimal damage to the gingival tissue, extended bur durability, improved proximal cavity access, reduced risk of hitting the adjacent tooth resulting from the high inclination angles, and minimal patient's risk of metal contamination. These innovative instruments also potentially eliminate some problems regarding decreased cutting efficiency of conventional diamond burs. This clinical report presents the benefits of using CVD diamond burs coupled with an ultrasonic handpiece in the treatment of incipient caries. CVD diamond burs coupled with an ultrasonic device offer a promising alternative for removal of carious lesions when ultraconservative cavity preparations are required. Additionally, this system provides a less-painful technique for caries removal, with minimal noise.

ZnS/diamond composite coatings for infrared transmission applications formed by the aerosol deposition method

NASA Astrophysics Data System (ADS)

Johnson, Scooter D.; Kub, Fritz J.; Eddy, Charles R.

2013-06-01

The deposition of nano-crystalline ZnS/diamond composite protective coatings on silicon, sapphire, and ZnS substrates, as a preliminary step to coating infrared transparent ZnS substrates from powder mixtures by the aerosol deposition method is presented. Advantages of the aerosol deposition method include the ability to form dense, nanocrystalline lms up to hundreds of microns thick at room temperature and at a high deposition rate on a variety of substrates. Deposition is achieved by creating a pressure gradient that accelerates micrometer- scale particles in an aerosol to high velocity. Upon impact with the target substrate the particles fracture and embed. Continued deposition forms the thick compacted lm. Deposition from an aerosolized mixture of ZnS and diamond powders onto all targets results in linear trend from apparent sputter erosion of the substrate at 100% diamond to formation of a lm with increasing fractions of ZnS. The crossover from abrasion to lm formation on sapphire occurs above about 50% ZnS and a mixture of 90% ZnS and 10% diamond forms a well-adhered lm of about 0.7 μm thickness at a rate of 0.14 μm/min. Resulting lms are characterized by scanning electron microscopy, pro lometry, infrared transmission spectroscopy, and x-ray photoemission spectroscopy. These initial lms mark progress toward the future goal of coating ZnS substrates for abrasion resistance.

Neutron diffraction study of water freezing on aircraft engine combustor soot.

PubMed

Tishkova, V; Demirdjian, B; Ferry, D; Johnson, M

2011-12-14

The study of the formation of condensation trails and cirrus clouds on aircraft emitted soot particles is important because of its possible effects on climate. In the present work we studied the freezing of water on aircraft engine combustor (AEC) soot particles under conditions of pressure and temperature similar to the upper troposphere. The microstructure of the AEC soot was found to be heterogeneous containing both primary particles of soot and metallic impurities (Fe, Cu, and Al). We also observed various surface functional groups such as oxygen-containing groups, including sulfate ions, that can act as active sites for water adsorption. Here we studied the formation of ice on the AEC soot particles by using neutron diffraction. We found that for low amount of adsorbed water, cooling even up to 215 K did not lead to the formation of hexagonal ice. Whereas, larger amount of adsorbed water led to the coexistence of liquid water (or amorphous ice) and hexagonal ice (I(h)); 60% of the adsorbed water was in the form of ice I(h) at 255 K. Annealing of the system led to the improvement of the crystal quality of hexagonal ice crystals as demonstrated from neutron diffraction.

Finite element design for the HPHT synthesis of diamond

NASA Astrophysics Data System (ADS)

Li, Rui; Ding, Mingming; Shi, Tongfei

2018-06-01

The finite element method is used to simulate the steady-state temperature field in diamond synthesis cell. The 2D and 3D models of the China-type cubic press with large deformation of the synthesis cell was established successfully, which has been verified by situ measurements of synthesis cell. The assembly design, component design and process design for the HPHT synthesis of diamond based on the finite element simulation were presented one by one. The temperature field in a high-pressure synthetic cavity for diamond production is optimized by adjusting the cavity assembly. A series of analysis about the influence of the pressure media parameters on the temperature field are examined through adjusting the model parameters. Furthermore, the formation mechanism of wasteland was studied in detail. It indicates that the wasteland is inevitably exists in the synthesis sample, the distribution of growth region of the diamond with hex-octahedral is move to the center of the synthesis sample from near the heater as the power increasing, and the growth conditions of high quality diamond is locating at the center of the synthesis sample. These works can offer suggestion and advice to the development and optimization of a diamond production process.

Hexagonal bubble formation and nucleation in sodium chloride solution

NASA Astrophysics Data System (ADS)

Wang, Lifen; Liu, Lei; Mohsin, Ali; Wen, Jianguo; Gu, Gong; Miller, Dean

The bubble is formed frequently at a solid-liquid interface when the surface of the solid or liquid has a tendency of accumulating molecular species due to unbalanced surface hydrophobicity attraction. Morphology and shape of the bubble are thought to be associated with the Laplace pressure that spherical-cap-shaped object are commonly observed. Dynamic surface nanobubble formation and nucleation in the controlled system have been not fully investigated due to the direct visualization challenge in liquid systems. Here, utilizing in situ TEM, dynamic formation and collapse of spherical-shaped nanobubbles were observed at the water-graphene interface, while hexagonal nanobubbles grew and merged with each other at water-crystalline sodium chloride interface. Our finding demonstrates that different hydrophobic-hydrophilic interaction systems give rise to the varied morphology of surface nanobubble, leading to the fundamental understanding of the interface-interaction-governed law on the formation of surface nanobubble.

Green synthesis and characterization of zinc oxide nanoparticle using insulin plant (Costus pictus D. Don) and investigation of its antimicrobial as well as anticancer activities

NASA Astrophysics Data System (ADS)

Suresh, Joghee; Pradheesh, Ganeshan; Alexramani, Vincent; Sundrarajan, Mahalingam; Hong, Sun Ig

2018-03-01

In this work we aim to synthesize biocompatible ZnO nanoparticles from the zinc nitrate via green process using leaf extracts of the Costus pictus D. Don medicinal plant. FTIR studies confirm the presence of biomolecules and metal oxides. X-ray diffraction (XRD) structural analysis reveals the formation of pure hexagonal phase structures of ZnO nanoparticles. The surface morphologies of ZnO nanoparticles observed under a scanning electron microscope (SEM) suggest that most ZnO crystallites are hexagonal. EDX analysis confirms the presence of primarily zinc and oxygen. TEM images show that biosynthesized zinc oxide nanoparticles are hexagonal and spherical. The plausible formation mechanisms of zinc oxide nanoparticles are also predicted. The biosynthesized zinc oxide nanoparticles exhibit strong antimicrobial behavior against bacterial and fungal species when employing the agar diffusion method. Synthesized ZnO nanoparticles exhibit anticancer activity against Daltons lymphoma ascites (DLA) cells as well as antimicrobial activity against some bacterial and fungal strains.

Crystallographic and magnetic structure of HAVAR under high-pressure using diamond anvil cell (DAC)

NASA Astrophysics Data System (ADS)

Halevy, Itzhak; Haroush, Shlomo; Eisen, Yosef; Silberman, Ido; Moreno, Dany; Hen, Amir; Winterrose, Mike L.; Ghose, Sanjit; Chen, Zhiqiang

2010-04-01

Annealed (H1) and cold-rolled (H2) HAVAR has been studied using high-pressure synchrotron X-ray diffraction. A structural phase transformation was discovered at ˜13 GPa at ambient temperature, transforming from m - 3 m (S.G. 225) to P 63/m m c (S.G. 194) symmetry. The transition was not reversible on pressure release. The low-pressure cubic phase was found to be more compressible than the high-pressure hexagonal phase. Conventional Mössbauer and NFS shows that the HAVAR is not magnetic at room temperature and no splitting is observed. The SQUID indicates a huge difference in the temperature dependence of the magnetic susceptibility between the cold Rolled HAVAR compared to the annealed HAVAR.

Benchmarks of simple, generic, shaped plates for validation of low-frequency electromagnetic computational codes

NASA Technical Reports Server (NTRS)

Deshpande, M. D.; Cockrell, C. R.; Beck, F. B.; Nguyen, T. X.

1993-01-01

The validation of low-frequency measurements and electromagnetic (EM) scattering computations for several simple, generic shapes, such as an equilateral-triangular plate, an equilateral-triangular plate with a concentric equilateral-triangular hole, and diamond- and hexagonal-shaped plates, is discussed. The plates were constructed from a thin aluminum sheet with a thickness of 0.08 cm. EM scattering by the planar plates was measured in the experimental test range (ETR) facility of NASA Langley Research Center. The dimensions of the plates were selected such that, over the frequency range of interest, the dimensions were in the range of lambda0 to 3(lambda0). In addition, the triangular plate with a triangular hole was selected to study internal-hole resonances.

Modeling of process of forming quality parameters for surfaces of parts by diamond burnishing taking into account technological heredity

NASA Astrophysics Data System (ADS)

Nagorkin, M. N.; Fyodorov, V. P.; Kovalyova, E. V.

2018-03-01

The paper presents a methodology for quantitative assessment of the influence of technological heredity on the formation of quality parameters for surfaces of machine parts. An example of an estimation of influence factors of technological subsystems of processing by end milling processing by composite 10 and the subsequent diamond burnishing is presented.

Engineered arrays of nitrogen-vacancy color centers in diamond based on implantation of CN- molecules through nanoapertures

NASA Astrophysics Data System (ADS)

Spinicelli, P.; Dréau, A.; Rondin, L.; Silva, F.; Achard, J.; Xavier, S.; Bansropun, S.; Debuisschert, T.; Pezzagna, S.; Meijer, J.; Jacques, V.; Roch, J.-F.

2011-02-01

We report a versatile method for engineering arrays of nitrogen-vacancy (NV) color centers in diamond at the nanoscale. The defects were produced in parallel by ion implantation through 80 nm diameter apertures patterned using electron beam lithography in a polymethyl methacrylate (PMMA) layer deposited on a diamond surface. The implantation was performed with CN- molecules that increased the NV defect-formation yield. This method could enable the realization of a solid-state coupled-spin array and could be used for positioning an optically active NV center on a photonic microstructure.

TiO2-NT electrodes modified with Ag and diamond like carbon (DLC) for hydrogen production by alkaline water electrolysis

NASA Astrophysics Data System (ADS)

Baran, Evrim; Baz, Zeynep; Esen, Ramazan; Yazici Devrim, Birgül

2017-10-01

In present work, the two-step anodization technique was applied for synthesis of TiO2 nanotube (NT). Silver and diamond like carbon (DLC) were coated on the surface of as prepared TiO2-NT using chemical reduction method and MW ECR plasma system. The morphology, composition and structure of the electrodes were examined by field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray spectroscopy (EDX) and X-ray diffraction (XRD). The results showed that Ag nanoparticles, having size in the range of 48-115 nm, are evenly distributed on the top, inside and outside surface of TiO2-NT and when DLC was coated on the surface of TiO2-NT and TiO2-NT-Ag, the top of nanotubes were partially open and the pore diameter of hexagonal structure decreased from 165 nm to of 38-80 nm. On the other hand, the microhardness test and contact angle measurements revealed that additions of Ag and diamond like carbon have a positive effect on the mechanical properties of TiO2-NT film. The electrocatalytic properties of the electrodes towards the hydrogen evolution reaction (HER) were investigated by the electrochemical measurements recorded in 1 M KOH solution. In addition, long-term durability of electrodes towards HER and the energy consumption of alkaline electrolysis were investigated. The energy requirement showed that while the deposition of silver provides approximately 14.95% savings of the energy consumption, the DLC coating causes increase in energy consumption.

Nickel sulfide formation at low temperature: initial precipitates, solubility and transformation products

EPA Science Inventory

The formation of nickel sulfides has been examined experimentally over the temperature range from 25 to 60°C. At all conditions studied, hexagonal (α-NiS) was the initial precipitate from solution containing Ni2+ and dissolved sulfide. The formation of millerite (β- NiS, rhombo...

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

Xiong, W; Zhou, Yunshen; Hou, Wenjia

Direct formation of graphene with controlled number of graphitic layers on dielectric surfaces is highly desired for practical applications. Despite significant progress achieved in understanding the formation of graphene on metallic surfaces through chemical vapor deposition (CVD) of hydrocarbons, very limited research is available elucidating the graphene formation process via rapid thermal processing (RTP) of solid-state amorphous carbon, through which graphene is formed directly on dielectric surfaces accompanied by autonomous nickel evaporation. It is suggested that a metastable hexagonal nickel carbide (Ni 3C) intermediate phase plays a critical role in transforming amorphous carbon to 2D crystalline graphene and contributing tomore » the autonomous Ni evaporation. Temperature resolved carbon and nickel evolution in the RTP process is investigated using Auger electron spectroscopic (AES) depth profiling and glancing-angle X-ray diffraction (GAXRD). Formation, migration and decomposition of the hexagonal Ni 3C are confirmed to be responsible for the formation of graphene and the evaporation of Ni at 1100 °C. The Ni 3C-assisted graphene formation mechanism expands the understanding of Ni-catalyzed graphene formation, and provides insightful guidance for controlled growth of graphene through the solid-state transformation process.« less

All-Diamond Microelectrodes as Solid State Probes for Localized Electrochemical Sensing.

PubMed

Silva, Eduardo L; Gouvêa, Cristol P; Quevedo, Marcela C; Neto, Miguel A; Archanjo, Braulio S; Fernandes, António J S; Achete, Carlos A; Silva, Rui F; Zheludkevich, Mikhail L; Oliveira, Filipe J

2015-07-07

The fabrication of an all-diamond microprobe is demonstrated for the first time. This ME (microelectrode) assembly consists of an inner boron doped diamond (BDD) layer and an outer undoped diamond layer. Both layers were grown on a sharp tungsten tip by chemical vapor deposition (CVD) in a stepwise manner within a single deposition run. BDD is a material with proven potential as an electrochemical sensor. Undoped CVD diamond is an insulating material with superior chemical stability in comparison to conventional insulators. Focused ion beam (FIB) cutting of the apex of the ME was used to expose an electroactive BDD disk. By cyclic voltammetry, the redox reaction of ferrocenemethanol was shown to take place at the BDD microdisk surface. In order to ensure that the outer layer was nonelectrically conductive, a diffusion barrier for boron atoms was established seeking the formation of boron-hydrogen complexes at the interface between the doped and the undoped diamond layers. The applicability of the microelectrodes in localized corrosion was demonstrated by scanning amperometric measurements of oxygen distribution above an Al-Cu-CFRP (Carbon Fiber Reinforced Polymer) galvanic corrosion cell.

Creation of deep blue light emitting nitrogen-vacancy center in nanosized diamond

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

Himics, L., E-mail: himics.laszlo@wigner.mta.hu; Tóth, S.; Veres, M.

2014-03-03

This paper reports on the formation of complex defect centers related to the N3 center in nanosized diamond by employing plasma immersion and focused ion beam implantation methods. He{sup +} ion implantation into nanosized diamond “layer” was performed with the aim of creating carbon atom vacancies in the diamond structure, followed by the introduction of molecular N{sub 2}{sup +} ion and heat treatment in vacuum at 750 °C to initiate vacancy diffusion. To decrease the sp{sup 2} carbon content of nanosized diamond formed during the implantation processes, a further heat treatment at 450 °C in flowing air atmosphere was used. The modificationmore » of the bonding properties after each step of defect creation was monitored by Raman scattering measurements. The fluorescence measurements of implanted and annealed nanosized diamond showed the appearance of an intensive and narrow emission band with fine structures at 2.98 eV, 2.83 eV, and 2.71 eV photon energies.« less

Physical-chemical processes of diamond grinding

NASA Astrophysics Data System (ADS)

Lobanov, D. V.; Arhipov, P. V.; Yanyushkin, A. S.; Skeeba, V. Yu

2017-10-01

The article focuses on the relevance of the research into the problem of diamond abrasive metal-bonded tool performance loss with a view to enhancing the effectiveness of high-strength materials finishing processing. The article presents the results of theoretical and empirical studies of loading layer formation on the surface of diamond wheels during processing high-strength materials. The theoretical part deals with the physical and chemical processes at the contact area of the diamond wheel and work surface with the viewpoint of the electrochemical potentials equilibrium state. We defined dependencies for calculating the loading layer dimensions. The practical part of work centers on various electron-microscopic, spectral and X-ray diffraction studies of the metal-bonded wheel samples during diamond grinding. The analysis of the research results revealed the composition and structure of the loading layer. The validity of the theoretical data is confirmed by sufficient convergence of the calculated values with the results of empirical research. In order to reduce the intensity of loading and improve the cutting properties of metal-bonded diamond abrasive tools, it is recommended to use combined methods for more efficient processing of high-strength materials.

Synthesis and characterization of a nanocrystalline diamond aerogel

PubMed Central

Pauzauskie, Peter J.; Crowhurst, Jonathan C.; Worsley, Marcus A.; Laurence, Ted A.; Kilcoyne, A. L. David; Wang, Yinmin; Willey, Trevor M.; Visbeck, Kenneth S.; Fakra, Sirine C.; Evans, William J.; Zaug, Joseph M.; Satcher, Joe H.

2011-01-01

Aerogel materials have myriad scientific and technological applications due to their large intrinsic surface areas and ultralow densities. However, creating a nanodiamond aerogel matrix has remained an outstanding and intriguing challenge. Here we report the high-pressure, high-temperature synthesis of a diamond aerogel from an amorphous carbon aerogel precursor using a laser-heated diamond anvil cell. Neon is used as a chemically inert, near-hydrostatic pressure medium that prevents collapse of the aerogel under pressure by conformally filling the aerogel’s void volume. Electron and X-ray spectromicroscopy confirm the aerogel morphology and composition of the nanodiamond matrix. Time-resolved photoluminescence measurements of recovered material reveal the formation of both nitrogen- and silicon- vacancy point-defects, suggesting a broad range of applications for this nanocrystalline diamond aerogel. PMID:21555550

Synthesis and characterization of a nanocrystalline diamond aerogel

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

Pauzauskie, Peter J.; Crowhurst, Jonathan C.; Worsley, Marcus A.

2011-07-06

Aerogel materials have myriad scientific and technological applications due to their large intrinsic surface areas and ultralow densities. However, creating a nanodiamond aerogel matrix has remained an outstanding and intriguing challenge. Here we report the high-pressure, high-temperature synthesis of a diamond aerogel from an amorphous carbon aerogel precursor using a laser-heated diamond anvil cell. Neon is used as a chemically inert, near-hydrostatic pressure medium that prevents collapse of the aerogel under pressure by conformally filling the aerogel's void volume. Electron and X-ray spectromicroscopy confirm the aerogel morphology and composition of the nanodiamond matrix. Time-resolved photoluminescence measurements of recovered material revealmore » the formation of both nitrogen- and silicon- vacancy point-defects, suggesting a broad range of applications for this nanocrystalline diamond aerogel.« less

Trace-element patterns of fibrous and monocrystalline diamonds: Insights into mantle fluids

NASA Astrophysics Data System (ADS)

Rege, S.; Griffin, W. L.; Pearson, N. J.; Araujo, D.; Zedgenizov, D.; O'Reilly, S. Y.

2010-08-01

During their growth diamonds may trap micron-scale inclusions of the fluids from which they grew, and these "time capsules" provide insights into the metasomatic processes that have modified the subcontinental lithospheric mantle. LAM-ICPMS analysis of trace elements in > 500 fibrous and monocrystalline diamonds worldwide has been used to understand the nature of these fluids. Analyses of fibrous diamonds define two general types of pattern, a "fibrous-high" (FH) one with high contents of LREE, Ba and K, and a "fibrous-low" (FL) pattern characterized by depletion in LREE/MREE, Ba and K, negative anomalies in Sr and Y, and subchondritic Zr/Hf and Nb/Ta. Both types may be found in fibrous diamonds from single deposits, and in three Yakutian pipes some diamonds show abrupt transitions from inclusion-rich cores with FH patterns to clearer rims with FL patterns. Most monocrystalline diamonds show FL-type patterns, but some have patterns that resemble those of FH fibrous diamonds. Peridotitic and eclogitic monocrystalline diamonds may show either patterns with relatively flat REE, or patterns with more strongly depleted LREE. Kimberlites that contain peridotitic diamonds with "high" patterns also contain eclogitic diamonds with "high" patterns. Strong similarities in the patterns of these two groups of diamonds may suggest high fluid/rock ratios. Many diamonds of the "superdeep" paragenesis have trace-element patterns similar to those of other monocrystalline diamonds. This may be evidence that the trace-element compositions of deep-seated fluids are generally similar to those that form diamonds in the subcontinental lithospheric mantle. The element fractionations observed between the FH and FL patterns are consistent with the immiscible separation of a silicic fluid from a carbonatite-silicate fluid, leaving a residual carbonatitic fluid strongly enriched in LREE, Ba and alkalies. This model would suggest that most monocrystalline diamonds crystallized from the more silicic fraction. Comparison with studies of single fluid inclusions in fibrous diamonds suggests that the FH patterns reflect trapped inclusions of high-Mg and low-Mg carbonatitic high-density fluids. In terms of the rock-forming elements, the fluids that precipitated the rims of some fibrous diamonds (FL pattern) and most monocrystalline diamonds are broadly similar to some hydro-silicic high-density fluids found in fibrous diamonds. However, there are still significant differences between the trace-element patterns of most monocrystalline diamonds and known high-density fluids, and further research is required to understand the formation and growth of these diamonds.

Boron doped diamond synthesized from detonation nanodiamond in a C-O-H fluid at high pressure and high temperature

NASA Astrophysics Data System (ADS)

Shakhov, Fedor M.; Abyzov, Andrey M.; Takai, Kazuyuki

2017-12-01

Boron doped diamond (BDD) was synthesized under high pressure and high temperature (HPHT) of 7 GPa, 1230 °C in a short time of 10 s from a powder mixtures of detonation nanodiamond (DND), pentaerythritol C5H8(OH)4 and amorphous boron. SEM, TEM, XRD, XPS, FTIR and Raman spectroscopy indicated that BDD nano- and micro-crystals have formed by consolidation of DND particles (4 nm in size). XRD showed the enlargement of crystallites size to 6-80 nm and the increase in diamond lattice parameter by 0.02-0.07% without appearance of any microstrains. Raman spectroscopy was used to estimate the content of boron atoms embedded in the diamond lattice. It was found that the Raman diamond peak shifts significantly from 1332 cm-1 to 1290 cm-1 without appearance of any non-diamond carbon. The correlation between Raman peak position, its width, and boron content in diamond is proposed. Hydrogenated diamond carbon in significant amount was detected by IR spectroscopy and XPS. Due to the doping with boron content of about 0.1 at%, the electrical conductivity of the diamond achieved approximately 0.2 Ω-1 cm-1. Reaction mechanism of diamond growth (models of recrystallization and oriented attachment) is discussed, including the initial stages of pentaerythritol pyrolysis and thermal desorption of functional groups from the surface of DND particles with the generation of supercritical fluid of low-molecular substances (H2O, CH4, CO, CO2, etc.), as well as byproducts formation (B2O3, B4C).

The stability of a crystal with diamond structure for patchy particles with tetrahedral symmetry.

PubMed

Noya, Eva G; Vega, Carlos; Doye, Jonathan P K; Louis, Ard A

2010-06-21

The phase diagram of model anisotropic particles with four attractive patches in a tetrahedral arrangement has been computed at two different values of the range of the potential, with the aim of investigating the conditions under which a diamond crystal can be formed. We find that the diamond phase is never stable for our longer-ranged potential. At low temperatures and pressures, the fluid freezes into a body-centered-cubic solid that can be viewed as two interpenetrating diamond lattices with a weak interaction between the two sublattices. Upon compression, an orientationally ordered face-centered-cubic crystal becomes more stable than the body-centered-cubic crystal, and at higher temperatures, a plastic face-centered-cubic phase is stabilized by the increased entropy due to orientational disorder. A similar phase diagram is found for the shorter-ranged potential, but at low temperatures and pressures, we also find a region over which the diamond phase is thermodynamically favored over the body-centered-cubic phase. The higher vibrational entropy of the diamond structure with respect to the body-centered-cubic solid explains why it is stable even though the enthalpy of the latter phase is lower. Some preliminary studies on the growth of the diamond structure starting from a crystal seed were performed. Even though the diamond phase is never thermodynamically stable for the longer-ranged model, direct coexistence simulations of the interface between the fluid and the body-centered-cubic crystal and between the fluid and the diamond crystal show that at sufficiently low pressures, it is quite probable that in both cases the solid grows into a diamond crystal, albeit involving some defects. These results highlight the importance of kinetic effects in the formation of diamond crystals in systems of patchy particles.

Substantiation of Epitaxial Growth of Diamond Crystals on the Surface of Carbide Fe3AlC0.66 Phase Nanoparticles.

PubMed

Dzevin, Ievgenij M; Mekhed, Alexander A

2017-12-01

Samples of Fe-Al-C alloys of varying composition were synthesized under high pressures and temperatures. From X-ray analysis data, only K-phase with usual for it average parameter of elemental lattice cell, a = 0.376 nm, carbide Fe 3 C and cubic diamond reflexes were present before and after cooling to the temperature of liquid nitrogen.Calculations were made of the parameters of unit cells, the enthalpy of formation of the Fe 3 AlC, Fe 3.125 Al 0.825 C 0.5 , Fe 3.5 Al 0.5 C 0.5 , Fe 3.5 Al 0.5 C, Fe 3 Al 0.66 C 0.66 , and Fe 3 AlC 0.66 unit cells and crystallographic planes were identified on which epitaxial growth of the diamond phase was possible, using density functional theory as implemented in the WIEN2k package.The possibility of epitaxial growth of diamond crystals on Fe 3 AlC 0.66 (K-phase) nanoparticles was, therefore, demonstrated. The [200] plane was established to be the most suitable plane for diamond growth, having four carbon atoms arranged in a square and a central vacancy which can be occupied by carbon during thermal-and-pressure treatment. Distances between carbon atoms in the [200] plane differ by only 5% from distances between the carbon atoms of a diamond. The electronic structure and energetic parameters of the substrate were also investigated. It was shown that the substrate with at least four intermediate layers of K-phase exhibits signs of stability such as negative enthalpy of formation and the Fermi level falling to minimum densities of states.

Lu-Hf, in-situ Sr and Pb isotope and trace element systematics for mantle eclogites from the Diavik diamond mine: Evidence for Paleoproterozoic subduction beneath the Slave craton, Canada

NASA Astrophysics Data System (ADS)

Schmidberger, Stefanie S.; Simonetti, Antonio; Heaman, Larry M.; Creaser, Robert A.; Whiteford, Sean

2007-02-01

Lu-Hf, Sm-Nd and in-situ clinopyroxene Sr and Pb isotope systematics, and mineral major and in-situ trace element compositions were obtained for a suite of non-diamond and diamond-bearing eclogites from the Diavik kimberlites (A154; 55 Ma old), Slave craton (Canada). Temperature estimates of last equilibration in the lithosphere for the non-diamond-bearing Diavik eclogites define two groups; low-temperature (800-1050 °C) and high-temperature eclogites (1100-1300 °C). Most diamond-eclogites indicate temperatures similar to those of the high-temperature eclogites. Isotopic and major and trace element systematics for the non-diamond- and diamond-bearing eclogites indicate overlapping chemical compositions suggesting similar rock formational histories. Calculated whole rock major and trace element abundances using chemical and modal abundances for constituent minerals exhibit broad similarities with mafic cumulates from ophiolite sequences. Most importantly the calculated whole rock eclogite compositions display positive Sr and Eu anomalies, typically interpreted as the result of plagioclase accumulation in cumulate rocks of oceanic crust sequences. Initial whole rock Hf isotopic values and in-situ Sr isotope data from clinopyroxene grains provide evidence that the eclogites were derived from precursor rocks with depleted mantle isotope characteristics. These combined results support the interpretation that the eclogites from Diavik represent remnants of subducted oceanic crust. Lu-Hf isotope systematics indicate that the oceanic protolith for the eclogites formed in the Paleoproterozoic at ˜ 2.1 Ga, which is in agreement with the in-situ Pb isotope data from clinopyroxene. This result also corroborates the ˜ 2.1 Ga Lu-Hf model ages recorded by mantle zircons from eclogite found within the Jericho kimberlite in the northern Slave Province (˜ 200 km northwest of Diavik). The results from both studies indicate a link between eclogite formation and Paleoproterozoic subduction of oceanic lithosphere along the present-day western margin of the Archean Slave craton.

Oxygen interaction with hexagonal OsB 2 at high temperature

DOE PAGES

Xie, Zhilin; Blair, Richard G.; Orlovskaya, Nina; ...

2016-08-10

The stability of ReB 2-type hexagonal OsB 2 powder at high temperature with oxygen presence has been studied by thermogravimetric analysis, differential scanning calorimetry, SEM, EDS, and high-temperature scanning transmission electron microscopy and XRD. Results of the study revealed that OsB 2 ceramics interact readily with oxygen present in reducing atmosphere, especially at high temperature and produces boric acid, which decomposes on the surface of the powder resulting in the formation of boron vacancies in the hexagonal OsB 2 lattice as well as changes in the stoichiometry of the compound. It was also found that under low oxygen partial pressure,more » sintering of OsB 2 powders occurred at a relatively low temperature (900°C). Finally, hexagonal OsB 2 ceramic is prone to oxidation and it is very sensitive to oxygen partial pressures, especially at high temperatures.« less

Oxygen interaction with hexagonal OsB 2 at high temperature

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

Xie, Zhilin; Blair, Richard G.; Orlovskaya, Nina

The stability of ReB 2-type hexagonal OsB 2 powder at high temperature with oxygen presence has been studied by thermogravimetric analysis, differential scanning calorimetry, SEM, EDS, and high-temperature scanning transmission electron microscopy and XRD. Results of the study revealed that OsB 2 ceramics interact readily with oxygen present in reducing atmosphere, especially at high temperature and produces boric acid, which decomposes on the surface of the powder resulting in the formation of boron vacancies in the hexagonal OsB 2 lattice as well as changes in the stoichiometry of the compound. It was also found that under low oxygen partial pressure,more » sintering of OsB 2 powders occurred at a relatively low temperature (900°C). Finally, hexagonal OsB 2 ceramic is prone to oxidation and it is very sensitive to oxygen partial pressures, especially at high temperatures.« less

Trace elements in Gem-Quality Diamonds - Origin and evolution of diamond-forming fluid inclusions

NASA Astrophysics Data System (ADS)

Pearson, Graham; Krebs, Mandy; Stachel, Thomas; Woodland, Sarah; Chinn, Ingrid; Kong, Julie

2017-04-01

In the same way that melt inclusions in phenocrysts have expanded our idea of melt formation and evolution in basalts, studying fluids trapped in diamonds is providing important new constraints on the nature of diamond-forming fluids. Fibrous and cloudy diamonds trap a high but variable density of fluid inclusions and so have been extensively studied using major and trace element compositions. In contrast, constraining the nature of the diamond-forming fluid for high purity gem-quality diamonds has been restricted by the rarity of available high quality trace element data. This is due to the extremely low concentrations of impurities that gem diamonds contain - often in the ppt range. The recent discovery of fluids in gem diamonds showing similar major element chemistry to fluid-rich diamonds suggest that many diamonds may share a common spectrum of parental fluids. Here we test this idea further. Recent advances in analytical techniques, in particular the development of the "off-line" laser ablation pre-concentration approach, have allowed fully quantitative trace element data to be recovered from "fluid-poor", high quality gem diamonds. We present trace element data for gem diamonds from a variety of locations from Canada, S. Africa and Russia, containing either silicate or sulphide inclusions to examine possible paragenetic or genetic differences between fluids. REE abundance in the "gem" diamonds vary from 0.1 to 0.0001 x chondrite. To a first order, we observe the same spectrum of trace element compositions in the gem diamonds as that seen in fluid-rich "fibrous" diamonds, supporting a common origin for the fluids. REE patterns range from extremely flat (Ce/Yb)n 2.5 to 5 (commonly in sulphide-bearing diamonds) to >70, the latter having significantly greater inter-element HFSE/LILE fractionation. In general, the fluids from the sulphide-bearing diamonds are less REE-enriched than the silicate-bearing diamonds, but the ranges overlap significantly. The very large range in REE fractionation mimics very closely that produced in high pressure (5-6 GPa) experimental melts of CO2-H2O fluxed peridotite. Hence, the elemental characteristics of the fluids could be reconciled by the diamonds growing from such melts over a range of T and hence F, with the sulphide-bearing diamonds generally being produced by larger fraction (higher T) melts that have reacted less with their wall rocks. It is also possible that the less REE enriched fluids are consistent with derivation from more reduced CH4-bearing fluids that have lower solute capacity than oxidised fluids. This option is being evaluated.

The influence of the focus position on laser machining and laser micro-structuring monocrystalline diamond surface

NASA Astrophysics Data System (ADS)

Wu, Mingtao; Guo, Bing; Zhao, Qingliang; Fan, Rongwei; Dong, Zhiwei; Yu, Xin

2018-06-01

Micro-structured surface on diamond is widely used in microelectronics, optical elements, MEMS and NEMS components, ultra-precision machining tools, etc. The efficient micro-structuring of diamond material is still a challenging task. In this article, the influence of the focus position on laser machining and laser micro-structuring monocrystalline diamond surface were researched. At the beginning, the ablation threshold and its incubation effect of monocrystalline diamond were determined and discussed. As the accumulated laser pulses ranged from 40 to 5000, the laser ablation threshold decreased from 1.48 J/cm2 to 0.97 J/cm2. Subsequently, the variation of the ablation width and ablation depth in laser machining were studied. With enough pulse energy, the ablation width mainly depended on the laser propagation attributes while the ablation depth was a complex function of the focus position. Raman analysis was used to detect the variation of the laser machined diamond surface after the laser machining experiments. Graphite formation was discovered on the machined diamond surface and graphitization was enhanced after the defocusing quantity exceeded 45 μm. At last, several micro-structured surfaces were successfully fabricated on diamond surface with the defined micro-structure patterns and structuring ratios just by adjusting the defocusing quantity. The experimental structuring ratio was consistent with the theoretical analysis.

Effect Of Chromium Underlayer On The Properties Of Nano-Crystalline Diamond Films

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

Garratt, Elias; AlFaify, Salem; Yoshitake, T.

2013-01-11

This paper investigated the effect of chromium underlayer on the structure, microstructure and composition of the nano-crystalline diamond films. Nano-crystalline diamond thin films were deposited at high temperature in microwave-induced plasma diluted with nitrogen, on silicon substrate with a thin film of chromium as an underlayer. The composition, structure and microstructure of the deposited layers were analyzed using non-Rutherford Backscattering Spectrometry, Raman Spectroscopy, Near-Edge X-Ray Absorption Fine Structure, X-ray Diffraction and Atomic Force Microscopy. Nanoindentation studies showed that the films deposited on chromium underlayer have higher hardness values compared to those deposited on silicon without an underlayer. Diamond and graphiticmore » phases of the films evaluated by x-ray and optical spectroscopic analysis determined consistency between sp2 and sp3 phases of carbon in chromium sample to that of diamond grown on silicon. Diffusion of chromium was observed using ion beam analysis which was correlated with the formation of chromium complexes by x-ray diffraction.« less

Formation of nanodiamonds at near-ambient conditions via microplasma dissociation of ethanol vapour.

PubMed

Kumar, Ajay; Ann Lin, Pin; Xue, Albert; Hao, Boyi; Khin Yap, Yoke; Sankaran, R Mohan

2013-01-01

Clusters of diamond-phase carbon, known as nanodiamonds, exhibit novel mechanical, optical and biological properties that have elicited interest for a wide range of technological applications. Although diamond is predicted to be more stable than graphite at the nanoscale, extreme environments are typically used to produce nanodiamonds. Here we show that nanodiamonds can be stably formed in the gas phase at atmospheric pressure and neutral gas temperatures <100 °C by dissociation of ethanol vapour in a novel microplasma process. Addition of hydrogen gas to the process allows in flight purification by selective etching of the non-diamond carbon and stabilization of the nanodiamonds. The nanodiamond particles are predominantly between 2 and 5 nm in diameter, and exhibit cubic diamond, n-diamond and lonsdaleite crystal structures, similar to nanodiamonds recovered from meteoritic residues. These results may help explain the origin of nanodiamonds in the cosmos, and offer a simple and inexpensive route for the production of high-purity nanodiamonds.

Effect of chromium underlayer on the properties of nano-crystalline diamond films

NASA Astrophysics Data System (ADS)

Garratt, E.; AlFaify, S.; Yoshitake, T.; Katamune, Y.; Bowden, M.; Nandasiri, M.; Ghantasala, M.; Mancini, D. C.; Thevuthasan, S.; Kayani, A.

2013-01-01

This paper investigated the effect of chromium underlayer on the structure, microstructure, and composition of the nano-crystalline diamond films. Nano-crystalline diamond thin films were deposited at high temperature in microwave-induced plasma diluted with nitrogen, on single crystal silicon substrate with a thin film of chromium as an underlayer. Characterization of the film was implemented using non-Rutherford backscattering spectrometry, Raman spectroscopy, near-edge x-ray absorption fine structure, x-ray diffraction, and atomic force microscopy. Nanoindentation studies showed that the films deposited on chromium underlayer have higher hardness values compared to those deposited on silicon without an underlayer. Diamond and graphitic phases of the films evaluated by x-ray and optical spectroscopic analyses determined consistency between the sp2 and sp3 phases of carbon in chromium sample to that of diamond grown on silicon. Diffusion of chromium was observed using ion beam analysis which was correlated with the formation of chromium complexes by x-ray diffraction.

Kankan diamonds (Guinea) III: δ13C and nitrogen characteristics of deep diamonds

NASA Astrophysics Data System (ADS)

Stachel, T.; Harris, J. W.; Aulbach, S.; Deines, P.

Diamonds from the Kankan area in Guinea formed over a large depth profile beginning within the cratonic mantle lithosphere and extending through the asthenosphere and transition zone into the lower mantle. The carbon isotopic composition, the concentration of nitrogen impurities and the nitrogen aggregation level of diamonds representing this entire depth range have been determined. Peridotitic and eclogitic diamonds of lithospheric origin from Kankan have carbon isotopic compositions (δ13C: peridotitic -5.4 to -2.2‰ eclogitic -19.7 to -0.7‰) and nitrogen characteristics (N: peridotitic 17-648 atomic ppm; eclogitic 0-1,313 atomic ppm; aggregation from IaA to IaB) which are generally typical for diamonds of these two suites worldwide. Geothermobarometry of peridotitic and eclogitic inclusion parageneses (worldwide sources) indicates that both suites formed under very similar conditions within the cratonic lithosphere, which is not consistent with a derivation of diamonds with light carbon isotopic composition from subducted organic matter within subducting oceanic slabs. Diamonds containing majorite garnet inclusions fall to the isotopically heavy side (δ13C: -3.1‰ to +0.9‰) of the worldwide diamond population. Nitrogen contents are low (0-126 atomic ppm) and one of the two nitrogen-bearing diamonds shows such a low level of nitrogen aggregation (30% B-centre) that it cannot have been exposed to ambient temperatures of the transition zone (>=1,400 °C) for more than 0.2 Ma. This suggests rapid upward transport and formation of some Kankan diamonds pene-contemporaneous to Cretaceous kimberlite activity. Similar to these diamonds from the asthenosphere and the transition zone, lower mantle diamonds show a small shift towards isotopic heavy compositions (-6.6 to -0.5‰, mode at -3.5‰). As already observed for other mines, the nitrogen contents of lower mantle diamonds were below detection (using FTIRS). The mutual shift of sublithospheric diamonds towards isotopic heavier compositions suggests a common carbon source, which may have inherited an isotopic heavy composition from a component consisting of subducted carbonates.

Kankan diamonds (Guinea) III: δ13C and nitrogen characteristics of deep diamonds

NASA Astrophysics Data System (ADS)

Stachel, T.; Harris, J. W.; Aulbach, S.; Deines, P.

2001-08-01

Diamonds from the Kankan area in Guinea formed over a large depth profile beginning within the cratonic mantle lithosphere and extending through the asthenosphere and transition zone into the lower mantle. The carbon isotopic composition, the concentration of nitrogen impurities and the nitrogen aggregation level of diamonds representing this entire depth range have been determined. Peridotitic and eclogitic diamonds of lithospheric origin from Kankan have carbon isotopic compositions (δ13C: peridotitic -5.4 to -2.2‰ eclogitic -19.7 to -0.7‰) and nitrogen characteristics (N: peridotitic 17-648 atomic ppm; eclogitic 0-1,313 atomic ppm; aggregation from IaA to IaB) which are generally typical for diamonds of these two suites worldwide. Geothermobarometry of peridotitic and eclogitic inclusion parageneses (worldwide sources) indicates that both suites formed under very similar conditions within the cratonic lithosphere, which is not consistent with a derivation of diamonds with light carbon isotopic composition from subducted organic matter within subducting oceanic slabs. Diamonds containing majorite garnet inclusions fall to the isotopically heavy side (δ13C: -3.1‰ to +0.9‰) of the worldwide diamond population. Nitrogen contents are low (0-126 atomic ppm) and one of the two nitrogen-bearing diamonds shows such a low level of nitrogen aggregation (30% B-centre) that it cannot have been exposed to ambient temperatures of the transition zone (>=1,400 °C) for more than 0.2 Ma. This suggests rapid upward transport and formation of some Kankan diamonds pene-contemporaneous to Cretaceous kimberlite activity. Similar to these diamonds from the asthenosphere and the transition zone, lower mantle diamonds show a small shift towards isotopic heavy compositions (-6.6 to -0.5‰, mode at -3.5‰). As already observed for other mines, the nitrogen contents of lower mantle diamonds were below detection (using FTIRS). The mutual shift of sublithospheric diamonds towards isotopic heavier compositions suggests a common carbon source, which may have inherited an isotopic heavy composition from a component consisting of subducted carbonates.

A novel Mo-W interlayer approach for CVD diamond deposition on steel

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

Kundrát, Vojtěch; Sullivan, John; Ye, Haitao, E-mail: h.ye@aston.ac.uk

Steel is the most widely used material in engineering for its cost/performance ratio and coatings are routinely applied on its surface to further improve its properties. Diamond coated steel parts are an option for many demanding industrial applications through prolonging the lifetime of steel parts, enhancement of tool performance as well as the reduction of wear rates. Direct deposition of diamond on steel using conventional chemical vapour deposition (CVD) processes is known to give poor results due to the preferential formation of amorphous carbon on iron, nickel and other elements as well as stresses induced from the significant difference inmore » the thermal expansion coefficients of those materials. This article reports a novel approach of deposition of nanocrystalline diamond coatings on high-speed steel (M42) substrates using a multi-structured molybdenum (Mo) – tungsten (W) interlayer to form steel/Mo/Mo-W/W/diamond sandwich structures which overcome the adhesion problem related to direct magnetron sputtering deposition of pure tungsten. Surface, interface and tribology properties were evaluated to understand the role of such an interlayer structure. The multi-structured Mo-W interlayer has been proven to improve the adhesion between diamond films and steel substrates by acting as an effective diffusion barrier during the CVD diamond deposition.« less

A novel Mo-W interlayer approach for CVD diamond deposition on steel

NASA Astrophysics Data System (ADS)

Kundrát, Vojtěch; Zhang, Xiaoling; Cooke, Kevin; Sun, Hailin; Sullivan, John; Ye, Haitao

2015-04-01

Steel is the most widely used material in engineering for its cost/performance ratio and coatings are routinely applied on its surface to further improve its properties. Diamond coated steel parts are an option for many demanding industrial applications through prolonging the lifetime of steel parts, enhancement of tool performance as well as the reduction of wear rates. Direct deposition of diamond on steel using conventional chemical vapour deposition (CVD) processes is known to give poor results due to the preferential formation of amorphous carbon on iron, nickel and other elements as well as stresses induced from the significant difference in the thermal expansion coefficients of those materials. This article reports a novel approach of deposition of nanocrystalline diamond coatings on high-speed steel (M42) substrates using a multi-structured molybdenum (Mo) - tungsten (W) interlayer to form steel/Mo/Mo-W/W/diamond sandwich structures which overcome the adhesion problem related to direct magnetron sputtering deposition of pure tungsten. Surface, interface and tribology properties were evaluated to understand the role of such an interlayer structure. The multi-structured Mo-W interlayer has been proven to improve the adhesion between diamond films and steel substrates by acting as an effective diffusion barrier during the CVD diamond deposition.

Formation of nanocrystalline diamond in polymer like carbon films deposited by plasma CVD.

PubMed

Bhaduri, A; Chaudhuri, P

2009-09-01

Conventional plasma enhanced chemical vapour deposition (PECVD) method is generally not suitable for the growth of nanocrystalline diamond (NCD) films. However, our study shows that conditions favourable for powder formation help to grow large amount of nanocrystallites in conventional PECVD. With CH4 as the carbon source gas, dilution with Ar and moderate (50 W) rf power enhances formations of powders (nanoparticles) and C2 dimers within the plasma. On the other hand, with pure CH4 or with hydrogen diluted CH4, powder formation as also NCD growth is hindered. It is proposed that the nanoparticles formed in the plasma act as the "islands" while the C2 dimers are the "seeds" for the NCD growth. The structure of the films deposited on the grounded anode under different conditions of dilution has been studied. It is observed that with high Ar dilution the films contain NCD embedded in polymer like carbon (PLC) matrix.

Diamonds in ophiolites: Contamination or a new diamond growth environment?

NASA Astrophysics Data System (ADS)

Howell, D.; Griffin, W. L.; Yang, J.; Gain, S.; Stern, R. A.; Huang, J.-X.; Jacob, D. E.; Xu, X.; Stokes, A. J.; O'Reilly, S. Y.; Pearson, N. J.

2015-11-01

For more than 20 years, the reported occurrence of diamonds in the chromites and peridotites of the Luobusa massif in Tibet (a complex described as an ophiolite) has been widely ignored by the diamond research community. This skepticism has persisted because the diamonds are similar in many respects to high-pressure high-temperature (HPHT) synthetic/industrial diamonds (grown from metal solvents), and the finding previously has not been independently replicated. We present a detailed examination of the Luobusa diamonds (recovered from both peridotites and chromitites), including morphology, size, color, impurity characteristics (by infrared spectroscopy), internal growth structures, trace-element patterns, and C and N isotopes. A detailed comparison with synthetic industrial diamonds shows many similarities. Cubo-octahedral morphology, yellow color due to unaggregated nitrogen (C centres only, Type Ib), metal-alloy inclusions and highly negative δ13C values are present in both sets of diamonds. The Tibetan diamonds (n = 3) show an exceptionally large range in δ15N (-5.6 to + 28.7 ‰) within individual crystals, and inconsistent fractionation between {111} and {100} growth sectors. This in contrast to large synthetic HPHT diamonds grown by the temperature gradient method, which have with δ15N = 0 ‰ in {111} sectors and + 30 ‰ in {100} sectors, as reported in the literature. This comparison is limited by the small sample set combined with the fact the diamonds probably grew by different processes. However, the Tibetan diamonds do have generally higher concentrations and different ratios of trace elements; most inclusions are a NiMnCo alloy, but there are also some small REE-rich phases never seen in HPHT synthetics. These characteristics indicate that the Tibetan diamonds grew in contact with a C-saturated Ni-Mn-Co-rich melt in a highly reduced environment. The stable isotopes indicate a major subduction-related contribution to the chemical environment. The unaggregated nitrogen, combined with the lack of evidence for resorption or plastic deformation, suggests a short (geologically speaking) residence in the mantle. Previously published models to explain the occurrence of the diamonds, and other phases indicative of highly reduced conditions and very high pressures, have failed to take into account the characteristics of the diamonds and the implications for their formation. For these diamonds to be seriously considered as the result of a natural growth environment requires a new understanding of mantle conditions that could produce them.

High pressure phase transitions in the rare earth metal erbium to 151 GPa.

PubMed

Samudrala, Gopi K; Thomas, Sarah A; Montgomery, Jeffrey M; Vohra, Yogesh K

2011-08-10

High pressure x-ray diffraction studies have been performed on the heavy rare earth metal erbium (Er) in a diamond anvil cell at room temperature to a pressure of 151 GPa and Er has been compressed to 40% of its initial volume. The rare earth crystal structure sequence hcp → Sm type → dhcp → distorted fcc (hcp: hexagonal close packed; fcc: face centered cubic; dhcp: double hcp) is observed in Er below 58 GPa. We have carried out Rietveld refinement of crystal structures in the pressure range between 58 GPa and 151 GPa. We have examined various crystal structures that have been proposed for the distorted fcc (dfcc) phase and the post-dfcc phase in rare earth metals. We find that the hexagonal hR 24 structure is the best fit between 58 and 118 GPa. Above 118 GPa, a structural transformation from hR 24 phase to a monoclinic C 2/m phase is observed with a volume change of - 1.9%. We have also established a clear trend for the pressure at which a post-dfcc phase is formed in rare earth metals and show that there is a monotonic increase in this pressure with the filling of 4f shell.

High pressure phase transitions in the rare earth metal erbium to 151 GPa

NASA Astrophysics Data System (ADS)

Samudrala, Gopi K.; Thomas, Sarah A.; Montgomery, Jeffrey M.; Vohra, Yogesh K.

2011-08-01

High pressure x-ray diffraction studies have been performed on the heavy rare earth metal erbium (Er) in a diamond anvil cell at room temperature to a pressure of 151 GPa and Er has been compressed to 40% of its initial volume. The rare earth crystal structure sequence {hcp} \\to {Sm}~ {type} \\to {dhcp} \\to {distorted} fcc (hcp: hexagonal close packed; fcc: face centered cubic; dhcp: double hcp) is observed in Er below 58 GPa. We have carried out Rietveld refinement of crystal structures in the pressure range between 58 GPa and 151 GPa. We have examined various crystal structures that have been proposed for the distorted fcc (dfcc) phase and the post-dfcc phase in rare earth metals. We find that the hexagonal hR 24 structure is the best fit between 58 and 118 GPa. Above 118 GPa, a structural transformation from hR 24 phase to a monoclinic C 2/m phase is observed with a volume change of - 1.9%. We have also established a clear trend for the pressure at which a post-dfcc phase is formed in rare earth metals and show that there is a monotonic increase in this pressure with the filling of 4f shell.

X-Ray Tomography of Diamondiferous Eclogites: Clues to the Origin of Diamonds.

NASA Astrophysics Data System (ADS)

Taylor, L. A.; Ketcham, R. A.

2009-05-01

During the last decade or so, considerable new and significant data have been gathered concerning the origin of diamonds. This has come from the mantle xenoliths that are the rocks in which the diamonds originated, namely eclogites and peridotites, the host rocks for diamonds in the mantle. Upon rising through the crust to the surface in their kimberlite magmatic carriers and subsequent weathering on the surface, the weak olivine commonly alters, thereby reducing the crushing strength of the peridotite xenoliths. However, the eclogite xenoliths often retain enough toughness to resist total shattering after initial crushing during diamond recovery process. Subjecting these eclogite nodules to X-rays (e.g., 1.54 Å Cu K) can reveal the bright-blue fluorescence of any diamonds exposed at the surface of the xenoliths. Slow and careful extraction can result in recovery of large diamonds. Many of these unique rocks are the ones upon which we have performed High- Resolution X-ray Computed Tomography (HRXCT) at UT Austin. These data have formed the basis for further eclogite dissections and diamond polishing at UT Knoxville. The size of the diamondiferous eclogites that were scanned by HRXCT are from 20 g to 8.8 kg, all with many diamonds ranging from <1 mm to >1 cm, most octahedral, several with mineral inclusions. These diamondiferous eclogites have both textures and fabrics that provide evidence indicating the secondary formation of the diamonds. These include lineations of diamonds along zones of metasomatic alteration, former zones of enhanced permeability; the non-association of sulfides (po, pn, cpy) with the diamonds, versus sulfide-immiscible melt for the diamond origin; lack of any diamonds in direct contact with the primary garnets or clinopyroxenes; and the presence of some dodecahedral diamonds, indicative of resorption processes, typically attributed to the kimberlite melt. Indeed, these eclogites are not igneous in origin, but metamorphic products of their subducted oceanic crustal protoliths. In addition, detailed studies of the extracted diamonds supply more unexpected results. Polished diamonds examined with cathodoluminescence show evidence for a torturous life of cubic nucleation, growth, resorption, octahedral growth, resorption, and even plastic deformation. These are anomalous observations of diamonds supposedly formed along with the primary minerals in their eclogite hosts. The mineral inclusions in the diamonds reveal additional compelling clues of their origin. Multiple clinopyroxene inclusions can have different compositions within a single diamond, different between diamonds, and even different from that of the host. It is proposed that diamonds present in mantle eclogite xenoliths are secondary, having little to do with their hosts, formed by metasomatic fluids penetrating the eclogites along zones of permeability, and causing extensive secondary alteration and even partial melting of the primary garnets and omphacites.

