X-ray diffraction studies of phase transformations in heavy-metal fluoride glasses

NASA Technical Reports Server (NTRS)

Bansal, N. P.; Doremus, R. H.

1985-01-01

Powder X-ray diffraction and differential scanning calorimetry studies of the crystallization properties of five ZrF4-based glass compositions have indicated that the crystalline phase in Zr-Ba-La-Pb fluoride glass is beta-BaZrF6; no such identification of crystal phases was obtainable, however, for the other glasses. Reversible polymorphic phase transformations occur in Zr-Ba-La-Li and Zr-Ba-La-Na fluoride glasses, upon heating to higher temperatures.

Chemical and physical controls on the transformation of amorphous calcium carbonate into crystalline CaCO3 polymorphs

NASA Astrophysics Data System (ADS)

Blue, C. R.; Giuffre, A.; Mergelsberg, S.; Han, N.; De Yoreo, J. J.; Dove, P. M.

2017-01-01

Calcite and other crystalline polymorphs of CaCO3 can form by pathways involving amorphous calcium carbonate (ACC). Apparent inconsistencies in the literature indicate the relationships between ACC composition, local conditions, and the subsequent crystalline polymorphs are not yet established. This experimental study quantifies the control of solution composition on the transformation of ACC into crystalline polymorphs in the presence of magnesium. Using a mixed flow reactor to control solution chemistry, ACC was synthesized with variable Mg contents by tuning input pH, Mg/Ca, and total carbonate concentration. ACC products were allowed to transform within the output suspension under stirred or quiescent conditions while characterizing the evolving solutions and solids. As the ACC transforms into a crystalline phase, the solutions record a polymorph-specific evolution of pH and Mg/Ca. The data provide a quantitative framework for predicting the initial polymorph that forms from ACC based upon the solution aMg2+/aCa2+ and aCO32-/aCa2+ and stirring versus quiescent conditions. This model reconciles discrepancies among previous studies that report on the nature of the polymorphs produced from ACC and supports the previous claim that monohydrocalcite may be an important, but overlooked, transient phase on the way to forming some aragonite and calcite deposits. By this construct, organic additives and extreme pH are not required to tune the composition and nature of the polymorph that forms. Our measurements show that the Mg content of ACC is recorded in the resulting calcite with a ≈1:1 dependence. By correlating composition of these calcite products with the Mgtot/Catot of the initial solutions, we find a ≈3:1 dependence that is approximately linear and general to whether calcite is formed via an ACC pathway or by the classical step-propagation process. Comparisons to calcite grown in synthetic seawater show a ≈1:1 dependence. The relationships suggest that the local Mg2+/Ca2+ at the time of precipitation determines the calcite composition, independent of whether growth occurs via an amorphous intermediate or classical pathway for a range of supersaturations and pH conditions. The findings reiterate the need to revisit the traditional picture of chemical and physical controls on CaCO3 polymorph selection. Mineralization by pathways involving ACC can lead to the formation of crystalline phases whose polymorphs and compositions are out of equilibrium with local growth media. As such, classical thermodynamic equilibria may not provide a reliable predictor of observed compositions.

The Pressure-Induced Polymorphic Transformations in Fluconazole.

PubMed

Gorkovenko, Ekaterina A; Kichanov, Sergey E; Kozlenko, Denis P; Belushkin, Alexandr V; Wąsicki, Jan; Nawrocik, Wojciech; Mielcarek, Jadwiga; Dubrovinsky, Leonid S; Lathe, Christian; Savenko, Boris N

2015-12-01

The structural properties and Raman spectra of fluconazole have been studied by means of X-ray diffraction and Raman spectroscopy at pressures up to 2.5 and 5.5 GPa, respectively. At a pressure of 0.8 GPa, a polymorphic phase transition from the initial form I to a new triclinic form VIII has been observed. At higher pressure of P = 3.2 GPa, possible transformation into another new polymorphic form IX has been detected. The unit cell parameters and volumes, and vibration modes as functions of pressure have been obtained for the different forms of fluconazole. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

Reduction of the allotropic transition temperature in nanocrystalline zirconium: Predicted by modified equation of state (MEOS) method and molecular dynamics simulation

NASA Astrophysics Data System (ADS)

Salati, Amin; Mokhtari, Esmail; Panjepour, Masoud; Aryanpour, Gholamreza

2013-04-01

The temperature at which polymorphic phase transformation occurs in nanocrystalline (NC) materials is different from that of coarse-grained specimens. This anomaly has been related to the role of grain boundary component in these materials and can be predicted by a dilated crystal model. In this study, based on this model, a modified equation of state (MEOS) method (instead of equation of state, EOS, method) is used to calculate the total Gibbs free energy of each phase (β-Zr or α-Zr) in NC Zr. Thereupon, the change in the total Gibbs free energy for β-Zr to α-Zr phase transformation (ΔGβ→α) via the grain size is calculated by this method. Similar to polymorphic transformation in other NC materials (Fe, Nb, Co, TiO2, Al2O3 and ZnS), it is found that the estimated transformation temperature in NC Zr (β→α) is reduced with decreasing grain size. Finally, a molecular dynamics (MD) simulation is employed to confirm the theoretical results.

Phenomenology of Polymorphism, III: p, TDiagram and Stability of Piracetam Polymorphs

NASA Astrophysics Data System (ADS)

Céolin, R.; Agafonov, V.; Louër, D.; Dzyabchenko, V. A.; Toscani, S.; Cense, J. M.

1996-02-01

The nootropic drug Piracetam is known to crystallize in three phases. In order to obtain their stability hierarchy from sublimation pressure inequalities, the drawing of a topologicalp,Tdiagram was attempted. For such a purpose and also for quality control, crystallographic and thermodynamic data were required. Powder X-ray diffractometry (XRD) and differential scanning calorimetry (DSC) were used. Molecular energy calculations were performed. Phase I melts at 426 K (ΔfusH(I) = +180 J·g-1). Phase II transforms into Phase I at 399 K (Δ(II→I)H= +24 J·g-1). Phase III transforms into phase I at 392 K (Δ(III→I)H= +28 J·g-1) or melts at 412 K (ΔfusH(III) = +210 J·g-1). Thep,Tdiagram shows that phase I is stable at higher temperature and phase II at lower temperature, like phase III, which is stable under high pressure. At room temperature, phase II is the more stable form, and phase I the less stable one. This agrees with the spontaneous I → II transformation observed at 298 K within a few hours, and with lattice energies, calculated previously. Molecular energy calculations and crystal structure comparison show how intermolecular hydrogen bonds and H-bonded dimers, in phases II and III, may stabilize conformations higher in energy than those of the isolated molecule and of phase I.

Comparison between thermochemical and phase stability data for the quartz-coesite-stishovite transformations

NASA Technical Reports Server (NTRS)

Weaver, J. S.; Chipman, D. W.; Takahashi, T.

1979-01-01

Phase stability and elasticity data have been used to calculate the Gibbs free energy, enthalpy, and entropy changes at 298 K and 1 bar associated with the quartz-coesite and coesite-stishovite transformations in the system SiO2. For the quartz-coesite transformation, these changes disagree by a factor of two or three with those obtained by calorimetric techniques. The phase boundary for this transformation appears to be well determined by experiment; the discrepancy, therefore, suggests that the calorimetric data for coesite are in error. Although the calorimetric and phase stability data for the coesite-stishovite transformation yield the same transition pressure at 298 K, the phase-boundary slopes disagree by a factor of two. At present, it is not possible to determine which of the data are in error. Thus serious inconsistencies exist in the thermodynamic data for the polymorphic transformations of silica.

Cristobalite X-I: A bridge between low and high density silica polymorphs

NASA Astrophysics Data System (ADS)

Shelton, H.; Tiange, B.; Zurek, E.; Smith, J.; Dera, P.

2017-12-01

SiO2 is one of the most common compounds found on Earth. Despite its chemical simplicity, and because of its crystal chemical characteristics, SiO2 exhibits a complex phase diagram. SiO2 has a wide variety of thermodynamically stable crystalline phases, as well as numerous metastable crystalline and amorphous polymorphs. Many of the phase transition sequences that produce metastable phases of SiO2 are strongly path-dependent, where the rate of change controls the transition just as much as the final conditions. The elusive metastable polymorphs of SiO2 may provide a better understanding of the factors controlling its densification. On compression of α-cristobalite (the high temperature tetrahedral phase of SiO2) to pressures above 12 GPa, a new polymorph known as cristobalite X-I forms. Existence of cristobalite X-I has been known for several decades, however, consensus regarding the exact atomic arrangement has not yet been reached. The X-I phase constitutes an important step in the silica densification process, separating low-density tetrahedral framework structures from high-density octahedral polymorphs. It is unique in being the only non-quenchable high-density SiO2 phase, which reverts back to the tetrahedral low-density form on decompression at ambient temperature. Our new single crystal synchrotron X-ray diffraction experiments, with quasihydrostatic neon as the pressure medium, revealed the structure of this enigmatic phase to consist of octahedral silicate chains with 4-60°-2 zigzag chain geometry. This geometry has not been considered before, but is closely related to post-quartz, stishovite and seifertite. Density functional theory calculations support this observation, confirming the dynamic stability of the X-I arrangement and reasonably reproducing the pressure at which the transformation takes place. The enthalpy of cristobalite X-I is higher than stishovite and seifertite, but it is favored as a high-pressure successor of cristobalite due to a unique transformation pathway.

Second amorphous-to-crystalline phase transformation in Cu(60)Ti(20)Zr(20) bulk metallic glass.

PubMed

Cao, Q P; Li, J F; Zhang, P N; Horsewell, A; Jiang, J Z; Zhou, Y H

2007-06-20

The second amorphous-to-crystalline phase transformation in Cu(60)Ti(20)Zr(20) bulk metallic glass was investigated by differential scanning calorimetry and x-ray diffractometry. The difference of the Gibbs free energies between the amorphous phase and the crystalline products during the transformation is estimated to be about 2.46 kJ mol(-1) at 753 K, much smaller than the 61 kJ mol(-1) obtained assuming that it is a polymorphic transformation. It was revealed that the phase transformation occurs through a eutectic crystallization of Cu(51)Zr(14) and Cu(2)TiZr, having an effective activation energy of the order of 400 kJ mol(-1). The average Avrami exponent n is about 2.0, indicating that the crystallization is diffusion controlled.

Synthesis, Characterization, and Self-Controlled Orthorhombic to Tetragonal Polymorphic Transformation in BaTiO3 Nanoparticles

NASA Astrophysics Data System (ADS)

Ram, S.; Jana, A.; Kundu, T. K.

The phase formation and thermal-induced phase transformation are studied in BaTiO3 nanoparticles. 2 h of heating a polymer precursor at 550°C in air formed a single phase BaTiO3 of 15 nm average crystallite size D. The X-ray diffraction peaks are analyzed assuming a Pnma orthorhombic (o) crystal structure of lattice parameters a = 0.6435 nm, b = 0.5306 nm, and c = 0.8854 nm. The lattice volume V = 0.3023 nm3, with z = 4 formula units, yields a density ρ = 5.124 g/cm3. This is a new polymorph in comparison to well-known Pm3m tetragonal (t) structure, V = 0.0644 nm3 or ρ = 6.016 g/cm3 (z = 1). An o ↦ t transformation appears on heating at temperature as high as 650°C in air. A proposed model explains the transformation above a certain D value in terms of the Gibbs free energy. Unless heating above 750°C, the two phases coexist in a composite structure (D≤27 nm), with as much residual o-phase trace as ~28 vol%. As a function of temperature both the phases decrease in the V values up to 0.2975 and 0.0643 nm3 at 750°C respectively (0.0650 nm3 at 650°C). This is an important parameter for designing useful ferroelectric and other properties in a hybrid composite structure.

In situ 3D-X-ray diffraction tracking of individual grains of olivine during high-pressure/ high-temperature phase transitions

NASA Astrophysics Data System (ADS)

Rosa, A. D.; Merkel, S.; Ghosh, S.; Hilairet, N.; Perrillat, J.; Mezouar, N.; Vaughan, G.

2013-12-01

The series of phase transitions between olivine, wadsleyite and ringwoodite play an essential role for large scale dynamical processes in the Earth mantle. Detailed knowledge of the microscopic mechanism at the origin of these high-pressure and high-temperature phase transformations is useful to connect global seismic observations and geodynamics. Indeed, the textures of these phases can be induced either during mantle flow or during the phase transformations and they greatly affect the characteristics of seismic wave propagation. Here, we present a new design of diamond anvil cell experiments to collect three-dimensional diffraction images and track individual grains inside a polycristalline sample at high pressure and high temperature. The instrumentation includes a new resistively heated diamond anvil cell developed at beamline ID27 of the ESRF which provided stable and homogenous temperature condition over more than 24 hours. In our experiments, the pressure is first increased up to 12 GPa at a constant temperature of T = 800 K. The temperature is then further increased to 1300 K to reach the stability field of the high-pressure polymorph. Upon further compression the transformation of olivine to its high-pressure polymorph is successfully monitored. At each pressure-temperature step and while the sample is transforming the crystallographic parameters, the orientations and positions of grains within the sample are tracked in situ using three-dimensional X-ray diffraction. This will provide important information on the micromechanical properties of olivine including orientation statistics, orientation relations between parent and daughter phases, and transformation textures at different stages of the phase transition. This in turn will help in interpreting the geophysical observations. Details of the experimental and analytical approach used in this study will be given.

The contribution of Raman spectroscopy to the analysis of phase transformations in pharmaceutical compounds.

PubMed

Hédoux, Alain; Guinet, Yannick; Descamps, Marc

2011-09-30

We show in this paper the contribution of the whole Raman spectrum including the phonon spectrum, to detect, identify and characterize polymorphic forms of molecular compounds, and study their stability and transformation. Obtaining these kinds of information is important in the area of pharmaceutical compounds. Two different polymorphic systems are analyzed through investigations in indomethacin and caffeine exposed to variable environmental conditions and various stresses, as possibly throughout the production cycle of the active pharmaceutical ingredient. It is shown the capability of the low-frequency Raman spectroscopy to reveal disorder in the crystalline state, to detect small amorphous or crystalline material, and to elucidate ambiguous polymorphic or polyamorphic situations. Copyright © 2011 Elsevier B.V. All rights reserved.

Preferential nucleation during polymorphic transformations

DOE PAGES

Sharma, H.; Sietsma, J.; Offerman, S. E.

2016-08-03

Polymorphism is the ability of a solid material to exist in more than one phase or crystal structure. Polymorphism may occur in metals, alloys, ceramics, minerals, polymers, and pharmaceutical substances. Unresolved are the conditions for preferential nucleation during polymorphic transformations in which structural relationships or special crystallographic orientation relationships (OR’s) form between the nucleus and surrounding matrix grains. We measured in-situ and simultaneously the nucleation rates of grains that have zero, one, two, three and four special OR’s with the surrounding parent grains. These experiments show a trend in which the activation energy for nucleation becomes smaller – and thereforemore » nucleation more probable - with increasing number of special OR’s. As a result, these insights contribute to steering the processing of polymorphic materials with tailored properties, since preferential nucleation affects which crystal structure forms, the average grain size and texture of the material, and thereby - to a large extent - the final properties of the material.« less

Solubility and conversion of carbamazepine polymorphs in supercritical carbon dioxide.

PubMed

Bettini, R; Bonassi, L; Castoro, V; Rossi, A; Zema, L; Gazzaniga, A; Giordano, F

2001-06-01

The aim of this work was to investigate whether mixtures of carbamazepine polymorphs could be processed in supercritical (SC) CO(2) in order to obtain the pure stable crystalline phase. To accomplish this goal the solubility of carbamazepine polymorphs I and III in supercritical CO(2) was first assessed using a low solvent flux dynamic method. Mixtures of Form I and Form III were processed in dynamic or static conditions in SC-CO(2). Differential scanning calorimetry, Fourier transformed infrared spectroscopy, and powder X-ray diffractometry were used to analyse solid samples in terms of polymorph composition. It was found that Form I and Form III of carbamazepine have different solubility in supercritical CO(2) at 55 degrees C above 300 bar. Due to the transformation of the metastable form, conversion of Form I into Form III can be carried out on a binary mixture of the two polymorphs by treating the mixture at 55 degrees C and 350 bar, under both static and dynamic conditions, via its solubilization in supercritical CO(2).

A Two-Dimensional 'Zigzag' Silica Polymorph on a Metal Support.

PubMed

Kuhness, David; Yang, Hyun Jin; Klemm, Hagen W; Prieto, Mauricio; Peschel, Gina; Fuhrich, Alexander; Menzel, Dietrich; Schmidt, Thomas; Yu, Xin; Shaikhutdinov, Shamil; Lewandowski, Adrian; Heyde, Markus; Kelemen, Anna; Włodarczyk, Radosław; Usvyat, Denis; Schütz, Martin; Sauer, Joachim; Freund, Hans-Joachim

2018-05-16

We present a new polymorph of the two-dimensional (2D) silica film with a characteristic 'zigzag' line structure and a rectangular unit cell which forms on a Ru(0001) metal substrate. This new silica polymorph may allow for important insights into growth modes and transformations of 2D silica films as a model system for the study of glass transitions. Based on scanning tunneling microscopy, low energy electron diffraction, infrared reflection absorption spectroscopy, and X-ray photoelectron spectroscopy measurements on the one hand, and density functional theory calculations on the other, a structural model for the 'zigzag' polymorph is proposed. In comparison to established monolayer and bilayer silica, this 'zigzag' structure system has intermediate characteristics in terms of coupling to the substrate and stoichiometry. The silica 'zigzag' phase is transformed upon reoxidation at higher annealing temperature into a SiO 2 silica bilayer film which is chemically decoupled from the substrate.

A combined crystallographic, thermal, Raman and computational study on polymorphism and phase transition in 1-(4-hexyloxy-3-hydroxyphenyl)ethanone.

PubMed

Suárez, Sebastián; Manzano, Veronica E; Fantoni, Adolfo C; Halac, Emilia; Baggio, Ricardo; Cukiernik, Fabio D

2017-12-01

The crystal structure of the triclinic polymorph of 1-(4-hexyloxy-3-hydroxyphenyl)ethanone, C 14 H 20 O 3 , differs markedly from that of the orthorhombic polymorph [Manzano et al. (2015). Acta Cryst. C71, 1022-1027]. The two molecular structures are alike with respect to their bond lengths and angles, but differ in their spatial arrangement. This gives rise to quite different packing schemes, even if built up by similar chains having the hydroxy-ethanone O-H...O hydrogen-bond synthon in common. Both phases were found to be related by a first-order thermally driven phase transformation at 338-340 K, which is discussed in detail. The relative stabilities of both polymorphs are explained on the basis of both the noncovalent interactions operating in each structure and quantum chemical calculations. The polymorphic phase transition has also been studied experimentally by means of differential scanning calorimetry (DSC) experiments, conducted on individual single crystals, Raman spectroscopy and controlled heating under a microscope of individual single crystals, which were further characterized by powder and single-crystal X-ray diffraction.

Phase transformations in Ln2O3 materials irradiated with swift heavy ions

NASA Astrophysics Data System (ADS)

Tracy, Cameron L.; Lang, Maik; Zhang, Fuxiang; Trautmann, Christina; Ewing, Rodney C.

2015-11-01

Phase transformations induced in the cubic C-type lanthanide sesquioxides, Ln2O3 (Ln = Sm, Gd, Ho, Tm, and Lu), by dense electronic excitation are investigated. The structural modifications resulting from exposure to beams of 185 MeV Xe and 2246 MeV Au ions are characterized using synchrotron x-ray diffraction and Raman spectroscopy. The formation of a B-type polymorph, an X-type nonequilibrium phase, and an amorphous phase are observed. The specific phase formed and the transformation rate show dependence on the material composition, as well as the ion beam mass and energy. Atomistic mechanisms for these transformations are determined, indicating that formation of the B-type phase results from the production of anti-Frenkel defects and the aggregation of anion vacancies into planar clusters, whereas formation of the X-type and amorphous phases requires extensive displacement of both anions and cations. The observed variations in phase behavior with changing lanthanide ionic radius and deposited electronic energy density are related to the energetics of these transformation mechanisms.

Polymorphism, mesomorphism, and metastability of monoelaidin in excess water.

PubMed

Chung, H; Caffrey, M

1995-11-01

The polymorphic and metastable phase behavior of monoelaidin dry and in excess water was studied by using high-sensitivity differential scanning calorimetry and time-resolved x-ray diffraction in the temperature range of 4 degrees C to 60 degrees C. To overcome problems associated with a pronounced thermal history-dependent phase behavior, simultaneous calorimetry and time-resolved x-ray diffraction measurements were performed on individual samples. Monoelaidin/water samples were prepared at room temperature and stored at 4 degrees C for up to 1 week before measurement. The initial heating scan from 4 degrees C to 60 degrees C showed complex phase behavior with the sample in the lamellar crystalline (Lc0) and cubic (Im3m, Q229) phases at low and high temperatures, respectively. The Lc0 phase transforms to the lamellar liquid crystalline (L alpha) phase at 38 degrees C. At 45 degrees C, multiple unresolved lines appeared that coexisted with those from the L alpha phase in the low-angle region of the diffraction pattern that have been assigned previously to the so-called X phase (Caffrey, 1987, 1989). With further heating the X phase converts to the Im3m cubic phase. Regardless of previous thermal history, cooling calorimetric scans revealed a single exotherm at 22 degrees C, which was assigned to an L alpha+cubic (Im3m, Q229)-to-lamellar gel (L beta) phase transition. The response of the sample to a cooling followed by a reheating or isothermal protocol depended on the length of time the sample was incubated at 4 degrees C. A model is proposed that reconciles the complex polymorphic, mesomorphic, and metastability interrelationships observed with this lipid/water system. Dry monoelaidin exists in the lamellar crystalline (beta) phase in the 4 degrees C to 45 degrees C range. The beta phase transforms to a second lamellar crystalline polymorph identified as beta* at 45 degrees C that subsequently melts at 57 degrees C. The beta phase observed with dry monoelaidin is identical to the LcO phase formed by monoelaidin that was dispersed in excess water and that had not been previously heated.

Polymorphism, mesomorphism, and metastability of monoelaidin in excess water.

PubMed Central

Chung, H; Caffrey, M

1995-01-01

The polymorphic and metastable phase behavior of monoelaidin dry and in excess water was studied by using high-sensitivity differential scanning calorimetry and time-resolved x-ray diffraction in the temperature range of 4 degrees C to 60 degrees C. To overcome problems associated with a pronounced thermal history-dependent phase behavior, simultaneous calorimetry and time-resolved x-ray diffraction measurements were performed on individual samples. Monoelaidin/water samples were prepared at room temperature and stored at 4 degrees C for up to 1 week before measurement. The initial heating scan from 4 degrees C to 60 degrees C showed complex phase behavior with the sample in the lamellar crystalline (Lc0) and cubic (Im3m, Q229) phases at low and high temperatures, respectively. The Lc0 phase transforms to the lamellar liquid crystalline (L alpha) phase at 38 degrees C. At 45 degrees C, multiple unresolved lines appeared that coexisted with those from the L alpha phase in the low-angle region of the diffraction pattern that have been assigned previously to the so-called X phase (Caffrey, 1987, 1989). With further heating the X phase converts to the Im3m cubic phase. Regardless of previous thermal history, cooling calorimetric scans revealed a single exotherm at 22 degrees C, which was assigned to an L alpha+cubic (Im3m, Q229)-to-lamellar gel (L beta) phase transition. The response of the sample to a cooling followed by a reheating or isothermal protocol depended on the length of time the sample was incubated at 4 degrees C. A model is proposed that reconciles the complex polymorphic, mesomorphic, and metastability interrelationships observed with this lipid/water system. Dry monoelaidin exists in the lamellar crystalline (beta) phase in the 4 degrees C to 45 degrees C range. The beta phase transforms to a second lamellar crystalline polymorph identified as beta* at 45 degrees C that subsequently melts at 57 degrees C. The beta phase observed with dry monoelaidin is identical to the LcO phase formed by monoelaidin that was dispersed in excess water and that had not been previously heated. Images FIGURE 3 PMID:8580338

Rayleigh analysis of domain dynamics across temperature induced polymorphic phase transitions in lead-free piezoceramics (1‑x)(BaTi0.88Sn0.12)–x(Ba0.7Ca0.3)TiO3

NASA Astrophysics Data System (ADS)

Abebe, Mulualem; Brajesh, Kumar; Singh Malhotra, Jaskaran; Ranjan, Rajeev

2018-05-01

We carried out a Rayleigh analysis of the dielectric permittivity of a lead-free piezoceramic system (1‑x)(BaTi0.88Sn0.12)–x(Ba0.7Ca0.3)TiO3 across the composition and temperature induced polymorphic phase transformations to determine the trend in the reversible and irreversible domain wall motion across the composition and temperature induced structural changes. Experiments were carried out on three representative compositions x  =  0.10, 0.2, and 0.25 exhibiting rhombohedral, orthorhombic, and tetragonal phases at room temperature. While confirming that the irreversible Rayleigh parameter is large in the orthorhombic phase, we discuss a correspondence between the reduction in the coercive field and the corresponding increase in the irreversible Rayleigh parameter. We also show how the proximity of the Curie point to the polymorphic phase boundary greatly undermines this correspondence.

Influence of temperature on the rhombic shape of paracetamol molecular crystals

NASA Astrophysics Data System (ADS)

Belyaev, A. P.; Rubets, V. P.; Antipov, V. V.

2017-04-01

The method of differential scanning ellipsometry has been used to study the influence of heating on the rhombic shape of paracetamol molecular crystals. Rhombic molecular paracetamol crystals have been synthesized in vacuum from the vapor phase of paracetamol as a result of complex transformation, which includes a second-order transition that gives rise to a pretransition phase. It has been found that these crystals contain monoclinic nuclei, which favor the form I-to-form II polymorphic transformation during heating.

Size-dependent pressure-induced amorphization: a thermodynamic panorama.

PubMed

Machon, Denis; Mélinon, Patrice

2015-01-14

Below a critical particle size, some pressurized compounds (e.g. TiO2, Y2O3, PbTe) undergo a crystal-to-amorphous transformation instead of a polymorphic transition. This effect reflects the greater propensity of nanomaterials for amorphization. In this work, a panorama of thermodynamic interpretations is given: first, a descriptive analysis based on the energy landscape concept gives a general comprehension of the balance between thermodynamics and kinetics to obtain an amorphous state. Then, a formal approach based on Gibbs energy to describe the thermodynamics and phase transitions in nanoparticles gives a basic explanation of size-dependent pressure-induced amorphization. The features of this transformation (amorphization occurs at pressures lower than the polymorphic transition pressure!) and the nanostructuration can be explained in an elaborated model based on the Ginzburg-Landau theory of phase transition and on percolation theory. It is shown that the crossover between polymorphic transition and amorphization is highly dependent on the defect density and interfacial energy, i.e., on the synthesis process. Their behavior at high pressure is a quality control test for the nanoparticles.

Evidence for charge-trapping inducing polymorphic structural-phase transition in pentacene.

PubMed

Ando, Masahiko; Kehoe, Tom B; Yoneya, Makoto; Ishii, Hiroyuki; Kawasaki, Masahiro; Duffy, Claudia M; Minakata, Takashi; Phillips, Richard T; Sirringhaus, Henning

2015-01-07

Trapped-charge-induced transformation of pentacene polymorphs is observed by using in situ Raman spectroscopy and molecular dynamics simulations reveal that the charge should be localized in pentacene molecules at the interface with static intermolecular disorder along the long axis. Quantum chemical calculations of the intermolecular transfer integrals suggest the disorder to be large enough to induce Anderson-type localization. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of Fat Polymorphic Transformation and Nonfat Particle Size Distribution on the Surface Changes of Untempered Model Chocolate, Based on Solid Cocoa Mass.

PubMed

Zhao, Huanhuan; Young, Ashley K; James, Bryony J

2018-04-01

This study aims to understand the bloom process in untempered chocolate by investigating the polymorphic transformation of cocoa butter and changes in chocolate surface. Cocoa mass with varying particle size distributions (PSD) were used to produce untempered model chocolate. Optical microscopy showed that during 25 d of storage, the chocolate surface gradually became honeycombed in appearance with dark spots surrounded by white sandy bloom areas. In conjunction with X-ray diffraction this indicates that the polymorphic transformation of form IV cocoa butter to more stable form V crystals caused the observed surface changes with the most significant changes occurring within 6 d. As bloom developed the surface whiteness increased, but the PSD of nonfat particles showed limited impact on the changes in whiteness. Moreover, scanning electron microscopy showed separated fat crystals on fat-rich dark spots and empty spaces between particles in bloom areas suggesting redistribution of fat in the chocolate matrix. The results reported in this work can facilitate the understanding of fat bloom formation in untempered chocolate with respect to the changes in microstructure and surface appearances. It also contributes to show the details of IV-to-V polymorphic transformation in the fat phase as time went by. © 2018 Institute of Food Technologists®.

Pressure Induced Phase Transformations of Silica Polymorphs and Glasses

NASA Astrophysics Data System (ADS)

Cagin, Tahir; Demiralp, Ersan; Goddard, William A., III

1998-03-01

Silica, SiO_2, is one of the most widely studied substance, and it has some complex and unusual properties. We have used a recently developed 2-body interaction force field (E. Demiralp, T. Cagin, W.A. Goddard, III, unpublished.) to study the structural phase transformations in silica under various pressure loading conditions. The specific transformations we studied are α-quartz to stishovite, coesite to stishovite and fused glass to stishovite-like dense, a dominantly six-coordinated glassy phase. Molecular dynamics simulations are performed under the constant loading rates ranging from 0.1 GPa/ps to 2.0 GPa/ps, pressures upto 100 GPa and at temperatures 300, 500, 700 and 900 K. We observe the crystal to crystal transformations to occur reconstructively, whereas it occurs in a smooth and displacive manner from glass to a stishovite-like phase confirming earlier conjectures. (E.M. Stolper and T.J. Ahrens, Geophys. Res. Let.) 14, 1231 (1987). To elucidate the shock loading experiments, we studied the dependence of transition pressure on the loading rate and the temperature. To assess the hysterisis effect we also studied the unloading behavior of each transformation.

CO2 packing polymorphism under pressure: Mechanism and thermodynamics of the I-III polymorphic transition

NASA Astrophysics Data System (ADS)

Gimondi, Ilaria; Salvalaglio, Matteo

2017-09-01

In this work, we describe the thermodynamics and mechanism of CO2 polymorphic transitions under pressure from form I to form III combining standard molecular dynamics, well-tempered metadynamics, and committor analysis. We find that the phase transformation takes place through a concerted rearrangement of CO2 molecules, which unfolds via an anisotropic expansion of the CO2 supercell. Furthermore, at high pressures, we find that defected form I configurations are thermodynamically more stable with respect to form I without structural defects. Our computational approach shows the capability of simultaneously providing an extensive sampling of the configurational space, estimates of the thermodynamic stability, and a suitable description of a complex, collective polymorphic transition mechanism.

CO2 packing polymorphism under pressure: Mechanism and thermodynamics of the I-III polymorphic transition.

PubMed

Gimondi, Ilaria; Salvalaglio, Matteo

2017-09-21

In this work, we describe the thermodynamics and mechanism of CO 2 polymorphic transitions under pressure from form I to form III combining standard molecular dynamics, well-tempered metadynamics, and committor analysis. We find that the phase transformation takes place through a concerted rearrangement of CO 2 molecules, which unfolds via an anisotropic expansion of the CO 2 supercell. Furthermore, at high pressures, we find that defected form I configurations are thermodynamically more stable with respect to form I without structural defects. Our computational approach shows the capability of simultaneously providing an extensive sampling of the configurational space, estimates of the thermodynamic stability, and a suitable description of a complex, collective polymorphic transition mechanism.

Polymorphic Transformation of Indomethacin during Hot Melt Extrusion Granulation: Process and Dissolution Control.

PubMed

Xu, Ting; Nahar, Kajalajit; Dave, Rutesh; Bates, Simon; Morris, Kenneth

2018-05-10

To study and elucidate the effect of the intensity and duration of processing stresses on the possible solid-state changes during a hot melt extrusion granulation process. Blends of α-indomethacin and PEG 3350 (w/w 4:1) were granulated using various screw sizes/designs on the melt extruder under different temperature regimes. Differential Scanning Calorimetry and X-ray Powder Diffraction were employed for characterization. The dissolution behavior of the pure polymorphs and the resulting granules was determined using in-situ fiber optic UV testing system. An XRPD quantitation method using Excel full pattern fitting was developed to determine the concentration of each constituent (amorphous, α and γ indomethacin and PEG) in samples collected from each functioning zone and in granules. Analysis of in-process samples and granules revealed that higher temperature (≥130°C) and shear stress accelerated the process induced phase transitions from amorphous and/or the α form to γ indomethacin during heating stage. However, rapid cooling resulted in an increased percentage of the α form allowing isolation of the meta-stable form. By determining the conditions that either prevent or facilitate process induced transformations of IMC polymorphs during melt granulation, a design space was developed to control the polymorph present in the resulting granules. This represents the conditions necessary to balance the thermodynamic relationships between the polymorphs of the IMC system and the kinetics of the possible transformations as a function of the processing stresses.

Relationship between crystal structure and solid-state properties of pharmaceuticals

NASA Astrophysics Data System (ADS)

Sheth, Agam R.

This thesis strives to understand the structure-property relationships of some pharmaceutical crystals at the molecular level with emphasis on the effect of secondary processing on the solid phase. Using single crystal X-ray diffractometry (SCXRD), the structure of warfarin sodium 2-propanol adduct (W) was established to be a true solvate, contrary to previous reports. Using dynamic water vapor sorption, optical and environmental scanning electron microscopy, SCXRD, powder X-ray diffractometry (PXRD), volume computations and molecular modeling, the effect of relative humidity and temperature on the crystal structure of W was investigated. Ab initio calculations on piroxicam showed that the difference in energy between the two polymorphs, I and II, arises predominantly from the difference between their lattice energies. The detailed hydrogen bonding networks of the two polymorphs are described and compared using graph sets. Despite stabilization of the polymorphs by hydrogen bonds, pair-wise distribution function transforms show a loss of polymorphic memory upon cryogrinding the two polymorphs, leading to a difference in recrystallization behavior between amorphous piroxicam prepared from polymorphs I and II. Structural and solid-state changes of piroxicam polymorphs under mechanical stress were investigated using cryogenic grinding, PXRD, diffuse-reflectance solid-state ultraviolet-visible spectroscopy, 13C solid-state nuclear magnetic resonance spectroscopy, and diffuse-reflectance solid-state Fourier-transform infrared spectroscopy. Intermolecular proton transfer was found to accompany changes in phase and color observed upon cryogrinding the two polymorphs. Model-free and model-fitting studies of the dehydration kinetics of piroxicam monohydrate (PM) showed the dependence of activation energy ( Ea) on both isothermal and non-isothermal heating conditions, and on the fraction of conversion. In the constant-E a region, isothermal dehydration follows the two-dimensional phase boundary model, while non-isothermal dehydration follows a mechanism intermediate between two- and three-dimensional diffusion that cannot be described by any of the common models. Structural studies suggest that the complex hydrogen bond pattern in PM is responsible for the observed dehydration behavior. Ab initio calculations provide an explanation for the changes in the molecular and crystal structures accompanying the reversible change in hydration state between anhydrous piroxicam Form I and PM. The thesis further demonstrates the utility of model-free analysis in describing complex dehydration kinetics.

Exploring the high-pressure behavior of the three known polymorphs of BiPO{sub 4}: Discovery of a new polymorph

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

Errandonea, D., E-mail: daniel.errandonea@uv.es; García-Domene, B.; Gomis, O.

We have studied the structural behavior of bismuth phosphate under compression. We performed x-ray powder diffraction measurements up to 31.5 GPa and ab initio calculations. Experiments were carried out on different polymorphs: trigonal (phase I) and monoclinic (phases II and III). Phases I and III, at low pressure (P < 0.2–0.8 GPa), transform into phase II, which has a monazite-type structure. At room temperature, this polymorph is stable up to 31.5 GPa. Calculations support these findings and predict the occurrence of an additional transition from the monoclinic monazite-type to a tetragonal scheelite-type structure (phase IV). This transition was experimentally found after the simultaneous applicationmore » of pressure (28 GPa) and temperature (1500 K), suggesting that at room temperature the transition might by hindered by kinetic barriers. Calculations also predict an additional phase transition at 52 GPa, which exceeds the maximum pressure achieved in the experiments. This transition is from phase IV to an orthorhombic barite-type structure (phase V). We also studied the axial and bulk compressibility of BiPO{sub 4}. Room-temperature pressure-volume equations of state are reported. BiPO{sub 4} was found to be more compressible than isomorphic rare-earth phosphates. The discovered phase IV was determined to be the less compressible polymorph of BiPO{sub 4}. On the other hand, the theoretically predicted phase V has a bulk modulus comparable with that of monazite-type BiPO{sub 4}. Finally, the isothermal compressibility tensor for the monazite-type structure is reported at 2.4 GPa showing that the direction of maximum compressibility is in the (0 1 0) plane at approximately 15° (21°) to the a axis for the case of our experimental (theoretical) study.« less

Evaluation of a biphasic in vitro dissolution test for estimating the bioavailability of carbamazepine polymorphic forms.

PubMed

Deng, Jia; Staufenbiel, Sven; Bodmeier, Roland

2017-07-15

The purpose of this study was to discriminate three crystal forms of carbamazepine (a BCS II drug) by in vitro dissolution testing and to correlate in vitro data with published in vivo data. A biphasic dissolution system (phosphate buffer pH6.8 and octanol) was used to evaluate the dissolution of the three polymorphic forms and to compare it with conventional single phase dissolution tests performed under sink and non-sink conditions. Similar dissolution profiles of three polymorphic forms were observed in the conventional dissolution test under sink conditions. Although a difference in dissolution was seen in the single phase dissolution test under non-sink conditions as well as in the aqueous phase of the biphasic test, little relevance for in vivo data was observed. In contrast, the biphasic dissolution system could discriminate between the different polymorphic forms in the octanol phase with a ranking of form III>form I>dihydrate form. This was in agreement with the in vivo performance. The dissolved drug available for oral absorption, which was dominated by dissolution and solution-mediated phase transformation, could be reflected in the biphasic dissolution test. Moreover, a good correlation was established between in vitro dissolution in the octanol phase of the biphasic test and in vivo pharmacokinetic data (R 2 =0.99). The biphasic dissolution method is a valuable tool to discriminate between different crystal forms in the formulations of poorly soluble drugs. Copyright © 2017. Published by Elsevier B.V.

Phase change in CoTi2 induced by MeV electron irradiation

NASA Astrophysics Data System (ADS)

Zensho, Akihiro; Sato, Kazuhisa; Yasuda, Hidehiro; Mori, Hirotaro

2018-07-01

The phase change induced by MeV electron irradiation in the intermetallic compound E93-CoTi2 was investigated using high-voltage electron microscopy. Under MeV electron irradiation, CoTi2 was first transformed into an amorphous phase and, with continued irradiation, crystallite formation in the amorphous phase (i.e. formation of crystallites of a solid-solution phase within the amorphous phase) was induced. The critical temperature for amorphisation was around 250 K. The total dose (dpa) required for crystallite formation (i.e. that required for partial crystallisation) was high (i.e. 27-80 dpa) and, even after prolonged irradiation, the amorphous phase was retained in the irradiated sample. Such partial crystallisation behaviour of amorphous Co33Ti67 was clearly different from the crystallisation behaviour (i.e. amorphous-to-solid solution, polymorphous transformation) of amorphous Cr67Ti33 reported in the literature. A possible cause of the difference is discussed.

Effect of deformation on the structural state of piracetam

NASA Astrophysics Data System (ADS)

Kanunnikova, O. M.; Mikhailova, S. S.; Karban', O. V.; Mukhgalin, V. V.; Aksenova, V. V.; Sen'kovskii, B. V.; Pechina, E. A.; Lad'yanov, V. I.

2016-04-01

The effect of various deformation actions on the structure-phase transformations in piracetam of modifications I and II with a sodium acetate addition is studied. Mechanical activation and pressing are shown to cause the polymorphic transformation of modification I into modification II, and modification III forms predominantly during severe plastic deformation by torsion. The structural difference between the piracetam molecules of modifications I and II is found to be retained in aqueous solutions.

Pressure induced Ag 2Te polymorphs in conjunction with topological non trivial to metal transition

DOE PAGES

Zhu, J.; Oganov, A. R.; Feng, W. X.; ...

2016-08-01

Silver telluride (Ag 2Te) is well known as superionic conductor and topologica insulator with polymorphs. Pressure induced three phase transitions in Ag 2Te hav been reported in previous. Here, we experimentally identified high pressure phas above 13 GPa of Ag 2Te by using high pressure synchrotron x ray diffraction metho in combination with evolutionary crystal structure prediction, showing it crystallize into a monoclinic structure of space group C2/m with lattice parameters a = 6.081Å b = 5.744Å, c = 6.797 Å, β = 105.53°. The electronic properties measurements of Ag 2Te reveal that the topologically non-trivial semiconducting phase I andmore » semimetalli phase II previously predicated by theory transformed into bulk metals fo high pressure phases in consistent with the first principles calculations« less

Characterization and Thermodynamic Relationship of Three Polymorphs of a Xanthine Oxidase Inhibitor, Febuxostat.

PubMed

Patel, Jinish; Jagia, Moksh; Bansal, Arvind Kumar; Patel, Sarsvatkumar

2015-11-01

Febuxostat (FXT), a xanthine oxidase inhibitor, is an interesting and unique molecule, which exhibits extensive polymorphism, with over 15 polymorphic forms reported to date. The primary purpose of the study was to characterize the three polymorphic forms with respect to their thermodynamic quantities and establish thermodynamic relationship between them. The polymorphs were characterized by thermal and powder X-ray diffraction methods. Three different methods were used to calculate the transition temperatures (Ttr) and thereby their thermodynamic relationships. Although the first and second method used calorimetric data (melting point and heat of fusion), the third method employed the use of configurational free energy phase diagram. The onset melting points of three polymorphic forms were found to be 482.89 ± 0.37 K for form I, 476.30 ± 1.21 K for form II, and 474.19 ± 0.11 K for form III. Moreover, the powder X-ray diffraction patterns for each form were also unique. The polymorphic pair of form I and II and of form I and III was found to be enantiotropic, whereas pair of form II and III was monotropic. Besides the relative thermodynamic aspects (free energy differences, enthalpy, entropy contributions) using different methods, the pharmaceutical implications and phase transformation aspects have also been covered. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

Sulfamerazine: Understanding the Influence of Slip Planes in the Polymorphic Phase Transformation through X-Ray Crystallographic Studies and ab Initio Lattice Dynamics.

PubMed

Pallipurath, Anuradha R; Skelton, Jonathan M; Warren, Mark R; Kamali, Naghmeh; McArdle, Patrick; Erxleben, Andrea

2015-10-05

Understanding the polymorphism exhibited by organic active-pharmaceutical ingredients (APIs), in particular the relationships between crystal structure and the thermodynamics of polymorph stability, is vital for the production of more stable drugs and better therapeutics, and for the economics of the pharmaceutical industry in general. In this article, we report a detailed study of the structure-property relationships among the polymorphs of the model API, Sulfamerazine. Detailed experimental characterization using synchrotron radiation is complemented by computational modeling of the lattice dynamics and mechanical properties, in order to study the origin of differences in millability and to investigate the thermodynamics of the phase equilibria. Good agreement is observed between the simulated phonon spectra and mid-infrared and Raman spectra. The presence of slip planes, which are found to give rise to low-frequency lattice vibrations, explains the higher millability of Form I compared to Form II. Energy/volume curves for the three polymorphs, together with the temperature dependence of the thermodynamic free energy computed from the phonon frequencies, explains why Form II converts to Form I at high temperature, whereas Form III is a rare polymorph that is difficult to isolate. The combined experimental and theoretical approach employed here should be generally applicable to the study of other systems that exhibit polymorphism.

Experimental and Theoretical Evaluation of the Stability of True MOF Polymorphs Explains Their Mechanochemical Interconversions.

PubMed

Akimbekov, Zamirbek; Katsenis, Athanassios D; Nagabhushana, G P; Ayoub, Ghada; Arhangelskis, Mihails; Morris, Andrew J; Friščić, Tomislav; Navrotsky, Alexandra

2017-06-14

We provide the first combined experimental and theoretical evaluation of how differences in ligand structure and framework topology affect the relative stabilities of isocompositional (i.e., true polymorph) metal-organic frameworks (MOFs). We used solution calorimetry and periodic DFT calculations to analyze the thermodynamics of two families of topologically distinct polymorphs of zinc zeolitic imidazolate frameworks (ZIFs) based on 2-methyl- and 2-ethylimidazolate linkers, demonstrating a correlation between measured thermodynamic stability and density, and a pronounced effect of the ligand substituent on their stability. The results show that mechanochemical syntheses and transformations of ZIFs are consistent with Ostwald's rule of stages and proceed toward thermodynamically increasingly stable, more dense phases.

Microstructural fingerprints of phase transitions in shock-loaded iron

NASA Astrophysics Data System (ADS)

Wang, S. J.; Sui, M. L.; Chen, Y. T.; Lu, Q. H.; Ma, E.; Pei, X. Y.; Li, Q. Z.; Hu, H. B.

2013-01-01

The complex structural transformation in crystals under static pressure or shock loading has been a subject of long-standing interest to materials scientists and physicists. The polymorphic transformation is of particular importance for iron (Fe), due to its technological and sociological significance in the development of human civilization, as well as its prominent presence in the earth's core. The martensitic transformation α-->ɛ (bcc-->hcp) in iron under shock-loading, due to its reversible and transient nature, requires non-trivial detective work to uncover its occurrence. Here we reveal refined microstructural fingerprints, needle-like colonies and three sets of {112}<111> twins with a threefold symmetry, with tell-tale features that are indicative of two sequential martensitic transformations in the reversible α-->ɛ phase transition, even though no ɛ is retained in the post-shock samples. The signature orientation relationships are consistent with previously-proposed transformation mechanisms, and the unique microstructural fingerprints enable a quantitative assessment of the volume fraction transformed.

Glass formation and crystallization in high-temperature glass-ceramics and Si3N4

NASA Technical Reports Server (NTRS)

Drummond, Charles H., III

1991-01-01

The softening of glassy grain boundaries in ceramic matrix composites and Si3N4 at high temperatures reduces mechanical strength and the upper-use temperature. By crystallizing this glass to a more refractory crystalline phase, a material which performs at higher temperatures may result. Three systems were examined: a cordierite composition with ZrO2 as a nucleating agent; celsian compositions; and yttrium silicate glasses both in bulk and intergranular in Si3N4. For the cordierite compositions, a series of metastable phases was obtained. The crystallization of these compositions was summarized in terms of metastable ternary isothermal sections. Zircon formed at the expense of ZrO2 and spinel. In SiC composites, the transformations were slower. In celsian, two polymorphs were crystallized. One phase, hexacelsian, which always crystallized, even when metastable, had an undesirable volume change. The other phase, celsian, was very difficult to crystallize. In yttrium silicate bulk glasses, similar in composition to the intergranular glass in Si3N4, a number of polymorphs of Y2Si2O7 were crystallized. The conditions under which these polymorphs formed are compared with crystallization in Si3N4.

Lithium ion conduction in sol-gel synthesized LiZr2(PO4)3 polymorphs

NASA Astrophysics Data System (ADS)

Kumar, Milind; Yadav, Arun Kumar; Anita, Sen, Somaditya; Kumar, Sunil

2018-04-01

Safety issue associated with the high flammability and volatility of organic electrolytes used in commercial rechargeable lithium ion batteries has led to significant attention to ceramic-based solid electrolytes. In the present study, lithium ion conduction in two polymorphs of LiZr2(PO4)3 synthesized via the sol-gel route has been investigated. Rietveld refinement of room temperature X-ray diffraction data of LiZr2(PO4)3 powders calcined at 900 °C and 1300 °C confirmed these to be the monoclinic phase with P21/n structure and rhombohedral phase with R3¯c structure, respectively. Increase in calcination temperature and resultant phase transformation improved the room temperature conductivity from 2.27×10-6 ohm-1m-1 for the monoclinic phase to 1.41×10-4 ohm-1m-1 for rhombohedral phase. Temperature dependence of conductivity was modeled using Arrhenius law and activation energy of ˜ 0.59 eV (for monoclinic phase) and ˜0.50 eV (for rhombohedral phase) were obtained.

High pressure phase-transformation induced texture evolution and strengthening in zirconium metal: Experiment and modeling

DOE PAGES

Yu, Xiaohui; Zhang, Ruifeng; Weldon, David; ...

2015-07-28

We studied the phase-transition induced texture changes and strengthening mechanism for zirconium metal under quasi-hydrostatic compression and uni-axial deformation under confined high pressure using the deformation-DIA (D-DIA) apparatus. It is shown that the experimentally obtained texture for ω-phase Zr can be qualitatively described by combining a subset of orientation variants previously proposed in two different models. The determined flow stress for the high-pressure ω-phase is 0.5–1.2 GPa, more than three times higher than that of the α-phase. Using first-principles calculations, we investigated the mechanical and electronic properties of the two Zr polymorphs. We find that the observed strengthening can bemore » attributed to the relatively strong directional bonding in the ω phase, which significantly increases its shear plastic resistance over the α-phase Zr. The present findings provide an alternate route for Zr metal strengthening by high-pressure phase transformation.« less

Polymorphism of Alprazolam (Xanax): a review of its crystalline phases and identification, crystallographic characterization, and crystal structure of a new polymorph (form III).