Evidence of subduction and crust-mantle mixing from a single diamond

NASA Astrophysics Data System (ADS)

Schulze, Daniel J.; Harte, Ben; Valley, John W.; Channer, Dominic M. DeR.

2004-09-01

Cathodoluminescence (CL) imaging of polished sections of a diamond from the Guaniamo region of Venezuela suggests a history of the diamond involving two periods of growth separated by a period of resorption and possibly brittle deformation. In situ electron probe analysis of multiple eclogitic garnet inclusions reveals a correlation between garnet composition and location in the stone. An early-formed garnet in the diamond core has higher Ca/(Ca+Mg) and lower Mg/(Mg+Fe) values than later garnets associated with the second period of diamond growth. This variation conforms to an extensive trend of variation in the suite of eclogitic garnets extracted from Venezuelan diamonds. The diamond is zoned in carbon isotope composition (in situ secondary ion mass spectrometry, SIMS, data). The core compositions ( δ13C PDB), corresponding to the first stage of growth, average -17.7‰. The second period of growth is apparently in two sub-sets of CL zones with mean values of -13.0‰ and -7.9‰. Nitrogen contents of diamond are low (30-300 atomic ppm) and do not correlate with carbon isotope composition. Oxygen isotope ratios of the garnet inclusions are elevated substantially above those expected for "common mantle"; δ18O VSMOW of early garnet is approximately +10.5‰ and two late garnets average +8.8‰. The evolutionary trend of magnesium enrichment in garnet is unlikely to represent igneous fractionation. The stable isotope data are consistent with diamond formation in subducted meta-basic rocks that had interacted with sea water at low temperatures at or near the sea floor and contained a substantial biogenic carbon component. During or following subduction, diamonds continued to form in an evolving system that was progressively modified by interaction with mantle material.

Infrared spectral and carbon isotopic characteristics of micro- and macro-diamonds from the Panda kimberlite (Central Slave Craton, Canada)

NASA Astrophysics Data System (ADS)

Melton, G. L.; Stachel, T.; Stern, R. A.; Carlson, J.; Harris, J. W.

2013-09-01

One hundred and twenty-one micro-diamonds (< 1 mm) and 90 macro-diamonds (2.5 mm to 3.4 mm) from the Panda kimberlite (Ekati mine, Central Slave Craton, Canada) were analyzed for nitrogen content, nitrogen aggregation state (%B) and platelet and hydrogen peak areas (cm- 2). Micro-diamond nitrogen concentrations range from < 10 at. ppm to 1696 at. ppm (median = 805 at. ppm) and the median aggregation state is 23%B. Macro-diamonds range from < 10 at. ppm to 1260 at. ppm (median = 187 at. ppm) nitrogen and have a median nitrogen aggregation of 26%B. Platelet and hydrogen peaks were observed in 37% and 79% of the micro-diamonds and 79% and 56% of the macro-diamonds, respectively. Nitrogen based time averaged residence temperatures indicate that micro- and macro-diamonds experienced similar thermal mantle residence histories, both populations displaying bimodal residence temperature distributions with a gap between 1130 °C and 1160 °C (at 3.5 Ga residence). In addition, SIMS carbon isotopic analyses for the micro-diamonds were obtained: δ13C compositions range from - 6.9‰ to + 1.8‰ (median = - 4.3‰). CL imaging reveals distinct growth layers that in some samples differ by > 2‰, but mostly vary by < 0.5‰. Comparison of only the “gem-quality” samples (n = 49 micro- and 90 macro-diamonds) between the two diamond sets, indicates a statistically significant shift of + 1.3‰ in average δ13C from macro- to micro-diamonds and this shift documents distinct diamond forming fluids, fractionation process or growth histories. A broad transition to heavier isotopic values is also observed in connection to decreasing mantle residence temperatures. The bimodal mantle residence temperature distribution may coincide with the transition from highly depleted shallow to more fertile deep lithospheric mantle observed beneath the Central Slave Craton. The increase in δ13C with decreasing residence temperature (proxy for decreasing depth) is interpreted to reflect diamond formation from a carbonate-bearing metasomatic fluid/melt that isotopically evolves as it percolates upward through the lithosphere.

Photothermal effects during nanodiamond synthesis from a carbon aerogel in a laser-heated diamond anvil cell

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

Crane, Matthew J.; Smith, Bennett E.; Meisenheimer, Peter B.

Nanodiamonds have emerged as promising materials for quantum computing, biolabeling, and sensing due to their ability to host color centers with remarkable photostability and long spin-coherence times at room temperature. Recently, a bottom-up, high-pressure, high-temperature (HPHT) approach was demonstrated for growing nanodiamonds with color centers from amorphous carbon precursors in a laser-heated diamond anvil cell (LH-DAC) that was supported by a near-hydrostatic noble gas pressure medium. However, a detailed understanding of the photothermal heating and its effect on diamond growth, including the phase conversion conditions and the temperature-dependence of color center formation, has not been reported. In this work, wemore » measure blackbody radiation during LH-DAC synthesis of nanodiamond from carbon aerogel to examine these temperature-dependent effects. Blackbody temperature measurements suggest that nanodiamond growth can occur at 16.3 GPa and 1800 K. We use Mie theory and analytical heat transport to develop a predictive photothermal heating model. This model demonstrates that melting the noble gas pressure medium during laser heating decreases the local thermal conductivity to drive a high spatial resolution of phase conversion to diamond. In conclusion, we observe a temperature-dependent formation of nitrogen vacancy centers and interpret this phenomenon in the context of HPHT carbon vacancy diffusion.« less

Photothermal effects during nanodiamond synthesis from a carbon aerogel in a laser-heated diamond anvil cell

DOE PAGES

Crane, Matthew J.; Smith, Bennett E.; Meisenheimer, Peter B.; ...

2018-05-17

Nanodiamonds have emerged as promising materials for quantum computing, biolabeling, and sensing due to their ability to host color centers with remarkable photostability and long spin-coherence times at room temperature. Recently, a bottom-up, high-pressure, high-temperature (HPHT) approach was demonstrated for growing nanodiamonds with color centers from amorphous carbon precursors in a laser-heated diamond anvil cell (LH-DAC) that was supported by a near-hydrostatic noble gas pressure medium. However, a detailed understanding of the photothermal heating and its effect on diamond growth, including the phase conversion conditions and the temperature-dependence of color center formation, has not been reported. In this work, wemore » measure blackbody radiation during LH-DAC synthesis of nanodiamond from carbon aerogel to examine these temperature-dependent effects. Blackbody temperature measurements suggest that nanodiamond growth can occur at 16.3 GPa and 1800 K. We use Mie theory and analytical heat transport to develop a predictive photothermal heating model. This model demonstrates that melting the noble gas pressure medium during laser heating decreases the local thermal conductivity to drive a high spatial resolution of phase conversion to diamond. In conclusion, we observe a temperature-dependent formation of nitrogen vacancy centers and interpret this phenomenon in the context of HPHT carbon vacancy diffusion.« less

Organophosphonate biofunctionalization of diamond electrodes.

PubMed

Caterino, R; Csiki, R; Wiesinger, M; Sachsenhauser, M; Stutzmann, M; Garrido, J A; Cattani-Scholz, A; Speranza, Giorgio; Janssens, S D; Haenen, K

2014-08-27

The modification of the diamond surface with organic molecules is a crucial aspect to be considered for any bioapplication of this material. There is great interest in broadening the range of linker molecules that can be covalently bound to the diamond surface. In the case of protein immobilization, the hydropathicity of the surface has a major influence on the protein conformation and, thus, on the functionality of proteins immobilized at surfaces. For electrochemical applications, particular attention has to be devoted to avoid that the charge transfer between the electrode and the redox center embedded in the protein is hindered by a thick insulating linker layer. This paper reports on the grafting of 6-phosphonohexanoic acid on OH-terminated diamond surfaces, serving as linkers to tether electroactive proteins onto diamond surfaces. X-ray photoelectron spectroscopy (XPS) confirms the formation of a stable layer on the surface. The charge transfer between electroactive molecules and the substrate is studied by electrochemical characterization of the redox activity of aminomethylferrocene and cytochrome c covalently bound to the substrate through this linker. Our work demonstrates that OH-terminated diamond functionalized with 6-phosphonohexanoic acid is a suitable platform to interface redox-proteins, which are fundamental building blocks for many bioelectronics applications.

Structural evolution of Ti destroyable interlayer in large-size diamond film deposition by DC arc plasma jet

NASA Astrophysics Data System (ADS)

Guo, Jianchao; Li, Chengming; Liu, Jinlong; Wei, Junjun; Chen, Liangxian; Hua, Chenyi; Yan, Xiongbo

2016-05-01

The addition of titanium (Ti) interlayer was verified to reduce the residual stress of diamond films by self-fracturing and facilitate the harvest of a crack-free free-standing diamond film prepared by direct current (DC) arc plasma jet. In this study, the evolution of the Ti interlayer between large-area diamond film and substrate was studied and modeled in detail. The evolution of the interlayer was found to be relevant to the distribution of the DC arc plasma, which can be divided into three areas (arc center, arc main, and arc edge). The formation rate of titanium carbide (TiC) in the arc main was faster than in the other two areas and resulted in the preferred generation of crack in the diamond film in the arc main during cooling. Sandwich structures were formed along with the growth of TiC until the complete transformation of the Ti interlayer. The interlayer released stress via self-fracture. Avoiding uneven fragile regions that formed locally in the interlayer and achieving cooperatively released stress are crucial for the preparation of large crack-free diamond films.

Thermodynamic approach to the paradox of diamond formation with simultaneous graphite etching in the low pressure synthesis of diamond

NASA Astrophysics Data System (ADS)

Hwang, Nong M.; Yoon, Duk Y.

1996-03-01

In spite of the critical handicap from the thermodynamic point of view, the atomic hydrogen hypothesis is strongly supported by experimental observations of diamond deposition with simultaneous graphite etching. Thermodynamic analysis of the CH system showed that at ˜ 1500 K, carbon solubility in the gas phase is minimal and thus, the equilibrium fraction of solid carbon is maximal. Depending on whether gas phase nucleation takes place or not, the driving force is for deposition or for etching of solid carbon below ˜ 1500 K for the input gas of the typical mixture of 1% CH 499% H 2. The previous observation of etching of the graphite substrate is not expected unless solid carbon precipitated in the gas phase. By rigorous thermodynamic analysis of the previous experimental observations of diamond deposition with simultaneous graphite etching, we suggested that the previous implicit assumption that diamond deposits by an atomic unit should be the weakest point leading to the thermodynamic paradox. The experimental observations could be successfully explained without violating thermodynamics by assuming that the diamond phase had nucleated in the gas phase as fine clusters.

A billion years of metasomatic alteration of the Kaapvaal SCLM encapsulated in fibrous diamonds

NASA Astrophysics Data System (ADS)

Weiss, Yaakov; Goldstein, Steven; Class, Cornelia; Winckler, Gisela

2017-04-01

Constraining the nature and timing of metasomatic events by C-O-H fluids in the sub-continental lithospheric mantle (SCLM) is an ongoing challenge in our understanding of the SCLM history. 'Fibrous' diamonds, which rapidly grow during such fluid-rock interaction, commonly encapsulate the C-O-H fluid metasomatic agents, which are trapped and encapsulated as μm-scale high-density fluid (HDF) inclusions and can be directly sampled. They thus offer a unique opportunity to investigate metasomatic events involving C-O-H fluids in the SCLM. We analyzed major and trace elements and the helium content and isotopic composition of the HDFs included in a set of diamonds from the DeBeers-Pool and Finsch kimberlites in the Kaapvaal craton, South Africa. Saline HDF micro-inclusions in 3 of the DeBeers diamonds and in 2 from Finsch have very similar major and trace element compositions, suggesting they formed in related metasomatic events. They are characterized by high alkalis (K, Rb and Cs), Ba and LREEs compared to Th, U, Nb and Ta, and by Ti, Zr, Hf and Y negative anomalies relative to REEs of similar compatibility. Their 3He/4He ratios vary between 3-4 Ra. Plotting the 3 DeBeers-Pool diamonds on an 4He/3He vs 238U/3He diagram defines an 'isochron' with an age of 96±45 Ma. This result represents the first radiometric age reported for fibrous diamonds and the C-O-H mantle fluids they carry. In addition, 1 diamond from DeBeers-Pool has silicic microinclusion compositions while 2 diamonds from Finsch carry carbonatitic HDFs. These diamonds display more radiogenic 3He/4He ratios between 0.07-0.6 Ra, which suggests formation during earlier and different metasomatic events. Using the measured U, Th, 4He and 3He content of these diamonds, and the equation for 4He production by U and Th, we calculate 3He/4He ratios as a function of time. Assuming that the HDFs initial R/Ra values varied between 3-11, representing common values for MORB, the SCLM and subducted components, the silicic and carbonatitic HDFs signify two older metasomatic events that took place in the Kaapvaal lithosphere at 350 and 850 Ma, respectively. Thus, our new data reveal 3 episodes of chemical changes in the Kaapvaal craton SCLM during the last 1 Ga, each by a different metasomatic agent. The youngest episodes indicate direct relationships between highly-saline fluid metasomatism, fibrous diamond formation and late-Mesozoic kimberlite eruptions, while the older silicic and carbonatitic metasomatic events may be related to the regional Namaqua-Natal Orogeny and Damara Orogeny at 1 Ga and 500 Ma, respectively.

Diamond growth beneath Letlhakane established by Re-Os and Sm-Nd systematics of individual eclogitic sulphide, garnet and clinopyroxene inclusions

NASA Astrophysics Data System (ADS)

Gress, Michael U.; Pearson, D. Graham; Timmerman, Suzette; Chinn, Ingrid L.; Koornneef, Janne M.; Davies, Gareth R.

2017-04-01

The diamondiferous Letlhakane kimberlites are part of the Orapa kimberlite cluster (˜ 93.1 Ma) in north-eastern Botswana, located on the edge of the Zimbabwe Craton, close to the Proterozoic Magondi Mobile Belt. Here we report the first Re-Os ages of six individual eclogitic sulphide inclusions (3.0 to 35.7μg) from Letlhakane diamonds along with their rhenium, osmium, iridium and platinum concentrations, and carbon isotope, nitrogen content and N-aggregation data from the corresponding growth zones of the host diamonds. For the first time, Re-Os data will be compared to Sm-Nd ages of individual eclogitic silicate inclusions recovered from the same diamonds using a Triton Plus equipped with four 1013Ω amplifiers. The analysed inclusion set currently encompasses pairs of individual sulphides from two diamonds (LK040 sf4 & 5, LK113 sf1 & 2) and two sulphide inclusions from separate diamonds (LK048, LK362). Ongoing work will determine the Sm-Nd ages and element composition of multiple individual eclogitic garnets (LK113/LK362, n=4) and an eclogitic clinopyroxene (LK040) inclusion. TMA ages of the six sulphides range from 1.06 to 2.38 Ga (± 0.1 to 0.54 Ga) with Re and Os contents between 7 and 68 ppb and 0.03 and 0.3 ppb, respectively. The host diamond growth zones have low nitrogen abundances (21 to 43 ppm N) and high N-aggregation (53 to 90% IaB). Carbon isotope data suggests the involvement of crustal carbon (δ13C between -19.3 to -22.7 ± 0.2 per mill) during diamond precipitation. Cathodoluminescence imaging of central plates from LK040 and LK113 displays homogenous internal structure with no distinct zonation. The two sulphide inclusions from LK040 define an 'isochron' of 0.92 ± 0.23 Ga (2SD) with initial 187Os/188Os = 1.31 ± 0.24. Sulphides from LK113 have clear imposed diamond morphology and indicate diamond formation at 0.93 ± 0.36 Ga (2SD) with initial 187Os/188Os = 0.69 ± 0.44. The variation in the initial 187Os/188Os does not justify including these inclusions (or any from other diamonds) on the same isochron and implies an extremely heterogeneous diamond crystallisation environment that incorporated recycled Os. C1-normalized osmium, iridium and platinum (PGE) compositions from the analysed sulphide inclusions display enrichment in Ir (3.4 to 33) and Pt (2.3 to 28.1) in comparison to eclogitic xenolith data from Orapa that are depleted relative to chondrite. The Re-Os isochrons determined in this study are within error of previously reported ages from the adjacent (˜40km) Orapa diamond mine (1.0 to 2.9 Ga) based on sulphide inclusions and a multi-point 990 ± 50 Ma (2SD) isochron for composite (n=730) silicate inclusions. Together with additional new Sm-Nd isochron age determinations from individual silicate inclusions from Letlhakane (2.3 ± 0.02 (n = 3); 1.0 ± 0.14 (n = 4) and 0.25 ± 0.04 Ga (n = 3), all 2SE) these data suggest a phase of Mesoproterozoic diamond formation as well as Neoarchean/Paleoproterozoic and Mesozoic diamond growth, in punctuated events spanning >2.0 Ga.

Microscopic Mechanism and Kinetics of Ice Formation at Complex Interfaces: Zooming in on Kaolinite

PubMed Central

2016-01-01

Most ice in nature forms because of impurities which boost the exceedingly low nucleation rate of pure supercooled water. However, the microscopic details of ice nucleation on these substances remain largely unknown. Here, we have unraveled the molecular mechanism and the kinetics of ice formation on kaolinite, a clay mineral playing a key role in climate science. We find that the formation of ice at strong supercooling in the presence of this clay is about 20 orders of magnitude faster than homogeneous freezing. The critical nucleus is substantially smaller than that found for homogeneous nucleation and, in contrast to the predictions of classical nucleation theory (CNT), it has a strong two-dimensional character. Nonetheless, we show that CNT describes correctly the formation of ice at this complex interface. Kaolinite also promotes the exclusive nucleation of hexagonal ice, as opposed to homogeneous freezing where a mixture of cubic and hexagonal polytypes is observed. PMID:27269363

Epitaxial growth of hexagonal boron nitride monolayers by a three-step boration-oxidation-nitration process

NASA Astrophysics Data System (ADS)

Müller, Frank; Hüfner, Stefan; Sachdev, Hermann; Gsell, Stefan; Schreck, Matthias

2010-08-01

The formation of well-ordered monolayers of hexagonal boron nitride on the surface of a Rh/YSZ/Si(111) multilayer substrate via a three-step boration-oxidation-nitration process was investigated by x-ray photoelectron spectroscopy (XPS), x-ray photoelectron diffraction (XPD) and low-energy electron diffraction (LEED). The chemical vapor deposition (CVD) of trimethylborate B(OCH3)3 results in a selective decomposition of the precursor, leading to a dilute distribution of boron within the interstitials of the Rh lattice. After oxidation, the layer of a boron oxygen species of about 1 nm thickness can be transformed into a hexagonal monolayer of BN by annealing in NH3 atmosphere. The results of the present study clearly show that the formation of BN monolayers is also possible when boron and nitrogen are provided successively from separate sources. This procedure represents an alternative routine for the preparation of well-ordered BN monolayers, which benefits from a strong reduction of hazardous potential and economic costs compared to the use of borazine as the current standard precursor.

Towards NV-based magnetic sensing in the time domain

NASA Astrophysics Data System (ADS)

Urbach, Elana; Sumarac, Tamara; Lovchinsky, Igor; Landig, Renate; Sanchez-Yamagishi, Javier; Andersen, Trond; Park, Hongkun; Lukin, Mikhail

2017-04-01

The study of protein folding dynamics is an outstanding problem in the biological sciences. We show that nitrogen-vacancy (NV) centers in diamond can be used to dynamically sense the conformational states of individual proteins under ambient conditions. We present preliminary data on time-domain detection of electronic spin labels which were chemically attached to the proteins, as well as label-free detection of native hydrogen nuclear spins within the protein. In addition, we discuss work towards polarizing boron-11 spins in atomically-thin hexagonal boron nitride using Hartmann-Hahn double resonance, with the ultimate goal of studying many-body spin dynamics and performing quantum simulation. This material is based upon work supported by the National Science Foundation Graduate Research Fellowship Program under Grant No. DGE1144152.

Transformations in methane hydrates

USGS Publications Warehouse

Chou, I.-Ming; Sharma, A.; Burruss, R.C.; Shu, J.; Mao, Ho-kwang; Hemley, R.J.; Goncharov, A.F.; Stern, L.A.; Kirby, S.H.

2000-01-01

Detailed study of pure methane hydrate in a diamond cell with in situ optical, Raman, and x-ray microprobe techniques reveals two previously unknown structures, structure II and structure H, at high pressures. The structure II methane hydrate at 250 MPa has a cubic unit cell of a = 17.158(2) A?? and volume V = 5051.3(13) A??3; structure H at 600 MPa has a hexagonal unit cell of a = 11.980(2) A??, c = 9.992(3) A??, and V = 1241.9(5) A??3. The compositions of these two investigated phases are still not known. With the effects of pressure and the presence of other gases in the structure, the structure II phase is likely to dominate over the known structure I methane hydrate within deep hydrate-bearing sediments underlying continental margins.

Diamond brecciation and annealing accompanying major metasomatism in eclogite xenoliths from the Sask Craton, Canada

NASA Astrophysics Data System (ADS)

Czas, Janina; Stachel, Thomas; Pearson, D. Graham; Stern, Richard A.; Read, George H.

2018-05-01

We studied eclogite xenoliths (diamond-free n = 28; diamondiferous n = 22) from the Cretaceous Fort à la Corne Kimberlite Field in Western Canada for their major element, trace element and oxygen isotope compositions to assess their origin and metasomatic history, and possible relationships between metasomatism and diamond formation. All eclogites have major element and oxygen isotope compositions consistent with a derivation from different levels of subducted, seawater altered oceanic crust. While barren xenoliths are more likely to be of gabbroic origin, diamond-bearing samples commonly have signatures consistent with shallow basaltic protoliths. The mineral chemistry in bimineralic diamond-free eclogites spans a wide compositional range, yet it is typically homogenous within individual xenoliths. Temperatures calculated from Mg-Fe exchange between garnet and clinopyroxene range widely for these eclogites, from 740 to 1300 °C, indicating the presence of eclogite through most of the lithospheric mantle. Diamondiferous samples are restricted to high temperatures (1180-1390 °C), consistent with derivation from the zone of diamond stability. Compositionally, diamond-bearing eclogites span a broad range similar to their barren counterparts, but there is also heterogeneity in mineral chemistry on the intra-sample level and in particular garnets are characterised by strong internal chemical gradients. This intra-sample heterogeneity is interpreted as the result of intense melt metasomatism, which occurred in temporal proximity to host kimberlite magmatism, strongly affected major, trace and even oxygen isotope values and resulted in diamond brecciation and annealing.

3-D X-ray tomography of diamondiferous mantle eclogite xenoliths, Siberia: A review

NASA Astrophysics Data System (ADS)

Howarth, Geoffrey H.; Sobolev, Nikolay V.; Pernet-Fisher, John F.; Ketcham, Richard A.; Maisano, Jessica A.; Pokhilenko, Lyudmila N.; Taylor, Dawn; Taylor, Lawrence A.

2015-04-01

Diamonds form over billions of years, hundreds of kilometers beneath the Earth's surface, and in combination with inclusions trapped within, provide important constraints on the evolution of the mantle over geological time. Diamonds are generally studied as individual crystals sourced from highly explosive kimberlite pipes, which entrain and subsequently disaggregate mantle fragments (xenoliths) en route to the surface. This has resulted in a general absence of robust textural descriptions of diamonds relative to their hosting mantle protolith. The textural associations of diamonds within their mantle host rocks are reviewed here on the basis of a compilation of X-ray tomographic data for 17 diamondiferous eclogite xenoliths from Siberian kimberlites. This review represents a comprehensive description of diamonds relative to their host silicates. The lack of such descriptions in previous studies is largely due to the rarity of these xenoliths, the difficulty in preparing petrographic thin sections containing diamonds, and their high-monetary value. High-resolution computed X-ray tomography (HRCXT) produces up to 1200 sequential 2-D slices through individual xenoliths, each of which represents a 'pseudo thin-section' with a resolution on the order of 5-20 μm. The improved resolution of X-ray imaging in recent studies allows for the identification of not only primary minerals, but metasomatic minerals assemblages, including: 'spongy' textured clinopyroxene, phlogopite/K-richterite, and hercynitic spinel, allowing for the delineation of distinct metasomatic pathways through the xenoliths and their relationship to diamonds. Diamonds are observed in three distinct textural settings, potentially representing several temporally distinct diamond growth events, these setting includes: (1) diamonds completely enclosed in garnet; (2) diamonds associated with highly embayed silicate grain boundaries; and (3) diamonds contained within distinct metasomatic 'plumbing-systems'. Diamonds observed completely enclosed in garnets suggest an early diamond-forming event prior to major re-crystallization and eclogite formation during subduction. The occurrence of diamond in association with embayed garnets suggests that diamond grew at the expense of the hosting silicate protolith. In addition, the spatial relationships of diamonds with metasomatic pathways, which are generally interpreted to result from late-stage proto-kimberlitic fluid percolation, indicate a period of diamond growth occurring close to, but prior to, the time of kimberlite emplacement. Furthermore, the paragenesis of sulfides within eclogite xenoliths are described using 3-D models for entire xenoliths volumes, providing important constraints of the timing of sulfide mobilization within the mantle. Three-D animations created using X-ray tomography data for ten of the xenoliths can be viewed at the following link: http://eps.utk.edu/faculty/taylor/tomography.php

Solvation Dynamics in Different Phases of the Lyotropic Liquid Crystalline System.

PubMed

Roy, Bibhisan; Satpathi, Sagar; Gavvala, Krishna; Koninti, Raj Kumar; Hazra, Partha

2015-09-03

Reverse hexagonal (HII) liquid crystalline material based on glycerol monooleate (GMO) is considered as a potential carrier for drugs and other important biomolecules due to its thermotropic phase change and excellent morphology. In this work, the dynamics of encapsulated water, which plays important role in stabilization and formation of reverse hexagonal mesophase, has been investigated by time dependent Stokes shift method using Coumarin-343 as a solvation probe. The formation of the reverse hexagonal mesophase (HII) and transformation to the L2 phase have been monitored using small-angle X-ray scattering and polarized light microscopy experiments. REES studies suggest the existence of different polar regions in both HII and L2 systems. The solvation dynamics study inside the reverse hexagonal (HII) phase reveals the existence of two different types of water molecules exhibiting dynamics on a 120-900 ps time scale. The estimated diffusion coefficients of both types of water molecules obtained from the observed dynamics are in good agreement with the measured diffusion coefficient collected from the NMR study. The calculated activation energy is found to be 2.05 kcal/mol, which is associated with coupled rotational-translational water relaxation dynamics upon the transition from "bound" to "quasi-free" state. The observed ∼2 ns faster dynamics of the L2 phase compared to the HII phase may be associated with both the phase transformation as well as thermotropic effect on the relaxation process. Microviscosities calculated from time-resolved anisotropy studies infer that the interface is almost ∼22 times higher viscous than the central part of the cylinder. Overall, our results reveal the unique dynamical features of water inside the cylinder of reverse hexagonal and inverse micellar phases.

Silicon Carbide in Heavy-Mineral Samples: Indicator of Diamond Deposits

NASA Astrophysics Data System (ADS)

Leung, I. S.; Wang, W.

2013-12-01

Since kimberlite Pipe 50 of Wafangdian, 120 km northeast of the port city Dalian in Liaoning Province, ceased production in 2002, exploration programs have been conducted along tributaries of the Fuzhou River south of Wafangdian. The heavy-mineral method is often based on finding deep red G10 pyrope garnets which can be identified accurately by means of microprobe analysis to confirm their particular range of composition: high chromium, low calcium. Garnets are prone to hydrothermal alteration during kimberlite eruption, oxidation on Earth's surface, or be broken during mass transport. Unlike garnet, silicon carbide (SiC) resists chemical and mechanical alterations, but it crystallized at similarly high temperatures as diamond in Earth's mantle, and has the same atomic structure as diamond. Thus, SiC seems to be an ideal diamond indicator, although it is one of the rarest minerals in nature. Because of its characteristic blue-green color and adamantine luster, it can be recognized easily, no matter how minute the grains may be. We decided to re-examine small samples of heavy minerals collected and previously studied by exploration geologists, respectively from 3 tributaries of the Fuzhou River (Laogugao, Saocentun, Pingiaying), and from 3 ravines in the vicinity of Wafangdian (Songiagao, Dlitun, Lidianzhun), among which Songiagao, flowing into Qingnian Reservoir, is apparently a pristine water system, unpolluted by human activities. We found one grain of SiC in all the samples. From Fuzhou River: (1) Blue-green, euhedral, hexagonal shape, water-clear, one edge slightly chipped. (2) Light green, slightly corroded edges. (3) Green, half of the crystal's surface is covered by a blister-like yellow overgrowth; this material protrudes out on one side like a thick tapering paint brush. From Wafandian Vicinity: (1) Blue-green, with patchy black edges. (2) Green, with deep green rims and one brown inclusion. (3) Pale green, subhedral with one beige inclusion. All the crystals show various hues of green and blue, variable color saturation both within itself and between different grains. All crystals have different shapes, forms, coatings, types of reaction rims, while two crystals carry one or two inclusions, The multitude of features suggests a history of intricacies in the growth environment, an implication worthy of our contemplation as we try to understand the problem of diamond genesis.

Solid-state graphene formation via a nickel carbide intermediate phase [Nickel carbide (Ni 3C) as an intermediate phase for graphene formation

DOE PAGES

Xiong, W; Zhou, Yunshen; Hou, Wenjia; ...

2015-11-10

Direct formation of graphene with controlled number of graphitic layers on dielectric surfaces is highly desired for practical applications. Despite significant progress achieved in understanding the formation of graphene on metallic surfaces through chemical vapor deposition (CVD) of hydrocarbons, very limited research is available elucidating the graphene formation process via rapid thermal processing (RTP) of solid-state amorphous carbon, through which graphene is formed directly on dielectric surfaces accompanied by autonomous nickel evaporation. It is suggested that a metastable hexagonal nickel carbide (Ni 3C) intermediate phase plays a critical role in transforming amorphous carbon to 2D crystalline graphene and contributing tomore » the autonomous Ni evaporation. Temperature resolved carbon and nickel evolution in the RTP process is investigated using Auger electron spectroscopic (AES) depth profiling and glancing-angle X-ray diffraction (GAXRD). Formation, migration and decomposition of the hexagonal Ni 3C are confirmed to be responsible for the formation of graphene and the evaporation of Ni at 1100 °C. The Ni 3C-assisted graphene formation mechanism expands the understanding of Ni-catalyzed graphene formation, and provides insightful guidance for controlled growth of graphene through the solid-state transformation process.« less

Imaging the atomic structure and local chemistry of platelets in natural type Ia diamond

NASA Astrophysics Data System (ADS)

Olivier, E. J.; Neethling, J. H.; Kroon, R. E.; Naidoo, S. R.; Allen, C. S.; Sawada, H.; van Aken, P. A.; Kirkland, A. I.

2018-03-01

In the past decades, many efforts have been devoted to characterizing {001} platelet defects in type Ia diamond. It is known that N is concentrated at the defect core. However, an accurate description of the atomic structure of the defect and the role that N plays in it is still unknown. Here, by using aberration-corrected transmission electron microscopy and electron energy-loss spectroscopy we have determined the atomic arrangement within platelet defects in a natural type Ia diamond and matched it to a prevalent theoretical model. The platelet has an anisotropic atomic structure with a zigzag ordering of defect pairs along the defect line. The electron energy-loss near-edge fine structure of both carbon K- and nitrogen K-edges obtained from the platelet core is consistent with a trigonal bonding arrangement at interstitial sites. The experimental observations support an interstitial aggregate mode of formation for platelet defects in natural diamond.

Imaging the atomic structure and local chemistry of platelets in natural type Ia diamond.

PubMed

Olivier, E J; Neethling, J H; Kroon, R E; Naidoo, S R; Allen, C S; Sawada, H; van Aken, P A; Kirkland, A I

2018-03-01

In the past decades, many efforts have been devoted to characterizing {001} platelet defects in type Ia diamond. It is known that N is concentrated at the defect core. However, an accurate description of the atomic structure of the defect and the role that N plays in it is still unknown. Here, by using aberration-corrected transmission electron microscopy and electron energy-loss spectroscopy we have determined the atomic arrangement within platelet defects in a natural type Ia diamond and matched it to a prevalent theoretical model. The platelet has an anisotropic atomic structure with a zigzag ordering of defect pairs along the defect line. The electron energy-loss near-edge fine structure of both carbon K- and nitrogen K-edges obtained from the platelet core is consistent with a trigonal bonding arrangement at interstitial sites. The experimental observations support an interstitial aggregate mode of formation for platelet defects in natural diamond.

Diamond synthesis at atmospheric pressure by microwave capillary plasma chemical vapor deposition

NASA Astrophysics Data System (ADS)

Hemawan, Kadek W.; Gou, Huiyang; Hemley, Russell J.

2015-11-01

Polycrystalline diamond has been synthesized on silicon substrates at atmospheric pressure, using a microwave capillary plasma chemical vapor deposition technique. The CH4/Ar plasma was generated inside of quartz capillary tubes using 2.45 GHz microwave excitation without adding H2 into the deposition gas chemistry. Electronically excited species of CN, C2, Ar, N2, CH, Hβ, and Hα were observed in the emission spectra. Raman measurements of deposited material indicate the formation of well-crystallized diamond, as evidenced by the sharp T2g phonon at 1333 cm-1 peak relative to the Raman features of graphitic carbon. Field emission scanning electron microscopy images reveal that, depending on the growth conditions, the carbon microstructures of grown films exhibit "coral" and "cauliflower-like" morphologies or well-facetted diamond crystals with grain sizes ranging from 100 nm to 10 μm.

Charge transport properties of intrinsic layer in diamond vertical pin diode

NASA Astrophysics Data System (ADS)

Shimaoka, Takehiro; Kuwabara, Daisuke; Hara, Asuka; Makino, Toshiharu; Tanaka, Manobu; Koizumi, Satoshi

2017-05-01

Diamond is hoped to be utilized in ultimate power electronic devices exhibiting ultra-high blocking voltages. For practical device formation, it is important to characterize the electric properties to precisely simulate carrier transport and to practically design optimum device structures. In this study, we experimentally evaluated the charge transport properties of intrinsic layers in diamond vertical pin diodes using alpha-particle induced charge distribution measurements. The charge collection efficiencies were 98.1 ± 0.6% for a {111} pin diode and 96.9 ± 0.6% for a {100} pin diode, which means that almost all generated charges are collected accordingly equivalent to conventional Silicon pin photodiodes. Mobility-lifetime (μτ) products of holes were (2.2 ± 0.3) × 10-6 cm2/V for {111} and (1.8 ± 0.1) × 10-5 cm2/V for {100} diamond pin diodes.

Diamond synthesis at atmospheric pressure by microwave capillary plasma chemical vapor deposition

DOE PAGES

Gou, Huiyang; Hemley, Russell J.; Hemawan, Kadek W.

2015-11-02

Polycrystalline diamond has been successfully synthesized on silicon substrates at atmospheric pressure using a microwave capillary plasma chemical vapor deposition technique. The CH 4/Ar plasma was generated inside of quartz capillary tubes using 2.45 GHz microwave excitation without adding H2 into the deposition gas chemistry. Electronically excited species of CN, C 2, Ar, N 2, CH, H β and H α were observed in emission spectra. Raman measurements of deposited material indicate the formation of well-crystallized diamond, as evidenced by the sharp T 2g phonon at 1333 cm -1 peak relative to the Raman features of graphitic carbon. Furthermore, fieldmore » emission scanning electron microscopy (SEM) images reveal that, depending on the on growth conditions, the carbon microstructures of grown films exhibit “coral” and “cauliflower-like” morphologies or well-facetted diamond crystals with grain sizes ranging from 100 nm to 10 μm.« less

The modeling and synthesis of nanodiamonds by laser ablation of graphite and diamond-like carbon in liquid-confined ambient

NASA Astrophysics Data System (ADS)

Basso, L.; Gorrini, F.; Bazzanella, N.; Cazzanelli, M.; Dorigoni, C.; Bifone, A.; Miotello, A.

2018-01-01

Nanodiamonds have attracted considerable interest for their potential applications in quantum computation, sensing, and bioimaging. However, synthesis of nanodiamonds typically requires high pressures and temperatures, and is still a challenge. Here, we demonstrate production of nanodiamonds by pulsed laser ablation of graphite and diamond-like carbon in water. Importantly, this technique enables production of nanocrystalline diamonds at room temperature and standard pressure conditions. Moreover, we propose a method for the purification of nanodiamonds from graphitic and amorphous carbon phases that do not require strong acids and harsh chemical conditions. Finally, we present a thermodynamic model that describes the formation of nanodiamonds during pulsed laser ablation. We show that synthesis of the crystalline phase is driven by a graphite-liquid-diamond transition process that occurs at the extreme thermodynamic conditions reached inside the ablation plume.

Origins of diamond-forming fluids: An isotopic and trace element study of diamonds and silicates from diamondiferous xenoliths

NASA Astrophysics Data System (ADS)

Laiginhas, Fernando; Pearson, D. Graham; McNeill, John; Gurney, John; Nowell, Geoff; Ottley, Chris

2010-05-01

While there is increasing understanding of the age of formation and nature of "gem" diamonds, significant debate revolves around the nature of the fluids/melts from which they form. Stable C and N isotopes have been shown to be highly variable and yet the role of subduction-related fluids remains strongly debated. Recent studies on fibrous diamonds have yielded new trace and major element data (e.g., Weiss et al., 2009) that, together with new radiogenic isotope data (Klein BenDavid et al., 2010) indicate such diamonds grow from fluids that comprise mixtures of hydrous silicic, hydrous saline and carbonatitic fluids, derived from different source components of asthenospheric and lithospheric origin. However, until now such data has been lacking from gem diamonds. Using a new laser-based technique (McNeill et al., 2009), we have analysed a suite of diamonds plus co-existing host silicates from several diamondiferous xenoliths (6 harzburgites, 1 eclogite) from the Finsch and Newlands kimberlites in order to try to understand the fluid compositions that produce gem diamonds and better understand their effects of their mantle wall rocks. Diamonds from the xenoliths show a wide variety of trace element enrichment levels. While the eclogitic diamond shows similar trace element systematics to some of the harzburgitic diamonds there are significant differences within the harzburgitic diamonds from different xenoliths, with those from Finsch being significantly enriched in Ba, Sr and Pb relative to other elements. Nd isotope data on the host silicates is variable and dominantly unradiogenic, indicative of long-term enrichment typically associated with the source of some diamond-forming fluids. We will present Sr isotopic data on host silicates and diamond fluids to constrain whether the "gem" diamonds require the complex sources of fluids that characterise the growth of fibrous diamonds. 1) Y. Weiss, R. Kessel, W.L. Griffin, I. Kiflawi, O. Klein-BenDavid, D.R. Bell, J.W. Harris and O. Navon (2009). A new model for the evolution of diamond-forming fluids: Evidence from microinclusion-bearing diamonds from Kankan, Guinea. Lithos 112, Supp. 2: 660-674. 2) O. Klein-BenDavid, D.G. Pearson, G.M. Nowell, C. Ottley, J.C.R. McNeill, P. Cartigny (2010). Mixed fluid sources involved in diamond growth constrained by Sr-Nd-Pb-C-N isotopes and trace elements. EPSL 289, 1-2: 123-133. 3) J. McNeill, D.G. Pearson, O. Klein-BenDavid, G.M. Nowell, C.J. Ottley and I. Chinn (2009). Quantitative analysis of trace element concentrations in some gem-quality diamonds. J. Phys.: Condens. Matter 21: 364207 (13pp).

Transitions induced by solubilized fat into reverse hexagonal mesophases.

PubMed

Amar-Yuli, Idit; Garti, Nissim

2005-06-25

Lyotropic liquid crystals of glycerol monooleate (GMO) and water binary mixtures have been extensively studied and their resemblance to human membranes has intrigued many scientists. Biological systems as well as food mixtures are composed of lipids and fat components including triacylglycerols (TAGs, triglycerides) that can affect the nature of the assembly of the mesophase. The present study examines the effect of TAGs of different chain lengths (C(2)-C(18)) at various water/GMO compositions, on phase transitions from lamellar or cubic to reverse hexagonal (L(alpha)-H(II) and Q-H(II)). The ability of the triglycerides to promote the formation of an H(II) mesophase is chain length-dependent. It was found that TAG molecules with very short acyl chains (triacetin) can hydrate the head groups of the lipid and do not affect the critical packing parameter (CPP) of the amphiphile; therefore, they do not affect the self-assembly of the GMO in water, and the mesophase remains lamellar or cubic. However, TAGs with medium chain fatty acids will solvate the tails of the lipid, and will affect the CPP of the GMO, and transform the lamellar or cubic phases into hexagonal mesophase. TAGs with long chain fatty acids are very bulky, not very miscible with the GMO, and therefore, kinetically are very slow to solvate the lipid tails of the amphiphile and are difficult to accommodate into the lipophilic parts of the GMO. Their effect on the transitions from a lamellar or cubic phase to hexagonal is detected only after months of equilibration. In order to enhance the effect of the TAG on the phase transitions in the GMO/triglyceride/water systems, temperature and electrolytes effects were examined. In the presence of short and medium chain triglycerides, increasing temperature caused a transition from lamellar or hexagonal to L(2) phase (highest CPP value). However, in the presence of long chain TAGs, increasing temperature to ca. 40 degrees C caused a formation of H(II) mesophase. In addition, it was found that in tricaprylin/GMO/water systems, the increase in temperature caused a decrease in the lattice parameter. The effect of NaCl on the H(II) mesophase revealed interesting results. At low concentration of tricaprylin (5 wt%), the addition of only 0.1 wt% of NaCl was sufficient to cause the formation of well-defined H(II) mesophase, while further addition of electrolyte increased the hexagonal lattice parameters. At higher TAGs concentrations (10 wt%), addition of electrolyte resulted in the formation of H(II) with modifications of the lattice parameter. All the examined effects were more pronounced with increasing water content.

Nano-crystalline diamond-coated titanium dental implants - a histomorphometric study in adult domestic pigs.

PubMed

Metzler, Philipp; von Wilmowsky, Cornelius; Stadlinger, Bernd; Zemann, Wolfgang; Schlegel, Karl Andreas; Rosiwal, Stephan; Rupprecht, Stephan

2013-09-01

Promising biomaterial characteristics of diamond-coatings in biomedicine have been described in the literature. However, there is a lack of knowledge about implant osseointegration of this surface modification compared to the currently used sandblasted acid-etched Ti-Al6-V4 implants. The aim of this study was to investigate the osseointegration of microwave plasma-chemical-vapour deposition (MWP-CVD) diamond-coated Ti-Al6-V4 dental implants after healing periods of 2 and 5 months. Twenty-four MWP-CVD diamond-coated and 24 un-coated dental titanium-alloy implants (Ankylos(®)) were placed in the frontal skull of eight adult domestic pigs. To evaluate the effects of the nano-structured surfaces on bone formation, a histomorphometric analysis was performed after 2 and 5 months of implant healing. Histomorphometry analysed the bone-to-implant contact (BIC). No significant difference in BIC for the diamond-coated implants in comparison to reference implants could be observed for both healing periods. Scanning electron microscopy revealed an adequate interface between the bone and the diamond surface. No delamination or particle-dissociation due to shearing forces could be detected. In this study, diamond-coated dental titanium-alloy implants and sandblasted acid-etched implants showed a comparable degree of osseointegration. Copyright © 2012 European Association for Cranio-Maxillo-Facial Surgery. Published by Elsevier Ltd. All rights reserved.

Optical characterization of single-crystal diamond grown by DC arc plasma jet CVD

NASA Astrophysics Data System (ADS)

Hei, Li-fu; Zhao, Yun; Wei, Jun-jun; Liu, Jin-long; Li, Cheng-ming; Lü, Fan-xiu

2017-12-01

Optical centers of single-crystal diamond grown by DC arc plasma jet chemical vapor deposition (CVD) were examined using a low-temperature photoluminescence (PL) technique. The results show that most of the nitrogen-vacancy (NV) complexes are present as NV- centers, although some H2 and H3 centers and B-aggregates are also present in the single-crystal diamond because of nitrogen aggregation resulting from high N2 incorporation and the high mobility of vacancies under growth temperatures of 950-1000°C. Furthermore, emissions of radiation-induced defects were also detected at 389, 467.5, 550, and 588.6 nm in the PL spectra. The reason for the formation of these radiation-induced defects is not clear. Although a Ni-based alloy was used during the diamond growth, Ni-related emissions were not detected in the PL spectra. In addition, the silicon-vacancy (Si-V)-related emission line at 737 nm, which has been observed in the spectra of many previously reported microwave plasma chemical vapor deposition (MPCVD) synthetic diamonds, was absent in the PL spectra of the single-crystal diamond prepared in this work. The high density of NV- centers, along with the absence of Ni-related defects and Si-V centers, makes the single-crystal diamond grown by DC arc plasma jet CVD a promising material for applications in quantum computing.

Diamond film deposition on WC-Co and steel substrates with a CrN interlayer for tribological applications

NASA Astrophysics Data System (ADS)

Chandran, Maneesh; Hoffman, Alon

2016-06-01

The most renowned property of diamond is its exceptional hardness. By depositing diamond films on tungsten carbide (WC-Co) and steel substrates, the hardness of diamond can be combined with the toughness of these materials, resulting in an excellent wear resistance material for tribological applications. However, poor adhesion of diamond coating on these substrates leads to a lesser lifetime for the diamond coated tools than expected. The prime reasons for the lack of proper adhesion are the preferential formation of graphitic layer at the interface due to the catalytic activities of cobalt/iron and the interfacial residual stresses due to the mismatch in thermal expansion coefficients of diamond (1.5  ×  10-6 K-1) and WC-Co (5.2  ×  10-6 K-1) or steel (12  ×  10-6 K-1). In this review, we discuss the possibility of using a Cr-N interlayer as a diffusion barrier to prevent the catalytic activities of cobalt/iron and also to relax the interfacial residual stresses to some extent to enhance the adhesion of diamond coatings on these substrates. An overview of the most pertinent results of the last two decades, including the recent progress is introduced. We describe in detail how the Cr-N interlayer with the desired properties is fabricated. We give a concise overview of diamond deposition process, including the methods to vary the grain size from microcrystalline to nanocrystalline, which are suitable for some tribological applications. We describe in detail on surface and interface analysis, residual stress measurements, assessment adhesion strength and tribological performance of diamond coated WC-Co and steel substrates using various characterization techniques. We conclude by highlighting the current progress and future perspectives of diamond coatings on these substrates for tribological applications.

Ultra-Smooth Nanostructured Diamond Films Deposited from He/H2/CH4/N2 Microwave Plasmas

PubMed Central

Konovalov, Valery V.; Melo, Andrew; Catledge, Shane A.; Chowdhury, Shafiul

2008-01-01

Addition of He to a high CH4 content (10.7 vol%) H2/CH4/N2 feedgas mixture for microwave plasma chemical vapor deposition produced hard (56–72 GPa), ultra-smooth nanostructured diamond films on Ti-6Al-4V alloy substrates. Upon increase in He content up to 71 vol%, root mean squared (RMS) surface roughness of the film decreased to 9–10 nm and average diamond grain size to 5–6 nm. Our studies show that increased nanocrystallinity with He addition in plasma is related to plasma dilution, enhanced fragmentation of carbon containing species, and enhanced formation of CN radical. PMID:16573106

Effect of the quantum zero-point atomic motion on the optical and electronic properties of diamond and trans-polyacetylene.

PubMed

Cannuccia, Elena; Marini, Andrea

2011-12-16

The quantum zero-point motion of the carbon atoms is shown to induce strong effects on the optical and electronic properties of diamond and trans-polyacetylene, a conjugated polymer. By using an ab initio approach, we interpret the subgap states experimentally observed in diamond in terms of entangled electron-phonon states. These states also appear in trans-polyacetylene causing the formation of strong structures in the band structure that even call into question the accuracy of the band theory. This imposes a critical revision of the results obtained for carbon-based nanostructures by assuming the atoms frozen in their equilibrium positions. © 2011 American Physical Society

Effect of doping with nickel ions on the structural state of a zinc oxide crystal

NASA Astrophysics Data System (ADS)

Dubinin, S. F.; Sokolov, V. I.; Parkhomenko, V. D.; Maksimov, V. I.; Gruzdev, N. B.

2009-10-01

The fine structure of a hexagonal zinc oxide crystal doped with nickel ions of the composition Zn1 - x Ni x O has been studied using neutron diffraction and magnetic measurements. It is established that even at very low doping levels ( x = 0.0004), the crystal undergoes local distortions in basal planes of the initial hexagonal lattice. The local distortions are assumed to be sources of the formation of ferromagnetism in compounds of this class.

Genesis of diamond inclusions: An integrated cathodoluminescence (CL) and Electron backscatter diffraction (EBSD) study on eclogitic and peridotitic inclusions and their diamond host.

NASA Astrophysics Data System (ADS)

van den Heuvel, Quint; Matveev, Sergei; Drury, Martyn; Gress, Michael; Chinn, Ingrid; Davies, Gareth

2017-04-01

Diamond inclusions are potentially fundamental to understanding the formation conditions of diamond and the volatile cycles in the deep mantle. In order to fully understand the implications of the compositional information recorded by inclusions it is vital to know whether the inclusions are proto-, syn-, or epigenetic and the extent to which they have equilibrated with diamond forming fluids. In previous studies, the widespread assumption was made that the majority of diamond inclusions are syngenetic, based upon observation of cubo-octahedral morphology imposed on the inclusions. Recent work has reported the crystallographic relationship between inclusions and the host diamond to be highly complex and the lack of crystallographic relationships between inclusions and diamonds has led some to question the significance of imposed cubo-octahedral morphology. This study presents an integrated EBSD and CL study of 9 diamonds containing 20 pyropes, 2 diopsides, 1 forsterite and 1 rutile from the Jwaneng and Letlhakane kimberlite clusters, Botswana. A new method was developed to analyze the crystallographic orientation of the host diamond and the inclusions with EBSD. Diamonds plates were sequentially polished to expose inclusions at different levels in the diamond. CL imaging at different depths was performed in order to produce a 3D view of diamond growth zones around the inclusions. Standard diamond polishing techniques proved too aggressive for silicate inclusions as they were damaged to such a degree that EBSD measurements on the inclusions were impossible. The inclusions were milled with a Ga+ focused ion beam (FIB) at a 12° angle to clean the surface for EBSD measurements. Of the 24 inclusions, 9 have an imposed cubo-octahedral morphology. Of these inclusions, 6 have faces orientated parallel to diamond growth zones and/or appear to have nucleated on a diamond growth surface, implying syngenesis. In contrast, other diamonds record resorption events such that inclusions now cut diamond growth zones. In most cases, the growth zonation around inclusions is not well defined due to CL haloes but some inclusions clearly disrupt diamond growth. Crystallographic orientations of diamond and the inclusions, determined using EBSD, revealed that each inclusion has a homogeneous orientation and record no compositional zonation. The diamonds also showed no angular deviations despite many having multiple growth and resorption zones; implying epitaxial growth of diamond. Crystallographic alignment between diamond and inclusions was not recorded for the principle planes and limited to 3 possible coincidences on minor planes from the 24 inclusions studied. The CL data show no evidence of syngenesis for these 3 inclusions. Analyses of two diamonds with inclusion clusters in different growth zones, 400 µm apart, revealed the same chemical composition and orientation, potentially implying they originated from an original larger inclusion. Combined EBSD and CL data suggest that there is no direct orientational correlation (epitaxial growth) between silicate inclusions and the host diamond, even when the mineral phases are of the same symmetry group. The presentation will provide a detailed evaluation of the genesis of individual inclusions.

Hexagonal OsB 2: Sintering, microstructure and mechanical properties

DOE PAGES

Xie, Zhilin; Lugovy, Mykola; Orlovskaya, Nina; ...

2015-02-07

In this study, the metastable high pressure ReB 2-type hexagonal OsB 2 bulk ceramics was produced by spark plasma sintering. The phase composition, microstructure, and mechanical behavior of the sintered OsB 2 were studied by X-ray diffraction, optical microscopy, TEM, SEM, EDS, and nanoindentation. The produced ceramics was rather porous and contained a mixture of hexagonal (~80 wt.%) and orthorhombic (~20 wt.%) phases as identified by X-ray diffraction and EBSD analysis. Two boron-rich phases, which do not contain Os, were also identified by TEM and SEM/EDS analysis. Nanoindentation measurements yielded a hardness of 31 ± 9 GPa and Young’s modulusmore » of 574 ± 112 GPa, indicating that the material is rather hard and very stiff; but, it is very prone to crack formation and propagation, which is indicative of a very brittle nature of this material. Improvements in the sintering regime are required in order to produce dense, homogeneous and single phase hexagonal OsB 2 bulk ceramics.« less

Layer Protecting the Surface of Zirconium Used in Nuclear Reactors.

PubMed

Ashcheulov, Petr; Skoda, Radek; Skarohlíd, Jan; Taylor, Andrew; Fendrych, Frantisek; Kratochvílová, Irena

2016-01-01

Zirconium alloys have very useful properties for nuclear facilities applications having low absorption cross-section of thermal electrons, high ductility, hardness and corrosion resistance. However, there is also a significant disadvantage: it reacts with water steam and during this (oxidative) reaction it releases hydrogen gas, which partly diffuses into the alloy forming zirconium hydrides. A new strategy for surface protection of zirconium alloys against undesirable oxidation in nuclear reactors by polycrystalline diamond film has been patented- Czech patent 305059: Layer protecting the surface of zirconium alloys used in nuclear reactors and PCT patent: Layer for protecting surface of zirconium alloys (Patent Number: WO2015039636-A1). The zirconium alloy surface was covered by polycrystalline diamond layer grown in plasma enhanced chemical vapor deposition apparatus with linear antenna delivery system. Substantial progress in the description and understanding of the polycrystalline diamond/ zirconium alloys interface and material properties under standard and nuclear reactors conditions (irradiation, hot steam oxidation experiments and heating-quenching cycles) was made. In addition, process technology for the deposition of protective polycrystalline diamond films onto the surface of zirconium alloys was optimized. Zircaloy2 nuclear fuel pins were covered by 300 nm thick protective polycrystalline diamond layer (PCD) using plasma enhanced chemical vapor deposition apparatus with linear antenna delivery system. The polycrystalline diamond layer protects the zirconium alloy surface against undesirable oxidation and consolidates its chemical stability while preserving its functionality. PCD covered Zircaloy2 and standard Zircaloy2 pins were for 30 min. oxidized in 1100°C hot steam. Under these conditions α phase of zirconium changes to β phase (more opened for oxygen/hydrogen diffusion). PCD anticorrosion protection of Zircaloy nuclear fuel assemblies can significantly prolong lifetime of Zirconium alloy in nuclear reactors even above Zirconium phase transition temperatures. Even after ion beam irradiation (10 dpa, 3 MeV Fe(2+)) the diamond film still shows satisfactory structural integrity with both sp(3) and sp(2) carbon phases. Zircaloy2 under the carbon-based protective layer after hot steam oxidation test differed from the original Zircaloy2 material composition only very slightly, proving that the diamond coating increases the material resistance to high temperature oxidation. Zirconium alloys nuclear fuel pins' surfaces were covered by compact and homogeneous polycrystalline diamond layers consisting of sp(3) and sp(2) carbon phases with a high crystalline diamond content and low roughness. Diamond withstands very high temperatures, has excellent thermal conductivity and low chemical reactivity, it does not degrade over time and (important for the nuclear fuel cladding) being pure carbon, it has perfect neutron cross-section properties. Moreover, polycrystalline diamond layers consisting of crystalline (sp(3)) and amorphous (sp(2)) carbon phases could have suitable thermal expansion. Zirconium alloys coated with polycrystalline diamond film are protected against undesirable changes and processes. Further, the polycrystalline diamond layer prevents the reaction between the alloy surface and water vapor. During such reaction, water molecules dissociate and initiate formation of zirconium dioxide and hydrogen, accompanied by the release of large amount of heat. Thus the protective layer prevents the formation of hydrogen and the release of reaction heat. Few relevant patents to the topic have been reviewed and cited.

Redox Equilibria Involving Chromium Minerals in Aqueous Fluids in the Deep Earth - Implications for Diamond Formation

NASA Astrophysics Data System (ADS)

Huang, J.; Huang, F.; Hao, J.; Sverjensky, D. A.

2017-12-01

Diamonds are often associated with inclusions of garnet that are characteristically Cr-rich and Ca-poor, suggesting metasomatic reactions involving fluids [1]. To investigate these reactions, we developed a thermodynamic characterization of Cr-bearing minerals and integrated it with our database for the thermodynamic properties of aqueous Cr-species [2]. We retrieved thermodynamic properties of picrochromite (MgCr2O4), and knorringite (Mg3Cr2Si3O12) consistent with minerals in the Berman (1988) using calorimetric data and experimental phase equilibria involving the reactions: MgCr2O4 + SiO2 = Cr2O3 + MgSiO3 [2] and MgCr2O4 + 4MgSiO3 = Mg3Cr2Si3O12 + Mg2SiO4 [3], respectively.At high temperatures and pressures, neutral pH and FMQ, the predicted solubilities of eskolaite and knorringite equilibrium with Cr2+ in a pure water system are very low. However, we found that complexes of Cr2+ and Cl- could increase the solubilities of chromium minerals significantly. At 500°C and 0.2 - 1.0 GPa, we retrieved the CrCl(OH)0 neutral complex from experiments on the solubility of Cr2O3 in HCl solutions [4]. At 1,000°C and 4.0 GPa, we retrieved the properties of a CrCl3- complex from experiments on the solubility of Cr2O3 in KCl solutions [5]. The predicted solubility of a garnet containing 23 mole% of knorringite in equilibrium with CrCl3- in a peridotitic diamond-forming fluid is 22 millimolal (1,144 ppm). This result suggests that a redox reaction relating to diamond formation might involveMg3Al2Si3O12 + 0.5CO2(aq) + 2 CrCl3- + 2H+ = Mg3Cr2Si3O12 + 0.5C-Diamond + 2Al3+ + 6Cl-. In this way, high temperature and pressure fluids containing Cr(II)-complexes might promote the mobility of chromium and be involved in metasomatic reactions and diamond formation.[1]Boyd et al. (1993)[2] Hao et al. (submitted to Geochem. Persp. Letters)[3] Berman (1988)[4] Klemme et al. (2000)[5] Klemme et al. (2004)[6] Watenphul et al. (2014)[7] Klein-BenDavid et al. (2011)

Low water contents in diamond mineral inclusions: Proto-genetic origin in a dry cratonic lithosphere

NASA Astrophysics Data System (ADS)

Taylor, Lawrence A.; Logvinova, Alla M.; Howarth, Geoffrey H.; Liu, Yang; Peslier, Anne H.; Rossman, George R.; Guan, Yunbin; Chen, Yang; Sobolev, Nikolay V.

2016-01-01

The mantle is the major reservoir of Earth's water, hosted within Nominally Anhydrous Minerals (NAMs) (e.g., Bell and Rossman, 1992; Peslier et al., 2010; Peslier, 2010; Nestola and Smyth, 2015), in the form of hydrogen bonded to the silicate's structural oxygen. From whence cometh this water? Is the water in these minerals representative of the Earth's primitive upper mantle or did it come from melting events linked to crustal formation or to more recent metasomatic/re-fertilization events? During diamond formation, NAMs are encapsulated at hundreds of kilometers depth within the mantle, thereby possibly shielding and preserving their pristine water contents from re-equilibrating with fluids and melts percolating through the lithospheric mantle. Here we show that the NAMs included in diamonds from six locales on the Siberian Craton contain measurable and variable H2O concentrations from 2 to 34 parts per million by weight (ppmw) in olivine, 7 to 276 ppmw in clinopyroxene, and 11-17 ppmw in garnets. Our results suggest that if the inclusions were in equilibrium with the diamond-forming fluid, the water fugacity would have been unrealistically low. Instead, we consider the H2O contents of the inclusions, shielded by diamonds, as pristine representatives of the residual mantle prior to encapsulation, and indicative of a protogenetic origin for the inclusions. Hydrogen diffusion in the diamond does not appear to have modified these values significantly. The H2O contents of NAMs in mantle xenoliths may represent some later metasomatic event(s), and are not always representative of most of the continental lithospheric mantle. Results from the present study also support the conclusions of Peslier et al. (2010) and Novella et al. (2015) that the dry nature of the SCLM of a craton may provide stabilization of its thickened continental roots.

Selected Topics in CVD Diamond Research

NASA Astrophysics Data System (ADS)

Koizumi, Satoshi; Nebel, Christoph E.; Nesladek, Milos

2006-10-01

Since the discovery of Chemical Vapor Deposition (CVD) diamond growth in 1976, the steady scientific progress often resulted in surprising new discoveries and breakthroughs. This brought us to the idea to publish the special issue Selected Topics in CVD Diamond Research in physica status solidi (a), reflecting such advancements and interesting results at the leading edge of diamond research.The present issue summarizes this progress in the CVD diamond field by selecting contributions from several areas such as superconductivity, super-excitonic radiation, quantum computing, bio-functionalization, surface electronic properties, the nature of phosphorus doping, transport properties in high energy detectors, CVD growth and properties of nanocrystalline diamond. In all these directions CVD diamond appears to be very competitive in comparison with other semiconducting materials.As Editors of this special issue, we must admit that the selection is biased by our opinion. Nonetheless, we are sure that each contribution introduces new ideas and results which will improve the understanding of the current level of physics and chemistry of this attractive wide-bandgap semiconductor and which will help to bring it closer to applications.All submissions were invited based on the contributions of the authors to their specific research field. The Feature Articles have the format of topical reviews to give the reader a comprehensive summary. Partially, however, they are written in research paper style to report new results of ongoing research.We hope that this issue will attract the attention of a broad community of scientists and engineers, and that it will facilitate the utilization of diamond in electronic applications and technologies of the future.

Effect of reductant and PVP on morphology and magnetic property of ultrafine Ni powders prepared via hydrothermal route

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

Zhang, Jun, E-mail: j-zhang@126.com; Wang, Xiucai; Li, Lili

2013-10-15

Graphical abstract: The ultrafine Ni powders with the shapes including sphere, pearl-string, leaf, fish-bone, hexagonal sheet and silknet were prepared through one-step hydrothermal reduction using different reductants. Their saturation magnetization, remanent magnetization and coercivity sequentially increase, and the coercivity of hexagonal sheet-like Ni powders increases by 25% compared with the Ni bulk counterpart. - Highlights: • The ultrafine Ni powders with various shapes of sphere, fish-bone, hexagonal sheet, etc. • Facile and one-step hydrothermal reduction using three reductants and PVP additive was developed. • Magnetic properties of the ultrafine Ni powders with different shapes were measured. • Compared with bulkmore » Ni material, coercivity of hexagonal sheet Ni increases by 25%. • The formation mechanism of the shapes was suggested. - Abstract: The ultrafine nickel particles with different shapes including sphere, pearl-string, leaf, fish-bone, hexagonal sheet and silknet were prepared through one-step hydrothermal reduction using hydrazine hydrate, sodium hypophosphite and ethylene glycol as reductants, polyvinylpyrrolidone as structure-directing agent. It has been verified with the characterization of X-ray powder diffraction and transmission/scanning electronic microscopy that as-prepared products belong to face-centered cubic structure of nickel microcrystals with high purity and fine dispersity. The magnetic hysteresis loops measured at room temperature reveal that the values of saturation magnetization, remanent magnetization and coercivity rise sequentially from silknet, sphere to hexagonal sheet. In comparison with nickel bulk counterpart, the coercivity of the hexagonal sheet nickel powders increases by 25%.« less

Dated eclogitic diamond growth zones reveal variable recycling of crustal carbon through time

NASA Astrophysics Data System (ADS)

Timmerman, S.; Koornneef, J. M.; Chinn, I. L.; Davies, G. R.

2017-04-01

Monocrystalline diamonds commonly record complex internal structures reflecting episodic growth linked to changing carbon-bearing fluids in the mantle. Using diamonds to trace the evolution of the deep carbon cycle therefore requires dating of individual diamond growth zones. To this end Rb-Sr and Sm-Nd isotope data are presented from individual eclogitic silicate inclusions from the Orapa and Letlhakane diamond mines, Botswana. δ13 C values are reported from the host diamond growth zones. Heterogeneous 87Sr/86Sr ratios (0.7033-0.7097) suggest inclusion formation in multiple and distinct tectono-magmatic environments. Sm-Nd isochron ages were determined based on groups of inclusions with similar trace element chemistry, Sr isotope ratios, and nitrogen aggregation of the host diamond growth zone. Diamond growth events at 0.14 ± 0.09, 0.25 ± 0.04, 1.1 ± 0.09, 1.70 ± 0.34 and 2.33 ± 0.02 Ga can be directly related to regional tectono-magmatic events. Individual diamonds record episodic growth with age differences of up to 2 Ga. Dated diamond zones have variable δ13 C values (-5.0 to -33.6‰ vs PDB) and appear to imply changes in subducted material over time. The studied Botswanan diamonds are interpreted to have formed in different tectono-magmatic environments that involve mixing of carbon from three sources that represent: i) subducted biogenic sediments (lightest δ13 C, low 87Sr/86Sr); ii) subducted carbonate-rich sediments (heavy δ13 C, high 87Sr/86Sr) and iii) depleted upper mantle (heavy δ13 C, low 87Sr/86Sr). We infer that older diamonds from these two localities are more likely to have light δ13 C due to greater subduction of biogenic sediments that may be related to hotter and more reduced conditions in the Archaean before the Great Oxidation Event at 2.3 Ga. These findings imply a marked temporal change in the nature of subducted carbon beneath Botswana and warrant further study to establish if this is a global phenomenon.

Phase stability and mechanical properties of Mo1-xNx with 0 ≤ x ≤ 1

NASA Astrophysics Data System (ADS)

Balasubramanian, Karthik; Huang, Liping; Gall, Daniel

2017-11-01

First-principle density-functional calculations coupled with the USPEX evolutionary phase-search algorithm are employed to calculate the convex hull of the Mo-N binary system. Eight molybdenum nitride compound phases are found to be thermodynamically stable: tetragonal β-Mo3N, hexagonal δ-Mo3N2, cubic γ-Mo11N8, orthorhombic ɛ-Mo4N3, cubic γ-Mo14N11, monoclinic σ-MoN and σ-Mo2N3, and hexagonal δ-MoN2. The convex hull is a straight line for 0 ≤ x ≤ 0.44 such that bcc Mo and the five listed compound phases with x ≤ 0.44 are predicted to co-exist in thermodynamic equilibrium. Comparing the convex hulls of cubic and hexagonal Mo1-xNx indicates that cubic structures are preferred for molybdenum rich (x < 0.3) compounds, and hexagonal phases are favored for nitrogen rich (x > 0.5) compositions, while similar formation enthalpies for cubic and hexagonal phases at intermediate x = 0.3-0.5 imply that kinetic factors play a crucial role in the phase formation. The volume per atom Vo of the thermodynamically stable Mo1-xNx phases decreases from 13.17 to 9.56 Å3 as x increases from 0.25 to 0.67, with plateaus at Vo = 11.59 Å3 for hexagonal and cubic phases and Vo = 10.95 Å3 for orthorhombic and monoclinic phases. The plateaus are attributed to the changes in the average coordination numbers of molybdenum and nitrogen atoms, which increase from 2 to 6 and decrease from 6 to 4, respectively, indicating an increasing covalent bonding character with increasing x. The change in bonding character and the associated phase change from hexagonal to cubic/orthorhombic to monoclinic cause steep increases in the isotropic elastic modulus E = 387-487 GPa, the shear modulus G = 150-196 GPa, and the hardness H = 14-24 GPa in the relatively narrow composition range x = 0.4-0.5. This also causes a drop in Poisson's ratio from 0.29 to 0.24 and an increase in Pugh's ratio from 0.49 to 0.64, indicating a ductile-to-brittle transition between x = 0.44 and 0.5.

Numerical Analysis of Incipient Separation on 53 Deg Swept Diamond Wing

NASA Technical Reports Server (NTRS)

Frink, Neal T.

2015-01-01

A systematic analysis of incipient separation and subsequent vortex formation from moderately swept blunt leading edges is presented for a 53 deg swept diamond wing. This work contributes to a collective body of knowledge generated within the NATO/STO AVT-183 Task Group titled 'Reliable Prediction of Separated Flow Onset and Progression for Air and Sea Vehicles'. The objective is to extract insights from the experimentally measured and numerically computed flow fields that might enable turbulence experts to further improve their models for predicting swept blunt leading-edge flow separation. Details of vortex formation are inferred from numerical solutions after establishing a good correlation of the global flow field and surface pressure distributions between wind tunnel measurements and computed flow solutions. From this, significant and sometimes surprising insights into the nature of incipient separation and part-span vortex formation are derived from the wealth of information available in the computational solutions.

Microstructural evolution of diamond films from CH{sub 4}/H{sub 2}/N{sub 2} plasma and their enhanced electrical properties

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

Sankaran, K. J.; Tai, N. H., E-mail: nhtai@mx.nthu.edu.tw; Lin, I. N., E-mail: inanlin@mail.tku.edu.tw

2015-02-21

The influence of N{sub 2} concentration in CH{sub 4}/H{sub 2}/N{sub 2} plasma on microstructural evolution and electrical properties of diamond films is systematically investigated. While the diamond films grown in CH{sub 4}/H{sub 2} plasma contain large diamond grains, for the diamond films grown using CH{sub 4}/H{sub 2}/(4%)N{sub 2} plasma, the microstructure drastically changed, resulting in ultra-nanosized diamond grains with Fd3m structure and a{sub 0} = 0.356 nm, along with the formation of n-diamond (n-D), a metastable form of diamond with space group Fm3m and a{sub 0} = 0.356 nm, and i-carbon (i-C) clusters, the bcc structured carbon with a{sub 0} = 0.432 nm. In addition, these films contain widemore » grain boundaries containing amorphous carbon (a-C). The electron field emission (EFE) studies show the best EFE behavior for 4% N{sub 2} films among the CH{sub 4}/H{sub 2}/N{sub 2} grown diamond films. They possess the lowest turn-on field value of 14.3 V/μm and the highest EFE current density value of 0.37 mA/cm{sup 2} at an applied field of 25.4 V/μm. The optical emission spectroscopy studies confirm that CN species are the major criterion to judge the changes in the microstructure of the films. It seems that the grain boundaries can provide electron conduction networks to transport efficiently the electrons to emission sites for field emission, as long as they have sufficient thickness. Whether the matrix nano-sized grains are 3C-diamond, n-D or i-C is immaterial.« less

Microdiamonds from the European Variscan Orogenic Belt

NASA Astrophysics Data System (ADS)

Kotkova, J.; Jakubova, P.; Whitehouse, M.; Fedortchouk, Y.

2014-12-01

Diamond, along with coesite, has been discovered recently in the continental crustal rocks of the European Variscan orogenic belt, namely the Bohemian Massif (BM). In addition to the garnet-phengite gneiss in Germany, western BM, microdiamond occurs in major rock forming minerals - garnet, kyanite - and in zircon in ultrahigh-pressure rocks overprinted under high-pressure granulite facies conditions (c. 16-20 kbar, c. 1000°C) in the northern and eastern BM. Well-preserved 10-30 μm-sized microdiamonds from northern BM exhibit diverse morphologies (SEM data) depending upon the host rock type. Octahedral diamond occurs in felsic garnet-kyanite-feldspar-quartz rock (metasediment), whereas intermediate garnet-clinopyroxene-feldspar-quartz rock contains a cubo-octahedral variety. Diamond morphology can be thus controlled by solid impurities available in the medium of crystallization (K- vs. Ca-bearing fluids or melts), as shown by experiments. Pointed-bottom negatively oriented trigonal etch pits on the octahedral diamond faces developed due to diamond resorption at CO2-dominated environment (less than 50 wt % of H2O, experimental data), possibly by action of a residual fluid. SIMS determined δ13C values range from -22 to -21 ‰ for the felsic rock and from - 26 to - 33 for the intermediate one, corresponding to the typical range of organic carbon δ13C and inconsistent with a significant mantle carbon (δ13C ~ - 5 ‰) input. Diamond-bearing domains in zircon, also analysed by SIMS, yielded a Variscan U-Pb age of c. 340 Ma. The present stage of knowledge allows us to conclude that (i) metamorphic diamonds in the BM occur in lithologies of metasedimentary character, and their carbon source was organic; (ii) crustal-derived CO2-rich fluids with impurities played an important role in diamond formation and dissolution; (iii) diamonds formed during the Variscan orogenic cycle and (iv) diamonds are best preserved in the external domain of the Variscan orogenic belt.

Trace element analyses of fluid-bearing diamonds from Jwaneng, Botswana

NASA Astrophysics Data System (ADS)

Schrauder, Marcus; Koeberl, Christian; Navon, Oded

1996-12-01

Fibrous diamonds from Botswana contain abundant micro-inclusions, which represent syngenetic mantle fluids under high pressure. The major element composition of the fluids within individual diamonds was found to be uniform, but a significant compositional variation exists between different diamond specimens. The composition of the fluids varies between a carbonatitic and a hydrous endmember. To constrain the composition of fluids in the mantle, the trace element contents of thirteen micro-inclusion-bearing fibrous diamonds from Botswana was studied using neutron activation analysis. The concentrations of incompatible elements (including K, Na, Br, Rb, Sr, Zr, Cs, Ba, Hf, Ta, Th, U, and the LREEs) in the fluids are higher than those of mantle-derived rocks and melt inclusions. The compatible elements (e.g., Cr, Co, Ni) have abundances that are similar to those of the primitive mantle. The concentrations of most trace elements decrease by a factor of two from the carbonate-rich fluids to the hydrous fluids. Several models may explain the observed elemental variations. Minerals in equilibrium with the fluid were most likely enriched in incompatible elements, which does not agree with derivation of the fluids by partial melting of common peridotites or eclogites. Fractional crystallization of a kimberlite-like magma at depth may yield carbonatitic fluids with low mg numbers (atomic ratio [Mg/(Mg+Fe)]) and high trace element contents. Fractionation of carbonates and additional phases (e.g., rutile, apatite, zircon) may, in general, explain the concentrations of incompatible elements in the fluids, which preferably partition into these phases. Alternatively, mixing of fluids with compositions similar to those of the two endmembers may explain the observed variation of the elemental contents. The fluids in fibrous diamonds might have equilibrated with mineral inclusions in eclogitic diamonds, while peridotitic diamonds do not show evidence of interaction with these fluids. The chemical composition of the fluids in fibrous diamonds indicates that, at p, T conditions that are characteristic for diamond formation, carbonatitic and hydrous fluids are efficient carriers of incompatible elements.

The Magnetic Properties Of Aggregate Polycrystalline Diamond: Implications For Carbonado Petrogenesis

NASA Technical Reports Server (NTRS)

Kleteschka, Gunther; Taylor, Patrick T.; Wasilewski, Peter J.; Hill, Hugh G. M.

2000-01-01

Carbonados are a type of diamond, which are made up of many aggregrates of small crystalline diamonds or microdiamonds. The term "carbonado" comes from the Portuguese word carbonated. They are only found in sedimentary deposits in the Central African Republic (CAR) and the Bahia Province of Brazil. They were once the source of the world's supply of industrial diamonds. Their origin is uncertain but several mutually exclusive hypotheses have been proposed. This theories are: (1) extraterrestrial, that is they formed from the dust cloud of original solar nebulae; (2) produced by the high temperatures and pressures of the Earth's mantle; (3) or as the result of an extra-terrestrial impact into a carbon rich layer of sediment. Our study was done to further the understanding of their origin. We measured the magnetic properties on some twenty samples from the CAR. An earlier study was done on whole samples of carbonados and the "common" or kimberlitic diamond. Our work differed in that we started at the surface and subsequently removed the surface layers (by days of acid immersion) into the interior; measuring the magnetic properties at each interval. This procedure permits us to monitor the distribution of magnetic substances within the samples. Our results showed that the magnetic carriers are distributed on the surface including the open pores and that the carbonado interior is essentially non-magnetic. This result suggests that the initial formation environment was deficient in magnetic particles. Such a situation could indicate that their formation was the result of an extra-terrestrial body impacting carbon-rich sediment. Obviously, more work will be required on isotopic and chemical analyses before a more detailed ori-in can be determined.

Mechanical response of spiral interconnect arrays for highly stretchable electronics

NASA Astrophysics Data System (ADS)

Qaiser, N.; Khan, S. M.; Nour, M.; Rehman, M. U.; Rojas, J. P.; Hussain, M. M.

2017-11-01

A spiral interconnect array is a commonly used architecture for stretchable electronics, which accommodates large deformations during stretching. Here, we show the effect of different geometrical morphologies on the deformation behavior of the spiral island network. We use numerical modeling to calculate the stresses and strains in the spiral interconnects under the prescribed displacement of 1000 μm. Our result shows that spiral arm elongation depends on the angular position of that particular spiral in the array. We also introduce the concept of a unit-cell, which fairly replicates the deformation mechanism for full complex hexagon, diamond, and square shaped arrays. The spiral interconnects which are axially connected between displaced and fixed islands attain higher stretchability and thus experience the maximum deformations. We perform tensile testing of 3D printed replica and find that experimental observations corroborate with theoretical study.

Thermal transport across high-pressure semiconductor-metal transition in Si and Si 0.991 Ge 0.009

DOE PAGES

Hohensee, Gregory T.; Fellinger, Michael R.; Trinkle, Dallas R.; ...

2015-05-07

Time-domain thermoreflectance (TDTR) can be applied to metallic samples at high pressures in the diamond anvil cell (DAC) and provide non-contact measurements of thermal transport properties. We have performed regular and beam-offset TDTR to establish the thermal conductivities of Si and Si 0.991Ge 0.009 across the semiconductor-metal phase transition and up to 45 GPa. The thermal conductivities of metallic Si and Si(Ge) are comparable to aluminum and indicative of predominantly electronic heat carriers. Metallic Si and Si(Ge) have an anisotropy of approximately 1.4, similar to that of beryllium, due to the primitive hexagonal crystal structure. Furthermore, we used the Wiedemann-Franzmore » law to derive the associated electrical resistivity, and found it consistent with the Bloch-Gruneisen model.« less

Thermal stability of hexagonal OsB2

NASA Astrophysics Data System (ADS)

Xie, Zhilin; Blair, Richard G.; Orlovskaya, Nina; Cullen, David A.; Andrew Payzant, E.

2014-11-01

The synthesis of novel hexagonal ReB2-type OsB2 ceramic powder was performed by high energy ball milling of elemental Os and B powders. Two different sources of B powder have been used for this mechanochemical synthesis. One B powder consisted of a mixture of amorphous and crystalline phases and a mixture of 10B and 11B isotopes with a fine particle size, while another B powder was a purely crystalline (rhombohedral) material consisting of enriched 11B isotope with coarse particle size. The same Os powder was used for the synthesis in both cases. It was established that, in the first case, the hexagonal OsB2 phase was the main product of synthesis with a small quantity of Os2B3 phase present after synthesis as an intermediate product. In the second case, where coarse crystalline 11B powder was used as a raw material, only Os2B3 boride was synthesized mechanochemically. The thermal stability of hexagonal OsB2 powder was studied by heating under argon up to 876 °C and cooling in vacuo down to -225 °C. During the heating, the sacrificial reaction 2OsB2+3O2→2Os+2B2O3 took place due to presence of O2/water vapor molecules in the heating chamber, resulting in the oxidation of B atoms and formation of B2O3 and precipitation of Os metal out of the OsB2 lattice. As a result of such phase changes during heating, the lattice parameters of hexagonal OsB2 changed significantly. The shrinkage of the a lattice parameter was recorded in 276-426 °C temperature range upon heating, which was attributed to the removal of B atoms from the OsB2 lattice due to oxidation followed by the precipitation of Os atoms and formation of Os metal. While significant structural changes occurred upon heating due to presence of O2, the hexagonal OsB2 ceramic demonstrated good phase stability upon cooling in vacuo with linear shrinkage of the lattice parameters and no phase changes detected during cooling.

A mantle origin for Paleoarchean peridotitic diamonds from the Panda kimberlite, Slave Craton: Evidence from 13C-, 15N- and 33,34S-stable isotope systematics

NASA Astrophysics Data System (ADS)

Cartigny, Pierre; Farquhar, James; Thomassot, Emilie; Harris, Jeffrey W.; Wing, Bozwell; Masterson, Andy; McKeegan, Kevin; Stachel, Thomas

2009-11-01

In order to address diamond formation and origin in the lithospheric mantle underlying the Central Slave Craton, we report N- and C-stable isotopic compositions and N-contents and aggregation states for 85 diamonds of known paragenesis (73 peridotitic, 8 eclogitic and 4 from lower mantle) from the Panda kimberlite (Ekati Mine, Lac de Gras Area, Canada). For 12 peridotitic and two eclogitic sulfide inclusion-bearing diamonds from this sample set, we also report multiple-sulfur isotope ratios. The 73 peridotitic diamonds have a mean δ13C-value of - 5.2‰ and range from - 6.9 to - 3.0‰, with one extreme value at - 14.1‰. The associated δ15N-values range from - 17.0 to + 8.5‰ with a mean value of - 4.0‰. N-contents range from 0 to 1280 ppm. The 8 eclogitic diamonds have δ13C-values ranging from - 11.2 to - 4.4‰ with one extreme value at - 19.4‰. Their δ15N ranges from - 2.1 to + 7.9‰ and N-contents fall between 0 and 3452 ppm. Four diamonds with an inferred lower mantle origin are all Type II (i.e. nitrogen-free) and have a narrow range of δ13C values, between - 4.5 and - 3.5‰. The δ34S of the 14 analyzed peridotitic and eclogitic sulfide inclusions ranges from - 3.5 to +5.7‰. None of them provide evidence for anomalous δ33S-values; observed variations in δ33S are from +0.19 to - 0.33‰, i.e. within the 2 sigma uncertainties of mantle sulfur ( δ33S = 0‰). At Panda, the N contents and the δ13C of sulfide-bearing peridotitic diamonds show narrower ranges than silicate-bearing peridotitic diamonds. This evidence supports the earlier suggestion established from eclogitic diamonds from the Kaapvaal that sulfide-(±silicate) bearing diamonds sample a more restricted portion of sublithospheric mantle than silicate-(no sulfide) bearing diamonds. Our findings at Panda suggest that sulfide-bearing diamonds should be considered as a specific diamond population on a global-scale. Based on our study of δ34S, Δ 33S, δ15N and δ13C, we find no evidence for subduction-related isotopic signatures in the mantle sampled by Panda diamonds.

Optimization of reaction parameters in hydrothermal synthesis: a strategy towards the formation of CuS hexagonal plates

PubMed Central

2013-01-01

Background For decades, copper sulphide has been renowned as the superior optical and semiconductor materials. Its potential applications can be ranged from solar cells, lithium-ion batteries, sensors, and catalyst systems. The synthesis methodologies of copper sulphide with different controlled morphology have been widely explored in the literature. Nevertheless, the understanding on the formation chemistry of CuS is still limited. The ultimate approach undertaking in this article is to investigate the formation of CuS hexagonal plates via the optimization of reaction parameters in hydrothermal reaction between copper (II) nitrate and sodium thiosulphate without appending any assistant agent. Results Covellite (CuS) hexagonal plates were formed at copper ion: thiosulphate ion (Cu2+:S2O32−) mole ratio of 1:2 under hydrothermal treatment of 155°C for 12 hours. For synthesis conducted at reaction temperature lower than 155°C, copper sulphate (CuSO4), krohnite (NaCu2(SO4)(H2O)2] and cyclooctasulphur (S8) were present as main impurities with covellite (CuS). When Cu2+:S2O32− mole ratio was varied to 1: 1 and 1: 1.5, phase pure plate-like natrochalcite [NaCu2(SO4)(H2O)] and digenite (Cu9S5) were produced respectively. Meanwhile, mixed phases of covellite (CuS) and cyclooctasulphur (S8) were both identified when Cu2+:S2O32− mole ratio was varied to 1: 2.5, 1: 3 and 1: 5 as well as when reaction time was shortened to 1 hour. Conclusions CuS hexagonal plates with a mean edge length of 1 μm, thickness of 100 nm and average crystallite size of approximately (45 ± 2) nm (Scherrer estimation) were successfully synthesized via assisting agent- free hydrothermal method. Under a suitable Cu2+:S2O32− mole ratio, we evidenced that the formation of covellite (CuS) is feasible regardless of the reaction temperature applied. However, a series of impurities were attested with CuS if reaction temperature was not elevated high enough for the additional crystallite phase decomposition. It was also identified that Cu2+:S2O32− mole ratio plays a vital role in controlling the amount of cyclooctasulphur (S8) in the final powder obtained. Finally, reaction time was recognized as an important parameter in impurity decomposition as well as increasing the crystallite size and crystallinity of the CuS hexagonal plates formed. PMID:23575312

Solvothermal synthesis of fusiform hexagonal prism SrCO{sub 3} microrods via ethylene glycol solution

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

Shi Liange; Du Fanglin

2007-08-07

Fusiform hexagonal prism SrCO{sub 3} microrods were prepared by a simple solvothermal route at 120 deg. C, and characterized by X-ray powder diffraction (XRD), field-emission scanning electron microscopy (FE-SEM) and Fourier transform infrared (FT-IR) spectroscopy. By controlling the content of ethylene glycol (EG), it was found that ethylene glycol (EG) played an important role in the formation of such SrCO{sub 3} microrods. Finally, effects of other solvents on the products, including 1,2-propanediol and glycerin, were also investigated.

Hippocampal Spike-Timing Correlations Lead to Hexagonal Grid Fields

NASA Astrophysics Data System (ADS)

Monsalve-Mercado, Mauro M.; Leibold, Christian

2017-07-01

Space is represented in the mammalian brain by the activity of hippocampal place cells, as well as in their spike-timing correlations. Here, we propose a theory for how this temporal code is transformed to spatial firing rate patterns via spike-timing-dependent synaptic plasticity. The resulting dynamics of synaptic weights resembles well-known pattern formation models in which a lateral inhibition mechanism gives rise to a Turing instability. We identify parameter regimes in which hexagonal firing patterns develop as they have been found in medial entorhinal cortex.

A superhard, quenchable carbon polymorph formed by the room-temperature compression of graphite (Invited)

NASA Astrophysics Data System (ADS)

Wang, Y.; Kiefer, B.; Lee, K. K.

2010-12-01

As one of the revolutionary inventions of the 20th century, synthetic diamond has had a large impact on industry and on scientific research. However, the necessities of high pressures, high temperatures and a metal catalyst during the manufacturing of synthetic diamond make it energy consuming thus limits its availability and use. Here, we report on the synthesis of a superhard non-diamond material resulting from the compression of graphite above ~20 GPa at room temperature without the utilization of metal catalysts. The final product includes a nano-sized phase of carbon that is recoverable at ambient conditions. Furthermore, the ring cracks left on the diamond anvils suggest that the hardness of this post-graphite phase is at least comparable to that of diamond. We use high-resolution synchrotron x-ray diffraction and micro-Raman spectroscopy to monitor the structural transformation in graphite under high pressure and room temperature and find the transition to be sluggish. The possible crystal structure of the new, quenchable phase will be discussed and the time-dependent formation of this superhard post-graphite carbon will be addressed and compared to first-principle predictions.

Profiling of Current Transients in Capacitor Type Diamond Sensors.

PubMed

Gaubas, Eugenijus; Ceponis, Tomas; Meskauskaite, Dovile; Kazuchits, Nikolai

2015-06-08

The operational characteristics of capacitor-type detectors based on HPHT and CVD diamond have been investigated using perpendicular and parallel injection of carrier domain regimes. Simulations of the drift-diffusion current transients have been implemented by using dynamic models based on Shockley-Ramo's theorem, under injection of localized surface domains and of bulk charge carriers. The bipolar drift-diffusion regimes have been analyzed for the photo-induced bulk domain (packet) of excess carriers. The surface charge formation and polarization effects dependent on detector biasing voltage have been revealed. The screening effects ascribed to surface charge and to dynamics of extraction of the injected bulk excess carrier domain have been separated and explained. The parameters of drift mobility of the electrons μ(e) = 4000 cm2/Vs and holes μ(h) = 3800 cm2/Vs have been evaluated for CVD diamond using the perpendicular profiling of currents. The coefficient of carrier ambipolar diffusion D(a) = 97 cm2/s and the carrier recombination lifetime τ(R,CVD) ≌ 110 ns in CVD diamond were extracted by combining analysis of the transients of the sensor current and the microwave probed photoconductivity. The carrier trapping with inherent lifetime τR,HPHT ≌ 2 ns prevails in HPHT diamond.

Self-Organization of Amorphous Carbon Nanocapsules into Diamond Nanocrystals Driven by Self-Nanoscopic Excessive Pressure under Moderate Electron Irradiation without External Heating.

PubMed

Wang, Chengbing; Ling, San; Yang, Jin; Rao, Dewei; Guo, Zhiguang

2018-01-01

Phase transformation between carbon allotropes usually requires high pressures and high temperatures. Thus, the development of low-temperature phase transition approaches between carbon allotropes is highly desired. Herein, novel amorphous carbon nanocapsules are successfully synthesized by pulsed plasma glow discharge. These nanocapsules are comprised of highly strained carbon clusters encapsulated in a fullerene-like carbon matrix, with the formers serving as nucleation sites. These nucleation sites favored the formation of a diamond unit cell driven by the self-nanoscopic local excessive pressure, thereby significantly decreasing the temperature required for its transformation into a diamond nanocrystal. Under moderate electron beam irradiation (10-20 A cm -2 ) without external heating, self-organization of the energetic carbon clusters into diamond nanocrystals is achieved, whereas the surrounding fullerene-like carbon matrix remains nearly unchanged. Molecular dynamics simulations demonstrate that the defective rings as the active sites dominate the phase transition of amorphous carbon to diamond nanocrystal. The findings may open a promising route to realize phase transformation between carbon allotropes at a lower temperature. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DNA-controlled assembly of a NaTl lattice structure from gold nanoparticles and protein nanoparticles

NASA Astrophysics Data System (ADS)

Cigler, Petr; Lytton-Jean, Abigail K. R.; Anderson, Daniel G.; Finn, M. G.; Park, Sung Yong

2010-11-01

The formation of diamond structures from tailorable building blocks is an important goal in colloidal crystallization because the non-compact diamond lattice is an essential component of photonic crystals for the visible-light range. However, designing nanoparticle systems that self-assemble into non-compact structures has proved difficult. Although several methods have been proposed, single-component nanoparticle assembly of a diamond structure has not been reported. Binary systems, in which at least one component is arranged in a diamond lattice, provide alternatives, but control of interparticle interactions is critical to this approach. DNA has been used for this purpose in a number of systems. Here we show the creation of a non-compact lattice by DNA-programmed crystallization using surface-modified Qβ phage capsid particles and gold nanoparticles, engineered to have similar effective radii. When combined with the proper connecting oligonucleotides, these components form NaTl-type colloidal crystalline structures containing interpenetrating organic and inorganic diamond lattices, as determined by small-angle X-ray scattering. DNA control of assembly is therefore shown to be compatible with particles possessing very different properties, as long as they are amenable to surface modification.

Diamonds: Exploration, mines and marketing

NASA Astrophysics Data System (ADS)

Read, George H.; Janse, A. J. A. (Bram)

2009-11-01

The beauty, value and mystique of exceptional quality diamonds such as the 603 carat Lesotho Promise, recovered from the Letseng Mine in 2006, help to drive a multi-billion dollar diamond exploration, mining and marketing industry that operates in some 45 countries across the globe. Five countries, Botswana, Russia, Canada, South Africa and Angola account for 83% by value and 65% by weight of annual diamond production, which is mainly produced by four major companies, De Beers, Alrosa, Rio Tinto and BHP Billiton (BHPB), which together account for 78% by value and 72% by weight of annual diamond production for 2007. During the last twelve years 16 new diamond mines commenced production and 4 re-opened. In addition, 11 projects are in advanced evaluation and may begin operations within the next five years. Exploration for diamondiferous kimberlites was still energetic up to the last quarter of 2008 with most work carried out in Canada, Angola, Democratic Republic of the Congo (DRC) and Botswana. Many kimberlites were discovered but no new economic deposits were outlined as a result of this work, except for the discovery and possible development of the Bunder project by Rio Tinto in India. Exploration methods have benefitted greatly from improved techniques of high resolution geophysical aerial surveying, new research into the geochemistry of indicator minerals and further insights into the formation of diamonds and the relation to tectonic/structural events in the crust and mantle. Recent trends in diamond marketing indicate that prices for rough diamonds and polished goods were still rising up to the last quarter of 2008 and subsequently abruptly sank in line with the worldwide financial crisis. Most analysts predict that prices will rise again in the long term as the gap between supply and demand will widen because no new economic diamond discoveries have been made recently. The disparity between high rough and polished prices and low share prices of publicly traded diamond companies may be due to investors losing patience with the slow pace or absence of new promising discoveries and switching into shares of base metals and fertilizers for agriculture (potash and phosphates).

Characterization of SrCo1.5Ti1.5Fe9O19 hexagonal ferrite synthesized by sol-gel combustion and solid state route

NASA Astrophysics Data System (ADS)

Vinaykumar, R.; Mazumder, R.; Bera, J.

2017-05-01

Co-Ti co-substituted SrM hexagonal ferrite (SrCo1.5Ti1.5Fe9O19) was synthesized by sol-gel combustion and solid state route. The effects of sources of TiO2 raw materials; titanium tetra-isopropoxide (TTIP) and titanyl nitrate (TN) on the phase formation behavior and properties of the ferrite were studied. The thermal decomposition behavior of the gel was studied using TG-DSC. The phase formation behavior of the ferrite was studied by using X-ray powder diffraction and FTIR analysis. Phase formation was comparatively easier in the TN-based sol-gel process. The morphology of powder and sintered ferrite was investigated using scanning electron microscope. Magnetic properties like magnetization, coercivity, permeability, tan δμ and dielectric properties were investigated. The ferrite synthesized by sol-gel based chemical route showed higher saturation magnetization, permeability and permittivity compared to the ferrite synthesized by solid state route.

Global Formation of Topological Defects in the Multiferroic Hexagonal Manganites

DOE PAGES

Meier, Q. N.; Lilienblum, M.; Griffin, S. M.; ...

2017-10-20

The spontaneous transformations associated with symmetry-breaking phase transitions generate domain structures and defects that may be topological in nature. The formation of these defects can be described according to the Kibble-Zurek mechanism, which provides a generic relation that applies from cosmological to interatomic length scales. Its verification is challenging, however, in particular at the cosmological scale where experiments are impractical. While it has been demonstrated for selected condensed-matter systems, major questions remain regarding, e.g., its degree of universality. Here, we develop a global Kibble-Zurek picture from the condensed-matter level. We show theoretically that a transition between two fluctuation regimes (Ginzburgmore » and mean field) can lead to an intermediate region with reversed scaling, and we verify experimentally this behavior for the structural transition in the series of multiferroic hexagonal manganites. Trends across the series allow us to identify additional intrinsic features of the defect formation beyond the original Kibble-Zurek paradigm.« less

Global Formation of Topological Defects in the Multiferroic Hexagonal Manganites

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

Meier, Q. N.; Lilienblum, M.; Griffin, S. M.

The spontaneous transformations associated with symmetry-breaking phase transitions generate domain structures and defects that may be topological in nature. The formation of these defects can be described according to the Kibble-Zurek mechanism, which provides a generic relation that applies from cosmological to interatomic length scales. Its verification is challenging, however, in particular at the cosmological scale where experiments are impractical. While it has been demonstrated for selected condensed-matter systems, major questions remain regarding, e.g., its degree of universality. Here, we develop a global Kibble-Zurek picture from the condensed-matter level. We show theoretically that a transition between two fluctuation regimes (Ginzburgmore » and mean field) can lead to an intermediate region with reversed scaling, and we verify experimentally this behavior for the structural transition in the series of multiferroic hexagonal manganites. Trends across the series allow us to identify additional intrinsic features of the defect formation beyond the original Kibble-Zurek paradigm.« less

Experimental studies of transplutonium metals and compounds under pressure

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

Peterson, J.R.; Haire, R.G.; Benedict, U.

1986-01-01

The structural behavior of the first four transplutonium metals and two Bk-Cf alloys as a function of pressure has been studied in diamond anvil cells via x-ray diffraction. The sequence of structures exhibited as pressure is increased is dhcp ..-->.. ccp ..-->.. orthorhombic. In addition a distorted ccp phase is observed in Am, Bk/sub 0.40/Cf/sub 0.60/, and Cf between the ccp and orthorhombic phases. Diamond anvil cells have also been used to contain AmI/sub 3/, CfBr/sub 3/, and CfCl/sub 3/ under pressure for investigation by absorption spectrophotometry. Both AmI/sub 3/ and CfBr/sub 3/ exhibit pressure-induced, irreversible phase transformations to themore » PuBr/sub 3/-type orthorhombic structure, a more dense form of these compounds. Thus the driving force for these transformations is more efficient crystal packing. Both hexagonal (to 22 GPa) and orthorhombic (to 35 GPa) CfCl/sub 3/ exhibit only reversible spectral changes with pressure. This probably reflects their nearly identical RTP unit cell volumes. In both cases the spectra obtained are consistent with a continuous alteration of the RTP structure with pressure; physical compression seems to make a given f-f transition easier. Additional data are being sought to elucidate more completely the behavior of CfCl/sub 3/ under pressure. 23 refs., 4 figs.« less

The Formation and Characterization of GaN Hexagonal Pyramids

NASA Astrophysics Data System (ADS)

Zhang, Shi-Ying; Xiu, Xiang-Qian; Lin, Zeng-Qin; Hua, Xue-Mei; Xie, Zi-Li; Zhang, Rong; Zheng, You-Dou

2013-05-01

GaN with hexagonal pyramids is fabricated using the photo-assisted electroless chemical etching method. Defective areas of the GaN substrate are selectively etched in a mixed solution of KOH and K2S2O8 under ultraviolet illumination, producing submicron-sized pyramids. Hexagonal pyramids on the etched GaN with well-defined {101¯1¯} facets and very sharp tips are formed. High-resolution x-ray diffraction shows that etched GaN with pyramids has a higher crystal quality, and micro-Raman spectra reveal a tensile stress relaxation in GaN with pyramids compared with normal GaN. The cathodoluminescence intensity of GaN after etching is significantly increased by three times, which is attributed to the reduction in the internal reflection, high-quality GaN with pyramids and the Bragg effect.

Simulations of chemical vapor deposition diamond film growth using a kinetic Monte Carlo model and two-dimensional models of microwave plasma and hot filament chemical vapor deposition reactors

NASA Astrophysics Data System (ADS)

May, P. W.; Harvey, J. N.; Allan, N. L.; Richley, J. C.; Mankelevich, Yu. A.

2010-12-01

A one-dimensional kinetic Monte Carlo (KMC) model has been developed to simulate the chemical vapor deposition of a diamond (100) surface under conditions used to grow single-crystal diamond (SCD), microcrystalline diamond (MCD), nanocrystalline diamond (NCD), and ultrananocrystalline diamond (UNCD) films. The model considers adsorption, etching/desorption, lattice incorporation and surface migration but not defect formation or renucleation processes. Two methods have been devised for estimation of the gas phase concentrations of species at the growing diamond surface, and are used to determine adsorption rates for C1Hx hydrocarbons for the different conditions. The rate of migration of adsorbed carbon species is governed by the availability of neighboring radical sites, which, in turn, depend upon the rates of H abstraction and of surface-radical migration. The KMC model predicts growth rates and surface roughness for each of diamond types consistent with experiment. In the absence of defect formation and renucleation the average surface diffusion length, ℓ, is a key parameter controlling surface morphology. When ℓ <2, surface migration is limited by the lack of availability of surface radical sites, and the migrating surface species simply hop back and forth between two adjacent sites but do not travel far beyond their initial adsorption site. Thus, Eley-Rideal processes dominate the growth, leading to the rough surfaces seen in NCD and UNCD. The maximum or "intrinsic" surface roughness occurs for nominally zero-migration conditions (ℓ =0) with an rms value of approximately five carbon atoms. Conversely, when migration occurs over greater distances (ℓ >2), Langmuir-Hinshelwood processes dominate the growth producing the smoother surfaces of MCD and SCD. By extrapolation, we predict that atomically smooth surfaces over large areas should occur once migrating species can travel approximately five sites (ℓ ˜5). β-scission processes are found to be unimportant for MCD and SCD growth conditions, but can remove up to 5% of the adsorbing carbon for NCD and UNCD growth. C1Hx insertion reactions also contribute <1% to the growth for nearly all conditions, while C2Hx (x <2) insertion reactions are negligible due their very low concentrations at the surface. Finally, the predictions for growth rate and morphology for UNCD deposition in a microwave system were found to be anomalous compared to those for all the other growth conditions, suggesting that carbonaceous particulates created in these plasmas may significantly affect the gas chemistry.

Study of ZnO and Mg doped ZnO nanoparticles by sol-gel process

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

Ansari, Mohd Meenhaz, E-mail: meenhazphysics@gmail.com; Arshad, Mohd; Tripathi, Pushpendra

Nano-crystalline undoped and Mg doped ZnO (Mg-ZnO) nanoparticles with compositional formula Mg{sub x}Zn{sub 1-x}O (x=0,1,3,5,7,10 and 12 %) were synthesized using sol-gel process. The XRD diffraction peaks match with the pattern of the standard hexagonal structure of ZnO that reveals the formation of hexagonal wurtzite structure in all samples. SEM images demonstrates clearly the formation of spherical ZnO nanoparticles, and change of the morphology of the nanoparticles with the concentration of the magnesium, which is in close agreement with that estimated by Scherer formula based on the XRD pattern. To investigate the doping effect on optical properties, the UV–VIS absorptionmore » spectra was obtained and the band gap of the samples calculated.« less

Endo-Fullerene and Doped Diamond Nanocrystallite Based Models of Qubits for Solid-State Quantum Computers

NASA Technical Reports Server (NTRS)

Park, Seongjun; Srivastava, Deepak; Cho, Kyeongjae; Biegel, Bryan (Technical Monitor)

2001-01-01

Models of encapsulated 1/2 nuclear spin H-1 and P-31 atoms in fullerene and diamond nanocrystallite, respectively, are proposed and examined with ab-initio local density functional method for possible applications as single quantum bits (qubits) in solid-state quantum computers. A H-1 atom encapsulated in a fully deuterated fullerene, C(sub 20)D(sub 20), forms the first model system and ab-initio calculation shows that H-1 atom is stable in atomic state at the center of the fullerene with a barrier of about 1 eV to escape. A P-31 atom positioned at the center of a diamond nanocrystallite is the second model system, and 3 1P atom is found to be stable at the substitutional site relative to interstitial sites by 15 eV, Vacancy formation energy is 6 eV in diamond so that substitutional P-31 atom will be stable against diffusion during the formation mechanisms within the nanocrystallite. The coupling between the nuclear spin and weakly bound (valance) donor electron coupling in both systems is found to be suitable for single qubit applications, where as the spatial distributions of (valance) donor electron wave functions are found to be preferentially spread along certain lattice directions facilitating two or more qubit applications. The feasibility of the fabrication pathways for both model solid-state qubit systems within practical quantum computers is discussed with in the context of our proposed solid-state qubits.