PubMed

de Armas, Héctor Novoa; Peeters, Oswald M; Van den Mooter, Guy; Blaton, Norbert

2007-05-01

A new polymorphic form of Alprazolam (Xanax), 8-chloro-1-methyl-6-phenyl-4H-[1,2,4]triazolo-[4,3-alpha][1,4]benzodiazepine, C(17)H(13)ClN(4), has been investigated by means of X-ray powder diffraction (XRPD), single crystal X-ray diffraction, and differential scanning calorimetry (DSC). This polymorphic form (form III) was obtained during DSC experiments after the exothermic recrystallization of the melt of form I. The crystal unit cell dimensions for form III were determined from diffractometer methods. The monoclinic unit cell found for this polymorph using XRPD after indexing the powder diffractogram was confirmed by the cell parameters obtained from single crystal X-ray diffractometry on a crystal isolated from the DSC pans. The single crystal unit cell parameters are: a = 28.929(9), b = 13.844(8), c = 7.361(3) angstroms, beta = 92.82(3) degrees , V = 2944(2) angstroms(3), Z = 8, space group P2(1) (No.4), Dx = 1.393 Mg/m(3). The structure obtained from single crystal X-ray diffraction was used as initial model for Rietveld refinement on the powder diffraction data of form III. The temperature phase transformations of alprazolam were also studied using high temperature XRPD. A review of the different phases available in the Powder Diffraction File (PDF) database for this drug is described bringing some clarification and corrections. (c) 2007 Wiley-Liss, Inc. and the American Pharmacists Association.

Dolomite III: A new candidate lower mantle carbonate

NASA Astrophysics Data System (ADS)

Mao, Zhu; Armentrout, Matt; Rainey, Emma; Manning, Craig E.; Dera, Przemyslaw; Prakapenka, Vitali B.; Kavner, Abby

2011-11-01

Dolomite is a major constituent of subducted carbonates; therefore evaluation of its phase stability and equation of state at high pressures and temperatures is important for understanding the deep Earth carbon cycle. X-ray diffraction experiments in the diamond anvil cell show that Ca0.988Mg0.918Fe0.078Mn0.016(CO3)2 dolomite transforms to dolomite-II at ∼17 GPa and 300 K and then upon laser-heating transforms to a new monoclinic phase (dolomite-III), that is observed between 36 and 83 GPa. Both high-pressure polymorphs are stable up to 1500 K, indicating that addition of minor Fe stabilizes dolomite to Earth's deep-mantle conditions.

Understanding metastable phase transformation during crystallization of RDX, HMX and CL-20: experimental and DFT studies.

PubMed

Ghosh, Mrinal; Banerjee, Shaibal; Shafeeuulla Khan, Md Abdul; Sikder, Nirmala; Sikder, Arun Kanti

2016-09-14

Multiphase growth during crystallization severely affects deliverable output of explosive materials. Appearance and incomplete transformation of metastable phases are a major source of polymorphic impurities. This article presents a methodical and molecular level understanding of the metastable phase transformation mechanism during crystallization of cyclic nitramine explosives, viz. RDX, HMX and CL-20. Instantaneous reverse precipitation yielded metastable γ-HMX and β-CL-20 which undergo solution mediated transformation to the respective thermodynamic forms, β-HMX and ε-CL-20, following 'Ostwald's rule of stages'. However, no metastable phase, anticipated as β-RDX, was evidenced during precipitation of RDX, which rather directly yielded the thermodynamically stable α-phase. The γ→β-HMX and β→ε-CL-20 transformations took 20 and 60 minutes respectively, whereas formation of α-RDX was instantaneous. Density functional calculations were employed to identify the possible transition state conformations and to obtain activation barriers for transformations at wB97XD/6-311++G(d,p)(IEFPCM)//B3LYP/6-311G(d,p) level of theory. The computed activation barriers and lattice energies responsible for transformation of RDX, HMX and CL-20 metastable phases to thermodynamic ones conspicuously supported the experimentally observed order of phase stability. This precise result facilitated an understanding of the occurrence of a relatively more sensitive and less dense β-CL-20 phase in TNT based melt-cast explosive compositions, a persistent and critical problem unanswered in the literature. The crystalline material recovered from such compositions revealed a mixture of β- and ε-CL-20. However, similar compositions of RDX and HMX never showed any metastable phase. The relatively long stability with the highest activation barrier is believed to restrict complete β→ε-CL-20 transformation during processing. Therefore a method is suggested to overcome this issue.

Polymorphism in a high-entropy alloy

DOE PAGES

Zhang, Fei; Wu, Yuan; Lou, Hongbo; ...

2017-06-01

Polymorphism, which describes the occurrence of different lattice structures in a crystalline material, is a critical phenomenon in materials science and condensed matter physics. Recently, configuration disorder was compositionally engineered into single lattices, leading to the discovery of high-entropy alloys and high-entropy oxides. For these novel entropy-stabilized forms of crystalline matter with extremely high structural stability, is polymorphism still possible? Here by employing in situ high-pressure synchrotron radiation X-ray diffraction, we reveal a polymorphic transition from face-centred-cubic (fcc) structure to hexagonal-close-packing (hcp) structure in the prototype CoCrFeMnNi high-entropy alloy. The transition is irreversible, and our in situ high-temperature synchrotron radiationmore » X-ray diffraction experiments at different pressures of the retained hcp high-entropy alloy reveal that the fcc phase is a stable polymorph at high temperatures, while the hcp structure is more thermodynamically favourable at lower temperatures. Lastly, as pressure is increased, the critical temperature for the hcp-to-fcc transformation also rises.« less

Spin-liquid polymorphism in a correlated electron system on the threshold of superconductivity.

PubMed

Zaliznyak, Igor; Savici, Andrei T; Lumsden, Mark; Tsvelik, Alexei; Hu, Rongwei; Petrovic, Cedomir

2015-08-18

We report neutron scattering measurements which reveal spin-liquid polymorphism in an "11" iron chalcogenide superconductor. It occurs when a poorly metallic magnetic state of FeTe is tuned toward superconductivity by substitution of a small amount of tellurium with isoelectronic sulfur. We observe a liquid-like magnetic response, which is described by the coexistence of two disordered magnetic phases with different local structures whose relative abundance depends on temperature. One is the ferromagnetic (FM) plaquette phase observed in undoped, nonsuperconducting FeTe, which preserves the C4 symmetry of the underlying square lattice and is favored at high temperatures, whereas the other is the antiferromagnetic plaquette phase with broken C4 symmetry, which emerges with doping and is predominant at low temperatures. These findings suggest the coexistence of and competition between two distinct liquid states, and a liquid-liquid phase transformation between these states, in the electronic spin system of FeTe(1-x)(S,Se)(x). We have thus discovered the remarkable physics of competing spin-liquid polymorphs in a correlated electron system approaching superconductivity. Our results facilitate an understanding of large swaths of recent experimental data in unconventional superconductors. In particular, the phase with lower C2 local symmetry, whose emergence precedes superconductivity, naturally accounts for a propensity for forming electronic nematic states which have been observed experimentally, in cuprate and iron-based superconductors alike.

Spin-liquid polymorphism in a correlated electron system on the threshold of superconductivity

PubMed Central

Zaliznyak, Igor; Savici, Andrei T.; Lumsden, Mark; Tsvelik, Alexei; Hu, Rongwei; Petrovic, Cedomir

2015-01-01

We report neutron scattering measurements which reveal spin-liquid polymorphism in an “11” iron chalcogenide superconductor. It occurs when a poorly metallic magnetic state of FeTe is tuned toward superconductivity by substitution of a small amount of tellurium with isoelectronic sulfur. We observe a liquid-like magnetic response, which is described by the coexistence of two disordered magnetic phases with different local structures whose relative abundance depends on temperature. One is the ferromagnetic (FM) plaquette phase observed in undoped, nonsuperconducting FeTe, which preserves the C4 symmetry of the underlying square lattice and is favored at high temperatures, whereas the other is the antiferromagnetic plaquette phase with broken C4 symmetry, which emerges with doping and is predominant at low temperatures. These findings suggest the coexistence of and competition between two distinct liquid states, and a liquid–liquid phase transformation between these states, in the electronic spin system of FeTe1−x(S,Se)x. We have thus discovered the remarkable physics of competing spin-liquid polymorphs in a correlated electron system approaching superconductivity. Our results facilitate an understanding of large swaths of recent experimental data in unconventional superconductors. In particular, the phase with lower C2 local symmetry, whose emergence precedes superconductivity, naturally accounts for a propensity for forming electronic nematic states which have been observed experimentally, in cuprate and iron-based superconductors alike. PMID:26240327

Polymorphism in 2-X-adamantane derivatives (X = Cl, Br).

PubMed

Negrier, Philippe; Barrio, María; Tamarit, Josep Ll; Mondieig, Denise

2014-08-14

The polymorphism of two 2-X-adamantane derivatives, X = Cl, X = Br, has been studied by X-ray powder diffraction and normal- and high-pressure (up to 300 MPa) differential scanning calorimetry. 2-Br-adamantane displays a low-temperature orthorhombic phase (space group P212121, Z = 4) and a high-temperature plastic phase (Fm3̅m, Z = 4) from 277.9 ± 1.0 K to the melting point at 413.4 ± 1.0 K. 2-Cl-adamantane presents a richer polymorphic behavior through the temperature range studied. At low temperature it displays a triclinic phase (P1̅, Z = 2), which transforms to a monoclinic phase (C2/c, Z = 8) at 224.4 ± 1.0 K, both phases being ordered. Two high-temperature orientationally disordered are found for this compound, one hexagonal (P63/mcm, Z = 6) at ca. 241 K and the highest one, cubic (Fm3̅m, Z = 4), being stable from 244 ± 1.0 K up to the melting point at 467.5 ± 1.0 K. No additional phase appears due to the increase in pressure within the studied range. The intermolecular interactions are found to be weak, especially for the 2-Br-adamantane compound for which the Br···Br as well as C-Br···H distances are larger than the addition of the van der Waals radii, thus confirming the availability of this compound for building up diamondoid blocks.

Thermal collapse and hierarchy of polymorphs in a faujasite-type zeolite and its analogous melt-quenched glass

NASA Astrophysics Data System (ADS)

Palenta, Theresia; Fuhrmann, Sindy; Greaves, G. Neville; Schwieger, Wilhelm; Wondraczek, Lothar

2015-02-01

We examine the route of structural collapse and re-crystallization of faujasite-type (Na,K)-LSX zeolite. As the first step, a rather stable amorphous high density phase HDAcollapse is generated through an order-disorder transition from the original zeolite via a low density phase LDAcollapse, at around 790 °C. We find that the overall amorphization is driven by an increase in the bond angle distribution within T-O-T and a change in ring statistics to 6-membered TO4 (T = Si4+, Al3+) rings at the expense of 4-membered rings. The HDAamorph transforms into crystalline nepheline, though, through an intermediate metastable carnegieite phase. In comparison, the melt-derived glass of similar composition, HDAMQ, crystallizes directly into the nepheline phase without the occurrence of intermediate carnegieite. This is attributed to the higher structural order of the faujasite-derived HDAcollapse which prefers the re-crystallization into the highly symmetric carnegieite phase before transformation into nepheline with lower symmetry.

Building solids inside nano-space: from confined amorphous through confined solvate to confined 'metastable' polymorph.

PubMed

Nartowski, K P; Tedder, J; Braun, D E; Fábián, L; Khimyak, Y Z

2015-10-14

The nanocrystallisation of complex molecules inside mesoporous hosts and control over the resulting structure is a significant challenge. To date the largest organic molecule crystallised inside the nano-pores is a known pharmaceutical intermediate - ROY (259.3 g mol(-1)). In this work we demonstrate smart manipulation of the phase of a larger confined pharmaceutical - indomethacin (IMC, 357.8 g mol(-1)), a substance with known conformational flexibility and complex polymorphic behaviour. We show the detailed structural analysis and the control of solid state transformations of encapsulated molecules inside the pores of mesoscopic cellular foam (MCF, pore size ca. 29 nm) and controlled pore glass (CPG, pore size ca. 55 nm). Starting from confined amorphous IMC we drive crystallisation into a confined methanol solvate, which upon vacuum drying leads to the stabilised rare form V of IMC inside the MCF host. In contrast to the pure form, encapsulated form V does not transform into a more stable polymorph upon heating. The size of the constraining pores and the drug concentration within the pores determine whether the amorphous state of the drug is stabilised or it recrystallises into confined nanocrystals. The work presents, in a critical manner, an application of complementary techniques (DSC, PXRD, solid-state NMR, N2 adsorption) to confirm unambiguously the phase transitions under confinement and offers a comprehensive strategy towards the formation and control of nano-crystalline encapsulated organic solids.

Optical phonon characteristics of an orthorhombic-transformed polymorph of CaTa2O6 single crystal fibre

NASA Astrophysics Data System (ADS)

Almeida, R. M.; Andreeta, M. R. B.; Hernandes, A. C.; Dias, A.; Moreira, R. L.

2014-03-01

Infrared-reflectivity spectroscopy and micro-Raman scattering were used to determine the optical phonon features of orthorhombic calcium tantalite (CaTa2O6) single crystal fibres. The fibres, obtained by the Laser-Heated Pedestal Growth method, grew into an ordered cubic structure \\left( Pm\\bar{3} \\right). Long-time annealing was used to induce a polymorphic transformation to an aeschynite orthorhombic structure (Pnma space group). The phase transformation led to the appearance of structural domains and micro-cracks, responsible for diffuse scattering and depolarization of the scattered light in the visible range, but not in the infrared region. Thus, polarized infrared spectroscopy could be performed within oriented single domains, with an appropriate microscope, allowing us to determine all relevant polar phonons of the orthorhombic CaTa2O6. The obtained phononic dielectric response, {{\\epsilon }_{r}} = 22.4 and = 86 × 103 GHz, shows the appropriateness of the material for microwave applications. Totally symmetric Raman modes could be resolved by polarization, after re-polishing the cracked sample surface.

Methylene tetrahydrofolate reductase (MTHFR) gene polymorphisms in chronic myeloid leukemia: an Egyptian study.

PubMed

Khorshied, Mervat Mamdooh; Shaheen, Iman Abdel Mohsen; Abu Khalil, Reham E; Sheir, Rania Elsayed

2014-01-01

Methylenetetrahydrofolate reductase (MTHFR) gene plays a pivotal role in folate metabolism. Several genetic variations in MTHFR gene as MTHFR-C677T and MTHFR-A1298C result in decreased MTHFR activity, which could influence efficient DNA methylation and explain susceptibility to different cancers. The etiology of chronic myeloid leukemia (CML) is obscure and little is known about individual's susceptibility to CML. In order to assess the influence of these genetic polymorphisms on the susceptibility to CML and its effect on the course of the disease among Egyptians, we performed an age-gender-ethnic matched case-control study. The study included 97 CML patients and 130 healthy controls. Genotyping of MTHFR-C677T and -A1298C was performed by polymerase chain reaction-restriction fragment length polymorphism (PCR-RFLP) technique. The results showed no statistical difference in the distribution of MTHFR-C677T and -A1298C polymorphic genotypes between CML patients and controls. The frequency of MTHFR 677-TT homozygous variant was significantly higher in patients with accelerated/blastic transformation phase when compared to those in the chronic phase of the disease. In conclusion, our study revealed that MTHFR-C677T and -A1298C polymorphisms could not be considered as genetic risk factors for CML in Egyptians. However, MTHFR 677-TT homozygous variant might be considered as a molecular predictor for disease progression.

Polymorphism of the hydroxide perovskite Ga(OH)3 and possible proton-driven transformational behaviour

NASA Astrophysics Data System (ADS)

Welch, M. D.; Kleppe, A. K.

2016-07-01

The crystal structure of hydroxide perovskite Ga(OH)3, the mineral söhngeite, has been determined for a natural sample by single-crystal XRD in space group P42/ nmc to R 1 = 0.031, wR 2 = 0.071, GoF = 1.208, and for comparison also in space group P42/ n to R 1 = 0.031, wR 2 = 0.073, GoF = 1.076. Unit cell parameters are a = 7.4546(2) Å, c = 7.3915(2) Å, V = 410.75(2) Å3. The two structures are very similar and both have tilt system a + a + c -. The approximate positions of all H atoms in each structure have been refined. In the P42/ nmc structure all five H sites are half-occupied, whereas in the P42/ n structure four sites are half-occupied and one is fully occupied. The presence of five non-equivalent OH groups in söhngeite is confirmed by single-crystal Raman spectroscopy, but does not allow a choice between these two space groups to be made. There is only a single very weak violator of the c-glide of P42/ nmc and the two refined structures are essentially the same, but are significantly different from that of the original description in which orthorhombic space group Pmn21 was reported with corresponding tilt system a 0 a 0 c +. It is argued here that such a structure is very implausible for a hydroxide perovskite. On heating söhngeite to 423 K, transformation to a cubic structure with Imbar{3} symmetry ( a + a + a +) of the aristotype occurs. This cubic phase was recovered on cooling to 293 K without back-transformation to the tetragonal polymorph. As there is no continuous group/subgroup pathway from P42/ nmc (or P42/ n) to Imbar{3}, the transformation must be first-order, which is consistent with the large hysteresis observed. The change from the tetragonal to cubic structures involves a change in tilt system a + a + c - → a + a + a +, with a significant reconfiguration of hydrogen-bonding topology. The very different tilt systems and hydrogen-bonding configurations of the two polymorphs are responsible for hysteresis and metastable preservation of the cubic phase at 293 K. As the Ga(OH)6 octahedra of the low- and high- T polymorphs are very similar it is inferred that the transformation is driven by proton behaviour, presumably involving proton re-ordering.

High-Pressure γ-CaMgSi2O6: Does Penta-Coordinated Silicon Exist in the Earth's Mantle?

NASA Astrophysics Data System (ADS)

Hu, Yi; Kiefer, Boris; Bina, Craig R.; Zhang, Dongzhou; Dera, Przemeslaw K.

2017-11-01

In situ X-ray diffraction experiments with natural Fe- and Al- bearing diopside single crystals and density functional theory (DFT) calculations on diopside end-member composition indicate the existence of a new high-pressure γ-diopside polymorph with rare penta-coordinated silicon. On compression α-diopside transforms to the γ-phase at ˜50 GPa, which in turn, on decompression is observed to convert to the known β-phase below 47 GPa. The new γ-diopside polymorph constitutes another recent example of penta-coordinated silicon (VSi) in overcompressed metastable crystalline silicates, suggesting that VSi may exist in the transition zone and the uppermost lower mantle in appreciable quantities, not only in silicate glass and melts but also in crystalline phases contained in the coldest parts of subducted stagnant slabs. VSi may have significant influences on buoyancy, wave velocity anomalies, deformation mechanisms, chemical reactivity of silicate rocks, and seismicity within the slab.

The structure, thermal expansion and phase transition properties of Ho{sub 2}Mo{sub 3−x}W{sub x}O{sub 12} (x = 0, 1.0, 2.0) solid solutions

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

Liu, X.Z.; Hao, L.J.; Wu, M.M.

Graphical abstract: A polymorph with Gd{sub 2}Mo{sub 3}O{sub 12}-type structure (space group: Pba2) for negative thermal expansion material Ho{sub 2}Mo{sub 3}O{sub 12} is observed above 700 °C, this polymorphism could be effectively supressed by W-substiution for Mo, the give the temperature dependence of Pba2 phase contents for Ho{sub 2}Mo{sub 3−x}W{sub x}O{sub 12} (x = 0.0, 1.0, 2.0). - Highlights: • The solid solution Ho{sub 2}Mo{sub 3−x}W{sub x}O{sub 12} was investigated by in situ X-ray diffraction. • It is found that the substitution slightly influence thermal expansion property. • A polymorph of Ho{sub 2}Mo{sub 3}O{sub 12} with Pba2 space group wasmore » observed above 700 °C. • The W-substitution for Mo effectively suppresses this transformation. - Abstract: Three solid solutions of Ho{sub 2}Mo{sub 3−x}W{sub x}O{sub 12}(x = 0, 1.0, 2.0) were prepared by solid state reaction method, the temperature dependent in-situ X-ray diffraction and thermal analysis were performed to investigate their structure and thermal expansion. All samples have orthorhombic structure(space group Pbcn# 60) with negative thermal expansion at the room temperature. the substitution of W for Mo enlarges the lattice constant and slightly influences the negative thermal expansion. An irreversible phase transformation to the Pba2 phase(Tb{sub 2}Mo{sub 3}O{sub 12} structure) was observed at high temperature for Mo-rich samples. This ploymorphism could be effectively suppressed by the W-substitution for Mo, this phenomenon could be explained by the lower electronegativity of W{sup 6+} than Mo{sup 6+}.« less

Solvent effects and polymorphic transformation of organic nonlinear optical crystal L-pyroglutamic acid in solution growth processes . I. Solvent effects and growth morphology

NASA Astrophysics Data System (ADS)

Wang, W. S.; Aggarwal, M. D.; Choi, J.; Gebre, T.; Shields, Angela D.; Penn, Benjamin G.; Frazier, Donald O.

1999-03-01

Single crystals of a new promising nonlinear optical material for the tunable UV harmonic generation, L-pyroglutamic acid 60×20×20 mm 3 in size were obtained from aqueous solution by using the temperature-lowering method. Solubility of L-pyroglutamic acid in different solvents was measured. The single crystals showed different morphological characteristics and growth rate in different solvents with different crystallographic orientations. Methanol or ethanol solutions yielded needle-like crystals. In mixed solution such as methanol/H 2O or ethanol/ H 2O plate-like crystals with a thickness in the direction [0 1 0] were observed. The water as a good solvent, however, produced long prism-like crystals. The two polymorphs of L-pyroglutamic acid (α and β phases) were found for the first time. The growth shapes of α-phase is mainly a prism and β phases is a rhombic plate.The growth rate of α and β phases is mainly a function of the supersaturation of the L-pyroglutamic acid in solution.

Comparison of the thermal stability of the α, β and γ phases in poly(vinylidene fluoride) based on in situ thermal Fourier transform infrared spectroscopy

NASA Astrophysics Data System (ADS)

Biswas, Anirban; Henkel, Karsten; Schmeißer, Dieter; Mandal, Dipankar

2017-12-01

The electroactive β phase of poly(vinylidene fluoride) (PVDF) is induced due to the aging time of PVDF solutions. The feasibility of the combination of the three crystalline polymorphs (α, β and γ) is demonstrated where their relative proportion within the PVDF film can be tailored by the simple monitoring of the preparation conditions. To identify all these phases, Fourier transform infrared (FT-IR) spectroscopy is carried out and it is spotlighted that the vibrational bands at 510 and 841 cm-1 are not sufficient to state the formation of the β phase. The main aim of this work is devoted to develop a better understanding on the thermal stability of these several phases of PVDF, which has a longstanding ambiguity persisting in this area. It has been found that the in situ thermal FT-IR spectroscopy is one of the best alternatives to understand this important issue. It is ascertained that the β phase is the least thermally stable phase among α, β and γ phases, whereas the γ phase is the most thermally stable phase.

Spin liquid polymorphism in a correlated electron system on the threshold of superconductivity

DOE PAGES

Zalinznyak, Igor; Savici, Andrei T.; Lumsden, Mark D.; ...

2015-08-18

We report neutron scattering measurements which reveal spin-liquid polymorphism in an “11” iron chalcogenide superconductor. It occurs when a poorly metallic magnetic state of FeTe is tuned toward superconductivity by substitution of a small amount of tellurium with isoelectronic sulfur. We also observe a liquid-like magnetic response, which is described by the coexistence of two disordered magnetic phases with different local structures whose relative abundance depends on temperature. One is the ferromagnetic (FM) plaquette phase observed in undoped, nonsuperconducting FeTe, which preserves the C 4 symmetry of the underlying square lattice and is favored at high temperatures, whereas the othermore » is the antiferromagnetic plaquette phase with broken C 4 symmetry, which emerges with doping and is predominant at low temperatures. These findings suggest the coexistence of and competition between two distinct liquid states, and a liquid–liquid phase transformation between these states, in the electronic spin system of FeTe 1-x(S,Se) x. We have thus discovered the remarkable physics of competing spin-liquid polymorphs in a correlated electron system approaching superconductivity. These results facilitate an understanding of large swaths of recent experimental data in unconventional superconductors. In particular, the phase with lower C 2 local symmetry, whose emergence precedes superconductivity, naturally accounts for a propensity for forming electronic nematic states which have been observed experimentally, in cuprate and iron-based superconductors alike.« less

Shock wave compression of iron-silicate garnet.

NASA Technical Reports Server (NTRS)

Graham, E. K.; Ahrens, T. J.

1973-01-01

Shock wave compression data to over 650 kb are presented for single-crystal almandine garnet. The data indicate the initiation of a phase transformation near 200 kb. Total transition to the high-pressure polymorph occurs at approximately 300 kb. The elastic properties of the high-pressure phase are calculated from the metastable Hugoniot data by using the linear shock velocity-particle velocity relationships. The overall results obtained strongly suggest that upper mantle minerals are likely to occur in the ilmenite structure over a substantial part of the lower mantle.

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

Zhang, Fei; Wu, Yuan; Lou, Hongbo

Polymorphism, which describes the occurrence of different lattice structures in a crystalline material, is a critical phenomenon in materials science and condensed matter physics. Recently, configuration disorder was compositionally engineered into single lattices, leading to the discovery of high-entropy alloys and high-entropy oxides. For these novel entropy-stabilized forms of crystalline matter with extremely high structural stability, is polymorphism still possible? Here by employing in situ high-pressure synchrotron radiation X-ray diffraction, we reveal a polymorphic transition from face-centred-cubic (fcc) structure to hexagonal-close-packing (hcp) structure in the prototype CoCrFeMnNi high-entropy alloy. The transition is irreversible, and our in situ high-temperature synchrotron radiationmore » X-ray diffraction experiments at different pressures of the retained hcp high-entropy alloy reveal that the fcc phase is a stable polymorph at high temperatures, while the hcp structure is more thermodynamically favourable at lower temperatures. Lastly, as pressure is increased, the critical temperature for the hcp-to-fcc transformation also rises.« less

Structural characterization of a new high-pressure phase of GaAsO4.

PubMed

Santamaría-Pérez, David; Haines, Julien; Amador, Ulises; Morán, Emilio; Vegas, Angel

2006-12-01

As in SiO2 which, at high pressures, undergoes the alpha-quartz-->stishovite transition, GaAsO4 transforms into a dirutile structure at 9 GPa and 1173 K. In 2002, a new GaAsO4 polymorph was found by quenching the compound from 6 GPa and 1273 K to ambient conditions. The powder diagram was indexed on the basis of a hexagonal cell (a=8.2033, c=4.3941 A, V=256.08 A3), but the structure did not correspond to any known structure of other AXO4 compounds. We report here the ab initio crystal structure determination of this hexagonal polymorph from powder data. The new phase is isostructural to beta-MnSb2O6 and it can be described as a lacunary derivative of NiAs with half the octahedral sites being vacant, but it also contains fragments of the rutile-like structure.

Reducing the Schottky barrier between few-layer MoTe2 and gold

NASA Astrophysics Data System (ADS)

Qi, Dianyu; Wang, Qixing; Han, Cheng; Jiang, Jizhou; Zheng, Yujie; Chen, Wei; Zhang, Wenjing; Thye Shen Wee, Andrew

2017-12-01

Schottky barriers greatly influence the performance of optoelectronic devices. Schottky barriers can be reduced by harnessing the polymorphism of 2D metal transition dichalcogenides, since both semiconducting and metallic phases exist. However, high energy, high temperature or chemicals are normally required for phase transformation, or the processes are complex. In this work, stable low-resistance contacts between few layer MoTe2 flakes and gold electrodes are achieved by a simple thermal annealing treatment at low temperature (200-400 °C). The resulting Schottky barrier height of the annealed MoTe2/Au interface is low (~23 meV). A new Raman A g mode of the 1T‧ metallic phase of MoTe2 on gold electrode is observed, indicating that the low-resistance contact is due to the phase transition of 2H-MoTe2. The gold substrate plays an important role in the transformation, and a higher gold surface roughness increases the transformation rate. With this method, the mobility and ON-state current of the MoTe2 transistor increase by ~3-4 orders of magnitude, the photocurrent of vertically stacked graphene/MoTe2/Au device increases ~300%, and the response time decreases by ~20%.

Deformation of olivine during phase transformation to wadsleyite

NASA Astrophysics Data System (ADS)

Mohiuddin, A.; Girard, J.; Karato, S. I.

2017-12-01

The strength of subducting slabs in the transition zone is critical in controlling the style of mantle convection. However, rheological properties of a subducted slab are elusive: low temperatures of a slab would make slabs strong, but in many regions there is evidence of intense deformation of slabs in the transition zone. One potential cause of intense deformation of subducting slabs is grain size reduction and accompanied microstructural changes during phase transformation of olivine to its higher-pressure polymorphs. There have been no experimental studies to quantify the influence of grain-size evolution. In addition to grain size reduction, distribution of small grains during phase transformation governs the degree of weakening during phase transformation (for e.g. load bearing framework vs. inter-connected layered framework). We conducted laboratory studies on the size and spatial distribution of new grains of wadsleyite after the transformation from olivine. Our results under static conditions show that an interconnected microstructure develops during the initial stage of phase transformation and that the grain size of the interconnected phase (wadsleyite) depends on the temperature at which the phase transformation occurs (smaller grains at lower temperatures). Development of an interconnected microstructure may lead to strain localization in the weaker phase, i.e. the fine-grained interconnected network accommodates most of the strain and therefore weakening of the entire composite. We will test this model through a series of two synchrotron in-situ deformation experiments: (i) Olivine aggregate will be deformed during slow pressure increase from deep upper mantle pressure ( 10 GPa) to transition zone pressure ( 15 GPa) at a given temperature simulating the deformation of a slab penetrating into the transition zone (ii) olivine is partially transformed to wadsleyite in a multi anvil apparatus at Yale and will be deformed within the stability field where olivine and wadsleyite coexist. We will use the Rotational Drickamer Apparatus (RDA) at a synchrotron facility (Argonne National Lab, 6-BM-B beamline, white beam and x-ray radiography) and characterize the stresses acting on olivine and wadsleyite during such simulations. We plan to present our preliminary results.

Attainment of unstable β nucleation of glycine in presence of L-tyrosine and its analytical interpretation-A combined approach

NASA Astrophysics Data System (ADS)

Renuka Devi, K.; Srinivasan, K.

2015-05-01

The ability of L-tyrosine molecules to act as a template and to facilitate the nucleation of unstable β polymorph in the solution has been revealed through in-situ nucleation study. This nucleation of β occurs along with the existing α nucleation at the critical concentration of additive in the solution. The presence of L-tyrosine molecules lowers the inherent barrier that exists for β nucleation in the solution. No nucleation of γ was observed over the entire range of concentrations studied. The molecular recognition capability and stereo selective inhibitory action of the added L-tyrosine molecules towards glycine molecule have been successfully revealed in terms of habit modification observed in the nucleated polymorphs. In the case of α polymorph, L-tyrosine induces a change in the morphology along the enantiopolar -b direction while in the case of β polymorph, habit modification from needle to plate like structure is observed. With the increase in time span, solution mediated phase transformation from β to α polymorph has been observed in the solution. Analytically the nucleation parameters of α and β polymorphs were estimated based on Classical Nucleation Theory. Form of crystallization of the nucleated polymorphs of glycine was confirmed by a powder x-ray diffraction analysis.

Insights into the phase diagram of bismuth ferrite from quasiharmonic free-energy calculations

NASA Astrophysics Data System (ADS)

Cazorla, Claudio; Iñiguez, Jorge

2013-12-01

We have used first-principles methods to investigate the phase diagram of multiferroic bismuth ferrite (BiFeO3 or BFO), revealing the energetic and vibrational features that control the occurrence of various relevant structures. More precisely, we have studied the relative stability of four low-energy BFO polymorphs by computing their free energies within the quasiharmonic approximation, introducing a practical scheme that allows us to account for the main effects of spin disorder. As expected, we find that the ferroelectric ground state of the material (with R3c space group) transforms into an orthorhombic paraelectric phase (Pnma) upon heating. We show that this transition is not significantly affected by magnetic disorder, and that the occurrence of the Pnma structure relies on its being vibrationally (although not elastically) softer than the R3c phase. We also investigate a representative member of the family of nanotwinned polymorphs recently predicted for BFO [S. Prosandeev et al., Adv. Funct. Mater. 23, 234 (2013), 10.1002/adfm.201201467] and discuss their possible stabilization at the boundaries separating the R3c and Pnma regions in the corresponding pressure-temperature phase diagram. Finally, we elucidate the intriguing case of the so-called supertetragonal phases of BFO: Our results explain why such structures have never been observed in the bulk material, despite their being stable polymorphs of very low energy. Quantitative comparison with experiment is provided whenever possible, and the relative importance of various physical effects (zero-point motion, spin fluctuations, thermal expansion) and technical features (employed exchange-correlation energy density functional) is discussed. Our work attests the validity and usefulness of the quasiharmonic scheme to investigate the phase diagram of this complex oxide, and prospective applications are discussed.

Prevalence and prognostic impact of allelic imbalances associated with leukemic transformation of Philadelphia chromosome–negative myeloproliferative neoplasms

PubMed Central

Krug, Utz O.; Lee, Dhong Hyun Tony; Kawamata, Norihiko; Iwanski, Gabriela B.; Lasho, Terra; Weiss, Tamara; Nowak, Daniel; Koren-Michowitz, Maya; Kato, Motohiro; Sanada, Masashi; Shih, Lee-Yung; Nagler, Arnon; Raynaud, Sophie D.; Müller-Tidow, Carsten; Mesa, Ruben; Haferlach, Torsten; Gilliland, D. Gary; Tefferi, Ayalew; Ogawa, Seishi; Koeffler, H. Phillip

2010-01-01

Philadelphia chromosome–negative myeloproliferative neoplasms (MPNs) including polycythemia vera, essential thrombocythemia, and primary myelofibrosis show an inherent tendency for transformation into leukemia (MPN-blast phase), which is hypothesized to be accompanied by acquisition of additional genomic lesions. We, therefore, examined chromosomal abnormalities by high-resolution single nucleotide polymorphism (SNP) array in 88 MPN patients, as well as 71 cases with MPN-blast phase, and correlated these findings with their clinical parameters. Frequent genomic alterations were found in MPN after leukemic transformation with up to 3-fold more genomic changes per sample compared with samples in chronic phase (P < .001). We identified commonly altered regions involved in disease progression including not only established targets (ETV6, TP53, and RUNX1) but also new candidate genes on 7q, 16q, 19p, and 21q. Moreover, trisomy 8 or amplification of 8q24 (MYC) was almost exclusively detected in JAK2V617F− cases with MPN-blast phase. Remarkably, copy number–neutral loss of heterozygosity (CNN-LOH) on either 7q or 9p including homozygous JAK2V617F was related to decreased survival after leukemic transformation (P = .01 and P = .016, respectively). Our high-density SNP-array analysis of MPN genomes in the chronic compared with leukemic stage identified novel target genes and provided prognostic insights associated with the evolution to leukemia. PMID:20068225

Possible existence of two amorphous phases of d-mannitol related by a first-order transition

NASA Astrophysics Data System (ADS)

Zhu, Men; Wang, Jun-Qiang; Perepezko, John H.; Yu, Lian

2015-06-01

We report that the common polyalcohol d-mannitol may have two amorphous phases related by a first-order transition. Slightly above its glass transition temperature Tg (284 K), the supercooled liquid (SCL) of d-mannitol transforms to a low-energy, apparently amorphous phase with stronger hydrogen bonds. The enthalpy of this so-called Phase X is approximately halfway between those of the known amorphous and crystalline phases, a position low for glass aging and high for crystal polymorphs. Similar to the SCL, Phase X is transparent with broad X-ray diffraction and Raman scattering; upon temperature cycling, it exhibits a glass-transition-like change of heat capacity. On fast heating, Phase X transforms back to the SCL near Tg + 50 K, enabling a determination of their equilibrium temperature. The presence of d-sorbitol as a plasticizer enables observation of a first-order transition from the SCL to Phase X entirely in the liquid state (liquid-liquid transition). The transition from d-mannitol's SCL to Phase X has intriguing similarities with the formation of the glacial phase of triphenyl phosphite (TPP) and the conversion from high-density to low-density amorphous ice, both studied intensely in the context of polyamorphism. All three processes occur near Tg with substantial enthalpy decrease toward the crystalline phases; the processes in water and d-mannitol both strengthen the hydrogen bonds. In contrast to TPP, d-mannitol's Phase X forms more rapidly and can transform back to the SCL. These features make d-mannitol a valuable new model for understanding polyamorphism.

Improved phase stability of formamidinium lead triiodide perovskite by strain relaxation

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

Zheng, Xiaojia; Wu, Congcong; Jha, Shikhar K.

2016-10-18

Though formamidinium lead triiodide (FAPbI 3) possesses a suitable band gap and good thermal stability, the phase transition from the pure black perovskite phase (α-phase) to the undesirable yellow nonperovskite polymorph (δ-phase) at room temperature, especially under humid air, hinders its practical application. Here, we investigate the intrinsic instability mechanism of the α-phase at ambient temperature and demonstrate the existence of an anisotropic strained lattice in the (111) plane that drives phase transformation into the δ-phase. Methylammonium bromide (MABr) alloying (or FAPbI 3-MABr) was found to cause lattice contraction, thereby balancing the lattice strain. This led to dramatic improvement inmore » the stability of α-FAPbI 3. As a result, solar cells fabricated using FAPbI 3-MABr demonstrated significantly enhanced stability under the humid air.« less

Transforming Growth Factor-β1 T869C Gene Polymorphism Is Associated with Acquired Sick Sinus Syndrome via Linking a Higher Serum Protein Level

PubMed Central

Chen, Jan-Yow; Liu, Jiung-Hsiun; Wu, Hong-Dar Isaac; Lin, Kuo-Hung; Chang, Kuan-Cheng; Liou, Ying-Ming

2016-01-01

Background Familial sick sinus syndrome is associated with gene mutations and dysfunction of ion channels. In contrast, degenerative fibrosis of the sinus node tissue plays an important role in the pathogenesis of acquired sick sinus syndrome. There is a close relationship between transforming growth factor-β1 mediated cardiac fibrosis and acquired arrhythmia. It is of interest to examine whether transforming growth factor-β1 is involved in the pathogenesis of acquired sick sinus syndrome. Methods Overall, 110 patients with acquired SSS and 137 age/gender-matched controls were screened for transforming growth factor-β1 and cardiac sodium channel gene polymorphisms using gene sequencing or restriction fragment length polymorphism methods. An enzyme-linked immunosorbent assay was used to determine the serum level of transforming growth factor-β1. Results Two transforming growth factor-β1 gene polymorphisms (C-509T and T+869C) and one cardiac sodium channel gene polymorphism (H588R) have been identified. The C-dominant CC/CT genotype frequency of T869C was significantly higher in acquired sick sinus syndrome patients than in controls (OR 2.09, 95% CI 1.16–3.75, P = 0.01). Consistently, the level of serum transforming growth factor-β1 was also significantly greater in acquired sick sinus syndrome group than in controls (5.3±3.4 ng/ml vs. 3.7±2.4 ng/ml, P = 0.01). In addition, the CC/CT genotypes showed a higher transforming growth factor-β1 serum level than the TT genotype (4.25 ± 2.50 ng/ml vs. 2.71± 1.76 ng/ml, P = 0.028) in controls. Conclusion Transforming growth factor-β1 T869C polymorphism, correlated with high serum transforming growth factor-β1 levels, is associated with susceptibility to acquired sick sinus syndrome. PMID:27380173

In Vitro versus In Vivo Phase Instability of Zirconia-Toughened Alumina Femoral Heads: A Critical Comparative Assessment

PubMed Central

Pezzotti, Giuseppe; Affatato, Saverio; Rondinella, Alfredo; Yorifuji, Makiko; Marin, Elia; Zhu, Wenliang; McEntire, Bryan; Bal, Sonny B.; Yamamoto, Kengo

2017-01-01

A clear discrepancy between predicted in vitro and actual in vivo surface phase stability of BIOLOX®delta zirconia-toughened alumina (ZTA) femoral heads has been demonstrated by several independent research groups. Data from retrievals challenge the validity of the standard method currently utilized in evaluating surface stability and raise a series of important questions: (1) Why do in vitro hydrothermal aging treatments conspicuously fail to model actual results from the in vivo environment? (2) What is the preponderant microscopic phenomenon triggering the accelerated transformation in vivo? (3) Ultimately, what revisions of the current in vitro standard are needed in order to obtain consistent predictions of ZTA transformation kinetics in vivo? Reported in this paper is a new in toto method for visualizing the surface stability of femoral heads. It is based on CAD-assisted Raman spectroscopy to quantitatively assess the phase transformation observed in ZTA retrievals. Using a series of independent analytical probes, an evaluation of the microscopic mechanisms responsible for the polymorphic transformation is also provided. An outline is given of the possible ways in which the current hydrothermal simulation standard for artificial joints can be improved in an attempt to reduce the gap between in vitro simulation and reality. PMID:28772828

Understanding strain-induced phase transformations in BiFeO 3 thin films

DOE PAGES

Dixit, Hemant; Beekman, Christianne; Schlepütz, Christian M.; ...

2015-05-01

Bismuth ferrite (BiFeO 3) is a promising lead free multiferroic with large polarization, ferroelectricity and robust antiferomagnetism. Experiments demonstrate that epitaxial strain substantially enhance the piezoelectric response of BiFeO 3 thin films. Here, through a synergestic combination of theory and experiments, we characterize the co-existing polymorphs (specifically an intermediate S' phase between the bulk rhombohedral-R and the pseudotetragonal T' phases) observed in strained BiFeO 3 thin films. We show that the S' phase, although energetically very close to the T' phase, exhibits structural similarities with the bulk R phase. G-type antiferromagnetic ordering is predicted for the S' and R phases,more » whereas, the G/C-type antiferromagnetic order types are energetically indistinguishable for the T' phase. Furthermore, we predict a blue-shift in the band gap Eg when moving from R to S' to T', which we confirm by Electron Energy Loss Spectroscopy measurements. The flat energy landscape and the absence of an energy barrier between the T and S' phases indicate that a reversible phase transformation between the two is possible under the application of an external electric field. This may make it possible to strain engineer the electromechanical response or, utilizing the corresponding changes in Eg, create unique photonic structures.« less

Coordination polymer flexibility leads to polymorphism and enables a crystalline solid-vapour reaction: a multi-technique mechanistic study.

PubMed

Vitórica-Yrezábal, Iñigo J; Libri, Stefano; Loader, Jason R; Mínguez Espallargas, Guillermo; Hippler, Michael; Fletcher, Ashleigh J; Thompson, Stephen P; Warren, John E; Musumeci, Daniele; Ward, Michael D; Brammer, Lee

2015-06-08

Despite an absence of conventional porosity, the 1D coordination polymer [Ag4 (O2 C(CF2 )2 CF3 )4 (TMP)3 ] (1; TMP=tetramethylpyrazine) can absorb small alcohols from the vapour phase, which insert into AgO bonds to yield coordination polymers [Ag4 (O2 C(CF2 )2 CF3 )4 (TMP)3 (ROH)2 ] (1-ROH; R=Me, Et, iPr). The reactions are reversible single-crystal-to-single-crystal transformations. Vapour-solid equilibria have been examined by gas-phase IR spectroscopy (K=5.68(9)×10(-5) (MeOH), 9.5(3)×10(-6) (EtOH), 6.14(5)×10(-5) (iPrOH) at 295 K, 1 bar). Thermal analyses (TGA, DSC) have enabled quantitative comparison of two-step reactions 1-ROH→1→2, in which 2 is the 2D coordination polymer [Ag4 (O2 C(CF2 )2 CF3 )4 (TMP)2 ] formed by loss of TMP ligands exclusively from singly-bridging sites. Four polymorphic forms of 1 (1-A(LT) , 1-A(HT) , 1-B(LT) and 1-B(HT) ; HT=high temperature, LT=low temperature) have been identified crystallographically. In situ powder X-ray diffraction (PXRD) studies of the 1-ROH→1→2 transformations indicate the role of the HT polymorphs in these reactions. The structural relationship between polymorphs, involving changes in conformation of perfluoroalkyl chains and a change in orientation of entire polymers (A versus B forms), suggests a mechanism for the observed reactions and a pathway for guest transport within the fluorous layers. Consistent with this pathway, optical microscopy and AFM studies on single crystals of 1-MeOH/1-A(HT) show that cracks parallel to the layers of interdigitated perfluoroalkyl chains develop during the MeOH release/uptake process. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Transformation and crystallization energetics of synthetic and biogenic amorphous calcium carbonate.

PubMed

Radha, A V; Forbes, Tori Z; Killian, Christopher E; Gilbert, P U P A; Navrotsky, Alexandra

2010-09-21

Amorphous calcium carbonate (ACC) is a metastable phase often observed during low temperature inorganic synthesis and biomineralization. ACC transforms with aging or heating into a less hydrated form, and with time crystallizes to calcite or aragonite. The energetics of transformation and crystallization of synthetic and biogenic (extracted from California purple sea urchin larval spicules, Strongylocentrotus purpuratus) ACC were studied using isothermal acid solution calorimetry and differential scanning calorimetry. Transformation and crystallization of ACC can follow an energetically downhill sequence: more metastable hydrated ACC → less metastable hydrated ACC ⇒ anhydrous ACC ∼ biogenic anhydrous ACC ⇒ vaterite → aragonite → calcite. In a given reaction sequence, not all these phases need to occur. The transformations involve a series of ordering, dehydration, and crystallization processes, each lowering the enthalpy (and free energy) of the system, with crystallization of the dehydrated amorphous material lowering the enthalpy the most. ACC is much more metastable with respect to calcite than the crystalline polymorphs vaterite or aragonite. The anhydrous ACC is less metastable than the hydrated, implying that the structural reorganization during dehydration is exothermic and irreversible. Dehydrated synthetic and anhydrous biogenic ACC are similar in enthalpy. The transformation sequence observed in biomineralization could be mainly energetically driven; the first phase deposited is hydrated ACC, which then converts to anhydrous ACC, and finally crystallizes to calcite. The initial formation of ACC may be a first step in the precipitation of calcite under a wide variety of conditions, including geological CO(2) sequestration.

Thermal vibrations and polymorphic β → γ transition in cerium

NASA Astrophysics Data System (ADS)

Agafonov, S. S.; Blanter, M. S.; Glazkov, V. P.; Somenkov, V. A.; Shushunov, M. N.

2010-10-01

Method of neutron diffraction was used to determine the temperature dependence of the Debye-Waller factor and the related thermal atomic displacements for two polymorphic modifications of cerium, namely, for β-Ce with a double hexagonal closed-packed (dhcp) structure and for γ-Ce with a face-centered cubic (fcc) structure. It has been shown that the phase transition does not lead to substantial changes in the root-mean-square thermal atomic displacements and that the Debye temperatures of the two modifications are close: 131 K for β-Ce and 127 K for γ-Ce. However, the relative (with respect to the lattice parameters) displacements along the axes change considerably. The transition from the anisotropic hexagonal to the isotropic cubic modification leads, because of a redistribution of thermal atomic displacements along the crystallographic axes, to a decrease in the maximum values of these quantities and to a weakening of their temperature dependence. It has also been shown that a change in the thermal atomic vibrations and in the vibrational contribution to the entropy of the polymorphic transformations is connected with the sign of the volume effect of the transformation (stronger upon a positive effect and weaker, upon a negative one). The reasons for this behavior are discussed.

Monotropic polymorphism in a glass-forming metallic alloy

NASA Astrophysics Data System (ADS)

Pogatscher, S.; Leutenegger, D.; Schawe, J. E. K.; Maris, P.; Schäublin, R.; Uggowitzer, P. J.; Löffler, J. F.

2018-06-01

This study investigates the crystallization and phase transition behavior of the amorphous metallic alloy Au70Cu5.5Ag7.5Si17. This alloy has been recently shown to exhibit a transition of a metastable to a more stable crystalline state, occurring via metastable melting under strong non-equilibrium conditions. Such behavior had so far not been observed in other metallic alloys. In this investigation fast differential scanning calorimetry (FDSC) is used to explore crystallization and the solid–liquid–solid transition upon linear heating and during isothermal annealing, as a function of the conditions under which the metastable phase is formed. It is shown that the occurrence of the solid–liquid–solid transformation in FDSC depends on the initial conditions; this is explained by a history-dependent nucleation of the stable crystalline phase. The microstructure was investigated by scanning and transmission electron microscopy and x-ray diffraction. Chemical mapping was performed by energy dispersive x-ray spectrometry. The relationship between the microstructure and the phase transitions observed in FSDC is discussed with respect to the possible kinetic paths of the solid–liquid–solid transition, which is a typical phenomenon in monotropic polymorphism.

Crystallization and transformation of polymorphic forms of trioleoyl glycerol and 1,2-dioleoyl-3-rac-linoleoyl glycerol.

PubMed

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

2013-08-08

This study examined the influence of different thermal treatments on the crystallization and transformation of trioleoyl glycerol (OOO) and 1,2-dioleoyl-3-rac-linoleoyl glycerol (OOL). Two triacylglycerol (TAG) samples were cooled at 0.5-15 °C·min(-1) and heated at 2 and 15 °C·min(-1). The polymorphic characteristics of the two TAGs were analyzed in situ using differential scanning calorimetry, Raman spectroscopy, and synchrotron radiation X-ray diffraction. Multiple polymorphic forms were identified in OOO (α, β'2, β'1, β2, and β1) and OOL (α, β'2, and β'1). Larger quantities of more stable forms (e.g., β2 and β1 of OOO and β'1 of OOL) were obtained when the samples were slowly cooled and heated. In contrast, less stable polymorphs were obtained with increased cooling and heating rates. Polymorphic transformations occurred in either solid-state or melt-mediation and were influenced by heating rates. The results were analyzed by considering the activation energies for crystallization and transformation of stable and less stable polymorphic forms in comparison with previous studies on 1,3-dipalmitoyl-2-oleoyl-glycerol and 1, 3-dioleoyl-2-palmitoyl-glycerol.

Structure-property relationship of supramolecular ferroelectric [H-66dmbp][Hca] accompanied by high polarization, competing structural phases, and polymorphs.

PubMed

Kobayashi, Kensuke; Horiuchi, Sachio; Ishibashi, Shoji; Kagawa, Fumitaka; Murakami, Youichi; Kumai, Reiji

2014-12-22

Three polymorphic forms of 6,6'-dimethyl-2,2'-bipyridinium chloranilate crystals were characterized to understand the origin of polarization properties and the thermal stability of ferroelectricity. According to the temperature-dependent permittivity, differential scanning calorimetry, and X-ray diffraction, structural phase transitions were found in all polymorphs. Notably, the ferroelectric α-form crystal, which has the longest hydrogen bond (2.95 Å) among the organic acid/base-type supramolecular ferroelectrics, transformed from a polar structure (space group, P21) into an anti-polar structure (space group, P21/c) at 378 K. The non-ferroelectric β- and γ-form crystals also exhibited structural rearrangements around hydrogen bonds. The hydrogen-bonded geometry and ferroelectric properties were compared with other supramolecular ferroelectrics. A positive relationship between the phase-transition temperature (TC ) and hydrogen-bond length () was observed, and was attributed to the potential barrier height for proton off-centering or order/disorder phenomena. The optimized spontaneous polarization (Ps ) agreed well with the results of the first-principles calculations, and could be amplified by separating the two equilibrium positions of protons with increasing . These data consistently demonstrated that stretching is a promising way to enhance the polarization performance and thermal stability of hydrogen-bonded organic ferroelectrics. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An Investigation into the Polymorphism and Crystallization of Levetiracetam and the Stability of its Solid Form.

PubMed

Xu, Kailin; Xiong, Xinnuo; Guo, Liuqi; Wang, Lili; Li, Shanshan; Tang, Peixiao; Yan, Jin; Wu, Di; Li, Hui

2015-12-01

Levetiracetam (LEV) crystals were prepared using different solvents at different temperatures. The LEV crystals were systematically characterized by X-ray powder diffraction (XRPD) and morphological analysis. The results indicated that many kinds of crystal habits exist in a solid form of LEV. To investigate the effects of LEV concentration, crystallization temperature, and crystallization type on crystallization and solid phase transformation of LEV, multiple methods were performed for LEV aqueous solution to determine if a new solid form exists in solid-state LEV. However, XRPD data demonstrate that the LEV solid forms possess same spatial arrangements that are similar to the original solid form. This result indicates that the LEV concentration, crystallization temperature, and crystallization type in aqueous solution have no influence on the crystallization and solid phase transformation of LEV. Moreover, crystallization by sublimation, melt cooling, and quench cooling, as well as mechanical effect, did not result in the formation of new LEV solid state. During melt cooling, the transformation of solid form LEV is a direct process from melting amorphous phase to the original LEV crystal phase, and the conversion rate is very quick. In addition, stability investigation manifested that LEV solid state is very stable under various conditions. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

Pressure-induced structural change in liquid GaIn eutectic alloy.

PubMed

Yu, Q; Ahmad, A S; Ståhl, K; Wang, X D; Su, Y; Glazyrin, K; Liermann, H P; Franz, H; Cao, Q P; Zhang, D X; Jiang, J Z

2017-04-25

Synchrotron x-ray diffraction reveals a pressure induced crystallization at about 3.4 GPa and a polymorphic transition near 10.3 GPa when compressed a liquid GaIn eutectic alloy up to ~13 GPa at room temperature in a diamond anvil cell. Upon decompression, the high pressure crystalline phase remains almost unchanged until it transforms to the liquid state at around 2.3 GPa. The ab initio molecular dynamics calculations can reproduce the low pressure crystallization and give some hints on the understanding of the transition between the liquid and the crystalline phase on the atomic level. The calculated pair correlation function g(r) shows a non-uniform contraction reflected by the different compressibility between the short (1st shell) and the intermediate (2nd to 4th shells). It is concluded that the pressure-induced liquid-crystalline phase transformation likely arises from the changes in local atomic packing of the nearest neighbors as well as electronic structures at the transition pressure.

Investigation of partitionless growth of ɛ-Al60Sm11 phase in Al-10 at% Sm liquid

NASA Astrophysics Data System (ADS)

Sun, Yang; Ye, Zhuo; Zhang, Feng; Ding, Ze Jun; Wang, Cai-Zhuang; Kramer, Matthew J.; Ho, Kai-Ming

2018-01-01

Recent experiments on devitrification of Al90Sm10 amorphous alloys revealed an unusual polymorphic transformation to a complex cubic crystal structure called the ɛ-Al60Sm11 phase. Molecular dynamics simulations of the growth of the stoichiometric ɛ-phase seed in contact with an undercooled Al-10 at% Sm liquid are performed to elucidate the microscopic process of transformation. The as-grown crystal and undercooled liquid possess similar local order around Al atoms whereas a rigid network defined by the Sm sub-lattice develops during the growth. Using a template-cluster alignment method, we define an order parameter to characterize the structural evolution in the system. Estimates of the attachment rate is {R}{{a}}=8.70× {10}-4 Å-2 ns-1 and detachment rate is {R}{{d}}=3.83× {10}-4 Å-2 ns-1 at the interface between ɛ-Al60Sm11 and Al-10 at% Sm liquid at 800 K.

Nucleation and phase transformation pathways in electrolyte solutions investigated by in situ microscopy techniques

DOE PAGES

Tao, Jinhui; Nielsen, Michael H.; De Yoreo, James J.

2018-04-27

Identification of crystal nucleation and growth pathways is of fundamental importance for synthesis of functional materials, which requires control over size, orientation, polymorph, and hierarchical structure, often in the presence of additives used to tune the energy landscape defining these pathways. Furthermore we summarize the recent progress in application of in situ TEM and AFM techniques to monitor or even tune the pathway of crystal nucleation and growth.

Nucleation and phase transformation pathways in electrolyte solutions investigated by in situ microscopy techniques

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

Tao, Jinhui; Nielsen, Michael H.; De Yoreo, James J.

Identification of crystal nucleation and growth pathways is of fundamental importance for synthesis of functional materials, which requires control over size, orientation, polymorph, and hierarchical structure, often in the presence of additives used to tune the energy landscape defining these pathways. Furthermore we summarize the recent progress in application of in situ TEM and AFM techniques to monitor or even tune the pathway of crystal nucleation and growth.

Polymorphisms of genes involved in polycyclic aromatic hydrocarbons’ biotransformation and atherosclerosis

PubMed Central

Marinković, Natalija; Pašalić, Daria; Potočki, Slavica

2013-01-01

Polycyclic aromatic hydrocarbons (PAHs) are among the most prevalent environmental pollutants and result from the incomplete combustion of hydrocarbons (coal and gasoline, fossil fuel combustion, byproducts of industrial processing, natural emission, cigarette smoking, etc.). The first phase of xenobiotic biotransformation in the PAH metabolism includes activities of cytochrome P450 from the CYP1 family and microsomal epoxide hydrolase. The products of this biotransformation are reactive oxygen species that are transformed in the second phase through the formation of conjugates with glutathione, glucuronate or sulphates. PAH exposure may lead to PAH-DNA adduct formation or induce an inflammatory atherosclerotic plaque phenotype. Several genetic polymorphisms of genes encoded for enzymes involved in PAH biotransformation have been proven to lead to the development of diseases. Enzyme CYP P450 1A1, which is encoded by the CYP1A1 gene, is vital in the monooxygenation of lipofilic substrates, while GSTM1 and GSTT1 are the most abundant isophorms that conjugate and neutralize oxygen products. Some single nucleotide polymorphisms of the CYP1A1 gene as well as the deletion polymorphisms of GSTT1 and GSTM1 may alter the final specific cellular inflammatory respond. Occupational exposure or conditions from the living environment can contribute to the production of PAH metabolites with adverse effects on human health. The aim of this study was to obtain data on biotransformation and atherosclerosis, as well as data on the gene polymorphisms involved in biotransformation, in order to better study gene expression and further elucidate the interaction between genes and the environment. PMID:24266295

Buckling failure of square ice-nanotube arrays constrained in graphene nanocapillaries.

PubMed

Zhu, YinBo; Wang, FengChao; Wu, HengAn

2016-08-07

Graphene confinement provides a new physical and mechanical environment with ultrahigh van der Waals pressure, resulting in new quasi-two-dimensional phases of few-layer ice. Polymorphic transition can occur in bilayer constrained water/ice system. Here, we perform a comprehensive study of the phase transition of AA-stacked bilayer water constrained within a graphene nanocapillary. The compression-limit and superheating-limit (phase) diagrams are obtained, based on the extensive molecular-dynamics simulations at numerous thermodynamic states. Liquid-to-solid, solid-to-solid, and solid-to-liquid-to-solid phase transitions are observed in the compression and superheating of bilayer water. Interestingly, there is a temperature threshold (∼275 K) in the compression-limit diagram, which indicates that the first-order and continuous-like phase transitions of bilayer water depend on the temperature. Two obviously different physical processes, compression and superheating, display similar structural evolution; that is, square ice-nanotube arrays (BL-VHDI) will bend first and then transform into bilayer triangular AA stacking ice (BL-AAI). The superheating limit of BL-VHDI exhibits local maxima, while that of BL-AAI increases monotonically. More importantly, from a mechanics point of view, we propose a novel mechanism of the transformation from BL-VHDI to BL-AAI, both for the compression and superheating limits. This structural transformation can be regarded as the "buckling failure" of the square-ice-nanotube columns, which is dominated by the lateral pressure.

Possible existence of two amorphous phases of D-mannitol related by a first-order transition

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

Zhu, Men; Yu, Lian, E-mail: lian.yu@wisc.edu; Wang, Jun-Qiang

2015-06-28

We report that the common polyalcohol D-mannitol may have two amorphous phases related by a first-order transition. Slightly above its glass transition temperature T{sub g} (284 K), the supercooled liquid (SCL) of D-mannitol transforms to a low-energy, apparently amorphous phase with stronger hydrogen bonds. The enthalpy of this so-called Phase X is approximately halfway between those of the known amorphous and crystalline phases, a position low for glass aging and high for crystal polymorphs. Similar to the SCL, Phase X is transparent with broad X-ray diffraction and Raman scattering; upon temperature cycling, it exhibits a glass-transition-like change of heat capacity.more » On fast heating, Phase X transforms back to the SCL near T{sub g} + 50 K, enabling a determination of their equilibrium temperature. The presence of D-sorbitol as a plasticizer enables observation of a first-order transition from the SCL to Phase X entirely in the liquid state (liquid-liquid transition). The transition from D-mannitol’s SCL to Phase X has intriguing similarities with the formation of the glacial phase of triphenyl phosphite (TPP) and the conversion from high-density to low-density amorphous ice, both studied intensely in the context of polyamorphism. All three processes occur near T{sub g} with substantial enthalpy decrease toward the crystalline phases; the processes in water and D-mannitol both strengthen the hydrogen bonds. In contrast to TPP, D-mannitol’s Phase X forms more rapidly and can transform back to the SCL. These features make D-mannitol a valuable new model for understanding polyamorphism.« less

Natural occurrence and synthesis of two new postspinel polymorphs of chromite.

PubMed

Chen, Ming; Shu, Jinfu; Mao, Ho-kwang; Xie, Xiande; Hemley, Russell J

2003-12-09

A high-pressure polymorph of chromite, the first natural sample with the calcium ferrite structure, has been discovered in the shock veins of the Suizhou meteorite. Synchrotron x-ray diffraction analyses reveal an orthorhombic CaFe2O4-type (CF) structure. The unit-cell parameters are a = 8.954(7) A, b = 2.986(2) A, c = 9.891(7) A, V = 264.5(4) A3 (Z = 4) with space group Pnma. The new phase has a density of 5.62 g/cm3, which is 9.4% denser than chromite-spinel. We performed laser-heated diamond anvil cell experiments to establish that chromite-spinel transforms to CF at 12.5 GPa and then to the recently discovered CaTi2O4-type (CT) structure above 20 GPa. With the ubiquitous presence of chromite, the CF and CT phases may be among the important index minerals for natural transition sequence and pressure and temperature conditions in mantle rocks, shock-metamorphosed terrestrial rocks, and meteorites.

Stability limits and transformation pathways of α-quartz under high pressure

NASA Astrophysics Data System (ADS)

Hu, Q. Y.; Shu, J.-F.; Yang, W. G.; Park, C.; Chen, M. W.; Fujita, T.; Mao, H.-K.; Sheng, H. W.

2017-03-01

Ubiquitous on Earth, α-quartz plays an important role in modern science and technology. However, despite extensive research in the past, the mechanism of the polymorphic transitions of α-quartz at high pressures remains poorly understood. Here, combining in situ single-crystal x-ray diffraction experiment and advanced ab initio modeling, we report two stability limits and competing transition pathways of α-quartz under high pressure. Under near-equilibrium compression conditions at room temperature, α-quartz transits to a new P 2 /c silica phase via a structural intermediate. If the thermally activated transition is kinetically suppressed, the ultimate stability of α-quartz is controlled by its phonon instability and α-quartz collapses into a different crystalline phase. Our studies reveal that pressure-induced solid-state transformation of α-quartz undergoes a succession of structural stability limits, due to thermodynamic and mechanical catastrophes, and exhibits a hierarchy of transition pathways contingent upon kinetic conditions.

A 2 TiO 5 (A = Dy, Gd, Er, Yb) at High Pressure

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

Park, Sulgiye; Rittman, Dylan R.; Tracy, Cameron L.

The structural evolution of lanthanide A2TiO5 (A = Dy, Gd, Yb, and Er) at high pressure is investigated using synchrotron X-ray diffraction. The effects of A-site cation size and of the initial structure are systematically examined by varying the composition of the isostructural lanthanide titanates, and the structure of dysprosium titanate polymorphs (orthorhombic, hexagonal and cubic), respectively. All samples undergo irreversible high pressure phase transformations, but with different onset pressures depending on the initial structure. While individual phase exhibits different phase transformation histories, all samples commonly experience a sluggish transformation to a defect cotunnite-like (Pnma) phase for a certain pressuremore » range. Orthorhombic Dy2TiO5 and Gd2TiO5 form P21am at pressures below 9 GPa and Pnma above 13 GPa. Pyrochlore-type Dy2TiO5 and Er2TiO5 as well as defect-fluorite-type Yb2TiO5 form Pnma at ~ 21 GPa, followed by Im-3m. Hexagonal Dy2TiO5 forms Pnma directly, although a small amount of remnants of hexagonal Dy2TiO5 is observed even at the highest pressure (~ 55 GPa) reached, indicating a kinetic limitations in the hexagonal Dy2TiO5 phase transformations at high pressure. Decompression of these materials leads to different metastable phases. Most interestingly, a high pressure cubic X-type phase (Im-3m) is confirmed using highresolution transmission electron microscopy on recovered pyrochlore-type Er2TiO5. The kinetic constraints on this metastable phase yield a mixture of both the X-type phase and amorphous domains upon pressure release. This is the first observation of an X-type phase for an A2BO5 composition at high pressure.« less

MDM2 promoter polymorphism and p53 codon 72 polymorphism in chronic myeloid leukemia: the association between MDM2 promoter genotype and disease susceptibility, age of onset, and blast-free survival in chronic phase patients receiving imatinib.

PubMed

Liu, Yi-Chang; Hsiao, Hui-Hua; Yang, Wen-Chi; Liu, Ta-Chih; Chang, Chao-Sung; Yang, Ming-Yu; Lin, Pai-Mei; Hsu, Jui-Feng; Lee, Ching-Ping; Lin, Sheng-Fung

2014-12-01

The genetic or functional inactivation of the p53 pathway plays an important role with regards to disease progression from the chronic phase (CP) to blast phase (BP) and imatinib treatment response in chronic myeloid leukemia (CML). Two functional single nucleotide polymorphisms (SNPs), p53 R72P and MDM2 SNP309, are associated with alternation of p53 activity, however the association regarding CML susceptibility and BP transformation under imatinib treatment is unclear. The MDM2 SNP309 genotype was determined by polymerase chain reaction-restriction fragment length polymorphism and confirmed by direct sequencing from 116 CML patients, including 104 in the CP at diagnosis, and 162 healthy Taiwanese controls. The p53 R72P polymorphism was examined in all CML patients. The SNP309 G/G genotype was associated with an increased risk of CML susceptibility (OR: 1.82, 95% CI: 1.03-3.22, P = 0.037), and an earlier age of disease onset (log-rank P = 0.005) compared with the T/T + T/G genotypes. Higher MDM2 mRNA expression was found in G/G genotype compared with T/T (P = 0.034) and T/T + T/G (P = 0.056) genotypes. No associations were found between the p53 R72P genotypes and clinical parameters and survival outcomes. Among 62 CP patients receiving imatinib as first-line therapy, the G/G genotype was associated with a shorter blast-free survival (log-rank P = 0.048) and more clonal evolution compared with the T/T + T/G genotypes. In patients with advanced diseases at diagnosis, the G/G genotype was associated with a poor overall survival (log-rank P = 0.006). Closely monitoring CML patients harboring the G/G genotype and further large-scale studies are warranted. © 2013 Wiley Periodicals, Inc.

Transformation and crystallization energetics of synthetic and biogenic amorphous calcium carbonate

PubMed Central

Radha, A. V.; Forbes, Tori Z.; Killian, Christopher E.; Gilbert, P. U. P. A.; Navrotsky, Alexandra

2010-01-01

Amorphous calcium carbonate (ACC) is a metastable phase often observed during low temperature inorganic synthesis and biomineralization. ACC transforms with aging or heating into a less hydrated form, and with time crystallizes to calcite or aragonite. The energetics of transformation and crystallization of synthetic and biogenic (extracted from California purple sea urchin larval spicules, Strongylocentrotus purpuratus) ACC were studied using isothermal acid solution calorimetry and differential scanning calorimetry. Transformation and crystallization of ACC can follow an energetically downhill sequence: more metastable hydrated ACC → less metastable hydrated ACC⇒anhydrous ACC ∼ biogenic anhydrous ACC⇒vaterite → aragonite → calcite. In a given reaction sequence, not all these phases need to occur. The transformations involve a series of ordering, dehydration, and crystallization processes, each lowering the enthalpy (and free energy) of the system, with crystallization of the dehydrated amorphous material lowering the enthalpy the most. ACC is much more metastable with respect to calcite than the crystalline polymorphs vaterite or aragonite. The anhydrous ACC is less metastable than the hydrated, implying that the structural reorganization during dehydration is exothermic and irreversible. Dehydrated synthetic and anhydrous biogenic ACC are similar in enthalpy. The transformation sequence observed in biomineralization could be mainly energetically driven; the first phase deposited is hydrated ACC, which then converts to anhydrous ACC, and finally crystallizes to calcite. The initial formation of ACC may be a first step in the precipitation of calcite under a wide variety of conditions, including geological CO2 sequestration. PMID:20810918

Kinetic control in the synthesis of metastable polymorphs: Bixbyite-to-Rh{sub 2}O{sub 3}(II)-to-corundum transition in In{sub 2}O{sub 3}

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

Bekheet, Maged F., E-mail: maged.bekheet@ceramics.tu-berlin.de; Fachgebiet Keramische Werkstoffe, Institut für Werkstoffwissenschaften und -technologien, Technische Universität Berlin, Hardenbergstraße 40, 10623 Berlin; Schwarz, Marcus R.

2015-09-15

An example for kinetic control of a solid-state phase transformation, in which the system evolves via the path with the lowest activation barrier rather than ending in the thermodynamically most favorable state, has been demonstrated. As a case study, the phase transitions of indium sesquioxide (In{sub 2}O{sub 3}) have been guided by theoretical calculations and followed in situ under high-pressure high-temperature conditions in multi-anvil assemblies. The corundum-type rh-In{sub 2}O{sub 3} has been synthesized from stable bixbyite-type c-In{sub 2}O{sub 3} in two steps: first generating orthorhombic Rh{sub 2}O{sub 3}-II-type o′-In{sub 2}O{sub 3} which is thermodynamically stable at 8.5 GPa/850 °C and,more » thereafter, exploiting the preferred kinetics in the subsequent transformation to the rh-In{sub 2}O{sub 3} during decompression. This synthesis strategy of rh-In{sub 2}O{sub 3} was confirmed ex situ in a toroid-type high-pressure apparatus at 8 GPa and 1100 °C. The pressure–temperature phase diagrams have been constructed and the stability fields of In{sub 2}O{sub 3} polymorphs and the crystallographic relationship between them have been discussed. - Graphical abstract: In situ energy-dispersive XRD patterns in multi-anvil assemblies show the sequence of phase transition c-In{sub 2}O{sub 3}→o′-In{sub 2}O{sub 3}→rh-In{sub 2}O{sub 3} under particular pressure and temperature conditions. The tick marks refer to the calculated Bragg positions of bixbyite-type (c-In{sub 2}O{sub 3}), Rh{sub 2}O{sub 3}-II-type (o–-In2O{sub 3}) and corundum-type (rh-In{sub 2}O{sub 3}). - Highlights: • The solid-state synthesis methods can be employed for obtaining metastable phases. • The phase transition of In{sub 2}O{sub 3} was guided by DFT calculations. • The phase transition of In{sub 2}O{sub 3} was followed in situ under HP–HT conditions. • Orthorhombic o′-In{sub 2}O{sub 3} polymorph was synthesized from c-In{sub 2}O{sub 3} at 8.5 GPa/850 °C. • Metastable rh-In{sub 2}O{sub 3} was obtained from o′-In{sub 2}O{sub 3} at 5.5 GPa during decompression.« less

Surface-functionalized cockle shell–based calcium carbonate aragonite polymorph as a drug nanocarrier

PubMed Central

Mohd Abd Ghafar, Syairah Liyana; Hussein, Mohd Zobir; Rukayadi, Yaya; Abu Bakar Zakaria, Md Zuki

2017-01-01

Calcium carbonate aragonite polymorph nanoparticles derived from cockle shells were prepared using surface functionalization method followed by purification steps. Size, morphology, and surface properties of the nanoparticles were characterized using transmission electron microscopy, field emission scanning electron microscopy, dynamic light scattering, zetasizer, X-ray powder diffraction, and Fourier transform infrared spectrometry techniques. The potential of surface-functionalized calcium carbonate aragonite polymorph nanoparticle as a drug-delivery agent were assessed through in vitro drug-loading test and drug-release test. Transmission electron microscopy, field emission scanning electron microscopy, and particle size distribution analyses revealed that size, morphology, and surface characterization had been improved after surface functionalization process. Zeta potential of the nanoparticles was found to be increased, thereby demonstrating better dispersion among the nanoparticles. Purification techniques showed a further improvement in the overall distribution of nanoparticles toward more refined size ranges <100 nm, which specifically favored drug-delivery applications. The purity of the aragonite phase and their chemical analyses were verified by X-ray powder diffraction and Fourier transform infrared spectrometry studies. In vitro biological response of hFOB 1.19 osteoblast cells showed that surface functionalization could improve the cytotoxicity of cockle shell–based calcium carbonate aragonite nanocarrier. The sample was also sensitive to pH changes and demonstrated good abilities to load and sustain in vitro drug. This study thus indicates that calcium carbonate aragonite polymorph nanoparticles derived from cockle shells, a natural biomaterial, with modified surface characteristics are promising and can be applied as efficient carriers for drug delivery. PMID:28572724

Solid-state NMR and IR for the analysis of pharmaceutical solids: polymorphs of fosinopril sodium.

PubMed

Brittain, H G; Morris, K R; Bugay, D E; Thakur, A B; Serajuddin, A T

1993-01-01

The two polymorphic modifications of fosinopril sodium have been characterized as to their differences in melting behaviour, powder X-ray diffraction patterns, Fourier transform infrared spectra (FTIR), and solid-state 31P- and 13C-NMR spectra. The polymorphs were found to be enantiotropically related based upon melting point, heat of fusion, and solution mediated transformation data. Analysis of the solid-state FTIR and 13C-NMR data indicated that the environment of the acetal side chain of fosinopril sodium differed in two polymorphs, and that there might be cis-trans isomerization about the C6-N peptide bond. These conformational differences are postulated as the origin of the observed polymorphism.

Atomic structure and pressure-induced phase transformations in a phase-change alloy

NASA Astrophysics Data System (ADS)

Xu, Ming

Phase-change materials exist in at least two phases under the ambient condition. One is the amorphous state and another is crystalline phase. These two phases have vastly different physical properties, such as electrical conductivity, optical reflectivity, mass density, thermal conductivity, etc. The distinct physical properties and the fast transformation between amorphous and crystalline phases render these materials the ability to store information. For example, the DVD and the Blue-ray discs take advantage of the optical reflectivity contrast, and the newly developed solid-state memories make use of the large conductivity difference. In addition, both the amorphous and crystalline phases in phase-change memories (PCMs) are very stable at room temperature, and they are easy to be scaled up in the production of devices with large storage density. All these features make phase-change materials the ideal candidates for the next-generation memories. Despite of the fast development of these new memory materials in industry, many fundamental physics problems underlying these interesting materials are still not fully resolved. This thesis is aiming at solving some of the key issues in phase-change materials. Most of phase-change materials are composed of Ge-Sb-Te constituents. Among all these Ge-Sb-Te based materials, Ge2Sb2Te5 (GST) has the best performance and has been frequently studied as a prototypical phase-change material. The first and foremost issue is the structure of the two functioning phases. In this thesis, we investigate the unique atomic structure and bonding nature of amorphous GST (a-GST) and crystalline GST ( c-GST), using ab initio tools and X-ray diffraction (XRD) methods. Their local structures and bonding scenarios are then analyzed using electronic structure calculations. In order to gain insight into the fast phase transformation mechanism, we also carried out a series of high-pressure experiments on GST. Several new polymorphs and their transformations have been revealed under high pressure via in situ XRD and in situ electrical resistivity measurements. The mechanisms of the structural and property changes have been uncovered via ab initio molecular dynamics simulations.

Nanoparticle titanium dioxide aqueous interfacial energy can be modified to control phase stability, coarsening, and morphology

NASA Astrophysics Data System (ADS)

Finnegan, Michael Patrick

The effect of solution chemistry on the phase stability, coarsening kinetics and morphology of titanium dioxide (TiO2) nanoparticles is investigated in order to attain efficient production pathways to desired nano-structures with optimal properties. To obtain sample, TiO2 was synthesized via hydrolysis of titanium isopropoxide producing an 85% anatase/15% brookite mixture. The titania was hydrothermally heated in an array of temperatures and pH values for various times. There are distinct phase stability fields for nanoscale titania based on pH alone due to slight interface charging behavior differences among the polymorphs. The mixture transforms to rutile below the pH of zero point of charge (ZPC) and remains anatase above the ZPC. This phenomenon is partially reversible. The solution chemistry also dictates the hydrothermal coarsening mechanism of the anatase polymorph. Ostwald ripening (OR) takes place in basic pH where titania solubility is elevated relative to neutral pH where lower solubility prevents rapid OR but allows for coarsening via oriented attachment (OA) of nanoparticles. This OA event can alter the symmetry of anatase causing unexpected and perhaps technically useful morphologies such as straight and curved nanorods during coarsening.

Buckling failure of square ice-nanotube arrays constrained in graphene nanocapillaries

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

Zhu, YinBo; Wang, FengChao, E-mail: wangfc@ustc.edu.cn; Wu, HengAn

Graphene confinement provides a new physical and mechanical environment with ultrahigh van der Waals pressure, resulting in new quasi-two-dimensional phases of few-layer ice. Polymorphic transition can occur in bilayer constrained water/ice system. Here, we perform a comprehensive study of the phase transition of AA-stacked bilayer water constrained within a graphene nanocapillary. The compression-limit and superheating-limit (phase) diagrams are obtained, based on the extensive molecular-dynamics simulations at numerous thermodynamic states. Liquid-to-solid, solid-to-solid, and solid-to-liquid-to-solid phase transitions are observed in the compression and superheating of bilayer water. Interestingly, there is a temperature threshold (∼275 K) in the compression-limit diagram, which indicates thatmore » the first-order and continuous-like phase transitions of bilayer water depend on the temperature. Two obviously different physical processes, compression and superheating, display similar structural evolution; that is, square ice-nanotube arrays (BL-VHDI) will bend first and then transform into bilayer triangular AA stacking ice (BL-AAI). The superheating limit of BL-VHDI exhibits local maxima, while that of BL-AAI increases monotonically. More importantly, from a mechanics point of view, we propose a novel mechanism of the transformation from BL-VHDI to BL-AAI, both for the compression and superheating limits. This structural transformation can be regarded as the “buckling failure” of the square-ice-nanotube columns, which is dominated by the lateral pressure.« less

Very high-pressure orogenic garnet peridotites

PubMed Central

Liou, J. G.; Zhang, R. Y.; Ernst, W. G.

2007-01-01

Mantle-derived garnet peridotites are a minor component in many very high-pressure metamorphic terranes that formed during continental subduction and collision. Some of these mantle rocks contain trace amounts of zircon and micrometer-sized inclusions. The constituent minerals exhibit pre- and postsubduction microstructures, including polymorphic transformation and mineral exsolution. Experimental, mineralogical, petrochemical, and geochronological characterizations using novel techniques with high spatial, temporal, and energy resolutions are resulting in unexpected discoveries of new phases, providing better constraints on deep mantle processes. PMID:17519341

Analysis of Crystallization Kinetics

NASA Technical Reports Server (NTRS)

Kelton, Kenneth F.

1997-01-01

A realistic computer model for polymorphic crystallization (i.e., initial and final phases with identical compositions), which includes time-dependent nucleation and cluster-size-dependent growth rates, is developed and tested by fits to experimental data. Model calculations are used to assess the validity of two of the more common approaches for the analysis of crystallization data. The effects of particle size on transformation kinetics, important for the crystallization of many systems of limited dimension including thin films, fine powders, and nanoparticles, are examined.

Hydrothermal Synthesis of VO2 Polymorphs: Advantages, Challenges and Prospects for the Application of Energy Efficient Smart Windows.

PubMed

Li, Ming; Magdassi, Shlomo; Gao, Yanfeng; Long, Yi

2017-09-01

Vanadium dioxide (VO 2 ) is a widely studied inorganic phase change material, which has a reversible phase transition from semiconducting monoclinic to metallic rutile phase at a critical temperature of τ c ≈ 68 °C. The abrupt decrease of infrared transmittance in the metallic phase makes VO 2 a potential candidate for thermochromic energy efficient windows to cut down building energy consumption. However, there are three long-standing issues that hindered its application in energy efficient windows: high τ c , low luminous transmittance (T lum ), and undesirable solar modulation ability (ΔT sol ). Many approaches, including nano-thermochromism, porous films, biomimetic surface reconstruction, gridded structures, antireflective overcoatings, etc, have been proposed to tackle these issues. The first approach-nano-thermochromism-which is to integrate VO 2 nanoparticles in a transparent matrix, outperforms the rest; while the thermochromic performance is determined by particle size, stoichiometry, and crystallinity. A hydrothermal method is the most common method to fabricate high-quality VO 2 nanoparticles, and has its own advantages of large-scale synthesis and precise phase control of VO 2 . This Review focuses on hydrothermal synthesis, physical properties of VO 2 polymorphs, and their transformation to thermochromic VO 2 (M), and discusses the advantages, challenges, and prospects of VO 2 (M) in energy-efficient smart windows application. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-temperature phase transformations. The properties of the phases and their equilibrium under shock loading.

NASA Astrophysics Data System (ADS)

Zaretsky, Eugene

2011-06-01

Introducing the temperature as a variable parameter in shock wave experiments extends essentially the scope of these investigations. The influence of the temperature variations on either high strain rate elastic-plastic response of solids or parameters of the shock-induces phase transformations are not trivial and are not quite clear yet. The technique of VISAR-monitored planar impact experiments with the samples preheated up to 1400 K was developed and used for the studies of the effect of the preheating on the impact response and on the ``dynamic'' phase diagrams of pure metals (U, Ti, Fe, Co, Ag), and ionic compounds (KCl, KBr). The studies show that the increase of the shear strength of the shock-loaded metal with temperature (first reported by Kanel et al. 1996) is typical for pure FCC (Al, Ag, Cu) and some other (Sn, U) metals, and for the ionic crystals. In the metals with BCC lattice (Mo: Duffy and Ahrens 1994, Fe: Zaretsky 2009) such thermal hardening was not found. The abrupt strength anomalies (either yield or spall or both) were observed in a narrow vicinity of the temperature of any, polymorphic, magnetic, or melting, phase transformation. It was found that when a pure element approaches the phase boundary (the line of either first or second order phase transition) the result is a 50-100-% increase of the shear strength of the low-temperature phase. At the same time the presence of a small (~0.5%) amount of impurities may lead to a five-fold decrease of the strength as it takes place in the vicinity of the Curie point of Ni. The same technique being applied to the study of the shear stress relaxation (elastic precursor decay) near the transformation line may be useful for understanding the mechanisms responsible of these anomalies.

Relationships between molecular structure and kinetic and thermodynamic controls in lipid systems. Part II: Phase behavior and transformation paths of SSS, PSS and PPS saturated triacylglycerols--effect of chain length mismatch.

PubMed

Bouzidi, Laziz; Narine, Suresh S

2012-01-01

The kinetic phase behavior and phase transformation paths of purified tristearoylglycerol (SSS), 3-palmitoyl-1,2-distearoyl-sn-glycerol (PSS) and 1,2-dipalmitoyl-3-stearoyl-sn-glycerol (PPS) were investigated in terms of polymorphism, crystallization and melting. The details of the phase transformation paths were obtained using the heating cycles of two sets of experiments: (a) cooling rate was varied and heating rate fixed and (b) cooling rate was fixed and heating rate varied. Kinetic effects were manifest in all measured properties, underscoring the complexity of the phase transformation paths for each TAG, and the intricate thermodynamics-molecular relationships. For the first time, XRD data obtained for SSS, PSS and PPS TAGs, cooled at rates higher than 0.5°C/min, suggested the formation of a transient structure similar to the so-called α(2)-phase which has been observed in mixed saturated-unsaturated TAGs quenched from the melt. The more stable phases (β' in PSS and PPS, and β in SSS) were only observed for cooling rates lower than 1.0°C/min. The kinetic and thermodynamic differences observed in the crystallization, structure and melting of SSS, PSS and PPS are proposed to be mainly due to the disturbances introduced at the "terrace" level via methyl-end group interactions, i.e., the missing of two or four CH(2) groups compared to SSS. The symmetrical SSS with a relatively flat "terrace" crystallizes preferably in the most stable β-form. Two missing CH(2) groups at the sn-1 position (PSS) introduces enough structural disturbances to promote the relative prevalence and persistence of the β'-phase, and four missing CH(2) groups at the sn-1 and sn-2 positions (PPS) is relatively too large of a disturbance and therefore favors the α-form. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

Metastable high-pressure transformations of orthoferrosilite Fs82

NASA Astrophysics Data System (ADS)

Dera, Przemyslaw; Finkelstein, Gregory J.; Duffy, Thomas S.; Downs, Robert T.; Meng, Yue; Prakapenka, Vitali; Tkachev, Sergey

2013-08-01

High-pressure single-crystal X-ray diffraction experiments with natural ferrosilite Fs82 (Fe2+0.82Mg0.16Al0.01Ca0.01)(Si0.99Al0.01)O3 orthopyroxene (opx) reveal that at ambient temperature the sample does not transform to the clinopyroxene (cpx) structure, as reported earlier for a synthetic Fs100 end-member (Hugh-Jones et al., 1996), but instead undergoes a series of two polymorphic transitions, first above 10.1(1) GPa, to the monoclinic P21/c phase β-opx (distinctly different from both P21/c and C2/c cpx), also observed in natural enstatite (Zhang et al., 2012), and then, above 12.3(1) GPa to a high-pressure orthorhombic Pbca phase γ-opx, predicted for MgSiO3 by atomistic simulations (Jahn, 2008). The structures of phases α, β and γ have been determined from the single-crystal data at pressures of 2.3(1), 11.1(1), and 14.6(1) GPa, respectively. The two new high-pressure transitions, very similar in their character to the P21/c-C2/c transformation of cpx, make opx approximately as dense as cpx above 12.3(1) GPa and significantly change the elastic anisotropy of the crystal, with the [1 0 0] direction becoming almost twice as stiff as in the ambient α-opx phase. Both transformations involve mainly tetrahedral rotation, are reversible and are not expected to leave microstructural evidence that could be used as a geobarometric proxy. The high Fe2+ content in Fs82 shifts the α-β transition to slightly lower pressure, compared to MgSiO3, and has a very dramatic effect on reducing the (meta) stability range of the β-phase.

Thermally-prepared polymorphic forms of cilostazol.

PubMed

Stowell, Grayson W; Behme, Robert J; Denton, Stacy M; Pfeiffer, Inigo; Sancilio, Frederick D; Whittall, Linda B; Whittle, Robert R

2002-12-01

Prior to this study, cilostazol, an antithrombotic drug, was thought to exist as a single crystalline phase with a melting point of approximately 159 degrees C (Form A). On cooling, melts often form a glass that, when heated, may crystallize as additional crystalline polymorphic forms. Cilostazol, when reheated, subsequently forms polymorphs that melt at approximately 136 degrees C (Form B) and 146 degrees C (Form C). Free-energy temperature diagrams estimated from calorimetry data reveal that each pair of the cilostazol polymorphs (A-B, B-C, and A-C) is monotropic. Essentially pure samples of suitable crystalline shape and size permitted single crystal structural analysis of Forms A and C. Theoretical solubility ratios calculated using calorimetry data indicate that at 37 degrees C, Form B should be more than four times more soluble and Form C should be more than two times more soluble than Form A. Forms B and C could not be crystallized from solvents. Metastable forms from super cooled melts analyzed by intrinsic dissolution and Fourier transform-Raman experiments demonstrated that Forms B and C undergo a rapid, solvent-mediated recrystallization to Form A, making dissolution rate measurements difficult. Copyright 2002 Wiley-Liss, Inc. and the American Pharmaceutical Association J Pharm Sci 91:2481-2488, 2002

Epitaxial stabilization and phase instability of VO2 polymorphs

NASA Astrophysics Data System (ADS)

Lee, Shinbuhm; Ivanov, Ilia N.; Keum, Jong K.; Lee, Ho Nyung

2016-01-01

The VO2 polymorphs, i.e., VO2(A), VO2(B), VO2(M1) and VO2(R), have a wide spectrum of functionalities useful for many potential applications in information and energy technologies. However, synthesis of phase pure materials, especially in thin film forms, has been a challenging task due to the fact that the VO2 polymorphs are closely related to each other in a thermodynamic framework. Here, we report epitaxial stabilization of the VO2 polymorphs to synthesize high quality single crystalline thin films and study the phase stability of these metastable materials. We selectively deposit all the phases on various perovskite substrates with different crystallographic orientations. By investigating the phase instability, phonon modes and transport behaviours, not only do we find distinctively contrasting physical properties of the VO2 polymorphs, but that the polymorphs can be on the verge of phase transitions when heated as low as ~400 °C. Our successful epitaxy of both VO2(A) and VO2(B) phases, which are rarely studied due to the lack of phase pure materials, will open the door to the fundamental studies of VO2 polymorphs for potential applications in advanced electronic and energy devices.

Epitaxial stabilization and phase instability of VO2 polymorphs.

PubMed

Lee, Shinbuhm; Ivanov, Ilia N; Keum, Jong K; Lee, Ho Nyung

2016-01-20

The VO2 polymorphs, i.e., VO2(A), VO2(B), VO2(M1) and VO2(R), have a wide spectrum of functionalities useful for many potential applications in information and energy technologies. However, synthesis of phase pure materials, especially in thin film forms, has been a challenging task due to the fact that the VO2 polymorphs are closely related to each other in a thermodynamic framework. Here, we report epitaxial stabilization of the VO2 polymorphs to synthesize high quality single crystalline thin films and study the phase stability of these metastable materials. We selectively deposit all the phases on various perovskite substrates with different crystallographic orientations. By investigating the phase instability, phonon modes and transport behaviours, not only do we find distinctively contrasting physical properties of the VO2 polymorphs, but that the polymorphs can be on the verge of phase transitions when heated as low as ~400 °C. Our successful epitaxy of both VO2(A) and VO2(B) phases, which are rarely studied due to the lack of phase pure materials, will open the door to the fundamental studies of VO2 polymorphs for potential applications in advanced electronic and energy devices.

Epitaxial stabilization and phase instability of VO2 polymorphs

PubMed Central

Lee, Shinbuhm; Ivanov, Ilia N.; Keum, Jong K.; Lee, Ho Nyung

2016-01-01

The VO2 polymorphs, i.e., VO2(A), VO2(B), VO2(M1) and VO2(R), have a wide spectrum of functionalities useful for many potential applications in information and energy technologies. However, synthesis of phase pure materials, especially in thin film forms, has been a challenging task due to the fact that the VO2 polymorphs are closely related to each other in a thermodynamic framework. Here, we report epitaxial stabilization of the VO2 polymorphs to synthesize high quality single crystalline thin films and study the phase stability of these metastable materials. We selectively deposit all the phases on various perovskite substrates with different crystallographic orientations. By investigating the phase instability, phonon modes and transport behaviours, not only do we find distinctively contrasting physical properties of the VO2 polymorphs, but that the polymorphs can be on the verge of phase transitions when heated as low as ~400 °C. Our successful epitaxy of both VO2(A) and VO2(B) phases, which are rarely studied due to the lack of phase pure materials, will open the door to the fundamental studies of VO2 polymorphs for potential applications in advanced electronic and energy devices. PMID:26787259

Thermal, spectroscopic, and ab initio structural characterization of carprofen polymorphs.

PubMed

Bruni, Giovanna; Gozzo, Fabia; Capsoni, Doretta; Bini, Marcella; Macchi, Piero; Simoncic, Petra; Berbenni, Vittorio; Milanese, Chiara; Girella, Alessandro; Ferrari, Stefania; Marini, Amedeo

2011-06-01

Commercial and recrystallized polycrystalline samples of carprofen, a nonsteroidal anti-inflammatory drug, were studied by thermal, spectroscopic, and structural techniques. Our investigations demonstrated that recrystallized sample, stable at room temperature (RT), is a single polymorphic form of carprofen (polymorph I) that undergoes an isostructural polymorphic transformation by heating (polymorph II). Polymorph II remains then metastable at ambient conditions. Commercial sample is instead a mixture of polymorphs I and II. The thermodynamic relationships between the two polymorphs were determined through the construction of an energy/temperature diagram. The ab initio structural determination performed on synchrotron X-Ray powder diffraction patterns recorded at RT on both polymorphs allowed us to elucidate, for the first time, their crystal structure. Both crystallize in the monoclinic space group type P2(1) /c, and the unit cell similarity index and the volumetric isostructurality index indicate that the temperature-induced polymorphic transformation I → II is isostructural. Polymorphs I and II are conformational polymorphs, sharing a very similar hydrogen bond network, but with different conformation of the propanoic skeleton, which produces two different packing. The small conformational change agrees with the low value of transition enthalpy obtained by differential scanning calorimetry measurements and the small internal energy computed with density functional methods. Copyright © 2011 Wiley-Liss, Inc.

Pressure-induced reversible amorphization and an amorphous–amorphous transition in Ge2Sb2Te5 phase-change memory material

PubMed Central

Sun, Zhimei; Zhou, Jian; Pan, Yuanchun; Song, Zhitang; Mao, Ho-Kwang; Ahuja, Rajeev

2011-01-01

Ge2Sb2Te5 (GST) is a technologically very important phase-change material that is used in digital versatile disks-random access memory and is currently studied for the use in phase-change random access memory devices. This type of data storage is achieved by the fast reversible phase transition between amorphous and crystalline GST upon heat pulse. Here we report pressure-induced reversible crystalline-amorphous and polymorphic amorphous transitions in NaCl structured GST by ab initio molecular dynamics calculations. We have showed that the onset amorphization of GST starts at approximately 18 GPa and the system become completely random at approximately 22 GPa. This amorphous state has a cubic framework (c-amorphous) of sixfold coordinations. With further increasing pressure, the c-amorphous transforms to a high-density amorphous structure with trigonal framework (t-amorphous) and an average coordination number of eight. The pressure-induced amorphization is investigated to be due to large displacements of Te atoms for which weak Te–Te bonds exist or vacancies are nearby. Upon decompressing to ambient conditions, the original cubic crystalline structure is restored for c-amorphous, whereas t-amorphous transforms to another amorphous phase that is similar to the melt-quenched amorphous GST. PMID:21670255

Pressure-induced reversible amorphization and an amorphous-amorphous transition in Ge₂Sb₂Te₅ phase-change memory material.

PubMed

Sun, Zhimei; Zhou, Jian; Pan, Yuanchun; Song, Zhitang; Mao, Ho-Kwang; Ahuja, Rajeev

2011-06-28

Ge(2)Sb(2)Te(5) (GST) is a technologically very important phase-change material that is used in digital versatile disks-random access memory and is currently studied for the use in phase-change random access memory devices. This type of data storage is achieved by the fast reversible phase transition between amorphous and crystalline GST upon heat pulse. Here we report pressure-induced reversible crystalline-amorphous and polymorphic amorphous transitions in NaCl structured GST by ab initio molecular dynamics calculations. We have showed that the onset amorphization of GST starts at approximately 18 GPa and the system become completely random at approximately 22 GPa. This amorphous state has a cubic framework (c-amorphous) of sixfold coordinations. With further increasing pressure, the c-amorphous transforms to a high-density amorphous structure with trigonal framework (t-amorphous) and an average coordination number of eight. The pressure-induced amorphization is investigated to be due to large displacements of Te atoms for which weak Te-Te bonds exist or vacancies are nearby. Upon decompressing to ambient conditions, the original cubic crystalline structure is restored for c-amorphous, whereas t-amorphous transforms to another amorphous phase that is similar to the melt-quenched amorphous GST.

Multiphase Equations of State for Polymer Materials at High Dynamic Pressures

NASA Astrophysics Data System (ADS)

Khishchenko, Konstantin V.

2015-06-01

Equations of state for materials over a wide range of pressures and temperatures are necessary for numerical simulations of shock-wave processes in condensed matter. Accuracy of calculation results is determined mainly by adequacy of equation of state of a medium. In this work, a new multiphase equation-of-state model is proposed with taking into account the polymorphic phase transformations, melting and evaporation. Thermodynamic calculations are carried out for 2 polymer materials (polymethylmethacrylate and polytetrafluoroethylene) in a broad region of the phase diagram. Obtained results are presented in comparison with available data of experiments at high dynamic pressures in shock and release waves. This work is supported by RSF, Grant 14-50-00124.

Crystallography of in-situ transformations of the M 7C3 carbide in the cast Fe-Cr-Ni alloy

NASA Astrophysics Data System (ADS)

Kraposhin, V. S.; Kondrat'ev, S. Yu.; Talis, A. L.; Anastasiadi, G. P.

2017-03-01

In the process of holding of the cast heat-resistant Fe-Cr-Ni (0.45C-25Cr-35Ni) alloy at 1150°C, the eutectic chromium carbide present in its structure undergoes a gradual transition M 7C3 → M 23C6. The gradual formation of domains of the M 23C6 carbide inside the particles of the M 7C3 carbide makes it possible to assume that the observed phase transition is the well-known carbide transformation of the in situ type. The mechanism of the in situ transformation of the crystal structure of the carbide from M 7C3 into M 23C6 with a change in the number of nearest metal neighbors of carbon atoms is explained within the previously developed combinatory model of polymorphic transitions in the metals.

Epitaxial stabilization and phase instability of VO 2 polymorphs

DOE PAGES

Lee, Shinbuhm; Ivanov, Ilia N.; Keum, Jong K.; ...