Calculation of intrinsic stresses in the diamond-like coatings produced by plasma ion deposition in modes of DC and pulse bias potentials

NASA Astrophysics Data System (ADS)

Kalinichenko, A. A.; Perepelkin, S. S.; Strel'nitskij, V. E.

2015-04-01

The formula derivation for calculation of intrinsic stress in diamond-like coatings deposited from the ion flux in modes of continuous and pulsed potentials in view of process of defects formation is given. The criterion of applicability of obtained formula allowing to determine critical parameters of the pulsed potential mode is suggested. Results of calculation of stresses in diamond-like coatings at deposition of low-energy ions C+ from filtered vacuum arc plasma are adduced. The influence of the bias potential, repetition frequency and pulse duration, on the value of intrinsic stress is discussed. Qualitative agreement of calculated stress and experimental data is stated. The important role of deposition temperature in control of intrinsic stress in deposited coating is noted.

Diamond-like nanoparticles influence on flavonoids transport: molecular modelling

NASA Astrophysics Data System (ADS)

Plastun, Inna L.; Agandeeva, Ksenia E.; Bokarev, Andrey N.; Zenkin, Nikita S.

2017-03-01

Intermolecular interaction of diamond-like nanoparticles and flavonoids is investigated by numerical simulation. Using molecular modelling by the density functional theory method, we analyze hydrogen bonds formation and their influence on IR - spectra and structure of molecular complex which is formed due to interaction between flavonoids and nanodiamonds surrounded with carboxylic groups. Enriched adamantane (1,3,5,7 - adamantanetetracarboxylic acid) is used as an example of diamond-like nanoparticles. Intermolecular forces and structure of hydrogen bonds are investigated. IR - spectra and structure parameters of quercetin - adamantanetetracarboxylic acid molecular complex are obtained by numerical simulation using the Gaussian software complex. Received data coincide well with experimental results. Intermolecular interactions and hydrogen bonding structure in the obtained molecular complex are examined. Possibilities of flavonoids interaction with DNA at the molecular level are also considered.

Multienergy gold ion implantation for enhancing the field electron emission characteristics of heterogranular structured diamond films grown on Au-coated Si substrates

NASA Astrophysics Data System (ADS)

Sankaran, K. J.; Manoharan, D.; Sundaravel, B.; Lin, I. N.

2016-09-01

Multienergy Au-ion implantation enhanced the electrical conductivity of heterogranular structured diamond films grown on Au-coated Si substrates to a high level of 5076.0 (Ω cm)-1 and improved the field electron emission (FEE) characteristics of the films to low turn-on field of 1.6 V/μm, high current density of 5.4 mA/cm2 (@ 2.65 V/μm), and high lifetime stability of 1825 min. The catalytic induction of nanographitic phases in the films due to Au-ion implantation and the formation of diamond-to-Si eutectic interface layer due to Au-coating on Si together encouraged the efficient conducting channels for electron transport, thereby improved the FEE characteristics of the films.

Formation and Evolution of the Continental Lithospheric Mantle: Perspectives From Radiogenic Isotopes of Silicate and Sulfide Inclusions in Macrodiamonds

NASA Astrophysics Data System (ADS)

Shirey, S. B.; Richardson, S. H.

2007-12-01

Silicate and sulfide inclusions that occur in diamonds comprise the oldest (>3 Ga), deepest (>140 km) samples of mantle-derived minerals available for study. Their relevance to the evolution of the continental lithosphere is clear because terrestrial macrodiamonds are confined to regions of the Earth with continental lithospheric mantle keels. The goals of analytical work on inclusions in diamond are to obtain paragenesis constraints, radiogenic ages, and initial isotopic compositions. The purpose is to place diamond formation episodes into the broader framework of the geological processes that create and modify the continental lithosphere and to relate the source of the C and N in diamond-forming fluids to understanding the Earth's C and N cycles in the Archean. Although sulfide and silicate inclusions rarely occur in the same diamond, they both can be grouped according to their geochemical similarity with the chief rock types that comprise the mantle keel: peridotite and eclogite. Silicate inclusions are classified as harzburgitic (depleted; olivine > Fo91, garnet Cr2O3 > 3 wt% and CaO from 0 to 5 wt%), lherzolitic (fertile), or eclogitic (basaltic; garnet Cr2O3 < 2 wt% and CaO from 3 to 15 wt%, clinopyroxene with higher Na2O, Al2O3, and FeO); they are amenable for trace element study by SIMS and for Sm-Nd and Rb-Sr analysis by conventional P-TIMS after grouping by mineralogical similarity. Sulfide inclusions (chiefly FeS with lesser Ni, Cu, and Co) are classified as peridotitic (Ni > 14 wt%; Os > 2 ppm) versus eclogitic (Ni < 10 wt%; Os < 200 ppb); single sulfides are amenable for S isotopic study by SIMS or TIMS, and Re-Os analysis by N-TIMS. Work on inclusions in diamonds depends on the distribution of mined, diamond-bearing kimberlites, and the generosity of mining companies because of the extreme rarity of inclusions in suites of mostly gem-quality diamonds. Most isotopic work has been on the Kaapvaal-Zimbabwe craton with lesser work on the Slave, Siberian, and Australian cratons. Sm-Nd ages on silicate suites and Re-Os ages on sulfide suites confirm diamond formation from the Mesoarchean though the Neoproterozoic. Most important are the systematics across cratons in the context of crustal geology that lead to generalities about craton evolution. Inclusion suites date mantle keels as Mesoarchean and clearly point to subduction as the major process to form the earliest continental nuclei and to amalgamate the cratons in their present form. This is evident from the elevated initial Os isotopic compositions in 3.5 Ga Slave (Panda) and 2.9 Ga Kaapvaal (Kimberley) sulfides, the low Sm/Nd and elevated initial Sr isotopic compositions of 3.4 Ga Kaapvaal (Kimberley) harzburgitic garnets, the preponderance of 2.9 Ga eclogitic sulfides in every western Kaapvaal craton locality, and the occurrence of surficial, volcanogenic S in Kaapvaal (Orapa) sulfides. The continental lithosphere was accessible to melts and fluids from the asthenosphere throughout the Proterozoic as evident from silicate and sulfide inclusion suites of 0.9 to 2.0 Ga age in every locality studied in the Kaapvaal craton. The correspondence of silicate inclusion type with current seismic velocity structure of the Kaapvaal mantle keel shows that its structure is at least Bushveld age (2 Ga) and due to compositional differences. Seismic velocity structures of continental mantle keels may be more a function of their geologic history than current temperature distribution.

Appropriate salt concentration of nanodiamond colloids for electrostatic self-assembly seeding of monosized individual diamond nanoparticles on silicon dioxide surfaces.

PubMed

Yoshikawa, Taro; Zuerbig, Verena; Gao, Fang; Hoffmann, René; Nebel, Christoph E; Ambacher, Oliver; Lebedev, Vadim

2015-05-19

Monosized (∼4 nm) diamond nanoparticles arranged on substrate surfaces are exciting candidates for single-photon sources and nucleation sites for ultrathin nanocrystalline diamond film growth. The most commonly used technique to obtain substrate-supported diamond nanoparticles is electrostatic self-assembly seeding using nanodiamond colloidal suspensions. Currently, monodisperse nanodiamond colloids, which have a narrow distribution of particle sizes centering on the core particle size (∼4 nm), are available for the seeding technique on different substrate materials such as Si, SiO2, Cu, and AlN. However, the self-assembled nanoparticles tend to form small (typically a few tens of nanometers or even larger) aggregates on all of those substrate materials. In this study, this major weakness of self-assembled diamond nanoparticles was solved by modifying the salt concentration of nanodiamond colloidal suspensions. Several salt concentrations of colloidal suspensions were prepared using potassium chloride as an inserted electrolyte and were examined with respect to seeding on SiO2 surfaces. The colloidal suspensions and the seeded surfaces were characterized by dynamic light scattering and atomic force microscopy, respectively. Also, the interaction energies between diamond nanoparticles in each of the examined colloidal suspensions were compared on the basis of the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. From these investigations, it became clear that the appropriate salt concentration suppresses the formation of small aggregates during the seeding process owing to the modified electrostatic repulsive interaction between nanoparticles. Finally, monosized (<10 nm) individual diamond nanoparticles arranged on SiO2 surfaces have been successfully obtained.

New Stability Field of Jeffbenite (ex-"TAPP"): Possibility of Super-Deep Origin

NASA Astrophysics Data System (ADS)

Anzolini, C.; Drewitt, J.; Lord, O. T.; Walter, M. J.; Nestola, F.

2016-12-01

Jeffbenite is a new tetragonal phase with garnet-like stoichiometry (Nestola et al., 2016) previously referred to as TAPP (Tetragonal Almandine-Pyrope Phase), which is found exclusively in nature as inclusions in super-deep diamonds and may provide key information about their depth of formation. Nevertheless, whether jeffbenite forms as a primary phase in the transition zone (TZ) or in the lower mantle (LM), or is the product of retrogression from high-pressure mantle phases is still controversial. At present two possibilities are proposed for its formation: 1) entrapment as a primary mineral by diamond in the upper mantle at pressures up to 13 GPa (Armstrong & Walter, 2012); 2) retrograde formation from a bridgmanite or a majoritic garnet below 13 GPa (Armstrong & Walter, 2012; Brenker et al., 2002; Harte & Hudson, 2013). The only previously experimentally determined stability field for jeffbenite is that of Armstrong & Walter (2012), which provides a maximum pressure for jeffbenite stability of 13 GPa ( 390 km) at 1700 K. This suggested that jeffbenite is a sub-lithospheric mineral, but ruled out direct incorporation of jeffbenite into diamond at the TZ-LM boundary. These results were obtained on a Ti-rich jeffbenite, which is usually found as part of composite inclusions, and not on a Ti-free jeffbenite, which occurs as single-phase inclusions in diamonds. We therefore performed new laser heated diamond-anvil cell experiments from 5 to 30 GPa on a Ti-free jeffbenite, in order to determine the role that TiO2 plays in its stability field and to determine if jeffbenite can be directly incorporated into diamond in the TZ or LM. Our preliminary results indicate that the absence of TiO2 extends the stability field of jeffbenite to higher pressures than previously determined. This work was supported by Fondazione CaRiPaRo, NERC Grant NE/M000419/1 to MJW, NERC Fellowship Grant NE/J018945/1 to OTL and ERC-2012-StG 307322 to FN. Armstrong, L.S. & Walter, M.J. (2012) Eur J Mineral, 24:587-597. Brenker, F.E., Stachel, T., Harris, J.W. (2002) Earth Planet Sci Lett, 198:1-9. Harte & Hudson (2013) Proceedings of 10th International Kimberlite Conference, 235-253. Nestola, F., Burnham, A.D., Peruzzo, L., Tauro, L., Alvaro, M., Walter, M.J., Gunter, M., Anzolini, C., Kohn, S.C. (2016) Mineral Mag, DOI: 10.1180/minmag.2016.080.059

Effect of graphite particle size and content on the formation mechanism of detonation polycrystalline diamond

NASA Astrophysics Data System (ADS)

Tong, Y.; Cao, Y.; Liu, R.; Shang, S. Y.; Huang, F. L.

2018-03-01

The formation mechanism of detonation polycrystalline diamond (DPD) generated from the detonation of a mixed RDX/graphite explosive is investigated. It is found experimentally that the DPD conversion rate decreases with both the content and the particle size of the graphite. Moreover, the particle sizes of the generated DPD powder are analyzed, which shows that, with the decrease in the graphite particle size, the mean number diameter of DPD decreases, but the mean volume diameter increases. In addition, with the help of scanning electron microscopy, it is observed that the in situ phase change occurs in the graphite particles, by which the small particles combine to form numerous large DPD particles. Based on both the experimental data and the classical ZND detonation model, we divide such a DPD synthesis process into two stages: In the first stage, the in situ phase change from graphite to diamond is dominant, supplemented by some coalescence growth at high pressure and temperature, which is affected mainly by the detonation performance of the mixed explosive under consideration. In the second stage, the graphitization of DPD caused by the residual heat is dominant, which is affected mainly by the unloading rate of the particle temperature.

Radiation Halos, a Rare Microstructure in Diamonds From the Central African Republic

NASA Astrophysics Data System (ADS)

Vicenzi, E. P.; Heaney, P. J.; Snyder, K.; Armstrong, L.

2002-05-01

The geochemical characterization of bulk diamonds and associated inclusions as a tool for determining provenance carries significant inherent limitations. Isotopic and trace element signatures are imparted within the mantle during diamond growth; hence, discriminating crystals from a particular region on the Earth's surface on this basis is difficult at best, and impossible (using current technologies) in many cases. In contrast, rare diamond characteristics may provide a partial solution for recognizing stones from a limited number of localities. Here we discuss an analysis of radiation halos in alluvially deposited polycrystalline diamonds (carbonados) from the Central African Republic (CAR). Large amounts of implanted Xe and Kr, as well as isotopic ratios of those elements consistent with fission, in carbonado strongly suggest that diamond crystallization took place in the presence of significant quantities of uranium [1]. Such ionizing radiation ultimately results in the loss of periodicity of the diamond structure. Crystallographically damaged areas produce fewer photons in cathodoluminescence microscopy, and therefore, the metamict regions resulting from point source radiation in diamond can be visualized on the scale of ~1-25 micrometers [2]. Because intermediate daughter products in the decay chain release alpha particles at differing energies, a ``bull's eye'' pattern is produced in 2-D by the point source radiation. Radiation haloes have been previously observed in carbonados and are thought to result from U deposition associated with fluids following diamond formation [3,4]. We have made a series of measurements of the apparent diameter of the largest circle within a damage halo. By comparing the statistical distribution of this dimension to the distribution expected for a series of circles resulting from random sectioning of mono-sized spheres, one can estimate whether the radiation resulted from one or more fluid pulses widely separated in time. Preliminary data are consistent with a single pulse of uranium deposition in CAR carbonado. [1] Ozima et al. 1991, Nature 351 : 472. [2] Mendelssohn et al. 1979, Diamond Research:35. [3] Milledge et al. 1998, 7th Intl. Kimberlite Conf: 589. [4] Magee 2001, Ph.D. ANU 247p.

Spontaneously Flowing Crystal of Self-Propelled Particles

NASA Astrophysics Data System (ADS)

Briand, Guillaume; Schindler, Michael; Dauchot, Olivier

2018-05-01

We experimentally and numerically study the structure and dynamics of a monodisperse packing of spontaneously aligning self-propelled hard disks. The packings are such that their equilibrium counterparts form perfectly ordered hexagonal structures. Experimentally, we first form a perfect crystal in a hexagonal arena which respects the same crystalline symmetry. Frustration of the hexagonal order, obtained by removing a few particles, leads to the formation of a rapidly diffusing "droplet." Removing more particles, the whole system spontaneously forms a macroscopic sheared flow, while conserving an overall crystalline structure. This flowing crystalline structure, which we call a "rheocrystal," is made possible by the condensation of shear along localized stacking faults. Numerical simulations very well reproduce the experimental observations and allow us to explore the parameter space. They demonstrate that the rheocrystal is induced neither by frustration nor by noise. They further show that larger systems flow faster while still remaining ordered.

Wet formation and structural characterization of quasi-hexagonal monolayers.

PubMed

Batys, Piotr; Weroński, Paweł; Nosek, Magdalena

2016-01-01

We have presented a simple and efficient method for producing dense particle monolayers with controlled surface coverage. The method is based on particle sedimentation, manipulation of the particle-substrate electrostatic interaction, and gentle mechanical vibration of the system. It allows for obtaining quasi-hexagonal structures under wet conditions. Using this method, we have produced a monolayer of 3 μm silica particles on a glassy carbon substrate. By optical microscopy, we have determined the coordinates of the particles and surface coverage of the obtained structure to be 0.82. We have characterized the monolayer structure by means of the pair-correlation function and power spectrum. We have also compared the results with those for a 2D hexagonal monolayer and monolayer generated by random sequential adsorption at the coverage 0.50. We have found the surface fractal dimension to be 2.5, independently of the monolayer surface coverage. Copyright © 2015 Elsevier Inc. All rights reserved.

Hexagonally ordered nanodots: Result of substrate rotation during oblique incidence low energy IBS

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

Chowdhury, Debasree, E-mail: debasree.chowdhury@saha.ac.in; Ghose, Debabrata, E-mail: debasree.chowdhury@saha.ac.in

The anisotropic regular patterns are often results during oblique incidence ion beam sputtering (IBS). Simultaneous substrate rotation (SR) during IBS can suppress surface roughening and removes anisotropic nature of surface pattern. Here, the evolution of Si surface morphology as result of with and without SR is studied during oblique incidence low energy Ar{sup +} sputtering. Resultant topography shows smooth surface to hexagonally ordered nanodots at different rotating conditions. Interestingly, surface roughness exhibits non-monotonic dependence on rotation frequency. The underlying mechanism for dot formation can be described within the framework of isotropic DKS equation.

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

Halevy, I.; Zamir, G; Winterrose, M

The phase stability of a commercial purity (Ti-CP), high purity (Ti-HP) and Ti-6Al-4V alloy were investigated in a diamond anvil cell up to 32 GPa and 298 K using a polychromatic X-ray beam. The Ti-CP and Ti-HP shown the same HCP (c/a {approx} 0.632) to Hexagonal (c/a {approx} 1.63) non reversible martensitic transition at about 9 GPa. The as received Ti-6Al-4V shows a very low relative volume fraction {beta}-Ti/{alpha}-Ti. No phase changes were observed in the Ti-6Al-4V alloy in the pressure range of this study. The {alpha} phase of the Ti-6Al-4V shows monotonic volume cell pressure dependence. This volume changemore » is reversible and non-hysteretic. The cell of the a phase recovered its original volume when the pressure was released.« less

Novel 3D metallic boron nitride containing only sp2 bonds

NASA Astrophysics Data System (ADS)

Wang, Hao; Zhang, Wei; Huai, Ping

2017-09-01

As the closest isoelectronic analogue of carbon, boron nitride (BN) shares a similar structure with carbon from 1D nanotubes, 2D nanosheets, and 3D diamond structures. However, most BN structures are insulators, which limits their application. In this work, under the inspiration of the sp2 hybridized carbon honeycomb, we propose a hexagonal phase of BN consisting of only sp2 bonds, which exhibits intriguingly intrinsic metallicity. First-principles calculations confirm that this phase is both thermally and dynamically stable. Moreover, the calculations on the band structure, partial density states and electron localization function suggest that the metallic behavior is attributable to the delocalized B-2p electrons, leading to second-neighbor interaction between the p z states of sp2-bonded B atoms in adjacent layers. Our findings not only enrich the BN allotrope family with 3D structures but also stimulate further experimental interest in applications of metallic BN in electronic devices.

Disproportionation of (Mg,Fe)SiO 3 perovskite in Earth's deep lower mantle

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

Zhang, L.; Meng, Y.; Yang, W.

2014-05-22

The mineralogical constitution of the Earth's mantle dictates the geophysical and geochemical properties of this region. Previous models of a perovskite-dominant lower mantle have been built on the assumption that the entire lower mantle down to the top of the D" layer contains ferromagnesian silicate [(Mg,Fe)SiO 3] with nominally 10 mole percent Fe. On the basis of experiments in laser-heated diamond anvil cells, at pressures of 95 to 101 gigapascals and temperatures of 2200 to 2400 kelvin, we found that such perovskite is unstable; it loses its Fe and disproportionates to a nearly Fe-free MgSiO 3 perovskite phase and anmore » Fe-rich phase with a hexagonal structure. This observation has implications for enigmatic seismic features beyond ~2000 kilometers depth and suggests that the lower mantle may contain previously unidentified major phases.« less

Disproportionation of (Mg,Fe)SiO3 perovskite in Earth's deep lower mantle

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

Zhang, L.; Meng, Y.; Yang, W.

2014-05-22

The mineralogical constitution of the Earth’s mantle dictates the geophysical and geochemical properties of this region. Previous models of a perovskite-dominant lower mantle have been built on the assumption that the entire lower mantle down to the top of the D'' layer contains ferromagnesian silicate [(Mg,Fe)SiO3] with nominally 10 mole percent Fe. On the basis of experiments in laser-heated diamond anvil cells, at pressures of 95 to 101 gigapascals and temperatures of 2200 to 2400 kelvin, we found that such perovskite is unstable; it loses its Fe and disproportionates to a nearly Fe-free MgSiO3 perovskite phase and an Fe-rich phasemore » with a hexagonal structure. This observation has implications for enigmatic seismic features beyond ~2000 kilometers depth and suggests that the lower mantle may contain previously unidentified major phases.« less

Evolution of diamond resorption in a silicic aqueous fluid at 1-3 GPa: Application to kimberlite emplacement and mantle metasomatism

NASA Astrophysics Data System (ADS)

Zhang, Zhihai; Fedortchouk, Yana; Hanley, Jacob J.

2015-06-01

Natural diamonds grow and partially dissolve during mantle metasomatism and undergo further resorption during the ascent to the Earth's surface in kimberlite magmas. This study uses atomic force microscopy (AFM) for quantitative characterization of diamond resorption morphology in order to provide robust constraints of the composition of kimberlitic and mantle metasomatic fluids. We performed experiments in a piston-cylinder apparatus at pressures (P) of 1-3 GPa and temperatures (T) of 1150-1400 °C to examine the impact of P, T, and silica content of an aqueous fluid on diamond dissolution. Petrographic observation and microthermometry of synthetic fluid inclusions trapped in olivine at the run conditions provide constraints on the composition and density of the fluid reacting with the diamond. Our results confirm an inverse relationship between P and T on diamond dissolution kinetics. A P increase of 1 GPa suppresses diamond oxidation rates by the same value as a T decrease by 50 °C, while the transformation rate of diamond crystal morphology from octahedron to tetrahexahedron increases with both P and T. All dissolved diamonds develop glossy surfaces, ditrigonal {111} faces, sheaf striations, and negative trigons, while circular pits only occur in aqueous fluids with low silica content (≤ 4.2 mol/kg) at 1 GPa. We identify five distinct morphological groups of trigons: two types of point-bottomed (p/b) (trumpet- and V-shaped) and three types of flat-bottomed (f/b) (trumpet-shaped, trapezoid-shaped and rounded). AFM measurements of trigons from two successive runs showed three stages of their evolution. Etch pits nucleate at defects as trumpet p/b trigons with the vertical dissolution rate (Vd) faster than the dissolution rates at the surface free of defects; they further develop by growth of the bottoms in (111) plane to create trumpet-shaped f/b trigons accompanied by decrease in Vd; and finally form trapezoid-shaped f/b trigon with constant wall angles. The diameter of f/b trigons developed in the aqueous fluids depends on the diamond weight loss and dissolution kinetics, and does not correlate with their depth. Integration of our AFM data with the theoretical model for trigon formation suggests that the change from point- to flat-bottomed trigons depends on the defect sizes and dissolution conditions. Application of our results to the diamonds from Ekati diamond Mine, Canada, suggests that variations in diamond rounding in different pipes implies variable depth of fluid exsolution; presence of circular pits on diamonds indicates predominantly aqueous fluid during the latest stages of kimberlite emplacement; and comparison to the mantle-derived morphologies on Ekati diamonds implies the importance of CO2-rich fluids and/or carbonate melts during mantle metasomatism. The constrained effect of P on diamond dissolution kinetics indicates that appreciable diamond weight loss can only happen at P < 1 GPa and therefore the conditions at the latest stages of kimberlite emplacement are very important for assessments of diamond preservation in a kimberlite pipe.

Orientation relationship between diamond and magnesiochromite inclusions

NASA Astrophysics Data System (ADS)

Alvaro, Matteo; Angel, Ross; Nimis, Paolo; Milani, Sula; Harris, Jeff; Nestola, Fabrizio

2017-04-01

The correct determination of the relative crystallographic orientations of single crystals has many applications. When single crystals undergo phase transitions, especially at high pressures, the relative orientations of the two phases yields insights into transition mechanisms (Dobson et al 2013). On the other hand, determination of the crystallographic orientations of minerals included in diamonds can provide insights into the mechanisms of their entrapment and the timing of their formation relative to the host diamond (e.g. Nestola et al. 2014, Milani et al. 2016). The reported occurrence of non-trivial orientations for some minerals in diamonds, suggesting an epitaxial relationship, has long been considered to reflect contemporaneous growth of the diamond and the inclusion (e.g. syngenesis). Correct interpretation of such orientations requires (i) a statistically significant crystallographic data set for single and multiple inclusions in a large number of diamonds, and (ii) a robust data-processing method, capable of removing ambiguities derived from the high symmetry of the diamond and the inclusion. We have developed a software to perform such processing (OrientXplot, Angel et al. 2015), starting from crystallographic orientation matrixes obtained by X-ray diffractometry or EBSD data. Previous studies of inclusions in lithospheric diamonds, by single-crystal X-ray diffraction and EBSD, indicate a wide variety in the orientations of different inclusion phases with respect to their diamond host (Futergendler & Frank-Kamenetsky 1961; Frank-Kamenetsky 1964; Wiggers de Vries et al. 2011; Nestola et al. 2014, Milani et al. 2016). For example, olivine inclusions in lithospheric diamonds from Udachnaya do not show any preferred orientations with respect to their diamond hosts, but multiple inclusions in a single diamond often show very similar orientations within few degrees. In the present work on magnesiochromite inclusions in diamonds from Udachnaya, there is a partial orientation between inclusion and host. A (111) plane of each inclusion is sub-parallel to a {111} plane of their diamond host, but with random orientations of the magnesiochromite [100], [010] and [001] relative to the diamond. In one case, where a single inclusion comprised a magnesiochromite-olivine touching pair, the magnesiochromite was oriented as noted above and the olivine showed a random orientation. The implications of these observations for the mechanisms of diamond growth will be explored and the results will be compared and combined with previous work. This work was supported by ERC starting grant "INDIMEDEA" (307322) to F. Nestola and by the MIUR-SIR grant "MILE DEEp" (RBSI140351) to M. Alvaro. References Angel R. J. et al., J. Appl. Crystallogr. 48, 1330-1334 (2015). Wiggers de Vries D.F. et al., Contrib Mineral Petr 161, 565-579 (2011). Dobson D. P. et al., Nat. Geosci. 6, 575-578 (2013). Frank-Kamenetsky V.A. The nature of structural impurities and inclusions in minerals. Leningrad, Gos. Univ. (1964) Futergendler S.I. and Frank-Kamenetsky V.A. Zap Vsesoyuzn Mineral Obs 90, 230 (1961). Nestola F. et al., Int. Geol. Rev. 56(13), 1658-1667 (2014).

Geometry and material choices govern hard-rock drilling performance of PDC drag cutters.

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

Wise, Jack LeRoy

2005-06-01

Sandia National Laboratories has partnered with industry on a multifaceted, baseline experimental study that supports the development of improved drag cutters for advanced drill bits. Different nonstandard cutter lots were produced and subjected to laboratory tests that evaluated the influence of selected design and processing parameters on cutter loads, wear, and durability pertinent to the penetration of hard rock with mechanical properties representative of formations encountered in geothermal or deep oil/gas drilling environments. The focus was on cutters incorporating ultrahard PDC (polycrystalline diamond compact) overlays (i.e., diamond tables) on tungsten-carbide substrates. Parameter variations included changes in cutter geometry, material composition,more » and processing conditions. Geometric variables were the diamond-table thickness, the cutting-edge profile, and the PDC/substrate interface configuration. Material and processing variables for the diamond table were, respectively, the diamond particle size and the sintering pressure applied during cutter fabrication. Complementary drop-impact, granite-log abrasion, linear cutting-force, and rotary-drilling tests examined the response of cutters from each lot. Substantial changes in behavior were observed from lot to lot, allowing the identification of features contributing major (factor of 10+) improvements in cutting performance for hard-rock applications. Recent field demonstrations highlight the advantages of employing enhanced cutter technology during challenging drilling operations.« less

Profiling of Current Transients in Capacitor Type Diamond Sensors

PubMed Central

Gaubas, Eugenijus; Ceponis, Tomas; Meskauskaite, Dovile; Kazuchits, Nikolai

2015-01-01

The operational characteristics of capacitor-type detectors based on HPHT and CVD diamond have been investigated using perpendicular and parallel injection of carrier domain regimes. Simulations of the drift-diffusion current transients have been implemented by using dynamic models based on Shockley-Ramo’s theorem, under injection of localized surface domains and of bulk charge carriers. The bipolar drift-diffusion regimes have been analyzed for the photo-induced bulk domain (packet) of excess carriers. The surface charge formation and polarization effects dependent on detector biasing voltage have been revealed. The screening effects ascribed to surface charge and to dynamics of extraction of the injected bulk excess carrier domain have been separated and explained. The parameters of drift mobility of the electrons μe = 4000 cm2/Vs and holes μh = 3800 cm2/Vs have been evaluated for CVD diamond using the perpendicular profiling of currents. The coefficient of carrier ambipolar diffusion Da = 97 cm2/s and the carrier recombination lifetime τR,CVD ≌ 110 ns in CVD diamond were extracted by combining analysis of the transients of the sensor current and the microwave probed photoconductivity. The carrier trapping with inherent lifetime τR,HPHT ≌ 2 ns prevails in HPHT diamond. PMID:26061200

Controlled in situ boron doping of diamond thin films using solution phase

NASA Astrophysics Data System (ADS)

Roy, M.; Dua, A. K.; Nuwad, J.; Girija, K. G.; Tyagi, A. K.; Kulshreshtha, S. K.

2006-12-01

Controlled boron doping of diamond film using nontoxic reagents is a challenge in itself. During the present study, attempts have been made to dope diamond films in situ with boron from a solution of boric acid (H3BO3) in methanol (CH3OH) using a specially designed bubbler that ensured continuous and controlled flow of vapors of boron precursors during deposition. The samples are thoroughly characterized using a host of techniques comprising of x-ray photoelectron spectroscopy, Raman, x-ray diffraction, and current-voltage measurements (I-V). Cross-sectional micro-Raman spectroscopy has been used to obtain depth profile of boron in diamond films. Boron concentration ([B]) in the films is found to vary linearly on a semilog scale with molarity (M) of H3BO3 in CH3OH. Lattice constant of our samples is smaller than the reported American society for testing and materials (ASTM) values due to oxygen incorporation and it increases with [B] in the diamond samples. Heavily boron doped samples exhibit Fano deformation of the Raman line shape and negative and/zero activation barrier in temperature dependent I-V measurements that indicate the formation of metallic phase in the samples. The present study illustrates the feasibility of safe and controlled boron doping of diamond films using a solution of H3BO3 in CH3OH over a significant range of [B] from semiconductor to metallic regime but with a little adverse effect due to unintentional but unavoidable incorporation of oxygen.

Moiré-Modulated Conductance of Hexagonal Boron Nitride Tunnel Barriers.

PubMed

Summerfield, Alex; Kozikov, Aleksey; Cheng, Tin S; Davies, Andrew; Cho, Yong-Jin; Khlobystov, Andrei N; Mellor, Christopher J; Foxon, C Thomas; Watanabe, Kenji; Taniguchi, Takashi; Eaves, Laurence; Novoselov, Kostya S; Novikov, Sergei V; Beton, Peter H

2018-06-27

Monolayer hexagonal boron nitride (hBN) tunnel barriers investigated using conductive atomic force microscopy reveal moiré patterns in the spatial maps of their tunnel conductance consistent with the formation of a moiré superlattice between the hBN and an underlying highly ordered pyrolytic graphite (HOPG) substrate. This variation is attributed to a periodc modulation of the local density of states and occurs for both exfoliated hBN barriers and epitaxially grown layers. The epitaxial barriers also exhibit enhanced conductance at localized subnanometer regions which are attributed to exposure of the substrate to a nitrogen plasma source during the high temperature growth process. Our results show clearly a spatial periodicity of tunnel current due to the formation of a moiré superlattice and we argue that this can provide a mechanism for elastic scattering of charge carriers for similar interfaces embedded in graphene/hBN resonant tunnel diodes.

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

Hemawan, Kadek W.; Gou, Huiyang; Hemley, Russell J.

Polycrystalline diamond has been synthesized on silicon substrates at atmospheric pressure, using a microwave capillary plasma chemical vapor deposition technique. The CH4/Ar plasma was generated inside of quartz capillary tubes using 2.45 GHz microwave excitation without adding H2 into the deposition gas chemistry. Electronically excited species of CN, C2, Ar, N2, CH, Hβ, and Hα were observed in the emission spectra. Raman measurements of deposited material indicate the formation of well-crystallized diamond, as evidenced by the sharp T2g phonon at 1333 cm-1 peak relative to the Raman features of graphitic carbon. Field emission scanning electron microscopy images reveal that, dependingmore » on the growth conditions, the carbon microstructures of grown films exhibit “coral” and “cauliflower-like” morphologies or well-facetted diamond crystals with grain sizes ranging from 100 nm to 10 μm.« less

Optical patterning of trapped charge in nitrogen-doped diamond

NASA Astrophysics Data System (ADS)

Dhomkar, Siddharth; Jayakumar, Harishankar; Pagliero, Daniela; Laraoui, Abdelghani; Albu, Remus; Manson, Neil; Doherty, Marcus; Henshaw, Jacob; Meriles, Carlos

The nitrogen-vacancy (NV) center in diamond is emerging as a promising platform for solid-state quantum information processing and nanoscale metrology. Of interest in these applications is the manipulation of the NV charge state, which can be attained by optical illumination. Here we use two-color optical microscopy to investigate the dynamics of NV photo-ionization, charge diffusion, and trapping in type-1b diamond. We combine fixed-point laser excitation and scanning fluorescence imaging to locally alter the concentration of negatively charged NVs and to subsequently probe the corresponding redistribution of charge. We uncover the formation of various spatial patterns of trapped charge, which we semi-quantitatively reproduce via a model of the interplay between photo-excited carriers and atomic defects in the diamond lattice. Further, by using the NV as a local probe, we map the relative fraction of positively charged nitrogen upon localized optical excitation. These observations may prove important to various technologies, including the transport of quantum information between remote NVs and the development of three-dimensional, charge-based memories. We acknowledge support from the National Science Foundation through Grant NSF-1314205.

Atomistic aspects of ductile responses of cubic silicon carbide during nanometric cutting

PubMed Central

2011-01-01

Cubic silicon carbide (SiC) is an extremely hard and brittle material having unique blend of material properties which makes it suitable candidate for microelectromechanical systems and nanoelectromechanical systems applications. Although, SiC can be machined in ductile regime at nanoscale through single-point diamond turning process, the root cause of the ductile response of SiC has not been understood yet which impedes significant exploitation of this ceramic material. In this paper, molecular dynamics simulation has been carried out to investigate the atomistic aspects of ductile response of SiC during nanometric cutting process. Simulation results show that cubic SiC undergoes sp3-sp2 order-disorder transition resulting in the formation of SiC-graphene-like substance with a growth rate dependent on the cutting conditions. The disorder transition of SiC causes the ductile response during its nanometric cutting operations. It was further found out that the continuous abrasive action between the diamond tool and SiC causes simultaneous sp3-sp2 order-disorder transition of diamond tool which results in graphitization of diamond and consequent tool wear. PMID:22078069

Atomistic aspects of ductile responses of cubic silicon carbide during nanometric cutting.

PubMed

Goel, Saurav; Luo, Xichun; Reuben, Robert L; Rashid, Waleed Bin

2011-11-11

Cubic silicon carbide (SiC) is an extremely hard and brittle material having unique blend of material properties which makes it suitable candidate for microelectromechanical systems and nanoelectromechanical systems applications. Although, SiC can be machined in ductile regime at nanoscale through single-point diamond turning process, the root cause of the ductile response of SiC has not been understood yet which impedes significant exploitation of this ceramic material. In this paper, molecular dynamics simulation has been carried out to investigate the atomistic aspects of ductile response of SiC during nanometric cutting process. Simulation results show that cubic SiC undergoes sp3-sp2 order-disorder transition resulting in the formation of SiC-graphene-like substance with a growth rate dependent on the cutting conditions. The disorder transition of SiC causes the ductile response during its nanometric cutting operations. It was further found out that the continuous abrasive action between the diamond tool and SiC causes simultaneous sp3-sp2 order-disorder transition of diamond tool which results in graphitization of diamond and consequent tool wear.

A novel electroless method to prepare a platinum electrocatalyst on diamond for fuel cell applications

NASA Astrophysics Data System (ADS)

Lyu, Xiao; Hu, Jingping; Foord, John S.; Wang, Qiang

2013-11-01

A novel electroless deposition method was demonstrated to prepare a platinum electrocatalyst on boron doped diamond (BDD) substrates without the need for pre-activation. This green method addresses the uniformity and particle size issues associated with electrodeposition and circumvents the pre-activation procedure which is necessary for conventional electroless deposition. The inert BDD substrate formed a galvanic couple with an iron wire, to overcome the activation barrier associated with conventional electroless deposition on diamond, leading to the formation of Pt nanoparticles on the electrode surface in a galvanic process coupled to a chemical process. When sodium hypophosphite was employed as the reducing agent to drive the electroless reaction Pt deposits which were contaminated with iron and phosphorus resulted. In contrast, the reducing agent ascorbic acid gave rise to high purity Pt nanoparticles. Optimal deposition conditions with respect to bath temperature, pH value and stabilizing additives are identified. Using this approach, high purity and uniformly distributed platinum nanoparticles are obtained on the diamond electrode surface, which demonstrate a high electrochemical activity towards methanol oxidation.

Optimization of Deep Drilling Performance - Development and Benchmark Testing of Advanced Diamond Product Drill Bits & HP/HT Fluids to Significantly Improve Rates of Penetration

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

Alan Black; Arnis Judzis

2005-09-30

This document details the progress to date on the OPTIMIZATION OF DEEP DRILLING PERFORMANCE--DEVELOPMENT AND BENCHMARK TESTING OF ADVANCED DIAMOND PRODUCT DRILL BITS AND HP/HT FLUIDS TO SIGNIFICANTLY IMPROVE RATES OF PENETRATION contract for the year starting October 2004 through September 2005. The industry cost shared program aims to benchmark drilling rates of penetration in selected simulated deep formations and to significantly improve ROP through a team development of aggressive diamond product drill bit--fluid system technologies. Overall the objectives are as follows: Phase 1--Benchmark ''best in class'' diamond and other product drilling bits and fluids and develop concepts for amore » next level of deep drilling performance; Phase 2--Develop advanced smart bit-fluid prototypes and test at large scale; and Phase 3--Field trial smart bit--fluid concepts, modify as necessary and commercialize products. As of report date, TerraTek has concluded all Phase 1 testing and is planning Phase 2 development.« less

The structure of ice crystallized from supercooled water

NASA Astrophysics Data System (ADS)

Murray, Benjamin

2013-03-01

The freezing of water to ice is fundamentally important to fields as diverse as cloud formation to cryopreservation. Traditionally ice was thought to exist in two well-crystalline forms: stable hexagonal ice and metastable cubic ice. It has recently been shown, using X-ray diffraction data, that ice which crystallizes homogeneously and heterogeneously from supercooled water is neither of these phases. The resulting ice is disordered in one dimension and therefore possesses neither cubic nor hexagonal symmetry and is instead composed of randomly stacked layers of cubic and hexagonal sequences. We refer to this ice as stacking-disordered ice I (ice Isd) . This result is consistent with a number of computational studies of the crystallization of water. Review of the literature reveals that almost all ice that has been identified as cubic ice in previous diffraction studies and generated in a variety of ways was most likely stacking-disordered ice I with varying degrees of stacking disorder, which raises the question of whether cubic ice exists. New data will be presented which shows significant stacking disorder (or stacking faults on the order of 1 in every 100 layers of ice Ih) in droplets which froze heterogeneously as warm as 257 K. The identification of stacking-disordered ice from heterogeneous ice nucleation supports the hypothesis that the structure of ice that initially crystallises from supercooled water is stacking-disordered ice I, independent of nucleation mechanism, but this ice can relax to the stable hexagonal phase subject to the kinetics of recrystallization. The formation and persistence of stacking disordered ice in the Earth's atmosphere will also be discussed. Funded by the European Research Council (FP7, 240449 ICE)

Biomineralized diamond-like carbon films with incorporated titanium dioxide nanoparticles improved bioactivity properties and reduced biofilm formation.

PubMed

Lopes, F S; Oliveira, J R; Milani, J; Oliveira, L D; Machado, J P B; Trava-Airoldi, V J; Lobo, A O; Marciano, F R

2017-12-01

Recently, the development of coatings to protect biomedical alloys from oxidation, passivation and to reduce the ability for a bacterial biofilm to form after implantation has emerged. Diamond-like carbon films are commonly used for implanted medical due to their physical and chemical characteristics, showing good interactions with the biological environment. However, these properties can be significantly improved when titanium dioxide nanoparticles are included, especially to enhance the bactericidal properties of the films. So far, the deposition of hydroxyapatite on the film surface has been studied in order to improve biocompatibility and bioactive behavior. Herein, we developed a new route to obtain a homogeneous and crystalline apatite coating on diamond-like carbon films grown on 304 biomedical stainless steel and evaluated its antibacterial effect. For this purpose, films containing two different concentrations of titanium dioxide (0.1 and 0.3g/L) were obtained by chemical vapor deposition. To obtain the apatite layer, the samples were soaked in simulated body fluid solution for up to 21days. The antibacterial activity of the films was evaluated by bacterial eradication tests using Staphylococcus aureus biofilm. Scanning electron microscopy, X-ray diffraction, Raman scattering spectroscopy, and goniometry showed that homogeneous, crystalline, and hydrophilic apatite films were formed independently of the titanium dioxide concentration. Interestingly, the diamond-like films containing titanium dioxide and hydroxyapatite reduced the biofilm formation compared to controls. A synergism between hydroxyapatite and titanium dioxide that provided an antimicrobial effect against opportunistic pathogens was clearly observed. Copyright © 2017 Elsevier B.V. All rights reserved.

Phase transitions of BaTi{sub 0.9}Rh{sub 0.1}O{sub 3±δ} perovskite-type oxides under reducing environments

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

Rodríguez, G.C.Mondragón, E-mail: guillermo.mondragon-rodriguez@dlr.de; Gönüllü, Y.; Ferri, Davide

2015-01-15

Highlights: • Solid solution formation BaTi{sub 0.9}Rh{sub 0.1}O{sub 3±δ} with a new wet chemical synthesis method. • Rhodium in the BaTiO{sub 3} perovskite stabilizes the hexagonal structure. • New Rh segregation mechanism for hexagonal BaTi{sub 0.9}Rh{sub 0.1}O{sub 3±δ} upon reduction. - Abstract: Perovskite-type oxides of composition BaTi{sub 0.9}Rh{sub 0.1}O{sub 3±δ} were prepared following a new chemical route that avoids the formation of hydroxyl species and precipitation, and allows the homogeneous distribution of Rh in the final mixed metal oxide. The high dispersion of Rh and the formation of the solid solution between Rh and the BaTiO{sub 3} perovskite is confirmedmore » by means of X-ray diffraction (XRD) and extended X-ray absorption fine structure spectroscopy (EXAFS). The presence of Rh stabilized the hexagonal BaTi{sub 0.9}Rh{sub 0.1}O{sub 3±δ} phase, which decomposes into barium orthotitanate (BaTi{sub 2}O{sub 4}) and metallic Rh° in reducing environment. This phase transition starts already at 700 °C and is only partially completed at 900 °C suggesting that part of the Rh present in the perovskite lattice might not be easily reduced by hydrogen. These aspects and further open questions are discussed.« less

Mixed fluid sources involved in diamond growth constrained by Sr-Nd-Pb-C-N isotopes and trace elements

NASA Astrophysics Data System (ADS)

Klein-BenDavid, Ofra; Pearson, D. Graham; Nowell, Geoff M.; Ottley, Chris; McNeill, John C. R.; Cartigny, Pierre

2010-01-01

Sub-micrometer inclusions in diamonds carry high-density fluids (HDF) from which the host diamonds have precipitated. The chemistry of these fluids is our best opportunity of characterizing the diamond-forming environment. The trace element patterns of diamond fluids vary within a limited range and are similar to those of carbonatitic/kimberlitic melts that originate from beneath the lithospheric mantle. A convecting mantle origin for the fluid is also implied by C isotopic compositions and by a preliminary Sr isotopic study (Akagi, T., Masuda, A., 1988. Isotopic and elemental evidence for a relationship between kimberlite and Zaire cubic diamonds. Nature 336, 665-667.). Nevertheless, the major element chemistry of HDFs is very different from that of kimberlites and carbonatites, varying widely and being characterized by extreme K enrichment (up to ˜ 39 wt.% on a water and carbonate free basis) and high volatile contents. The broad spectrum of major element compositions in diamond-forming fluids has been related to fluid-rock interaction and to immiscibility processes. Elemental signatures can be easily modified by a variety of mantle processes whereas radiogenic isotopes give a clear fingerprint of the time-integrated evolution of the fluid source region. Here we present the results of the first multi radiogenic-isotope (Sr, Nd, Pb) and trace element study on fluid-rich diamonds, implemented using a newly developed off-line laser sampling technique. The data are combined with N and C isotope analysis of the diamond matrix to better understand the possible sources of fluid involved in the formation of these diamonds. Sr isotope ratios vary significantly within single diamonds. The highly varied but unsupported Sr isotope ratios cannot be explained by immiscibility processes or fluid-mineral elemental fractionations occurring at the time of diamond growth. Our results demonstrate the clear involvement of a mixed fluid, with one component originating from ancient incompatible element-enriched parts of the lithospheric mantle while the trigger for releasing this fluid source was probably carbonatitic/kimberlitic melts derived from greater depths. We suggest that phlogopite mica was an integral part of the enriched lithospheric fluid source and that breakdown of this mica releases K and radiogenic Sr into a fluid phase. The resulting fluids operate as a major metasomatic agent in the sub-continental lithospheric mantle as reflected by the isotopic composition and trace element patterns of G10 garnets.

Upper mantle fluids evolution, diamond formation, and mantle metasomatism

NASA Astrophysics Data System (ADS)

Huang, F.; Sverjensky, D. A.

2017-12-01

During mantle metasomatism, fluid-rock interactions in the mantle modify wall-rock compositions. Previous studies usually either investigated mineral compositions in xenoliths and xenocrysts brought up by magmas, or examined fluid compositions preserved in fluid inclusions in diamonds. However, a key study of Panda diamonds analysed both mineral and fluid inclusions in the diamonds [1] which we used to develop a quantitative characterization of mantle metasomatic processes. In the present study, we used an extended Deep Earth Water model [2] to simulate fluid-rock interactions at upper mantle conditions, and examine the fluids and mineral assemblages together simultaneously. Three types of end-member fluids in the Panda diamond fluid inclusions include saline, rich in Na+K+Cl; silicic, rich in Si+Al; and carbonatitic, rich in Ca+Mg+Fe [1, 3]. We used the carbonatitic end-member to represent fluid from a subducting slab reacting with an excess of peridotite + some saline fluid in the host environment. During simultaneous fluid mixing and reaction with the host rock, the logfO2 increased by about 1.6 units, and the pH increased by 0.7 units. The final minerals were olivine, garnet and diamond. The Mg# of olivine decreased from 0.92 to 0.85. Garnet precipitated at an early stage, and its Mg# also decreased with reaction progress, in agreement with the solid inclusions in the Panda diamonds. Phlogopite precipitated as an intermediate mineral and then disappeared. The aqueous Ca, Mg, Fe, Si and Al concentrations all increased, while Na, K, and Cl concentrations decreased during the reaction, consistent with trends in the fluid inclusion compositions. Our study demonstrates that fluids coming from subducting slabs could trigger mantle metasomatism, influence the compositions of sub-lithospherc cratonic mantle, precipitate diamonds, and change the oxygen fugacity and pH of the upper mantle fluids. [1] Tomlinson et al. EPSL (2006); [2] Sverjensky, DA et al., GCA (2014), Huang, F, Ph. D. thesis, Johns Hopkins University, (2017); [3] Shirey et al., Rev. Mineral. Geochem. (2013)

Volatile composition of microinclusions in diamonds from the Panda kimberlite, Canada: Implications for chemical and isotopic heterogeneity in the mantle

NASA Astrophysics Data System (ADS)

Burgess, Ray; Cartigny, Pierre; Harrison, Darrell; Hobson, Emily; Harris, Jeff

2009-03-01

In order to better investigate the compositions and the origins of fluids associated with diamond growth, we have carried-out combined noble gas (He and Ar), C and N isotope, K, Ca and halogen (Cl, Br, I) determinations on fragments of individual microinclusion-bearing diamonds from the Panda kimberlite, North West Territories, Canada. The fluid concentrations of halogens and noble gases in Panda diamonds are enriched by several orders of magnitude over typical upper mantle abundances. However, noble gas, C and N isotopic ratios ( 3He/ 4He = 4-6 Ra, 40Ar/ 36Ar = 20,000-30,000, δ 13C = -4.5‰ to -6.9‰ and δ 15N = -1.2‰ to -8.8‰) are within the worldwide range determined for fibrous diamonds and similar to the mid ocean ridge basalt (MORB) source value. The high 36Ar content of the diamonds (>1 × 10 -9 cm 3/g) is at least an order of magnitude higher than any previously reported mantle sample and enables the 36Ar content of the subcontinental lithospheric mantle to be estimated at ˜0.6 × 10 -12 cm 3/g, again similar to estimates for the MORB source. Three fluid types distinguished on the basis of Ca-K-Cl compositions are consistent with carbonatitic, silicic and saline end-members identified in previous studies of diamonds from worldwide sources. These fluid end-members also have distinct halogen ratios (Br/Cl and I/Cl). The role of subducted seawater-derived halogens, originally invoked to explain some of the halogen ratio variations in diamonds, is not considered an essential component in the formation of the fluids. In contrast, it is considered that large halogen fractionation of a primitive mantle ratio occurs during fluid-melt partitioning in forming silicic fluids, and during separation of an immiscible saline fluid.

Characterization of the secondary flow in hexagonal ducts

NASA Astrophysics Data System (ADS)

Marin, O.; Vinuesa, R.; Obabko, A. V.; Schlatter, P.

2016-12-01

In this work we report the results of DNSs and LESs of the turbulent flow through hexagonal ducts at friction Reynolds numbers based on centerplane wall shear and duct half-height Reτ,c ≃ 180, 360, and 550. The evolution of the Fanning friction factor f with Re is in very good agreement with experimental measurements. A significant disagreement between the DNS and previous RANS simulations was found in the prediction of the in-plane velocity, and is explained through the inability of the RANS model to properly reproduce the secondary flow present in the hexagon. The kinetic energy of the secondary flow integrated over the cross-sectional area yz decreases with Re in the hexagon, whereas it remains constant with Re in square ducts at comparable Reynolds numbers. Close connection between the values of Reynolds stress u w ¯ on the horizontal wall close to the corner and the interaction of bursting events between the horizontal and inclined walls is found. This interaction leads to the formation of the secondary flow, and is less frequent in the hexagon as Re increases due to the 120∘ aperture of its vertex, whereas in the square duct the 90∘ corner leads to the same level of interaction with increasing Re. Analysis of turbulence statistics at the centerplane and the azimuthal variance of the mean flow and the fluctuations shows a close connection between hexagonal ducts and pipe flows, since the hexagon exhibits near-axisymmetric conditions up to a distance of around 0.15DH measured from its center. Spanwise distributions of wall-shear stress show that in square ducts the 90∘ corner sets the location of a high-speed streak at a distance zv+≃50 from it, whereas in hexagons the 120∘ aperture leads to a shorter distance of zv+≃38 . At these locations the root mean square of the wall-shear stresses exhibits an inflection point, which further shows the connections between the near-wall structures and the large-scale motions in the outer flow.