2016-01-20

The VO 2 polymorphs, i.e., VO 2(A), VO 2(B), VO 2(M1) and VO 2(R), have a wide spectrum of functionalities useful for many potential applications in information and energy technologies. However, synthesis of phase pure materials, especially in thin film forms, has been a challenging task due to the fact that the VO 2 polymorphs are closely related to each other in a thermodynamic framework. Here, we report epitaxial stabilization of the VO 2 polymorphs to synthesize high quality single crystalline thin films and study the phase stability of these metastable materials. We selectively deposit all the phases on variousmore » perovskite substrates with different crystallographic orientations. By investigating the phase instability, phonon modes and transport behaviours, not only do we find distinctively contrasting physical properties of the VO 2 polymorphs, but that the polymorphs can be on the verge of phase transitions when heated as low as ~400 °C. In conclusion, our successful epitaxy of both VO 2(A) and VO 2(B) phases, which are rarely studied due to the lack of phase pure materials, will open the door to the fundamental studies of VO 2 polymorphs for potential applications in advanced electronic and energy devices.« less

Control of temperature and aqueous Mg2+/Ca2+ ratio on the (trans-)formation of ikaite

NASA Astrophysics Data System (ADS)

Purgstaller, B.; Dietzel, M.; Baldermann, A.; Mavromatis, V.

2017-11-01

The calcium carbonate hexahydrate mineral ikaite (CaCO3 ṡ 6 H2O) has been documented in aquatic environments at near-freezing temperatures. An increase of the prevailing temperature in the depositional environment, results in the transformation of natural ikaite into less soluble calcium carbonate phases occasionally leaving calcite pseudomorphs in the sediments, which are considered as an indicator for primary cold water temperatures. Detailed understanding on the physicochemical parameters controlling ikaite (trans-)formation however, such as temperature and reactive solution chemical composition, are still under debate. In order to study the formation of ikaite, we conducted precipitation experiments under controlled physicochemical conditions (pH = 8.3 ± 0.1; T = 6, 12, and 18 ± 0.1 °C) at defined aqueous molar Mg/Ca ratios. The transformation of ikaite into anhydrous calcium carbonate polymorphs was investigated in solution and at air exposure. The obtained results reveal the formation of ikaite at temperatures up to 12 °C, whereas Mg-rich amorphous calcium carbonate precipitated at 18 °C. In contact with the reactive solution ikaite transformed into aragonite at aqueous molar Mg2+/Ca2+ ratios of ≥14. In contrast, ikaite separated from the Mg-rich solution and exposed to air transformed in all cases into calcite/vaterite. The herein obtained temperature limit of ≤12 for ikaite formation is significantly higher than formerly expected and most probably caused by (i) the high saturation degree of the solution with respect to ikaite and (ii) the slow dehydration of the aqueous Ca2+ ion at low temperatures. This result questions the suitability of calcite pseudomorphs (i.e. glendonites) as a proxy for near-freezing temperatures. Moreover, our findings show that the CaCO3 polymorph formed from ikaite is strongly controlled by the physicochemical conditions, such as aqueous molar Mg2+/Ca2+ ratio of the reactive fluid and H2O availability throughout the transformation process.

High-pressure phase transitions of α-quartz under nonhydrostatic dynamic conditions: A reconnaissance study at PETRA III

NASA Astrophysics Data System (ADS)

Carl, Eva-Regine; Mansfeld, Ulrich; Liermann, Hanns-Peter; Danilewsky, Andreas; Langenhorst, Falko; Ehm, Lars; Trullenque, Ghislain; Kenkmann, Thomas

2017-07-01

Hypervelocity collisions of solid bodies occur frequently in the solar system and affect rocks by shock waves and dynamic loading. A range of shock metamorphic effects and high-pressure polymorphs in rock-forming minerals are known from meteorites and terrestrial impact craters. Here, we investigate the formation of high-pressure polymorphs of α-quartz under dynamic and nonhydrostatic conditions and compare these disequilibrium states with those predicted by phase diagrams derived from static experiments under equilibrium conditions. We create highly dynamic conditions utilizing a mDAC and study the phase transformations in α-quartz in situ by synchrotron powder X-ray diffraction. Phase transitions of α-quartz are studied at pressures up to 66.1 and different loading rates. At compression rates between 0.14 and 1.96 GPa s-1, experiments reveal that α-quartz is amorphized and partially converted to stishovite between 20.7 GPa and 28.0 GPa. Therefore, coesite is not formed as would be expected from equilibrium conditions. With the increasing compression rate, a slight increase in the transition pressure occurs. The experiments show that dynamic compression causes an instantaneous formation of structures consisting only of SiO6 octahedra rather than the rearrangement of the SiO4 tetrahedra to form a coesite. Although shock compression rates are orders of magnitude faster, a similar mechanism could operate in impact events.

Polymorphism in Strontium Tungstate SrWO4 under Quasi-Hydrostatic Compression.

PubMed

Santamaria-Perez, David; Errandonea, Daniel; Rodriguez-Hernandez, Placida; Muñoz, Alfonso; Lacomba-Perales, Raul; Polian, Alain; Meng, Yue

2016-10-03

The structural and vibrational properties of SrWO 4 have been studied experimentally up to 27 and 46 GPa, respectively, by angle-dispersive synchrotron X-ray diffraction and Raman spectroscopy measurements as well as using ab initio calculations. The existence of four polymorphs upon quasi-hydrostatic compression is reported. The three phase transitions were found at 11.5, 19.0, and 39.5 GPa. The ambient-pressure SrWO 4 tetragonal scheelite-type structure (S.G. I4 1 /a) undergoes a transition to a monoclinic fergusonite-type structure (S.G. I2/a) at 11.5 GPa with a 1.5% volume decrease. Subsequently, at 19.0 GPa, another structural transformation takes place. Our calculations indicate two possible post-fergusonite phases, one monoclinic and the other orthorhombic. In the diffraction experiments, we observed the theoretically predicted monoclinic LaTaO 4 -type phase coexisting with the fergusonite-type phase up to 27 GPa. The coexistence of the two phases and the large volume collapse at the transition confirm a kinetic hindrance typical of first-order phase transitions. Significant changes in Raman spectra suggest a third pressure-induced transition at 39.5 GPa. The conclusions extracted from the experiments are complemented and supported by ab initio calculations. Our data provides insight into the structural mechanism of the first transition, with the formation of two additional W-O contacts. The fergusonite-type phase can be therefore considered as a structural bridge between the scheelite structure, composed of [WO 4 ] tetrahedra, and the new higher pressure phases, which contain [WO 6 ] octahedra. All the observed phases are compatible with the high-pressure structural systematics predicted for ABO 4 compounds using crystal-chemistry arguments such as the diagram proposed by Bastide.

Polymorphism and metal-induced structural transformation in 5,5'-bis(4-pyridyl)(2,2'-bispyrimidine) adlayers on Au(111).

PubMed

Hötger, Diana; Carro, Pilar; Gutzler, Rico; Wurster, Benjamin; Chandrasekar, Rajadurai; Klyatskaya, Svetlana; Ruben, Mario; Salvarezza, Roberto C; Kern, Klaus; Grumelli, Doris

2018-05-31

Metal-organic coordination networks self-assembled on surfaces have emerged as functional low-dimensional architectures with potential applications ranging from the fabrication of functional nanodevices to electrocatalysis. Among them, bis-pyridyl-bispyrimidine (PBP) and Fe-PBP on noble metal surfaces appear as interesting systems in revealing the details of the molecular self-assembly and the effect of metal incorporation on the organic network arrangement. Herein, we report a combined STM, XPS, and DFT study revealing polymorphism in bis-pyridyl-bispyrimidine adsorbed adlayers on the reconstructed Au(111) surface. The polymorphic structures are converted by the addition of Fe adatoms into one unique Fe-PBP surface structure. DFT calculations show that while all PBP phases exhibit a similar thermodynamic stability, metal incorporation selects the PBP structure that maximizes the number of metal-N close contacts. Charge transfer from the Fe adatoms to the Au substrate and N-Fe interactions stabilize the Fe-PBP adlayer. The increased thermodynamic stability of the metal-stabilized structure leads to its sole expression on the surface.

Polymorphism and disorder in caffeine: Dielectric investigation of molecular mobilities

NASA Astrophysics Data System (ADS)

Descamps, M.; Decroix, A. A.

2014-12-01

Using dielectric relaxation data we have characterized the molecular mobilities of caffeine both in phase I (stable and metastable) and in phase II. In phase I effects of sublimation and phase transformation kinetics were carefully considered. In plane rotational motions were followed on a wide temperature range. A noticeable antiferroelectric short range order developing at the approach of the glass-like transition is characterized. Condition for occurrence of a critical-like behaviour is discussed. At high temperature the emergence of an additional ultra slow relaxation process is highlighted. Possible molecular mechanisms are proposed for both processes. In phase II the existence of a less intense relaxation process is confirmed. Close similarity with the main process developing in phase I hints at a common origin of the dipolar motions. Careful consideration of recent structure determinations leads to suggest that this process is associated to similar molecular in plane rotations but developing at the surface of crystalline samples. Lower cooperativity at the surface is reflected in the smaller activation entropy of the relaxation.

Phase diagram and transformations of iron pentacarbonyl to nm layered hematite and carbon-oxygen polymer under pressure

DOE PAGES

Ryu, Young Jay; Kim, Minseob; Yoo, Choong -Shik

2015-10-12

In this study, we present the phase diagram of Fe(CO) 5, consisting of three molecular polymorphs (phase I, II and III) and an extended polymeric phase that can be recovered at ambient condition. The phase diagram indicates a limited stability of Fe(CO) 5 within a pressure-temperature dome formed below the liquid- phase II- polymer triple point at 4.2 GPa and 580 K. The limited stability, in turn, signifies the temperature-induced weakening of Fe-CO back bonds, which eventually leads to the dissociation of Fe-CO at the onset of the polymerization of CO. The recovered polymer is a composite of novel nm-lamellarmore » layers of crystalline hematite Fe 2O 3 and amorphous carbon-oxygen polymers. These results, therefore, demonstrate the synthesis of carbon-oxygen polymer by compressing Fe(CO) 5, which advocates a novel synthetic route to develop atomistic composite materials by compressing organometallic compounds.« less

Navigating the Waters of Unconventional Crystalline Hydrates

PubMed Central

2015-01-01

Elucidating the crystal structures, transformations, and thermodynamics of the two zwitterionic hydrates (Hy2 and HyA) of 3-(4-dibenzo[b,f][1,4]oxepin-11-yl-piperazin-1-yl)-2,2-dimethylpropanoic acid (DB7) rationalizes the complex interplay of temperature, water activity, and pH on the solid form stability and transformation pathways to three neutral anhydrate polymorphs (Forms I, II°, and III). HyA contains 1.29 to 1.95 molecules of water per DB7 zwitterion (DB7z). Removal of the essential water stabilizing HyA causes it to collapse to an amorphous phase, frequently concomitantly nucleating the stable anhydrate Forms I and II°. Hy2 is a stoichiometric dihydrate and the only known precursor to Form III, a high energy disordered anhydrate, with the level of disorder depending on the drying conditions. X-ray crystallography, solid state NMR, and H/D exchange experiments on highly crystalline phase pure samples obtained by exquisite control over crystallization, filtration, and drying conditions, along with computational modeling, provided a molecular level understanding of this system. The slow rates of many transformations and sensitivity of equilibria to exact conditions, arising from its varying static and dynamic disorder and water mobility in different phases, meant that characterizing DB7 hydration in terms of simplified hydrate classifications was inappropriate for developing this pharmaceutical. PMID:26075319

Dynamics of Polymorphic Transformations in Palm Oil, Palm Stearin and Palm Kernel Oil Characterized by Coupled Powder XRD-DSC.

PubMed

Zaliha, Omar; Elina, Hishamuddin; Sivaruby, Kanagaratnam; Norizzah, Abd Rashid; Marangoni, Alejandro G

2018-06-01

The in situ polymorphic forms and thermal transitions of refined, bleached and deodorized palm oil (RBDPO), palm stearin (RBDPS) and palm kernel oil (RBDPKO) were investigated using coupled X-ray diffraction (XRD) and differential scanning calorimetry (DSC). Results indicated that the DSC onset crystallisation temperature of RBDPO was at 22.6°C, with a single reflection at 4.2Å started to appear from 23.4 to 17.1°C, and were followed by two prominent exothermic peaks at 20.1°C and 8.5°C respectively. Further cooling to -40°C leads to the further formation of a β'polymorph. Upon heating, a of β'→βtransformation was observed between 32.1 to 40.8°C, before the sample was completely melted at 43.0°C. The crystallization onset temperature of RBDPS was 44.1°C, with the appearance of the α polymorph at the same temperature as the appearance of the first sharp DSC exothermic peak. This quickly changed from α→β´ in the range 25 to 21.7°C, along with the formation of a small β peak at -40°C. Upon heating, a small XRD peak for the β polymorph was observed between 32.2 to 36.0°C, becoming a mixture of (β´+ β) between 44.0 to 52.5°C. Only the β polymorph survived further heating to 59.8°C. For RBDPKO, the crystallization onset temperature was 11.6°C, with the formation of a single sharp exothermic peak at 6.5°C corresponding to the β' polymorphic form until the temperature reached -40°C. No transformation of the polymorphic form was observed during the melting process of RBDPKO, before being completely melted at 33.2°C. This work has demonstrated the detailed dynamics of polymorphic transformations of PKO and PS, two commercially important hardstocks used widely by industry and will contribute to a greater understanding of their crystallization and melting dynamics.

Polymorphic transformation of helical flagella of bacteria

NASA Astrophysics Data System (ADS)

Lim, Sookkyung; Howard Berg Collaboration; William Ko Collaboration; Yongsam Kim Collaboration; Wanho Lee Collaboration; Charles Peskin Collaboration

2016-11-01

Bacteria such as E. coli swim in an aqueous environment by utilizing the rotation of flagellar motors and alternate two modes of motility, runs and tumbles. Runs are steady forward swimming driven by bundles of flagellar filaments whose motors are turning CCW; tumbles involve a reorientation of the direction of swimming triggered by motor reversals. During tumbling, the helical flagellum undergoes polymorphic transformations, which is a local change in helical pitch, helical radius, and handedness. In this work, we investigate the underlying mechanism of structural conformation and how this polymorphic transition plays a role in bacterial swimming. National Science Foundation.

Potential of carrageenans to protect drugs from polymorphic transformation.

PubMed

Schmidt, Andrea G; Wartewig, Siegfried; Picker, Katharina M

2003-07-01

Carrageenans were analysed in mixture with polymorphic drugs to test their potential for minimising polymorphic or pseudopolymorphic transitions, which are induced by the tableting process. The kappa-carrageenans Gelcarin GP-812 NF and Gelcarin GP-911 NF and the iota-carrageenan Gelcarin GP-379 NF were tested in comparison to the well-known tableting excipients microcrystalline cellulose (MCC), hydroxypropyl methylcellulose (HPMC), and dicalcium phosphate dihydrate (DCPD). Amorphous indomethacin was chosen as model drug since its well-known recrystallisation behaviour can be mechanically stimulated. Further on, theophylline monohydrate was used. Its dehydration is induced by tableting. Pure materials and mixtures containing 20% (w/w) drug were compressed up to different maximum relative densities. The data obtained during tableting were analysed by three-dimensional (3D) modelling. Afterwards tablets were broken and examined by Fourier transform Raman spectroscopy in order to determine the degree of transformation inside the tablet. For quantitative interpretation, the intensities of representative bands were used. Thermal analysis was used additionally. Using 3D modelling a decrease of plastic deformation can be noticed in the order HPMC>MCC>carrageenans, whereas DCPD represents an exception because of brittle fracture. Best hindrance of polymorphic transformation showed the carrageenans, the hindrance was slightly worse for HPMC. MCC and DCPD could not hinder transformation. A complete protection of the amorphous form could not be achieved. For theophylline monohydrate, the results were similar.

Modeling dynamic beta-gamma polymorphic transition in Tin

NASA Astrophysics Data System (ADS)

Chauvin, Camille; Montheillet, Frank; Petit, Jacques; CEA Gramat Collaboration; EMSE Collaboration

2015-06-01

Solid-solid phase transitions in metals have been studied by shock waves techniques for many decades. Recent experiments have investigated the transition during isentropic compression experiments and shock-wave compression and have highlighted the strong influence of the loading rate on the transition. Complementary data obtained with velocity and temperature measurements around the polymorphic transition beta-gamma of Tin on gas gun experiments have displayed the importance of the kinetics of the transition. But, even though this phenomenon is known, modeling the kinetic remains complex and based on empirical formulations. A multiphase EOS is available in our 1D Lagrangian code Unidim. We propose to present the influence of various kinetic laws (either empirical or involving nucleation and growth mechanisms) and their parameters (Gibbs free energy, temperature, pressure) on the transformation rate. We compare experimental and calculated velocities and temperature profiles and we underline the effects of the empirical parameters of these models.

Tuning Phase Composition of Polymer Nanocomposites toward High Energy Density and High Discharge Efficiency by Nonequilibrium Processing.

PubMed

Jiang, Jianyong; Zhang, Xin; Dan, Zhenkang; Ma, Jing; Lin, Yuanhua; Li, Ming; Nan, Ce-Wen; Shen, Yang

2017-09-06

Polymer nanocomposite dielectrics with high energy density and low loss are major enablers for a number of applications in modern electronic and electrical industry. Conventional fabrication of nanocomposites by solution routes involves equilibrium process, which is slow and results in structural imperfections, hence high leakage current and compromised reliability of the nanocomposites. We propose and demonstrate that a nonequilibrium process, which synergistically integrates electrospinning, hot-pressing and thermal quenching, is capable of yielding nanocomposites of very high quality. In the nonequilibrium nanocomposites of poly(vinylidene fluoride-co-hexafluoropropylene) (P(VDF-HFP)) and BaTiO 3 nanoparticles (BTO_nps), an ultrahigh Weibull modulus β of ∼30 is achieved, which is comparable to the quality of the bench-mark biaxially oriented polypropylene (BOPP) fabricated with melt-extrusion process by much more sophisticated and expensive industrial apparatus. Favorable phase composition and small crystalline size are also induced by the nonequilibrium process, which leads to concomitant enhancement of electric displacement and breakdown strength of the nanocomposite hence a high energy density of ∼21 J/cm 3 . Study on the polarization behavior and phase transformation at high electric field indicates that BTO_nps could facilitate the phase transformation from α- to β-polymorph at low electric field.

Workshop Report: Fundamental Reactions in Solid Propellant Combustion

DTIC Science & Technology

1979-05-01

combustion conditions. 6. What effect might a pressure-induced phase transition to a polymorph other than 6- HMX have on the pressure slope break during...pure HMX as well. Nevertheless, it is recommended that the high pressure polymorphs of HMX and RDX be determined. It was also felt that there...plateau burning phenomena E. Solid phase, surface, gas phase reactions F. Phase transitions : melting, vaporization, polymorphs G. Flame

Surface-mediated nucleation in the solid-state polymorph transformation of terephthalic acid.

PubMed

Beckham, Gregg T; Peters, Baron; Starbuck, Cindy; Variankaval, Narayan; Trout, Bernhardt L

2007-04-18

A molecular mechanism for nucleation for the solid-state polymorph transformation of terephthalic acid is presented. New methods recently developed in our group, aimless shooting and likelihood maximization, are employed to construct a model for the reaction coordinate for the two system sizes studied. The reaction coordinate approximation is validated using the committor probability analysis. The transformation proceeds via a localized, elongated nucleus along the crystal edge formed by fluctuations in the supramolecular synthons, suggesting a nucleation and growth mechanism in the macroscopic system.

Final Scientific/Technical Report

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

Reeder, Richard; Phillips, Brian

A variety of calcifying organisms produce a transient or metastable amorphous calcium carbonate (ACC) precursor phase that is assembled and subsequently transformed into a crystalline biomineral, typically calcite or aragonite. The complex shapes, hierarchical structures, and unique physical properties of the biominerals that result from this calcification pathway have stimulated interest in adapting these concepts for the design and creation of bio-inspired functional materials in the laboratory. ACC also forms as a reactive precursor in diverse inorganic systems and is likely to play a much broader role in calcium carbonate formation. Knowledge of the structure, composition, and behavior of thismore » metastable phase is critical for establishing a structural and mechanistic framework for calcium carbonate formation and its role in biogeochemical processes, including carbon cycling. Minor additives, such as magnesium, phosphorus, and organic macromolecules, are known to play important roles in controlling ACC stability, transformation kinetics, and selection of final crystalline polymorph. Molecular water also occurs in many types of ACC and is thought to play a structural role in its stability and transformation behavior. One of the major challenges that remain unresolved is identification of the structural basis for the role of these minor additives and molecular water. The absence of long-range order in ACC, and other amorphous phases, has posed a challenge for study by techniques commonly used for crystalline solids. Preliminary studies in our group show that the combination of two techniques, synchrotron X-ray-based pair distribution function (PDF) analysis and nuclear magnetic resonance (NMR) spectroscopy can provide entirely new insight to structural properties of synthetic ACC over length scales that are most relevant for understanding its transformation properties. Building on preliminary experiments, we propose a systematic study of synthesis, structure, and transformation behavior in abiotic systems. The work will specifically address the influence of phosphate as a minor additive. PDF analysis will utilize total X-ray scattering data collected at synchrotron facilities optimized for this method and will provide direct characterization of the short- and intermediate-range structure of ACC synthesized under controlled conditions. Parallel computational work using reverse Monte Carlo methods will allow structural models to be constructed for a more complete analysis of PDF results. NMR spectroscopy, using a variety of single- and double-resonance techniques, will provide information on H and CO3 components, including dynamical properties, and their relationship to stabilizing additives. PDF and NMR results will be complemented by parallel studies using X-ray absorption and FT-IR spectroscopy to allow direct comparison to previous studies. These techniques will be used to follow the transformation of different ACC samples, with specific additives, to crystalline phases under controlled condition (e.g., relative humidity). This work will provide the structural and mechanistic basis for understanding ACC stability, its transformation behavior, and the factors that govern polymorph selection. This new insight will directly benefit researchers in diverse fields, as well as adding to the framework of knowledge for understanding and controlling calcium carbonate formation in natural and engineered systems.« less

Fracture-induced amorphization of polycrystalline SiO2 stishovite: a potential platform for toughening in ceramics

PubMed Central

Nishiyama, Norimasa; Wakai, Fumihiro; Ohfuji, Hiroaki; Tamenori, Yusuke; Murata, Hidenobu; Taniguchi, Takashi; Matsushita, Masafumi; Takahashi, Manabu; Kulik, Eleonora; Yoshida, Kimiko; Wada, Kouhei; Bednarcik, Jozef; Irifune, Tetsuo

2014-01-01

Silicon dioxide has eight stable crystalline phases at conditions of the Earth's rocky parts. Many metastable phases including amorphous phases have been known, which indicates the presence of large kinetic barriers. As a consequence, some crystalline silica phases transform to amorphous phases by bypassing the liquid via two different pathways. Here we show a new pathway, a fracture-induced amorphization of stishovite that is a high-pressure polymorph. The amorphization accompanies a huge volume expansion of ~100% and occurs in a thin layer whose thickness from the fracture surface is several tens of nanometers. Amorphous silica materials that look like strings or worms were observed on the fracture surfaces. The amount of amorphous silica near the fracture surfaces is positively correlated with indentation fracture toughness. This result indicates that the fracture-induced amorphization causes toughening of stishovite polycrystals. The fracture-induced solid-state amorphization may provide a potential platform for toughening in ceramics. PMID:25297473

Fracture-induced amorphization of polycrystalline SiO2 stishovite: a potential platform for toughening in ceramics.

PubMed

Nishiyama, Norimasa; Wakai, Fumihiro; Ohfuji, Hiroaki; Tamenori, Yusuke; Murata, Hidenobu; Taniguchi, Takashi; Matsushita, Masafumi; Takahashi, Manabu; Kulik, Eleonora; Yoshida, Kimiko; Wada, Kouhei; Bednarcik, Jozef; Irifune, Tetsuo

2014-10-09

Silicon dioxide has eight stable crystalline phases at conditions of the Earth's rocky parts. Many metastable phases including amorphous phases have been known, which indicates the presence of large kinetic barriers. As a consequence, some crystalline silica phases transform to amorphous phases by bypassing the liquid via two different pathways. Here we show a new pathway, a fracture-induced amorphization of stishovite that is a high-pressure polymorph. The amorphization accompanies a huge volume expansion of ~100% and occurs in a thin layer whose thickness from the fracture surface is several tens of nanometers. Amorphous silica materials that look like strings or worms were observed on the fracture surfaces. The amount of amorphous silica near the fracture surfaces is positively correlated with indentation fracture toughness. This result indicates that the fracture-induced amorphization causes toughening of stishovite polycrystals. The fracture-induced solid-state amorphization may provide a potential platform for toughening in ceramics.

Surface-Accelerated Decomposition of δ-HMX.

PubMed

Sharia, Onise; Tsyshevsky, Roman; Kuklja, Maija M

2013-03-07

Despite extensive efforts to study the explosive decomposition of HMX, a cyclic nitramine widely used as a solid fuel, explosive, and propellant, an understanding of the physicochemical processes, governing the sensitivity of condensed HMX to detonation initiation is not yet achieved. Experimental and theoretical explorations of the initiation of chemistry are equally challenging because of many complex parallel processes, including the β-δ phase transition and the decomposition from both phases. Among four known polymorphs, HMX is produced in the most stable β-phase, which transforms into the most reactive δ-phase under heat or pressure. In this study, the homolytic NO2 loss and HONO elimination precursor reactions of the gas-phase, ideal crystal, and the (100) surface of δ-HMX are explored by first principles modeling. Our calculations revealed that the high sensitivity of δ-HMX is attributed to interactions of surfaces and molecular dipole moments. While both decomposition reactions coexist, the exothermic HONO-isomer formation catalyzes the N-NO2 homolysis, leading to fast violent explosions.

Application of Fourier transform infrared spectroscopy to silica diagenesis: The opal-A to opal-CT transformation

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

Rice, S.B.; Freund, H.; Huang, W.L.

An important goal in silica diagenesis research is to understand the kinetics of opal transformation from noncrystalline opal-A to the disordered silica polymorph opal-CT. Because the conventional technique for monitoring the transformation, powder X-ray diffraction (XRD), is applicable only to phases with long-range order, the authors used Fourier transform infrared spectroscopy (FTIR) to monitor the transformation. They applied this technique, combined with XRD and TEM, to experimental run products and natural opals from the Monterey Formation and from siliceous deposits in the western Pacific Ocean. Using a ratio of two infrared absorption intensities ({omega} = I{sub 472 cm{sup {minus}1}}/I{sub 500more » cm{sup {minus}1}}), the relative proportions of opal-A and opal-CT can be determined. The progress of the transformation is marked by changes in slope of {omega} vs. depth or time when a sufficient stratigraphic profile is available. There are three stages in the opal-A to opal-CT reaction: (1) opal-A dissolution; (2) opal-CT precipitation, whose end point is marked by completion of opal-A dissolution; and (3) opal-CT ordering, during which tridymite stacking is eliminated in favor of crystobalite stacking.« less

High-Pressure Behavior of Difluorides: The Case of SrF2

NASA Astrophysics Data System (ADS)

Swadba, K. E.; Stan, C. V.; Dutta, R.; Prakapenka, V.; Duffy, T. S.

2016-12-01

The high-pressure behavior of compounds in the AX2 family has attracted much attention due to their extensive polymorphism, highly coordinated structures, and diverse transformation pathways. The canonical transformation sequence for alkaline earth difluorides is from the fluorite-type structure (8 coordinated) to cotunnite (9 coordinated) to Ni2In (11 coordinated). Lead Fluoride, on the other hand, undergoes an unusual isosymmetric transition from cotunnite to a Co2Si-type structure (10 coordinated) at high pressures, during which it exhibits highly anisotropic lattice parameter trends (Haines et al, 1998; Stan et al 2016). Sr has a similar ionic radius as Pb, and is thus a good candidate for further exploring the compressional anisotropy in alkaline earth fluorides. In this study, we report a detailed examination of the compressional behavior of SrF2 to identify whether an intermediate phase occurs in this system prior to transformation to the Ni2In structure. Raman spectroscopy and x-ray diffraction experiments, performed at Princeton University and the Advanced Photon Source GSECARS beamline, respectively, were carried out on SrF2 up to 63 GPa using a diamond anvil cell. From Raman spectroscopy, we observed evidence for a high-pressure phase transition between 38.9 and 51.0 GPa. The x-ray diffraction data in this region show evidence for highly anisotropic compression, most notably a strong negative compressibility in the b direction, in the pressure region from 45.2 to 51.6 GPa. Comparison of our data with lattice parameter systematics for AX2 phases indicates that our results are consistent with the formation of the Co2Si phase in this region, along with a sluggish transformation to the Ni2In-type structure. Our findings contribute to a broader understanding of AX2 compounds and their phase transition pathways.

Transformations to granular zircon revealed: Twinning, reidite, and ZrO2 in shocked zircon from Meteor Crater (Arizona, USA)

USGS Publications Warehouse

Cavosie, Aaron; Timms, Nicholas E.; Erickson, Timmons M.; Hagerty, Justin J.; Hörz, Friedrich

2016-01-01

Granular zircon in impact environments has long been recognized but remains poorly understood due to lack of experimental data to identify mechanisms involved in its genesis. Meteor Crater in Arizona (United States) contains abundant evidence of shock metamorphism, including shocked quartz, the high pressure polymorphs coesite and stishovite, diaplectic SiO2 glass, and lechatelierite (fused SiO2). Here we report the presence of granular zircon, a new shocked mineral discovery at Meteor Crater, that preserve critical orientation evidence of specific transformations that occurred during its formation at extreme impact conditions. The zircon grains occur as aggregates of sub-µm neoblasts in highly shocked Coconino Formation Sandstone (CFS) comprised of lechatelierite. Electron backscatter diffraction shows that each grain consists of multiple domains, some with boundaries disoriented by 65°, a known {112} shock-twin orientation. Other domains have crystallographic c-axes in alignment with {110} of neighboring domains, consistent with the former presence of the high pressure ZrSiO4 polymorph reidite. Additionally, nearly all zircon preserve ZrO2 + SiO2, providing evidence of partial dissociation. The genesis of CFS granular zircon started with detrital zircon that experienced shock-twinning and reidite formation from 20 to 30 GPa, ultimately yielding a phase that retained crystallographic memory; this phase subsequently recrystallized to systematically oriented zircon neoblasts, and in some areas partially dissociated to ZrO2. The lechatelierite matrix, experimentally constrained to form at >2000 °C, provided an ultra high-temperature environment for zircon dissociation (~1670 °C) and neoblast formation. The capacity of granular zircon to preserve a cumulative P-T record has not been recognized previously, and provides a new method for retrieving histories of impact-related mineral transformations in the crust at conditions far beyond which most rocks melt.

High-pressure phase transitions of α-quartz under nonhydrostatic dynamic conditions: A reconnaissance study at PETRA III

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

Carl, Eva-Regine; Mansfeld, Ulrich; Liermann, Hanns-Peter

Hypervelocity collisions of solid bodies occur frequently in the solar system and affect rocks by shock waves and dynamic loading. A range of shock metamorphic effects and high-pressure polymorphs in rock-forming minerals are known from meteorites and terrestrial impact craters. In this paper, we investigate the formation of high-pressure polymorphs of α-quartz under dynamic and nonhydrostatic conditions and compare these disequilibrium states with those predicted by phase diagrams derived from static experiments under equilibrium conditions. We create highly dynamic conditions utilizing a mDAC and study the phase transformations in α-quartz in situ by synchrotron powder X-ray diffraction. Phase transitions ofmore » α-quartz are studied at pressures up to 66.1 and different loading rates. At compression rates between 0.14 and 1.96 GPa s -1, experiments reveal that α-quartz is amorphized and partially converted to stishovite between 20.7 GPa and 28.0 GPa. Therefore, coesite is not formed as would be expected from equilibrium conditions. With the increasing compression rate, a slight increase in the transition pressure occurs. The experiments show that dynamic compression causes an instantaneous formation of structures consisting only of SiO 6 octahedra rather than the rearrangement of the SiO 4 tetrahedra to form a coesite. Although shock compression rates are orders of magnitude faster, a similar mechanism could operate in impact events.« less

High-pressure phase transitions of α-quartz under nonhydrostatic dynamic conditions: A reconnaissance study at PETRA III

DOE PAGES

Carl, Eva-Regine; Mansfeld, Ulrich; Liermann, Hanns-Peter; ...

2017-03-27

Hypervelocity collisions of solid bodies occur frequently in the solar system and affect rocks by shock waves and dynamic loading. A range of shock metamorphic effects and high-pressure polymorphs in rock-forming minerals are known from meteorites and terrestrial impact craters. In this paper, we investigate the formation of high-pressure polymorphs of α-quartz under dynamic and nonhydrostatic conditions and compare these disequilibrium states with those predicted by phase diagrams derived from static experiments under equilibrium conditions. We create highly dynamic conditions utilizing a mDAC and study the phase transformations in α-quartz in situ by synchrotron powder X-ray diffraction. Phase transitions ofmore » α-quartz are studied at pressures up to 66.1 and different loading rates. At compression rates between 0.14 and 1.96 GPa s -1, experiments reveal that α-quartz is amorphized and partially converted to stishovite between 20.7 GPa and 28.0 GPa. Therefore, coesite is not formed as would be expected from equilibrium conditions. With the increasing compression rate, a slight increase in the transition pressure occurs. The experiments show that dynamic compression causes an instantaneous formation of structures consisting only of SiO 6 octahedra rather than the rearrangement of the SiO 4 tetrahedra to form a coesite. Although shock compression rates are orders of magnitude faster, a similar mechanism could operate in impact events.« less

Effect of a core-softened O-O interatomic interaction on the shock compression of fused silica

NASA Astrophysics Data System (ADS)

Izvekov, Sergei; Weingarten, N. Scott; Byrd, Edward F. C.

2018-03-01

Isotropic soft-core potentials have attracted considerable attention due to their ability to reproduce thermodynamic, dynamic, and structural anomalies observed in tetrahedral network-forming compounds such as water and silica. The aim of the present work is to assess the relevance of effective core-softening pertinent to the oxygen-oxygen interaction in silica to the thermodynamics and phase change mechanisms that occur in shock compressed fused silica. We utilize the MD simulation method with a recently published numerical interatomic potential derived from an ab initio MD simulation of liquid silica via force-matching. The resulting potential indicates an effective shoulder-like core-softening of the oxygen-oxygen repulsion. To better understand the role of the core-softening we analyze two derivative force-matching potentials in which the soft-core is replaced with a repulsive core either in the three-body potential term or in all the potential terms. Our analysis is further augmented by a comparison with several popular empirical models for silica that lack an explicit core-softening. The first outstanding feature of shock compressed glass reproduced with the soft-core models but not with the other models is that the shock compression values at pressures above 20 GPa are larger than those observed under hydrostatic compression (an anomalous shock Hugoniot densification). Our calculations indicate the occurrence of a phase transformation along the shock Hugoniot that we link to the O-O repulsion core-softening. The phase transformation is associated with a Hugoniot temperature reversal similar to that observed experimentally. With the soft-core models, the phase change is an isostructural transformation between amorphous polymorphs with no associated melting event. We further examine the nature of the structural transformation by comparing it to the Hugoniot calculations for stishovite. For stishovite, the Hugoniot exhibits temperature reversal and associated phase transformation, which is a transition to a disordered phase (liquid or dense amorphous), regardless of whether or not the model accounts for core-softening. The onset pressures of the transformation predicted by different models show a wide scatter within 60-110 GPa; for potentials without core-softening, the onset pressure is much higher than 110 GPa. Our results show that the core-softening of the interaction in the oxygen subsystem of silica is the key mechanism for the structural transformation and thermodynamics in shock compressed silica. These results may provide an important contribution to a unified picture of anomalous response to shock compression observed in other network-forming oxides and single-component systems with core-softening of effective interactions.

Ferroelasticity and domain physics in two-dimensional transition metal dichalcogenide monolayers.

PubMed

Li, Wenbin; Li, Ju

2016-02-24

Monolayers of transition metal dichalcogenides can exist in several structural polymorphs, including 2H, 1T and 1T'. The low-symmetry 1T' phase has three orientation variants, resulting from the three equivalent directions of Peierls distortion in the parental 1T phase. Using first-principles calculations, we predict that mechanical strain can switch the relative thermodynamic stability between the orientation variants of the 1T' phase. We find that such strain-induced variant switching only requires a few percent elastic strain, which is eminently achievable experimentally with transition metal dichalcogenide monolayers. Calculations indicate that the transformation barrier associated with such variant switching is small (<0.2 eV per chemical formula unit), suggesting that strain-induced variant switching can happen under laboratory conditions. Monolayers of transition metal dichalcogenides with 1T' structure therefore have the potential to be ferroelastic and shape memory materials with interesting domain physics.

Rietveld analysis of the effect of annealing atmosphere on phase evolution of nanocrystalline TiO2 powders.

PubMed

Salari, M; Rezaee, M; Chidembo, A T; Konstantinov, K; Liu, H K

2012-06-01

The structural evolution of nanocrystalline TiO2 was studied by X-ray diffraction (XRD) and the Rietveld refinement method (RRM). TiO2 powders were prepared by the sol-gel technique. Post annealing of as-synthesized powders in the temperature range from 500 degrees C to 800 degrees C under air and argon atmospheres led to the formation of TiO2 nanoparticles with mean crystallite size in the range of 37-165 nm, based on the Rietveld refinement results. It was found that the phase structure, composition, and crystallite size of the resulting particles were dependent on not only the annealing temperature, but also the annealing atmosphere. Rietveld refinement of the XRD data showed that annealing the powders under argon atmosphere promoted the polymorphic phase transformation from anatase to rutile. Field emission scanning electron microscopy (FESEM) was employed to investigate the morphology and size of the annealed powders.

Ferroelasticity and domain physics in two-dimensional transition metal dichalcogenide monolayers

DOE PAGES

Li, Wenbin; Li, Ju

2016-02-24

Monolayers of transition metal dichalcogenides can exist in several structural polymorphs, including 2H, 1T and 1T'. The low-symmetry 1T' phase has three orientation variants, resulting from the three equivalent directions of Peierls distortion in the parental 1T phase. Using first-principles calculations, we predict that mechanical strain can switch the relative thermodynamic stability between the orientation variants of the 1T' phase. We find that such strain-induced variant switching only requires a few percent elastic strain, which is eminently achievable experimentally with transition metal dichalcogenide monolayers. Calculations indicate that the transformation barrier associated with such variant switching is small (<0.2 eV permore » chemical formula unit), suggesting that strain-induced variant switching can happen under laboratory conditions. Furthermore, monolayers of transition metal dichalcogenides with 1T' structure therefore have the potential to be ferroelastic and shape memory materials with interesting domain physics.« less

Shock-induced decomposition of a high density glass (ZF6)

NASA Astrophysics Data System (ADS)

Zhou, Xianming; Liu, Xun; Li, Jiabo; Li, Jun; Cao, Xiuxia

2011-07-01

The dynamic high-pressure behavior of a high density glass (ZF6) was investigated in this study. The Hugoniot data, shock temperature (TH) and release sound velocity (C) of ZF6 were measured by a time-resolved multi-channel pyrometer in the shock pressure (PH) range of 50-170 GPa. The Hugoniot data is in accord with the Los Alamos Scientific Laboratory (LASL) shock Hugoniot data and shows a good linearity over 21 GPa. Polymorphic phase transitions were identified by the kinks in the measured TH-PH and C-PH relationships. The onset pressures of the transformations are ˜75 and ˜128 GPa, respectively. A thermodynamic calculation suggests that the phase transition at 75 GPa is its disproportionation to massicot (high pressure phase of PbO) and melted silica while the transition at 128 GPa is from the melting of massicot.

An occurrence of metastable cristobalite in high-pressure garnet Granulite

USGS Publications Warehouse

Darling, R.S.; Chou, I.-Ming; Bodnar, R.J.

1997-01-01

High-pressure (0.8 gigapascals) granulite facies garnet from Gore Mountain, New York, hosts multiple solid inclusions containing the low- pressure silica polymorph cristobalite along with albite and minor ilmenite. Identification of cristobalite is based on Raman spectra, electron microprobe analysis, and microthermometric measurements on the ??/?? phase transformation. The cristobalite plus albite inclusions may have originated as small, trapped samples of hydrous sodium-aluminum-siliceous melt. Diffusive loss of water from these inclusions under isothermal, isochoric conditions may have resulted in a large enough internal pressure decrease to promote the metastable crystallization of cristobalite.

Salting out the polar polymorph: analysis by alchemical solvent transformation.

PubMed

Duff, Nathan; Dahal, Yuba Raj; Schmit, Jeremy D; Peters, Baron

2014-01-07

We computationally examine how adding NaCl to an aqueous solution with α- and γ-glycine nuclei alters the structure and interfacial energy of the nuclei. The polar γ-glycine nucleus in pure aqueous solution develops a melted layer of amorphous glycine around the nucleus. When NaCl is added, a double layer is formed that stabilizes the polar glycine polymorph and eliminates the surface melted layer. In contrast, the non-polar α-glycine nucleus is largely unaffected by the addition of NaCl. To quantify the stabilizing effect of NaCl on γ-glycine nuclei, we alchemically transform the aqueous glycine solution into a brine solution of glycine. The alchemical transformation is performed both with and without a nucleus in solution and for nuclei of α-glycine and γ-glycine polymorphs. The calculations show that adding 80 mg/ml NaCl reduces the interfacial free energy of a γ-glycine nucleus by 7.7 mJ/m(2) and increases the interfacial free energy of an α-glycine nucleus by 3.1 mJ/m(2). Both results are consistent with experimental reports on nucleation rates which suggest: J(α, brine) < J(γ, brine) < J(α, water). For γ-glycine nuclei, Debye-Hückel theory qualitatively, but not quantitatively, captures the effect of salt addition. Only the alchemical solvent transformation approach can predict the results for both polar and non-polar polymorphs. The results suggest a general "salting out" strategy for obtaining polar polymorphs and also a general approach to computationally estimate the effects of solvent additives on interfacial free energies for nucleation.

An unusual type of polymorphism in a liquid crystal

DOE PAGES

Li, Lin; Salamonczyk, Miroslaw; Shadpour, Sasan; ...

2018-02-19

Polymorphism is a remarkable concept in chemistry, materials science, computer science, and biology. Whether it is the ability of a material to exist in two or more crystal structures, a single interface connecting to two different entities, or alternative phenotypes of an organism, polymorphism determines function and properties. In materials science, polymorphism can be found in an impressively wide range of materials, including crystalline materials, minerals, metals, alloys, and polymers. Here in this paper we report on polymorphism in a liquid crystal. A bent-core liquid crystal with a single chiral side chain forms two structurally and morphologically significantly different liquidmore » crystal phases solely depending on the cooling rate from the isotropic liquid state. On slow cooling, the thermodynamically more stable oblique columnar phase forms, and on rapid cooling, a not heretofore reported helical microfilament phase. Since structure determines function and properties, the structural color for these phases also differs.« less

An unusual type of polymorphism in a liquid crystal

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

Li, Lin; Salamonczyk, Miroslaw; Shadpour, Sasan

Polymorphism is a remarkable concept in chemistry, materials science, computer science, and biology. Whether it is the ability of a material to exist in two or more crystal structures, a single interface connecting to two different entities, or alternative phenotypes of an organism, polymorphism determines function and properties. In materials science, polymorphism can be found in an impressively wide range of materials, including crystalline materials, minerals, metals, alloys, and polymers. Here in this paper we report on polymorphism in a liquid crystal. A bent-core liquid crystal with a single chiral side chain forms two structurally and morphologically significantly different liquidmore » crystal phases solely depending on the cooling rate from the isotropic liquid state. On slow cooling, the thermodynamically more stable oblique columnar phase forms, and on rapid cooling, a not heretofore reported helical microfilament phase. Since structure determines function and properties, the structural color for these phases also differs.« less

The Boson peak in confined water: An experimental investigation of the liquid-liquid phase transition hypothesis

DOE PAGES

Mallamace, Francesco; Corsaro, Carmelo; Mallamace, Domenico; ...

2015-12-05

The Boson peak (BP) of deeply cooled confined water is studied by using inelastic neutron scattering (INS) in a large interval of the (P, T) phase plane. By taking into account the different behavior of such a collective vibrational mode in both strong and fragile glasses as well as in glass-forming materials, we were able to determine the Widom line that characterizes supercooled bulk water within the frame of the liquid-liquid phase transition (LLPT) hypothesis. The peak frequency and width of the BP correlated with the water polymorphism of the LLPT scenario, allowing us to distinguish the “low-density liquid” (LDL)more » and “high-density liquid” (HDL) phases in deeply cooled bulk water.Moreover, the BP properties afford a further confirmation of theWidom line temperature T W as the (P, T) locus in which the local structure of water transforms from a predominately LDL form to a predominately HDL form.« less

The Boson peak in confined water: An experimental investigation of the liquid-liquid phase transition hypothesis

NASA Astrophysics Data System (ADS)

Mallamace, Francesco; Corsaro, Carmelo; Mallamace, Domenico; Wang, Zhe; Chen, Sow-Hsin

2015-10-01

The Boson peak (BP) of deeply cooled confined water is studied by using inelastic neutron scattering (INS) in a large interval of the ( P, T) phase plane. By taking into account the different behavior of such a collective vibrational mode in both strong and fragile glasses as well as in glass-forming materials, we were able to determine the Widom line that characterizes supercooled bulk water within the frame of the liquid-liquid phase transition (LLPT) hypothesis. The peak frequency and width of the BP correlated with the water polymorphism of the LLPT scenario, allowing us to distinguish the "low-density liquid" (LDL) and "high-density liquid" (HDL) phases in deeply cooled bulk water.Moreover, the BP properties afford a further confirmation of theWidom line temperature T W as the ( P, T) locus in which the local structure of water transforms from a predominately LDL form to a predominately HDL form.

The Boson peak in confined water: An experimental investigation of the liquid-liquid phase transition hypothesis

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

Mallamace, Francesco; Corsaro, Carmelo; Mallamace, Domenico

The Boson peak (BP) of deeply cooled confined water is studied by using inelastic neutron scattering (INS) in a large interval of the (P, T) phase plane. By taking into account the different behavior of such a collective vibrational mode in both strong and fragile glasses as well as in glass-forming materials, we were able to determine the Widom line that characterizes supercooled bulk water within the frame of the liquid-liquid phase transition (LLPT) hypothesis. The peak frequency and width of the BP correlated with the water polymorphism of the LLPT scenario, allowing us to distinguish the “low-density liquid” (LDL)more » and “high-density liquid” (HDL) phases in deeply cooled bulk water.Moreover, the BP properties afford a further confirmation of theWidom line temperature T W as the (P, T) locus in which the local structure of water transforms from a predominately LDL form to a predominately HDL form.« less

Polymorphic Transformation in Mixtures of High- and Low-Melting Fractions of Milk Fat

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

Cisneros,A.; Mazzanti, G.; Campos, R.

2006-01-01

The kinetics of crystallization of high-melting fraction (HMF) and a mixture of 40% HMF and 60% low-melting fraction (LMF) of milk fat were studied at 5 C by time-resolved in-situ synchrotron X-ray diffraction. HMF crystallized in the {alpha} polymorph, had a longer lifetime than the ones previously reported in pure milk fat, and was almost completely solid. The HMF/LMF mixture crystallized initially in the {alpha} form and transformed into the {beta}' polymorph, with a solid fat content much lower than that of HMF. The polymorphic change was therefore attributed to a delayed sudden formation of {beta}' mixed crystals from themore » uncrystallized melt. These findings are important for the food industry and as fundamental knowledge to improve our understanding of the origin of the macroscopic physical properties of solid milk fat fractions used in many manufacturing processes.« less

Crystallization of D-mannitol in binary mixtures with NaCl: phase diagram and polymorphism.

PubMed

Telang, Chitra; Suryanarayanan, Raj; Yu, Lian

2003-12-01

To study the crystallization, polymorphism, and phase behavior of D-mannitol in binary mixtures with NaCl to better understand their interactions in frozen aqueous solutions. Differential scanning calorimetry, hot-stage microscopy, Raman microscopy, and variable-temperature X-ray diffractometry were used to characterize D-mannitol-NaCl mixtures. NaCl and D-mannitol exhibited significant melt miscibility (up to 7.5% w/w or 0.20 mole fraction of NaCl) and a eutectic phase diagram (eutectic composition 7.5% w/w NaCl; eutectic temperature 150 degrees C for the alpha and beta polymorphs of D-mannitol and 139 degrees C for the delta). The presence of NaCl did not prevent mannitol from crystallizing but, depending on sample size, affected the polymorph crystallized: below 10 mg, delta was obtained; above 100 mg, alpha was obtained. Pure mannitol crystallized under the same conditions first as the delta polymorph and then as the a polymorph, with the latter nucleating on the former. KCl showed similar eutectic points and melt miscibility with D-mannitol as NaCl. LiCl yielded lower eutectic melting points, inhibited the crystallization of D-mannitol during cooling, and enabled the observation of its glass transition. Despite their structural dissimilarity, significant melt miscibility exists between D-mannitol and NaCl. Their phase diagram has been determined and features polymorph-dependent eutectic points. NaCl influences the polymorphic behavior of mannitol, and the effect is linked to the crystallization of mannitol in two polymorphic stages.

First principles study of pressure induced polymorphic phase transition in KNO3

NASA Astrophysics Data System (ADS)

Yedukondalu, N.; Vaitheeswaran, G.

2015-06-01

We report the structural, elastic, electronic, and vibrational properties of polymorphic phases II and III of KNO3 based on density functional theory (DFT). Using semi-empirical dispersion correction (DFT-D2) method, we predicted the correct thermodynamic ground state of KNO3 and the obtained ground state properties of the polymorphs are in good agreement with the experiments. We further used this method to calculate the elastic constants, IR and Raman spectra, vibrational frequencies and their assignment of these polymorphs. The calculated Tran Blaha-modified Becke Johnson (TB-mBJ) electronic structure shows that both the polymorphic phases are direct band gap insulators with mixed ionic and covalent bonding. Also the TB-mBJ band gaps are improved over standard DFT functionals which are comparable with the available experiments.

The 3R polymorph of CaSi{sub 2}

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

Nedumkandathil, Reji; Benson, Daryn E.; Grins, Jekabs

The Zintl phase CaSi{sub 2} commonly occurs in the 6R structure where puckered hexagon layers of Si atoms are stacked in an AA′BB′CC′ fashion. In this study we show that sintering of CaSi{sub 2} in a hydrogen atmosphere (30 bar) at temperatures between 200 and 700 °C transforms 6R-CaSi{sub 2} quantitatively into 3R-CaSi{sub 2}. In the 3R polymorph (space group R-3m (no. 166), a=3.8284(1), c=15.8966(4), Z=3) puckered hexagon layers are stacked in an ABC fashion. The volume per formula unit is about 3% larger compared to 6R-CaSi{sub 2}. First principles density functional calculations reveal that 6R and 3R-CaSi{sub 2} aremore » energetically degenerate at zero Kelvin. With increasing temperature 6R-CaSi{sub 2} stabilizes over 3R because of its higher entropy. This suggests that 3R-CaSi{sub 2} should revert to 6R at elevated temperatures, which however is not observed up to 800 °C. 3R-CaSi{sub 2} may be stabilized by small amounts of incorporated hydrogen and/or defects. - Graphical abstract: The common 6R form of CaSi{sub 2} can be transformed quantitatively into 3R-CaSi{sub 2} upon sintering in a hydrogen atmosphere. - Highlights: • Quantitative and reproducible bulk synthesis of the rare 3R polymorph of CaSi{sub 2}. • Clarification of the energetic relation between 3R and conventional 6R form. • 3R-CaSi{sub 2} is presumably stabilized by small amounts of incorporated hydrogen and/or defects.« less

Microstructure characterization and phase transformation kinetic study of ball-milled m-ZrO 2-30 mol% a-TiO 2 mixture by Rietveld method

NASA Astrophysics Data System (ADS)

Pradhan, S. K.; Dutta, H.

2005-05-01

High-energy ball milling of monoclinic ZrO 2-30 mol% anatase TiO 2 mixture at different durations results in the formation of m-ZrO 2-a-TiO 2 solid solution from which the nucleation of nanocrystalline cubic (c) ZrO 2 polymorphic phase sets in. Post-annealing of 12 h ball-milled sample at different elevated temperatures for 1 h results in almost complete formation of c-ZrO 2 phase. Microstructure of the unmilled, all the ball milled and annealed samples has been characterized by Rietveld's X-ray powder structure refinement method. Particle size, rms lattice strain, change in lattice parameters and phase content of individual phases have been estimated from Rietveld analysis, and are utilized to interpret the results. In course of milling, (1 1 1) of cubic lattice became parallel to ( 1bar 1 1) plane of monoclinic lattice due to the orientation effect and cubic phase may have been formed on the (0 0 1) of the m-ZrO 2-a-TiO 2 solid solution lattice. A comparative study of microstructure and phase transformation kinetics of ZrO 2-10, 20 and 30 mol% a-TiO 2 ball-milled and post-annealed samples reveals that rate of phase transformation m→c-ZrO 2 increases with increasing a-TiO 2 concentration and ∼30 mol% of nanocrystalline c-ZrO 2 phase can be obtained within 4 h of milling time in the presence of 30 mol% of a-TiO 2. The post-annealing treatment at 773, 873 and 973 K for 1 h duration each reveals that rate of c-ZrO 2 formation with increasing temperature is retarded with increasing a-TiO 2 concentration but the amount of c-ZrO 2 becomes almost equal (∼95 mol%) at 973 K. It suggests that almost fully stabilized nanocrystalline c-ZrO 2 can be formed by adding a tetravalent solute to m-ZrO 2.

Roughness-controlled self-assembly of mannitol/LB agar microparticles by polymorphic transformation for pulmonary drug delivery.

PubMed

Zhang, Fengying; Ngoc, Nguyen Thi Quynh; Tay, Bao Hui; Mendyk, Aleksander; Shao, Yu-Hsuan; Lau, Raymond

2015-01-05

Novel roughness-controlled mannitol/LB Agar microparticles were synthesized by polymorphic transformation and self-assembly method using hexane as the polymorphic transformation reagent and spray-dried mannitol/LB Agar microparticles as the starting material. As-prepared microparticles were characterized by Fourier transform infrared spectra (FTIR), X-ray diffraction spectra (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), thermal gravimetric analysis (TGA), and Andersen Cascade Impactor (ACI). The XRD and DSC results indicate that after immersing spray-dried mannitol/LB Agar microparticles in hexane, β-mannitol was completely transformed to α-mannitol in 1 h, and all the δ-mannitol was transformed to α form after 14 days. SEM shows that during the transformation the nanobelts on the spray-dried mannitol/LB Agar microparticles become more dispersed and the contour of the individual nanobelts becomes more noticeable. Afterward, the nanobelts self-assemble to nanorods and result in rod-covered mannitol/LB Agar microparticles. FTIR indicates new hydrogen bonds were formed among mannitol, LB Agar, and hexane. SEM images coupled with image analysis software reveal that different surface morphology of the microparticles have different drug adhesion mechanisms. Comparison of ACI results and image analysis of SEM images shows that an increase in the particle surface roughness can increase the fine particle fractions (FPFs) using the rod-covered mannitol microparticles as drug carriers. Transformed microparticles show higher FPFs than commercially available lactose carriers. An FPF of 28.6 ± 2.4% was achieved by microparticles transformed from spray-dried microparticles using 2% mannitol(w/v)/LB Agar as feed solution. It is comparable to the highest FPF reported in the literature using lactose and spray-dried mannitol as carriers.

Polymorphism complexity and handedness inversion in serum albumin amyloid fibrils.

PubMed

Usov, Ivan; Adamcik, Jozef; Mezzenga, Raffaele

2013-12-23

Protein-based amyloid fibrils can show a great variety of polymorphic structures within the same protein precursor, although the origins of these structural homologues remain poorly understood. In this work we investigate the fibrillation of bovine serum albumin--a model globular protein--and we follow the polymorphic evolution by a statistical analysis of high-resolution atomic force microscopy images, complemented, at larger length scales, by concepts based on polymer physics formalism. We identify six distinct classes of coexisting amyloid fibrils, including flexible left-handed twisted ribbons, rigid right-handed helical ribbons and nanotubes. We show that the rigid fibrils originate from flexible fibrils through two diverse polymorphic transitions, first, via a single-fibril transformation when the flexible left-handed twisted ribbons turn into the helical left-handed ribbons, to finally evolve into nanotube-like structures, and second, via a double-fibril transformation when two flexible left-handed twisted ribbons wind together resulting in a right-handed twisted ribbon, followed by a rigid right-handed helical ribbon polymorphic conformation. Hence, the change in handedness occurs with an increase in the level of the fibril's structural organization.

Application of virtual phase-shifting speckle-interferometry for detection of polymorphism in the Chlamydia trachomatis omp1 gene

NASA Astrophysics Data System (ADS)

Feodorova, Valentina A.; Saltykov, Yury V.; Zaytsev, Sergey S.; Ulyanov, Sergey S.; Ulianova, Onega V.

2018-04-01

Method of phase-shifting speckle-interferometry has been used as a new tool with high potency for modern bioinformatics. Virtual phase-shifting speckle-interferometry has been applied for detection of polymorphism in the of Chlamydia trachomatis omp1 gene. It has been shown, that suggested method is very sensitive to natural genetic mutations as single nucleotide polymorphism (SNP). Effectiveness of proposed method has been compared with effectiveness of the newest bioinformatic tools, based on nucleotide sequence alignment.

First principles study of structural, electronic and optical properties of polymorphic forms of Rb 2Te

NASA Astrophysics Data System (ADS)

Alay-e-Abbas, S. M.; Shaukat, A.

2011-05-01

First-principles density functional theory calculations have been performed for structural, electronic and optical properties of three polymorphic forms of rubidium telluride. Our calculations show that the sequence of pressure induced phase transitions for Rb 2Te is Fm3¯m → Pnma → P6 3/mmc which is governed by the coordination numbers of the anions. From our calculated low transition pressure value for the Fm3¯m phase to the Pnma phase transition of Rb 2Te, the experimentally observed meta-stability of Fm3¯m phase at ambient conditions seems reasonable. The electronic band structure has been calculated for all the three phases and the change in the energy band gap is discussed for the transitioning phases. The energy band gaps obtained for the three phases of Rb 2Te decrease on going from the meta-stable phase to the high-pressure phases. Total and partial density of states for the polymorphs of Rb 2Te has been computed to elucidate the contribution of various atomic states on the electronic band structure. Furthermore, optical properties for all the polymorphic forms have been presented in form of the complex dielectric function.

Varieties of Dioptase: Their Magnetic Structure and Collective Excitations

NASA Astrophysics Data System (ADS)

Prisk, T.; Hoffmann, C.; Kolesnikov, A.; Anovitz, L. M.; Matsuda, M.; Podlesnyak, A.; Yan, J.

2017-12-01

Diopase [Cu6Si6O18 * 6 H2O] is a copper cyclosilicate mineral that exists within three different polymorphic forms. In the naturally occurring green phase, micropore channels are formed by corrugated rings of Si6O18 connected by Cu2+ ions. These channels contain rings of water molecules H2O which are co-ordinated to the Cu2+ ions, forming Jahn-Teller distorted octahedra. This results in the polymorph's green color. When the mineral is annealed at 400 C, it transforms into a blue polymorph where the positions of the the water molecules H2O become disordered within the channels. If annealed at 600 C, the water molecules are expelled from crystal structure altogether, leaving intact a framework where where the copper atom has quasi-planar co-ordination with neighboring oxygen atoms. The Cu2+ ions are responsible for the appearance of long-range antiferromagnetic order in green dioptase at 14 K. Comparative magnetic susceptibility measurements of these polymorphs demonstrate that altering the hydration state of the mineral leads to profound changes in its magnetic properties. This is presumably due to the fact that the local environment of the Cu2+ ions is modified by changes in the Cu atom's co-ordination with the water oxygen. Green, blue, and black dioptase together provide a case study in the coupling of a mineral's hydration state to its magnetic properties. In this presentation, we report upon a comparative study of dioptase polymorphs. We have applied heat capacity, magnetic susceptibility, single-crystal diffraction, and inelastic neutron scattering techniques. Magnetic diffraction patterns were obtained using the Polarized Triple Axis Spectrometer at the High Flux Isotope Reactor, while measurements of the spin wave dispersion were performed using the Cold Neutron Chopper Spectrometer at the Spallation Neutron Source. We find that, in green dioptase, the Cu2+ ions form spiral antiferromagnetic chains parallel to the micropore channels. However, in blue dioptase, long-range antiferromagnetic order is completely suppressed down to at least 2 K. Black dioptase undergoes a phase transition at 7 K into a low dimensional antiferromagnet, apparently having a different magnetic structure from its green counterpart.

Studying Individual Plant AOX Gene Functionality in Early Growth Regulation: A New Approach.

PubMed

Arnholdt-Schmitt, Birgit; Patil, Vinod Kumar

2017-01-01

AOX1 and AOX2 genes are thought to play different physiological roles. Whereas AOX1 is typically expected to associate to stress and growth responses, AOX2 was more often found to be linked to development and housekeeping functions. However, this view is questioned by several adverse observations. For example, co-regulated expression for DcAOX1 and DcAOX2a genes was recently reported during growth induction in carrot (Daucus carota L.). Early expression peaks for both genes during the lag phase of growth coincided with a critical time point for biomass prediction, a result achieved by applying calorespirometry. The effect of both AOX family member genes cannot easily be separated. However, separate functional analysis is required in order to identify important gene-specific polymorphisms or patterns of polymorphisms for functional marker development and its use in breeding. Specifically, a methodology is missing that enables studying functional effects of individual genes or polymorphisms/polymorphic patterns on early growth regulation.This protocol aims to provide the means for identifying plant alternative oxidase (AOX) gene variants as functional markers for early growth regulation. Prerequisite for applying this protocol is available Schizosaccharomyces pombe strains that were transformed with individual AOX genes following published protocols from Anthony Moore's group (Albury et al., J Biol Chem 271:17062-17066, 1996; Affourtit et al., J Biol Chem 274:6212-6218, 1999). The novelty of the present protocol comes by modifying yeast cell densities in a way that allows studying critical qualitative and quantitative effects of AOX gene variants (isoenzymes or polymorphic genes) during the early phase of growth. Calorimetry is used as a novel tool to confirm differences obtained by optical density measurements in early growth regulation by metabolic phenotyping (released heat rates). This protocol enables discriminating between AOX genes that inhibit growth and AOX genes that enhance growth under comparable conditions. It also allows studying dependency of AOX gene effects on gene copy number. The protocol can also be combined with laser microdissection of individual cells from target tissues for specified breeding traits.

Modeling polymorphic transformation of rotating bacterial flagella in a viscous fluid

NASA Astrophysics Data System (ADS)

Ko, William; Lim, Sookkyung; Lee, Wanho; Kim, Yongsam; Berg, Howard C.; Peskin, Charles S.

2017-06-01

The helical flagella that are attached to the cell body of bacteria such as Escherichia coli and Salmonella typhimurium allow the cell to swim in a fluid environment. These flagella are capable of polymorphic transformation in that they take on various helical shapes that differ in helical pitch, radius, and chirality. We present a mathematical model of a single flagellum described by Kirchhoff rod theory that is immersed in a fluid governed by Stokes equations. We perform numerical simulations to demonstrate two mechanisms by which polymorphic transformation can occur, as observed in experiments. First, we consider a flagellar filament attached to a rotary motor in which transformations are triggered by a reversal of the direction of motor rotation [L. Turner et al., J. Bacteriol. 182, 2793 (2000), 10.1128/JB.182.10.2793-2801.2000]. We then consider a filament that is fixed on one end and immersed in an external fluid flow [H. Hotani, J. Mol. Biol. 156, 791 (1982), 10.1016/0022-2836(82)90142-5]. The detailed dynamics of the helical flagellum interacting with a viscous fluid is discussed and comparisons with experimental and theoretical results are provided.

Polymorphism and thermodynamic ground state of silver fulminate studied from van der Waals density functional calculations

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

Yedukondalu, N.; Vaitheeswaran, G., E-mail: gvsp@uohyd.ernet.in

2014-06-14

Silver fulminate (AgCNO) is a primary explosive, which exists in two polymorphic phases, namely, orthorhombic (Cmcm) and trigonal (R3{sup ¯}) forms at ambient conditions. In the present study, we have investigated the effect of pressure and temperature on relative phase stability of the polymorphs using planewave pseudopotential approaches based on Density Functional Theory (DFT). van der Waals interactions play a significant role in predicting the phase stability and they can be effectively captured by semi-empirical dispersion correction methods in contrast to standard DFT functionals. Based on our total energy calculations using DFT-D2 method, the Cmcm structure is found to bemore » the preferred thermodynamic equilibrium phase under studied pressure and temperature range. Hitherto Cmcm and R3{sup ¯} phases denoted as α- and β-forms of AgCNO, respectively. Also a pressure induced polymorphic phase transition is seen using DFT functionals and the same was not observed with DFT-D2 method. The equation of state and compressibility of both polymorphic phases were investigated. Electronic structure and optical properties were calculated using full potential linearized augmented plane wave method within the Tran-Blaha modified Becke-Johnson potential. The calculated electronic structure shows that α, β phases are indirect bandgap insulators with a bandgap values of 3.51 and 4.43 eV, respectively. The nature of chemical bonding is analyzed through the charge density plots and partial density of states. Optical anisotropy, electric-dipole transitions, and photo sensitivity to light of the polymorphs are analyzed from the calculated optical spectra. Overall, the present study provides an early indication to experimentalists to avoid the formation of unstable β-form of AgCNO.« less

Inverted electro-mechanical behaviour induced by the irreversible domain configuration transformation in (K,Na)NbO3-based ceramics

PubMed Central

Huan, Yu; Wang, Xiaohui; Koruza, Jurij; Wang, Ke; Webber, Kyle G.; Hao, Yanan; Li, Longtu

2016-01-01

Miniaturization of domains to the nanometer scale has been previously reported in many piezoelectrics with two-phase coexistence. Despite the observation of nanoscale domain configuration near the polymorphic phase transition (PPT) regionin virgin (K0.5Na0.5)NbO3 (KNN) based ceramics, it remains unclear how this domain state responds to external loads and influences the macroscopic electro-mechanical properties. To this end, the electric-field-induced and stress-induced strain curves of KNN-based ceramics over a wide compositional range across PPT were characterized. It was found that the coercive field of the virgin samples was highest in PPT region, which was related to the inhibited domain wall motion due to the presence of nanodomains. However, the coercive field was found to be the lowest in the PPT region after electrical poling. This was related to the irreversible transformation of the nanodomains into micron-sized domains during the poling process. With the similar micron-sized domain configuration for all poled ceramics, the domains in the PPT region move more easily due to the additional polarization vectors. The results demonstrate that the poling process can give rise to the irreversible domain configuration transformation and then account for the inverted macroscopic piezoelectricity in the PPT region of KNN-based ceramics. PMID:26915972

From Trioleoyl glycerol to extra virgin olive oil through multicomponent triacylglycerol mixtures: Crystallization and polymorphic transformation examined with differential scanning calorimetry and X-ray diffration techniques.

PubMed

Bayés-García, L; Calvet, T; Cuevas-Diarte, M A; Ueno, S

2017-09-01

The polymorphic crystallization and transformation behavior of extra virgin olive oil (EVOO) was examined by using differential scanning calorimetry (DSC) and X-ray diffraction with both laboratory-scale (XRD) and synchrotron radiation source (SR-XRD). The complex behavior observed was studied by previously analyzing mixtures composed by its main 2 to 6 triacylglycerol (TAG) components. Thus, component TAGs were successively added to simulate EVOO composition, until reaching a 6 TAGs mixture, composed by trioleoyl glycerol (OOO), 1-palmitoyl-2,3-dioleoyl glycerol (POO), 1,2-dioleoyl-3-linoleoyl glycerol (OOL), 1-palmitoyl-2-oleoyl-3-linoleoyl glycerol (POL), 1,2-dipalmitoyl-3-oleoyl glycerol (PPO) and 1-stearoyl-2,3-dioleoyl glycerol (SOO). Molten samples were cooled from 25°C to -80°C at a controlled rate of 2°C/min and subsequently heated at the same rate. The polymorphic behavior observed in multicomponent TAG mixtures was interpreted by considering three main groups of TAGs with different molecular structures: triunsaturated OOO and OOL, saturated-unsaturated-unsaturated POO, POL and SOO, and saturated-saturated-unsaturated PPO. As confirmed by our previous work, TAGs belonging to the same structural group displayed a highly similar polymorphic behavior. EVOO exhibited two different β'-2L polymorphic forms (β' 2 -2L and β' 1 -2L), which transformed into β'-3L when heated. Equivalent polymorphic pathways were detected when the same experimental conditions were applied to the 6 TAG components mixture. Hence, minor components may not exert a strong influence in this case. Copyright © 2017 Elsevier Ltd. All rights reserved.

Coplanar semiconductor-metal circuitry defined on few-layer MoTe2 via polymorphic heteroepitaxy

NASA Astrophysics Data System (ADS)

Sung, Ji Ho; Heo, Hoseok; Si, Saerom; Kim, Yong Hyeon; Noh, Hyeong Rae; Song, Kyung; Kim, Juho; Lee, Chang-Soo; Seo, Seung-Young; Kim, Dong-Hwi; Kim, Hyoung Kug; Yeom, Han Woong; Kim, Tae-Hwan; Choi, Si-Young; Kim, Jun Sung; Jo, Moon-Ho

2017-11-01

Crystal polymorphism selectively stabilizes the electronic phase of atomically thin transition-metal dichalcogenides (TMDCs) as metallic or semiconducting, suggesting the potential to integrate these polymorphs as circuit components in two-dimensional electronic circuitry. Developing a selective and sequential growth strategy for such two-dimensional polymorphs in the vapour phase is a critical step in this endeavour. Here, we report on the polymorphic integration of distinct metallic (1T‧) and semiconducting (2H) MoTe2 crystals within the same atomic planes by heteroepitaxy. The realized polymorphic coplanar contact is atomically coherent, and its barrier potential is spatially tight-confined over a length of only a few nanometres, with a lowest contact barrier height of ∼25 meV. We also demonstrate the generality of our synthetic integration approach for other TMDC polymorph films with large areas.

Investigation of the effect of hydroxypropyl methylcellulose on the phase transformation and release profiles of carbamazepine-nicotinamide cocrystal.

PubMed

Li, Mingzhong; Qiu, Shi; Lu, Yan; Wang, Ke; Lai, Xiaojun; Rehan, Mohammad

2014-09-01

The aim of this work was to investigate the influence of hydroxypropyl methylcellulose (HPMC) on the phase transformation and release profile of carbamazepine-nicotinamide (CBZ-NIC) cocrystal in solution and in sustained release matrix tablets. The polymorphic transitions of the CBZ-NIC cocrystal and its crystalline properties were examined by differential scanning calorimetry (DSC), X-ray powder diffraction (XRPD), Raman spectroscopy, and scanning electron microscopy (SEM). The apparent CBZ solubility and dissolution rate of CBZ-NIC cocrystal were constant in different concentrations of HPMC solutions. In a lower percentage of HPMC in the matrix tablets, the CBZ release profile of the CBZ-NIC cocrystal was nonlinear and declined over time. With an increased HPMC content in the tablets, the CBZ-NIC cocrystal formulation showed a significantly higher CBZ release rate in comparison with the other two formulations of CBZ III and the physical mixture. Because of a significantly improved dissolution rate of the CBZ-NIC cocrystal, the rate of CBZ entering into solution is significantly faster than the rate of formation of the CBZ-HPMC soluble complex in solution, leading to a higher supersaturation level of CBZ and subsequently precipitation of CBZ dihydrate.

Investigation of polymorphic transitions of piracetam induced during wet granulation.

PubMed

Potter, Catherine B; Kollamaram, Gayathri; Zeglinski, Jacek; Whitaker, Darren A; Croker, Denise M; Walker, Gavin M

2017-10-01

Piracetam was investigated as a model API which is known to exhibit a number of different polymorphic forms. It is freely soluble in water so the possibility exists for polymorphic transformations to occur during wet granulation. Analysis of the polymorphic form present during lab-scale wet granulation, using water as a granulation liquid, was studied with powder X-ray diffraction and Raman spectroscopy as off-line and inline analysis tools respectively. Different excipients with a range of hydrophilicities, aqueous solubilities and molecular weights were investigated to examine their influence on these solution-mediated polymorphic transitions and experimental results were rationalised using molecular modelling. Our results indicated that as an increasing amount of water was added to the as-received piracetam FIII, a greater amount of the API dissolved which recrystallised upon drying to the metastable FII(6.403) via a monohydrate intermediary. Molecular level analysis revealed that the observed preferential transformation of monohydrate to FII is linked with a greater structural similarity between the monohydrate and FII polymorph in comparison to FIII. The application of Raman spectroscopy as a process analytical technology (PAT) tool to monitor the granulation process for the production of the monohydrate intermediate as a precursor to the undesirable metastable form was demonstrated. Copyright © 2017 Elsevier B.V. All rights reserved.

First-principles calculations of high-pressure iron-bearing monoclinic dolomite and single-cation carbonates with internally-consistent Hubbard U

NASA Astrophysics Data System (ADS)

Solomatova, N. V.; Asimow, P. D.

2017-12-01

It has been proposed that iron has a significant effect on the relative stability of carbonate phases at high pressures, possibly even stabilizing double-cation carbonates (e.g., dolomite) with respect to single-cation carbonates (e.g., magnesite, aragonite and siderite). X-ray diffraction experiments have shown that dolomite transforms at 35 GPa to a high-pressure polymorph that is stable to decomposition; however, there has been disagreement on the structure of the high-pressure phase [1,2]. Ab initio calculations interfaced with an evolutionary structure prediction algorithm demonstrated that a C2/c polymorph of pure CaMg(CO3)2 dolomite is more stable than previously reported structures [3]. In this study, we calculate the relative enthalpies up to 80 GPa for a set of carbonate phases including Fe-bearing solutions and endmembers, using the generalized gradient approximation and a Hubbard U parameter calculated through linear response theory to accurately characterize the electronic structure of Fe. When calculated with a constant U of 4 eV, the spin transition pressure of (Mg,Fe)CO3 agrees well with experiments, whereas an internally-consistent U overestimates the spin transition pressure by 50 GPa. However, whether we use constant or internally-consistent U values, a higher iron concentration increases the stability field of dolomite C2/c with respect to single-cation carbonate assemblages, but iron-free dolomite is not stable with respect to single-cation carbonates at any pressure. Thus, high-pressure polymorphs of Fe-bearing dolomite could in fact represent an important reservoir for carbon storage within oxidized sections of Earth's mantle. [1] Mao, Z. et al. (2011) Geophysical Research Letters, 38. [2] Merlini, M. et al. (2012) Proceedings of the National Academy of Sciences, 109, 13509-13514. [3] Solomatova, N. V. and Asimow, P. D. (2017) American Mineralogist, 102, 210-215.

Quasi-dynamic pressure and temperature initiated β<-->δ solid phase transitions in HMX

NASA Astrophysics Data System (ADS)

Zaug, Joseph M.; Farber, Daniel L.; Craig, Ian M.; Blosch, Laura L.; Shuh, David K.; Hansen, Donald W.; Aracne-Ruddle, Chantel M.

2000-04-01

The phase transformation of β-HMX (>0.5% RDX) to δ phase has been studied for over twenty years and more recently with an high-contrast optical second harmonic generation technique. Shock studies of the plastic binder composites of HMX have indicated that the transition is perhaps irreversible, a result that concurs with the static pressure results published by F. Goetz et al. [1] in 1978. However, the stability field favors the β polymorph over δ as pressure is increased (up to 5.4 GPa) along any thermodynamically reasonable isotherm. In this experiment, strict control of pressure and temperature is maintained while x-ray and optical diagnostics are applied to monitor the conformational dynamics of HMX. Unlike the temperature induced β→δ transition, the pressure induced is heterogeneous in nature. The 1 bar 25 °C δ→β transition is not immediate, occuring over tens of hours. Transition points and kinetics are path dependent and consequently this paper describes our work in progress.

Acute and chronic gregarisation are associated with distinct DNA methylation fingerprints in desert locusts.

PubMed

Mallon, Eamonn B; Amarasinghe, Harindra E; Ott, Swidbert R

2016-10-18

Desert locusts (Schistocerca gregaria) show a dramatic form of socially induced phenotypic plasticity known as phase polyphenism. In the absence of conspecifics, locusts occur in a shy and cryptic solitarious phase. Crowding with conspecifics drives a behavioural transformation towards gregariousness that occurs within hours and is followed by changes in physiology, colouration and morphology, resulting in the full gregarious phase syndrome. We analysed methylation-sensitive amplified fragment length polymorphisms (MS-AFLP) to compare the effect of acute and chronic crowding on DNA methylation in the central nervous system. We find that crowd-reared and solitary-reared locusts show markedly different neural MS-AFLP fingerprints. However, crowding for a day resulted in neural MS-AFLP fingerprints that were clearly distinct from both crowd-reared and uncrowded solitary-reared locusts. Our results indicate that changes in DNA methylation associated with behavioural gregarisation proceed through intermediate states that are not simply partial realisations of the endpoint states.

Acoustic Velocities Across the Olivine - Wadsleyite - Ringwoodite Transitions and the Seismic Signature of the 410 km Mantle Discontinuity

NASA Astrophysics Data System (ADS)

Perrillat, J. P.; Chantel, J.; Tauzin, B.; Jonfal, J.; Daniel, I.; Jing, Z.; Wang, Y.

2017-12-01

The phase changes of olivine (Mg,Fe)2SiO4 to its high pressure polymorphs, wadsleyite and ringwoodite, have long been associated with the seismic discontinuities observed at 410 and 520 km depth in the Earth's mantle. The position and thickness of these discontinuities potentially provide basic constraints on the temperature, chemical composition and water content of the mantle. A common practice is to infer these properties by comparing seismic observations with modeled velocities from equilibrium phase relations and elastic moduli of the individual phases. Here, we propose to directly measure the evolution of velocities across the olivine phase changes in order to investigate the transient, i.e. time-dependent, processes of the transformation. We developed an experimental method that combines in situ X-ray diffraction and ultrasonic interferometry to follow the elastic wave velocities as a function of reaction progress, with a time resolution of 30 s. The experiments were carried out on the 1000 t multi-anvil press of the ID-13D beamline of the APS synchrotron (Chicago, USA). Samples were sintered polycrystalline powders of olivine with XFe=0.10 and XFe=0.52 composition, that have been reacted in the stability field of wadsleyite or ringwoodite at 7-12 GPa and 1000-1200 K. Measurements show an unexpected decrease in shear waves velocity at the onset of reaction, followed by a steady increase that correlates with the percentage of transformation. This velocity anomaly is coupled with an increase in attenuation as observed from amplitudes of S-waves echoes. We interpret this softening at the early stage of transformation as the result of the presence of an intermediate spinelloid phase, as observed in the pseudo-martensitic reaction mechanism, and discuss the implication on the structure and sharpness of 410km discontinuity.

New Insights into the Diverse Electronic Phases of a Novel Vanadium Dioxide Polymorph: A Terahertz Spectroscopy Study

PubMed Central

Lourembam, James; Srivastava, Amar; La-o-vorakiat, Chan; Rotella, H.; Venkatesan, T.; Chia, Elbert E. M.

2015-01-01

A remarkable feature of vanadium dioxide is that it can be synthesized in a number of polymorphs. The conductivity mechanism in the metastable layered polymorph VO2(B) thin films has been investigated by terahertz time-domain spectroscopy (THz-TDS). In VO2(B), a critical temperature of 240 K marks the appearance of a non-zero Drude term in the observed complex conductivity, indicating the evolution from a pure insulating state towards a metallic state. In contrast, the THz conductivity of the well-known VO2(M1) is well fitted only by a modification of the Drude model to include backscattering. We also identified two different THz conductivity regimes separated by temperature in these two polymorphs. The electronic phase diagram is constructed, revealing that the width and onset of the metal-insulator transition in the B phase develop differently from the M1 phase. PMID:25777320

First principles study of pressure induced polymorphic phase transition in trimethylamine

NASA Astrophysics Data System (ADS)

Abraham, B. Moses; Vaitheeswaran, G.

2018-04-01

The pressure induced variations on the crystal structure of various polymorphs of Trimethyamine (TMA-I, TMA-II, TMAIII) has been studied theoretically using first principles calculations up to 5 GPa. The obtained equilibrium lattice parameters using standard PBE-GGA functional for the ambient and high pressure phases are found to be in good agreement with the experimental values. We calculated the enthalpies of each phase to assess their relative stability. Our results also supports the existence of additional phase transitions of TMA into two new polymorphs under external pressure. The TMA-I to TMA-II transition is found to occur at 1.41 GPa and the TMA-II to TMA-III transition at 3.33 GPa. The electronic band structure calculations using Tran Blaha-modified Becke Johnson (TB-mBJ) potential show that these polymorphs of TMA are indirect band gap insulators.

Concomitance of oncogenic HPV types, CHEK2 gene mutations, and CYP1B1 gene polymorphism as an increased risk factor for malignancy.

PubMed

Banaszkiewicz, Monika; Constantinou, Maria; Pietrusiński, Michał; Kępczyński, Lukasz; Jędrzejczyk, Adam; Rożniecki, Marek; Marks, Piotr; Kałużewski, Bogdan

2013-01-01

Urinary bladder carcinoma ranks the fourth position in malignancy incidence rates in men (6.1%) and the 17th position in women (1.6%). In general, neoplastic diseases should be approached from two perspectives: prevention with implementation of prophylactic measures and early diagnostics. Prophylactics is possible in the preclinical phase of neoplasm, being both justified and plausible in patients from high-risk groups. Thus, it is particularly important to select such groups, not only by referring to environmental carcinogenic factors (occupational and extra-occupational) but also from genetic predisposition, which may be conductive for neoplasm formation. The mutations / polymorphisms of CHEK2 and CYP1B1 genes predispose to neoplasm via multiorgan mechanisms, while the human papilloma virus (HPV) may participate in the neoplastic transformation as an environmental factor. 131 patients with diagnosed urinary bladder cancer were qualified to the study. Mutations/polymorphisms of CHEK2 (IVS2 + 1G > A gene, 1100delC, del5395, I157T) and CYP1B1- 355T/T were identified by the PCR in DNA isolated directly from the tumor and from peripheral blood. The ELISA test was used for the studies of 37 HPV genotypes in DNA, isolated tumour tissue. 11 mutations of CHEK2 gene were found, 355T/T polymorphism if CYP1B1 gene occurred in 18 patients (12.9%). Oncogenic HPV was found in 36 (29.3%), out of 123 examined patients. The concomitance of CHEK2 gene mutations or 355T/T polymorphism of CYP1B1 gene and the presence of oncogenic HPV types statistically significantly correlates with histological malignancy grades of urinary bladder carcinoma.

Semiempirical equations for modeling solid-state kinetics based on a Maxwell-Boltzmann distribution of activation energies: applications to a polymorphic transformation under crystallization slurry conditions and to the thermal decomposition of AgMnO4 crystals.

PubMed

Skrdla, Peter J; Robertson, Rebecca T

2005-06-02

Many solid-state reactions and phase transformations performed under isothermal conditions give rise to asymmetric, sigmoidally shaped conversion-time (x-t) profiles. The mathematical treatment of such curves, as well as their physical interpretation, is often challenging. In this work, the functional form of a Maxwell-Boltzmann (M-B) distribution is used to describe the distribution of activation energies for the reagent solids, which, when coupled with an integrated first-order rate expression, yields a novel semiempirical equation that may offer better success in the modeling of solid-state kinetics. In this approach, the Arrhenius equation is used to relate the distribution of activation energies to a corresponding distribution of rate constants for the individual molecules in the reagent solids. This distribution of molecular rate constants is then correlated to the (observable) reaction time in the derivation of the model equation. In addition to providing a versatile treatment for asymmetric, sigmoidal reaction curves, another key advantage of our equation over other models is that the start time of conversion is uniquely defined at t = 0. We demonstrate the ability of our simple, two-parameter equation to successfully model the experimental x-t data for the polymorphic transformation of a pharmaceutical compound under crystallization slurry (i.e., heterogeneous) conditions. Additionally, we use a modification of this equation to model the kinetics of a historically significant, homogeneous solid-state reaction: the thermal decomposition of AgMnO4 crystals. The potential broad applicability of our statistical (i.e., dispersive) kinetic approach makes it a potentially attractive alternative to existing models/approaches.

Significance of "stretched" mineral inclusions for reconstructing P- T exhumation history

NASA Astrophysics Data System (ADS)

Ashley, Kyle T.; Darling, Robert S.; Bodnar, Robert J.; Law, Richard D.

2015-06-01

Analysis of mineral inclusions in chemically and physically resistant hosts has proven to be valuable for reconstructing the P- T exhumation history of high-grade metamorphic rocks. The occurrence of cristobalite-bearing inclusions in garnets from Gore Mountain, New York, is unexpected because the peak metamorphic conditions reached are well removed (>600 °C too cold) from the stability field of this low-density silica polymorph that typically forms in high temperature volcanic environments. A previous study of samples from this area interpreted polymineralic inclusions consisting of cristobalite, albite and ilmenite as representing crystallized droplets of melt generated during a garnet-in reaction, followed by water loss from the inclusion to explain the reduction in inclusion pressure that drove the transformation of quartz to cristobalite. However, the recent discovery of monomineralic inclusions of cristobalite from the nearby Hooper Mine cannot be explained by this process. For these inclusions, we propose that the volume response to pressure and temperature changes during exhumation to Earth's surface resulted in large tensile stresses within the silica phase that would be sufficient to cause transformation to the low-density (low-pressure) form. Elastic modeling of other common inclusion-host systems suggests that this quartz-to-cristobalite example may not be a unique case. The aluminosilicate polymorph kyanite also has the capacity to retain tensile stresses if exhumed to Earth's surface after being trapped as an inclusion in plagioclase at P- T conditions within the kyanite stability field, with the stresses developed during exhumation sufficient to produce a transformation to andalusite. These results highlight the elastic environment that may arise during exhumation and provide a potential explanation of observed inclusions whose stability fields are well removed from P- T paths followed during exhumation.

A molecular dynamics study of ambient and high pressure phases of silica: structure and enthalpy variation with molar volume.

PubMed

Rajappa, Chitra; Sringeri, S Bhuvaneshwari; Subramanian, Yashonath; Gopalakrishnan, J

2014-06-28

Extensive molecular dynamics studies of 13 different silica polymorphs are reported in the isothermal-isobaric ensemble with the Parrinello-Rahman variable shape simulation cell. The van Beest-Kramer-van Santen (BKS) potential is shown to predict lattice parameters for most phases within 2%-3% accuracy, as well as the relative stabilities of different polymorphs in agreement with experiment. Enthalpies of high-density polymorphs - CaCl2-type, α-PbO2-type, and pyrite-type - for which no experimental data are available as yet, are predicted here. Further, the calculated enthalpies exhibit two distinct regimes as a function of molar volume-for low and medium-density polymorphs, it is almost independent of volume, while for high-pressure phases a steep dependence is seen. A detailed analysis indicates that the increased short-range contributions to enthalpy in the high-density phases arise not only from an increased coordination number of silicon but also shorter Si-O bond lengths. Our results indicate that amorphous phases of silica exhibit better optimization of short-range interactions than crystalline phases at the same density while the magnitude of Coulombic contributions is lower in the amorphous phase.

On the polymorphic and morphological changes of cellulose nanocrystals (CNC-I) upon mercerization and conversion to CNC-II.

PubMed

Jin, Ersuo; Guo, Jiaqi; Yang, Fang; Zhu, Yangyang; Song, Junlong; Jin, Yongcan; Rojas, Orlando J

2016-06-05

Polymorphic and morphological transformations of cellulosic materials are strongly associated to their properties and applications, especially in the case of emerging nanocelluloses. Related changes that take place upon treatment of cellulose nanocrystals (CNC) in alkaline conditions are studied here by XRD, TEM, AFM, and other techniques. The results indicate polymorphic transformation of CNC proceeds gradually in a certain range of alkali concentrations, i.e. from about 8% to 12.5% NaOH. In such transition alkali concentration, cellulose I and II allomorphs coexists. Such value and range of the transition concentration is strongly interdependent with the crystallite size of CNCs. In addition, it is distinctively lower than that for macroscopic fibers (12-15% NaOH). Transmission electron microscopy and particle sizing reveals that after mercerization CNCs tend to associate. Furthermore, TEMPO-oxidized mercerized CNC reveals the morphology of individual nanocrystal of the cellulose II type, which is composed of some interconnected granular structures. Overall, this work reveals how the polymorphism and morphology of individual CNC change in alkali conditions and sheds light onto the polymorphic transition from cellulose I to II. Copyright © 2016 Elsevier Ltd. All rights reserved.

Chemistry-driven structural alterations in short-term retrieved ceramic-on-metal hip implants: Evidence for in vivo incompatibility between ceramic and metal counterparts.

PubMed

Zhu, Wenliang; Pezzotti, Giuseppe; Boffelli, Marco; Chotanaphuti, Thanainit; Khuangsirikul, Saradej; Sugano, Nobuhiko

2017-08-01

Ceramic-on-metal (CoM) hip implants were reported to experience lower wear rates in vitro as compared to metal-on-metal (MoM) bearings, thus hinting metal-ion release at lower levels in vivo. In this article, we show a spectroscopic study of two short-term retrieval cases of zirconia-toughened alumina (ZTA) femoral heads belonging to CoM hip prostheses, which instead showed poor wear performances in vivo. Metal contamination and abnormally high fractions of tetragonal-to-monoclinic (t→m) polymorphic transformation of the zirconia phase could be found on both ZTA heads, which contrasted with the optimistic predictions of in vitro experiments. At the molecular scale, incorporation of metal ions into the ceramic lattices could be recognized as due to frictionally assisted phenomena occurring at the ceramic surface. Driven by abnormal friction, diffusion of metal ions induced lattice shrinkage in the zirconia phases, while residual stress fields became stored at the surface of the femoral head. Diffusional alterations destabilized the chemistry of the ceramic surface and resulted in an abnormal increase in t→m phase transformation in vivo. Frictionally driven metal transfer to the ceramic lattice thus hinders the in vivo performance of CoM prostheses. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 1469-1480, 2017. © 2016 Wiley Periodicals, Inc.

Using reweighting and free energy surface interpolation to predict solid-solid phase diagrams

NASA Astrophysics Data System (ADS)

Schieber, Natalie P.; Dybeck, Eric C.; Shirts, Michael R.

2018-04-01

Many physical properties of small organic molecules are dependent on the current crystal packing, or polymorph, of the material, including bioavailability of pharmaceuticals, optical properties of dyes, and charge transport properties of semiconductors. Predicting the most stable crystalline form at a given temperature and pressure requires determining the crystalline form with the lowest relative Gibbs free energy. Effective computational prediction of the most stable polymorph could save significant time and effort in the design of novel molecular crystalline solids or predict their behavior under new conditions. In this study, we introduce a new approach using multistate reweighting to address the problem of determining solid-solid phase diagrams and apply this approach to the phase diagram of solid benzene. For this approach, we perform sampling at a selection of temperature and pressure states in the region of interest. We use multistate reweighting methods to determine the reduced free energy differences between T and P states within a given polymorph and validate this phase diagram using several measures. The relative stability of the polymorphs at the sampled states can be successively interpolated from these points to create the phase diagram by combining these reduced free energy differences with a reference Gibbs free energy difference between polymorphs. The method also allows for straightforward estimation of uncertainties in the phase boundary. We also find that when properly implemented, multistate reweighting for phase diagram determination scales better with the size of the system than previously estimated.

Association of functional polymorphisms of the transforming growth factor B1 gene with survival and graft-versus-host disease after unrelated donor hematopoietic stem cell transplantation

PubMed Central

Berro, Mariano; Mayor, Neema P.; Maldonado-Torres, Hazael; Cooke, Louise; Kusminsky, Gustavo; Marsh, Steven G.E.; Madrigal, J. Alejandro; Shaw, Bronwen E.

2010-01-01

Background Many genetic factors play major roles in the outcome of hematopoietic stem cell transplants from unrelated donors. Transforming growth factor β1 is a member of a highly pleiotrophic family of growth factors involved in the regulation of numerous immunomodulatory processes. Design and Methods We investigated the impact of single nucleotide polymorphisms at codons 10 and 25 of TGFB1, the gene encoding for transforming growth factor β1, on outcomes in 427 mye-loablative-conditioned transplanted patients. In addition, transforming growth factor β1 plasma levels were measured in 263 patients and 327 donors. Results Patients homozygous for the single nucleotide polymorphism at codon 10 had increased non-relapse mortality (at 3 years: 46.8% versus 29.4%, P=0.014) and reduced overall survival (at 5 years 29.3% versus 42.2%, P=0.013); the differences remained statistically significant in multivariate analysis. Donor genotype alone had no impact, although multiple single nucleotide polymorphisms within the pair were significantly associated with higher non-relapse mortality (at 3 years: 44% versus 29%, P=0.021) and decreased overall survival (at 5 years: 33.8% versus 41.9%, P=0.033). In the 10/10 HLA matched transplants (n=280), recipients of non-wild type grafts tended to have a higher incidence of acute graft-versus-host disease grades II-IV (P=0.052). In multivariate analysis, when analyzed with patients’ genotype, the incidences of both overall and grades II-IV acute graft-versus-host disease were increased (P=0.025 and P=0.009, respectively) in non-wild-type pairs. Conclusions We conclude that increasing numbers of single nucleotide polymorphisms in codon 10 of TGFB1 in patients and donors are associated with a worse outcome following hematopoietic stem cell transplantation from unrelated donors. PMID:19713222

Glass polymorphism in glycerol–water mixtures: II. Experimental studies

PubMed Central

Bachler, Johannes; Fuentes-Landete, Violeta; Jahn, David A.; Wong, Jessina; Giovambattista, Nicolas

2016-01-01

We report a detailed experimental study of (i) pressure-induced transformations in glycerol–water mixtures at T = 77 K and P = 0–1.8 GPa, and (ii) heating-induced transformations of glycerol–water mixtures recovered at 1 atm and T = 77 K. Our samples are prepared by cooling the solutions at ambient pressure at various cooling rates (100 K s–1–10 K h–1) and for the whole range of glycerol mole fractions, χ g. Depending on concentration and cooling rates, cooling leads to samples containing amorphous ice (χ g ≥ 0.20), ice (χ g ≤ 0.32), and/or “distorted ice” (0 < χ g ≤ 0.38). Upon compression, we find that (a) fully vitrified samples at χ g ≥ 0.20 do not show glass polymorphism, in agreement with previous works; (b) samples containing ice show pressure-induced amorphization (PIA) leading to the formation of high-density amorphous ice (HDA). PIA of ice domains within the glycerol–water mixtures is shown to be possible only up to χ g ≈ 0.32 (T = 77 K). This is rather surprising since it has been known that at χ g < 0.38, cooling leads to phase-separated samples with ice and maximally freeze-concentrated solution of χ g ≈ 0.38. Accordingly, in the range 0.32 < χ g < 0.38, we suggest that the water domains freeze into an interfacial ice, i.e., a highly-distorted form of layered ice, which is unable to transform to HDA upon compression. Upon heating samples recovered at 1 atm, we observe a rich phase behavior. Differential scanning calorimetry indicates that only at χ g ≤ 0.15, the water domains within the sample exhibit polyamorphism, i.e., the HDA-to-LDA (low-density amorphous ice) transformation. At 0.15 < χ g ≤ 0.38, samples contain ice, interfacial ice, and/or HDA domains. All samples (χ g ≤ 0.38) show: the crystallization of amorphous ice domains, followed by the glass transition of the vitrified glycerol–water domains and, finally, the melting of ice at high temperatures. Our work exemplifies the complex “phase” behavior of glassy binary mixtures due to phase-separation (ice formation) and polyamorphism, and the relevance of sample preparation, concentration as well as cooling rates. The presence of the distorted ice (called “interphase” by us) also explains the debated “drift anomaly” upon melting. These results are compatible with the high-pressure study by Suzuki and Mishima indicating disappearance of polyamorphism at P ≈ 0.03–0.05 GPa at χ g ≈ 0.12–0.15 [J. Chem. Phys., 2014, 141, 094505]. PMID:27044677

The Pressure-Temperature Phase Diagram of Metacetamol and Its Comparison to the Phase Diagram of Paracetamol.

PubMed

Barrio, Maria; Huguet, Judit; Rietveld, Ivo B; Robert, Benoît; Céolin, René; Tamarit, Josep-Lluis

2017-06-01

Understanding the polymorphic behavior of active pharmaceutical ingredients is important for formulation purposes and regulatory reasons. Metacetamol is an isomer of paracetamol and it similarly exhibits polymorphism. In the present article, it has been found that one of the polymorphs of metacetamol is only stable under increased pressure, which has led to the conclusion that metacetamol like paracetamol is a monotropic system under ordinary (= laboratory) conditions and that it becomes enantiotropic under pressure with the I-II-L triple point coordinates for metacetamol T I-II-L  = 535 ± 10 K and P I-II-L  = 692 ± 70 MPa. However, whereas for paracetamol the enantiotropy under pressure can be foreseen, because the metastable polymorph is denser, in the case of metacetamol this is not possible, as the metastable polymorph is less dense than the stable one. The existence of the stability domain for the less dense polymorph of metacetamol can only be demonstrated by the construction of the topological phase diagram as presented in this article. It is a delicate interplay between the specific volume differences and the enthalpy differences causing the stability domain of the less dense polymorph to be sandwiched between the denser polymorph and the liquid. Metacetamol shares this behavior with bicalutamide and fluoxetine nitrate. Copyright © 2017 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Metastable mantle phase transformations and deep earthquakes in subducting oceanic lithosphere

NASA Astrophysics Data System (ADS)

Kirby, Stephen H.; Stein, Seth; Okal, Emile A.; Rubie, David C.