Characterization of the secondary flow in hexagonal ducts

DOE PAGES

Marin, O.; Vinuesa, R.; Obabko, A. V.; ...

2016-12-06

In this work we report the results of DNSs and LESs of the turbulent flow through hexagonal ducts at friction Reynolds numbers based on centerplane wall shear and duct half-height Re τ,c ≃ 180, 360, and 550. The evolution of the Fanning friction factor f with Re is in very good agreement with experimental measurements. A significant disagreement between the DNS and previous RANS simulations was found in the prediction of the in-plane velocity, and is explained through the inability of the RANS model to properly reproduce the secondary flow present in the hexagon. The kinetic energy of the secondarymore » flow integrated over the cross-sectional area < K > yz decreases with Re in the hexagon, whereas it remains constant with Re in square ducts at comparable Reynolds numbers. Close connection between the values of Reynolds stress uw¯ on the horizontal wall close to the corner and the interaction of bursting events between the horizontal and inclined walls is found. This interaction leads to the formation of the secondary flow, and is less frequent in the hexagon as Re increases due to the 120° aperture of its vertex, whereas in the square duct the 90° corner leads to the same level of interaction with increasing Re. Analysis of turbulence statistics at the centerplane and the azimuthal variance of the mean flow and the fluctuations shows a close connection between hexagonal ducts and pipe flows, since the hexagon exhibits near-axisymmetric conditions up to a distance of around 0.15 DH measured from its center. Spanwise distributions of wall-shear stress show that in square ducts the 90° corner sets the location of a high-speed streak at a distance z + v≃50 from it, whereas in hexagons the 120° aperture leads to a shorter distance of z + v≃38. Finally, at these locations the root mean square of the wall-shear stresses exhibits an inflection point, which further shows the connections between the near-wall structures and the large-scale motions in the outer flow.« less

Methods of nanoassembly of a fractal polymer and materials formed thereby

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

Newkome, George R; Moorefield, Charles N

2012-07-24

The invention relates to the formation of synthesized fractal constructs and the methods of chemical self-assembly for the preparation of a non-dendritic, nano-scale, fractal constructs or molecules. More particularly, the invention relates to fractal constructs formed by molecular self-assembly, to create synthetic, nanometer-scale fractal shapes. In an embodiment, a nanoscale Sierpinski hexagonal gasket is formed. This non-dendritic, perfectly self-similar fractal macromolecule is comprised of bisterpyridine building blocks that are bound together by coordination to 36 Ru and 6 Fe ions to form a nearly planar array of increasingly larger hexagons around a hollow center.

Methods of nanoassembly of a fractal polymer and materials formed thereby

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

Newkome, George R; Moorefield, Charles N

2014-09-23

The invention relates to the formation of synthesized fractal constructs and the methods of chemical self-assembly for the preparation of a non-dendritic, nano-scale, fractal constructs or molecules. More particularly, the invention relates to fractal constructs formed by molecular self-assembly, to create synthetic, nanometer-scale fractal shapes. In an embodiment, a nanoscale Sierpinski hexagonal gasket is formed. This non-dendritic, perfectly self-similar fractal macromolecule is comprised of bisterpyridine building blocks that are bound together by coordination to (36) Ru and (6) Fe ions to form a nearly planar array of increasingly larger hexagons around a hollow center.

Diamond like carbon nanocomposites with embedded metallic nanoparticles

NASA Astrophysics Data System (ADS)

Tamulevičius, Sigitas; Meškinis, Šarūnas; Tamulevičius, Tomas; Rubahn, Horst-Günter

2018-02-01

In this work we present an overview on structure formation, optical and electrical properties of diamond like carbon (DLC) based metal nanocomposites deposited by reactive magnetron sputtering and treated by plasma and laser ablation methods. The influence of deposition mode and other technological conditions on the properties of the nanosized filler, matrix components and composition were studied systematically in relation to the final properties of the nanocomposites. Applications of the nanocomposites in the development of novel biosensors combining resonance response of wave guiding structures in DLC based nanocomposites as well as plasmonic effects are also presented.

Cubic ice and large humidity with respect to ice in cold cirrus clouds

NASA Astrophysics Data System (ADS)

Bogdan, A.; Loerting, T.

2009-04-01

Recently several studies have reported about the possible formation of cubic ice in upper-tropospheric cirrus ice clouds and its role in the observed elevated relative humidity with respect to hexagonal ice, RHi, within the clouds. Since cubic ice is metastable with respect to stable hexagonal ice, its vapour pressure is higher. A key issue in determining the ratio of vapour pressures of cubic ice Pc and hexagonal ice Ph is the enthalpy of transformation from cubic to hexagonal ice Hc→h. By dividing the two integrated forms of the Clausius-Clapeyron equation for cubic ice and hexagonal ice, one obtains the relationship (1): ln Pc-- ln P*c-=--(Hc→h--) Ph P*h R 1T-- 1T* (1) from which the importance of Hc→h is evident. In many literature studies the approximation (2) is used: ln Pc-= Hc-→h. Ph RT (2) Using this approximated form one can predict the ratio of vapour pressures by measuring Hc→h. Unfortunately, the measurement of Hc→h is difficult. First, the enthalpy difference is very small, and the transition takes place over a broad temperature range, e.g., between 230 K and 260 K in some of our calorimetry experiments. Second, cubic ice (by contrast to hexagonal ice) can not be produced as a pure crystal. It always contains hexagonal stacking faults, which are evidenced by the (111)-hexagonal Bragg peak in the powder diffractogram. If the number of hexagonal stacking faults in cubic ice is high, then one could even consider this material as hexagonal ice with cubic stacking faults. Using the largest literature value of the change of enthalpy of transformation from cubic to hexagonal ice, Hc→h ? 160 J/mol, Murphy and Koop (2005) calculated that Pc would be ~10% higher than that of hexagonal ice Phat 180 K - 190 K, which agrees with the measurements obtained later by Shilling et al. (2006). Based on this result Shilling et al. concluded that "the formation of cubic ice at T < 202 K may significantly contribute to the persistent in-cloud water supersaturations" in the upper-tropospheric cold cirrus clouds. Using instead the value of Hc→h ? 50 J/mol (Handa et al., 1986; Mayer and Hallbrucker, 1987) the calculation gives that Pc is only ~3% larger than that of Ph. Recently it has been reported that emulsified water droplets freeze to cubic ice when being cooled at a rate of 10 K/min (Murray and Bertram, 2006,). We prepared emulsified droplets using the same emulsification technique and studied them with a differential scanning calorimeter (DSC) between 278 and 180 K using a scanning rate of 10 K/min. During the warming of the samples we observed a very broad, tiny exothermal peak approximately between 230 and 260 K. Kohl et al. (2000) observed exothermal peak at ~230 K during the warming at 30 K/min of several samples of hyperquenched glassy water (HGW) prepared at temperature between 130 and 190 K. They attributed this peak to the cubic-to-hexagonal ice transition and estimated Hc→h to be between ~33 and 75 J/mol. Johari (2005) used the value of Hc→h ? 37 J/mol. Assuming that in our case the broad peak between 230 and 260 K is also due to the cubic-to-hexagonal ice transition we obtained approximately between 10 and 25 J/mol for Hc→h. This low enthalpy of transformation suggests that cubic ice in the atmosphere contains many hexagonal stacking faults. Using these values of Hc→h for cubic ice as produced at atmospheric cooling rates, the above mentioned formula gives that Pc is larger than that of Ph only by ~1%. We, therefore, suggest that the difference in the water vapor pressures between ice Ic and ice Ih is small and does not play a significant role in the elevation of RHi in cold cirrus clouds. Murphy, D. M., and T. Koop (2005), Q. J. R. Meteorol. Soc. 131, 1539-1565. Shilling, J. E. et al. (2006). Geophys. Res. Lett. 33, L17801, doi:1029/2006GL026671. Handa, P. Y., D. D. Klug, and E. Whalley (1986). J. Chem. Phys. 84, 7009-7010. Mayer, E., and A. Hallbrucker (1987), Nature, 325, 601-602. Murray, B. J. and A. K. Bertram (2006), Phys. Chem. Chem. Phys. 8, 186-192. Kohl, I., E. Mayer, and A. Hallbrucker (2000), Phys. Chem. Chem. Phys. 2, 1579-1586. G. P. Johari, (2005), J. Chem. Phys. 122, 194504.

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

Gou, Huiyang; Hemley, Russell J.; Hemawan, Kadek W.

Polycrystalline diamond has been successfully synthesized on silicon substrates at atmospheric pressure using a microwave capillary plasma chemical vapor deposition technique. The CH 4/Ar plasma was generated inside of quartz capillary tubes using 2.45 GHz microwave excitation without adding H2 into the deposition gas chemistry. Electronically excited species of CN, C 2, Ar, N 2, CH, H β and H α were observed in emission spectra. Raman measurements of deposited material indicate the formation of well-crystallized diamond, as evidenced by the sharp T 2g phonon at 1333 cm -1 peak relative to the Raman features of graphitic carbon. Furthermore, fieldmore » emission scanning electron microscopy (SEM) images reveal that, depending on the on growth conditions, the carbon microstructures of grown films exhibit “coral” and “cauliflower-like” morphologies or well-facetted diamond crystals with grain sizes ranging from 100 nm to 10 μm.« less

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

Hemawan, Kadek W.; Gou, Huiyang; Hemley, Russell J.

Polycrystalline diamond has been synthesized on silicon substrates at atmospheric pressure, using a microwave capillary plasma chemical vapor deposition technique. The CH{sub 4}/Ar plasma was generated inside of quartz capillary tubes using 2.45 GHz microwave excitation without adding H{sub 2} into the deposition gas chemistry. Electronically excited species of CN, C{sub 2}, Ar, N{sub 2}, CH, H{sub β}, and H{sub α} were observed in the emission spectra. Raman measurements of deposited material indicate the formation of well-crystallized diamond, as evidenced by the sharp T{sub 2g} phonon at 1333 cm{sup −1} peak relative to the Raman features of graphitic carbon. Field emission scanningmore » electron microscopy images reveal that, depending on the growth conditions, the carbon microstructures of grown films exhibit “coral” and “cauliflower-like” morphologies or well-facetted diamond crystals with grain sizes ranging from 100 nm to 10 μm.« less

Formation of diamond nanoparticle thin films by electrophoretic deposition

NASA Astrophysics Data System (ADS)

Goto, Yosuke; Ohishi, Fujio; Tanaka, Kuniaki; Usui, Hiroaki

2016-03-01

Thin films of diamond nanoparticles were prepared by electrophoretic deposition (EPD) using 0.5 wt % dispersions in water, ethanol, and 2-propanol. The film growth rate increased with increasing voltage applied to the electrodes. However, an excessive increase in voltage caused the degradation of film morphology. The optimum voltage was 4 V with an electrode separation of 5 mm. The film growth rate was higher in organic solvents than in water. The deposited film had a smooth surface with an average surface roughness comparable to the size of primary particles of the source material. It is notable that the EPD films had a considerably higher physical stability than spin-coated and cast films. The stability was further improved by thermally annealing the films. IR analysis revealed that the diamond nanoparticles have carboxy and amino groups on their surfaces. It is considered that the stability of the EPD films originate from a chemical reaction between these functional groups.

Silicon Sheet Growth Development for the Large Area Sheet Task of the Low Cost Solar Array Project. Heat Exchanger Method - Ingot Casting Fixed Abrasive Method - Multi-Wire Slicing

NASA Technical Reports Server (NTRS)

Schmid, F.; Khattak, C. P.

1978-01-01

Solar cells fabricated from HEM cast silicon yielded up to 15% conversion efficiencies. This was achieved in spite of using unpurified graphite parts in the HEM furnace and without optimization of material or cell processing parameters. Molybdenum retainers prevented SiC formation and reduced carbon content by 50%. The oxygen content of vacuum cast HEM silicon is lower than typical Czochralski grown silicon. Impregnation of 45 micrometers diamonds into 7.5 micrometers copper sheath showed distortion of the copper layer. However, 12.5 micrometers and 15 micrometers copper sheath can be impregnated with 45 micrometers diamonds to a high concentration. Electroless nickel plating of wires impregnated only in the cutting edge showed nickel concentration around the diamonds. This has the possibility of reducing kerf. The high speed slicer fabricated can achieve higher speed and longer stroke with vibration isolation.

Polygon patterns on Europa

NASA Technical Reports Server (NTRS)

Smalley, I. J.

1981-01-01

The formation of polygon patterns in the development of crack networks in cooling basalt flows and similar contracting systems, and under natural conditions in an essentially unbounded basalt flow, are analyzed, and the characteristics of hexagonal and pentagonal patterns in isotropic stress fields are discussed.

Identification of Clathrate Hydrates, Hexagonal Ice, Cubic Ice, and Liquid Water in Simulations: the CHILL+ Algorithm.

PubMed

Nguyen, Andrew H; Molinero, Valeria

2015-07-23

Clathrate hydrates and ice I are the most abundant crystals of water. The study of their nucleation, growth, and decomposition using molecular simulations requires an accurate and efficient algorithm that distinguishes water molecules that belong to each of these crystals and the liquid phase. Existing algorithms identify ice or clathrates, but not both. This poses a challenge for cases in which ice and hydrate coexist, such as in the synthesis of clathrates from ice and the formation of ice from clathrates during self-preservation of methane hydrates. Here we present an efficient algorithm for the identification of clathrate hydrates, hexagonal ice, cubic ice, and liquid water in molecular simulations. CHILL+ uses the number of staggered and eclipsed water-water bonds to identify water molecules in cubic ice, hexagonal ice, and clathrate hydrate. CHILL+ is an extension of CHILL (Moore et al. Phys. Chem. Chem. Phys. 2010, 12, 4124-4134), which identifies hexagonal and cubic ice but not clathrates. In addition to the identification of hydrates, CHILL+ significantly improves the detection of hexagonal ice up to its melting point. We validate the use of CHILL+ for the identification of stacking faults in ice and the nucleation and growth of clathrate hydrates. To our knowledge, this is the first algorithm that allows for the simultaneous identification of ice and clathrate hydrates, and it does so in a way that is competitive with respect to existing methods used to identify any of these crystals.

Low resolution crystal structure of Arenicola erythrocruorin: influence of coiled coils on the architecture of a megadalton respiratory protein.

PubMed

Royer, William E; Omartian, Michael N; Knapp, James E

2007-01-05

Annelid erythrocruorins are extracellular respiratory complexes assembled from 180 subunits into hexagonal bilayers. Cryo-electron microscopic experiments have identified two different architectural classes. In one, designated type I, the vertices of the two hexagonal layers are partially staggered, with one hexagonal layer rotated by about 16 degrees relative to the other layer, whereas in the other class, termed type II, the vertices are essentially eclipsed. We report here the first crystal structure of a type II erythrocruorin, that from Arenicola marina, at 6.2 A resolution. The structure reveals the presence of long continuous triple-stranded coiled-coil "spokes" projecting towards the molecular center from each one-twelfth unit; interdigitation of these spokes provides the only contacts between the two hexagonal layers of the complex. This arrangement contrasts with that of a type I erythrocruorin from Lumbricus terrestris in which the spokes are broken into two triple-stranded coiled coils with a disjointed connection. The disjointed connection allows formation of a more compact structure in the type I architecture, with the two hexagonal layers closer together and additional extensive contacts between the layers. Comparison of sequences of the coiled-coil regions of various linker subunits shows that the linker subunits from type II erythrocruorins possess continuous heptad repeats, whereas a sequence gap places these repeats out of register in the type I linker subunits, consistent with a disjointed coiled-coil arrangement.

Carbonate Mineral Assemblages as Inclusions in Yakutian Diamonds: TEM Verifications

NASA Astrophysics Data System (ADS)

Logvinova, A. M.; Wirth, R.; Sobolev, N. V.; Taylor, L. A.

2014-12-01

Carbonate mineral inclusions are quite rare in diamonds from the upper mantle, but are evidence for a carbonate abundance in the mantle. It is believed that such carbonatitic inclusions originated from high-density fluids (HDFs) that were enclosed in diamond during its growth. Using TEM and EPMA, several kinds of carbonate inclusions have been identified in Yakutian diamonds : aragonite, dolomite, magnesite, Ba-, Sr-, and Fe-rich carbonates. Most of them are represented by multi-phase inclusions of various chemically distinct carbonates, rich in Ca, Mg, and K and associated with minor amounts of silicate, oxide, saline, and volatile phases. Volatiles, leaving some porosity, played a significant role in the diamond growth. A single crystal of aragonite (60μm) is herein reported for the first time. This inclusion is located in the center of a diamond from the Komsomolskaya pipe. Careful CL imaging reveals the total absence of cracks around the aragonite inclusion - i.e., closed system. This inclusion has been identified by X-ray diffraction and microprobe analysis. At temperatures above 1000 0C, aragonite is only stable at high pressures of 5-6 GPa. Inside this aragonite, we observed nanocrystalline inclusions of titanite, Ni-rich sulfide, magnetite, water-bearing Mg-silicate, and fluid bubbles. Dolomite is common in carbonate multi-phase inclusions in diamonds from the Internatsionalnaya, Yubileinaya, and Udachnaya kimberlite pipes. Alluvial diamonds of the northeastern Siberian Platform are divided into two groups based on the composition of HDFs: 1) Mg-rich multi-phase inclusions (60% magnesite + dolomite + Fe-spinel + Ti-silicate + fluid bubbles); and 2) Ca-rich multi-phase inclusions (Ca,Ba-, Ca,Sr-, Ca,Fe-carbonates + Ti-silicate + Ba-apatite + fluid bubbles). High-density fluids also contain K. Volatiles in the fluid bubbles are represented by water, Cl, F, S, CO2, CH4, and heavy hydrocarbons. Origin of the second group of HDFs may be related to the non-silicate carbonatitic melt. We consider the primary hydrous, Сa-rich and Mg-poor carbonate melts as having formed in subducted oceanic crust. Variations of carbonate-inclusion compositions among diamonds indicate the variability in the source media during the formation of diamond and may be the result of metasomatic interaction with host rocks.

Accelerated aggregation of donor nitrogen in diamond containing NV centers

NASA Astrophysics Data System (ADS)

Lobanov, Sergey; Vins, Victor; Yelisseev, Alexander; Afonin, Dmitry; Blinkov, Alexander; Maximov, Yuriy

2010-05-01

The aggregation of donor nitrogen (C centers) into nitrogen pairs (A centers) is considered to be a second-order chemical reaction and the kinetics of this reaction can be written as follows: Kt = 1-- -1- Ct C0 where K is the aggregation rate constant that depends exponentially on temperature and activation energy K = Aexp (- Ea-kT ) and C0 and CT are C center concentrations before and after the aggregation. The activation energy Ea in natural diamonds is equal to 5±0.3 eV. However, it was shown by Vins (2004) that Ea varied in synthetic diamonds depending on Ni concentration from 3 to 6 eV; and in synthetic diamonds containing cobalt the activation energy exceeded 4 eV. The aggregation rate of C centers also increased dramatically in diamonds irradiated with high-energy electrons (Collins, 1980). An HPHT diamond single crystal grown in the Fe-Co-C system using the TGG method was studied. The initial C center concentration determined from the intensity of the 1130 cm-1 IR absorption band was equal to 118 ppm. In order to determine the influence of NV centers on the activation energy of aggregation, the crystal was at first irradiated with high-energy electrons (3MeV, 2×1018cm-2) and annealed in a quartz ampoule in vacuum (8000C, 2 hrs). This led to the formation of over 5 ppm of NV centers. After that the sample was annealed at high temperatures in the argon flow (15300C, 30 minutes). The IR absorption spectra revealed an

Influence of molecular weight on the phase behavior and structure formation of branched side-chain hairy-rod polyfluorene in bulk phase

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

Knaapila, M.; Lyons, B.P.; Foreman, J.P.

We report on an experimental study of the self-organization and phase behavior of hairy-rod {pi}-conjugated branched side-chain polyfluorene, poly[9,9-bis(2-ethylhexyl)-fluorene-2,7-diyl] - i.e., poly[2,7-(9,9-bis(2-ethylhexyl)fluorene] (PF2/6) - as a function of molecular weight (M{sub n}). The results have been compared to those of phenomenological theory. Samples for which M{sub n}=3-147 kg/mol were used. First, the stiffness of PF2/6, the assumption of the theory, has been probed by small-angle neutron scattering in solution. Thermogravimetry has been used to show that PF2/6 is thermally stable over the conditions studied. Second, the existence of nematic and hexagonal phases has been phenomenologically identified for lower and highermore » M{sub n} (LMW, M{sub n}M{sub n}{sup *}) regimes, respectively, based on free-energy argument of nematic and hexagonal hairy rods and found to correspond to the experimental x-ray diffraction (XRD) results for PF2/6. By using the lattice parameters of PF2/6 as an experimental input, the nematic-hexagonal transition has been predicted in the vicinity of glassification temperature (T{sub g}) of PF2/6. Then, by taking the orientation parts of the free energies into account the nematic-hexagonal transition has been calculated as a function of temperature and M{sub n} and a phase diagram has been formed. Below T{sub g} of 80 deg. C only (frozen) nematic phase is observed for M{sub n}M{sub n}*. The nematic-hexagonal transition upon heating is observed for the HMW regime depending weakly on M{sub n}, being at 140-165 deg. C for M{sub n}>M{sub n}*. Third, the phase behavior and structure formation as a function of M{sub n} have been probed using powder and fiber XRD and differential scanning calorimetry and reasonable semiquantitative agreement with theory has been found for M{sub n}{>=}3 kg/mol. Fourth, structural characteristics are widely discussed. The nematic phase of LMW materials has been observed to be denser than high-temperature nematic phase of HMW compounds. The hexagonal phase has been found to be paracrystalline in the (ab0) plane but a genuine crystal meridionally. We also find that all these materials including the shortest 10-mer possess the formerly observed rigid five-helix hairy-rod molecular structure.« less

Synthesis, characterization and photocatalytic activity of magnetically separable hexagonal Ni/ZnO nanostructure

NASA Astrophysics Data System (ADS)

Senapati, Samarpita; Srivastava, Suneel K.; Singh, Shiv B.

2012-09-01

The hexagonal zinc oxide coated nickel (Ni/ZnO) nanostructure photocatalyst has successfully been prepared by the reduction of nickel chloride hexahydrate using hydrazine hydrate through the solvothermal process at 140 °C followed by surface modification of the product by the reflux method at 110 °C for 1 h. The X-ray diffraction (XRD) pattern showed that the `as prepared' sample consists of face centered cubic Ni and hexagonal wurtzite ZnO without any traces of impurity. Field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) images confirmed the formation of nickel nanoparticles under solvothermal conditions. These nickel nanoparticles, when subjected to reflux, formed the hexagonal zinc oxide coated nickel nanostructure. Fourier transform infrared (FTIR) spectra, photoluminescence (PL) and Raman studies also confirmed the presence of zinc oxide in the hybrid nanostructure. The growth mechanism for the development of the hexagonal zinc oxide coated nickel (Ni/ZnO) nanostructure has also been proposed. The appearance of the hysteresis loop, in the as-prepared Ni/ZnO hybrid nanostructure, demonstrated its ferromagnetic character at room temperature. The hexagonal Ni/ZnO nanostructure also acts as an efficient photocatalyst in the degradation of methylene blue under ultraviolet light irradiation. It is observed that the catalytic efficiency of the hybrid nanocatalyst is better compared to pure zinc oxide. Most importantly, the Ni/ZnO catalyst could also be easily separated, simply by applying an external magnetic field, and reused.The hexagonal zinc oxide coated nickel (Ni/ZnO) nanostructure photocatalyst has successfully been prepared by the reduction of nickel chloride hexahydrate using hydrazine hydrate through the solvothermal process at 140 °C followed by surface modification of the product by the reflux method at 110 °C for 1 h. The X-ray diffraction (XRD) pattern showed that the `as prepared' sample consists of face centered cubic Ni and hexagonal wurtzite ZnO without any traces of impurity. Field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) images confirmed the formation of nickel nanoparticles under solvothermal conditions. These nickel nanoparticles, when subjected to reflux, formed the hexagonal zinc oxide coated nickel nanostructure. Fourier transform infrared (FTIR) spectra, photoluminescence (PL) and Raman studies also confirmed the presence of zinc oxide in the hybrid nanostructure. The growth mechanism for the development of the hexagonal zinc oxide coated nickel (Ni/ZnO) nanostructure has also been proposed. The appearance of the hysteresis loop, in the as-prepared Ni/ZnO hybrid nanostructure, demonstrated its ferromagnetic character at room temperature. The hexagonal Ni/ZnO nanostructure also acts as an efficient photocatalyst in the degradation of methylene blue under ultraviolet light irradiation. It is observed that the catalytic efficiency of the hybrid nanocatalyst is better compared to pure zinc oxide. Most importantly, the Ni/ZnO catalyst could also be easily separated, simply by applying an external magnetic field, and reused. Electronic supplementary information (ESI) available: Fig. S1 Ni/ZnO hybrid nanostructure prepared using (a) 0.195 and (b) 0.25 M [Zn2+] at 90 °C Fig. S2 FTIR spectra of nickel nanoparticles prepared at 140 °C (a), and Ni/ZnO hybrid nanostructure prepared using (b) 0.063, (c) 0.125, (d) 0.195 and (e) 0.25 M [Zn2+]; Fig. S3 Raman spectra of Ni/ZnO nanostructure prepared using (a) 0.063, (b) 0.125, (c) 0.195 and (d) 0.25 M [Zn2+]; Fig. S4 Room temperature PL spectra of (a) ZnO and (b) Ni/ZnO nanostructure prepared using 0.25 M [Zn2+]. See DOI: 10.1039/c2nr31831h

Magnetic properties of point defects in proton irradiated diamond

NASA Astrophysics Data System (ADS)

Makgato, T. N.; Sideras-Haddad, E.; Ramos, M. A.; García-Hernández, M.; Climent-Font, A.; Zucchiatti, A.; Muñoz-Martin, A.; Shrivastava, S.; Erasmus, R.

2016-09-01

We investigate the magnetic properties of ultra-pure type-IIa diamond following irradiation with proton beams of ≈1-2 MeV energy. SQUID magnetometry indicate the formation of Curie type paramagnetism according to the Curie law. Raman and Photoluminescence spectroscopy measurements show that the primary structural features created by proton irradiation are the centers: GR1, ND1, TR12 and 3H. The Stopping and Range of Ions in Matter (SRIM) Monte Carlo simulations together with SQUID observations show a strong correlation between vacancy production, proton fluence and the paramagnetic factor. At an average surface vacancy spacing of ≈1-1.6 nm and bulk (peak) vacancy spacing of ≈0.3-0.5 nm Curie paramagnetism is induced by formation of ND1 centres with an effective magnetic moment μeff~(0.1-0.2)μB. No evidence of long range magnetic ordering is observed in the temperature range 4.2-300 K.

Carbon solids in oxygen-deficient explosives (LA-UR-13-21151)

NASA Astrophysics Data System (ADS)

Peery, Travis

2013-06-01

The phase behavior of excess carbon in oxygen-deficient explosives has a significant effect on detonation properties and product equations of state. Mixtures of fuel oil in ammonium nitrate (ANFO) above a stoichiometric ratio demonstrate that even small amounts of graphite, on the order of 5% by mole fraction, can substantially alter the Chapman-Jouget (CJ) state properties, a central ingredient in modeling the products equation of state. Similar effects can be seen for Composition B, which borders the carbon phase boundary between graphite and diamond. Nano-diamond formation adds complexity to the product modeling because of surface adsorption effects. I will discuss these carbon phase issues in our equation of state modeling of detonation products, including our statistical mechanics description of carbon clustering and surface chemistry to properly treat solid carbon formation. This work is supported by the Advanced Simulation and Computing Program, under the NNSA.

Synthesis of ultrasmooth nanostructured diamond films by microwave plasma chemical vapor deposition using a He/H(2)/CH(4)/N(2) gas mixture.

PubMed

Chowdhury, S; Hillman, Damon A; Catledge, Shane A; Konovalov, Valery V; Vohra, Yogesh K

2006-10-01

Ultrasmooth nanostructured diamond (USND) films were synthesized on Ti-6Al-4V medical grade substrates by adding helium in H(2)/CH(4)/N(2) plasma and changing the N(2)/CH(4) gas flow from 0 to 0.6. We were able to deposit diamond films as smooth as 6 nm (root-mean-square), as measured by an atomic force microscopy (AFM) scan area of 2 μm(2). Grain size was 4-5 nm at 71% He in (H(2) + He) and N(2)/CH(4) gas flow ratio of 0.4 without deteriorating the hardness (~50-60 GPa). The characterization of the films was performed with AFM, scanning electron microscopy, x-ray diffraction (XRD), Raman spectroscopy, and nanoindentation techniques. XRD and Raman results showed the nanocrystalline nature of the diamond films. The plasma species during deposition were monitored by optical emission spectroscopy. With increasing N(2)/CH(4) feedgas ratio (CH(4) was fixed) in He/H(2)/CH(4)/N(2) plasma, a substantial increase of CN radical (normalized by Balmer H(α) line) was observed along with a drop in surface roughness up to a critical N(2)/CH(4) ratio of 0.4. The CN radical concentration in the plasma was thus correlated to the formation of ultrasmooth nanostructured diamond films.

Plasma boriding of a cobalt-chromium alloy as an interlayer for nanostructured diamond growth

NASA Astrophysics Data System (ADS)

Johnston, Jamin M.; Jubinsky, Matthew; Catledge, Shane A.

2015-02-01

Chemical vapor deposited (CVD) diamond coatings can potentially improve the wear resistance of cobalt-chromium medical implant surfaces, but the high cobalt content in these alloys acts as a catalyst to form graphitic carbon. Boriding by high temperature liquid baths and powder packing has been shown to improve CVD diamond compatibility with cobalt alloys. We use the microwave plasma-enhanced (PE) CVD process to deposit interlayers composed primarily of the borides of cobalt and chromium. The use of diborane (B2H6) in the plasma feedgas allows for the formation of a robust boride interlayer for suppressing graphitic carbon during subsequent CVD of nano-structured diamond (NSD). This metal-boride interlayer is shown to be an effective diffusion barrier against elemental cobalt for improving nucleation and adhesion of NSD coatings on a CoCrMo alloy. Migration of elemental cobalt to the surface of the interlayer is significantly reduced and undetectable on the surface of the subsequently-grown NSD coating. The effects of PECVD boriding are compared for a range of substrate temperatures and deposition times and are evaluated using glancing-angle X-ray diffraction (XRD), cross-sectional scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), and micro-Raman spectroscopy. Boriding of CoCrMo results in adhered nanostructured diamond coatings with low surface roughness.

Transient photoresponse of nitrogen-doped ultrananocrystalline diamond electrodes in saline solution

NASA Astrophysics Data System (ADS)

Ahnood, Arman; Simonov, Alexandr N.; Laird, Jamie S.; Maturana, Matias I.; Ganesan, Kumaravelu; Stacey, Alastair; Ibbotson, Michael R.; Spiccia, Leone; Prawer, Steven

2016-03-01

Beyond conventional electrically-driven neuronal stimulation methods, there is a growing interest in optically-driven approaches. In recent years, nitrogen-doped ultrananocrystalline diamond (N-UNCD) has emerged as a strong material candidate for use in electrically-driven stimulation electrodes. This work investigates the electrochemical activity of N-UNCD in response to pulsed illumination, to assess its potential for use as an optically-driven stimulation electrode. Whilst N-UNCD in the as-grown state exhibits a weak photoresponse, the oxygen plasma treated film exhibits two orders of magnitude enhancement in its sub-bandgap open circuit photovoltage response. The enhancement is attributed to the formation of a dense network of oxygen-terminated diamond nanocrystals at the N-UNCD surface. Electrically connected to the N-UNCD bulk via sub-surface graphitic grain boundaries, these diamond nanocrystals introduce a semiconducting barrier between the sub-surface graphitic semimetal and the electrolyte solution, leading to a photovoltage under irradiation with wavelengths of λ = 450 nm and shorter. Within the safe optical exposure limit of 2 mW mm-2, charge injection capacity of 0.01 mC cm-2 is achieved using a 15 × 15 μm electrode, meeting the requirements for extracellular and intercellular stimulation. The nanoscale nature of processes presented here along with the diamond's biocompatibility and biostability open an avenue for the use of oxygen treated N-UNCD as optically driven stimulating electrodes.

Additives and solvents-induced phase and morphology modification of NaYF{sub 4} for improving up-conversion emission

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

Zhuang, Jianle, E-mail: zhuangjianle@126.com; MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275; Yang, Xianfeng

Both cubic and hexagonal NaYF{sub 4} were synthesized in different reaction systems via hydro/solvo-thermal route. The effects of reaction temperature, solvents, and additives on the synthesis of NaYF{sub 4} have been studied in detail. It has been shown that phase transformation from cubic NaYF{sub 4} to hexagonal NaYF{sub 4} always occurred. The sequence of the ability for inducing the phase transformation was ethanol>H{sub 2}O>acetic acid. It is found that ethanol can not only facilitate the formation of hexagonal NaYF{sub 4} but also control the growth of the crystal. This is quite unusual for the growth of H-NaYF{sub 4}. The up-conversionmore » emission properties of Yb/Er co-doped NaYF{sub 4} have also been investigated and the results demonstrated some general principles for improving up-conversion emission. - Graphical abstract: Additives and solvents can induce the phase transformation of NaYF{sub 4}, typically the use of organic sodium salt and ethanol. - Highlights: • The effect of additives and solvents on the synthesis of NaYF{sub 4} was studied in detail. • Ethanol can facilitate the formation of H-NaYF{sub 4} while acetic acid restrain it. • Three general principles for improving up-conversion emission were summarized.« less

Isotopic Characterization of Diamond Growth in Fluids

NASA Astrophysics Data System (ADS)

Bureau, Hélène; Remusat, Laurent; Esteve, Imène; Pinti, Daniele; Cartigny, Pierre

2017-04-01

Trapping inclusions in diamonds has been used as a diagnostic to constrain diamond growth media (e.g. Navon et al., 1994; Weiss et al., 2015) in the Earth's upper mantle. Experimental works now generate inclusion-bearing diamonds from seeds in mixtures of carbonates, graphite, and silicates in the presence of excess of pure water or saline fluids (H2O-NaCl) and investigate in more details the conditions of natural diamond growth (Bureau et al., 2012; 2016). Experiments were carried at conditions compatible with the Earth's geotherm between 6-7 GPa (1300-1675°C) in multi-anvil presses at the Bayerisches Geoinstitut, Bayreuth from a few hours two a few days. Results show that within the timescale of the experiments diamond growth occurs on seeds if water and alkali-bearing carbonates are present. We show that water promotes fast diamond growth, which is favorable to the formation of inclusions. Thin sections of a few diamond seeds containing exposed inclusions were prepared using a Focus Ion Beam (about 2 to 5 µm thickness). These sections were deposited on silicon wafers and gold coated for micron-scale determination of the delta 13C isotopic compositions using the NanoSIMS 50 installed at the Muséum National d'Histoire Naturelle, Paris. Carbon isotope measurement with NanoSIMS were calibrated against a natural Ia and a synthetic IIa diamond used for diamond anvil cells, whose compositions were determined by gas-source mass spectrometry at IPGP at 3.6±0.1‰ and -20.9±0.1‰, respectively (Pinti et al., 2016). All the starting materials used for the experiments were also characterized for their delta 13C by the same technique at GEOTOP, Montréal. The isotopic composition of the new diamond grown areas were measured close to the inclusions. They exhibit a different isotopic signature than that of the starting seeds (starting diamond composition: -29.6 to -30.4±1.4‰). The new diamond signatures are falling into the range of signatures of the starting carbonates used for the experiments (- 4.8±0.1 to -16.2±0.1‰) when they are far away from the composition of the starting graphite (-26.4±0.1‰). This shows that the carbon source for diamond growth must be the carbonates present either as CO32- ions dissolved in the melt or as carbon dioxide species CO2 in the aqueous fluid and that diamond growth occurred from carbonate reduction rather that from graphite dissolved in the melt. We suggest that the presence of small discrete or isolated volumes of water-carbonate-rich fluids are necessary to grow inclusion-bearing peridotitic, eclogitic, fibrous, cloudy and coated diamonds, and may also be involved in the growth of ultrahigh pressure metamorphic diamonds. Bureau, H., Langenhorst, F., Auzende, A.-L., Frost, D.J., Estève, I., Siebert, J., (2012). Geochimica et Cosmochimica Acta, 77, 202-214. H. Bureau, D.J. Frost, N. Bolfan-Casanova, C. Leroy, I. Esteve, P. Cordier (2016) Lithos 265, 4-15. D.L. Pinti, A. Ishida, N. Takahata, Y. Sano, H. Bureau, P. Cartigny (2016) Geochemical Journal 50/4, E7-E12. DOI: 10.2343/geochemj.2.0427 Navon, O., Hutcheon, I.D., Rossman, G.R., Wasserburg, G.J., 1988. Nature 335, 784-789. Weiss, Y.; McNeill, J.; Pearson, D. Graham; et al. 2015 Nature 524 : 339-344.

The P-T conditions of garnet inclusion formation in diamond: thermal expansion of synthetic end-member pyrope

NASA Astrophysics Data System (ADS)

Milani, Sula; Mazzucchelli, Matteo; Nestola, Fabrizio; Alvaro, Matteo; Angel, Ross J.; Geiger, Charles A.; Domeneghetti, Chiara

2013-04-01

Pyrope, Mg3Al2Si3O12, due to the abundance of garnet in Earths's upper mantle, has been studied many times. A number of different investigations have measured its physical and thermodynamic properties at high temperature or pressure and, even more recently, under simultaneous high P-T conditions (e.g. Zou et al., 2012). This abstract reports thermal expansion results on pyrope, as part of a much wider project on the determination of the physical properties of garnet, in order to obtain geobarometric information on the formation conditions of its inclusion in diamond. Our experimental approach is based on the elastic method (e.g. Izraeli et al., 1999; Howell et al., 2010; Nestola et al., 2011; Howell et al., 2012), which takes into account the thermoelastic properties of both diamond and any tiny solid phase inclusion within it. The method requires accurate and precise knowledge of thermal expansion and compressibility behavior in order to calculate precisely the pressure and temperature formation conditions of the diamond-inclusion pair. Thus, in order to do this, we measured the thermal expansion of an end-member synthetic single crystal of pyrope up to 1100 K at 52 different temperatures. This was done by measuring the ao unit-cell edge with high precision and accuracy under heating and cooling conditions. This allows excellent experimental reproducibility, which is also checked by monitoring any diffraction peak broadening over the entire range of temperatures. Fitting the temperature-volume data to the thermal expansion equation of Berman (1988), we obtained a room temperature volume-thermal expansion coefficient equal to 2.72(2)×10-5K-1. Using the same pyrope crystal, in situ high-pressure measurements are now in progress in order to determine its isothermal bulk modulus. The use of our results, along with the dK/dT data of Zou et al ( 2012), we plan to calculate the pressure of formation of diamonds containing pyrope-rich garnet inclusions. References Berman, R.G. (1988) J. Petrol., 29, 445-522. Zou Y., Irifune T., Greaux S., Whitaker M.L., Ohfuji H., Shinmei T., Higo Y., Baosheng L. (2012) Abstract n° MR43C-2333, AGU FALL MEETING 2012. Howell, D., Wood, I.G., Dobson, D.P., Jones, A.P., Nasdala, L., Harris, J.W. (2010) Contrib. Mineral. Petrol., 160, 705-717. Howell, D., Wood, I.G., Nestola, F., Nimis, P., Nasdala, L. (2012) Eur. J. Mineral., ,. Izraeli, E.S., Harris, J.W., Navon, O. (1999) Earth Planet Sci. Lett., 173, 351-360. Nestola, F., Nimis, P., Ziberna, L., Longo, M., Marzoli, A., Harris, J.W., Manghnani, M.H., Fedortchouk, Y. (2011) Earth Plan. Sc. Lett., 305, 249-255.

Growth and Brilliant Photo-Emission of Crystalline Hexagonal Column of Alq3 Microwires

PubMed Central

Kim, Seokho; Kim, Do Hyoung; Choi, Jinho; Lee, Hojin; Kim, Sun-Young; Park, Jung Woon; Park, Dong Hyuk

2018-01-01

We report the growth and nanoscale luminescence characteristics of 8-hydroxyquinolinato aluminum (Alq3) with a crystalline hexagonal column morphology. Pristine Alq3 nanoparticles (NPs) were prepared using a conventional reprecipitation method. Crystal hexagonal columns of Alq3 were grown by using a surfactant-assisted self-assembly technique as an adjunct to the aforementioned reprecipitation method. The formation and structural properties of the crystalline and non-crystalline Alq3 NPs were analyzed with scanning electron microscopy and X-ray diffraction. The nanoscale photoluminescence (PL) characteristics and the luminescence color of the Alq3 single NPs and their crystal microwires (MWs) were evaluated from color charge-coupled device images acquired using a high-resolution laser confocal microscope. In comparison with the Alq3 NPs, the crystalline MWs exhibited a very bright and sharp emission. This enhanced and sharp emission from the crystalline Alq3 single MWs originated from effective π-π stacking of the Alq3 molecules due to strong interactions in the crystalline structure. PMID:29565306

Morphological, Raman, electrical and dielectric properties of rare earth doped X-type hexagonal ferrites

NASA Astrophysics Data System (ADS)

Majeed, Abdul; Khan, Muhammad Azhar; ur Raheem, Faseeh; Ahmad, Iftikhar; Akhtar, Majid Niaz; Warsi, Muhammad Farooq

2016-12-01

The influence of rare-earth metals (La, Nd, Gd, Tb, Dy) on morphology, Raman, electrical and dielectric properties of Ba2NiCoRExFe28-xO46 ferrites were studied. The scanning electron microscopy (SEM) exhibited the platelet like structure of these hexagonal ferrites. The surface morphology indicated the formation of ferrite grains in the nano-regime scale. The bands obtained at lower wave number may be attributed to the metal-oxygen vibration at octahedral site which confirm the development of hexagonal phase of these ferrites. The resonance peaks were observed in dielectric constant, dielectric loss factor and quality factor versus frequency graphs. These dielectric parameters indicate that these ferrites nano-materials are potential candidates in the high frequency applications. The enhancement in DC electric resistivity from 2.48×108 to 1.20×109 Ω cm indicates that the prepared materials are beneficial for decreasing the eddy current losses at high frequencies and for the fabrication of multilayer chip inductor (MLCI) devices.

Pressure-induced Structural Transformations in LanthanideTitanates: La2TiO5 and Nd2TiO5

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

F Zhang; J Wang; M Lang

The structure of orthorhombic rare earth titanates of La{sub 2}TiO{sub 5} and Nd{sub 2}TiO{sub 5}, where Ti cations are in five-fold coordination with oxygen, has been studied at high pressures by X-ray diffraction (XRD), Raman scattering measurements, and quantum mechanical calculations. Both XRD and Raman results indicated two pressure-induced phase transitions during the process. An orthorhombic super cell (a x b x 2c) formed at a pressure between 6 and 10 GPa, and then transformed to a hexagonal high-pressure phase accompanied by partial decomposition. The hexagonal high-pressure phase is quenchable. Detailed structural analysis indicated that the five-coordinated TiO{sub 5} polyhedramore » remain during the formation of super cell, but the orthorhombic-to-hexagonal phase transition at high pressures is a reconstructive process, and the five-fold Ti-O coordination increased to more than 6. This phase transition sequence was verified by quantum mechanical calculations.« less

Hydrothermal synthesis of In2O3 nanoparticles hybrid twins hexagonal disk ZnO heterostructures for enhanced photocatalytic activities and stability

NASA Astrophysics Data System (ADS)

Liu, Hairui; Zhai, Haifa; Hu, Chunjie; Yang, Jien; Liu, Zhiyong

2017-07-01

In2O3 nanoparticles hybrid twins hexagonal disk (THD) ZnO with different ratios were fabricated by a hydrothermal method. The as-obtained ZnO/In2O3 composites are constituted by hexagonal disks ZnO with diameters of about 1 μm and In2O3 nanoparticles with sizes of about 20-50 nm. With the increase of In2O3 content in ZnO/In2O3 composites, the absorption band edges of samples shifted from UV to visible light region. Compared with pure ZnO, the ZnO/In2O3 composites show enhanced photocatalytic activities for degradation of methyl orange (MO) and 4-nitrophenol (4-NP) under solar light irradiation. Due to suitable alignment of their energy band-gap structure of the In2O3 and ZnO, the formation of type п heterostructure can enhance efficient separation of photo-generate electro-hole pairs and provides convenient carrier transfer paths.

Formation of the Fe,Mg-Silicates, Fe0, and Graphite (Diamond) Assemblage as a Result of Cohenite Oxidation under Lithospheric Mantle Conditions

NASA Astrophysics Data System (ADS)

Bataleva, Yu. V.; Palyanov, Yu. N.; Borzdov, Yu. M.; Zdrokov, E. V.; Novoselov, I. D.; Sobolev, N. V.

2018-03-01

Experimental studies in the Fe3C-SiO2-MgO system ( P = 6.3 GPa, T = 1100-1500°C, t = 20-40 h) have been carried out. It has been established that carbide-oxide interaction resulted in the formation of Fe-orthopyroxene, graphite, wustite, and cohenite (1100 and 1200°C), as well as a Fe-C-O melt (1300-1500°C). The main processes occurring in the system at 1100 and 1200°C are the oxidation of cohenite, the extraction of carbon from carbide, and the crystallization of metastable graphite, as well as the formation of ferrosilicates. At T ≥ 1300°C, graphite crystallization and diamond growth occur as a result of the redox interaction of a predominantly metallic melt (Fe-C-O) with oxides and silicates. The carbide-oxide interaction studied can be considered as the basis for modeling a number of carbon-producing processes in the lithospheric mantle at fO2 values near the iron-wustite buffer.

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

Dumpala, Ravikumar; Nano Functional Materials Technology Centre, Department of Physics, Indian Institute of Technology Madras, Chennai 600036; Kumar, N.

Tribo-layer formation and frictional characteristics of the SiC ball were studied with the sliding test against nanocrystalline diamond coating under atmospheric test conditions. Unsteady friction coefficients in the range of 0.04 to 0.1 were observed during the tribo-test. Friction and wear characteristics were found to be influenced by the formation of cohesive tribo-layer (thickness ∼ 1.3 μm) in the wear track of nanocrystalline diamond coating. Hardness of the tribo-layer was measured using nanoindentation technique and low hardness of ∼ 1.2 GPa was observed. The presence of silicon and oxygen in the tribo-layer was noticed by the energy dispersive spectroscopy mappingmore » and the chemical states of the silicon were analyzed using X-ray photoelectron spectroscopy. Large amount of oxygen content in the tribo-layer indicated tribo-oxidation wear mechanism. - Highlights: • Sliding wear and friction characteristics of SiC were studied against NCD coating. • Silicon oxide tribo-layer formation was observed in the NCD coating wear track. • Low hardness 1.2 GPa of tribo-layer was measured using nanoindentation technique. • Chemical states of silicon were analyzed using X-ray photoelectron spectroscopy.« less

Nitrogen-doped diamond electrode shows high performance for electrochemical reduction of nitrobenzene.

PubMed

Zhang, Qing; Liu, Yanming; Chen, Shuo; Quan, Xie; Yu, Hongtao

2014-01-30

Effective electrode materials are critical to electrochemical reduction, which is a promising method to pre-treat anti-oxidative and bio-refractory wastewater. Herein, nitrogen-doped diamond (NDD) electrodes that possess superior electrocatalytic properties for reduction were fabricated by microwave-plasma-enhanced chemical vapor deposition technology. Nitrobenzene (NB) was chosen as the probe compound to investigate the material's electro-reduction activity. The effects of potential, electrolyte concentration and pH on NB reduction and aniline (AN) formation efficiencies were studied. NDD exhibited high electrocatalytic activity and selectivity for reduction of NB to AN. The NB removal efficiency and AN formation efficiency were 96.5% and 88.4% under optimal conditions, respectively; these values were 1.13 and 3.38 times higher than those of graphite electrodes. Coulombic efficiencies for NB removal and AN formation were 27.7% and 26.1%, respectively; these values were 4.70 and 16.6 times higher than those of graphite electrodes under identical conditions. LC-MS analysis revealed that the dominant reduction pathway on the NDD electrode was NB to phenylhydroxylamine (PHA) to AN. Copyright © 2013 Elsevier B.V. All rights reserved.

Metal-Silicate Partitioning of Various Siderophile Elements at High Pressure and High Temperatures: a Diamond Anvil Cell Study

NASA Astrophysics Data System (ADS)

Badro, J.; Blanchard, I.; Siebert, J.

2015-12-01

Core formation is the major chemical fractionation that occurred on Earth. This event is widely believed to have happened at pressures of at least 40 GPa and temperatures exceeding 3000 K. It has left a significant imprint on the chemistry of the mantle by removing most of the siderophile (iron-loving) elements from it. Abundances of most siderophile elements in the bulk silicate Earth are significantly different than those predicted from experiments at low P-T. Among them, vanadium, chromium, cobalt and gallium are four siderophile elements which abundances in the mantle have been marked by core formation processes. Thus, understand their respective abundance in the mantle can help bringing constraints on the conditions of Earth's differentiation. We performed high-pressure high-temperature experiments using laser heating diamond anvil cell to investigate the metal-silicate partitioning of those four elements. Homogeneous glasses doped in vanadium, chromium, cobalt and gallium were synthesized using a levitation furnace and load inside the diamond anvil cell along with metallic powder. Samples were recovered using a Focused Ion Beam and chemically analyzed using an electron microprobe. We investigate the effect of pressure, temperature and metal composition on the metal-silicate partitioning of V, Cr, Co and Ga. Three previous studies focused on V, Cr and Co partitioning at those conditions of pressure and temperature, but none explore gallium partitioning at the relevant extreme conditions of core formation. We will present the first measurements of gallium metal-silicate partitioning performed at the appropriate conditions of pressure and temperature of Earth's differentiation.

Iron-carbonate interaction at Earth's core-mantle boundary

NASA Astrophysics Data System (ADS)

Dorfman, S. M.; Badro, J.; Nabiei, F.; Prakapenka, V.; Gillet, P.

2015-12-01

Carbon storage and flux in the deep Earth are moderated by oxygen fugacity and interactions with iron-bearing phases. The amount of carbon stored in Earth's mantle versus the core depends on carbon-iron chemistry at the core-mantle boundary. Oxidized carbonates subducted from Earth's surface to the lowermost mantle may encounter reduced Fe0 metal from disproportionation of Fe2+ in lower mantle silicates or mixing with the core. To understand the fate of carbonates in the lowermost mantle, we have performed experiments on sandwiches of single-crystal (Ca0.6Mg0.4)CO3 dolomite and Fe foil in the laser-heated diamond anvil cell at lower mantle conditions of 49-110 GPa and 1800-2500 K. Syntheses were conducted with in situ synchrotron X-ray diffraction to identify phase assemblages. After quench to ambient conditions, samples were sectioned with a focused Ga+ ion beam for composition analysis with transmission electron microscopy. At the centers of the heated spots, iron melted and reacted completely with the carbonate to form magnesiowüstite, iron carbide, diamond, magnesium-rich carbonate and calcium carbonate. In samples heated at 49 and 64 GPa, the two carbonates exhibit a eutectoid texture. In the sample heated at 110 GPa, the carbonates form rounded ~150-nm-diameter grains with a higher modal proportion of interspersed diamonds. The presence of reduced iron in the deep lower mantle and core-mantle boundary region will promote the formation of diamonds in carbonate-bearing subducted slabs. The complete reaction of metallic iron to oxides and carbides in the presence of mantle carbonate supports the formation of these phases at the Earth's core-mantle boundary and in ultra-low velocity zones.