1996-05-01

Earth's deepest earthquakes occur as a population in subducting or previously subducted lithosphere at depths ranging from about 325 to 690 km. This depth interval closely brackets the mantle transition zone, characterized by rapid seismic velocity increases resulting from the transformation of upper mantle minerals to higher-pressure phases. Deep earthquakes thus provide the primary direct evidence for subduction of the lithosphere to these depths and allow us to investigate the deep thermal, thermodynamic, and mechanical ferment inside slabs. Numerical simulations of reaction rates show that the olivine → spinel transformation should be kinetically hindered in old, cold slabs descending into the transition zone. Thus wedge-shaped zones of metastable peridotite probably persist to depths of more than 600 km. Laboratory deformation experiments on some metastable minerals display a shear instability called transformational faulting. This instability involves sudden failure by localized superplasticity in thin shear zones where the metastable host mineral transforms to a denser, finer-grained phase. Hence in cold slabs, such faulting is expected for the polymorphic reactions in which olivine transforms to the spinel structure and clinoenstatite transforms to ilmenite. It is thus natural to hypothesize that deep earthquakes result from transformational faulting in metastable peridotite wedges within cold slabs. This consideration of the mineralogical states of slabs augments the traditional largely thermal view of slab processes and explains some previously enigmatic slab features. It explains why deep seismicity occurs only in the approximate depth range of the mantle transition zone, where minerals in downgoing slabs should transform to spinel and ilmenite structures. The onset of deep shocks at about 325 km is consistent with the onset of metastability near the equilibrium phase boundary in the slab. Even if a slab penetrates into the lower mantle, earthquakes should cease at depths near 700 km, because the seismogenic phase transformations in the slab are completed or can no longer occur. Substantial metastability is expected only in old, cold slabs, consistent with the observed restriction of deep earthquakes to those settings. Earthquakes should be restricted to the cold cores of slabs, as in any model in which the seismicity is temperature controlled, via the distribution of metastability. However, the geometries of recent large deep earthquakes pose a challenge for any such models. Transformational faulting may give insight into why deep shocks lack appreciable aftershocks and why their source characteristics, including focal mechanisms indicating localized shear failure rather than implosive deformation, are so similar to those of shallow earthquakes. Finally, metastable phase changes in slabs would produce an internal source of stress in addition to those due to the weight of the sinking slab. Such internal stresses may explain the occurrence of earthquakes in portions of lithosphere which have foundered to the bottom of the transition zone and/or are detached from subducting slabs. Metastability in downgoing slabs could have considerable geodynamic significance. Metastable wedges would reduce the negative buoyancy of slabs, decrease the driving force for subduction, and influence the state of stress in slabs. Heat released by metastable phase changes would raise temperatures within slabs and facilitate the transformation of spinel to the lower mantle mineral assemblage, causing slabs to equilibrate more rapidly with the ambient mantle and thus contribute to the cessation of deep seismicity. Because wedge formation should occur only for fast subducting slabs, it may act as a "parachute" and contribute to regulating plate speeds. Wedge formation would also have consequences for mantle evolution because the density of a slab stagnated near the bottom of the transition zone would increase as it heats up and the wedge transforms to denser spinel, favoring the subsequent sinking of the slab into the lower mantle.

Electrostatic control of phospholipid polymorphism.

PubMed

Tarahovsky, Y S; Arsenault, A L; MacDonald, R C; McIntosh, T J; Epand, R M

2000-12-01

A regular progression of polymorphic phase behavior was observed for mixtures of the anionic phospholipid, cardiolipin, and the cationic phospholipid derivative, 1, 2-dioleoyl-sn-glycero-3-ethylphosphocholine. As revealed by freeze-fracture electron microscopy and small-angle x-ray diffraction, whereas the two lipids separately assume only lamellar phases, their mixtures exhibit a symmetrical (depending on charge ratio and not polarity) sequence of nonlamellar phases. The inverted hexagonal phase, H(II,) formed from equimolar mixtures of the two lipids, i.e., at net charge neutrality (charge ratio (CR((+/-))) = 1:1). When one type of lipid was in significant excess (CR((+/-)) = 2:1 or CR((+/-)) = 1:2), a bicontinuous cubic structure was observed. These cubic phases were very similar to those sometimes present in cellular organelles that contain cardiolipin. Increasing the excess of cationic or anionic charge to CR((+/-)) = 4:1 or CR((+/-)) = 1:4 led to the appearance of membrane bilayers with numerous interlamellar contacts, i.e., sponge structures. It is evident that interactions between cationic and anionic moieties can influence the packing of polar heads and hence control polymorphic phase transitions. The facile isothermal, polymorphic interconversion of these lipids may have important biological and technical implications.

Thermodynamic Investigation of Carbamazepine-Saccharin Co-Crystal Polymorphs.

PubMed

Pagire, Sudhir K; Jadav, Niten; Vangala, Venu R; Whiteside, Benjamin; Paradkar, Anant

2017-08-01

Polymorphism in active pharmaceutical ingredients can be regarded as critical for the potential that crystal form can have on the quality, efficacy, and safety of the final drug product. The current contribution aims to characterize thermodynamic interrelationship of a dimorphic co-crystal, FI and FII, involving carbamazepine (CBZ) and saccharin (SAC) molecules. Supramolecular synthesis of CBZ-SAC FI and FII has been performed using thermokinetic methods and systematically characterized by differential scanning calorimetry, powder X-ray diffraction, solubility, and slurry measurements. According to the heat of fusion rule by Burger and Ramberger, FI (ΔH fus  = 121.1 J/g; melting point, 172.5°C) and FII (ΔH fus  = 110.3 J/g; melting point, 164.7°C) are monotropically related. The solubility and van't Hoff plot results suggest FI stable and FII metastable forms. This study reveals that CBZ-SAC co-crystal phases, FI or FII, could be stable to heat-induced stresses; however, FII converts to FI during solution-mediated transformation. Copyright © 2017 The Authors. Published by Elsevier Inc. All rights reserved.

Rivastigmine hydrogen tartrate polymorphs: Solid-state characterisation of transition and polymorphic conversion via milling

NASA Astrophysics Data System (ADS)

Amaro, Maria Inês; Simon, Alice; Cabral, Lúcio Mendes; de Sousa, Valéria Pereira; Healy, Anne Marie

2015-11-01

Rivastigmine (RHT) is an active pharmaceutical ingredient that is used for the treatment of mild to moderately severe dementia in Alzheimer's disease, and is known to present two polymorphic forms and to amorphise upon granulation. To date there is no information in the scientific or patent literature on polymorphic transition and stability. Hence, the aim of the current study was to gain a fundamental understanding of the polymorphic forms by (1) evaluating RHT thermodynamic stability (monotropy or enantiotropy) and (2) investigating the potential for polymorphic transformation upon milling. The two polymorphic and amorphous forms were characterised using X-ray powder diffractometry, thermal analyses, infra-red spectroscopy and water sorption analysis. The polymorphic transition was found to be spontaneous (ΔG0 < 0) and exothermic (ΔH0 < 0), indicative of a monotropic polymorph pair. The kinetic studies showed a fast initial polymorphic transition characterised by a heterogeneous nucleation, followed by a slow crystal growth. Ball milling can be used to promote the polymorphic transition and for the production of RHT amorphous form.

Composition and formations conditions of andalusite-kyanite-sillimanite pegmatoid segregstions in metamorphic rocks of the Tseel block (Mongolian Altai)

NASA Astrophysics Data System (ADS)

Sukhorukov, Vasiliy

2010-05-01

Quartz veins and pegmatoid segregations containing polymorphous Al2SiO5 modifications often occur in metamorphic complexes. Metapelites abound in various combinations of two Al2SiO5 polymorphs, e.g., andalusite + sillimanite and sillimanite + kyanite (Kerrick, 1990). Rocks with three polymorphs are much scarcer; they result from subsequent crystallization during progressive metamorphism or combined regional and contact metamorphism or from metastable crystallization (Kerrick, 1990). Study of veins containing various Al2SiO5 modifications can give insight into the PT-conditions of metamorphism and their temporal changes. The Tsel block is localized in the basins of the Tseliyn, Hudjertiyn, Sharin, and Deresetuin Rivers and is part of the Hercynides structure on the southern flank of Mongolian Altay. Pegmatoid segregations containing polymorphous Al2SiO5 modifications were discovered in the vicinity of the western contact of one of the largest basic-rock massifs, Buren-Hairhan.They are hosted by schists bearing paragenesis Bt + Ms + St + Grt + Ky + Sill + And + Fibr + Pl + Qtz. Visual examination of the pegmatoid segregations showed the presence of large (up to 4-5 cm) mineral aggregates —kyanite pseudomorphs developed after andalusite. They are prismatic, with rhombic sections, and are composed of chaotically arranged kyanite crystals with irregular-shaped andalusite relics between them. The samples also contain large (1 cm) muscovite plates localized between the pseudomorphs as well as quartz grains. The pegmatoid segregations bear the following mineral assemblage: And + Ky + Sil + Fibr + Ms + Qtz + Pl + St +Grt + Bt. Predominant minerals are Al2SiO5 polymorphs (30-50 vol.%), muscovite (30-60 vol.%), and quartz (up to 20 vol.%). Biotite and plagioclase are present in small amounts; staurolite and garnet are occasional. Based on the observed mineral correlations, the following sequence of formation of Al2SiO5 polymorphs has been established: First, andalusite was replaced by kyanite to form pseudomorphs; then, fibrolite was produced, which, in turn, gave way to prismatic sillimanite. The fact that fibrolite formed after kyanite is proved by its presence in muscovite developed after the latter mineral. Sillimanite was, most likely, produced later than or synchronously with large muscovite replacing andalusite grains and kyanite pseudomorphs developed after andalusite. 2. Though the estimated P and T values are close to those of the triple point (Pattison, 1992), the studied rocks bear evidence for the replacement of andalusite by kyanite and sillimanite. The mineral assemblages pointing to the kyanitesillimanite type of metamorphism of the host rocks and the presence of andalusite relics in the latter suggest that the andalusite formed during earlier metamorphic events. This polymorph formation sequence agrees with Kozakov's (1986) data on change of the regional metamorphism from andalusite-sillimanite to kyanite-sillimanite one. 3. The great amounts of muscovite in veins containing Al2SiO5 polymorphs and its presence at phase contacts suggest a great role of muscovite in the phase transitions between different polymorphs. Since phases other than Al2SiO5 and muscovite are present in negligible amounts, it is not ruled out that the polymorphs were transformed by the ion exchange mechanism (Carmichael, 1969). 1. Carmichael, D.M., 1969. On the mechanism of prograde metamorphic reaction in quartz-bearing pelitic rocks. Contr. Miner. Petrol. 20, 244-267. 2. Kerrick, D.M., 1990. The Al2SiO5 polymorphs. Rev. Miner. 22, p. 406. 3. Kozakov, I.K., 1986. Precambrian infrastructure complexes of Mongolia [in Russian]. Nauka, Leningrad. 4. Pattison, D.R.M., 1992. Stability of andalusite and sillimanite and the Al2SiO5 triple point: constraints from the Ballachulish aureole, Scotland. J. Geol. 100, 423-446.

Phase transformation upon cooling path in Ca2SiO4: Possible geological implication

NASA Astrophysics Data System (ADS)

Chang, Yun-Ting; Kung, Jennifer; Hsu, Han

2016-04-01

At the contact metamorphism zone two different Ca2SiO4 phases can be found; calcio-olivine (γ phase) and larnite (β phase). In-situ experiments illustrated the existence of five various polymorphs in Ca2SiO4, i.e., α, α'H, α'L, β and γ. The path of phase transformation and the transformation temperatures are shown as follows. γ → α'L(700° C) → α'H(1100° C) → α (1450° C) α'L → β (680° C) → γ (500° C) Experiments showed that the phase transitions at lower temperature is not reversible and seemed to be complicated; β phase is only stable from 500° C to 680° C upon cooling. To understand the possible mechanism of the β phase being metastable at room temperature, atmosphere condition, we were motivated to investigate the route of phase transition in Ca2SiO4 in different thermal process. Powder samples were synthesized by the solid-state reaction. Pure reagent oxides CaCO3 and SiO2 were mixed in 2:1 stoichiometric mole. Two control factors were designated in the experiments; the sintering temperature of starting materials and the cooling path. The sintering temperature was set within the range of stable phase field of α'L phase (˜900° C) and α'H phase (1300° C). The cooling process was designed in three different routes: 1) the quenched procedure from sintering temperature with rate of 900° C/min and 1300° C/min, 2) the furnace cooling procedure, 3) set a slow cooling rate (0.265 ° C/min). The products were examined for the crystal structure by X-ray powder diffraction. First-principle calculation was also applied to investigate the thermodynamic properties of α'H, β and γ phases. A major finding in this study showed that the γ phase presented in the final product when the sintering temperature was set at the stable field of α'H phase; on the other hand, the β phase would present when the sintering temperature was set within the field of α'L phase. It was noted that the existing phase in the product would be modified by the cooling procedures. Our calculation indicates the enthalpy of beta phase was slightly higher than that of the gamma phase at zero pressure, verifying the metastable β phase observed in the natural. In this meeting we present the detailed experimental results and discuss the potential implication for the thermal history of geological setting using the phase transition path upon cooling of Ca2SiO4.

Disorder-induced amorphization

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

Lam, N.Q.; Okamoto, P.R.; Li, Mo

1997-03-01

Many crystalline materials undergo a crystalline-to-amorphous (c-a) phase transition when subjected to energetic particle irradiation at low temperatures. By focusing on the mean-square static atomic displacement as a generic measure of chemical and topological disorder, we are led quite naturally to a generalized version of the Lindemann melting criterion as a conceptual framework for a unified thermodynamic approach to solid-state amorphizing transformations. In its simplest form, the generalized Lindemann criterion assumes that the sum of the static and dynamic mean-square atomic displacements is constant along the polymorphous melting curve so that c-a transformations can be understood simply as melting ofmore » a critically-disordered crystal at temperatures below the glass transition temperature where the supercooled liquid can persist indefinitely in a configurationally-frozen state. Evidence in support of the generalized Lindemann melting criterion for amorphization is provided by a large variety of experimental observations and by molecular dynamics simulations of heat-induced melting and of defect-induced amorphization of intermetallic compounds.« less

Metastable mantle phase transformations and deep earthquakes in subducting oceanic lithosphere

USGS Publications Warehouse

Kirby, S.H.; Stein, S.; Okal, E.A.; Rubie, David C.

1996-01-01

Earth's deepest earthquakes occur as a population in subducting or previously subducted lithosphere at depths ranging from about 325 to 690 km. This depth interval closely brackets the mantle transition zone, characterized by rapid seismic velocity increases resulting from the transformation of upper mantle minerals to higher-pressure phases. Deep earthquakes thus provide the primary direct evidence for subduction of the lithosphere to these depths and allow us to investigate the deep thermal, thermodynamic, and mechanical ferment inside slabs. Numerical simulations of reaction rates show that the olivine ??? spinel transformation should be kinetically hindered in old, cold slabs descending into the transition zone. Thus wedge-shaped zones of metastable peridotite probably persist to depths of more than 600 km. Laboratory deformation experiments on some metastable minerals display a shear instability called transformational faulting. This instability involves sudden failure by localized superplasticity in thin shear zones where the metastable host mineral transforms to a denser, finer-grained phase. Hence in cold slabs, such faulting is expected for the polymorphic reactions in which olivine transforms to the spinel structure and clinoenstatite transforms to ilmenite. It is thus natural to hypothesize that deep earthquakes result from transformational faulting in metastable peridotite wedges within cold slabs. This consideration of the mineralogical states of slabs augments the traditional largely thermal view of slab processes and explains some previously enigmatic slab features. It explains why deep seismicity occurs only in the approximate depth range of the mantle transition zone, where minerals in downgoing slabs should transform to spinel and ilmenite structures. The onset of deep shocks at about 325 km is consistent with the onset of metastability near the equilibrium phase boundary in the slab. Even if a slab penetrates into the lower mantle, earthquakes should cease at depths near 700 km, because the seismogenic phase transformations in the slab are completed or can no longer occur. Substantial metastability is expected only in old, cold slabs, consistent with the observed restriction of deep earthquakes to those settings. Earthquakes should be restricted to the cold cores of slabs, as in any model in which the seismicity is temperature controlled, via the distribution of metastability. However, the geometries of recent large deep earthquakes pose a challenge for any such models. Transformational faulting may give insight into why deep shocks lack appreciable aftershocks and why their source characteristics, including focal mechanisms indicating localized shear failure rather than implosive deformation, are so similar to those of shallow earthquakes. Finally, metastable phase changes in slabs would produce an internal source of stress in addition to those due to the weight of the sinking slab. Such internal stresses may explain the occurrence of earthquakes in portions of lithosphere which have foundered to the bottom of the transition zone and/or are detached from subducting slabs. Metastability in downgoing slabs could have considerable geodynamic significance. Metastable wedges would reduce the negative buoyancy of slabs, decrease the driving force for subduction, and influence the state of stress in slabs. Heat released by metastable phase changes would raise temperatures within slabs and facilitate the transformation of spinel to the lower mantle mineral assemblage, causing slabs to equilibrate more rapidly with the ambient mantle and thus contribute to the cessation of deep seismicity. Because wedge formation should occur only for fast subducting slabs, it may act as a "parachute" and contribute to regulating plate speeds. Wedge formation would also have consequences for mantle evolution because the density of a slab stagnated near the bottom of the transition zone would increase as it heats up and the wedge tra

Understanding Polymorphism Formation in Electrospun Fibers of Immiscible Poly(vinylidene fluoride) Blends

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

G Zhong; L Zhang; R Su

2011-12-31

Effects of electric poling, mechanical stretching, and dipolar interaction on the formation of ferroelectric ({beta} and/or {gamma}) phases in poly(vinylidene fluoride) (PVDF) have been studied in electrospun fibers of PVDF/polyacrylonitrile (PAN) and PVDF/polysulfone (PSF) blends with PVDF as the minor component, using wide-angle X-ray diffraction and Fourier transform infrared techniques. Experimental results of as-electrospun neat PVDF fibers (beaded vs. bead-free) showed that mechanical stretching during electrospinning, rather than electric poling, was effective to induce ferroelectric phases. For as-electrospun PVDF blend fibers with the non-polar PSF matrix, mechanical stretching during electrospinning again was capable of inducing some ferroelectric phases in additionmore » to the major paraelectric ({alpha}) phase. However, after removing the mechanical stretching in a confined melt-recrystallization process, only the paraelectric phase was obtained. For as-electrospun PVDF blend fibers with the polar (or ferroelectric) PAN matrix, strong intermolecular interactions between polar PAN and PVDF played an important role in the ferroelectric phase formation in addition to the mechanical stretching effect during electrospinning. Even after the removal of mechanical stretching through the confined melt-recrystallization process, a significant amount of ferroelectric phases persisted. Comparing the ferroelectric phase formation between PVDF/PSF and PVDF/PAN blend fibers, we concluded that the local electric field-dipole interactions were the determining factor for the nucleation and growth of polar PVDF phases.« less

In Situ Monitoring and Modeling of the Solution-Mediated Polymorphic Transformation of Rifampicin: From Form II to Form I.

PubMed

Guo, Nannan; Hou, Baohong; Wang, Na; Xiao, Yan; Huang, Jingjing; Guo, Yanmei; Zong, Shuyi; Hao, Hongxun

2018-01-01

In this article, the solution-mediated polymorphic transformation of rifampicin was investigated and simulated in 3 solvents at 30°C. The solid-state form I and form II of rifampicin was characterized by powder X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, Raman spectroscopy, and Fourier transform infrared spectroscopy (FTIR). To explore the relative stability, solubility data of form I and form II of rifampicin in butan-1-ol were determined using a dynamical method. In addition, Raman spectroscopy and focused beam reflectance measurement were used to in situ monitor the transformation of rifampicin from form II to form I. The liquid state concentration of rifampicin was measured by UV spectroscopic method. To investigate the effect of solvent on transformation, the transformation experiments were carried out in 3 solvents. Furthermore, a mathematical model was built to describe the kinetics of dissolution, nucleation, and growth processes during transformation by using experimental data. By combination of experimental and simulation results, it was found that the transformation process of rifampicin is controlled by dissolution of form II in heptane, whereas the transformation in hexane and octane was firstly controlled by dissolution of solid-state form and then controlled by growth of form I. Copyright © 2018 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Use of in situ FT-Raman spectroscopy to study the kinetics of the transformation of carbamazepine polymorphs.

PubMed

O'Brien, Laura E; Timmins, Peter; Williams, Adrian C; York, Peter

2004-10-29

The solid-state transformation of carbamazepine from form III to form I was examined by Fourier Transform Raman spectroscopy. Using a novel environmental chamber, the isothermal conversion was monitored in situ at 130 degrees C, 138 degrees C, 140 degrees C and 150 degrees C. The rate of transformation was monitored by taking the relative intensities of peaks arising from two CH bending modes; this approach minimised errors due to thermal artefacts and variations in power intensities or scattering efficiencies from the samples in which crystal habit changed from a characteristic prism morphology (form III) to whiskers (form I). The solid-state transformation at the different temperatures was fitted to various solid-state kinetic models of which four gave good fits, thus indicating the complexity of the process which is known to occur via a solid-gas-solid mechanism. Arrhenius plots from the kinetic models yielded activation energies from 344 kJ mol(-1) to 368 kJ mol(-1) for the transformation. The study demonstrates the value of a rapid in situ analysis of drug polymorphic type which can be of value for at-line in-process control.

High-pressure polymorphism of Pb F 2 to 75 GPa

DOE PAGES

Stan, Camelia V.; Dutta, Rajkrishna; White, Claire E.; ...

2016-07-06

Lead fluoride, PbF 2, was investigated experimentally in the laser-heated diamond anvil cell by x-ray diffraction to pressures of 75 GPa at room temperature and to 64.5 GPa and 2430 K, as well as through first-principles density functional theory calculations up to 70 GPa. During room temperature compression, no discontinuous changes in the x-ray diffraction pattern or volume were observed, but the lattice parameters displayed highly anomalous trends between 10-22 GPa with enhanced compressibility along the a direction and reduced or even negative compressibility along b and c. Theoretical calculations of valence electron densities at 22 GPa showed that α-PbFmore » 2 underwent a pressure-induced isosymmetric phase transition to a postcotunnite Co 2Si structure and also revealed the detailed atomic rearrangements associated with the development of an extra Pb-F bond in the high-pressure phase. Our x-ray results and theoretical calculations are consistent with an isosymmetric phase transition smoothly occurring over 10-22 GPa rather than abruptly as previously suggested. The characteristic values for the cell constants a/c and (a+c)/b, which are used to distinguish among cotunnite-, Co 2Si-, and Ni 2In-type phases, require modification based on our results. An equation of state fit yields a bulk modulus, K 0, of 72(3) GPa for the cotunnite-type, and an ambient-pressure volume, V 0, of 182(2)Å 3, and K 0=81(4)GPa for the Co 2Si-type phase when fixing the pressure derivative of the bulk modulus, K 0'=4. Upon heating above 1200 K at pressures at or above 25.9 GPa, PbF 2 partially transformed to the hexagonal Ni 2In-type phase but wholly or partially reverted back to Co 2Si-type phase upon temperature quench. From 43-65 GPa, nearly complete transformation to the Ni 2In-type PbF 2 was observed at high temperature, but the material partially transformed back to the orthorhombic phase upon temperature quench. Our results show that high-pressure behavior of PbF 2 is distinct from that of the alkaline earth fluorides with similar ionic radii. These results also have relevance to understanding the behavior of lanthanide and actinide dioxides, which have been predicted theoretically to exhibit similar isosymmetric transitions at Mbar pressures.« less

High-pressure polymorphism of Pb F2 to 75 GPa

NASA Astrophysics Data System (ADS)

Stan, Camelia V.; Dutta, Rajkrishna; White, Claire E.; Prakapenka, Vitali; Duffy, Thomas S.

2016-07-01

Lead fluoride, Pb F2 , was investigated experimentally in the laser-heated diamond anvil cell by x-ray diffraction to pressures of 75 GPa at room temperature and to 64.5 GPa and 2430 K, as well as through first-principles density functional theory calculations up to 70 GPa. During room temperature compression, no discontinuous changes in the x-ray diffraction pattern or volume were observed, but the lattice parameters displayed highly anomalous trends between 10-22 GPa with enhanced compressibility along the a direction and reduced or even negative compressibility along b and c . Theoretical calculations of valence electron densities at 22 GPa showed that α -Pb F2 underwent a pressure-induced isosymmetric phase transition to a postcotunnite C o2Si structure and also revealed the detailed atomic rearrangements associated with the development of an extra Pb-F bond in the high-pressure phase. Our x-ray results and theoretical calculations are consistent with an isosymmetric phase transition smoothly occurring over 10-22 GPa rather than abruptly as previously suggested. The characteristic values for the cell constants a /c and (a +c )/b , which are used to distinguish among cotunnite-, C o2Si -, and N i2In -type phases, require modification based on our results. An equation of state fit yields a bulk modulus, K0, of 72(3) GPa for the cotunnite-type, and an ambient-pressure volume, V0, of 182 (2 ) Å3 , and K0=81 (4 ) GPa for the C o2Si -type phase when fixing the pressure derivative of the bulk modulus, K0 '=4 . Upon heating above 1200 K at pressures at or above 25.9 GPa, Pb F2 partially transformed to the hexagonal N i2In -type phase but wholly or partially reverted back to C o2Si -type phase upon temperature quench. From 43-65 GPa, nearly complete transformation to the N i2In -type Pb F2 was observed at high temperature, but the material partially transformed back to the orthorhombic phase upon temperature quench. Our results show that high-pressure behavior of Pb F2 is distinct from that of the alkaline earth fluorides with similar ionic radii. Our results also have relevance to understanding the behavior of lanthanide and actinide dioxides, which have been predicted theoretically to exhibit similar isosymmetric transitions at Mbar pressures.

Inherited Variation in Cytokine, Acute Phase Response, and Calcium Metabolism Genes Affects Susceptibility to Infective Endocarditis

PubMed Central

Rutkovskaya, Natalia V.; Kondyukova, Natalia V.; Odarenko, Yuri N.; Kazachek, Yana V.; Tsepokina, Anna V.; Barbarash, Leonid S.

2017-01-01

Infective endocarditis (IE) is a septic inflammation of the endocardium. Recognition of microbial patterns, cytokine and acute phase responses, hemostasis features, and alterations in plasma lipid and calcium profile all have been reported to affect pathogenesis and clinical course of IE. Having recruited 123 patients with IE and 300 age-, sex-, and ethnicity-matched healthy blood donors, we profiled their genomic DNA for 35 functionally significant polymorphisms within the 22 selected genes involved in the abovementioned pathways, with the further genetic association analysis. We found that the G/A genotype of the rs1143634 polymorphism within the IL1B gene, the G/T genotype of the rs3212227 polymorphism within the IL12B gene, the A/G genotype of the rs1130864 polymorphism within the CRP gene, and the G allele of the rs1801197 polymorphism within the CALCR gene were associated with a decreased risk of IE whereas the T/T genotype of the rs1205 polymorphism within the CRP gene was associated with a higher risk of IE. Furthermore, heterozygous genotypes of the rs1143634 and rs3212227 polymorphisms were associated with the higher plasma levels of IL-1β and IL-12, respectively. Our results indicate that inherited variation in the cytokine, acute phase response, and calcium metabolism pathways may be linked to IE. PMID:28659664

Genome-wide gene-asbestos exposure interaction association study identifies a common susceptibility variant on 22q13.31 associated with lung cancer risk

PubMed Central

Liu, Chen-yu; Stücker, Isabelle; Chen, Chu; Goodman, Gary; McHugh, Michelle K.; D’Amelio, Anthony M.; Etzel, Carol J.; Li, Su; Lin, Xihong; Christiani, David C.

2015-01-01

Background Occupational asbestos exposure has been found to increase lung cancer risk in epidemiological studies. Methods We conducted an asbestos exposure-gene interaction analyses among several Caucasian populations who were current or ex-smokers. The discovery phase included 833 Caucasian cases and 739 Caucasian controls, and used a genome-wide association study (GWAS) to identify single nucleotide polymorphisms (SNPs) with gene-asbestos interaction effects. The top ranked SNPs from the discovery phase were replicated within the International Lung and Cancer Consortium (ILCCO). First, in silico replication was conducted in those groups that had GWAS and asbestos exposure data, including 1,548 cases and 1,527 controls. This step was followed by de novo genotyping to replicate the results from the in silico replication, and included 1,539 cases and 1,761 controls. Multiple logistic regression was used to assess the SNP-asbestos exposure interaction effects on lung cancer risk. Results We observed significantly increased lung cancer risk among MIRLET7BHG (MIRLET7B host gene located at 22q13.31) polymorphisms rs13053856, rs11090910, rs11703832, and rs12170325 heterozygous and homozygous variant allele(s) carriers [p<5×10−7 by likelihood ratio test; df=1]. Among the heterozygous and homozygous variant allele(s) carriers of polymorphisms rs13053856, rs11090910, rs11703832, and rs12170325, each unit increase in the natural log-transformed asbestos exposure score was associated with age-, sex-, smoking status- and center-adjusted ORs of 1.34 (95%CI=1.18–1.51), 1.24 (95%CI=1.14–1.35), 1.28 (95%CI=1.17–1.40), and 1.26 (95%CI=1.15–1.38), respectively for lung cancer risk. Conclusion Our findings suggest that MIRLET7BHG polymorphisms may be important predictive markers for asbestos exposure-related lung cancer. Impact To our knowledge, our study is the first report using a systematic genome-wide analysis in combination with detailed asbestos exposure data and replication to evaluate asbestos-associated lung cancer risk. PMID:26199339

Altering the Polymorphic Accessibility of Polycyclic Aromatic Hydrocarbons with Fluorination

DOE PAGES

Hiszpanski, Anna M.; Woll, Arthur R.; Kim, Bumjung; ...

2017-04-25

Here, substituting hydrogen with fluorine is an extensively employed strategy to improve the macroscopic properties of compounds for use in fields as diverse as pharmaceutics and optoelectronics. The role fluorine substitution plays on polymorphism—the ability of a compound to adopt more than one crystal structure—has not been previously studied. Yet, this understanding is important as different polymorphs of the same compound can result in drastically different bulk properties (e.g., solubility, absorptivity, and conductivity). Strategies to either promote or suppress the crystallization of particular polymorphs are thus desired. Here, we show that substituting hydrogen with fluorine affects the polymorphic behavior ofmore » contorted hexabenzocoronene (cHBC). A polycyclic aromatic hydrocarbon and molecular semiconductor, cHBC exhibits two polymorphs (i.e., P2 1/c crystal structure which we refer to as polymorph I and a triclinic crystal structure which we refer to as polymorph II) that are accessible through postdeposition processing of amorphous films. While the same two polymorphs remain accessible in fluorinated derivatives of cHBC, fluorination appears to favor the formation of polymorph I, with progressively smaller energy barrier for transformation from polymorph II to polymorph I with fluorination.« less

Altering the Polymorphic Accessibility of Polycyclic Aromatic Hydrocarbons with Fluorination

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

Hiszpanski, Anna M.; Woll, Arthur R.; Kim, Bumjung

Here, substituting hydrogen with fluorine is an extensively employed strategy to improve the macroscopic properties of compounds for use in fields as diverse as pharmaceutics and optoelectronics. The role fluorine substitution plays on polymorphism—the ability of a compound to adopt more than one crystal structure—has not been previously studied. Yet, this understanding is important as different polymorphs of the same compound can result in drastically different bulk properties (e.g., solubility, absorptivity, and conductivity). Strategies to either promote or suppress the crystallization of particular polymorphs are thus desired. Here, we show that substituting hydrogen with fluorine affects the polymorphic behavior ofmore » contorted hexabenzocoronene (cHBC). A polycyclic aromatic hydrocarbon and molecular semiconductor, cHBC exhibits two polymorphs (i.e., P2 1/c crystal structure which we refer to as polymorph I and a triclinic crystal structure which we refer to as polymorph II) that are accessible through postdeposition processing of amorphous films. While the same two polymorphs remain accessible in fluorinated derivatives of cHBC, fluorination appears to favor the formation of polymorph I, with progressively smaller energy barrier for transformation from polymorph II to polymorph I with fluorination.« less

In-situ x-ray diffraction of a shock-induced phase transition in fluorite, CaF2

NASA Astrophysics Data System (ADS)

Glam, Benny; June Tracy, Sally; Turneaure, Stefan; Duffy, Thomas

2017-06-01

The difluorides are an important class of ionic compounds that show extensive polymorphism under both static and dynamic loading. In this study, the shock-induced phase transitions in CaF2 were investigated by in situ x-ray diffraction measurements in plate impact experiments carried out with the two-stage gas gun at the Dynamic Compression Sector of Argonne National Laboratory. Single-crystal samples in (100) and (111) orientations were shock loaded to pressures between 32 GPa to 70 GPa. The particle velocities at the interface between the sample and a LiF window were measured by VISAR and PDV. Synchrotron x-ray diffraction data were recorded at 153.4 ns intervals using a four-frame detector. The measured diffraction patterns show a high degree of sample texturing at all pressures. We observe evidence for a transition to a high-pressure phase followed by reverse transformation at late times during release. This study provides the first direct constraints on the high-pressure lattice structure of fluorite under shock compression.

Influence of Ar-ion implantation on the structural and mechanical properties of zirconia as studied by Raman spectroscopy and nanoindentation techniques

NASA Astrophysics Data System (ADS)

Kurpaska, L.; Jasinski, J.; Wyszkowska, E.; Nowakowska-Langier, K.; Sitarz, M.

2018-04-01

In this study, structural and nanomechanical properties of zirconia polymorphs induced by ion irradiation were investigated by means of Raman spectroscopy and nanoindentation techniques. The zirconia layer have been produced by high temperature oxidation of pure zirconium at 600 °C for 5 h at normal atmospheric pressure. In order to distinguish between the internal and external parts of zirconia, the spherical metallographic sections have been prepared. The samples were irradiated at room temperature with 150 keV Ar+ ions at fluences ranging from 1 × 1015 to 1 × 1017 ions/cm2. The main objective of this study was to distinguish and confirm different structural and mechanical properties between the interface layer and fully developed scale in the internal/external part of the oxide. Conducted studies suggest that increasing ion fluence impacts Raman bands positions (especially characteristic for tetragonal phase) and increases the nanohardness and Young's modulus of individual phases. This phenomenon has been examined from the point of view of stress-induced hardening effect and classical monoclinic → tetragonal (m → t) martensitic phase transformation.

Temperatures of shock-induced shear instabilities and their relationship to fusion curves. [emission from glass

NASA Technical Reports Server (NTRS)

Schmitt, D. R.; Ahrens, T. J.

1983-01-01

New emission spectra for MgO and CaAl2Si2O8 (glass) are observed from 430 to 820 nm. Taken with previous data, it is suggested that transparent solids display three regimes of light emission upon shock compression to successively higher pressures: (1) characteristic radiation such as observed in MgO and previously in other minerals, (2) heterogeneous hot spot (greybody) radiation observed in CaAl2Si2O8 and previously in all transparent solids undergoing shock-induced phase transformations, and (3) blackbody emission observed in the high pressure phase regime in NaCl, SiO2, CaO, CaAl2Si2O8, and Mg2SiO4. The onset of the second regime may delineate the onset of shock-induced polymorphism whereas the onset of the third regime delineates the Hugoniot pressure required to achieve local thermal equilibrium in the shocked solid. It is also proposed that the hot spot temperatures and corresponding shock pressures determined in the second regime delineate points on the fusion curves of the high pressure phase.

Entropic Anomaly Observed in Lipid Polymorphisms Induced by Surfactant Peptide SP-B(1-25).

PubMed

Tran, Nhi; Kurian, Justin; Bhatt, Avni; McKenna, Robert; Long, Joanna R

2017-10-05

The N-terminal 25 amino-acid residues of pulmonary surfactant protein B (SP-B 1-25 ) induces unusual lipid polymorphisms in a model lipid system, 4:1 DPPC/POPG, mirroring the lipid composition of native pulmonary surfactant. It is widely suggested that SP-B 1-25 -induced lipid polymorphisms within the alveolar aqueous subphase provide a structural platform for rapid lipid adsorption to the air-water interface. Here, we characterize in detail the phase behavior of DPPC and POPG in hydrated lipid assemblies containing therapeutic levels of SP-B 1-25 using 2 H and 31 P solid state NMR spectroscopy. The appearance of a previously observed isotropic lipid phase is found to be highly dependent on the thermal cycling of the samples. Slow heating of frozen samples leads to phase separation of DPPC into a lamellar phase whereas POPG lipids interact with the peptide to form an isotropic phase at physiologic temperature. Rapid heating of frozen samples to room temperature leads to strongly isotropic phase behavior for both DPPC and POPG lipids, with DPPC in exchange between isotropic and interdigitated phases. 31 P T 2 relaxation times confirm the isotropic phase to be consistent with a lipid cubic phase. The observed phases exhibit thermal stability up to physiologic temperature (37 °C) and are consistent with the formation of a ripple phase containing a large number of peptide-induced membrane structural defects enabling rapid transit of lipids between lipid lamellae. The coexistance of a lipid cubic phase with interdigitated lipids suggests a specific role for the highly conserved N-terminus of SP-B in stabilizing this unusual lipid polymorphism.

Dielectric Dispersion, Diffuse Phase Transition, and Electrical Properties of BCT-BZT Ceramics Sintered at a Low-Temperature

NASA Astrophysics Data System (ADS)

Tian, Yongshang; Gong, Yansheng; Meng, Dawei; Li, Yuanjian; Kuang, Boya

2015-08-01

Lead-free ceramics 0.50Ba0.9Ca0.1TiO3-0.50BaTi1- x Zr x O3 (BCT-BZT) were prepared via sintering BCT and BZT nanoparticles, which were synthesized using a modified Pechini polymeric precursor method, at a low temperature of 1260°C. The relative densities of the ceramics prepared with different zirconium contents ( x) were all above 95.3%, reaching a maximum of 97% when x = 0.08. X-ray diffraction results confirmed the onset of phase transformation from orthorhombic to rhombohedral symmetry with increasing zirconium contents, and the polymorphic phase transition was observed at x = 0.10. The dielectric dispersion, diffuse phase transition (DPT), and relaxor-like ferroelectric characteristics as a function of zirconium content were thoroughly studied. Optimum physical properties, remnant polarization ( P r) = 16.4 μC/cm2, piezoelectric constant ( d 33) = ~240 pC/N, and electromechanical coupling factor ( k p) = 0.22, were obtained at x = 0.10. The findings of the current DPT behavior study of BCT-BZT ceramics are believed to be insightful to the development of ferroelectric materials.

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

Negative thermal expansion materials related to cubic zirconium tungstate

NASA Astrophysics Data System (ADS)

Lind, Cora

2001-12-01

A non-hydrolytic sol-gel method for the preparation of ZrW2O 8 was developed. A new trigonal polymorph was discovered, which is structurally related to trigonal ZrMO2O8 and MnRe2O 8 as evidenced by powder x-ray diffraction and EXAFS studies. Seeding of the starting mixtures with cubic ZrW2O8 promoted crystallization of the cubic phase instead of trigonal material. Dehydration of ZrW2O7(OH)2·2H 2O gave cubic ZrW2O8 at 650°C, and a modification of this route led to the discovery of the new NTE materials cubic ZrMo 2O8 and HfMo2O8. These compounds crystallize in the same temperature range as the more stable trigonal AMo2O 8 polymorphs. To facilitate preparation of phase pure cubic molybdates, the influence of precursor chemistry on the crystallization behavior was investigated. The synthesis was extended to the solid solution system ZrxHf 1-xMoyW2-yO8 (0 ≤ x ≤ 1, 0 ≤ y ≤ 2). All compounds showed negative thermal expansion between 77 and 573 K. High-pressure in situ diffraction experiments were conducted on several AM2O8 polymorphs. With the exception of monoclinic ZrMo2O8, all materials underwent at least one pressure induced phase transition. Quasi-hydrostatic experiments on cubic AMo 2O8 led to a reversible transition to a new high-pressure structure, while low-pressure amorphization was observed under non-hydrostatic conditions. Isothermal kinetic studies of the cubic to trigonal transformation for ZrMo2O8 were carried out on four samples. Apparent activation energies of 170--290 kJ/mol were obtained using an Avrami model in combination with an Arrhenius analysis. This corresponds to 5% conversion levels after one year at temperatures between 220 and 315°C. Ex situ studies showed that the conversion at lower temperatures was considerably slower than what would be expected from extrapolation of the kinetic data. Drop solution calorimetry was carried out on several polymorphs of ZrMo 2O8, HfMo2O8 and ZrW2O 8. Only monoclinic ZrMo2O8 was enthalpically stabilized with respect to the binary oxides. For all other polymorphs, the differences in enthalpies of formation from the binary oxides for each AM2O 8 system (A = Zr, Hf; M = Mo, W) were small. Attempts to synthesize new materials MIIRe2O 8 (M = Mg, Zn, Mn, Co) with the cubic ZrW2O8 structure from a hydrate precursor were not successful.

Rotigotine: Unexpected Polymorphism with Predictable Overall Monotropic Behavior.

PubMed

Rietveld, Ivo B; Céolin, René

2015-12-01

Crystallization of polymorphs still has a touch of art, as even prior observations of polymorphs do not guarantee their crystallization. However, once crystals of various polymorphs have been obtained, their relative stabilities can be established with a straightforward thermodynamic approach even if the conclusion will depend on the quality of the experimental data. Rotigotine is an active pharmaceutical ingredient, which has suffered the same setback as Ritonavir: a sudden appearance of a more stable crystalline polymorph than the one used for the formulation. Although the cause of the defect in the formulation was quickly established, the interpretation of the phase behavior of rotigotine has been lacking in clarity. In the present paper, data published in the patents resulting from the discovery of the new polymorph have been used to establish the pressure-temperature phase diagram of the two known solid forms of rotigotine. The analysis clearly demonstrates that form II is the stable solid phase and form I is metastable in the entire pressure-temperature domain: form I is overall monotropic in relation to form II. Thus, it was a sensible decision of European Medicines Agency to ask for a reformulation, as the first formulation was metastable even if crystallization appeared to be very slow. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

Thermodynamic Properties of M2EO4, M2Mo x O3 x + 1 and Double Chromates (M = Li, Na, K, Rb, Cs; E = Cr, Mo, W)

NASA Astrophysics Data System (ADS)

Suponitskiy, Yu. L.; Zolotova, E. S.; Dyunin, A. G.; Liashenko, S. E.

2018-03-01

The phase transition temperatures of chromates and molybdates of certain alkali metals, and the melting temperature and enthalpy of polymorphic transformations for tungstates, are determined by means of thermal analysis. Enthalpies of dissolution of rubidium and cesium chromates in water and enthalpies of dissolution of alkali metal tungstates in a melt at 923 K are measured via calorimetry. Standard enthalpies of formation of sought chromates are calculated. The linear correlations between the enthalpies of formation of sulfates, selenates, chromates, tungstates, and molybdates are established, and a linear correlation within - (Δ G o ox)-1-(Δ MV)ox)-1 coordinates is found for isopolymolybdates.

Crystallization of pure anhydrous polymorphs of carbamazepine by solution enhanced dispersion with supercritical fluids (SEDS).

PubMed

Edwards, A D; Shekunov, B Y; Kordikowski, A; Forbes, R T; York, P

2001-08-01

Pure anhydrous polymorphs of carbamazepine were prepared by solution-enhanced dispersion with supercritical fluids (SEDS). Crystallization of the polymorphs was studied. Mechanisms are proposed that consider the thermodynamics of carbamazepine, supersaturation in the SEDS process, and the binary phase equilibria of organic solvents and the carbon dioxide antisolvent. alpha-Carbamazepine was crystallized at high supersaturations and low temperatures, beta-carbamazepine crystallized from a methanol-carbon dioxide phase split, and gamma-carbamazepine crystallized via nucleation at high temperatures and low supersaturation. Copyright 2001 Wiley-Liss, Inc.

Electron petrography of silica polymorphs associated with pseudotachylite, Vredefort structure, South Africa

NASA Technical Reports Server (NTRS)

White, J. C.

1992-01-01

High-pressure silica polymorphs (coesite and stishovite) were described from the Vredefort structure in association with pseudotachylite veinlets. In addition to the fundamental significance of the polymorphs to genetic interpretations of the structure, it was additionally argued that the type of pseudotachylite with which they occur forms during the compressional phase of the shock process, while the larger, classic pseudotachylite occurrences are barren of polymorphs and formed during passage of the rarefaction wave. This identification of temporal relationships among transient shock features at a regional scale is similar to observations from the Manicouagan structure, Quebec, where texturally distinct diaplectic plagioclase glasses formed during both compressional and decompressional phases of the shock process. The clarification of such relationships impinges directly on interpretations of natural shock processes and the identification of high probability targets for polymorph searches. Detailed analytical scanning (SEM) and transmission electron microscopy (TEM) were utilized to further establish the nature of both the pseudotachylite and the silica polymorph occurrences in the Vredefort rocks. The results of this investigation are discussed.

Quantum size effects in the size-temperature phase diagram of gallium: structural characterization of shape-shifting clusters.

PubMed

Steenbergen, Krista G; Gaston, Nicola

2015-02-09

Finite temperature analysis of cluster structures is used to identify signatures of the low-temperature polymorphs of gallium, based on the results of first-principle Born-Oppenheimer molecular dynamics simulations. Pre-melting structural transitions proceed from either the β- and/or the δ-phase to the γ- or δ-phase, with a size- dependent phase progression. We relate the stability of each isomer to the electronic structures of the different phases, giving new insight into the origin of polymorphism in this complicated element. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Experimental evidence of new tetragonal polymorphs of silicon formed through ultrafast laser-induced confined microexplosion

DOE PAGES

Rapp, L.; Haberl, B.; Pickard, C. J.; ...

2015-06-29

Ordinary materials can transform into novel phases with new crystal structures at extraordinary high pressure and temperature applied under both equilibrium and non-equilibrium conditions 1-6. The recently developed method of ultra-short laser-induced confined microexplosions 7-9 extends the range of possible new phases by initiating a highly non-equilibrium plasma state deep inside a bulk material 7-12. Ultra-high quenching rates can help to overcome kinetic barriers to the formation of new metastable phases, while the surrounding pristine crystal confines the affected material and preserves it for further study 10-12. Here we demonstrate that ultra-rapid pressure release from a completely disordered plasma statemore » in silicon produces several new metastable end phases quenched to ambient conditions. Their structure is determined from comparison to an ab initio random structure search which revealed six new energetically competitive potential phases, four tetragonal and two monoclinic ones. We show the presence of bt8 and st12, which have been predicted theoretically previously 13-15, but have not been observed in nature or in laboratory experiments. Additionally, the presence of the as yet unidentified silicon phase, Si-VIII and two of our other predicted tetragonal phases are highly likely within laser-affected zones. These findings pave the way for new materials with novel and exotic properties.« less

Computational Approach for Epitaxial Polymorph Stabilization through Substrate Selection.

PubMed

Ding, Hong; Dwaraknath, Shyam S; Garten, Lauren; Ndione, Paul; Ginley, David; Persson, Kristin A

2016-05-25

With the ultimate goal of finding new polymorphs through targeted synthesis conditions and techniques, we outline a computational framework to select optimal substrates for epitaxial growth using first principle calculations of formation energies, elastic strain energy, and topological information. To demonstrate the approach, we study the stabilization of metastable VO2 compounds which provides a rich chemical and structural polymorph space. We find that common polymorph statistics, lattice matching, and energy above hull considerations recommends homostructural growth on TiO2 substrates, where the VO2 brookite phase would be preferentially grown on the a-c TiO2 brookite plane while the columbite and anatase structures favor the a-b plane on the respective TiO2 phases. Overall, we find that a model which incorporates a geometric unit cell area matching between the substrate and the target film as well as the resulting strain energy density of the film provide qualitative agreement with experimental observations for the heterostructural growth of known VO2 polymorphs: rutile, A and B phases. The minimal interfacial geometry matching and estimated strain energy criteria provide several suggestions for substrates and substrate-film orientations for the heterostructural growth of the hitherto hypothetical anatase, brookite, and columbite polymorphs. These criteria serve as a preliminary guidance for the experimental efforts stabilizing new materials and/or polymorphs through epitaxy. The current screening algorithm is being integrated within the Materials Project online framework and data and hence publicly available.

Computational Approach for Epitaxial Polymorph Stabilization through Substrate Selection

DOE PAGES

Ding, Hong; Dwaraknath, Shyam S.; Garten, Lauren; ...

2016-05-04

With the ultimate goal of finding new polymorphs through targeted synthesis conditions and techniques, we outline a computational framework to select optimal substrates for epitaxial growth using first principle calculations of formation energies, elastic strain energy, and topological information. To demonstrate the approach, we study the stabilization of metastable VO 2 compounds which provides a rich chemical and structural polymorph space. Here, we find that common polymorph statistics, lattice matching, and energy above hull considerations recommends homostructural growth on TiO 2 substrates, where the VO 2 brookite phase would be preferentially grown on the a-c TiO 2 brookite plane whilemore » the columbite and anatase structures favor the a-b plane on the respective TiO 2 phases. Overall, we find that a model which incorporates a geometric unit cell area matching between the substrate and the target film as well as the resulting strain energy density of the film provide qualitative agreement with experimental observations for the heterostructural growth of known VO 2 polymorphs: rutile, A and B phases. The minimal interfacial geometry matching and estimated strain energy criteria provide several suggestions for substrates and substrate-film orientations for the heterostructural growth of the hitherto hypothetical anatase, brookite, and columbite polymorphs. Our criteria serve as a preliminary guidance for the experimental efforts stabilizing new materials and/or polymorphs through epitaxy. The current screening algorithm is being integrated within the Materials Project online framework and data and hence publicly available.« less

Computational Approach for Epitaxial Polymorph Stabilization through Substrate Selection

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

Ding, Hong; Dwaraknath, Shyam S.; Garten, Lauren

With the ultimate goal of finding new polymorphs through targeted synthesis conditions and techniques, we outline a computational framework to select optimal substrates for epitaxial growth using first principle calculations of formation energies, elastic strain energy, and topological information. To demonstrate the approach, we study the stabilization of metastable VO2 compounds which provides a rich chemical and structural polymorph space. We find that common polymorph statistics, lattice matching, and energy above hull considerations recommends homostructural growth on TiO2 substrates, where the VO2 brookite phase would be preferentially grown on the a-c TiO2 brookite plane while the columbite and anatase structuresmore » favor the a-b plane on the respective TiO2 phases. Overall, we find that a model which incorporates a geometric unit cell area matching between the substrate and the target film as well as the resulting strain energy density of the film provide qualitative agreement with experimental observations for the heterostructural growth of known VO2 polymorphs: rutile, A and B phases. The minimal interfacial geometry matching and estimated strain energy criteria provide several suggestions for substrates and substrate-film orientations for the heterostructural growth of the hitherto hypothetical anatase, brookite, and columbite polymorphs. These criteria serve as a preliminary guidance for the experimental efforts stabilizing new materials and/or polymorphs through epitaxy. The current screening algorithm is being integrated within the Materials Project online framework and data and hence publicly available.« less

Computational Approach for Epitaxial Polymorph Stabilization through Substrate Selection

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

Ding, Hong; Dwaraknath, Shyam S.; Garten, Lauren

With the ultimate goal of finding new polymorphs through targeted synthesis conditions and techniques, we outline a computational framework to select optimal substrates for epitaxial growth using first principle calculations of formation energies, elastic strain energy, and topological information. To demonstrate the approach, we study the stabilization of metastable VO 2 compounds which provides a rich chemical and structural polymorph space. Here, we find that common polymorph statistics, lattice matching, and energy above hull considerations recommends homostructural growth on TiO 2 substrates, where the VO 2 brookite phase would be preferentially grown on the a-c TiO 2 brookite plane whilemore » the columbite and anatase structures favor the a-b plane on the respective TiO 2 phases. Overall, we find that a model which incorporates a geometric unit cell area matching between the substrate and the target film as well as the resulting strain energy density of the film provide qualitative agreement with experimental observations for the heterostructural growth of known VO 2 polymorphs: rutile, A and B phases. The minimal interfacial geometry matching and estimated strain energy criteria provide several suggestions for substrates and substrate-film orientations for the heterostructural growth of the hitherto hypothetical anatase, brookite, and columbite polymorphs. Our criteria serve as a preliminary guidance for the experimental efforts stabilizing new materials and/or polymorphs through epitaxy. The current screening algorithm is being integrated within the Materials Project online framework and data and hence publicly available.« less

Polymorphism and Superconductivity in Bilayer Molecular Metals (CNB-EDT-TTF)4I3.

PubMed

Rabaça, Sandra; Oliveira, Sandrina; Santos, Isabel C; Gama, Vasco; Belo, Dulce; Lopes, Elsa B; Canadell, Enric; Almeida, Manuel

2016-10-17

Electrocrystallization from solutions of the dissymmetrical ET derivative cyanobenzene-ethylenedithio-tetrathiafulvalene (CNB-EDT-TTF) in the presence of triiodide I 3 - affords two different polymorphs (β″ and κ) with the composition (CNB-EDT-TTF) 4 I 3 , both with a bilayer structure of the donors. These polymorphs differ in the packing patterns (β″- and κ-type) of the donor molecules in each layer, in both cases with bifurcated C-N···H interactions effectively coupling head-to-head donor molecules between layer pairs. Two β″ polymorphs can be obtained with different degrees of anionic ordering. In one disordered phase, β″ d , with a smaller unit cell, the triiodide anions are disordered over two possible positions in a channel between the donor bilayers, while in the ordered phase, β″ o , the triiodide anions occupy only one of those positions in this channel, leading to the doubling of the unit cell in the layer plane. These results for β″ phases contrast with the κ polymorph previously reported, for which weaker disorder of the triiodide anions, over two possible orientations with 94 and 6% occupation factors, was observed. While the β″ polymorphs remains metallic down to 1.5 K with a ρ 300K /ρ 4K resistivity ratio of 250, the κ polymorph presents a much smaller resistivity ratio in the range of 4-10 and superconductivity with an onset temperature of 3.5 K.

Phase stability of iron germanate, FeGeO3, to 127 GPa

NASA Astrophysics Data System (ADS)

Dutta, R.; Tracy, S. J.; Stan, C. V.; Prakapenka, V. B.; Cava, R. J.; Duffy, T. S.

2018-04-01

The high-pressure behavior of germanates is of interest as these compounds serve as analogs for silicates of the deep Earth. Current theoretical and experimental studies of iron germanate, FeGeO3, are limited. Here, we have examined the behavior of FeGeO3 to 127 GPa using the laser-heated diamond anvil cell combined with in situ synchrotron X-ray diffraction. Upon compression at room temperature, the ambient-pressure clinopyroxene phase transforms to a disordered triclinic phase [FeGeO3 (II)] at 18 GPa in agreement with earlier studies. An additional phase transition to FeGeO3 (III) occurs above 54 GPa at room temperature. Laser-heating experiments ( 1200-2200 K) were conducted at three pressures (33, 54, and 123 GPa) chosen to cover the stability regions of different GeO2 polymorphs. In all cases, we observe that FeGeO3 dissociates into GeO2 + FeO at high pressure and temperature conditions. Neither the perovskite nor the post-perovskite phase was observed up to 127 GPa at ambient or high temperatures. The results are consistent with the behavior of FeSiO3, which also dissociates into a mixture of the oxides (FeO + SiO2) at least up to 149 GPa.

Creep of water ices at planetary conditions: A compilation

USGS Publications Warehouse

Durham, W.B.; Kirby, S.H.; Stern, L.A.

1997-01-01

Many constitutive laws for the flow of ice have been published since the advent of the Voyager explorations of the outer solar system. Conflicting data have occasionally come from different laboratories, and refinement of experimental techniques has led to the publication of laws that supersede earlier ones. In addition, there are unpublished data from ongoing research that also amend the constitutive laws. Here we compile the most current laboratory-derived flow laws for water ice phases I, II, III, V, and VI, and ice I mixtures with hard particulates. The rheology of interest is mainly that of steady state, and the conditions reviewed are the pressures and temperatures applicable to the surfaces and interiors of icy moons of the outer solar system. Advances in grain-size-dependent creep in ices I and II as well as in phase transformations and metastability under differential stress are also included in this compilation. At laboratory strain rates the several ice polymorphs are rheologically distinct in terms of their stress, temperature, and pressure dependencies but, with the exception of ice III, have fairly similar strengths. Hard particulates strengthen ice I significantly only at high particulate volume fractions. Ice III has the potential for significantly affecting mantle dynamics because it is much weaker than the other polymorphs and its region of stability, which may extend metastably well into what is nominally the ice II field, is located near likely geotherms of large icy moons. Copyright 1997 by the American Geophysical Union.

Effect of luminescence transport through adipose tissue on measurement of tissue temperature by using ZnCdS nanothermometers

NASA Astrophysics Data System (ADS)

Volkova, Elena K.; Yanina, Irina Yu.; Sagaydachnaya, Elena; Konyukhova, Julia G.; Kochubey, Vyacheslav I.; Tuchin, Valery V.

2018-02-01

The spectra of luminescence of ZnCdS nanoparticles (ZnCdS NPs) were measured and analyzed in a wide temperature range: from room to human body and further to a hyperthermic temperature resulting in tissue morphology change. The results show that the signal of luminescence of ZnCdS NPs placed within the tissue is reasonably good sensitive to temperature change and accompanied by phase transitions of lipid structures of adipose tissue. It is shown that the presence of a phase transition in adipose tissue upon its heating (polymorphic transformations of lipids) leads to a nonmonotonic temperature dependence of the intensity of luminescence for the nanoparticles introduced into adipose tissue. This is due to a change in the light scattering by the tissue. The light scattering of adipose tissue greatly distorts the results of temperature measurements. The application of these nanoparticles is possible for temperature measurements in very thin or weakly scattering samples.

Physicochemical, textural and viscoelastic properties of palm diacylglycerol bakery shortening during storage.

PubMed

Cheong, Ling-Zhi; Tan, Chin-Ping; Long, Kamariah; Affandi Yusoff, Mohd Suria; Lai, Oi-Ming

2010-10-01

Diacylglycerol (DAG), which has health-enhancing properties, is sometimes added to bakery shortening to produce baked products with enhanced physical functionality. Nevertheless, the quantity present is often too little to exert any positive healthful effects. This research aimed to produce bakery shortenings containing significant amounts of palm diacyglycerol (PDG). Physicochemical, textural and viscoelastic properties of the PDG bakery shortenings during 3 months storage were evaluated and compared with those of commercial bakery shortening (CS). PDG bakery shortenings (DS55, DS64 and DS73) had less significant increments in slip melting point (SMP), solid fat content (SFC) and hardness during storage as compared to CS. Unlike CS, melting behaviour and viscoelastic properties of PDG bakery shortenings remained unchanged during storage. As for polymorphic transformation, CS contained only β crystals after 8 weeks of storage. PDG bakery shortenings managed to retard polymorphic transformation for up to 10 weeks of storage in DS55 and 12 weeks of storage in DS64 and DS73. PDG bakery shortenings had similar if not better storage stability as compared to CS. This is mainly due to the ability of DAG to retard polymorphic transformation from β' to β crystals. Thus, incorporation of DAG improved physical functionality of bakery shortening. Copyright © 2010 Society of Chemical Industry.

Gender and single nucleotide polymorphisms in MTHFR, BHMT, SPTLC1, CRBP2R, and SCARB1 are significant predictors of plasma homocysteine normalized by RBC folate in healthy adults.

USDA-ARS?s Scientific Manuscript database

Using linear regression models, we studied the main and two-way interaction effects of the predictor variables gender, age, BMI, and 64 folate/vitamin B-12/homocysteine/lipid/cholesterol-related single nucleotide polymorphisms (SNP) on log-transformed plasma homocysteine normalized by red blood cell...

Careful with That Axe, Gene, Genome Perturbation after a PEG-Mediated Protoplast Transformation in Fusarium verticillioides.

PubMed

Scala, Valeria; Grottoli, Alessandro; Aiese Cigliano, Riccardo; Anzar, Irantzu; Beccaccioli, Marzia; Fanelli, Corrado; Dall'Asta, Chiara; Battilani, Paola; Reverberi, Massimo; Sanseverino, Walter

2017-05-31

Fusarium verticillioides causes ear rot disease in maize and its contamination with fumonisins, mycotoxins harmful for humans and livestock. Lipids, and their oxidized forms, may drive the fate of this disease. In a previous study, we have explored the role of oxylipins in this interaction by deleting by standard transformation procedures a linoleate diol synthase-coding gene, lds1 , in F. verticillioides . A profound phenotypic diversity in the mutants generated has prompted us to investigate more deeply the whole genome of two lds1 -deleted strains. Bioinformatics analyses pinpoint significant differences in the genome sequences emerged between the wild type and the lds1 -mutants further than those trivially attributable to the deletion of the lds1 locus, such as single nucleotide polymorphisms, small deletion/insertion polymorphisms and structural variations. Results suggest that the effect of a (theoretically) punctual transformation event might have enhanced the natural mechanisms of genomic variability and that transformation practices, commonly used in the reverse genetics of fungi, may potentially be responsible for unexpected, stochastic and henceforth off-target rearrangements throughout the genome.

Careful with That Axe, Gene, Genome Perturbation after a PEG-Mediated Protoplast Transformation in Fusarium verticillioides

PubMed Central

Scala, Valeria; Grottoli, Alessandro; Aiese Cigliano, Riccardo; Anzar, Irantzu; Beccaccioli, Marzia; Fanelli, Corrado; Dall’Asta, Chiara; Battilani, Paola; Reverberi, Massimo; Sanseverino, Walter

2017-01-01

Fusarium verticillioides causes ear rot disease in maize and its contamination with fumonisins, mycotoxins harmful for humans and livestock. Lipids, and their oxidized forms, may drive the fate of this disease. In a previous study, we have explored the role of oxylipins in this interaction by deleting by standard transformation procedures a linoleate diol synthase-coding gene, lds1, in F. verticillioides. A profound phenotypic diversity in the mutants generated has prompted us to investigate more deeply the whole genome of two lds1-deleted strains. Bioinformatics analyses pinpoint significant differences in the genome sequences emerged between the wild type and the lds1-mutants further than those trivially attributable to the deletion of the lds1 locus, such as single nucleotide polymorphisms, small deletion/insertion polymorphisms and structural variations. Results suggest that the effect of a (theoretically) punctual transformation event might have enhanced the natural mechanisms of genomic variability and that transformation practices, commonly used in the reverse genetics of fungi, may potentially be responsible for unexpected, stochastic and henceforth off-target rearrangements throughout the genome. PMID:28561789

Shock-Induced Phase Transitions in the Martian Meteorite Tissint: Mechanisms and Constraints on Shock Pressure

NASA Astrophysics Data System (ADS)

Sharp, T. G.; Hu, J.; Walton, E. L.

2013-12-01

Martian meteorites are important samples for understanding the origin and age of the Martian crust. All of these samples have been shocked to some degree during their ejection from Mars or earlier. Tissint, a picritic shergottite, has many high-pressure phases that have been used to constrain shock conditions and suggest a deep crustal origin [1] and to argue for multiple impact events [2]. Here we investigate the products and mechanisms of various olivine transformation reactions. Olivine in and adjacent to shock-melt veins and pockets is transformed into high-pressure minerals. In the hottest parts of the sample, olivine dissociated into 50-nm crystals of magnesiowüstite intergrown with either a pyroxene-composition glass or with low-Ca clinopyroxene. In both cases, the olivine is inferred to have transformed to silicate perovskite + magnesiowüstite during shock with subsequent breakdown of the perovskite after pressure release. Olivine along the margins of shock veins transformed into ringwoodite. Polycrystalline ringwoodite formed at the olivine-melt interface wheras coherent ringwoodite lamellae formed farther from the melt. These ringwoodite lamellae have the same topotaxial relationship to olivine as seen in static high-pressure experiments [3] and shocked meteorites [4]: (100)Ol || {111}Rw and [011]Ol || <110>Rw. The various olivine reactions can be explained by a single shock to above 24 GPa where only the highest temperatures allowed the dissociation of olivine to silicate-perovskite plus magnesiowüstite. The silicate perovskite in the melt pocket transformed to pyroxene because the melt pocket remained very hot after pressure release. At lower temperatures, the kinetically easier polymorphic transformation of olivine to metastable ringwoodite occurred. At the lowest temperatures, this reaction was facilitated by nucleation of ringwoodite lamellae on stacking faults in olivine. The variation in assemblages that we see are consistent with a single shock and a relatively short shock pulse. References: [1] Baziotis1, I. P. et. al 2013 Nature Communications 4:1404, [2] El Goresey, A. et. al 2013 #1037. 44th LPSC. [3] Kerschhofer, L. et. al 1996 Science 274, 79-81. [4] Miyahara et. al, 2010 EPSL. 295, 321-327.

Synthesis and characterization of metastable, 20 nm-sized Pna2{sub 1}-LiCoPO{sub 4} nanospheres

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

Ludwig, Jennifer; Nordlund, Dennis; Doeff, Marca M.

The majority of research activities on LiCoPO{sub 4} are focused on the phospho-olivine (space group Pnma), which is a promising high-voltage cathode material for Li-ion batteries. In contrast, comparably little is known about its metastable Pna2{sub 1} modification. Herein, we present a comprehensive study on the structure–property relationships of 15–20 nm Pna2{sub 1}-LiCoPO{sub 4} nanospheres prepared by a simple microwave-assisted solvothermal process. Unlike previous reports, the results indicate that the compound is non-stoichiometric and shows cation-mixing with Co ions on the Li sites, which provides an explanation for the poor electrochemical performance. Co L{sub 2,3}-edge X-ray absorption spectroscopic data confirmmore » the local tetrahedral symmetry of Co{sup 2+}. Comprehensive studies on the thermal stability using thermogravimetric analysis, differential scanning calorimetry, and in situ powder X-ray diffraction show an exothermic phase transition to olivine Pnma-LiCoPO{sub 4} at 527 °C. The influence of the atmosphere and the particle size on the thermal stability is also investigated. - Graphical abstract: Blue nano-sized Pna2{sub 1}-LiCoPO{sub 4,} featuring tetrahedrally-coordinated Co{sup 2+}, was synthesized in a rapid one-step microwave-assisted solvothermal process. The phase relation between this metastable and the stable polymorph was analyzed and electrochemical properties are discussed. - Highlights: • Preparation of uniform 15–20 nm nanospheres of metastable Pna2{sub 1}-LiCoPO{sub 4} polymorph. • Structure redetermination shows cation-mixing (Co blocking Li sites). • In situ investigation of phase transformation to olivine Pnma-LiCoPO{sub 4} at 527 °C. • Pna2{sub 1}-LiCoPO{sub 4} reemerges as a stable high-temperature phase above 800 °C. • X-ray absorption spectroscopy confirms local tetrahedral symmetry (T{sub d} Co{sup 2+}).« less

Exploring the Phase Diagram SiO2-CO2 at High Pressures and Temperatures

NASA Astrophysics Data System (ADS)

Kavner, A.

2015-12-01

CO2 is an important volatile system relevant for planetary sciences and fundamental chemistry. Molecular CO2 has doubly bonded O=C=O units but high pressure-high temperature (HP-HT) studies have recently shown its transformation into a three-dimensional network of corner-linked [CO4] units analogous to the silica mineral polymorphs, through intermediate non-molecular phases. Here, we report P-V-T data on CO2-IV ice from time-of-flight neutron diffraction experiments, which allow determining the compressibility and thermal expansivity of this intermediate molecular-to-non-molecular phase.1 Aditionally, we have explored the SiO2-CO2 phase diagram and the potential formation of silicon carbonate compounds. New data obtained by laser-heating diamond-anvil experiments in CO2-filled microporous silica polymorphs will be shown. In particular, these HP-HT experiments explore the existence of potential CO2/SiO2 compounds with tetrahedrally-coordinated C/Si atoms by oxygens, which are predicted to be stable (or metastable) by state-of-the-art ab initio simulations.2,3 These theoretical predictions were supported by a recent study that reports the formation of a cristobalite-type Si0.4C0.6O2 solid solution at high-pressures and temperatures, which can be retained as a metastable solid down to ambient conditions.4 Entirely new families of structures could exist based on [CO4]4- units in various degrees of polymerisation, giving rise to a range of chain, sheet and framework solids like those found in silicate chemistry. References[1] S. Palaich et al., Am. Mineral. Submitted (2015) [2] A. Morales-Garcia et al., Theor. Chem. Acc. 132, 1308 (2013) [3] R. Zhou et al., Phys. Rev. X, 4, 011030 (2014) [4] M. Santoro et al. Nature Commun. 5, 3761 (2014)

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

Lavina, Barbara; Kim, Eunja; Cynn, Hyunchae

Using combined experimental and computational approaches, we show that at 43 GPa and 1300 K gallium phosphide adopts the super-Cmcm structure, here indicated with its Pearson notation oS24. First-principles enthalpy calculations demonstrate that this structure is more thermodynamically stable above ~20 GPa than previously proposed polymorphs. Here, in contrast to other polymorphs, the oS24 phase shows a strong bonding differentiation and distorted fivefold coordination geometries of both P atoms. The shortest bond of the phase is a single covalent P–P bond measuring 2.171(11) Å at synthesis pressure. Phosphorus dimerization in GaP sheds light on the nature of the super-Cmcm phasemore » and provides critical new insights into the high-pressure polymorphism of octet semiconductors. Bond directionality and anisotropy explain the relatively low symmetry of this high-pressure phase.« less

Essentials of Conservation Biotechnology: A mini review

NASA Astrophysics Data System (ADS)

Merlyn Keziah, S.; Subathra Devi, C.

2017-11-01

Equilibrium of biodiversity is essential for the maintenance of the ecosystem as they are interdependent on each other. The decline in biodiversity is a global problem and an inevitable threat to the mankind. Major threats include unsustainable exploitation, habitat destruction, fragmentation, transformation, genetic pollution, invasive exotic species and degradation. This review covers the management strategies of biotechnology which include sin situ, ex situ conservation, computerized taxonomic analysis through construction of phylogenetic trees, calculating genetic distance, prioritizing the group for conservation, digital preservation of biodiversities within the coding and decoding keys, molecular approaches to asses biodiversity like polymerase chain reaction, real time, randomly amplified polymorphic DNA, restriction fragment length polymorphism, amplified fragment length polymorphism, single sequence repeats, DNA finger printing, single nucleotide polymorphism, cryopreservation and vitrification.

The transformation of amorphous calcium carbonate, ACC, to crystalline phases as function of time and temperature.

NASA Astrophysics Data System (ADS)

Gies, Hermann; Happel, Marian; Niedermayr, Andrea; Immenhauser, Adrian

2017-04-01

We present results from a structural study of the transformation of freeze dried amorphous calcium carbonate, ACC, in crystalline material using pair distribution function analysis, PDF analysis, of X-ray powder diffraction data, XPD data. PDF analysis allows for the analysis of local order of structural subunit in the range between molecular unit (1. and 2. coordination sphere) and long range periodicity as in crystalline materials. ACC was precipitated from aqueous solutions at 298 K and 278 K using different amounts of Mg cations as stabilizer. The samples were immediately separated from the solution and freeze dried. For the transformation study, the samples were heated and analysed using XPD until they were crystallized. The radial distribution obtained from the XPD data were compared to simulated radial distributions of the calcium carbonate polymorphs and their hydrated phases. An ACC precipitated from a solution with Ca:Mg:CO3 = 1:5:4 at 298 K (ration in mmol, pH = 8.2) and freeze dried right after isolation from the solution revealed a close resemblance with ikaite in its local order. Another ACC with Ca:Mg:CO3 = 1:10:1.4 (T = 298, pH = 8.7) showed distinctly different local order resembling monohydrocalcite. Both ACC, however, still had considerable amounts of water dominating the Ca-coordination sphere. During the transformation to calcite, the structural changes in the sample concerned the hydrate water coordinating Ca which was removed and replaced by the carbonate oxygens. The study shows that ACC obtained from different starting solutions show specific local order. Freeze drying leads to solid ACC powder which still contain considerable amounts of hydrate water. Structural subunits are distinct in ACC and different from the crystalline phase. The study supplements recent reports presented by Konrad et al., Purgstaller et al., and Tobler et al.. F. Konrad et al., Cryst. Growth Des. 16, 6310-6317(2016) B. Purgstaller et al., Geochimica et Cosmochimica Acta 174, 180-195(2016) DJ. Tobler et al., Cryst. Growth Des. 16, 4500-4508(2016)

The Molecular Epidemiology of Malaria in Western Kenya

DTIC Science & Technology

2002-09-01

including tumor necrosis factor alpha (TNF- α), interleukin-10 (IL-10), transforming growth factor beta (TGF-β), interleukin-6 (IL-6), and interferon gamma...Ricard S, Troesch A, Mallet C, Generenaz L, Evans A, Arveiler D, Luc G, Ruidavets JB, Poirier O. Polymorphisms of the transforming growth factor- beta 1...transforming growth factor- beta 1 and tumour necrosis factor-alpha genes: a technical report. Transpl Immunol 1998 6(3): 193-7. 36. Olomolaiye OO

Molecular nucleation mechanisms and control strategies for crystal polymorph selection.

PubMed

Van Driessche, Alexander E S; Van Gerven, Nani; Bomans, Paul H H; Joosten, Rick R M; Friedrich, Heiner; Gil-Carton, David; Sommerdijk, Nico A J M; Sleutel, Mike

2018-04-04

The formation of condensed (compacted) protein phases is associated with a wide range of human disorders, such as eye cataracts, amyotrophic lateral sclerosis, sickle cell anaemia and Alzheimer's disease. However, condensed protein phases have their uses: as crystals, they are harnessed by structural biologists to elucidate protein structures, or are used as delivery vehicles for pharmaceutical applications. The physiochemical properties of crystals can vary substantially between different forms or structures ('polymorphs') of the same macromolecule, and dictate their usability in a scientific or industrial context. To gain control over an emerging polymorph, one needs a molecular-level understanding of the pathways that lead to the various macroscopic states and of the mechanisms that govern pathway selection. However, it is still not clear how the embryonic seeds of a macromolecular phase are formed, or how these nuclei affect polymorph selection. Here we use time-resolved cryo-transmission electron microscopy to image the nucleation of crystals of the protein glucose isomerase, and to uncover at molecular resolution the nucleation pathways that lead to two crystalline states and one gelled state. We show that polymorph selection takes place at the earliest stages of structure formation and is based on specific building blocks for each space group. Moreover, we demonstrate control over the system by selectively forming desired polymorphs through site-directed mutagenesis, specifically tuning intermolecular bonding or gel seeding. Our results differ from the present picture of protein nucleation, in that we do not identify a metastable dense liquid as the precursor to the crystalline state. Rather, we observe nucleation events that are driven by oriented attachments between subcritical clusters that already exhibit a degree of crystallinity. These insights suggest ways of controlling macromolecular phase transitions, aiding the development of protein-based drug-delivery systems and macromolecular crystallography.

Nucleation control and separation of paracetamol polymorphs through swift cooling crystallization process

NASA Astrophysics Data System (ADS)

Sudha, C.; Srinivasan, K.

2014-09-01

Polymorphic nucleation behavior of pharmaceutical solid paracetamol has been investigated by performing swift cooling crystallization process. Saturated aqueous solution prepared at 318 K was swiftly cooled to 274 K in steps of every 1 K in the temperature range from 274 K to 313 K with uniform stirring of 100 rpm. The resultant supersaturation generated in the mother solution favours the nucleation of three different polymorphs of paracetamol. Lower supersaturation region σ=0.10-0.83 favours stable mono form I; the intermediate supersaturation region σ=0.92-1.28 favours metastable ortho form II and the higher supersaturation region σ=1.33-1.58 favours unstable form III polymorphic nucleation. Depending upon the level of supersaturation generated during swift cooling process and the corresponding solubility limit and metastable zone width (MSZW) of each polymorph, the nucleation of a particular polymorph occurs in the system. The type of polymorphs was identified by in-situ optical microscopy and the internal structure was confirmed by Powder X-ray diffraction (PXRD) study. By this novel approach, the preferred nucleation regions of all the three polymorphs of paracetamol are optimized in terms of different cooling ranges employed during the swift cooling process. Also solution mediated polymorphic transformations from unstable to mono and ortho to mono polymorphs have been studied by in-situ.

Probing chemical transformation in picolitre volume aerosol droplets

NASA Astrophysics Data System (ADS)

Miloserdov, Anatolij; Day, Calum P. F.; Rosario, Gabriela L.; Horrocks, Benjamin R.; Carruthers, Antonia E.

2017-08-01

We have demonstrated chemical transformation in single microscopic-sized aerosol droplets localised in optical tweezers. Droplets in situ are measured during chemical transformation processes of solvent exchange and solute transformation through an ion exchange reaction. Solvent exchange between deionised water and heavy water in aerosol droplets is monitored through observation of the OH and OD Raman stretches. A change in solute chemistry of aerosol is achieved through droplet coalescence events between calcium chloride and sodium carbonate to promote ion exchange. The transformation forming meta-stable and stable states of CaCO3 is observed and analysed using Gaussian peak decomposition to reveal polymorphs.

Solid-state characterization and impurities determination of fluconazol generic products marketed in Morocco

PubMed Central

Bourichi, Houda; Brik, Youness; Hubert, Philipe; Cherrah, Yahia; Bouklouze, Abdelaziz

2012-01-01

In this paper, we report the results of quality control based in physicochemical characterization and impurities determination of three samples of fluconazole drug substances marketed in Morocco. These samples were supplied by different pharmaceuticals companies. The sample A, as the discovered product, was supplied by Pfizer, while samples B and C (generics), were manufactured by two different Indian industries. Solid-state characterization of the three samples was realized with different physicochemical methods as: X-ray powder diffraction, Fourier-transformation infrared spectroscopy, differential scanning calorimetry. High performance liquid chromatography was used to quantify the impurities in the different samples. The results from the physicochemical methods cited above, showed difference in polymorph structure of the three drug substances. Sample A consisted in pure polymorph III, sample B consisted in pure polymorph II, sample C consisted in a mixture of fluconazole Form III, form II and the monohydrate. This result was confirmed by differential scanning calorimetry. Also it was demonstrated that solvents used during the re-crystallization step were among the origins of these differences in the structure form. On the other hand, the result of the stability study under humidity and temperature showed that fluconazole polymorphic transformation could be owed to the no compliance with the conditions of storage. The HPLC analysis of these compounds showed the presence of specific impurities for each polymorphic form, and a possible relationship could be exist between impurities and crystalline form of fluconazole. PMID:29403776

Characterization of polymorphic states in energetic samples of 1,3,5-trinitro-1,3,5-triazine (RDX) fabricated using drop-on-demand inkjet technology.

PubMed

Emmons, Erik D; Farrell, Mikella E; Holthoff, Ellen L; Tripathi, Ashish; Green, Norman; Moon, Raphael P; Guicheteau, Jason A; Christesen, Steven D; Pellegrino, Paul M; Fountain, Augustus W

2012-06-01

The United States Army and the first responder community are evaluating optical detection systems for the trace detection of hazardous energetic materials. Fielded detection systems must be evaluated with the appropriate material concentrations to accurately identify the residue in theater. Trace levels of energetic materials have been observed in mutable polymorphic phases and, therefore, the systems being evaluated must be able to detect and accurately identify variant sample phases observed in spectral data. In this work, we report on the novel application of drop-on-demand technology for the fabrication of standardized trace 1,3,5-trinitro-1,3,5-triazine (RDX) samples. The drop-on-demand sample fabrication technique is compared both visually and spectrally to the more commonly used drop-and-dry technique. As the drop-on-demand technique allows for the fabrication of trace level hazard materials, concerted efforts focused on characterization of the polymorphic phase changes observed with low concentrations of RDX commonly used in drop-on-demand processing. This information is important when evaluating optical detection technologies using samples prepared with a drop-on-demand inkjet system, as the technology may be "trained" to detect the common bulk α phase of the explosive based on its spectral features but fall short in positively detecting a trace quantity of RDX (β-phase). We report the polymorphic shifts observed between α- and β-phases of this energetic material and discuss the conditions leading to the favoring of one phase over the other.

Arg25Pro polymorphism of transforming growth factor-beta1 and its role in the pathogenesis of essential hypertension in Russian population of the Central Chernozem Region.

PubMed

Ivanov, V P; Solodilova, M A; Polonnikov, A V; Belugin, D A; Shestakov, A M; Ushachev, D V; Khoroshaya, I V; Katargina, L N; Kozhukhov, M A; Kolesnikova, O E

2007-07-01

We studied the relationship between Arg25Pro polymorphism of TGFbeta1 gene and predisposition to essential hypertension in the Russian population of Central Chernozem Region (n=402). An association was found between 25Pro allele and 25ArgPro genotype with low risk of essential hypertension in male individuals.

Pharmaceutical properties of two ethenzamide-gentisic acid cocrystal polymorphs: Drug release profiles, spectroscopic studies and theoretical calculations.

PubMed

Sokal, Agnieszka; Pindelska, Edyta; Szeleszczuk, Lukasz; Kolodziejski, Waclaw

2017-04-30

The aim of this study was to evaluate the stability and solubility of the polymorphic forms of the ethenzamide (ET) - gentisic acid (GA) cocrystals during standard technological processes leading to tablet formation, such as compression and excipient addition. In this work two polymorphic forms of pharmaceutical cocrystals (ETGA) were characterized by 13 C and 15 N solid-state nuclear magnetic resonance and Fourier transformed infrared spectroscopy. Spectroscopic studies were supported by gauge including projector augmented wave (GIPAW) calculations of chemical shielding constants.Polymorphs of cocrystals were easily identified and characterized on the basis of solid-state spectroscopic studies. ETGA cocrystals behaviour during direct compressionand tabletting with excipient addition were tested. In order to choose the best tablet composition with suitable properties for the pharmaceutical industry dissolution profile studies of tablets containing polymorphic forms of cocrystals with selected excipients were carried out. Copyright © 2017. Published by Elsevier B.V.

Transforming growth factor-β and toll-like receptor-4 polymorphisms are not associated with fibrosis in haemochromatosis

PubMed Central

Wood, Marnie J; Powell, Lawrie W; Dixon, Jeannette L; Subramaniam, V Nathan; Ramm, Grant A

2013-01-01

AIM: To investigate the role of genetic polymorphisms in the progression of hepatic fibrosis in hereditary haemochromatosis. METHODS: A cohort of 245 well-characterised C282Y homozygous patients with haemochromatosis was studied, with all subjects having liver biopsy data and DNA available for testing. This study assessed the association of eight single nucleotide polymorphisms (SNPs) in a total of six genes including toll-like receptor 4 (TLR4), transforming growth factor-beta (TGF-β), oxoguanine DNA glycosylase, monocyte chemoattractant protein 1, chemokine C-C motif receptor 2 and interleukin-10 with liver disease severity. Genotyping was performed using high resolution melt analysis and sequencing. The results were analysed in relation to the stage of hepatic fibrosis in multivariate analysis incorporating other cofactors including alcohol consumption and hepatic iron concentration. RESULTS: There were significant associations between the cofactors of male gender (P = 0.0001), increasing age (P = 0.006), alcohol consumption (P = 0.0001), steatosis (P = 0.03), hepatic iron concentration (P < 0.0001) and the presence of hepatic fibrosis. Of the candidate gene polymorphisms studied, none showed a significant association with hepatic fibrosis in univariate or multivariate analysis incorporating cofactors. We also specifically studied patients with hepatic iron loading above threshold levels for cirrhosis and compared the genetic polymorphisms between those with no fibrosis vs cirrhosis however there was no significant effect from any of the candidate genes studied. Importantly, in this large, well characterised cohort of patients there was no association between SNPs for TGF-β or TLR4 and the presence of fibrosis, cirrhosis or increasing fibrosis stage in multivariate analysis. CONCLUSION: In our large, well characterised group of haemochromatosis subjects we did not demonstrate any relationship between candidate gene polymorphisms and hepatic fibrosis or cirrhosis. PMID:24409064

Transforming growth factor-β and toll-like receptor-4 polymorphisms are not associated with fibrosis in haemochromatosis.

PubMed

Wood, Marnie J; Powell, Lawrie W; Dixon, Jeannette L; Subramaniam, V Nathan; Ramm, Grant A

2013-12-28

To investigate the role of genetic polymorphisms in the progression of hepatic fibrosis in hereditary haemochromatosis. A cohort of 245 well-characterised C282Y homozygous patients with haemochromatosis was studied, with all subjects having liver biopsy data and DNA available for testing. This study assessed the association of eight single nucleotide polymorphisms (SNPs) in a total of six genes including toll-like receptor 4 (TLR4), transforming growth factor-beta (TGF-β), oxoguanine DNA glycosylase, monocyte chemoattractant protein 1, chemokine C-C motif receptor 2 and interleukin-10 with liver disease severity. Genotyping was performed using high resolution melt analysis and sequencing. The results were analysed in relation to the stage of hepatic fibrosis in multivariate analysis incorporating other cofactors including alcohol consumption and hepatic iron concentration. There were significant associations between the cofactors of male gender (P = 0.0001), increasing age (P = 0.006), alcohol consumption (P = 0.0001), steatosis (P = 0.03), hepatic iron concentration (P < 0.0001) and the presence of hepatic fibrosis. Of the candidate gene polymorphisms studied, none showed a significant association with hepatic fibrosis in univariate or multivariate analysis incorporating cofactors. We also specifically studied patients with hepatic iron loading above threshold levels for cirrhosis and compared the genetic polymorphisms between those with no fibrosis vs cirrhosis however there was no significant effect from any of the candidate genes studied. Importantly, in this large, well characterised cohort of patients there was no association between SNPs for TGF-β or TLR4 and the presence of fibrosis, cirrhosis or increasing fibrosis stage in multivariate analysis. In our large, well characterised group of haemochromatosis subjects we did not demonstrate any relationship between candidate gene polymorphisms and hepatic fibrosis or cirrhosis.

Vibrational spectroscopic study on polymorphism of erucic acid and palmitoleic acid: γ1→α1 and γ→α reversible solid state phase transitions

NASA Astrophysics Data System (ADS)

Kaneko, Fumitoshi; Yamazaki, Kazuhiro; Kobayashi, Masamichi; Sato, Kiyotaka; Suzuki, Masao

1994-08-01

The infrared and Raman spectra of four polymorphic phases (α, α1, γ and γ1) of erucic acid ( cis-13-docosenoic acid) and those of two polymorphic phases (α and γ) of palmitoleic acid ( cis-9-hexadecenoic acid) were investigated. The γ and γ1 phases of erucic acid were analyzed on the basis of crystal structures determined by us. There were large spectral differences between γ and γ1 phases, which could be ascribed to the differences in the conformation of cis-olefin groups and the subcell structure. Two types of reversible solid state phase transitions (γ→α and γ1→α1 transitions) were followed by the infrared and Raman spectra. It was concluded that the mechanism of the γ→α phase transition of erucic and palmitoleic acids is essentially the same as that of oleic acid previously reported by us [ J. Phys. Chem.90, 6371 (1986)], i.e. this phase transition is of order-disorder type accompanied by a conformational disordering at the methyl-terminal chain. Spectral changes on the γ1→α1 transition suggested that a similar structural change took place during this transition but there were large structural differences between α and α1.

Phase diagram of the Y–Y{sub 2}Se{sub 3} system, enthalpies of phase transformations

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

Andreev, O.V.; Kharitontsev, V.B.; Polkovnikov, A.A., E-mail: a.a.polkovnikov@yandex.ru

A phase diagram for the Y–Y{sub 2}Se{sub 3} system has been constructed in which the YSe and Y{sub 2}Se{sub 3} phases melt congruently. The daltonide type YSe phase (ST Y{sub 0,75}Se, a=1.1393 nm, melting point=2380 K, H=2200 MPa) forms a double-sided solid solution from 49–50–53 at% Se. In the 50–53 at% Se range, the unit cell parameter increases to 1.1500 nm, the microhardness increases to 4100 MPa and electrical resistivity increases from 0.018 to 0.114 Ω m. These changes are caused by the dominating influx of newly formed structural cationic vacancies arising from the selenium anions that are surplus formore » the 1:1 Y:Se stoichiometry. The full-valence Y{sub 2}Se{sub 3} composition exists as a low-temperature modification of ε-Y{sub 2}Se{sub 3} (ST Sc{sub 2}S{sub 3}, a=1.145 nm, b=0.818 nm, c=2.438 nm, melting point=1780 K, ∆fusion enthalpy=4±0.4 J/g) and transforms into a modification of ξ-Y{sub 2}Se{sub 3} that does not undergo fixing by thermo-hardening. The eutectic melting point between the YSe and Y{sub 2}Se{sub 3} phases is 1625±5 K, with a eutectic composition that is assumed to be 57.5 at% Se and have an enthalpy of fusion of 43±4.3 J/g. The eutectic for the Y and YSe phases appears at a temperature of 1600 K and 5 at% Se. - Highlights: • Phase equilibria in the Y–Y{sub 2}Se{sub 3} system from 1000 K to melt were studies. • High-temperature polymorphic transition for Y{sub 2}Se{sub 3} were observed. • Singular points in solid solutions areas for YSe and Y{sub 2}Se{sub 3} were found.« less

Phase transformation and microstructural evolution of nanostructured oxides and nitrides under ion irradiations

NASA Astrophysics Data System (ADS)

Lu, Fengyuan

Material design at the nanometer scale is an effective strategy for developing advanced materails with enhanced radiation tolerance for advanced nuclear energy systems as high densities of surfaces and interfaces of the nanostructured materials may behave as effective sinks for defect recovery. However, nanostructured materials may not be intrinsically radiation tolerant, and the interplay among the factors of crystal size, temperature, chemical composition, surface energy and radiation conditions may eventually determine material radiation behaviors. Therefore, it is necessary to understand the radiation effects of nanostructured materials and the underlying physics for the design of advanced nanostructured nuclear materials. The main objective of this doctoral thesis is to study the behavior of nanostructured oxides and nitrides used as fuel matrix and waste forms under extreme radiation conditions with the focus of phase transformation, microstructural evolution and damage mechanisms. Radiation experiments were performed using energetic ion beam techniques to simulate radiation damage resulting from energetic neutrons, alpha-decay events and fission fragments, and various experimental approaches were employed to characterize materials’ microstructural evolution and phase stability upon intense radiation environments including transmission electron microscopy (TEM), X-ray diffraction (XRD) and Raman spectroscopy. Thermal annealing experiments indicated that nanostructured ZrO2 phase stability is strongly affected by the grain size. Radiation results on nanostructured ZrO2 indicated that thermodynamically unstable or metastable high temperature phases can be induced by energetic beam irradiation at room temperature. Various phase transformation among different polymorphs of monoclinic, tetragonal and amorphous states can be induced, and different mechanisms are responsible for structural transformations including oxygen vacancies accumulation upon displacive damage, radiation-assistant recrystallization and thermal spike by ionization radiation. The radiation response of nanosized pyrochlores indicated that the radiation tolerance of nanoceramics is highly dependent on the composition and size. Nanosized tantalate pyrochlores KxLnyTa2O 7-v (Ln = Gd, Y, Lu) with the average grain size around 10 - 15 nm are highly sensitive to radiation-induced amorphization. The pyrochlore A to B site ionic radius ratio rA/rB is crucial in determining the radiation tolerance of pyrochlores, and a minimum rA/rB of 1.605 exists for the occurring of radiation induced amorphization. The interplay among chemical compositions, structural deviation and grain size eventually determines the phase stability and structural transformation processes of tantalate pyrochlores under intense radiation environments. ZrN shows extremely high phase stability under both displacive ion irradiation and ionizing swift heavy ion irradiation. However, a contraction in lattice constant up to ~ 1.42 % can be induced in nanocrystalline ZrN irradiated with displacive ion beams. In contrast, the strongly ionizing swift heavy ions cannot induce any lattice contraction. Such lattice contractions may be due to a negative strain field in the ZrN nanograins related to N vacancies built up upon displacive radiation. Ion irradiations also lead to the formation of orthorhombic ZrSi phase at the interface between ZrN and Si substrate, resulting from atom mixing and precipitation upon ion irradiations. The fundamental knowledge provides critical data for assessing and quantifying nanostructured ceramics as fuel matrix and waste forms utilized in the extreme environments of advanced nuclear energy systems. Further possibilities are being pursued in manipulating microstructure at the nano-scale, controlling phase stability and tailoring the physical properties of materials for various important engineering applications.

Bulk and Interface Thermodynamics of Calcia-, and Yttria-doped Zirconia Ceramics: Nanograined Phase Stability

NASA Astrophysics Data System (ADS)

Drazin, John Walter

Calcia-, and yttria- doped zirconia powders and samples are essential systems in academia and industry due to their observed bulk polymorphism. Pure zirconia manifests as Baddeleyite, a monoclinic structured mineral with 7-fold coordination. This bulk form of zirconia has little application due to its asymmetry. Therefore dopants are added to the grain in-order to induce phase transitions to either a tetragonal or cubic polymorph with the incorporation of oxygen vacancies due to the dopant charge mis-match with the zirconia matrix. The cubic polymorph has cubic symmetry such that these samples see applications in solid oxide fuel cells (SOFCs) due to the high oxygen vacancy concentrations and high ionic mobility at elevated temperatures. The tetragonal polymorph has slight asymmetry in the c-axis compared to the a-axis such that the tetragonal samples have increased fracture toughness due to an impact induced phase transformation to a cubic structure. These ceramic systems have been extensively studied in academia and used in various industries, but with the advent of nanotechnology one can wonder whether smaller grain samples will see improved characteristics similar to their bulk grain counterparts. However, there is a lack of data and knowledge of these systems in the nano grained region which provides us with an opportunity to advance the theory in these systems. The polymorphism seen in the bulk grains samples is also seen in the nano-grained samples, but at slightly distinct dopant concentrations. The current theory hypothesizes that a surface excess, gamma (J/m 2), can be added to the Gibbs Free energy equation to account for the additional free energy of the nano-grain atoms. However, these surface energies have been difficult to measure and therefore thermodynamic data on these nano-grained samples have been sparse. Therefore, in this work, I will use a well established water adsorption microcalorimetry apparatus to measure the water coverage isotherms while simultaneously collecting the energetic contribution of the adsorbing water vapor. With this data and apparatus, I have derived a 2nd order differential equation that relates the surface energy to the measured quantities such that I collected surfaces energies for over 35 specimens in the calcia-zirconia and yttria-zirconia systems for the first time. From the results, it was found that the monoclinic polymorph had the largest surface energy in the range of 1.9 - 2.1 ( J/m2) while the tetragonal surface energies were roughly 1.4 - 1.6 (J/m2), the cubic surface energies were roughly 0.8 - 1.0 (J/m2), and the amorphous surface energies were the smallest at roughly 0.7 - 0.8 (J/m 2). With the measured surface energy data, collected for the first time, we can create a nano-grain phase diagram similar to a bulk phase diagram that shows the stable polymorph as a function of dopant concentration and grain size using the bulk enthalpy data collected from high temperature oxide melt drop solution calorimetry. The phase diagrams show that pure zirconia will transform into tetragonal and cubic polymorphs from the monoclinic one at 7 and 5 nm respectively which confirms the experimental observations. The results are powerful predictive tools successfully applied in the nCZ and nYZ systems to a high degree of accuracy and adds a new development to conventional bulk phase diagrams. These diagrams should be the basis for nanotechnological efforts in nCZ and nYZ based systems, and suggest similar efforts are needed in other nano systems to pursue an in depth understanding and optimization of nanomaterials. After working on the theoretical aspects of phase stability, the focus of the research will shift to producing dense samples to measure observable quantities such as oxygen conduction and mechanical hardness. However, producing said samples with the nanocrystalline grain sizes has also been challenging as conventional sintering requires high temperatures which, as a consequence, induces grain growth of the samples limiting the minimum grain size of the samples. Therefore, in this work, we have developed a Pressure Assisted Rapid Sintering Technique (PARS) that uses high currents to Joule heat the samples to moderate temperatures (650-900 °C) for short durations (5-10 min) under large compressive pressures (600-2200 MPa). With this new technique, atomic level grain sizes (sub-10nm) can be easily achieved at high relative densities (>98 %). Using the PARS setup, multiple 3nYZ samples were produced with varied grain sizes down to 9 nm and as large as 5mum. The mechanical hardness of these samples were tested using a Vicker's microhardness indentation apparatus. The hardness of the "bulk" grains was roughly 12.9 GPa while the smallest grain size pellet had a hardness approaching 15 GPa. All of the 3nYZ pellets had a higher hardness with diminishing grain size, thereby extending the Hall-Petch relationship to 9 nm in the 3YZ system. This is an amazing and unprecedented result to date. After producing the extreme nano-grained samples (15nCZ and 17.5nYSZ), they were tested for inter- and intragranular oxygen ion conduction as well. The results showed that the smaller grained samples have increased levels of oxygen ion conduction from both inter- and intragranular diffusion regardless of the operating temperatures. In addition, it was seen that the activation energies for both modes of oxygen ion diffusion were lowered for the nCZ system while a plateaued effect was seen in the nYZ system. A new theoretical formulation was proposed to explain the trends such that there are two modifiable parameters to exploit; activation energy and grain size. With the lowering of the grain size, the number of interconnected grain boundaries would increase dramatically allowing for more efficient travel around and through the grains. The activation energy can be lowered by modifying the chemistry of the grain boundary by specifically choosing larger dopants with a positive enthalpy of segregation such the concentration of the dopants on the grain boundary would increase, spacing the unattached bonds further apart and reducing their number. Therefore, one can use an engineered nanograined SOFC to decrease the operating temperature of the device without altering the output power density; significantly improving safety and economics.