Origin of a needle-like granular structure for ultrananocrystalline diamond films grown in a N2/CH4 plasma

NASA Astrophysics Data System (ADS)

Sankaran, K. J.; Kurian, J.; Chen, H. C.; Dong, C. L.; Y Lee, C.; Tai, N. H.; Lin, I. N.

2012-09-01

Microstructural evolution as a function of substrate temperature (TS) for conducting ultrananocrystalline diamond (UNCD) films is systematically studied. Variation of the sp2 graphitic and sp3 diamond content with TS in the films is analysed from the Raman and near-edge x-ray absorption fine structure spectra. Morphological and microstructural studies confirm that at TS = 700 °C well-defined acicular structures evolve. These nanowire structures comprise sp3 phased diamond, encased in a sheath of sp2 bonded graphitic phase. TS causes a change in morphology and thereby the various properties of the films. For TS = 800 °C the acicular grain growth ceases, while that for TS = 700 °C ceases only upon termination of the deposition process. The grain-growth process for the unique needle-like granular structure is proposed such that the CN species invariably occupy the tip of the nanowire, promoting an anisotropic grain-growth process and the formation of acicular structure of the grains. The electron field emission studies substantiate that the films grown at TS = 700 °C are the most conducting, with conduction mediated through the graphitic phase present in the films.

Determining the microwave coupling and operational efficiencies of a microwave plasma assisted chemical vapor deposition reactor under high pressure diamond synthesis operating conditions

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

Nad, Shreya; Department of Physics and Astronomy, Michigan State University, East Lansing, Michigan 48824; Gu, Yajun

2015-07-15

The microwave coupling efficiency of the 2.45 GHz, microwave plasma assisted diamond synthesis process is investigated by experimentally measuring the performance of a specific single mode excited, internally tuned microwave plasma reactor. Plasma reactor coupling efficiencies (η) > 90% are achieved over the entire 100–260 Torr pressure range and 1.5–2.4 kW input power diamond synthesis regime. When operating at a specific experimental operating condition, small additional internal tuning adjustments can be made to achieve η > 98%. When the plasma reactor has low empty cavity losses, i.e., the empty cavity quality factor is >1500, then overall microwave discharge coupling efficienciesmore » (η{sub coup}) of >94% can be achieved. A large, safe, and efficient experimental operating regime is identified. Both substrate hot spots and the formation of microwave plasmoids are eliminated when operating within this regime. This investigation suggests that both the reactor design and the reactor process operation must be considered when attempting to lower diamond synthesis electrical energy costs while still enabling a very versatile and flexible operation performance.« less

Design, synthesis and photoelectrochemical properties of hexagonal metallomacrocycles based on triphenylamine: [M6(4,4'-bis(2,2':6',2''-terpyridinyl)triphenylamine)6(X)12]; [M = Fe(II), PF6- and Zn(II), BF4-].

PubMed

Hwang, Seok-Ho; Moorefield, Charles N; Wang, Pingshan; Fronczek, Frank R; Courtney, Brandy H; Newkome, George R

2006-08-07

Synthesis of a novel bis(terpyridine) ligand, 4,4'-bis(2,2':6',2''-terpyridinyl)triphenylamine, utilizing triphenylamine, as a specific angle controller, has led to the self-assembly of a unique hexagonal metallomacrocycle family, [Fe6(2)6(PF6)12] and [Zn6(2)6(BF4)12], utilizing terpyridine-metal(II)-terpyridine connectivity. The crystal structure of the novel ligand shows that the angle between the two terpyridinyl moieties is 119.69 degrees , which enabled the formation of the hexagonal-shaped macrocycles. The crystal packing architectures of this starting ligand revealed channels induced by solvent encapsulation. Following complexation of this ligand with transition metals [Fe(II) or Zn(II)] in a one-pot reaction, the resultant structures were characterized by (1)H and (13)C NMR, UV/Vis and mass spectroscopies. The expected metal-to-ligand charge transfer (MLCT; lambda(max) = 582 nm) and emission (lambda(em) = 575 nm) characteristics were exhibited by both [Fe6(2)6(PF6)12] and[Zn6(2)6(BF4)12]. The photoelectrochemical characteristics of these hexagonal metallomacrocycles demonstrate that they can be used as sensitizers in dye-sensitized solar cells.

Synthesis characterization and catalytic action of hexagonal gold nanoparticles using essential oils extracted from Anacardium occidentale

NASA Astrophysics Data System (ADS)

Sheny, D. S.; Mathew, Joseph; Philip, Daizy

2012-11-01

A new phytochemical method for the synthesis of gold nanoparticles is reported. The essential oils extracted from the fresh leaves of Anacardium occidentale are used for the reduction of auric acid to Au nanoparticles (NPs). The formation and morphology of synthesized NPs are investigated with the help of UV-visible, TEM and FTIR spectroscopy. The NPs synthesized at room temperature are mono-dispersed and hexagonal in shape with an average size of 36 nm while those prepared at higher temperature are composed of a mixture of anisotropic particles. The UV-visible absorption spectra of these anisotropic NPs show asymmetry in the longer wavelength side. The quantity of oil is an important criterion modulating the shape of NPs. Possible biochemical mechanism leading to the formation of NPs is studied using FTIR spectroscopy. The potential of synthesized Au NPs as catalyst is explored for the hydrogenation of p-nitro phenol to p-amino phenol at room temperature.

Synthesis characterization and catalytic action of hexagonal gold nanoparticles using essential oils extracted from Anacardium occidentale.

PubMed

Sheny, D S; Mathew, Joseph; Philip, Daizy

2012-11-01

A new phytochemical method for the synthesis of gold nanoparticles is reported. The essential oils extracted from the fresh leaves of Anacardium occidentale are used for the reduction of auric acid to Au nanoparticles (NPs). The formation and morphology of synthesized NPs are investigated with the help of UV-visible, TEM and FTIR spectroscopy. The NPs synthesized at room temperature are mono-dispersed and hexagonal in shape with an average size of 36 nm while those prepared at higher temperature are composed of a mixture of anisotropic particles. The UV-visible absorption spectra of these anisotropic NPs show asymmetry in the longer wavelength side. The quantity of oil is an important criterion modulating the shape of NPs. Possible biochemical mechanism leading to the formation of NPs is studied using FTIR spectroscopy. The potential of synthesized Au NPs as catalyst is explored for the hydrogenation of p-nitro phenol to p-amino phenol at room temperature. Copyright © 2012 Elsevier B.V. All rights reserved.

Chemical trends of Schottky barrier behavior on monolayer hexagonal B, Al, and Ga nitrides

NASA Astrophysics Data System (ADS)

Lu, Haichang; Guo, Yuzheng; Robertson, John

2016-08-01

The Schottky Barrier Heights (SBH) of metal layers on top of monolayer hexagonal X-nitrides (X = B, Al, Ga, and h-XN) are calculated using supercells and density functional theory so as to understand the chemical trends of contact formation on graphene and the 2D layered semiconductors such as the transition metal dichalcogenides. The Fermi level pinning factor S of SBHs on h-BN is calculated to be nearly 1, indicating no pinning. For h-AlN and h-GaN, the calculated pinning factor is about 0.63, less than for h-BN. We attribute this to the formation of stronger, chemisorptive bonds between the nitrides and the contact metal layer. Generally, the h-BN layer remains in a planar sp2 geometry and has weak physisorptive bonds to the metals, whereas h-AlN and h-GaN buckle out of their planar geometry which enables them to form the chemisorptive bonds to the metals.

A crystal plasticity model for slip in hexagonal close packed metals based on discrete dislocation simulations

NASA Astrophysics Data System (ADS)

Messner, Mark C.; Rhee, Moono; Arsenlis, Athanasios; Barton, Nathan R.

2017-06-01

This work develops a method for calibrating a crystal plasticity model to the results of discrete dislocation (DD) simulations. The crystal model explicitly represents junction formation and annihilation mechanisms and applies these mechanisms to describe hardening in hexagonal close packed metals. The model treats these dislocation mechanisms separately from elastic interactions among populations of dislocations, which the model represents through a conventional strength-interaction matrix. This split between elastic interactions and junction formation mechanisms more accurately reproduces the DD data and results in a multi-scale model that better represents the lower scale physics. The fitting procedure employs concepts of machine learning—feature selection by regularized regression and cross-validation—to develop a robust, physically accurate crystal model. The work also presents a method for ensuring the final, calibrated crystal model respects the physical symmetries of the crystal system. Calibrating the crystal model requires fitting two linear operators: one describing elastic dislocation interactions and another describing junction formation and annihilation dislocation reactions. The structure of these operators in the final, calibrated model reflect the crystal symmetry and slip system geometry of the DD simulations.

Homotopy-Theoretic Study & Atomic-Scale Observation of Vortex Domains in Hexagonal Manganites

PubMed Central

Li, Jun; Chiang, Fu-Kuo; Chen, Zhen; Ma, Chao; Chu, Ming-Wen; Chen, Cheng-Hsuan; Tian, Huanfang; Yang, Huaixin; Li, Jianqi

2016-01-01

Essential structural properties of the non-trivial “string-wall-bounded” topological defects in hexagonal manganites are studied through homotopy group theory and spherical aberration-corrected scanning transmission electron microscopy. The appearance of a “string-wall-bounded” configuration in RMnO3 is shown to be strongly linked with the transformation of the degeneracy space. The defect core regions (~50 Å) mainly adopt the continuous U(1) symmetry of the high-temperature phase, which is essential for the formation and proliferation of vortices. Direct visualization of vortex strings at atomic scale provides insight into the mechanisms and macro-behavior of topological defects in crystalline materials. PMID:27324701

On the Effect of Feedback Control on Benard Convection in a Boussinesq Fluid

NASA Technical Reports Server (NTRS)

Shortis, Trudi A.; Hall, Philip

1996-01-01

The effect of nonlinear feedback control strategies on the platform of convection in a Boussinesq fluid heated from below is investigated. In the absence of the control, given that non-Boussinesq effects may be neglected, it is well known that convection begins in the form of a supercritical bifurcation to rolls. Non-Boussinesq behaviour destroys the symmetry of the basic state, and through a subcritical bifurcation leads to the formation of hexagonal cells. Here we discuss the influence of regulation of the lower surface temperature by means of a control mechanism, made up of a combination of a proportional linear and nonlinear controller, on the stability of the hexagonal cell pattern.

Cavitations synthesis of carbon nanostructures

NASA Astrophysics Data System (ADS)

Voropaev, S.

2011-04-01

Originally an idea of diamonds production by hydrodynamical cavitation was presented by academician E M Galimov. He supposed the possibility of nature diamonds formation at fast magma flowing in kimberlitic pipes during bubbles collapse. This hypothesis assumes a number of processes, which were not under consideration until now. It concerns cavitation under high pressure, growth and stability of the gas- and vapors bubbles, their evolution, and corresponding physical- and chemical processes inside. Experimental setup to reproduce the high pressure and temperature reaction centers by means of the cavitation following the above idea was created. A few crystalline nanocarbon forms were successfully recovered after treatment of benzene (C6H6).

Epitaxial Hexagonal Ferrites for Millimeter Wave Tunable Filters.

DTIC Science & Technology

1982-12-13

form of thin films or slabs, the LPE format should be particularly suitable. Another potential advantage of the LPE format is that the insulating...flux (solvent). In effect, this emulates the successful LPE garnet (YIG) technology which employs this flux. In contrast to garnets , Pb atoms can be...member for a workshop entitled "Application of Garnet and Ferrite Thin Films to Microwave Devices." The principal investigator also attended the 6th

Concepts for diamond exploration in "on/off craton" areas—British Columbia, Canada

NASA Astrophysics Data System (ADS)

Simandl, George J.

2004-09-01

The tectonic setting of British Columbia (BC) differs from classic diamond-bearing intracratonic regions such as the Northwest Territories and South Africa. Nevertheless, several diamond occurrences have been reported in BC. It is also known that parts of the province are underlain by Proterozoic and possibly Archean basement. Because the continents of today are composites of fragments of ancient continents, it is possible that some of the regions underlain by old crystalline basement in eastern British Columbia were associated with a deep crustal keel. The keel may have predated the break-up of the early Neoproterozoic supercontinent called Rodinia and was preserved possibly until the Triassic. Some of these old continental fragments may have been displaced relative to their position of origin and dissociated from their keel, or the keel may have since been destroyed. Such fragments represent favourable exploration grounds in terms of the "Diamondiferous Mantle Root" model (DMR model) if they were intersected by kimberlites or lamproites prior to displacement or destruction of their underlying deep keel. Therefore, extrapolation of fragments of the diamond-bearing Precambrian basement from the Northwest Territories or Alberta to BC provides a sufficient reason for initiating reconnaissance indicator mineral surveys. The "Eclogite Subduction Zone" model (ES model) predicts formation of diamonds at lower pressure (i.e., depth) than required by the DMR model in convergent tectonic settings. Although not proven, this model is supported by thermal modeling of cold subduction zones and recent discoveries of diamonds in areas characterized by convergent tectonic settings. If the ES model is correct, then the parts of BC with a geological history similar to today's "cold" subduction zones, such as Honshu (Japan), or to continental collision zones, such as Kokchetav massif (Kazakhstan) and the Dabie-Sulu Terrane (east central China), may be diamondiferous. The terranes where geological evidences suggest an ultrahigh pressure (UHP) metamorphic event followed by rapid tectonic exhumation (which could have prevented complete resorption of diamonds on their journey to the surface) are worth investigating. If UHP rocks were intercepted at depth by syn- or post-subduction diamond elevators, such as kimberlites, lamproites, lamprophyres, nephelinites or other alkali volcanic rocks of deep-seated origin, the diamond potential of the area would be even higher.

Regional sub-cratonic mantle heterogeneities under the Kaapvaal craton recorded by sulfide inclusions in diamond.

NASA Astrophysics Data System (ADS)

Thomassot, E.; Lorand, J. P.

2016-12-01

Sulfide inclusions in diamonds (SID) have been trapped by their host at depth greater than 150 km and then protected from alteration or reequilibration processes. Subsequently, depending on their initial composition, there have experienced multiple exsolution events at temperatures between 650°C and 200°C. Mineralogical and isotopic composition of SID thus directly reflects their sources whereas their texture give information on the exhumation history of their diamond host. Our samples originating from Koffiefontein, De Beers Pool and Jwaneng kimberlites, include both peridotitic (P-type, n=6) and eclogitic (E-type, n=151) sulfides. P-type sulfides are monosulfide solid solutions (exsolved from a nickeliferous monosulfide solid solution, mss, stable at T>300°C). Their Ni and Cr content indicate that the sublithospheric mantle under Koffiefontein (Ni=26wt%; Cr=0.36 wt%) is more refractory than De Beers Pool (Ni=24wt%; Cr=0.28wt%) and Jwaneng (Ni=17wt%; Cr=0.22wt%). Sulfides from De Beers Pool have S/Se (3900±100) greater than the chondritic values ( 2540) pointing to a metasomatic overprint predating the formation of diamonds. S-isotopic composition (d34S=-0.9 ± 0.5‰, Δ33S=0‰) are homogeneous, and consistent with the composition of MORB. E-type sulfides are unmixed assemblage of chalcopyrite (crystallized from an intermediate solid solution formed at T 650°C) pentlandite (T° from 260 to >200°C) and pyrrhotite. Comparing the chemical composition of the unmixed phases with experimental data, we determined a blocking T° for E-type assemblages ranging from 540°C at Koffiefontein, to less than 200°C at Jwaneng and DeBeersPool. E-type sulfides thus confirm the chemical heterogeneity from one mine to the other, with d34S extended to fractionated values (-9 to +11‰). Our study indicates that SID are robust probes to explore regional scale mantle heterogeneities likely associated to discrete depletion events and possible recycling of ancient sediment, predating the formation of diamonds. Major, trace element and isotopes data will be presented at the conference in order to support this conclusion.

Surface structure of micro-diamond from ultrahigh-pressure felsic granulite, Bohemian Massif: AFM study of growth and resorption phenomena

NASA Astrophysics Data System (ADS)

Kotková, J.; Klapetek, P.

2012-04-01

Morphology, associated phases and retrogression phenomena of in-situ microdiamonds formed at extreme pressures in ultrahigh-pressure metamorphic terranes represent excellent tools to study character of diamond-forming media at great depths. Well-preserved microdiamonds discovered recently along with coesite in ultrahigh-pressure granulites of the north Bohemian crystalline basement, European Variscan belt (Kotková et al., 2011), provide unique material for such investigations. The diamonds are enclosed in major granulite phases, i.e. garnet both in felsic and intermediate lithologies and in kyanite in the felsic sample, as well as in zircon. Transmitted and reflected light microscopy of the felsic granulite sample, with peak mineral assemblage garnet, kyanite, feldspar and quartz, revealed presence of numerous, 5-20 μm-sized, perfectly preserved diamond crystals enclosed in kyanite grains. In contrast, diamonds within garnet are rare, can reach up to 30 μm in size, and graphite rims as well as polycrystalline graphite aggregates possibly representing complete diamond retrogression are common. We applied atomic force microscopy to study in-situ crystal morphology and surface microtopographic features, representing clues to the conditions and mechanisms of crystal formation as well as diamond resorption and retrogression. Both diamond enclosed in garnet and in kyanite of the felsic granulite occur exclusively as single crystals. The crystals have octahedral crystal shapes with straight but rounded edges and rounded corners. Concentric triangular terraces delimiting a flat triangular table on crystal scale and small micron-sized negatively oriented downward-pointing trigons developed on the octahedron crystal faces. Higher magnification reveals presence of discontinuous elongate hillocks oriented parallel to the octahedron face edge with positively oriented trigons. We suggest that the large-scale triangular terraces represent growth features. In contrast, the rounding of crystal edges and corners and development of negative trigons reflect diamond resorption. According to experimental works, such features are attributed to high temperature resorption, i.e. oxidation above ~ 950°C due to interaction with CO2 and/or H2O-bearing fluids (or fluid-bearing melts). Our results are consistent with presence of supercritical C-O-H fluid in the rocks in subduction zones documented from other ultrahigh-pressure metamorphic terranes, the resorption morphology corresponding rather to the interaction with water-rich than CO2-rich fluids. Kotková J., ÓBrien P., Ziemann M. (2011): Diamond and coesite discovered in Saxony-type granulite: Solution to the Variscan garnet peridotite enigma. Geology, 39, 7, 667-670.

Ultrabasic-basic change over primary inclusions in lower-mantle diamonds: Mineralogical and experimental evidence for crucial role of stishovite paradox

NASA Astrophysics Data System (ADS)

Litvin, Yuriy; Spivak, Anna

2017-04-01

Melting relations of the lower-mantle magmatic system MgO - FeO - CaO - SiO2 are characterized by peritectic reaction of bridgmanite (Mg,Fe)SiO3 and melt with formation of Fe-rich phases of periclase-wustite solid solutions (MgO•FeO)ss and stishovite SiO2. The reaction proceeds also in melts-solutions of lower-mantle diamond-parental system MgO - FeO - CaO - SiO2 - (Mg-Fe-Ca-Na-carbonate) - C. Xenoliths of lower mantle rocks were never found among the deep mantle derived materials. Estimation of lower-mantle mineralogy as ferropericlase+ bridgmanite+ Ca-perovskite association is inferred from high-pressure subsolidus experiments with ultrabasic pyrolite composition (Akaogi, 2007). The paradoxical in situ paragenesis of stishovite and ferropericlase as primary inclusions in lower-mantle diamonds (Kaminsky, 2012) takes its explanation from the bridgmanite peritectic reaction (effect of "stishovite paradox") (Litvin et al., 2014). Based on the data for inclusions, physico-chemical study on syngenesis of diamonds and primary inclusions has experimentally revealed the ferropericlase-bridgmanite-Ca-perovskite-stishovite-magnesiowustite-(Mg-Fe-Ca-Na-carbonate)-carbon compositions of the lower-mantle diamond-forming system .(Litvin et al., 2016). The generalized diagram of diamong-forming media characterizes the variable compositions of growths melts for diamonds and paragenetic phases and their genetic relationships with lower mantle matter, and it is the reason for genetic classifying primary inclusions. Fractional ultrabasic-basic evolution and continuous paragenetic transition from ultrabasic bridgmanite-ferropericlase to basic stishovite-magnesiowustite assemblages in the of lower-mantle diamond-parental melts-solutions are providing by the physico-chemical mechanism of stishovite paradox. References Akaogi M. (2007). Phase transformations of minerals in the transition zone and upper part of the lower mantle. In Advances in High-Pressure Mineralogy (Ohtani E., ed.). Geol. Soc. Am. Spec. Paper 421, 1-13. Kaminsky F.V. (2012). Mineralogy of the lower mantle: a review of "supper-deep" mineral inclusions in diamonds. Earth Sci. Rev. 110, 127-147. Litvin Yu.A., Spivak A.V., Solopova N.A., Dubrovinsky L.S. (2014). On origin of lower-mantle diamonds and their primary inclusions. Phys. Earth Planet. Inter. 228, 176-185. Litvin Yu.A., Spivak A.V., Dubrovinsky L.S. (2016). Magmatic evolution of the material of the Earth's lower mantle: stishovite paradox and origin of superdeep diamonds (experiments at 24-26 GPa). Geochemistry Internat. 54(11, 936-947.)

Carbon and nitrogen isotope systematics in diamond: Different sensitivities to isotopic fractionation or a decoupled origin?

NASA Astrophysics Data System (ADS)

Hogberg, K.; Stachel, T.; Stern, R. A.

2016-11-01

Using stable isotope data obtained on multiple aliquots of diamonds from worldwide sources, it has been argued that carbon and nitrogen in diamond are decoupled. Here we re-investigate the carbon-nitrogen relationship based on the most comprehensive microbeam data set to date of stable isotopes and nitrogen concentrations in diamonds (n = 94) from a single locality. Our diamond samples, derived from two kimberlites in the Chidliak Field (NE Canada), show large variability in δ13C (- 28.4 ‰ to - 1.1‰, mode at - 5.8‰), δ15N (- 5.8 to + 18.8‰, mode at - 3.0‰) and nitrogen contents ([N]; 3800 to less than 1 at.ppm). In combination, cathodoluminescence imaging and microbeam analyses reveal that the diamonds grew from multiple fluid pulses, with at least one major hiatus documented in some samples that was associated with a resorption event and an abrupt change from low δ13C and [N] to mantle-like δ13C and high [N]. Overall, δ13C appears to be uncorrelated to δ15N and [N] on both the inter- and intra-diamond levels. Co-variations of δ15N-log[N], however, result in at least two parallel, negatively correlated linear arrays, which are also present on the level of the individual diamonds falling on these two trends. These arrays emerge from the two principal data clusters, are characterized by slightly negative and slightly positive δ15N (about - 3 and + 2‰, respectively) and variable but overall high [N]. Using published values for the diamond-fluid nitrogen isotope fractionation factor and nitrogen partition coefficient, these trends are perfectly reproduced by a Rayleigh fractionation model. Overall, three key elements are identified in the formation of the diamond suite studied: (1.) a low δ13C and low [N] component that possibly is directly associated with an eclogitic diamond substrate or introduced during an early stage fluid event. (2.) Repeated influx of a variably nitrogen-rich mantle fluid (mildly negative δ13C and δ15N). (3.) In waning stages of influx, availability of the mantle-type fluid at the site of diamond growth became limited, leading to Rayleigh fractionation. These fractionation trends are clearly depicted by δ15N-[N] but are not detected when examining co-variation diagrams involving δ13C. Also on the level of individual diamonds, large (≥ 5‰) variations in δ15N are associated with δ13C values that typically are constant within analytical uncertainty. The much smaller isotope fractionation factor for carbon (considering carbonate- or methane-rich fluids as possible carbon sources) compared to nitrogen leads to an approximately one order of magnitude lower sensitivity of δ13C values to Rayleigh fractionation processes (i.e. during fractionation, a 1‰ change in δ13C is associated with a 10‰ change in δ15N). As a consequence, even minor heterogeneity in the primary isotopic composition of diamond forming carbon (e.g., due to addition of minor subducted carbon) will completely blur any possible co-variations with δ15N or [N]. We suggest this strong difference in isotope effects for C and N to be the likely cause of observations of an apparently decoupled behaviour of carbon and nitrogen isotopes in diamond.

Simulation and Experimental Study on Surface Formation Mechanism in Machining of SiCp/Al Composites

NASA Astrophysics Data System (ADS)

Du, Jinguang; Zhang, Haizhen; He, Wenbin; Ma, Jun; Ming, Wuyi; Cao, Yang

2018-03-01

To intuitively reveal the surface formation mechanism in machining of SiCp/Al composites, in this paper the removal mode of reinforced particle and aluminum matrix, and their influence on surface formation mechanism were analyzed by single diamond grit cutting simulation and single diamond grit scratch experiment. Simulation and experiment results show that when the depth of cut is small, the scratched surface of the workpiece is relatively smooth; however, there are also irregular pits on the machined surface. When increasing the depth of cut, there are many obvious laminar structures on the scratched surface, and the surface appearance becomes coarser. When the cutting speed is small, the squeezing action of abrasive grit on SiC particles plays a dominant role in the extrusion of SiC particles. When increasing the cutting speed, SiC particles also occur broken or fractured; but the machined surface becomes smooth. When machining SiCp/Al composites, the SiC may happen in such removal ways, such as fracture, debonding, broken, sheared, pulled into and pulled out, etc. By means of reasonably developing micro cutting finite element simulation model of SiCp/Al composites could be used to analyze the surface formation process and particle removal way in different machining conditions.

Minerals of the earth's deep interior

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

Schiferl, D.; Zhao, Y.; Shankland, T.J.

1998-11-01

This is the final report of a three-year, Laboratory Directed Research and Development (LDRD) project at Los Alamos National Laboratory (LANL). The project addresses the major geophysical issue of the nature of the seismic velocity and density discontinuity at 670 km depth (the boundary between upper and lower mantle with temperature about 1,900 K and pressure about 23 GPa). A phase change at this depth would represent a relatively small barrier to mantle convection through the discontinuity, but compositional change would inhibit thermal convection throughout the mantle. To address this problem the authors measured equation of state parameters in mantlemore » minerals as functions of high P-T using single crystal x-ray diffraction with a unique, new diamond-anvil cell (DAC) at simultaneous high temperature and pressure. Single-crystal diffraction improves absolute accuracy in lattice constants over those from powder diffraction by a factor of 5 to 10. The authors have measured equations of state of orthoenstatite MgSiO{sub 3} and hexagonal boron nitride hBN.« less

The Structure and Bonding State for Fullerene-Like Carbon Nitride Films with High Hardness Formed by Electron Cyclotron Resonance Plasma Sputtering

NASA Astrophysics Data System (ADS)

Kamata, Tomoyuki; Niwa, Osamu; Umemura, Shigeru; Hirono, Shigeru

2012-12-01

We studied pure carbon films and carbon nitride (CN) films by using electron cyclotron resonance (ECR) sputtering. The main feature of this method is high density ion irradiation during deposition, which enables the pure carbon films to have fullerene-like (FL) structures without nitrogen incorporation. Furthermore, without substrate heating, the ECR sputtered CN films exhibited an enhanced FL microstructure and hardness comparable to that of diamond at intermediate nitrogen concentration. This microstructure consisted of bent and cross-linked graphene sheets where layered areas remarkably decreased due to increased sp3 bonding. Under high nitrogen concentration conditions, the CN films demonstrated extremely low hardness because nitrile bonding not only decreased the covalent-bonded two-dimensional hexagonal network but also annihilated the bonding there. By evaluating lattice images obtained by transmission electron microscopy and the bonding state measured by X-ray photoelectron spectroscopy, we classified the ECR sputtered CN films and offered phase diagram and structure zone diagram.

Arctic curves in path models from the tangent method

NASA Astrophysics Data System (ADS)

Di Francesco, Philippe; Lapa, Matthew F.

2018-04-01

Recently, Colomo and Sportiello introduced a powerful method, known as the tangent method, for computing the arctic curve in statistical models which have a (non- or weakly-) intersecting lattice path formulation. We apply the tangent method to compute arctic curves in various models: the domino tiling of the Aztec diamond for which we recover the celebrated arctic circle; a model of Dyck paths equivalent to the rhombus tiling of a half-hexagon for which we find an arctic half-ellipse; another rhombus tiling model with an arctic parabola; the vertically symmetric alternating sign matrices, where we find the same arctic curve as for unconstrained alternating sign matrices. The latter case involves lattice paths that are non-intersecting but that are allowed to have osculating contact points, for which the tangent method was argued to still apply. For each problem we estimate the large size asymptotics of a certain one-point function using LU decomposition of the corresponding Gessel–Viennot matrices, and a reformulation of the result amenable to asymptotic analysis.

A diamond in the sky: an exclusion or normal situation?

NASA Astrophysics Data System (ADS)

Kochemasov, G. G.

2009-04-01

A diamond in the sky: an exclusion or normal situation? G. Kochemasov IGEM of the Russian Academy of Sciences, Moscow, Russia, kochem.36@mail.ru The September 2008 observation and imaging by the ESA-"Rosetta" spacecraft of the small asteroid (2867) Steins should have a rather deep impact at planetological thinking. The planetology community is accustomed to think that the only process making forms of small bodies is the impact (accretion) process. No other forces are considered as though there is none. But actually there is one mighty process - a wave process that affects all cosmic bodies by warping them in several (normally four) directions. An origin of these warping waves is quite simple. All cosmic bodies move (orbit) and rotate. After I. Kepler we know that all orbits are non-round but elliptical (time rounds them but ellipticity always remain), and this means that orbiting bodies periodically cyclically change their accelerations (speeding up and slowing down). Multiplied by masses these changes produce forces applied to the bodies and causing oscillations of their spheres. In rotating bodies (but all bodies rotate!) these oscillations are decomposed (split) into four orthogonal and diagonal directions. Interfering of these directions produces uplifting, subsiding and neutral tectonic blocks which are observed on any celestial body more or less clearly. The blocks dimensions depend on lengths of warping waves that acquire a stationary character in closed spheres. That is why celestial spheres are not like billiards-balls but consist of regularly placed depressions (lowlands) and highlands. The longest fundamental wave 1 produces ubiquitous tectonic dichotomy - an opposition of subsided and bulged hemispheres (segments). The Plato's tetrahedron is a structural expression of this configuration: in this simplest polyhedron there is an opposition of a vertex (bulging, extension) and a face (pressing in, contraction). A convexo-concave shape of small bodies is very typical [1]; in some viewpoints they look as tetrahedrons [2]. The first overtone of the fundamental wave - wave 2 - produces structural octahedron (diamond). Rarely in a full shape, more often in its parts {rectilinear crossing outlines) this shape is rather typical in many obtained images of small bodies [3]. Not perfection of this polyhedron in reality is due to its superposition on a tetrahedron structure and complication by wave structures of the lower ranges, like a cube, dodecahedron, and impacts. Still, in some cases "diamond" in the sky is rather clear - Yanus (PIA 06613), Steins. Dr. Schwehm's prediction of even larger asteroid "diamond' in shape of Lutetia is really significant [4]. If small bodies are able to demonstrate their natural polyhedron shapes due to negligible gravity, the larger bodies are reduced to a globe shape by a mighty gravity. Still their structural layout (ubiquitous dichotomy), some protruding vertices, edges and faces betray their polyhedron nature. In this relation, "mysterious" Saturn's northern hexagon is a reflection of three crossing tetrahedron faces making the fourth face, while the southern hurricane is an imprint of an opposite vertex. Thus looks a hidden polyhedron in a globe. ESA-Rosetta mission is a real clue to an adequate understanding, deciphering forces sculpturing celestial bodies. Images of asteroid Steins revealing its clear polyhedron (diamond) shape witness to an involvement of warping wave processes. References: [1] Kochemasov G.G. (1999) On convexo-concave shape of small celestial bodies // "Asteroids, Comets, Meteors" conference, Cornell Univ., U.S.A., July 1999, Abstract # 24. 22; [2] Kochemasov G.G. (2008) Plato' polyhedra as shapes of small icy satellites // Geophys. Res. Abstracts, Vol. 10, EGU2008-A-01271, CD-ROM ; [3] Kochemasov G.G. (1999) "Diamond" and "dumb-bells"-like shapes of celestial bodies induced by inertia-gravity waves // 30th Vernadsky-Brown microsymposium on comparative planetology, Abstracts, Moscow, Vernadsky Inst.,, 49-50; [4] ESA News. Steins: a diamond in the sky, 6 September, 2008 (http://www.esa.int/rosetta);

Diamond exploration and regional prospectivity of Western Australia

NASA Astrophysics Data System (ADS)

Hutchison, Mark T.

2018-06-01

Pre-1.6 Ga rocks comprise around 45% of the onshore area of Western Australia (WA), constituting the West Australian Craton (WAC) (including the Archean Yilgarn and Pilbara Cratons) and the western part of the North Australian Craton (NAC). These areas provide the conditions suitable for diamond formation at depth, and numerous diamondiferous lamproite and kimberlite fields are known. As emplacement ages span close to 2500 Ma, there are significant opportunities for diamond-affinity rocks being present near-surface in much of the State, including amongst Phanerozoic rocks. WA's size, terrain, infrastructure and climate, mean that many areas remain underexplored. However, continuous diamond exploration since the 1970s has resulted in abundant data. In order to advance future exploration, a comprehensive database of results of diamond exploration sampling (Geological Survey of Western Australia 2018) has been assessed. The Yilgarn and Pilbara Cratons have spinel indicators almost exclusively dominated by chromite (>90% of grains), whereas (Mg,Fe,Ti)-bearing Al-chromites account for more of the indicator spinels in the NAC, up to 50% of grains at the Northern Territory (NT) border. Increasing dominance of Al in chromites is interpreted as a sign of weathering or a shallower source than Al-depleted Mg-chromites. Garnet compositions across the State also correlate with geological subdivisions, with lherzolitic garnets showing more prospective compositions (Ca-depleted) in WAC samples compared to the NAC. WAC samples also show a much broader scatter into strongly diamond-prospective G10 and G10D compositions. Ilmenites from the NAC show Mg-enriched compositions (consistent with kimberlites), over and above those present in NT data. However, ilmenites from the WAC again show the most diamond-prospective trends. Numerous indicator mineral concentrations throughout the State have unknown sources. Due in part to the presence of diamondiferous lamproites, it is cautioned that some accepted indicator mineral criteria do not apply in parts of WA. For example Ca-depleted garnets, Mg-depleted ilmenites and Cr-depleted and Al-absent clinopyroxenes are all sometimes associated with strongly diamondiferous localities. Quantitative prospectivity analysis has also been carried out based on the extent and results of sampling, age of surface rocks relative to ages of diamond-prospective rocks, and the underlying mantle structure. Results show that locations within the NAC and with proximity to WA's diamond mines score well. However, results point to parts of the WAC being more prospective, consistent with mineral chemical data. Most notable are the Hamersley Basin, Eastern Goldfields Superterrane and the Goodin Inlier of the Yilgarn Craton. Despite prolific diamond exploration, WA is considerably underexplored and the ageing Argyle mine and recent closure of operations at Ellendale warrant a re-evaluation of diamond potential. Results of mineral chemistry and prospectivity analysis make a compelling case for renewed exploration.

Direct calculation of ice homogeneous nucleation rate for a molecular model of water.

PubMed

Haji-Akbari, Amir; Debenedetti, Pablo G

2015-08-25

Ice formation is ubiquitous in nature, with important consequences in a variety of environments, including biological cells, soil, aircraft, transportation infrastructure, and atmospheric clouds. However, its intrinsic kinetics and microscopic mechanism are difficult to discern with current experiments. Molecular simulations of ice nucleation are also challenging, and direct rate calculations have only been performed for coarse-grained models of water. For molecular models, only indirect estimates have been obtained, e.g., by assuming the validity of classical nucleation theory. We use a path sampling approach to perform, to our knowledge, the first direct rate calculation of homogeneous nucleation of ice in a molecular model of water. We use TIP4P/Ice, the most accurate among existing molecular models for studying ice polymorphs. By using a novel topological approach to distinguish different polymorphs, we are able to identify a freezing mechanism that involves a competition between cubic and hexagonal ice in the early stages of nucleation. In this competition, the cubic polymorph takes over because the addition of new topological structural motifs consistent with cubic ice leads to the formation of more compact crystallites. This is not true for topological hexagonal motifs, which give rise to elongated crystallites that are not able to grow. This leads to transition states that are rich in cubic ice, and not the thermodynamically stable hexagonal polymorph. This mechanism provides a molecular explanation for the earlier experimental and computational observations of the preference for cubic ice in the literature.

Geometric and electronic structures of monolayer hexagonal boron nitride with multi-vacancy

NASA Astrophysics Data System (ADS)

Kim, Do-Hyun; Kim, Hag-Soo; Song, Min Woo; Lee, Seunghyun; Lee, Sang Yun

2017-05-01

Hexagonal boron nitride (h-BN) is an electrical insulator with a large band gap of 5 eV and a good thermal conductor of which melting point reaches about 3000 °C. Due to these properties, much attention was given to the thermal stability rather than the electrical properties of h-BN experimentally and theoretically. In this study, we report calculations that the electronic structure of monolayer h-BN can be influenced by the presence of a vacancy defect which leads to a geometric deformation in the hexagonal lattice structure. The vacancy was varied from mono- to tri-vacancy in a supercell, and different defective structures under the same vacancy density were considered in the case of an odd number of vacancies. Consequently, all cases of vacancy defects resulted in a geometric distortion in monolayer h-BN, and new energy states were created between valence and conduction band with the Fermi level shift. Notably, B atoms around vacancies attracted one another while repulsion happened between N atoms around vacancies, irrespective of vacancy density. The calculation of formation energy revealed that multi-vacancy including more B-vacancies has much lower formation energy than vacancies with more N-vacancies. This work suggests that multi-vacancy created in monolayer h-BN will have more B-vacancies and that the presence of multi-vacancy can make monolayer h-BN electrically conductive by the new energy states and the Fermi level shift.

Geometric and electronic structures of monolayer hexagonal boron nitride with multi-vacancy.

PubMed

Kim, Do-Hyun; Kim, Hag-Soo; Song, Min Woo; Lee, Seunghyun; Lee, Sang Yun

2017-01-01

Hexagonal boron nitride (h-BN) is an electrical insulator with a large band gap of 5 eV and a good thermal conductor of which melting point reaches about 3000 °C. Due to these properties, much attention was given to the thermal stability rather than the electrical properties of h-BN experimentally and theoretically. In this study, we report calculations that the electronic structure of monolayer h-BN can be influenced by the presence of a vacancy defect which leads to a geometric deformation in the hexagonal lattice structure. The vacancy was varied from mono- to tri-vacancy in a supercell, and different defective structures under the same vacancy density were considered in the case of an odd number of vacancies. Consequently, all cases of vacancy defects resulted in a geometric distortion in monolayer h-BN, and new energy states were created between valence and conduction band with the Fermi level shift. Notably, B atoms around vacancies attracted one another while repulsion happened between N atoms around vacancies, irrespective of vacancy density. The calculation of formation energy revealed that multi-vacancy including more B-vacancies has much lower formation energy than vacancies with more N-vacancies. This work suggests that multi-vacancy created in monolayer h-BN will have more B-vacancies and that the presence of multi-vacancy can make monolayer h-BN electrically conductive by the new energy states and the Fermi level shift.

Direct calculation of ice homogeneous nucleation rate for a molecular model of water

PubMed Central

Haji-Akbari, Amir; Debenedetti, Pablo G.

2015-01-01

Ice formation is ubiquitous in nature, with important consequences in a variety of environments, including biological cells, soil, aircraft, transportation infrastructure, and atmospheric clouds. However, its intrinsic kinetics and microscopic mechanism are difficult to discern with current experiments. Molecular simulations of ice nucleation are also challenging, and direct rate calculations have only been performed for coarse-grained models of water. For molecular models, only indirect estimates have been obtained, e.g., by assuming the validity of classical nucleation theory. We use a path sampling approach to perform, to our knowledge, the first direct rate calculation of homogeneous nucleation of ice in a molecular model of water. We use TIP4P/Ice, the most accurate among existing molecular models for studying ice polymorphs. By using a novel topological approach to distinguish different polymorphs, we are able to identify a freezing mechanism that involves a competition between cubic and hexagonal ice in the early stages of nucleation. In this competition, the cubic polymorph takes over because the addition of new topological structural motifs consistent with cubic ice leads to the formation of more compact crystallites. This is not true for topological hexagonal motifs, which give rise to elongated crystallites that are not able to grow. This leads to transition states that are rich in cubic ice, and not the thermodynamically stable hexagonal polymorph. This mechanism provides a molecular explanation for the earlier experimental and computational observations of the preference for cubic ice in the literature. PMID:26240318

New Findings on the Phase Transitions in Li(sub 1-x)CoO(sub 2) and Li(sub 1-x)NiO(sub 2) Cathode Materials During Cycling: In Situ Synchrotron X-Ray Diffraction Studies

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

Yang, X. Q.; Sun, X.; McBreen, J.

The authors have utilized synchrotron x-ray radiation to perform ''in situ'' x-ray diffraction studies on Li{sub 1-x}CoO{sub 2} and Li{sub 1-x}NiO{sub 2} cathodes. A C/10 charging rate was used for a Li/Li{sub 1-x}CoO{sub 2} cell. For the Li/Li{sub 1-x}NiO{sub 2} cells, C/13 and C/84 rates were applied. The in situ XRD data were collected during the first charge from 3.5 to 5.2 V. For the Li{sub 1-x}CoO{sub 2} cathode, in the composition range of x = 0 to x = 0.5, a new intermediate phase H2a was observed in addition to the two expected hexagonal phases H1 and H2. Inmore » the region very close to x = 0.5, some spectral signatures for the formation of a monoclinic phase M1 were also observed. Further, in the x = 0.8 to x = 1 region, the formation of a CdI{sub 2} type hexagonal phase has been confirmed. However, this new phase is transformed from a CdCl{sub 2} type hexagonal phase, rather than from a monoclinic phase M2 as previously reported in the literature. For the Li{sub 1-x}NiO{sub 2} system, by taking the advantage of the high resolution in 2{theta} angles through the synchrotron based XRD technique, they were able to identify a two-phase coexistence region of hexagonal phase H1 and H2, which has been mistakenly indexed as a single phase region for monoclinic phase M1. Interesting similarities and differences between these two systems are also discussed.« less

Optical patterning of trapped charge in nitrogen-doped diamond

NASA Astrophysics Data System (ADS)

Jayakumar, Harishankar; Henshaw, Jacob; Dhomkar, Siddharth; Pagliero, Daniela; Laraoui, Abdelghani; Manson, Neil B.; Albu, Remus; Doherty, Marcus W.; Meriles, Carlos A.

2016-08-01

The nitrogen-vacancy (NV) centre in diamond is emerging as a promising platform for solid-state quantum information processing and nanoscale metrology. Of interest in these applications is the manipulation of the NV charge, which can be attained by optical excitation. Here, we use two-colour optical microscopy to investigate the dynamics of NV photo-ionization, charge diffusion and trapping in type-1b diamond. We combine fixed-point laser excitation and scanning fluorescence imaging to locally alter the concentration of negatively charged NVs, and to subsequently probe the corresponding redistribution of charge. We uncover the formation of spatial patterns of trapped charge, which we qualitatively reproduce via a model of the interplay between photo-excited carriers and atomic defects. Further, by using the NV as a probe, we map the relative fraction of positively charged nitrogen on localized optical excitation. These observations may prove important to transporting quantum information between NVs or to developing three-dimensional, charge-based memories.

Polymer Treatment by Plasma Immersion Ion Implantation of Nitrogen for Formation of Diamond-Like Carbon Film

NASA Astrophysics Data System (ADS)

Tan, Ing Hwie; Ueda, Mario; Kostov, Konstantin; Nascente, Pedro Augusto P.; Demarquette, Nicole Raymonde

2004-09-01

Nitrogen ions were implanted by plasma immersion in Kapton, Mylar and polypropylene, with the objective of forming a diamond-like carbon layer on these polymers. The Raman spectrum of the implanted polypropylene showed typical Diamond-Like Carbon (DLC) graphite (G) and disorder (D) peaks, with an sp3/sp2 hybridization ratio of approximately 0.4 to 0.6. The XPS analysis of the three implanted polymers also showed peaks of C-C and N-C bonds in the sp3 configuration, with hybridization ratios in the same range as the Raman result. The implanted polymers were exposed to oxygen plasma to test the resistance of the polymers to oxygen degradation. Mass loss rate results, however, showed that the DLC layer formed is not sufficiently robust for this application. Nevertheless, the layer formed can be suitable for other applications such as in gas barriers in beverage containers. Further study of implantation conditions may improve the quality of the DLC layer.

Diamond-like-carbon nanoparticle production and agglomeration following UV multi-photon excitation of static naphthalene/helium gas mixtures

NASA Astrophysics Data System (ADS)

Walsh, A. J.; Tielens, A. G. G. M.; Ruth, A. A.

2016-07-01

We report the formation of nanoparticles with significant diamond character after UV multi-photon laser excitation of gaseous naphthalene, buffered in static helium gas, at room temperature. The nanoparticles are identified in situ by their absorption and scattering spectra between 400 and 850 nm, which are modeled using Mie theory. Comparisons of the particles' spectroscopic and optical properties with those of carbonaceous materials indicate a sp3/sp2 hybridization ratio of 8:1 of the particles formed. The particle extinction in the closed static (unstirred) gas-phase system exhibits a complex and quasi-oscillatory time dependence for the duration of up to several hours with periods ranging from seconds to many minutes. The extinction dynamics of the system is based on a combination of transport features and particle interaction, predominantly agglomeration. The relatively long period of agglomeration allows for a unique analysis of the agglomeration process of diamond-like carbon nanoparticles in situ.

Enhanced field electron emission from aligned diamond-like carbon nanorod arrays prepared by reactive ion beam etching

NASA Astrophysics Data System (ADS)

Zhao, Yong; Qin, Shi-Qiao; Zhang, Xue-Ao; Chang, Sheng-Li; Li, Hui-Hui; Yuan, Ji-Ren

2016-05-01

Homogeneous diamond-like carbon (DLC) films were deposited on Si supports by a pulsed filtered cathodic vacuum arc deposition system. Using DLC films masked by Ni nanoparticles as precursors, highly aligned diamond-like carbon nanorod (DLCNR) arrays were fabricated by the etching of inductively coupled radio frequency oxygen plasma. The as-prepared DLCNR arrays exhibit excellent field emission properties with a low turn-on field of 2.005 V μm-1 and a threshold field of 4.312 V μm-1, respectively. Raman spectroscopy and x-ray photoelectron spectroscopy were employed to determine the chemical bonding structural change of DLC films before and after etching. It is confirmed that DLC films have good connection with Si supports via the formation of the SiC phase, and larger conductive sp2 domains are formed in the as-etched DLC films, which play essential roles in the enhanced field emission properties for DLCNR arrays.

Optical patterning of trapped charge in nitrogen-doped diamond.

PubMed

Jayakumar, Harishankar; Henshaw, Jacob; Dhomkar, Siddharth; Pagliero, Daniela; Laraoui, Abdelghani; Manson, Neil B; Albu, Remus; Doherty, Marcus W; Meriles, Carlos A

2016-08-30

The nitrogen-vacancy (NV) centre in diamond is emerging as a promising platform for solid-state quantum information processing and nanoscale metrology. Of interest in these applications is the manipulation of the NV charge, which can be attained by optical excitation. Here, we use two-colour optical microscopy to investigate the dynamics of NV photo-ionization, charge diffusion and trapping in type-1b diamond. We combine fixed-point laser excitation and scanning fluorescence imaging to locally alter the concentration of negatively charged NVs, and to subsequently probe the corresponding redistribution of charge. We uncover the formation of spatial patterns of trapped charge, which we qualitatively reproduce via a model of the interplay between photo-excited carriers and atomic defects. Further, by using the NV as a probe, we map the relative fraction of positively charged nitrogen on localized optical excitation. These observations may prove important to transporting quantum information between NVs or to developing three-dimensional, charge-based memories.

Optical patterning of trapped charge in nitrogen-doped diamond

PubMed Central

Jayakumar, Harishankar; Henshaw, Jacob; Dhomkar, Siddharth; Pagliero, Daniela; Laraoui, Abdelghani; Manson, Neil B.; Albu, Remus; Doherty, Marcus W.; Meriles, Carlos A.

2016-01-01

The nitrogen-vacancy (NV) centre in diamond is emerging as a promising platform for solid-state quantum information processing and nanoscale metrology. Of interest in these applications is the manipulation of the NV charge, which can be attained by optical excitation. Here, we use two-colour optical microscopy to investigate the dynamics of NV photo-ionization, charge diffusion and trapping in type-1b diamond. We combine fixed-point laser excitation and scanning fluorescence imaging to locally alter the concentration of negatively charged NVs, and to subsequently probe the corresponding redistribution of charge. We uncover the formation of spatial patterns of trapped charge, which we qualitatively reproduce via a model of the interplay between photo-excited carriers and atomic defects. Further, by using the NV as a probe, we map the relative fraction of positively charged nitrogen on localized optical excitation. These observations may prove important to transporting quantum information between NVs or to developing three-dimensional, charge-based memories. PMID:27573190

OPTIMIZATION OF DEEP DRILLING PERFORMANCE--DEVELOPMENT AND BENCHMARK TESTING OF ADVANCED DIAMOND PRODUCT DRILL BITS & HP/HT FLUIDS TO SIGNIFICANTLY IMPROVE RATES OF PENETRATION

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

Alan Black; Arnis Judzis

2004-10-01

The industry cost shared program aims to benchmark drilling rates of penetration in selected simulated deep formations and to significantly improve ROP through a team development of aggressive diamond product drill bit--fluid system technologies. Overall the objectives are as follows: Phase 1--Benchmark ''best in class'' diamond and other product drilling bits and fluids and develop concepts for a next level of deep drilling performance; Phase 2--Develop advanced smart bit-fluid prototypes and test at large scale; and Phase 3--Field trial smart bit-fluid concepts, modify as necessary and commercialize products. As of report date, TerraTek has concluded all major preparations for themore » high pressure drilling campaign. Baker Hughes encountered difficulties in providing additional pumping capacity before TerraTek's scheduled relocation to another facility, thus the program was delayed further to accommodate the full testing program.« less

Synthesis and characterization of two novel chiral-type formate frameworks templated by protonated diethylamine and ammonium cations

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

Mączka, Mirosław, E-mail: m.maczka@int.pan.wroc.pl; Gągor, Anna; Hanuza, Jerzy

2017-01-15

Two novel formate frameworks templated by ammonium and diethylammonium (DEtA{sup +}) cations have been synthesized. Chemical analysis as well as optical, Raman and IR studies showed partial substitution of nickel ions by Cr(III) or Fe(III). X-ray diffraction revealed that these compounds crystallize in the chiral-type structure of P6{sub 3}22 symmetry. The oxygen atoms from formate ligands form octahedral coordination around the metal centers and the octahedra are bridged by the formate groups in the anti-anti mode configuration forming the hexagonal structure with large channels expanding along the c direction. The channels are filled with disordered DEtA{sup +} and NH{sub 4}{supmore » +} ions and they show unusual compression with the c/a ratio of only 0.862 and 0.852 for the iron- and chromium-containing compound, respectively. Magnetic studies revealed that the both compounds order magnetically at low temperatures but the ordering temperature is significantly higher for the iron compound (37 K) compared to the chromium analogue (26 K). - Graphical abstract: Temperature dependence of magnetization M of DEtAFeNi showing magnetic order at 37 K. - Highlights: • Two novel chiral formates of P6{sub 3}22 symmetry were synthesized. • The structures contain strongly compressed hexagonal channels filled with disordered cations. • The obtained compounds exhibit magnetic order at low temperatures. • Raman, IR and absorption spectra prove incorporation of Cr(III) and Fe(III) in the frameworks.« less

Accelerated formation of cubic phases in phosphatidylethanolamine dispersions.

PubMed Central

Tenchov, B; Koynova, R; Rapp, G

1998-01-01

By means of x-ray diffraction we show that several sodium salts and the disaccharides sucrose and trehalose strongly accelerate the formation of cubic phases in phosphatidylethanolamine (PE) dispersions upon temperature cycling through the lamellar liquid crystalline-inverted hexagonal (Lalpha-HII) phase transition. Ethylene glycol does not have such an effect. The degree of acceleration increases with the solute concentration. Such an acceleration has been observed for dielaidoyl PE (DEPE), dihexadecyl PE, and dipalmitoyl PE. It was investigated in detail for DEPE dispersions. For DEPE (10 wt% of lipid) aqueous dispersions at 1 M solute concentration, 10-50 temperature cycles typically result in complete conversion of the Lalpha phase into cubic phase. Most efficient is temperature cycling executed by laser flash T-jumps. In that case the conversion completes within 10-15 cycles. However, the cubic phases produced by laser T-jumps are less ordered in comparison to the rather regular cubic structures produced by linear, uniform temperature cycling at 10 degrees C/min. Temperature cycles at scan rates of 1-3 degrees C/min also induce the rapid formation of cubic phases. All solutes used induce the formation of Im3m (Q229) cubic phase in 10 wt% DEPE dispersions. The initial Im3m phases appearing during the first temperature cycles have larger lattice parameters that relax to smaller values with continuation of the cycling after the disappearance of the Lalpha phase. A cooperative Im3m --> Pn3m transition takes place at approximately 85 degrees C and transforms the Im3m phase into a mixture of coexisting Pn3m (Q224) and Im3m phases. The Im3m/Pn3m lattice parameter ratio is 1. 28, as could be expected from a representation of the Im3m and Pn3m phases with the primitive and diamond infinite periodic minimal surfaces, respectively. At higher DEPE contents ( approximately 30 wt%), cubic phase formation is hindered after 20-30 temperature cycles. The conversion does not go through, but reaches a stage with coexisting Ia3d (Q230) and Lalpha phases. Upon heating, the Ia3d phase cooperatively transforms into a mixture of, presumably, Im3m and Pn3m phases at about the temperature of the Lalpha-HII transition. This transformation is readily reversible with the temperature. The lattice parameters of the DEPE cubic phases are temperature-insensitive in the Lalpha temperature range and decrease with the temperature in the range of the HII phase. PMID:9675186

Determination of graphene's edge energy using hexagonal graphene quantum dots and PM7 method.

PubMed

Vorontsov, Alexander V; Tretyakov, Evgeny V

2018-05-18

Graphene quantum dots (GQDs) are important for a variety of applications and designs, and the shapes of GQDs rely on the energy of their boundaries. Presently, many methods have been developed for the preparation of GQDs with the required boundaries, shapes and edge terminations. However, research on the properties of GQDs and their applications is limited due to the unavailability of these compounds in pure form. In the present computational study, the standard enthalpy of formation, the standard enthalpy of formation of edges and the standard enthalpy of hydrogenation are studied for hexagonal GQDs with purely zigzag and armchair edges in non-passivated and H-passivated forms using the semiempirical quantum chemistry method pm7. The standard enthalpy of formation of the edge is found to remain constant for GQDs studied in the range of 1 to 6 nm, and the enthalpies of edge C atoms are 32.4 and 35.5 kcal mol-1 for armchair and zigzag edges, respectively. In contrast to some literature data, the standard enthalpy of formation of hydrogenated edges is far from zero, and the values are 7.3 and 8.0 kcal mol-1 C for armchair and zigzag edges, respectively. The standard enthalpy of hydrogenation is found to be -10.2 and -9.72 eV nm-1 for the armchair and zigzag edges, respectively.

The creation of a biomimetic interface between boron-doped diamond and immobilized proteins.

PubMed

Hoffmann, René; Kriele, Armin; Obloh, Harald; Tokuda, Norio; Smirnov, Waldemar; Yang, Nianjun; Nebel, Christoph E

2011-10-01

Immobilization of proteins on a solid electrode is to date done by chemical cross-linking or by addition of an adjustable intermediate. In this paper we introduce a concept where a solid with variable surface properties is optimized to mediate binding of the electron-transfer protein Cytochrome c (Cyt c) by mimicking the natural binding environment. It is shown that, as a carbon-based material, boron-doped diamond can be adjusted by simple electrochemical surface treatments to the specific biochemical requirements of Cyt c. The structure and functionality of passively adsorbed Cyt c on variously terminated diamond surfaces were characterized in detail using a combination of electrochemical techniques and atomic force microscopy with single-molecule resolution. Partially oxidized diamond allowed stable immobilization of Cyt c together with high electron transfer activity, driven by a combination of electrostatic and hydrophobic interactions. This surface mimics the natural binding partner, where coarse orientation is governed by electrostatic interaction of the protein's dipole and hydrophobic interactions assist in formation of the electron transfer complex. The optimized surface mediated electron transfer kinetics around 100 times faster than those reported for other solids and even faster kinetics than on self-assembled monolayers of alkanethiols. Copyright © 2011 Elsevier Ltd. All rights reserved.

Osteoblast adhesion to orthopaedic implant alloys: Effects of cell adhesion molecules and diamond-like carbon coating

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

Kornu, R.; Kelly, M.A.; Smith, R.L.

1996-11-01

In total joint arthroplasty, long-term outcomes depend in part on the biocompatibility of implant alloys. This study analyzed effects of surface finish and diamond-like carbon coating on osteoblast cell adhesion to polished titanium-aluminum-vanadium and polished or grit-blasted cobalt-chromium-molybdenum alloys. Osteoblast binding was tested in the presence and absence of the cell adhesion proteins fibronectin, laminin, fibrinogen, and vitronectin and was quantified by measurement of DNA content. Although adherence occurred in serum-free medium, maximal osteoblast binding required serum and was similar for titanium and cobalt alloys at 2 and 12 hours. With the grit-blasted cobalt alloy, cell binding was reduced 48%more » (p < 0.05) by 24 hours. Coating the alloys with diamond-like carbon did not alter osteoblast adhesion, whereas fibronectin pretreatment increased cell binding 2.6-fold (p < 0.05). In contrast, fibrinogen, vitronectin, and laminin did not enhance cell adhesion. These results support the hypothesis that cell adhesion proteins can modify cell binding to orthopaedic alloys. Although osteoblast binding was not affected by the presence of diamond-like carbon, this coating substance may influence other longer term processes, such as bone formation, and deserves further study. 40 refs., 4 figs.« less

Diamond Head Revisited with Ammonium Dichromate.

ERIC Educational Resources Information Center

Arrigoni, Edward

1981-01-01

The classroom demonstration using ammonium dichromate to simulate a volcanic eruption can be modified into a more dramatic and accurate representation of the geologic processes involved in the formation of a volcanic crater. The materials, demonstration setup, safety procedures, and applications to instruction are presented. (Author/WB)

Technology Development and Field Trials of EGS Drilling Systems at Chocolate Mountain

DOE Data Explorer

Steven Knudsen

2012-01-01

Polycrystalline diamond compact (PDC) bits are routinely used in the oil and gas industry for drilling medium to hard rock but have not been adopted for geothermal drilling, largely due to past reliability issues and higher purchase costs. The Sandia Geothermal Research Department has recently completed a field demonstration of the applicability of advanced synthetic diamond drill bits for production geothermal drilling. Two commercially-available PDC bits were tested in a geothermal drilling program in the Chocolate Mountains in Southern California. These bits drilled the granitic formations with significantly better Rate of Penetration (ROP) and bit life than the roller cone bit they are compared with. Drilling records and bit performance data along with associated drilling cost savings are presented herein. The drilling trials have demonstrated PDC bit drilling technology has matured for applicability and improvements to geothermal drilling. This will be especially beneficial for development of Enhanced Geothermal Systems whereby resources can be accessed anywhere within the continental US by drilling to deep, hot resources in hard, basement rock formations.

Structure and strain relaxation mechanisms of ultrathin epitaxial Pr2O3 films on Si(111)

NASA Astrophysics Data System (ADS)

Schroeder, T.; Lee, T.-L.; Libralesso, L.; Joumard, I.; Zegenhagen, J.; Zaumseil, P.; Wenger, C.; Lupina, G.; Lippert, G.; Dabrowski, J.; Müssig, H.-J.

2005-04-01

The structure of ultrathin epitaxial Pr2O3 films on Si(111) was studied by synchrotron radiation-grazing incidence x-ray diffraction. The oxide film grows as hexagonal Pr2O3 phase with its (0001) plane attached to the Si(111) substrate. The hexagonal (0001) Pr2O3 plane matches the in-plane symmetry of the hexagonal Si(111) surface unit cell by aligning the ⟨101¯0⟩Pr2O3 along the ⟨112¯⟩ Si directions. The small lattice mismatch of 0.5% results in the growth of pseudomorphic oxide films of high crystalline quality with an average domain size of about 50 nm. The critical thickness tc for pseudomorphic growth amounts to 3.0±0.5nm. The relaxation of the oxide film from pseudomorphism to bulk behavior beyond tc causes the introduction of misfit dislocations, the formation of an in-plane small angle mosaicity structure, and the occurence of a phase transition towards a (111) oriented cubic Pr2O3 film structure. The observed phase transition highlights the influence of the epitaxial interface energy on the stability of Pr2O3 phases on Si(111). A mechanism is proposed which transforms the hexagonal (0001) into the cubic (111) Pr2O3 epilayer structure by rearranging the oxygen network but leaving the Pr sublattice almost unmodified.

Defect mediated van der Waals epitaxy of hexagonal boron nitride on graphene

NASA Astrophysics Data System (ADS)

Heilmann, M.; Bashouti, M.; Riechert, H.; Lopes, J. M. J.

2018-04-01

Van der Waals heterostructures comprising of hexagonal boron nitride and graphene are promising building blocks for novel two-dimensional devices such as atomically thin transistors or capacitors. However, demonstrators of those devices have been so far mostly fabricated by mechanical assembly, a non-scalable and time-consuming method, where transfer processes can contaminate the surfaces. Here, we investigate a direct growth process for the fabrication of insulating hexagonal boron nitride on high quality epitaxial graphene using plasma assisted molecular beam epitaxy. Samples were grown at varying temperatures and times and studied using atomic force microscopy, revealing a growth process limited by desorption at high temperatures. Nucleation was mostly commencing from morphological defects in epitaxial graphene, such as step edges or wrinkles. Raman spectroscopy combined with x-ray photoelectron measurements confirm the formation of hexagonal boron nitride and prove the resilience of graphene against the nitrogen plasma used during the growth process. The electrical properties and defects in the heterostructures were studied with high lateral resolution by tunneling current and Kelvin probe force measurements. This correlated approach revealed a nucleation apart from morphological defects in epitaxial graphene, which is mediated by point defects. The presented results help understanding the nucleation and growth behavior during van der Waals epitaxy of 2D materials, and point out a route for a scalable production of van der Waals heterostructures.

Interaction of peridotite with Ca-rich carbonatite melt at 3.1 and 6.5 GPa: Implication for merwinite formation in upper mantle, and for the metasomatic origin of sublithospheric diamonds with Ca-rich suite of inclusions

NASA Astrophysics Data System (ADS)

Sharygin, Igor S.; Shatskiy, Anton; Litasov, Konstantin D.; Golovin, Alexander V.; Ohtani, Eiji; Pokhilenko, Nikolay P.

2018-03-01

We performed an experimental study, designed to reproduce the formation of an unusual merwinite + olivine-bearing mantle assemblage recently described as a part of a Ca-rich suite of inclusions in sublithospheric diamonds, through the interaction of peridotite with an alkali-rich Ca-carbonatite melt, derived from deeply subducted oceanic crust. In the first set of experiments, we studied the reaction between powdered Mg-silicates, olivine and orthopyroxene, and a model Ca-carbonate melt (molar Na:K:Ca = 1:1:2), in a homogeneous mixture, at 3.1 and 6.5 GPa. In these equilibration experiments, we observed the formation of a merwinite + olivine-bearing assemblage at 3.1 GPa and 1200 °C and at 6.5 GPa and 1300-1400 °C. The melts coexisting with this assemblage have a low Si and high Ca content (Ca# = molar 100 × Ca/(Ca + Mg) > 0.57). In the second set of experiments, we investigated reaction rims produced by interaction of the same Ca-carbonate melt (molar Na:K:Ca = 1:1:2) with Mg-silicate, olivine and orthopyroxene, single crystals at 3.1 GPa and 1300 °C and at 6.5 GPa and 1400 °C. The interaction of the Ca-carbonate melt with olivine leads to merwinite formation through the expected reaction: 2Mg2SiO4 (olivine) + 6CaCO3 (liquid) = Ca3MgSi2O8 (merwinite) + 3CaMg(CO3)2 (liquid). Thus, our experiments confirm the idea that merwinite in the upper mantle may originate via interaction of peridotite with Ca-rich carbonatite melt, and that diamonds hosting merwinite may have a metasomatic origin. It is remarkable that the interaction of the Ca-carbonate melt with orthopyroxene crystals does not produce merwinite both at 3.1 and 6.5 GPa. This indicates that olivine grain boundaries are preferable for merwinite formation in the upper mantle.

Dirac cones in isogonal hexagonal metallic structures

NASA Astrophysics Data System (ADS)

Wang, Kang

2018-03-01

A honeycomb hexagonal metallic lattice is equivalent to a triangular atomic one and cannot create Dirac cones in its electromagnetic wave spectrum. We study in this work the low-frequency electromagnetic band structures in isogonal hexagonal metallic lattices that are directly related to the honeycomb one and show that such structures can create Dirac cones. The band formation can be described by a tight-binding model that allows investigating, in terms of correlations between local resonance modes, the condition for the Dirac cones and the consequence of the third structure tile sustaining an extra resonance mode in the unit cell that induces band shifts and thus nonlinear deformation of the Dirac cones following the wave vectors departing from the Dirac points. We show further that, under structure deformation, the deformations of the Dirac cones result from two different correlation mechanisms, both reinforced by the lattice's metallic nature, which directly affects the resonance mode correlations. The isogonal structures provide new degrees of freedom for tuning the Dirac cones, allowing adjustment of the cone shape by modulating the structure tiles at the local scale without modifying the lattice periodicity and symmetry.

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

Kalsi, Deepti; Rayaprol, S.; Siruguri, V.

We report the crystallographic properties of RE{sub 2}NiGe{sub 3} (RE=La, Ce) synthesized by arc melting. Rietveld refinement on the powder neutron diffraction (ND) data suggest both compounds are isostructural and crystallize in the non-centrosymmetric Er{sub 2}RhSi{sub 3} type structure having hexagonal space group P6{sup ¯}2c. In the crystal structure of RE{sub 2}NiGe{sub 3}, two dimensional arrangements of nickel and germanium atoms lead to the formation of hexagonal layers with rare earth atoms sandwiched between them. Magnetic susceptibility measurements performed in low fields exhibit antiferromagnetic ordering in cerium compound around (T{sub o}=) 3.2 K. Neutron diffraction measurements at 2.8 K (i.e.,more » at T« less

The Role of Hexon Protein as a Molecular Mold in Patterning the Protein IX Organization in Human Adenoviruses.

PubMed

Reddy, Vijay S

2017-09-01

Adenoviruses are respiratory, ocular and enteric pathogens that form complex capsids, which are assembled from seven different structural proteins and composed of several core proteins that closely interact with the packaged dsDNA genome. The recent near-atomic resolution structures revealed that the interlacing continuous hexagonal network formed by the protein IX molecules is conserved among different human adenoviruses (HAdVs), but not in non-HAdVs. In this report, we propose a distinct role for the hexon protein as a "molecular mold" in enabling the formation of such hexagonal protein IX network that has been shown to preserve the stability and infectivity of HAdVs. Copyright © 2017 Elsevier Ltd. All rights reserved.

Implant-abutment connections on single crowns: a systematic review.

PubMed

Ceruso, F M; Barnaba, P; Mazzoleni, S; Ottria, L; Gargari, M; Zuccon, A; Bruno, G; DI Fiore, A

2017-01-01

Different implant-abutment connections have been developed in the effort of reducing mechanical and biological failure. The most frequent complications are screw loosening, abutment or implant fracture and marginal bone loss due to overload and bacterial micro-leakage. Ideal connection should work as a one-piece implant avoiding the formation of a micro-gap at the implant-abutment interface. Different in vitro and in vivo researches have been published to compare the implant-abutment connections actually available: external hexagon, internal hexagon and conical finding different amount of micro-gap, micro-leakage and marginal bone loss. The aim of this article is to describe, according to the most recent literature, different kind of fixture-abutment connections and their clinical and mechanical advantages or disadvantages.

Carolinas Coastal Change Processes Project data report for observations near Diamond Shoals, North Carolina, January-May 2009

USGS Publications Warehouse

Armstrong, Brandy N.; Warner, John C.; Voulgaris, George; List, Jeffrey H.; Thieler, E. Robert; Martini, Marinna A.; Montgomery, Ellyn T.

2011-01-01

This Open-File Report provides information collected for an oceanographic field study that occurred during January - May 2009 to investigate processes that control the sediment transport dynamics at Diamond Shoals, North Carolina. The objective of this report is to make the data available in digital form and to provide information to facilitate further analysis of the data. The report describes the background, experimental setup, equipment, and locations of the sensor deployments. The edited data are presented in time-series plots for rapid visualization of the data set, and in data files that are in the Network Common Data Format (netcdf). Supporting observational data are also included.

Colloidal alloys with preassembled clusters and spheres.

PubMed

Ducrot, Étienne; He, Mingxin; Yi, Gi-Ra; Pine, David J

2017-06-01

Self-assembly is a powerful approach for constructing colloidal crystals, where spheres, rods or faceted particles can build up a myriad of structures. Nevertheless, many complex or low-coordination architectures, such as diamond, pyrochlore and other sought-after lattices, have eluded self-assembly. Here we introduce a new design principle based on preassembled components of the desired superstructure and programmed nearest-neighbour DNA-mediated interactions, which allows the formation of otherwise unattainable structures. We demonstrate the approach using preassembled colloidal tetrahedra and spheres, obtaining a class of colloidal superstructures, including cubic and tetragonal colloidal crystals, with no known atomic analogues, as well as percolating low-coordination diamond and pyrochlore sublattices never assembled before.

“Non-hydrolytic” sol–gel synthesis of molybdenum sulfides

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

Leidich, Saskia; Buechele, Dominique; Lauenstein, Raphael

2016-10-15

Non-hydrolytic sol–gel reactions provide a low temperature solution based synthetic approach to solid-state materials. In this paper, reactions between molybdenum chloride and hexamethyldisilthiane in chloroform were explored, which gave access to both MoS{sub 2} and Mo{sub 2}S{sub 3} after heat treatment of as-recovered amorphous samples to 600–1000 °C. Interesting morphologies were obtained for MoS{sub 2}, ranging from fused spherical particles to well-defined nanoplatelets and nanoflakes. Both 2H- and 3R-MoS{sub 2} were observed, which formed thin hexagonal and triangular platelets, respectively. The platelets exhibited thicknesses of 10–30 nm, which corresponds to 15–50 MoS{sub 2} layers. No attempts to prevent agglomeration weremore » made, however, well separated platelets were observed for many samples. Heating at 1000 °C led to formation of Mo{sub 2}S{sub 3} for samples that showed well-defined MoS{sub 2} at lower temperatures, while less crystalline samples had a tendency to retain the MoS{sub 2} structure. - Graphical abstract: Overlay of variable pressure X-ray diffraction data of Al{sub 2}Mo{sub 3}O{sub 12} collected in a diamond anvil cell. Both subtle and discontinuous phase transitions are clearly observed. - Highlights: • Molybdenum sulfides were prepared by non-hydrolytic sol–gel chemistry. • Nanocrystalline 3R-MoS{sub 2} and 2H-MoS{sub 2}, and microcrystalline Mo{sub 2}S{sub 3} were obtained. • Particle morphology correlated strongly with crystalline phases. • Ultrathin platelets with limited tendency to agglomerate were recovered.« less

Role of stacking disorder in ice nucleation

NASA Astrophysics Data System (ADS)

Lupi, Laura; Hudait, Arpa; Peters, Baron; Grünwald, Michael; Gotchy Mullen, Ryan; Nguyen, Andrew H.; Molinero, Valeria

2017-11-01

The freezing of water affects the processes that determine Earth’s climate. Therefore, accurate weather and climate forecasts hinge on good predictions of ice nucleation rates. Such rate predictions are based on extrapolations using classical nucleation theory, which assumes that the structure of nanometre-sized ice crystallites corresponds to that of hexagonal ice, the thermodynamically stable form of bulk ice. However, simulations with various water models find that ice nucleated and grown under atmospheric temperatures is at all sizes stacking-disordered, consisting of random sequences of cubic and hexagonal ice layers. This implies that stacking-disordered ice crystallites either are more stable than hexagonal ice crystallites or form because of non-equilibrium dynamical effects. Both scenarios challenge central tenets of classical nucleation theory. Here we use rare-event sampling and free energy calculations with the mW water model to show that the entropy of mixing cubic and hexagonal layers makes stacking-disordered ice the stable phase for crystallites up to a size of at least 100,000 molecules. We find that stacking-disordered critical crystallites at 230 kelvin are about 14 kilojoules per mole of crystallite more stable than hexagonal crystallites, making their ice nucleation rates more than three orders of magnitude higher than predicted by classical nucleation theory. This effect on nucleation rates is temperature dependent, being the most pronounced at the warmest conditions, and should affect the modelling of cloud formation and ice particle numbers, which are very sensitive to the temperature dependence of ice nucleation rates. We conclude that classical nucleation theory needs to be corrected to include the dependence of the crystallization driving force on the size of the ice crystallite when interpreting and extrapolating ice nucleation rates from experimental laboratory conditions to the temperatures that occur in clouds.

The phase behavior of cationic lipid-DNA complexes.

PubMed Central

May, S; Harries, D; Ben-Shaul, A

2000-01-01

We present a theoretical analysis of the phase behavior of solutions containing DNA, cationic lipids, and nonionic (helper) lipids. Our model allows for five possible structures, treated as incompressible macroscopic phases: two lipid-DNA composite (lipoplex) phases, namely, the lamellar (L(alpha)(C)) and hexagonal (H(II)(C)) complexes; two binary (cationic/neutral) lipid phases, that is, the bilayer (L(alpha)) and inverse-hexagonal (H(II)) structures, and uncomplexed DNA. The free energy of the four lipid-containing phases is expressed as a sum of composition-dependent electrostatic, elastic, and mixing terms. The electrostatic free energies of all phases are calculated based on Poisson-Boltzmann theory. The phase diagram of the system is evaluated by minimizing the total free energy of the three-component mixture with respect to all the compositional degrees of freedom. We show that the phase behavior, in particular the preferred lipid-DNA complex geometry, is governed by a subtle interplay between the electrostatic, elastic, and mixing terms, which depend, in turn, on the lipid composition and lipid/DNA ratio. Detailed calculations are presented for three prototypical systems, exhibiting markedly different phase behaviors. The simplest mixture corresponds to a rigid planar membrane as the lipid source, in which case, only lamellar complexes appear in solution. When the membranes are "soft" (i.e., low bending modulus) the system exhibits the formation of both lamellar and hexagonal complexes, sometimes coexisting with each other, and with pure lipid or DNA phases. The last system corresponds to a lipid mixture involving helper lipids with strong propensity toward the inverse-hexagonal phase. Here, again, the phase diagram is rather complex, revealing a multitude of phase transitions and coexistences. Lamellar and hexagonal complexes appear, sometimes together, in different regions of the phase diagram. PMID:10733951

Rotating non-Boussinesq Rayleigh-Benard convection

NASA Astrophysics Data System (ADS)

Moroz, Vadim Vladimir

This thesis makes quantitative predictions about the formation and stability of hexagonal and roll patterns in convecting system unbounded in horizontal direction. Starting from the Navier-Stokes, heat and continuity equations, the convection problem is then reduced to normal form equations using equivariant bifurcation theory. The relative stabilities of patterns lying on a hexagonal lattice in Fourier space are then determined using appropriate amplitude equations, with coefficients obtained via asymptotic expansion of the governing partial differential equations, with the conducting state being the base state, and the control parameter and the non-Boussinesq effects being small. The software package Mathematica was used to calculate amplitude coefficients of the appropriate coupled Ginzburg-Landau equations for the rigid-rigid and free-free case. A Galerkin code (initial version of which was written by W. Pesch et al.) is used to determine pattern stability further from onset and for strongly non-Boussinesq fluids. Specific predictions about the stability of hexagon and roll patterns for realistic experimental conditions are made. The dependence of the stability of the convective patterns on the Rayleigh number, planform wavenumber and the rotation rate is studied. Long- and shortwave instabilities, both steady and oscillatory, are identified. For small Prandtl numbers oscillatory sideband instabilities are found already very close to onset. A resonant mode interaction in hexagonal patterns arising in non-Boussinesq Rayleigh-Benard convection is studied using symmetry group methods. The lowest-order coupling terms for interacting patterns are identified. A bifurcation analysis of the resulting system of equations shows that the bifurcation is transcritical. Stability properties of resulting patterns are discussed. It is found that for some fluid properties the traditional hexagon convection solution does not exist. Analytical results are supported by numerical solutions of the convection equations using the Galerkin procedure and a Floquet analysis.

Role of stacking disorder in ice nucleation.

PubMed

Lupi, Laura; Hudait, Arpa; Peters, Baron; Grünwald, Michael; Gotchy Mullen, Ryan; Nguyen, Andrew H; Molinero, Valeria

2017-11-08

The freezing of water affects the processes that determine Earth's climate. Therefore, accurate weather and climate forecasts hinge on good predictions of ice nucleation rates. Such rate predictions are based on extrapolations using classical nucleation theory, which assumes that the structure of nanometre-sized ice crystallites corresponds to that of hexagonal ice, the thermodynamically stable form of bulk ice. However, simulations with various water models find that ice nucleated and grown under atmospheric temperatures is at all sizes stacking-disordered, consisting of random sequences of cubic and hexagonal ice layers. This implies that stacking-disordered ice crystallites either are more stable than hexagonal ice crystallites or form because of non-equilibrium dynamical effects. Both scenarios challenge central tenets of classical nucleation theory. Here we use rare-event sampling and free energy calculations with the mW water model to show that the entropy of mixing cubic and hexagonal layers makes stacking-disordered ice the stable phase for crystallites up to a size of at least 100,000 molecules. We find that stacking-disordered critical crystallites at 230 kelvin are about 14 kilojoules per mole of crystallite more stable than hexagonal crystallites, making their ice nucleation rates more than three orders of magnitude higher than predicted by classical nucleation theory. This effect on nucleation rates is temperature dependent, being the most pronounced at the warmest conditions, and should affect the modelling of cloud formation and ice particle numbers, which are very sensitive to the temperature dependence of ice nucleation rates. We conclude that classical nucleation theory needs to be corrected to include the dependence of the crystallization driving force on the size of the ice crystallite when interpreting and extrapolating ice nucleation rates from experimental laboratory conditions to the temperatures that occur in clouds.

Carbon isotope fractionation between Fe-carbide and diamond; a light C isotope reservoir in the deep Earth and Core?

NASA Astrophysics Data System (ADS)

Mikhail, S.; Jones, A. P.; Hunt, S. A.; Guillermier, C.; Dobson, D. P.; Tomlinson, E.; Dan, H.; Milledge, H.; Franchi, I.; Wood, I.; Beard, A.; Verchovsky, S.

2010-12-01

The largest accessible reservoir for terrestrial carbon is the mantle; however the core may yield even more. Carbon is commonly proposed as the light element (or one of) to make up the observed density deficit in the earth’s metallic core (NAKAJIMA et al., 2009). The potential isotopic effects of carbon incorporation into the core have not yet been investigated. In-situ ion probe (nanoSIMS) mapping and imaging of carbon isotope variations across rare sub-mm-scale Fe-rich carbide inclusions in mantle diamond (from Jagersfontein, South Africa) show the carbide to be significantly depleted in 13C relative to their diamond host. Distinctive textures suggest metallic liquid precipitates similar in geometry to (giant) nitrogen platelets, controlled by the octahedral symmetry of diamond, which we interpret as syngenic formation. The difference in δ13C values between the two natural phases for diamond-Fe carbide, gives an isotopic fractionation factor (ΔC) which agrees well with HPHT multi-anvil experiments (5-9 GPa and >1400°C). Our measured ΔC between Fe-carbide and diamond may only have local significance, but the measured isotopic values represent characterization of the highest PT carbide known (i.e. > minimum depth of the diamond stability field ≈ 150 km). The direction and magnitude of ΔC agrees with observations of the ΔC between cohenite-graphite in iron meteorites (DEINES and WICKMAN, 1975) and both agree with HPHT experiments, thus suggesting that carbon in the deep Earth, and particularly in the core, may be similarly fractionated (i.e. depleted in the 13C). Since metallic liquid drained from the silicate mantle to form the core during the early Earth, we can use our values as a proxy to constrain evolution of deep carbon reservoirs such as the core and bulk silicate Earth. For example, we can test the suggestion of Grady et al (2004) that the upper mantle value of δ13C ≈ -5 ‰ may not be representative of the bulk Earth, since solar system meteorites (from Mars, Vesta and the Moon) suggest a preferred value of δ13C ≈ -20 +/- 4 ‰. If we adopt this particular model, not only could we explain fractionation between a bulk silicate Earth δ13C value of -5 ‰ from an initial δ13C value of -20 ‰, but we can constrain the relative proportion of carbon in the core/mantle by using simple isotopic mass balance. Such fractionation of carbon isotopes between HPT carbides (and/or metallic iron) within the lower mantle and core would be expected immediately from the time of core formation. Therefore, isotopically light carbon reservoirs may have been present deep in the Earth throughout its history, offering an alternative explanation for light carbon (eg in diamonds) which was not formed by, and/or predated subduction of oceanic crust and organic carbon. Deines, P. and Wickman, F. E., 1975. GCA; Grady, M. M. et al. 2004. Int Journal of Astrobiology; Nakajima, Y. et al. K.-i., 2009. Physics of the Earth and Planetary Interiors.

In situ crystal chemical study of solid diamond inclusions from Quaternary alluvial deposit in the Siberian craton

NASA Astrophysics Data System (ADS)

Dera, P. K.; Manghnani, M. H.; Hushur, A.; Sobolev, N. V.; Logvinova, A. M.; Newville, M.; Lanzirotti, A.

2013-12-01

Kimberlites belong to rare rock type available only within the Earth's cratonic areas and have been a subject of detailed studies because of the great depth of their origin in the mantle. Kimberlitic diamonds often contain pristine inclusions derived from significant depths with different histories of their origins. Many of kimberlitic diamonds were formed in ultramafic (peridotitic) and mafic (eclogitic) environments of the upper mantle. Thus far only a handful of comprehensive in situ studies including single-crystal X-ray diffraction characterization of pristine diamond solid inclusions have been reported (e.g. Kunz et al. 2001, Nestola et al. 2011). In this study five single-crystal solid inclusions from diamonds found in the Quaternary alluvial deposit in NW of the Siberian craton have been investigated using a combination of in situ single-crystal X-ray diffraction, Raman spectroscopy, synchrotron X-ray microfluorescence and X-ray Absorption Near Edge Spectroscopy (XANES). The grains were identified to be a suite of major upper mantle minerals including olivine, enstatite orthopyroxene (opx), C2/c omphacite clinopyroxene (cpx) and majoritic garnet (two grains), indicating eclogitic origin. All five inclusions are chemically homogeneous, do not show compositional zoning, and exhibit very similar major element chemistry, with significant amounts of Mn2+, Ni2+ and Cr3+ incorporated into the crystal structures, suggesting common geologic origin. All samples were studied in situ, while still embedded in the diamond crystals. High quality single-crystal X-ray diffraction data was collected at the Advanced Photon Source, Argonne National Laboratory to reveal details of the crystal structures and provide crystal chemical information. Some of the structural characteristics of the solid inclusions were found to be fairly uncommon, e.g. the orthoenstatite exhibits an unusually high Ca2+ content (Carlson et al. 1988), and omphacite occurs as the less common C2/c polymorph (Banno, 1970), both of which are considered signatures of eclogitic high-temperature facies. Fe Ka-edge XANES was used to investigate the oxidation state of iron in the solid inclusions. All of the inclusions show predominantly Fe2+, indicating reducing conditions of formation. The combined results of our spectroscopic and diffraction experiments will be interpreted in the context of the conditions and mechanism of formation (syngenesis vs. protogenesis) and possible retrograde transformation the inclusions may have experienced when transported to the surface. References Carlson, W.D. J.S. Swinnea, D.E. Miser (1988) 'Stability of orthoenstatite at high temperature and low pressure' Amer. Mineral. 73: 1255-1263. Banno, S. (1970) 'Classification of eclogites in terms of physical condition of their origin' Phys. Earth. Planet. Interiors 3: 405-421. Kunz, M., P. Gillet, et al. (2002). "Combined in situ X-ray diffraction and Raman spectroscopy on majoritic garnet inclusions in diamonds." Earth and Planet. Sci. Lett. 198: 485-493. Nestola, F., P. Nimis, et al. (2011). "First crystal-structure determination of olivine in diamond: Composition and implications for provenance in the Earth's mantle." Earth and Planet. Sci. Lett. 305: 249-255.

The influence of sterilization on nitrogen-included ultrananocrystalline diamond for biomedical applications.

PubMed

Tong, Wei; Tran, Phong A; Turnley, Ann M; Aramesh, Morteza; Prawer, Steven; Brandt, Milan; Fox, Kate

2016-04-01

Diamond has shown great potential in different biomedical applications, but the effects of sterilization on its properties have not been investigated. Here, we studied the influence of five sterilization techniques (solvent cleaning, oxygen plasma, UV irradiation, autoclave and hydrogen peroxide) on nitrogen-included ultrananocrystalline diamond. The chemical modification of the diamond surface was evaluated using X-ray photoelectron spectroscopy and water contact angle measurements. Different degrees of surface oxidation and selective sp(2) bonded carbon etching were found following all sterilization techniques, resulting in an increase of hydrophilicity. Higher viabilities of in vitro mouse 3T3 fibroblasts and rat cortical neuron cells were observed on oxygen plasma, autoclave and hydrogen peroxide sterilized diamond, which correlated with their higher hydrophilicity. By examination of apatite formation in simulated body fluid, in vivo bioactivity was predicted to be best on those surfaces which have been oxygen plasma treated and lowest on those which have been exposed to UV irradiation. The charge injection properties were also altered by the sterilization process and there appears to be a correlation between these changes and the degree of oxygen termination of the surface. We find that the modification brought by autoclave, oxygen plasma and hydrogen peroxide were most consistent with the use of N-UNCD in biological applications as compared to samples sterilized by solvent cleaning or UV exposure or indeed non-sterilized. A two-step process of sterilization by hydrogen peroxide following oxygen plasma treatment was then suggested. However, the final choice of sterilization technique will depend on the intended end application. Copyright © 2015 Elsevier B.V. All rights reserved.

Formation of Nanostructures on the Nickel Metal Surface in Ionic Liquid under Anodizing

NASA Astrophysics Data System (ADS)

Lebedeva, O. K.; Root, N. V.; Kultin, D. Yu.; Kalmykov, K. B.; Kustov, L. M.

2018-05-01

The formation of nanostructures in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide on the surface of a nickel electrode during anodizing was studied. Hexagonal ordered surface nanostructures were found to form in a narrow range of current densities. The form of the potential transients of the nickel electrode corresponded to the morphology of the nickel surface obtained which was studied by electron microscopy. No other types of nanostructures were found under the electrosynthesis conditions under study.

Correlation of Structure, Tunable Colors, and Lifetimes of (Sr, Ca, Ba)Al₂O₄:Eu2+, Dy3+ Phosphors.

PubMed

Xie, Qidi; Li, Bowen; He, Xin; Zhang, Mei; Chen, Yan; Zeng, Qingguang

2017-10-18

(Sr, Ca, Ba)Al₂O₄:Eu 2+ , Dy 3+ phosphors were prepared via a high temperature solid-state reaction method. The correlation of phase structure, optical properties and lifetimes of the phosphors are investigated in this work. For the (Sr, Ca)Al₂O₄:Eu 2+ ,Dy 3+ phosphors, the different phase formation from monoclinic SrAl₂O₄ phase to hexagonal SrAl₂O₄ phase to monoclinic CaAl₂O₄ phase was observed when the Ca content increased. The emission color of SrAl₂O₄:Eu 2+ , Dy 3+ phosphors varied from green to blue. For the (Sr, Ba)Al₂O₄:Eu 2+ , Dy 3+ phosphors, different phase formation from the monoclinic SrAl₂O₄ phase to the hexagonal BaAl₂O₄ phase was observed, along with a shift of emission wavelength from 520 nm to 500 nm. More interestingly, the decay time of SrAl₂O₄:Eu 2+ , Dy 3+ changed due to the different phase formations. Lifetime can be dramatically shortened by the substitution of Sr 2+ with Ba 2+ cations, resulting in improving the performance of the alternating current light emitting diode (AC-LED). Finally, intense LEDs are successfully obtained by combining these phosphors with Ga(In)N near UV chips.

Phase composition and microstructure of WC-Co alloys obtained by selective laser melting

NASA Astrophysics Data System (ADS)

Khmyrov, Roman S.; Shevchukov, Alexandr P.; Gusarov, Andrey V.; Tarasova, Tatyana V.

2018-03-01

Phase composition and microstructure of initial WC, BK8 (powder alloy 92 wt.% WC-8 wt.% Co), Co powders, ball-milled powders with four different compositions (1) 25 wt.% WC-75 wt.% Co, (2) 30 wt.% BK8-70 wt.% Co, (3) 50 wt.% WC-50 wt.% Co, (4) 94 wt.% WC-6 wt.% Co, and bulk alloys obtained by selective laser melting (SLM) from as-milled powders in as-melted state and after heat treatment were investigated by scanning electron microscopy and X-ray diffraction analysis. Initial and ball-milled powders consist of WC, hexagonal α-Co and face-centered cubic β-Co. The SLM leads to the formation of major new phases W3Co3C, W4Co2C and face-centered cubic β-Co-based solid solution. During the heat treatment, there occurs partial decomposition of the face-centered cubic β-Co-based solid solution with the formation of W2C and hexagonal α-Co solid solution. The microstructure of obtained bulk samples, in general, corresponds to the observed phase composition.

Scanning tunneling microscopy of the formation, transformation, and property of oligothiophene self-organizations on graphite and gold surfaces.

PubMed

Yang, Zhi-Yong; Zhang, Hui-Min; Yan, Cun-Ji; Li, Shan-Shan; Yan, Hui-Juan; Song, Wei-Guo; Wan, Li-Jun

2007-03-06

Two alkyl-substituted dual oligothiophenes, quarterthiophene (4T)-trimethylene (tm)-octithiophene (8T) and 4T-tm-4T, were used to fabricate molecular structures on highly oriented pyrolytic graphite and Au(111) surfaces. The resulted structures were investigated by scanning tunneling microscopy. The 4T-tm-8T and 4T-tm-4T molecules self-organize into long-range ordered structures with linear and/or quasi-hexagonal patterns on highly oriented pyrolytic graphite at ambient temperature. Thermal annealing induced a phase transformation from quasi-hexagonal to linear in 4T-tm-8T adlayer. The molecules adsorbed on Au(111) surface in randomly folded and linear conformation. Based on scanning tunneling microscopy results, the structural models for different self-organizations were proposed. Scanning tunneling spectroscopy measurement showed the electronic property of individual molecules in the patterns. These results are significant in understanding the chemistry of molecular structure, including its formation, transformation, and electronic properties. They also help to fabricate oligothiophene assemblies with desired structures for future molecular devices.

Propagation of threading dislocations in heteroepitaxial diamond films with (111) orientation and their role in the formation of intrinsic stress

NASA Astrophysics Data System (ADS)

Gallheber, B.-C.; Klein, O.; Fischer, M.; Schreck, M.

2017-06-01

In the present study, systematic correlations were revealed between the propagation direction of threading dislocations, the off-axis growth conditions, and the stress state of heteroepitaxial diamond on Ir/YSZ/Si(111). Measurements of the strain tensor ɛ ⃡ by X-ray diffraction and the subsequent calculation of the tensor of intrinsic stress σ ⃡ showed stress-free samples as well as symmetric biaxial stress states for on-axis samples. Transmission electron microscopy (TEM) lamellas were prepared for plan-view studies along the [ 1 ¯ 1 ¯ 1 ¯ ] direction and for cross-section investigations along the [11 2 ¯ ] and [1 1 ¯ 0] zone axes. For samples grown on-axis with parameters which avoid the formation of intrinsic stress, the majority of dislocations have line vectors clearly aligned along [111]. A sudden change to conditions that promote stress formation is correlated with an abrupt bending of the dislocations away from [111]. This behaviour is in nice agreement with the predictions of a model that attributes formation of intrinsic stress to an effective climb of dislocations. Further growth experiments under off-axis conditions revealed the generation of stress states with pronounced in-plane anisotropy of several Gigapascal. Their formation is attributed to the combined action of two basic processes, i.e., the step flow driven dislocation tilting and the temperature dependent effective climb of dislocations. Again, our interpretation is supported by the dislocation propagation derived from TEM observations.

Fundamental Discovery of New Phases and Direct Conversion of Carbon into Diamond and hBN into cBN and Properties

NASA Astrophysics Data System (ADS)

Narayan, Jagdish; Bhaumik, Anagh

2016-04-01

We review the discovery of new phases of carbon (Q-carbon) and BN (Q-BN) and address critical issues related to direct conversion of carbon into diamond and hBN into cBN at ambient temperatures and pressures in air without any need for catalyst and the presence of hydrogen. The Q-carbon and Q-BN are formed as a result of quenching from super undercooled state by using high-power nanosecond laser pulses. We discuss the equilibrium phase diagram ( P vs T) of carbon, and show that by rapid quenching, kinetics can shift thermodynamic graphite/diamond/liquid carbon triple point from 5000 K/12 GPa to super undercooled carbon at atmospheric pressure in air. Similarly, the hBN-cBN-Liquid triple point is shifted from 3500 K/9.5 GPa to as low as 2800 K and atmospheric pressure. It is shown that nanosecond laser heating of amorphous carbon and nanocrystalline BN on sapphire, glass, and polymer substrates can be confined to melt in a super undercooled state. By quenching this super undercooled state, we have created a new state of carbon (Q-carbon) and BN (Q-BN) from which nanocrystals, microcrystals, nanoneedles, microneedles, and thin films are formed depending upon the nucleation and growth times allowed and the presence of growth template. The large-area epitaxial diamond and cBN films are formed, when appropriate planar matching or lattice matching template is provided for growth from super undercooled liquid. The Q-phases have unique atomic structure and bonding characteristics as determined by high-resolution SEM and backscatter diffraction, HRTEM, STEM-Z, EELS, and Raman spectroscopy, and exhibit new and improved mechanical hardness, electrical conductivity, and chemical and physical properties, including room-temperature ferromagnetism and enhanced field emission. The Q-carbon exhibits robust bulk ferromagnetism with estimated Curie temperature of about 500 K and saturation magnetization value of 20 emu g-1. We have also deposited diamond on cBN by using a novel pulsed laser evaporation of carbon and obtained cBN/diamond composites, where cBN acts as template for diamond growth. Both diamond and cBN grown from super undercooled liquid can be alloyed with both p- and n-type dopants. This process allows carbon to diamond and hBN to cBN conversions and formation of useful nanostructures and microstructures at ambient temperatures in air at atmospheric pressure on practical and heat-sensitive substrates in a controlled way without need for any catalysts and hydrogen to stabilize sp3 bonding for diamond and cBN phases.

Improvement on electrical conductivity and electron field emission properties of Au-ion implanted ultrananocrystalline diamond films by using Au-Si eutectic substrates

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

Sankaran, K. J.; Institute for Materials Research; Sundaravel, B.

2015-08-28

In the present work, Au-Si eutectic layer was used to enhance the electrical conductivity/electron field emission (EFE) properties of Au-ion implanted ultrananocrystalline diamond (Au-UNCD) films grown on Si substrates. The electrical conductivity was improved to a value of 230 (Ω cm){sup −1}, and the EFE properties was enhanced reporting a low turn-on field of 2.1 V/μm with high EFE current density of 5.3 mA/cm{sup 2} (at an applied field of 4.9 V/μm) for the Au-UNCD films. The formation of SiC phase circumvents the formation of amorphous carbon prior to the nucleation of diamond on Si substrates. Consequently, the electron transport efficiency of themore » UNCD-to-Si interface increases, thereby improving the conductivity as well as the EFE properties. Moreover, the salient feature of these processes is that the sputtering deposition of Au-coating for preparing the Au-Si interlayer, the microwave plasma enhanced chemical vapor deposition process for growing the UNCD films, and the Au-ion implantation process for inducing the nanographitic phases are standard thin film preparation techniques, which are simple, robust, and easily scalable. The availability of these highly conducting UNCD films with superior EFE characteristics may open up a pathway for the development of high-definition flat panel displays and plasma devices.« less

Chalcophile and siderophile elements in sulphide inclusions in eclogitic diamonds and metal cycling in a Paleoproterozoic subduction zone

NASA Astrophysics Data System (ADS)

Aulbach, Sonja; Stachel, Thomas; Seitz, Hans-Michael; Brey, Gerhard P.

2012-09-01

In the central Slave craton, eclogitic diamonds are suggested to have formed during Paleoproterozoic subduction in a meta-gabbroic substrate representing former lower oceanic crust that interacted with serpentinite-derived fluids at high fluid-rock ratios. In order to assess the behaviour of chalcophile and siderophile elements (CSE) during this process, we measured trace-element concentrations of sulphide inclusions in diamonds from the Diavik mine by laser ablation ICPMS. The nitrogen systematics of the diamonds (average N concentration of ˜600 ppm and aggregation state 4% N as B-aggregates) indicate average mantle residence temperatures of ˜1050 °C for a 1.85 Ga formation age, corresponding ˜170 km depth. Based on the available evidence from natural samples and experiments, we suggest that the highly siderophile elements (HSE: Os, Ir, Ru, Rh, Pd, Pt, Re) except Au behaved largely conservatively during fluid-induced metamorphism, which may point to a reducing and Cl-poor nature of the fluid. The abundances of the moderately siderophile and chalcophile elements Cr, Co, Ni, Cu, Ag, Sn, Mo and W may also have changed little, whereas As, Sb, Tl, Pb and Bi may have been mobilised from the subducting lower oceanic crust. The partitioning of CSE in eclogite and geochemical behaviour during oceanic crust formation was assessed for inferred conservative elements. Assuming an average sulphide mode of 0.3 wt.% for the oceanic crust, its abundances of HSE, Cu, Mo, Se and Te can mostly be accounted for by sulphide minerals alone. Lithophile behaviour of W, Cd, In and Sn and enrichment in residual melts may explain their lower abundances in the gabbroic eclogitic sulphide inclusions compared to MORB sulphide. These elements, as well as Cr, Co, Ni, Zn and Ga require additional host phases both in eclogite, where rutile partitions significant amounts of Cr, Zn, W, Ga and Sn, and in the oceanic crust.

Transformation of BCC and B2 High Temperature Phases to HCP and Orthorhombic Structures in the Ti-Al-Nb System. Part II: Experimental TEM Study of Microstructures

PubMed Central

Bendersky, L. A.; Boettinger, W. J.

1993-01-01

Possible transformation paths that involve no long range diffusion and their corresponding microstructural details were predicted by Bendersky, Roytburd, and Boettinger [J. Res. Natl. Inst. Stand. Technol. 98, 561 (1993)] for Ti-Al-Nb alloys cooled from the high temperature BCC/B2 phase field into close-packed orthorhombic or hexagonal phase fields. These predictions were based on structural and symmetry relations between the known phases. In the present paper experimental TEM results show that two of the predicted transformation paths are indeed followed for different alloy compositions. For Ti-25Al-12.5Nb (at%), the path includes the formation of intermediate hexagonal phases, A3 and DO19, and subsequent formation of a metastable domain structure of the low-temperature O phase. For alloys close to Ti-25Al-25Nb (at%), the path involves an intermediate B19 structure and subsequent formation of a translational domain structure of the O phase. The path selection depends on whether B2 order forms in the high temperature cubic phase prior to transformation to the close-packed structure. The paper also analyzes the formation of a two-phase modulated microstructure during long term annealing at 700 °C. The structure forms by congruent ordering of the DO19 phase to the O phase, and then reprecipitation of the DO19 phase, possibly by a spinodal mechanism. The thermodynamics underlying the path selection and the two-phase formation are also discussed. PMID:28053488

A novel procedure to obtain nanocrystalline diamond/porous silicon composite by chemical vapor deposition/infiltration processes.

PubMed

Miranda, C R B; Azevedo, A F; Baldan, M R; Beloto, A F; Ferreira, N G

2009-06-01

Nanocrystalline diamond (NCD) films were formed on porous silicon (PS) substrate by Chemical Vapor Deposition/Infiltration (CVD/CVI) process using a hot filament reactor. This innovative procedure is determinant to grow a controlled three-dimensional diamond structure with diamond grains formation in the pores, covering uniformly the different growth planes. In this CVI process, a piece of reticulated vitreous carbon (RVC) was used, under de PS substrate, as an additional solid source of hydrocarbon that ensures the production of pertinent carbon growth species directly on PS and into its pores. PS substrates were obtained by anodization etching process of n-type silicon wafer in a hydrofluoric acid (HF) solution containing acetonitrile (CH3CN) which result in an uniform and well controlled porous distribution and size when compared with the usual ethanol solution. Depositions were performed using Ar-H2-CH4 where the methane concentration varied from 0 up to 1.0 vol%, to analyze the influence of RVC use as an additional carbon source on growth mechanism. Scanning Electron Microscopy (SEM) and Field Emission Gun (FEG) were used to investigate PS and NCD film morphology. SEM images of NCD showed faceted nanograins with average size from 5 to 16 nm and uniform surface texture covering all the supports among the pores resulting in an apparent micro honeycomb structure. Raman spectra confirmed the existence of sp2-bonded carbon at the grain boundaries. The spectra showed a peak that may be deconvoluted in two components at 1332 cm(-1) (diamond) and 1345 cm(-1) (D band). Two shoulders at 1150 and 1490 cm(-1) also appear and are assigned to transpolyacetylene (TPA) segments at the grain boundaries of NCD surfaces. In addition, X-ray diffraction analyses of all films presented characteristic diamond diffraction peaks corresponding to (111), (220) and (311).

Ice formation on kaolinite: Insights from molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Sosso, Gabriele C.; Tribello, Gareth A.; Zen, Andrea; Pedevilla, Philipp; Michaelides, Angelos

2016-12-01

The formation of ice affects many aspects of our everyday life as well as important technologies such as cryotherapy and cryopreservation. Foreign substances almost always aid water freezing through heterogeneous ice nucleation, but the molecular details of this process remain largely unknown. In fact, insight into the microscopic mechanism of ice formation on different substrates is difficult to obtain even if state-of-the-art experimental techniques are used. At the same time, atomistic simulations of heterogeneous ice nucleation frequently face extraordinary challenges due to the complexity of the water-substrate interaction and the long time scales that characterize nucleation events. Here, we have investigated several aspects of molecular dynamics simulations of heterogeneous ice nucleation considering as a prototypical ice nucleating material the clay mineral kaolinite, which is of relevance in atmospheric science. We show via seeded molecular dynamics simulations that ice nucleation on the hydroxylated (001) face of kaolinite proceeds exclusively via the formation of the hexagonal ice polytype. The critical nucleus size is two times smaller than that obtained for homogeneous nucleation at the same supercooling. Previous findings suggested that the flexibility of the kaolinite surface can alter the time scale for ice nucleation within molecular dynamics simulations. However, we here demonstrate that equally flexible (or non flexible) kaolinite surfaces can lead to very different outcomes in terms of ice formation, according to whether or not the surface relaxation of the clay is taken into account. We show that very small structural changes upon relaxation dramatically alter the ability of kaolinite to provide a template for the formation of a hexagonal overlayer of water molecules at the water-kaolinite interface, and that this relaxation therefore determines the nucleation ability of this mineral.

Mechanical properties of additively manufactured octagonal honeycombs.

PubMed

Hedayati, R; Sadighi, M; Mohammadi-Aghdam, M; Zadpoor, A A

2016-12-01

Honeycomb structures have found numerous applications as structural and biomedical materials due to their favourable properties such as low weight, high stiffness, and porosity. Application of additive manufacturing and 3D printing techniques allows for manufacturing of honeycombs with arbitrary shape and wall thickness, opening the way for optimizing the mechanical and physical properties for specific applications. In this study, the mechanical properties of honeycomb structures with a new geometry, called octagonal honeycomb, were investigated using analytical, numerical, and experimental approaches. An additive manufacturing technique, namely fused deposition modelling, was used to fabricate the honeycomb from polylactic acid (PLA). The honeycombs structures were then mechanically tested under compression and the mechanical properties of the structures were determined. In addition, the Euler-Bernoulli and Timoshenko beam theories were used for deriving analytical relationships for elastic modulus, yield stress, Poisson's ratio, and buckling stress of this new design of honeycomb structures. Finite element models were also created to analyse the mechanical behaviour of the honeycombs computationally. The analytical solutions obtained using Timoshenko beam theory were close to computational results in terms of elastic modulus, Poisson's ratio and yield stress, especially for relative densities smaller than 25%. The analytical solutions based on the Timoshenko analytical solution and the computational results were in good agreement with experimental observations. Finally, the elastic properties of the proposed honeycomb structure were compared to those of other honeycomb structures such as square, triangular, hexagonal, mixed, diamond, and Kagome. The octagonal honeycomb showed yield stress and elastic modulus values very close to those of regular hexagonal honeycombs and lower than the other considered honeycombs. Copyright © 2016 Elsevier B.V. All rights reserved.

Eclogite formation beneath the northern Slave craton constrained by diamond inclusions: Oceanic lithosphere origin without a crustal signature

NASA Astrophysics Data System (ADS)

Smart, Katie A.; Chacko, Thomas; Stachel, Thomas; Tappe, Sebastian; Stern, Richard A.; Ickert, Ryan B.; EIMF

2012-02-01

We report the geochemical and oxygen isotope compositions for eclogitic mineral inclusions in diamonds hosted by high-MgO eclogite xenoliths from the Jericho kimberlite, Canada. These data are used to constrain the nature and evolution of the eclogite protolith. The garnet and clinopyroxene diamond inclusions (DIs) are compositionally different than their host eclogite counterparts. In particular, garnet DIs have much lower Mg-numbers (54 vs. 82) and Cr2O3 contents (0.1 vs. 0.6 wt.%) and higher CaO contents (7.6 vs. 4.3 wt.%) than host eclogite garnet. DI and host eclogite clinopyroxenes are more similar but differences include lower Mg-numbers (78-81 vs. 93) and higher Na2O contents (2.3 vs. 1.8 wt.%) in the DIs. The DIs lack typical shallow oceanic crust signatures such as strong positive Eu and Sr anomalies, and oxygen isotope compositions that deviate significantly from the pristine mantle average. On the contrary, both the Jericho DIs and host eclogite garnets have small negative Eu and Sr anomalies, fractionated HREE patterns ((LuN/GdN) ~ 3-5) and pristine mantle-like δ18O values of 5.2-6.0‰, indicating that shallow, plagioclase-rich oceanic crust protoliths are unlikely. The eclogitic DI trace-element characteristics require that both garnet and plagioclase were present in the protolith, which likely crystallized in the shallow upper mantle. DI-based reconstructed whole-rock eclogite compositions have higher Mg-numbers and lower Al2O3 contents than found in typical basaltic or gabbroic oceanic crust, and are similar to pyroxenitic veins found in orogenic peridotite massifs. Due to the lack of clear oceanic crust signatures and the mantle-like δ18O values of the studied DIs, we propose that the Jericho diamond eclogites originally crystallized as pyroxenite cumulates that formed veins within the oceanic mantle lithosphere. Following partial melt extraction, the eclogite protoliths were subducted into the diamond stability field beneath the evolving Slave craton. Hence, the Jericho DIs and host high-MgO eclogites may represent an example of eclogite formation in an oceanic setting without the diagnostic 'crustal signatures' that are typically observed in cratonic eclogite xenolith suites worldwide.

A first principles study of commonly observed planar defects in Ti/TiB system

DOE PAGES

Nandwana, Peeyush; Gupta, Niraj; Srinivasan, Srivilliputhur G.; ...

2018-04-20

Here, TiB exhibits a hexagonal cross-section with growth faults on (1 0 0) planes and contains B27-B f bicrystals. The hexagonal cross-section is presently explained by surface free energy minimization principle. We show that interfacial energy calculations explain the longer (1 0 0) facet compared to (1 0 1) type facets whereas free surface energy arguments do not provide the true picture. No quantitative explanation of stacking faults and B27-B f interfaces in TiB exists. We show that the low formation energy of stacking faults and B27-B f interfaces explain their abundance. The low energy barrier for B f formationmore » is shown to be responsible for their presence in TiB.« less

Defect-induced wetting on BaF 2(111) and CaF 2(111) at ambient conditions

NASA Astrophysics Data System (ADS)

Cardellach, M.; Verdaguer, A.; Fraxedas, J.

2011-12-01

The interaction of water with freshly cleaved (111) surfaces of isostructural BaF2 and CaF2 single crystals at ambient conditions (room temperature and under controlled humidity) has been studied using scanning force microscopy in different operation modes and optical microscopy. Such surfaces exhibit contrasting behaviors for both materials: while on BaF2(111) two-dimensional water layers are formed after accumulation at step edges, CaF2(111) does not promote the formation of such layers. We attribute such opposed behavior to lattice match (mismatch) between hexagonal water ice and the hexagonal (111) surfaces of BaF2(CaF2). Optical microscope images reveal that this behavior also determines the way the surfaces become wetted at a macroscopic level.

A first principles study of commonly observed planar defects in Ti/TiB system

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

Nandwana, Peeyush; Gupta, Niraj; Srinivasan, Srivilliputhur G.

Here, TiB exhibits a hexagonal cross-section with growth faults on (1 0 0) planes and contains B27-B f bicrystals. The hexagonal cross-section is presently explained by surface free energy minimization principle. We show that interfacial energy calculations explain the longer (1 0 0) facet compared to (1 0 1) type facets whereas free surface energy arguments do not provide the true picture. No quantitative explanation of stacking faults and B27-B f interfaces in TiB exists. We show that the low formation energy of stacking faults and B27-B f interfaces explain their abundance. The low energy barrier for B f formationmore » is shown to be responsible for their presence in TiB.« less

Growth of High-Density Zinc Oxide Nanorods on Porous Silicon by Thermal Evaporation

PubMed Central

Rusli, Nurul Izni; Tanikawa, Masahiro; Mahmood, Mohamad Rusop; Yasui, Kanji; Hashim, Abdul Manaf

2012-01-01

The formation of high-density zinc oxide (ZnO) nanorods on porous silicon (PS) substrates at growth temperatures of 600–1000 °C by a simple thermal evaporation of zinc (Zn) powder in the presence of oxygen (O2) gas was systematically investigated. The high-density growth of ZnO nanorods with (0002) orientation over a large area was attributed to the rough surface of PS, which provides appropriate planes to promote deposition of Zn or ZnOx seeds as nucleation sites for the subsequent growth of ZnO nanorods. The geometrical morphologies of ZnO nanorods are determined by the ZnOx seed structures, i.e., cluster or layer structures. The flower-like hexagonal-faceted ZnO nanorods grown at 600 °C seem to be generated from the sparsely distributed ZnOx nanoclusters. Vertically aligned hexagonal-faceted ZnO nanorods grown at 800 °C may be inferred from the formation of dense arrays of ZnOx clusters. The formation of disordered ZnO nanorods formed at 1000 °C may due to the formation of a ZnOx seed layer. The growth mechanism involved has been described by a combination of self-catalyzed vapor-liquid-solid (VLS) and vapor-solid (VS) mechanism. The results suggest that for a more precise study on the growth of ZnO nanostructures involving the introduction of seeds, the initial seed structures must be taken into account given their significant effects.

Aminosilane multilayer formed on a single-crystalline diamond surface with controlled nanoscopic hardness and bioactivity by a wet process.

PubMed

Amemiya, Yosuke; Hatakeyama, Akiko; Shimamoto, Nobuo

2009-01-06

Diamond could be an excellent support for nanodevices utilizing biomolecules if it is covered with a polymer layer immobilizing a variety of biomolecules. We report a wet method to form a 3-aminopropyltriethoxysilane (APTES) multilayer with a controlled hardness, roughness, and capacity for immobilizing protein. The method is feasible in typical biochemical laboratories where biomolecules are prepared. Atomic force microscopy (AFM) revealed that the surface geometries and nanoscopic hardness of the multilayers on an oxygen-terminated single-crystalline diamond surface depended on the dielectric constant of the solvent; the smaller the constant, the harder the layer. The hard multilayers had holes and APTES aggregates on the surfaces, while less hard ones had homogeneous surfaces with rare holes and little aggregates. The secondary deposition of APTES in a solvent with a large dielectric constant on a hard multilayer removed the holes, and further treatment of the multilayer in acidic ethanol solution diminished the aggregates. Such a surface can immobilize streptavidin with enough specificity against nonspecific adsorption using a combination of polyethylene glycol reagents. The results of a scratching test and nanoindentation test with AFM provided consistent results, suggesting some universality of the scratching test independent of the tip structure of the cantilever. The mechanism of formation of multilayers on the diamond surface and their binding to it is discussed.

Immersion Freezing of Aluminas: The Effect of Crystallographic Properties on Ice Nucleation

NASA Astrophysics Data System (ADS)

King, M.; Chong, E.; Freedman, M. A.

2017-12-01

Atmospheric aerosol particles serve as the nuclei for heterogeneous ice nucleation, a process that allows for ice to form at higher temperatures and lower supersaturations with respect to ice. This process is essential to the formation of ice in cirrus clouds. Heterogeneous ice nucleation is affected by many factors including the composition, crystal structure, porosity, and surface area of the particles. However, these factors are not well understood and, as such, are difficult to account for in climate models. To test the effects of crystal structure on ice nucleation, a system of transition aluminas (Al2O3) that differ only in their crystal structure, despite being compositionally similar, were tested using immersion freezing. Particles were immersed in water and placed into a temperature controlled chamber. Freezing events were then recorded as the chamber was cooled to negative 30 °. Alpha-alumina, which is a member of the hexagonal crystal system, showed a significantly higher temperature at which all particles froze in comparison to other samples. This supports the hypothesis that, since a hexagonal crystal structure is the lowest energy state for ice, hexagonal surface structures would best facilitate ice nucleation. However, a similar sample of hexagonal chi-alumina did not show the same results. Further analysis of the samples will be done to characterize surface structures and composition. These conflicting data sets raise interesting questions about the effect of other surface features, such as surface area and porosity, on ice nucleation.

Effects of various tool pin profiles on mechanical and metallurgical properties of friction stir welded joints of cryorolled AA2219 aluminium alloy

NASA Astrophysics Data System (ADS)

Kamal Babu, Karupannan; Panneerselvam, Kavan; Sathiya, Paulraj; Noorul Haq, Abdul Haq; Sundarrajan, Srinivasan; Mastanaiah, Potta; Srinivasa Murthy, Chunduri Venkata

2018-02-01

Friction stir welding (FSW) process was conducted on cryorolled (CR) AA2219 plate using different tool pin profiles such as cylindrical pin, threaded cylindrical pin, square pin and hexagonal pin profiles. The FSW was carried out with pairs of 6 mm thick CR aluminium plates with different tool pin profiles. The different tool pin profile weld portions' behaviors like mechanical (tensile strength, impact and hardness) and metallurgical characteristics were analyzed. The results of the mechanical analysis revealed that the joint made by the hexagonal pin tool had good strength compared to other pin profiles. This was due to the pulsating action and material flow of the tool resulting in dynamic recrystallization in the weld zone. This was confirmed by the ultra fine grain structure formation in Weld Nugget (WN) of hexagonal pin tool joint with a higher percentage of precipitate dissolution. The fractograph of the hexagonal tool pin weld portion confirmed the finer dimple structure morphology without having any interior defect compared to other tool pin profiles. The lowest weld joint strength was obtained from cylindrical pin profile weld joint due to insufficient material flow during welding. The Transmission Electron Microscope and EDX analysis showed the dissolution of the metastable θ″, θ' (Al2Cu) partial precipitates in the WN and proved the influence of metastable precipitates on enhancement of mechanical behavior of weld. The XRD results also confirmed the Al2Cu precipitation dissolution in the weld zone.

KSC-2009-2088

NASA Image and Video Library

2009-03-15

CAPE CANAVERAL, Fla. – As space shuttle Discovery roars toward space after launch from Launch Pad 39A at NASA's Kennedy Space Center in Florida, mach diamonds can be seen beneath the engine nozzles. Blue cones of light, the mach diamonds are a formation of shock waves in the exhaust plume of an aerospace propulsion system. Launch was on time at 7:43 p.m. EDT. The STS-119 mission is the 28th to the International Space Station and the 125th space shuttle flight. Discovery will deliver the final pair of power-generating solar array wings and the S6 truss segment. Installation of S6 will signal the station's readiness to house a six-member crew for conducting increased science. Photo credit: NASA/Rusty Backer, George Roberts

Nucleation of the diamond phase in aluminium-solid solutions

NASA Technical Reports Server (NTRS)

Hornbogen, E.; Mukhopadhyay, A. K.; Starke, E. A., Jr.

1993-01-01

Precipitation was studied from fcc solid solutions with silicon, germanium, copper and magnesium. Of all these elements only silicon and germanium form diamond cubic (DC) precipitates in fcc Al. Nucleation of the DC structure is enhanced if both types of atom are dissolved in the fcc lattice. This is interpreted as due to atomic size effects in the prenucleation stage. There are two modes of interference of fourth elements with nucleation of the DC phase in Al + Si, Ge. The formation of the DC phase is hardly affected if the atoms (for example, copper) are rejected from the (Si, Ge)-rich clusters. If additional types of atom are attracted by silicon and/or germanium, DC nuclei are replaced by intermetallic compounds (for example Mg2Si).

Facile MALDI-MS analysis of neutral glycans in NaOH-doped matrixes: microwave-assisted deglycosylation and one-step purification with diamond nanoparticles.

PubMed

Tzeng, Yan-Kai; Chang, Cheng-Chun; Huang, Chien-Ning; Wu, Chih-Che; Han, Chau-Chung; Chang, Huan-Cheng

2008-09-01

A streamlined protocol has been developed to accelerate, simplify, and enhance matrix-assisted laser desorption/ionization (MALDI) time-of-flight (TOF) mass spectrometry (MS) of neutral underivatized glycans released from glycoproteins. It involved microwave-assisted enzymatic digestion and release of glycans, followed by rapid removal of proteins and peptides with carboxylated/oxidized diamond nanoparticles, and finally treating the analytes with NaOH before mixing them with acidic matrix (such as 2,5-dihydroxybenzoic acid) to suppress the formation of both peptide and potassiated oligosaccharide ions in MS analysis. The advantages of this protocol were demonstrated with MALDI-TOF-MS of N-linked glycans released from ovalbumin and ribonuclease B.

Development of program package for investigation and modeling of carbon nanostructures in diamond like carbon films with the help of Raman scattering and infrared absorption spectra line resolving

NASA Astrophysics Data System (ADS)

Hayrapetyan, David B.; Hovhannisyan, Levon; Mantashyan, Paytsar A.

2013-04-01

The analysis of complex spectra is an actual problem for modern science. The work is devoted to the creation of a software package, which analyzes spectrum in the different formats, possesses by dynamic knowledge database and self-study mechanism, performs automated analysis of the spectra compound based on knowledge database by application of certain algorithms. In the software package as searching systems, hyper-spherical random search algorithms, gradient algorithms and genetic searching algorithms were used. The analysis of Raman and IR spectrum of diamond-like carbon (DLC) samples were performed by elaborated program. After processing the data, the program immediately displays all the calculated parameters of DLC.

Application of surface analysis to solve problems of wear

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1981-01-01

Results are presented for the use of surface analytical tools including field ion microscopy, Auger emission spectroscopy analysis (AES), cylindrical mirror Auger analysis and X-ray photoelectron spectroscopy (XPS). Data from the field ion microscope reveal adhesive transfer (wear) at the atomic level with the formation of surface compounds not found in the bulk, and AES reveals that this transfer will occur even in the presence of surface oxides. Both AES and XPS reveal that in abrasive wear with silicon carbide and diamond contacting the transition metals, the surface and the abrasive undergo a chemical or structural change which effects wear. With silicon carbide, silicon volatilizes leaving behind a pseudo-graphitic surface and the surface of diamond is observed to graphitize.

Direct observation and mechanism of increased emission sites in Fe-coated microcrystalline diamond films

NASA Astrophysics Data System (ADS)

Panda, Kalpataru; Sundaravel, B.; Panigrahi, B. K.; Huang, Pin-Chang; Shih, Wen-Ching; Chen, Huang-Chin; Lin, I.-Nan

2012-06-01

The electron field emission (EFE) properties of microcrystalline diamond (MCD) films are significantly enhanced due to the Fe coating and post-annealing processes. The 900 °C post-annealed Fe coated diamond films exhibit the best EFE properties, with a turn on field (E0) of 3.42 V/μm and attain EFE current density (Je) of 170 μA/cm2 at 7.5 V/μm. Scanning tunnelling spectroscopy (STS) in current imaging tunnelling spectroscopy mode clearly shows the increased number density of emission sites in Fe-coated and post-annealed MCD films than the as-prepared ones. Emission is seen from the boundaries of the Fe (or Fe3C) nanoparticles formed during the annealing process. In STS measurement, the normalized conductance dI /dV/I/V versus V curves indicate nearly metallic band gap, at the boundaries of Fe (or Fe3C) nanoparticles. Microstructural analysis indicates that the mechanism for improved EFE properties is due to the formation of nanographite that surrounds the Fe (or Fe3C) nanoparticles.

Highly photostable NV centre ensembles in CVD diamond produced by using N2O as the doping gas

NASA Astrophysics Data System (ADS)

Tallaire, A.; Mayer, L.; Brinza, O.; Pinault-Thaury, M. A.; Debuisschert, T.; Achard, J.

2017-10-01

High density Nitrogen-Vacancy (NV) centre ensembles incorporated in plasma assisted chemical vapour deposition (CVD) diamond are crucial to the development of more efficient sensing devices that use the properties of luminescent defects. Achieving high NV doping with N2 as the dopant gas source during diamond growth is, however, plagued by the formation of macroscopic and point defects that quench luminescence. Moreover, such NVs are found to exhibit poor photostability under high laser powers. Although this effect can be harnessed to locally and durably switch off NV luminescence for data storage, it is usually undesirable for most applications. In this work, the use of N2O as an alternative doping source is proposed. Much higher amounts of the doping gas can be added without significantly generating defects, which allows the incorporation of perfectly photostable and higher density NV ensembles. This effect is believed to be related to the lower dissociation energy of the N2O molecule together with the beneficial effect of the presence of a low and controlled amount of oxygen near the growing surface.

Phase relations in the system Fe-Si determined in an internally-resistive heated DAC

NASA Astrophysics Data System (ADS)

Komabayashi, T.; Antonangeli, D.; Morard, G.; Sinmyo, R.; Mezouar, N.

2015-12-01

It is believed that the iron-rich Earth's core contains some amounts of light elements on the basis of the density deficit of 7 % compared to pure iron. The identification of the kinds and amounts of the light elements in the core places constraints on the origin, formation, and evolution of the Earth because dissolution of light elements into an iron-rich core should place important constraints on the thermodynamic conditions (pressure (P), temperature (T), and oxygen fugacity) of the equilibration between liquid silicate and liquid iron during the core formation. Among potential light elements, silicon has been attracting attentions because it is abundant in the mantle, partitioned into both solid and liquid irons, and very sensitive to the oxygen fugacity. An important phase relation in iron alloy is a transition between the face-centred cubic (FCC) structure and hexagonal close-packed (HCP) structure. This boundary is a key to infer the stable structure in the inner core and is used to derive thermodynamic properties of the phases (Komabayashi, 2014). In the Fe-Si system, previous reports were based on experiments in laser-heated diamond anvil cells (DAC), which might have included large termperature uncertainties. We have revisited this boundary in the system Fe-Si using an internally resistive-heated DAC combined with synchrotron X-ray diffraction at the beamline ID27, ESRF. The internally-heated DAC (Komabayashi et al., 2009; 2012) provides much more stable heating than the laser-heated DAC and much higher temperature than externally resistive-heated DAC, which enables us to place tight constraints on the P-T locations of the boundaries. Also because the minimum measurable temperature is as low as 1000 K due to the stable electric heating, the internal heating is able to examine the low temperature phase stability which was not studied by the previous studies. We will report the P-T locations of the boundaries and evaluate the effect of Si on the phase relation of Earth's core materials. References Komabayashi, J. Geophys. Res., 119, 2014; Komabayashi et al., Earth Planet. Sci. Lett. 282, 2009; Komabayashi et al., Phys. Chem. Mineral 39, 2012.

Formation of carbon nanoclusters by implantation of keV carbon ions in fused silica followed by thermal annealing

NASA Astrophysics Data System (ADS)

Olivero, P.; Peng, J. L.; Liu, A.; Reichart, P.; McCallum, J. C.; Sze, J. Y.; Lau, S. P.; Tay, B. K.; Kalish, R.; Dhar, S.; Feldman, Leonard; Jamieson, David N.; Prawer, Steven

2005-02-01

In the last decade, the synthesis and characterization of nanometer sized carbon clusters have attracted growing interest within the scientific community. This is due to both scientific interest in the process of diamond nucleation and growth, and to the promising technological applications in nanoelectronics and quantum communications and computing. Our research group has demonstrated that MeV carbon ion implantation in fused silica followed by thermal annealing in the presence of hydrogen leads to the formation of nanocrystalline diamond, with cluster size ranging from 5 to 40 nm. In the present paper, we report the synthesis of carbon nanoclusters by the implantation into fused silica of keV carbon ions using the Plasma Immersion Ion Implantation (PIII) technique, followed by thermal annealing in forming gas (4% 2H in Ar). The present study is aimed at evaluating this implantation technique that has the advantage of allowing high fluence-rates on large substrates. The carbon nanostructures have been characterized with optical absorption and Raman spectroscopies, cross sectional Transmission Electron Microscopy (TEM), and Parallel Electron Energy Loss Spectroscopy (PEELS). Nuclear Reaction Analysis (NRA) has been employed to evaluate the deuterium incorporation during the annealing process, as a key mechanism to stabilize the formation of the clusters.

Nano-inclusions in diamond: Evidence of diamond genesis

NASA Astrophysics Data System (ADS)

Wirth, R.

2015-12-01

The use of Focused Ion Beam technology (FIB) for TEM sample preparation introduced approximately 15 years ago revolutionized the application of TEM in Geosciences. For the first time, FIB enabled cutting samples for TEM use from exactly the location we are interested in. Applied to diamond investigation, this technique revealed the presence of nanometre-sized inclusions in diamond that have been simply unknown before. Nanoinclusions in diamond from different location and origin such as diamonds from the Lower and Upper Mantle, metamorphic diamonds (Kazakhstan, Erzgebirge, Bohemia), diamonds from ophiolites (Tibet, Mongolia, Xinjiang, Ural Mountains), diamonds from igneous rocks (Hawaii, Kamchatka) and impact diamonds (Popigai Crater, Siberia) have been investigated during the last 15 years. The major conclusion of all these TEM studies is, that the nanoinclusions, their phases and phase composition together with the micro- and nanostructure evidence the origin of diamond and genesis of diamond. We can discriminate Five different mechanisms of diamond genesis in nature are observed: Diamond crystallized from a high-density fluid (Upper mantle and metamorphic diamond). Diamond crystallized from carbonatitic melt (Lower mantle diamond). Diamond precipitates from a metal alloy melt (Diamond from ophiolites). Diamond crystallized by gas phase condensation or chemical vapour condensation (CVD) (Lavas from Kamchatka, xenoliths in Hawaiian lavas). Direct transformation of graphite into diamond.

Hierarchically self-assembled hexagonal honeycomb and kagome superlattices of binary 1D colloids.

PubMed

Lim, Sung-Hwan; Lee, Taehoon; Oh, Younghoon; Narayanan, Theyencheri; Sung, Bong June; Choi, Sung-Min

2017-08-25

Synthesis of binary nanoparticle superlattices has attracted attention for a broad spectrum of potential applications. However, this has remained challenging for one-dimensional nanoparticle systems. In this study, we investigate the packing behavior of one-dimensional nanoparticles of different diameters into a hexagonally packed cylindrical micellar system and demonstrate that binary one-dimensional nanoparticle superlattices of two different symmetries can be obtained by tuning particle diameter and mixing ratios. The hexagonal arrays of one-dimensional nanoparticles are embedded in the honeycomb lattices (for AB 2 type) or kagome lattices (for AB 3 type) of micellar cylinders. The maximization of free volume entropy is considered as the main driving force for the formation of superlattices, which is well supported by our theoretical free energy calculations. Our approach provides a route for fabricating binary one-dimensional nanoparticle superlattices and may be applicable for inorganic one-dimensional nanoparticle systems.Binary mixtures of 1D particles are rarely observed to cooperatively self-assemble into binary superlattices, as the particle types separate into phases. Here, the authors design a system that avoids phase separation, obtaining binary superlattices with different symmetries by simply tuning the particle diameter and mixture composition.

Defect charge states in Si doped hexagonal boron-nitride monolayer

NASA Astrophysics Data System (ADS)

Mapasha, R. E.; Molepo, M. P.; Andrew, R. C.; Chetty, N.

2016-02-01

We perform ab initio density functional theory calculations to investigate the energetics, electronic and magnetic properties of isolated stoichiometric and non-stoichiometric substitutional Si complexes in a hexagonal boron-nitride monolayer. The Si impurity atoms substituting the boron atom sites SiB giving non-stoichiometric complexes are found to be the most energetically favourable, and are half-metallic and order ferromagnetically in the neutral charge state. We find that the magnetic moments and magnetization energies increase monotonically when Si defects form a cluster. Partial density of states and standard Mulliken population analysis indicate that the half-metallic character and magnetic moments mainly arise from the Si 3p impurity states. The stoichiometric Si complexes are energetically unfavorable and non-magnetic. When charging the energetically favourable non-stoichiometric Si complexes, we find that the formation energies strongly depend on the impurity charge states and Fermi level position. We also find that the magnetic moments and orderings are tunable by charge state modulation q  =  -2, -1, 0, +1, +2. The induced half-metallic character is lost (retained) when charging isolated (clustered) Si defect(s). This underlines the potential of a Si doped hexagonal boron-nitride monolayer for novel spin-based applications.

Structure of ice crystallized from supercooled water

PubMed Central

Malkin, Tamsin L.; Murray, Benjamin J.; Brukhno, Andrey V.; Anwar, Jamshed; Salzmann, Christoph G.

2012-01-01

The freezing of water to ice is fundamentally important to fields as diverse as cloud formation to cryopreservation. At ambient conditions, ice is considered to exist in two crystalline forms: stable hexagonal ice and metastable cubic ice. Using X-ray diffraction data and Monte Carlo simulations, we show that ice that crystallizes homogeneously from supercooled water is neither of these phases. The resulting ice is disordered in one dimension and therefore possesses neither cubic nor hexagonal symmetry and is instead composed of randomly stacked layers of cubic and hexagonal sequences. We refer to this ice as stacking-disordered ice I. Stacking disorder and stacking faults have been reported earlier for metastable ice I, but only for ice crystallizing in mesopores and in samples recrystallized from high-pressure ice phases rather than in water droplets. Review of the literature reveals that almost all ice that has been identified as cubic ice in previous diffraction studies and generated in a variety of ways was most likely stacking-disordered ice I with varying degrees of stacking disorder. These findings highlight the need to reevaluate the physical and thermodynamic properties of this metastable ice as a function of the nature and extent of stacking disorder using well-characterized samples. PMID:22232652

Structure of ice crystallized from supercooled water.

PubMed

Malkin, Tamsin L; Murray, Benjamin J; Brukhno, Andrey V; Anwar, Jamshed; Salzmann, Christoph G

2012-01-24

The freezing of water to ice is fundamentally important to fields as diverse as cloud formation to cryopreservation. At ambient conditions, ice is considered to exist in two crystalline forms: stable hexagonal ice and metastable cubic ice. Using X-ray diffraction data and Monte Carlo simulations, we show that ice that crystallizes homogeneously from supercooled water is neither of these phases. The resulting ice is disordered in one dimension and therefore possesses neither cubic nor hexagonal symmetry and is instead composed of randomly stacked layers of cubic and hexagonal sequences. We refer to this ice as stacking-disordered ice I. Stacking disorder and stacking faults have been reported earlier for metastable ice I, but only for ice crystallizing in mesopores and in samples recrystallized from high-pressure ice phases rather than in water droplets. Review of the literature reveals that almost all ice that has been identified as cubic ice in previous diffraction studies and generated in a variety of ways was most likely stacking-disordered ice I with varying degrees of stacking disorder. These findings highlight the need to reevaluate the physical and thermodynamic properties of this metastable ice as a function of the nature and extent of stacking disorder using well-characterized samples.

Growth of Ferromagnetic Epitaxial Film of Hexagonal FeGe on (111) Ge Surface

NASA Astrophysics Data System (ADS)

Kumar, Dushyant; Joshi, P. C.; Hossain, Z.; Budhani, R. C.

2014-03-01

The realization of semiconductors showing ferromagnetic order at easily accessible temperatures has been of interest due to their potential use in spintronic devices where long spin life times are of key interest. We have realized the growth of FeGe thin films on Ge (111) wafers using pulsed laser deposition (PLD). The stoichiometric and single phase FeGe target used in PLD chamber has been made by arc melting. A typical θ-2 θ diffraction spectra performed on 40 nm thick FeGe film suggests the stabilization of β-Ni2In (B82-type) hexagonal phase with an epitaxial orientation of (0001)FeGe ||(111)Ge and [11-20]FeGe ||[-110]Ge. SEM images shows a granular structure with the formation of very large grains of about 100 to 500 nm in lateral dimension. The magnetization vs. temperature data taken from SQUID reveal the TC of ~ 270K. Since, PLD technique makes it easier to stabilize the B82 (Ni2In) hexagonal phase in thin FeGe films, this work opens opportunities to reinvestigate many conflicting results on various properties of the FeGe system.

Structure, rheology and shear alignment of Pluronic block copolymer mixtures.

PubMed

Newby, Gemma E; Hamley, Ian W; King, Stephen M; Martin, Christopher M; Terrill, Nicholas J

2009-01-01

The structure and flow behaviour of binary mixtures of Pluronic block copolymers P85 and P123 is investigated by small-angle scattering, rheometry and mobility tests. Micelle dimensions are probed by dynamic light scattering. The micelle hydrodynamic radius for the 50/50 mixture is larger than that for either P85 or P123 alone, due to the formation of mixed micelles with a higher association number. The phase diagram for 50/50 mixtures contains regions of cubic and hexagonal phases similar to those for the parent homopolymers, however the region of stability of the cubic phase is enhanced at low temperature and concentrations above 40 wt%. This is ascribed to favourable packing of the mixed micelles containing core blocks with two different chain lengths, but similar corona chain lengths. The shear flow alignment of face-centred cubic and hexagonal phases is probed by in situ small-angle X-ray or neutron scattering with simultaneous rheology. The hexagonal phase can be aligned using steady shear in a Couette geometry, however the high modulus cubic phase cannot be aligned well in this way. This requires the application of oscillatory shear or compression.

Recognizing Creativity in the Music Classroom

ERIC Educational Resources Information Center

Kokotsaki, Dimitra; Newton, Douglas P.

2015-01-01

This study examined trainee music teachers' judgements of the musical creativity of secondary age students. Nine pieces of music composed by Year 8 students (13 years of age) were evaluated by 17 postgraduate, trainee teachers. These musical pieces were sorted into a diamond-shaped formation according to how creative they were perceived to be with…

Coast redwood responses to pruning

Treesearch

Kevin L. O' Hara

2012-01-01

A large-scale pruning study was established in the winter of 1999 to 2000 at seven different sites on Green Diamond Resource Company forestlands in Humboldt County. The objective of this study was to determine the effects of pruning on increment, epicormic sprouting, stem taper, heartwood formation, and bear damage on these young trees. Pruning treatments varied...

Topological Quantum Information Processing Mediated Via Hybrid Topogical Insulator Structures

DTIC Science & Technology

2014-03-28

formation, manipulation, entanglement and detection of Majorana fermions in diamond-topological insulator - superconductor heterojunctions. Furthermore...between Superconductors and Topological Insulators Recent advances have revealed a new type of information processing, topological quantum...Topological Insulator - Superconductor Heterostructures," Physical Review B 84, 144507 (2011). 7 Hsiang-Hsuan Hung, Pouyan Ghaemi, Taylor L

Large scale atomistic simulation of single-layer graphene growth on Ni(111) surface: molecular dynamics simulation based on a new generation of carbon-metal potential

NASA Astrophysics Data System (ADS)

Xu, Ziwei; Yan, Tianying; Liu, Guiwu; Qiao, Guanjun; Ding, Feng

2015-12-01

To explore the mechanism of graphene chemical vapor deposition (CVD) growth on a catalyst surface, a molecular dynamics (MD) simulation of carbon atom self-assembly on a Ni(111) surface based on a well-designed empirical reactive bond order potential was performed. We simulated single layer graphene with recorded size (up to 300 atoms per super-cell) and reasonably good quality by MD trajectories up to 15 ns. Detailed processes of graphene CVD growth, such as carbon atom dissolution and precipitation, formation of carbon chains of various lengths, polygons and small graphene domains were observed during the initial process of the MD simulation. The atomistic processes of typical defect healing, such as the transformation from a pentagon into a hexagon and from a pentagon-heptagon pair (5|7) to two adjacent hexagons (6|6), were revealed as well. The study also showed that higher temperature and longer annealing time are essential to form high quality graphene layers, which is in agreement with experimental reports and previous theoretical results.To explore the mechanism of graphene chemical vapor deposition (CVD) growth on a catalyst surface, a molecular dynamics (MD) simulation of carbon atom self-assembly on a Ni(111) surface based on a well-designed empirical reactive bond order potential was performed. We simulated single layer graphene with recorded size (up to 300 atoms per super-cell) and reasonably good quality by MD trajectories up to 15 ns. Detailed processes of graphene CVD growth, such as carbon atom dissolution and precipitation, formation of carbon chains of various lengths, polygons and small graphene domains were observed during the initial process of the MD simulation. The atomistic processes of typical defect healing, such as the transformation from a pentagon into a hexagon and from a pentagon-heptagon pair (5|7) to two adjacent hexagons (6|6), were revealed as well. The study also showed that higher temperature and longer annealing time are essential to form high quality graphene layers, which is in agreement with experimental reports and previous theoretical results. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06016h

Synthesis of mesoporous β-Ga2O3 nanorods using PEG as template: preparation, characterization and photocatalytic properties.

PubMed

Zhao, Weirong; Yang, Yong; Hao, Rui; Liu, Feifei; Wang, Yan; Tan, Min; Tang, Jing; Ren, Daqing; Zhao, Dongye

2011-09-15

Mesoporous wide bandgap semiconductors offer high photocatalytic oxidation and mineralization activities. In this study, mesoporous β-Ga(2)O(3) diamond nanorods with 200-300 nm in diameter and 1.0-1.2 μm in length were synthesized via a urea-based hydrothermal method using polyethylene glycol (PEG) as template agent. The UV photocatalytic oxidation activity of β-Ga(2)O(3) for gaseous toluene was evaluated, and 7 kinds of intermediates were monitored online by a proton transfer reaction mass spectrometry. Photoluminescence spectra manifested that the dosage and molecular weight of PEG are crucial for formation of vacancies and photocatalytic oxidation activities. A PEG-assisted hydrothermal formation mechanism of mesoporous β-Ga(2)O(3) diamond nanorods was proposed. Based on the health risk influence index (η) of the intermediates, the calculated health risks revealed that the β-Ga(2)O(3) nanorods with a η value of 9.6 are much safer than TiO(2) (η = 17.6). Copyright © 2011 Elsevier B.V. All rights reserved.

Strategies for single-point diamond machining a large format germanium blazed immersion grating

NASA Astrophysics Data System (ADS)

Montesanti, R. C.; Little, S. L.; Kuzmenko, P. J.; Bixler, J. V.; Jackson, J. L.; Lown, J. G.; Priest, R. E.; Yoxall, B. E.

2016-07-01

A large format germanium immersion grating was flycut with a single-point diamond tool on the Precision Engineering Research Lathe (PERL) at the Lawrence Livermore National Laboratory (LLNL) in November - December 2015. The grating, referred to as 002u, has an area of 59 mm x 67 mm (along-groove and cross-groove directions), line pitch of 88 line/mm, and blaze angle of 32 degree. Based on total groove length, the 002u grating is five times larger than the previous largest grating (ZnSe) cut on PERL, and forty-five times larger than the previous largest germanium grating cut on PERL. The key risks associated with cutting the 002u grating were tool wear and keeping the PERL machine running uninterrupted in a stable machining environment. This paper presents the strategies employed to mitigate these risks, introduces pre-machining of the as-etched grating substrate to produce a smooth, flat, damage-free surface into which the grooves are cut, and reports on trade-offs that drove decisions and experimental results.

Industrial diamond

USGS Publications Warehouse

Olson, D.W.

2001-01-01

An overview of the industrial diamond industry is provided. More than 90 percent of the industrial diamond consumed in the U.S. and the rest of the world is manufactured diamond. Ireland, Japan, Russia, and the U.S. produce 75 percent of the global industrial diamond output. In 2000, the U.S. was the largest market for industrial diamond. Industrial diamond applications, prices for industrial diamonds, imports and exports of industrial diamonds, the National Defense Stockpile of industrial diamonds, and the outlook for the industrial diamond market are discussed.

Shape and structural motifs control of MgTi bimetallic nanoparticles using hydrogen and methane as trace impurities.

PubMed

Krishnan, Gopi; de Graaf, Sytze; Ten Brink, Gert H; Verheijen, Marcel A; Kooi, Bart J; Palasantzas, George

2018-01-18

In this work we report the influence of methane/hydrogen on the nucleation and formation of MgTi bimetallic nanoparticles (NPs) prepared by gas phase synthesis. We show that a diverse variety of structural motifs can be obtained from MgTi alloy, TiC x /Mg/MgO, TiC x /MgO and TiH x /MgO core/shell NPs via synthesis using CH 4 /H 2 as a trace gas, and with good control of the final NP morphology and size distribution. Moreover, depending on the concentration of Ti and type of employed trace gas, the as prepared MgTi NPs can be tuned from truncated hexagonal pyramid to triangular and hexagonal platelet shapes. The shape of MgTi NPs is identified using detailed analysis from selected area electron diffraction (SAED) patterns and tomography (3D reconstruction based on a tilt series of Bright-Field transmission electron microscopy (TEM) micrographs). We observe the truncated hexagonal pyramid as a shape of MgTi alloy NPs in contrast to Mg NPs that show a hexagonal prismatic shape. Moreover, based on our experimental observations and generic geometrical model analysis, we also prove that the formation of the various structural motifs is based on a sequential growth mechanism instead of phase separation. One of the prime reasons for such mechanism is based on the inadequacy of Mg to nucleate without template in the synthesis condition. In addition, the shape of the TiC x /TiH x core, and the concentration of Mg have strong influence on the shape evolution of TiC x /MgO and TiH x /MgO NPs compared to TiC x /Mg/MgO NPs, where the thermodynamics and growth rates of the Mg crystal planes dominate the final shape. Finally, it is demonstrated that the core shape of TiC x and TiH x is affected by the Mg/Ti target ratio (affecting the composition in the plasma), and the type of the trace gas employed. In the case of CH 4 the TiC x core forms a triangular platelet, while in the case of H 2 the TiH x core transforms into a hexagonal platelet. We elucidate the reason for the TiC x /TiH x core shape based on the presence of (i) defects, and (ii) hydrogen and carbon adsorption on {111} planes that alter the growth rates and surface facet stabilization.

Pattern formation in a monolayer of magnetic spheres

NASA Astrophysics Data System (ADS)

Stambaugh, Justin; Lathrop, Daniel P.; Ott, Edward; Losert, Wolfgang

2003-08-01

Pattern formation is investigated for a vertically vibrated monolayer of magnetic spheres. The spheres of diameter D encase cylindrical magnetic cores of length l. For large D/l, we find that the particles form a hexagonal-close-packed pattern in which the particles’ dipole vectors assume a macroscopic circulating vortical pattern. For smaller D/l, the particles form concentric rings. The static configurational magnetic energy (which depends on D/l) appears to be a determining factor in pattern selection even though the experimental system is driven and dissipative.

Paleomagnetism studies at micrometer scales using quantum diamond microscopy

NASA Astrophysics Data System (ADS)

Kehayias, P.; Fu, R. R.; Glenn, D. R.; Lima, E. A.; Men, M.; Merryman, H.; Walsworth, A.; Weiss, B. P.; Walsworth, R. L.

2017-12-01

Traditional paleomagnetic experiments generally measure the net magnetic moment of cm-size rock samples. Field tests such as the conglomerate and fold tests, based on the measurements of such cm-size samples, are frequently used to constrain the timing of magnetization. However, structures permitting such field tests may occur at the micron scale in geological samples, precluding paleomagnetic field tests using traditional bulk measurement techniques. The quantum diamond microscope (QDM) is a recently developed technology that uses magnetically-sensitive nitrogen-vacancy (NV) color centers in diamond for magnetic mapping with micron resolution [1]. QDM data were previously used to identify the ferromagnetic carriers in chondrules and terrestrial zircons and to image the magnetization distribution in multi-domain dendritic magnetite. Taking advantage of new hardware components, we have developed an optimized QDM setup with a 1E-15 J/T moment sensitivity over a measurement area of several millimeters squared. The improved moment sensitivity of the new QDM setup permits us to image natural remanent magnetization (NRM) in weakly magnetized samples, thereby enabling paleomagnetic field tests at the millimeter scale. We will present recent and ongoing QDM measurements of (1) the Renazzo class carbonaceous (CR) chondrite GRA 95229 and (2) 1 cm scale folds in a post-Bitter Springs Stage ( 790 Ma) carbonate from the Svanbergfjellet Formation (Svalbard). Results from the GRA 95229 micro-conglomerate test, performed on single chondrules containing dusty olivine metals crystallized during chondrule formation, hold implications for the preservation of nebular magnetic field records. The Svanbergfjellet Formation micro-fold test can help confirm the primary origin of a paleomagnetic pole at 790 Ma, which has been cited as evidence for rapid true polar wander in the 820-790 Ma interval. In addition, we will detail technical aspects of the new QDM setup, emphasizing key elements that enable improved sensitivity. [1] D. R. Glenn et al., arXiv:1707.06714 (2017).

An Industry/DOE Program to Develop and Benchmark Advanced Diamond Product Drill Bits and HP/HT Drilling Fluids to Significantly Improve Rates of Penetration

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

TerraTek

2007-06-30

A deep drilling research program titled 'An Industry/DOE Program to Develop and Benchmark Advanced Diamond Product Drill Bits and HP/HT Drilling Fluids to Significantly Improve Rates of Penetration' was conducted at TerraTek's Drilling and Completions Laboratory. Drilling tests were run to simulate deep drilling by using high bore pressures and high confining and overburden stresses. The purpose of this testing was to gain insight into practices that would improve rates of penetration and mechanical specific energy while drilling under high pressure conditions. Thirty-seven test series were run utilizing a variety of drilling parameters which allowed analysis of the performance ofmore » drill bits and drilling fluids. Five different drill bit types or styles were tested: four-bladed polycrystalline diamond compact (PDC), 7-bladed PDC in regular and long profile, roller-cone, and impregnated. There were three different rock types used to simulate deep formations: Mancos shale, Carthage marble, and Crab Orchard sandstone. The testing also analyzed various drilling fluids and the extent to which they improved drilling. The PDC drill bits provided the best performance overall. The impregnated and tungsten carbide insert roller-cone drill bits performed poorly under the conditions chosen. The cesium formate drilling fluid outperformed all other drilling muds when drilling in the Carthage marble and Mancos shale with PDC drill bits. The oil base drilling fluid with manganese tetroxide weighting material provided the best performance when drilling the Crab Orchard sandstone.« less

The melting of subducted banded iron formations

NASA Astrophysics Data System (ADS)

Kang, Nathan; Schmidt, Max W.

2017-10-01

Banded iron formations (BIF) were common shelf and ocean basin sediments 3.5-1.8 Ga ago. To understand the fate of these dense rocks upon subduction, the melting relations of carbonated BIF were determined in Fe-Ca-(Mg)-Si-C-O2 at 950-1400 °C, 6 and 10 GPa, oxidizing (fO2 = hematite-magnetite, HM) and moderately reducing (fO2 ∼CO2-graphite/diamond, CCO) conditions. Solidus temperatures under oxidizing conditions are 950-1025 °C with H2O, and 1050-1150 °C anhydrous, but 250-175 °C higher at graphite saturation (values at 6-10 GPa). The combination of Fe3+ and carbonate leads to a strong melting depression. Solidus curves are steep with 17-20 °C/GPa. Near-solidus melts are ferro-carbonatites with ∼22 wt.% FeOtot, ∼48 wt% CO2 and 1-5 wt.% SiO2 at fO2 ∼ HM and ∼49 wt.% FeOtot, ∼20 wt% CO2 and 19-25 wt.% SiO2 at fO2 ∼ CCO . At elevated subduction geotherms, as likely for the Archean, C-bearing BIF could melt out all carbonate around 6 GPa. Fe-rich carbonatites would rise but stagnate gravitationally near the slab/mantle interface until they react with the mantle through Fe-Mg exchange and partial reduction. The latter would precipitate diamond and yield Fe- and C-rich mantle domains, yet, Fe-Mg is expected to diffusively re-equilibrate over Ga time scales. We propose that the oldest subduction derived diamonds stem from BIF derived melts.

Correlation of Structure, Tunable Colors, and Lifetimes of (Sr, Ca, Ba)Al2O4:Eu2+, Dy3+ Phosphors

PubMed Central

Xie, Qidi; Li, Bowen; He, Xin; Zhang, Mei; Chen, Yan; Zeng, Qingguang

2017-01-01

(Sr, Ca, Ba)Al2O4:Eu2+, Dy3+ phosphors were prepared via a high temperature solid-state reaction method. The correlation of phase structure, optical properties and lifetimes of the phosphors are investigated in this work. For the (Sr, Ca)Al2O4:Eu2+, Dy3+ phosphors, the different phase formation from monoclinic SrAl2O4 phase to hexagonal SrAl2O4 phase to monoclinic CaAl2O4 phase was observed when the Ca content increased. The emission color of SrAl2O4:Eu2+, Dy3+ phosphors varied from green to blue. For the (Sr, Ba)Al2O4:Eu2+, Dy3+ phosphors, different phase formation from the monoclinic SrAl2O4 phase to the hexagonal BaAl2O4 phase was observed, along with a shift of emission wavelength from 520 nm to 500 nm. More interestingly, the decay time of SrAl2O4:Eu2+, Dy3+ changed due to the different phase formations. Lifetime can be dramatically shortened by the substitution of Sr2+ with Ba2+ cations, resulting in improving the performance of the alternating current light emitting diode (AC-LED). Finally, intense LEDs are successfully obtained by combining these phosphors with Ga(In)N near UV chips. PMID:29057839

High-pressure x-ray diffraction study of YBO{sub 3}/Eu{sup 3+}, GdBO{sub 3}, and EuBO{sub 3}: Pressure-induced amorphization in GdBO{sub 3}

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

Wang, Pei; Xu, Chao; Ren, Xiangting

2014-01-28

Angle-dispersive synchrotron X-ray diffraction measurements were performed on vaterite-type YBO{sub 3}/Eu{sup 3+}, GdBO{sub 3}, and EuBO{sub 3}, respectively, up to 41 GPa at room temperature using a diamond-anvil cell. Pressure-induced amorphization was observed in hexagonal GdBO{sub 3} with a significant compression along the c-axis. Compared to the ions of the distorted GdBO{sub 3} phase, its anions may lose their long-range order prior to the cations at high pressures. Based on the experimental pressure-volume data, the obtained bulk moduli of YBO{sub 3}/Eu{sup 3+} and GdBO{sub 3} are 329 and 321 GPa, respectively, which are more than 90% larger than that of EuBO{sub 3}more » (167 GPa) and are presumably attributed to Gd{sup 3+} and Y{sup 3+} with a high density of d valence electrons.« less

Pressure-induced magneto-structural transition in iron via a modified solid-state nudged elastic band method

NASA Astrophysics Data System (ADS)

Zarkevich, Nikolai A.; Johnson, Duane D.

2015-03-01

Materials under pressure may exhibit critical electronic and structural transitions that affect equation of states, as known for superconductors and the magneto-structural transformations of iron with both geophysical and planetary implications. While experiments often use constant-pressure (diamond-anvil cell, DAC) measurements, many theoretical results address a constant-volume transitions, which avoid issues with magnetic collapse but cannot be directly compared to experiment. We establish a modified solid-state nudge elastic band (MSS-NEB) method to handle magnetic systems that may exhibit moment (and volume) collapse during transformation. We apply it to the pressure-induced transformation in iron between the low-pressure body-centered cubic (bcc) and the high-pressure hexagonal close-packed (hcp) phases, find the bcc-hcp equilibrium coexistence pressure and a transitional pathway, and compare to shock and DAC experiments. We use methods developed with support by the U.S. Department of Energy (DE-FG02-03ER46026 and DE-AC02-07CH11358). Ames Laboratory is operated for the DOE by Iowa State University under contract DE-AC02-07CH11358.

Automatic numerical evaluation of vacancy-mediated transport for arbitrary crystals: Onsager coefficients in the dilute limit using a Green function approach

NASA Astrophysics Data System (ADS)

Trinkle, Dallas R.

2017-10-01

A general solution for vacancy-mediated diffusion in the dilute-vacancy/dilute-solute limit for arbitrary crystal structures is derived from the master equation. A general numerical approach to the vacancy lattice Green function reduces to the sum of a few analytic functions and numerical integration of a smooth function over the Brillouin zone for arbitrary crystals. The Dyson equation solves for the Green function in the presence of a solute with arbitrary but finite interaction range to compute the transport coefficients accurately, efficiently and automatically, including cases with very large differences in solute-vacancy exchange rates. The methodology takes advantage of the space group symmetry of a crystal to reduce the complexity of the matrix inversion in the Dyson equation. An open-source implementation of the algorithm is available, and numerical results are presented for the convergence of the integration error of the bare vacancy Green function, and tracer correlation factors for a variety of crystals including wurtzite (hexagonal diamond) and garnet.