Phase Behavior of Complex Superprotonic Solid Acids

NASA Astrophysics Data System (ADS)

Panithipongwut, Chatr

Superprotonic phase transitions and thermal behaviors of three complex solid acid systems are presented, namely Rb3H(SO4) 2-RbHSO4 system, Rb3H(SeO4)2-Cs 3H(SeO4)2 solid solution system, and Cs6 (H2SO4)3(H1.5PO4) 4. These material systems present a rich set of phase transition characteristics that set them apart from other, simpler solid acids. A.C. impedance spectroscopy, high-temperature X-ray powder diffraction, and thermal analysis, as well as other characterization techniques, were employed to investigate the phase behavior of these systems. Rb3H(SO4)2 is an atypical member of the M3H(XO4)2 class of compounds (M = alkali metal or NH4+ and X = S or Se) in that a transition to a high-conductivity state involves disproportionation into two phases rather than a simple polymorphic transition [1]. In the present work, investigations of the Rb3H(SO4)2-RbHSO4 system have revealed the disproportionation products to be Rb2SO 4 and the previously unknown compound Rb5H3(SO 4)4. The new compound becomes stable at a temperature between 25 and 140 °C and is isostructural to a recently reported trigonal phase with space group P3m of Cs5H 3(SO4)4 [2]. At 185 °C the compound undergoes an apparently polymorphic transformation with a heat of transition of 23.8 kJ/mol and a slight additional increase in conductivity. The compounds Rb3H(SeO4)2 and Cs 3H(SeO4)2, though not isomorphous at ambient temperatures, are quintessential examples of superprotonic materials. Both adopt monoclinic structures at ambient temperatures and ultimately transform to a trigonal (R3m) superprotonic structure at slightly elevated temperatures, 178 and 183 °C, respectively. The compounds are completely miscible above the superprotonic transition and show extensive solubility below it. Beyond a careful determination of the phase boundaries, we find a remarkable 40-fold increase in the superprotonic conductivity in intermediate compositions rich in Rb as compared to either end-member. The compound Cs6(H2SO4)3(H 1.5PO4)4 is unusual amongst solid acid compounds in that it has a complex cubic structure at ambient temperature and apparently transforms to a simpler cubic structure of the CsCl-type (isostructural with CsH2PO4) at its transition temperature of 100-120 °C [3]. Here it is found that, depending on the level of humidification, the superprotonic transition of this material is superimposed with a decomposition reaction, which involves both exsolution of (liquid) acid and loss of H2O. This reaction can be suppressed by application of sufficiently high humidity, in which case Cs6(H2SO4)3(H 1.5PO4)4 undergoes a true superprotonic transition. It is proposed that, under conditions of low humidity, the decomposition/dehydration reaction transforms the compound to Cs6(H2-0.5xSO 4)3(H1.5PO4)4-x, also of the CsCl structure type at the temperatures of interest, but with a smaller unit cell. With increasing temperature, the decomposition/dehydration proceeds to greater and greater extent and unit cell of the solid phase decreases. This is identified to be the source of the apparent negative thermal expansion behavior. References: [1] L.A. Cowan, R.M. Morcos, N. Hatada, A. Navrotsky, S.M. Haile, Solid State Ionics 179 (2008) (9-10) 305. [2] M. Sakashita, H. Fujihisa, K.I. Suzuki, S. Hayashi, K. Honda, Solid State Ionics 178 (2007) (21-22) 1262. [3] C.R.I. Chisholm, Superprotonic Phase Transitions in Solid Acids: Parameters affecting the presence and stability of superprotonic transitions in the MHnXO4 family of compounds (X=S, Se, P, As; M=Li, Na, K, NH4, Rb, Cs), Materials Science, California Institute of Technology, Pasadena, California (2003).

Fabrication of vertically aligned ferroelectric polyvinylidene fluoride mesoscale rod arrays

DOE PAGES

Kim, Dongjin; Hong, Seungbum; Hong, Jongin; ...

2013-05-14

Here, we have fabricated vertically aligned ferroelectric PVDF mesoscale rod arrays comprising and phases using a 200 nm diameter anodized aluminum oxide (AAO) as the porous template. We could synthesize the ferroelectric phase in mesoscale rod forms by combining the well-established recipe for crystallizing the phase using dimethyl sulfoxide (DMSO) at low temperature and template-guided infiltration processing for the rods using AAO. We also measured the dimensions of the PVDF rods by scanning electron microscopy and identified the polymorph phases by X-ray diffraction and Fourier transform infrared spectroscopy. The length of the rods varied from 3.82 m to 1.09 mmore » and the diameter from 232 nm to 287 nm when the volume ratio between DMSO and acetone changed from 5 : 5 to 10 : 0. We obtained well-defined piezoresponse hysteresis loops for all rods with remnant piezoresponse ranging from 2.12 pm/V to 5.04 pm/V and coercive voltage ranging from 2.29 V to 2.71 V using piezoresponse force microscopy. These results serve as a processing platform for flexible electronic devices that need high capacitance and piezoelectric functionalities such as flexible memory devices or body energy harvesting devices for intelligent systems. (c) 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3842-3848, 2013« less

Are metastable, precrystallisation, density-fluctuations a universal phenomena?

PubMed

Heeley, Ellen L; Poh, C Kit; Li, Wu; Maidens, Anna; Bras, Wim; Dolbnya, Igor P; Gleeson, Anthony J; Terrill, Nicolas J; Fairclough, J Patrick A; Olmsted, Peter D; Ristic, Rile I; Hounslow, Micheal J; Ryan, Anthony J

2003-01-01

In-situ observations of crystallisation in minerals and organic polymers have been made by simultaneous, time-resolved small angle X-ray scattering (SAXS) and wide angle X-ray scattering (WAXS) techniques. In isotactic polypropylene slow quiescent crystallisation shows the onset of large scale ordering prior to crystal growth. Rapid crystallisations studied by melt extrusion indicate the development of well resolved oriented SAXS patterns associated with long range order before the development of crystalline peaks in the WAXS region. Block copolymers self-assemble into mesophases in polymer melts above a critical chain length (or above a critical temperature) and this self-assembly process is shown to be susceptible to an incipient crystallisation. Mesophase formation is observed at anomalously high temperatures in ethylene-oxide containing block copolymers below the normal melting point of the polyoxy ethylene chains. Formation of calcium carbonate from aqueous solutions of sodium carbonate and calcium nitrate is observed to be a two-stage process and precipitation proceeds by the production of an amorphous metastable phase. This phase grows until it is volume filling and leads to the formation of the two polymorphs Calcite and Vaterite. These three sets of results suggest pre-nucleation density fluctuations, leading to a metastable phase, play an integral role in all three classes of crystallisation. In due course, this phase undergoes transformation to "normal" crystals.

High pressure-temperature polymorphism of 1,1-diamino-2,2-dinitroethylene

NASA Astrophysics Data System (ADS)

Bishop, M. M.; Chellappa, R. S.; Liu, Z.; Preston, D. N.; Sandstrom, M. M.; Dattelbaum, D. M.; Vohra, Y. K.; Velisavljevic, N.

2014-05-01

1,1-diamino-2,2-dinitroethylene (FOX-7) is a low sensitivity energetic material with performance comparable to commonly used secondary explosives such as RDX and HMX. At ambient pressure, FOX-7 exhibits complex polymorphism with at least three structurally distinct phases (α, β, and γ). In this study, we have investigated the high pressure-temperature stability of FOX-7 polymorphs using synchrotron mid-infrared (MIR) spectroscopy. At ambient pressure, our MIR spectra and corresponding differential scanning calorimetry (DSC) measurements confirmed the known α → β (~110 °C) and α → β (~160 °C) structural phase transitions; as well as, indicated an additional transition γ → (~210 °C), with the δ phase being stable up to ~251 °C prior to decomposition. In situ MIR spectra obtained during isobaric heating at 0.9 GPa, revealed a potential α → β transition that could occur as early as 180 °C, while β → β+δ phase transition shifted to ~300 °C with suppression of γ phase. Decomposition was observed slightly above 325 °C at 0.9 GPa.

Adapting phase-switch Monte Carlo method for flexible organic molecules

NASA Astrophysics Data System (ADS)

Bridgwater, Sally; Quigley, David

2014-03-01

The role of cholesterol in lipid bilayers has been widely studied via molecular simulation, however, there has been relatively little work on crystalline cholesterol in biological environments. Recent work has linked the crystallisation of cholesterol in the body with heart attacks and strokes. Any attempt to model this process will require new models and advanced sampling methods to capture and quantify the subtle polymorphism of solid cholesterol, in which two crystalline phases are separated by a phase transition close to body temperature. To this end, we have adapted phase-switch Monte Carlo for use with flexible molecules, to calculate the free energy between crystal polymorphs to a high degree of accuracy. The method samples an order parameter , which divides a displacement space for the N molecules, into regions energetically favourable for each polymorph; which is traversed using biased Monte Carlo. Results for a simple model of butane will be presented, demonstrating that conformational flexibility can be correctly incorporated within a phase-switching scheme. Extension to a coarse grained model of cholesterol and the resulting free energies will be discussed.

Onset of ice VII phase during ps laser pulse propagation through liquid water

NASA Astrophysics Data System (ADS)

Paturi, Prem Kiran; Vaddapally, Rakesh Kumar; Acrhem Team

2015-06-01

Water dominantly present in liquid state on earth gets transformed to crystalline polymorphs under different dynamic loading conditions. Out of 15 different crystalline phases discovered till date, ice VII is observed to be stable over wide pressure (2-63 GPa) and temperature (>273 K) ranges. We present the onset of ice VII phase at low threshold of 2 mJ/pulse during 30 ps (532 nm, 10 Hz) laser pulse induced shock propagating through liquid water. Role of input pulse energy on the evolution of Stoke's and anti-Stoke's Raman shift of the dominant A1g mode of ice VII, filamentation, free-electrons, plasma shielding is presented. The H-bond network rearrangement, electron ion energy transfer time coinciding with the excitation pulse duration supported by the filamentation and plasma shielding of the ps laser pulses reduced the threshold of ice VII structure formation. Filamentation and the plasma shielding have shown the localized creation and sustenance of ice VII structure in liquid water over 3 mm length and 50 μm area of cross-section. The work is supported by Defence Research and Developement Organization, India through Grants-in-Aid Program.

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.

Mineralogical changes of a well cement in various H2S-CO2(-brine) fluids at high pressure and temperature.

PubMed

Jacquemet, Nicolas; Pironon, Jacques; Saint-Marc, Jérémie

2008-01-01

The reactivity of a crushed well cement in contact with (1) a brine with dissolved H2S-CO2; (2) a dry H2S-CO2 supercritical phase; (3) a two-phase fluid associating a brine with dissolved H2S-CO2 and a H2S-CO2 supercritical phase was investigated in batch experiments at 500 bar and 120, 200 degrees C. All of the experiments showed that following 15-60 days cement carbonation occurred. The H2S reactivity with cement is limited since it only transformed the ferrites (minor phases) by sulfidation. It appeared that the primary parameter controlling the degree of carbonation (i.e., the rate of calcium carbonates precipitation and CSH (Calcium Silicate Hydrates) decalcification) is the physical state of the fluid phase contacting the minerals. The carbonation degree is complete when the minerals contact at least the dry H2S-CO2 supercritical phase and partial when they contactthe brine with dissolved H2S-CO2. Aragonite (calcium carbonate polymorph) precipitated specifically within the dry H2S-CO2 supercritical phase. CSH cristallinity is improved by partial carbonation while CSH are amorphized by complete carbonation. However, the features evidenced in this study cannot be directly related to effective features of cement as a monolith. Further studies involving cement as a monolith are necessary to ascertain textural, petrophysical, and mechanical evolution of cement.

A conserved post-transcriptional BMP2 switch in lung cells.

PubMed

Jiang, Shan; Fritz, David T; Rogers, Melissa B

2010-05-15

An ultra-conserved sequence in the bone morphogenetic protein 2 (BMP2) 3' untranslated region (UTR) markedly represses BMP2 expression in non-transformed lung cells. In contrast, the ultra-conserved sequence stimulates BMP2 expression in transformed lung cells. The ultra-conserved sequence functions as a post-transcriptional cis-regulatory switch. A common single-nucleotide polymorphism (SNP, rs15705, +A1123C), which has been shown to influence human morphology, disrupts a conserved element within the ultra-conserved sequence and altered reporter gene activity in non-transformed lung cells. This polymorphism changed the affinity of the BMP2 RNA for several proteins including nucleolin, which has an increased affinity for the C allele. Elevated BMP2 synthesis is associated with increased malignancy in mouse models of lung cancer and poor lung cancer patient prognosis. Understanding the cis- and trans-regulatory factors that control BMP2 synthesis is relevant to the initiation or progression of pathologies associated with abnormal BMP2 levels. (c) 2010 Wiley-Liss, Inc.

Analysis of common transforming growth factor beta-1 gene polymorphisms in gastric and duodenal ulcer disease: pilot study.

PubMed

Polonikov, Alexey V; Ivanov, Vladimir P; Belugin, Dmitry A; Khoroshaya, Irina V; Kolchanova, Inessa O; Solodilova, Mariya A; Tutochkina, Margarita P; Stepchenko, Alexander A

2007-04-01

Transforming growth factor-beta1 (TGF-beta1) has been shown to be an important cytokine that plays a role in cell proliferation, differentiation, tissue injury repair and ulcer healing. The purpose of this pilot study was to investigate if common polymorphisms Leu10Pro, Arg25Pro and C-509T within the TGF-beta1 gene are associated with susceptibility to gastric and duodenal ulcer disease in Russians. Blood samples from 377 unrelated patients with gastric and duodenal ulcer disease and 226 sex- and age-matched healthy controls were used to determine TGF-beta1 gene polymorphisms by polymerase chain reaction-restriction fragment length polymorphism (PCR-RFLP). Leu10Pro substitution in the signal peptide of TGF-beta1 has been found to be associated with susceptibility to gastric ulcer (odds ratio [OR] 1.76, 95% confidence interval [CI] 1.12-2.77). A genotype combination of 10Leu/Leu x 25Arg/Arg x -509C/C was also associated with susceptibility to gastric ulcer disease (OR 1.81, P = 0.01). In addition, the frequency of a combination of genotypes 10Pro/Pro x 25Arg/Pro x -509C/T was statistically lower in patients with duodenal ulcer than in controls (OR 0.42, P = 0.05). A significant difference (P = 0.04) in the distribution of rare haplotypes of the TGF-beta1 gene between patients with duodenal ulcer and healthy controls has been found. Polymorphism Leu10Pro was in positive linkage disequilibrium with C-509T polymorphism (coefficient D = 0.191; P < 0.0001). These findings indicate that the Leu10Pro and C-509T polymorphisms may be involved in the modulation of expression of the TGF-beta1 gene, and therefore a predisposition to peptic ulcer disease could be linked to particular alleles of this gene. In particular, a possible role of TGF-beta1 in the pathogenesis of gastric ulcer disease is discussed.

Vapor-phase fabrication of β-iron oxide nanopyramids for lithium-ion battery anodes.

PubMed

Carraro, Giorgio; Barreca, Davide; Cruz-Yusta, Manuel; Gasparotto, Alberto; Maccato, Chiara; Morales, Julián; Sada, Cinzia; Sánchez, Luis

2012-12-07

The other polymorph: A vapor-phase route for the fabrication of β-Fe(2)O(3) nanomaterials on Ti substrates at 400-500 °C is reported. For the first time, the β polymorph is tested as anode for lithium batteries, exhibiting promising performances in terms of Li storage and rate capability. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polymorphism of a new Mannich base - [-4-methyl-2-((4-(4-nitrophenyl)piperazin-1-yl)methyl)phenol

NASA Astrophysics Data System (ADS)

Ayeni, Ayowole O.; Watkins, Gareth M.; Hosten, Eric C.

2018-05-01

Two polymorphs (forms I and II) of a new Mannich base 4-methyl-2-((4-(4-nitrophenyl)piperazin-1-yl)methyl)phenol have been isolated and characterized by single crystal and powder (experimental and theoretical) X-ray diffraction, thermal analysis (differential scanning calorimetry), Fourier transform infrared spectroscopy. 1H and 13C nuclear magnetic resonance spectroscopy was employed in characterising the new Mannich base. Single crystal X-ray diffraction revealed that the two polymorphs contain different conformers of the Mannich base whose hydrogen bonding schemes and packing arrangements in their respective crystals are different. Thermal analysis led to the conclusion that the two polymorphs are enantiotropically related, with a transition temperature of 138.5 °C.

Lab-X-ray multidimensional imaging of processes inside porous media

NASA Astrophysics Data System (ADS)

Godinho, Jose

2017-04-01

Time-lapse and other multidimensional X-ray imaging techniques have mostly been applied using synchrotron radiation, which limits accessibility and complicates data analysis. Here, we present new time-lapse imaging approaches using laboratory X-ray computed microtomography (CT) to study transformations inside porous media. Specifically, three methods will be presented: 1) Quantitative time-lapse radiography to study sub-second processes. For example to study the penetration of particles into fractures and pores, which is essential to understand how proppants keep fractures opened during hydraulic fracturing and how filter cakes form during borehole drilling. 2) Combination of time-lapse CT with diffraction tomography to study the transformation between bio-inspired polymorphs in 6D, e.g. mineral phase transformation between ACC, Vaterite and Calcite - CaCO3, and between ACS, Anhydrite and Gypsum - CaSO4. Crystals can be resolved in nanopores down to 7 nm (over 100 times smaller than the resolution of CT), which allows studying the effect of confinement on phase stability and growth rates. 3) Fast iterative helical micro-CT scanning to study samples of high ratio height to width (e.g. long cores) with optimal resolution. Here we show how this can be useful to study the distribution of the products from fluid-mediated mineral reactions throughout longer reaction paths and more representative volumes. Using state of the art reconstruction algorithms allows reducing the scanning times from over ten hours to below two hours enabling time-lapse studies. It is expected that these new techniques will open new possibilities for time-lapse imaging of a wider range of geological processes using laboratory X-ray CT, thereby increasing the accessibility of multidimensional imaging to a larger number of users and applications in geology.

Phase Transformations and Microstructural Evolution: Part II

DOE PAGES

Clarke, Amy Jean

2015-10-30

The activities of the Phase Transformations Committee of the Materials Processing & Manufacturing Division (MPMD) of The Minerals, Metals & Materials Society (TMS) are oriented toward understanding the fundamental aspects of phase transformations. Emphasis is placed on the thermodynamic driving forces for phase transformations, the kinetics of nucleation and growth, interfacial structures and energies, transformation crystallography, surface reliefs, and, above all, the atomic mechanisms of phase transformations. Phase transformations and microstructural evolution are directly linked to materials processing, properties, and performance. In this issue, aspects of liquid–solid and solid-state phase transformations and microstructural evolution are highlighted. Many papers in thismore » issue are highlighted by this paper, giving a brief summary of what they bring to the scientific community.« less

Template-assisted mineral formation via an amorphous liquid phase precursor route

NASA Astrophysics Data System (ADS)

Amos, Fairland F.

The search for alternative routes to synthesize inorganic materials has led to the biomimetic route of producing ceramics. In this method, materials are manufactured at ambient temperatures and in aqueous solutions with soluble additives and insoluble matrix, similar to the biological strategy for the formation of minerals by living organisms. Using this approach, an anionic polypeptide additive was used to induce an amorphous liquid-phase precursor to either calcium carbonate or calcium phosphate. This precursor was then templated on either organic or inorganic substrates. Non-equilibrium morphologies, such as two-dimensional calcium carbonate films, one-dimensional calcium carbonate mesostructures and "molten" calcium phosphate spherulites were produced, which are not typical of the traditional (additive-free) solution grown crystals in the laboratory. In the study of calcium carbonate, the amorphous calcium carbonate mineral formed via the liquid-phase precursor, either underwent a dissolution-recrystallization event or a pseudo-solid-state transformation to produce different morphologies and polymorphs of the mineral. Discrete or aggregate calcite crystals were formed via the dissolution of the amorphous phase to allow the reprecipitation of the stable crystal. Non-equilibrium morphologies, e.g., films, mesotubules and mesowires were templated using organic and inorganic substrates and compartments. These structures were generated via an amorphous solid to crystalline solid transformation. Single crystalline tablets and mesowires of aragonite, which are reported to be found only in nature as skeletal structures of marine organisms, such as mollusk nacre and echinoderm teeth, were successfully synthesized. These biomimetic structures were grown via the polymer-induced liquid-phase precursor route in the presence of magnesium. Only low magnesium-bearing calcite was formed in the absence of the polymer. A similar approach of using a polymeric additive was implemented in calcium phosphate. Spherulitic crystals and films, seemingly formed from a molten state, were produced. These structures served as nucleating surfaces for the radial formation of calcium oxalate minerals. The composite calcium phosphate-calcium oxalate assemblies are similar to the core-shell structures found in certain kidney stones.

A polymorph of terephthalaldehyde.

PubMed

Teng, Lei; Wang, Zhiguo

2008-07-23

A new ortho-rhom-bic polymorph of terephthalaldehyde, C(8)H(6)O(2), with a melting point of 372 K, has been obtained by recrystallization from ethanol. At room temperature, the crystals transform into the well known monoclinic form, with a melting point of 389 K. The crystal structure of the monoclinic form involves C-H⋯O hydrogen bonds, but no such bonds are observed in the orthorhombic form. The molecule is planar.

Polymorphism and mesomorphism of oligomeric surfactants: effect of the degree of oligomerization.

PubMed

Jurašin, D; Pustak, A; Habuš, I; Šmit, I; Filipović-Vinceković, N

2011-12-06

A series of cationic oligomeric surfactants (quaternary dodecyldimethylammonium ions with two, three, or four chains connected by an ethylene spacer at the headgroup level, abbreviated as dimer, trimer, and tetramer) were synthesized and characterized. The influence of the degree of oligomerization on their polymorphic and mesomorphic properties was investigated by means of X-ray diffraction, polarizing optical microscopy, thermogravimetry, and differential scanning calorimetry. All compounds display layered arrangements with interdigitated dodecyl chains. The increase in the degree of oligomerization increases the interlayer distance and decreases the ordering in the solid phase; whereas the dimer sample is fully crystalline with well-developed 3D ordering and the trimer and tetramer crystallize as highly ordered crystal smectic phases. The number of thermal phase transitions and sequence of phases are markedly affected by the number of dodecyl chains. Anhydrous samples exhibit polymorphism and thermotropic mesomorphism of the smectic type, with the exception of the tetramer that displays only transitions at higher temperature associated with decomposition and melting. All hydrated compounds form lyotropic mesophases showing reversible phase transitions upon heating and cooling. The sequence of liquid-crystalline phases for the dimer, typical of concentrated ionic surfactant systems, comprises a hexagonal phase at lower temperatures and a smectic phase at higher temperatures. In contrast, the trimer and tetramer reveal textures of the hexagonal phase. © 2011 American Chemical Society

Gender-dependent association of a β(2)-adrenergic gene variant with obesity parameters in Malaysian Malays.

PubMed

Apalasamy, Yamunah Devi; Ming, Moy Foong; Rampal, Sanjay; Bulgiba, Awang; Mohamed, Zahurin

2015-03-01

Recent findings have shown that the rs1042714 (Gln27Glu) single-nucleotide polymorphism (SNP) on the β2-adrenoceptor gene may predispose to obesity. The findings from other studies carried on different populations, however, have been inconsistent. The authors investigated the association between the rs1042714 SNP with obesity-related parameters. DNA of 672 Malaysian Malays was analyzed using real-time polymerase chain reaction. Univariate and multivariate linear regression analyses revealed significant associations between rs1042714 and diastolic blood pressure in the pooled Malaysian Malay subjects under additive and recessive models. After gender stratification, however, a significant association was found between the rs1042714 and triglyceride and the rs1042714 and log-transformed high-density lipoprotein cholesterol levels in Malaysian Malay men. No significant association was found between the SNP and log-transformed body mass index. This polymorphism may have an important role in the development of obesity-related traits in Malaysian Malays. Gender is an effect modifier for the effect of the rs1042714 polymorphism on obesity-related traits in Malaysian Malays. © 2011 APJPH.

The nature, distribution and genesis of the coesite and stishovite associated with the pseudotachylite of the Vredefort Dome, South Africa

NASA Astrophysics Data System (ADS)

Martini, J. E. J.

1991-04-01

The Vredefort Dome represents the uplift centre of a well known 2.00 Ga old impact structure of unusually large magnitude. Shock features like shatter cones, planar features and high-pressure silica polymorphs are common. The present study deals with the description, mode of occurrence, field distribution and post-shock metamorphic alteration of coesite and stishovite which were poorly documented up to now. These minerals occur as unusually large crystals in the quartzite of the wall rock in contact with very thin pseudotachylite veins. In the pseudotachylite itself, which can be interpreted as a friction and/or a shock recovery melt, fine needles of kyanite are ubiquitous. It is proposed that these thin pseudotachylites (A-type) formed during the transit of the shock wave. They preceded the development of thick pseudotachylite and microbreccia veins (B-type) which formed during the tensional period which immediately followed. From comparison with the model of formation of high-pressure polymorphs in porous sandstone, it is suggested that higher pressure and stress was concentrated along the A-type veins at the arrival of the shock front. At this time the quartz was transformed into a "high-pressure phase" which was probably poorly crystalline. Behind the shock front, that is during the rarefaction, the pressure was progressively released and the polymorphs crystallized from this initial "high-pressure phase". Stishovite crystallized first, followed by coesite. The high-pressure conditions may have lasted an unusually long time due to the magnitude of the Vredefort impact. This long time, probably about one second, may account for the large size of the coesite and stishovite crystals. Most of the high-pressure silica polymorphs are corroded to a variable degree by secondary quartz and preserved only in a restricted area of the impact structure. This alteration is attributed to post-shock metamorphism due to the temperature of the rock before impact plus the heat left after shock recovery. Some of the evidence put forward by authors against the impact model is discussed according to the facts arising from this investigation. It is concluded that an origin by impact remains the simplest and most realistic model to explain the origin of the Vredefort Dome.

Phase stability of iron germanate, FeGeO 3, to 127 GPa

DOE PAGES

Dutta, R.; Tracy, S. J.; Stan, C. V.; ...

2017-11-15

The high-pressure behavior of germanates is of interest as these compounds serve as analogs for silicates of the deep Earth. Current theoretical and experimental studies of iron germanate, FeGeO 3, are limited. Here in this paper, we have examined the behavior of FeGeO 3 to 127 GPa using the laser-heated diamond anvil cell combined with in situ synchrotron X-ray diffraction. Upon compression at room temperature, the ambient-pressure clinopyroxene phase transforms to a disordered triclinic phase [FeGeO 3 (II)] at ~ 18 GPa in agreement with earlier studies. An additional phase transition to FeGeO 3 (III) occurs above 54 GPa atmore » room temperature. Laser-heating experiments (~ 1200–2200 K) were conducted at three pressures (33, 54, and 123 GPa) chosen to cover the stability regions of different GeO 2 polymorphs. In all cases, we observe that FeGeO 3 dissociates into GeO 2 + FeO at high pressure and temperature conditions. Neither the perovskite nor the post-perovskite phase was observed up to 127 GPa at ambient or high temperatures. The results are consistent with the behavior of FeSiO 3, which also dissociates into a mixture of the oxides (FeO + SiO 2) at least up to 149 GPa.« less

Alpha – omega and omega – alpha phase transformations in zirconium under hydrostatic pressure: A 3D mesoscale study

DOE PAGES

Yeddu, Hemantha Kumar; Zong, Hongxiang; Lookman, Turab

2015-09-28

Here, a three dimensional (3D) elastoplastic phase-field model is developed for modeling the hydrostatic pressure-induced alpha – omega phase transformation and the reverse phase transformation, i.e. omega – alpha, in zirconium (Zr). Plastic deformation and strain hardening of the material are also considered in the model. The microstructure evolution during both phase transformations is studied. The transformation start pressures at different temperatures are predicted and are plotted as a phase diagram. The effect of phase transformations on the mechanical properties of the material is also studied. The input data corresponding to pure Zr are acquired from experimental studies as wellmore » as by using the CALPHAD method. Our simulations show that three different omega variants form as laths. On release of pressure, reverse phase transformation initiates at lath boundaries. We observe that both phase transformations are martensitic in nature and also occur at the same pressure, i.e. little hysteresis. The transformation start pressures and the kinetics of the transformation predicted by our model are in good agreement with experimental results.« less

Alpha – omega and omega – alpha phase transformations in zirconium under hydrostatic pressure: A 3D mesoscale study

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

Yeddu, Hemantha Kumar; Zong, Hongxiang; Lookman, Turab

Here, a three dimensional (3D) elastoplastic phase-field model is developed for modeling the hydrostatic pressure-induced alpha – omega phase transformation and the reverse phase transformation, i.e. omega – alpha, in zirconium (Zr). Plastic deformation and strain hardening of the material are also considered in the model. The microstructure evolution during both phase transformations is studied. The transformation start pressures at different temperatures are predicted and are plotted as a phase diagram. The effect of phase transformations on the mechanical properties of the material is also studied. The input data corresponding to pure Zr are acquired from experimental studies as wellmore » as by using the CALPHAD method. Our simulations show that three different omega variants form as laths. On release of pressure, reverse phase transformation initiates at lath boundaries. We observe that both phase transformations are martensitic in nature and also occur at the same pressure, i.e. little hysteresis. The transformation start pressures and the kinetics of the transformation predicted by our model are in good agreement with experimental results.« less

Phase Transformations and Microstructural Evolution: Part I

DOE PAGES

Clarke, Amy Jean

2015-08-29

The activities of the Phase Transformations Committee of the Materials Processing & Manufacturing Division (MPMD) of The Minerals, Metals & Materials Society (TMS) are oriented toward understanding the fundamental aspects of phase transformations. Emphasis is placed on the thermodynamic driving forces for phase transformations, the kinetics of nucleation and growth, interfacial structures and energies, transformation crystallography, surface reliefs, and, above all, the atomic mechanisms of phase transformations. Phase transformations and microstructural evolution are directly linked to materials processing, properties, and performance, including in extreme environments, of structural metal alloys. In this paper, aspects of phase transformations and microstructural evolution aremore » highlighted from the atomic to the microscopic scale for ferrous and non-ferrous alloys. Many papers from this issue are highlighted with small summaries of their scientific achievements given.« less

Crystallization of ikaite and its pseudomorphic transformation into calcite: Raman spectroscopy evidence

NASA Astrophysics Data System (ADS)

Sánchez-Pastor, N.; Oehlerich, Markus; Astilleros, José Manuel; Kaliwoda, Melanie; Mayr, Christoph C.; Fernández-Díaz, Lurdes; Schmahl, Wolfgang W.

2016-02-01

Ikaite (CaCO3·6H2O) is a metastable phase that crystallizes in nature from alkaline waters with high phosphate concentrations at temperatures close to 0 °C. This mineral transforms into anhydrous calcium carbonate polymorphs when temperatures rise or when exposed to atmospheric conditions. During the transformation in some cases the shape of the original ikaite crystal is preserved as a pseudomorph. Pseudomorphs after ikaite are considered as a valuable paleoclimatic indicator. In this work we conducted ikaite crystal growth experiments at near-freezing temperatures using the single diffusion silica gel technique, prepared with a natural aqueous solution from the polymictic lake Laguna Potrok Aike (51°57‧S, 70°23‧W) in Patagonia, Argentina. The ikaite crystals were recovered from the gels and the transformation reactions were monitored by in situ Raman spectroscopy at two different temperatures. The first spectra collected showed the characteristic features of ikaite. In successive spectra new bands at 1072, 1081 and 1086 cm-1 and changes in the intensity of bands corresponding to the OH modes were observed. These changes in the Raman spectra were interpreted as corresponding to intermediate stages of the transformation of ikaite into calcite and/or vaterite. After a few hours, the characteristics of the Raman spectrum were consistent with those of calcite. While ikaite directly transforms into calcite at 10 °C in contact with air, at 20 °C this transformation involves the formation of intermediate, metastable vaterite. During the whole process the external shape of ikaite crystals was preserved. Therefore, this transformation showed the typical characteristics of a pseudomorphic mineral replacement, involving the generation of a large amount of porosity to account for the large difference in molar volumes between ikaite and calcite. A mechanism involving the coupled dissolution of ikaite and crystallization of calcite/vaterite is proposed for this replacement.

Benzocaine polymorphism: pressure-temperature phase diagram involving forms II and III.

PubMed

Gana, Inès; Barrio, Maria; Do, Bernard; Tamarit, Josep-Lluís; Céolin, René; Rietveld, Ivo B

2013-11-18

Understanding the phase behavior of an active pharmaceutical ingredient in a drug formulation is required to avoid the occurrence of sudden phase changes resulting in decrease of bioavailability in a marketed product. Benzocaine is known to possess three crystalline polymorphs, but their stability hierarchy has so far not been determined. A topological method and direct calorimetric measurements under pressure have been used to construct the topological pressure-temperature diagram of the phase relationships between the solid phases II and III, the liquid, and the vapor phase. In the process, the transition temperature between solid phases III and II and its enthalpy change have been determined. Solid phase II, which has the highest melting point, is the more stable phase under ambient conditions in this phase diagram. Surprisingly, solid phase I has not been observed during the study, even though the scarce literature data on its thermal behavior appear to indicate that it might be the most stable one of the three solid phases. Copyright © 2013 Elsevier B.V. All rights reserved.

Glass polymorphism in glycerol-water mixtures: I. A computer simulation study.

PubMed

Jahn, David A; Wong, Jessina; Bachler, Johannes; Loerting, Thomas; Giovambattista, Nicolas

2016-04-28

We perform out-of-equilibrium molecular dynamics (MD) simulations of water-glycerol mixtures in the glass state. Specifically, we study the transformations between low-density (LDA) and high-density amorphous (HDA) forms of these mixtures induced by compression/decompression at constant temperature. Our MD simulations reproduce qualitatively the density changes observed in experiments. Specifically, the LDA-HDA transformation becomes (i) smoother and (ii) the hysteresis in a compression/decompression cycle decreases as T and/or glycerol content increase. This is surprising given the fast compression/decompression rates (relative to experiments) accessible in MD simulations. We study mixtures with glycerol molar concentration χ(g) = 0-13% and find that, for the present mixture models and rates, the LDA-HDA transformation is detectable up to χ(g) ≈ 5%. As the concentration increases, the density of the starting glass (i.e., LDA at approximately χ(g) ≤ 5%) rapidly increases while, instead, the density of HDA remains practically constant. Accordingly, the LDA state and hence glass polymorphism become inaccessible for glassy mixtures with approximately χ(g) > 5%. We present an analysis of the molecular-level changes underlying the LDA-HDA transformation. As observed in pure glassy water, during the LDA-to-HDA transformation, water molecules within the mixture approach each other, moving from the second to the first hydration shell and filling the first interstitial shell of water molecules. Interestingly, similar changes also occur around glycerol OH groups. It follows that glycerol OH groups contribute to the density increase during the LDA-HDA transformation. An analysis of the hydrogen bond (HB)-network of the mixtures shows that the LDA-HDA transformation is accompanied by minor changes in the number of HBs of water and glycerol. Instead, large changes in glycerol and water coordination numbers occur. We also perform a detailed analysis of the effects that the glycerol force field (FF) has on our results. By comparing MD simulations using two different glycerol models, we find that glycerol conformations indeed depend on the FF employed. Yet, the thermodynamic and microscopic mechanisms accompanying the LDA-HDA transformation and hence, our main results, do not. This work is accompanied by an experimental report where we study the glass polymorphism in glycerol-water mixtures prepared by isobaric cooling at 1 bar.

Glass polymorphism in glycerol–water mixtures: I. A computer simulation study

PubMed Central

Jahn, David A.; Wong, Jessina; Bachler, Johannes; Loerting, Thomas

2016-01-01

We perform out-of-equilibrium molecular dynamics (MD) simulations of water–glycerol mixtures in the glass state. Specifically, we study the transformations between low-density (LDA) and high-density amorphous (HDA) forms of these mixtures induced by compression/decompression at constant temperature. Our MD simulations reproduce qualitatively the density changes observed in experiments. Specifically, the LDA–HDA transformation becomes (i) smoother and (ii) the hysteresis in a compression/decompression cycle decreases as T and/or glycerol content increase. This is surprising given the fast compression/decompression rates (relative to experiments) accessible in MD simulations. We study mixtures with glycerol molar concentration χ g = 0–13% and find that, for the present mixture models and rates, the LDA–HDA transformation is detectable up to χ g ≈ 5%. As the concentration increases, the density of the starting glass (i.e., LDA at approximately χ g ≤ 5%) rapidly increases while, instead, the density of HDA remains practically constant. Accordingly, the LDA state and hence glass polymorphism become inaccessible for glassy mixtures with approximately χ g > 5%. We present an analysis of the molecular-level changes underlying the LDA–HDA transformation. As observed in pure glassy water, during the LDA-to-HDA transformation, water molecules within the mixture approach each other, moving from the second to the first hydration shell and filling the first interstitial shell of water molecules. Interestingly, similar changes also occur around glycerol OH groups. It follows that glycerol OH groups contribute to the density increase during the LDA–HDA transformation. An analysis of the hydrogen bond (HB)-network of the mixtures shows that the LDA–HDA transformation is accompanied by minor changes in the number of HBs of water and glycerol. Instead, large changes in glycerol and water coordination numbers occur. We also perform a detailed analysis of the effects that the glycerol force field (FF) has on our results. By comparing MD simulations using two different glycerol models, we find that glycerol conformations indeed depend on the FF employed. Yet, the thermodynamic and microscopic mechanisms accompanying the LDA–HDA transformation and hence, our main results, do not. This work is accompanied by an experimental report where we study the glass polymorphism in glycerol–water mixtures prepared by isobaric cooling at 1 bar. PMID:27063705

Sturgeon and paddlefish (Acipenseridae) saggital otoliths are composed of the calcium carbonate polymorphs vaterite and calcite: acipenseridae otoliths are vaterite and calcite

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

Pracheil, Brenda M.; Chakoumakos, Bryan C.; Feygenson, Mikhail

The otoliths of modern fishes are most commonly comprised of the metastable aragonite polymorph of calcium carbonate (CaCO3); however, sturgeons have otoliths reportedly comprised of the least stable of the three most-common polymorphs, vaterite. In this study, we used neutron diffraction to characterize CaCO3 polymorph composition of lake sturgeon and paddlefish otoliths. Based on previous summaries of CaCO3 composition over fish evolutionary history, we hypothesized that sturgeon and paddlefish otoliths would have similar polymorph composition. We found that despite previous reports of sturgeon otoliths being comprised entirely of vaterite, that all otoliths we examined in this study also had amore » calcite fraction that ranged from 17.9+ 6.0 wt. % to 35.9 + 2.9 wt. %. We also conducted a grinding experiment that demonstrated that calcite fractions were due to biological variation and not an artifact of polymorph transformation during preparation. Our study provides the initial characterization of the polymorph composition of the otoliths of lake sturgeon, and paddlefish and also provides the first-ever report of otoliths of Acipenserids as having a calcite fraction.« less

Sturgeon and paddlefish (Acipenseridae) saggital otoliths are composed of the calcium carbonate polymorphs vaterite and calcite: acipenseridae otoliths are vaterite and calcite

DOE PAGES

Pracheil, Brenda M.; Chakoumakos, Bryan C.; Feygenson, Mikhail; ...

2016-07-27

The otoliths of modern fishes are most commonly comprised of the metastable aragonite polymorph of calcium carbonate (CaCO3); however, sturgeons have otoliths reportedly comprised of the least stable of the three most-common polymorphs, vaterite. In this study, we used neutron diffraction to characterize CaCO3 polymorph composition of lake sturgeon and paddlefish otoliths. Based on previous summaries of CaCO3 composition over fish evolutionary history, we hypothesized that sturgeon and paddlefish otoliths would have similar polymorph composition. We found that despite previous reports of sturgeon otoliths being comprised entirely of vaterite, that all otoliths we examined in this study also had amore » calcite fraction that ranged from 17.9+ 6.0 wt. % to 35.9 + 2.9 wt. %. We also conducted a grinding experiment that demonstrated that calcite fractions were due to biological variation and not an artifact of polymorph transformation during preparation. Our study provides the initial characterization of the polymorph composition of the otoliths of lake sturgeon, and paddlefish and also provides the first-ever report of otoliths of Acipenserids as having a calcite fraction.« less

γ-Herringbone Polymorph of 6,13-Bis(trimethylsilylethynyl)pentacene: A Potential Material for Enhanced Hole Mobility.

PubMed

Bhat, Vinayak; Gopan, Gopika; Nair, Nanditha G; Hariharan, Mahesh

2018-04-06

The introduction of the trialkylsilylethynyl group to the acene core is known to predominantly transform the herringbone structure of pentacene to a slip-stacked packing. However, herein, the occurrence of an unforeseen polymorph of 6,13-bis(trimethylsilylethynyl)pentacene (TMS-pentacene), with an atypical γ-herringbone packing arrangement, is reported. Intermolecular noncovalent interactions in the γ-herringbone polymorph are determined from Hirshfeld surface and quantum theory of atoms-in-molecules (QTAIM) analyses. Furthermore, a comparative truncated symmetry-adapted perturbation theory (SAPT(0)) energy decomposition analysis discloses the role of exchange repulsions that govern molecular packing in the γ-herringbone polymorph. Moreover, the computationally predicted electronic coupling and anisotropic mobility reveal the possibility of enhanced hole transport (μ h =3.7 cm 2  V -1  s -1 ) in the γ-herringbone polymorph, in contrast to the reported polymorph with a hole mobility of μ h =0.1 cm 2  V -1  s -1 . © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

On the polymorphism of benzocaine; a low-temperature structural phase transition for form (II).

PubMed

Chan, Eric J; Rae, A David; Welberry, T Richard

2009-08-01

A low-temperature structural phase transition has been observed for form (II) of benzocaine (BZC). Lowering the temperature doubles the b-axis repeat and changes the space group from P2(1)2(1)2(1) to P112(1) with gamma now 99.37 degrees. The structure is twinned, the twin rule corresponding to a 2(1) screw rotation parallel to a. The phase transition is associated with a sequential displacement parallel to a of zigzag bi-layers of ribbons perpendicular to b*. No similar phase transition was observed for form (I) and this was attributed to the different packing symmetries of the two room-temperature polymorphic forms.

Shock-induced transformations in crystalline RDX: a uniaxial constant-stress Hugoniostat molecular dynamics simulation study.

PubMed

Bedrov, Dmitry; Hooper, Justin B; Smith, Grant D; Sewell, Thomas D

2009-07-21

Molecular dynamics (MD) simulations of uniaxial shock compression along the [100] and [001] directions in the alpha polymorph of hexahydro-1,3,5-trinitro-1,3,5-triazine (alpha-RDX) have been conducted over a wide range of shock pressures using the uniaxial constant stress Hugoniostat method [Ravelo et al., Phys. Rev. B 70, 014103 (2004)]. We demonstrate that the Hugoniostat method is suitable for studying shock compression in atomic-scale models of energetic materials without the necessity to consider the extremely large simulation cells required for an explicit shock wave simulation. Specifically, direct comparison of results obtained using the Hugoniostat approach to those reported by Thompson and co-workers [Phys. Rev. B 78, 014107 (2008)] based on large-scale MD simulations of shocks using the shock front absorbing boundary condition (SFABC) approach indicates that Hugoniostat simulations of systems containing several thousand molecules reproduced the salient features observed in the SFABC simulations involving roughly a quarter-million molecules, namely, nucleation and growth of nanoscale shear bands for shocks propagating along the [100] direction and the polymorphic alpha-gamma phase transition for shocks directed along the [001] direction. The Hugoniostat simulations yielded predictions of the Hugoniot elastic limit for the [100] shock direction consistent with SFABC simulation results.

High pressure-temperature polymorphism of 1,1-diamino-2,2-dinitroethylene

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

Bishop, M. M.; Chellappa, R. S.; Liu, Z.

Here, 1,1-diamino-2,2-dinitroethylene (FOX-7) is a low sensitivity energetic material with performance comparable to commonly used secondary explosives such as RDX and HMX. At ambient pressure, FOX-7 exhibits complex polymorphism with at least three structurally distinct phases (α, β, and γ). In this study, we have investigated the high pressure-temperature stability of FOX-7 polymorphs using synchrotron mid-infrared (MIR) spectroscopy. At ambient pressure, our MIR spectra and corresponding differential scanning calorimetry (DSC) measurements confirmed the known α → β (~110 °C) and β → γ (~160 °C) structural phase transitions; as well as, indicated an additional transition γ → δ (~210 °C),more » with the δ phase being stable up to ~251 degree C prior to decomposition. In situ MIR spectra obtained during isobaric heating at 0.9 GPa, revealed a potential α → β transition that could occur as early as 180 degree C, while β → β+δ phase transition shifted to ~300 °C with suppression of γ phase. Decomposition was observed slightly above 325 °C at 0.9 GPa..« less

High pressure-temperature polymorphism of 1,1-diamino-2,2-dinitroethylene

DOE PAGES

Bishop, M. M.; Chellappa, R. S.; Liu, Z.; ...

2014-05-07

Here, 1,1-diamino-2,2-dinitroethylene (FOX-7) is a low sensitivity energetic material with performance comparable to commonly used secondary explosives such as RDX and HMX. At ambient pressure, FOX-7 exhibits complex polymorphism with at least three structurally distinct phases (α, β, and γ). In this study, we have investigated the high pressure-temperature stability of FOX-7 polymorphs using synchrotron mid-infrared (MIR) spectroscopy. At ambient pressure, our MIR spectra and corresponding differential scanning calorimetry (DSC) measurements confirmed the known α → β (~110 °C) and β → γ (~160 °C) structural phase transitions; as well as, indicated an additional transition γ → δ (~210 °C),more » with the δ phase being stable up to ~251 degree C prior to decomposition. In situ MIR spectra obtained during isobaric heating at 0.9 GPa, revealed a potential α → β transition that could occur as early as 180 degree C, while β → β+δ phase transition shifted to ~300 °C with suppression of γ phase. Decomposition was observed slightly above 325 °C at 0.9 GPa..« less

Effect of in vitro aging on the flexural strength and probability to fracture of Y-TZP zirconia ceramics for all-ceramic restorations.

PubMed

Siarampi, Eleni; Kontonasaki, Eleana; Andrikopoulos, Konstantinos S; Kantiranis, Nikolaos; Voyiatzis, George A; Zorba, Triantafillia; Paraskevopoulos, Konstantinos M; Koidis, Petros

2014-12-01

Dental zirconia restorations should present long-term clinical survival and be in service within the oral environment for many years. However, low temperature degradation could affect their mechanical properties and survival. The aim of this study was to investigate the effect of in vitro aging on the flexural strength of yttrium-stabilized (Y-TZP) zirconia ceramics for ceramic restorations. One hundred twenty bar-shaped specimens were prepared from two ceramics (ZENO Zr (WI) and IPS e.max(®) ZirCAD (IV)), and loaded until fracture according to ISO 6872. The specimens from each ceramic (nx=60) were divided in three groups (control, aged for 5h, aged for 10h). One-way ANOVA was used to assess statistically significant differences among flexural strength values (P<0.05). The variability of the flexural strength values was analyzed using the two-parameter Weibull distribution function, which was applied for the estimation of Weibull modulus (m) and characteristic strength (σ0). The crystalline phase polymorphs of the materials (tetragonal, t, and monoclinic, m, zirconia) were investigated by X-ray diffraction (XRD) analysis, Raman spectroscopy and Fourier transform infrared (FTIR) spectroscopy. A slight increase of the flexural strength after 5h, and a decrease after 10h of aging, was recorded for both ceramics, however statistically significant was for the WI group (P<0.05). Both ceramics presented a t→m phase transformation, with the m-phase increasing from 4 to 5% at 5h to around 15% after 10h. The significant reduction of the flexural strength after 10h of in vitro aging, suggests high fracture probability for one of the zirconia ceramics tested. Copyright © 2014 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Peroxisome proliferator-activated receptor gamma (PPARG) rs1801282 C>G polymorphism is associated with cancer susceptibility in asians: an updated meta-analysis

PubMed Central

Wang, Yafeng; Chen, Yu; Jiang, Heping; Tang, Weifeng; Kang, Mingqiang; Liu, Tianyun; Guo, Zengqing; Ma, Zhiqiang

2015-01-01

Peroxisome proliferator-activated receptor gamma (PPARG) is related to inflammation and plays an important role in the development of cancer. PPARG rs1801282 C>G polymorphism might influence the risk of cancer by regulating production of PPARG gene. Hence, a comprehensive meta-analysis was conducted to explore the association of PPARG rs1801282 C>G polymorphism with cancer susceptibility. An extensive search of PubMed and Embase databases for all relevant publications was carried out. A total of 38 publications with 16,844 cancer cases and 23,736 controls for PPARG rs1801282 C>G polymorphism were recruited in our study. Our results indicated that PPARG rs1801282 C>G variants were associated with an increased cancer risk in Asian populations and gastric cancer. In summary, the findings suggest that PPARG rs1801282 C>G polymorphism may play a crucial role in malignant transformation and the development of cancer. PMID:26550180

Peroxisome proliferator-activated receptor gamma (PPARG) rs1801282 C>G polymorphism is associated with cancer susceptibility in asians: an updated meta-analysis.

PubMed

Wang, Yafeng; Chen, Yu; Jiang, Heping; Tang, Weifeng; Kang, Mingqiang; Liu, Tianyun; Guo, Zengqing; Ma, Zhiqiang

2015-01-01

Peroxisome proliferator-activated receptor gamma (PPARG) is related to inflammation and plays an important role in the development of cancer. PPARG rs1801282 C>G polymorphism might influence the risk of cancer by regulating production of PPARG gene. Hence, a comprehensive meta-analysis was conducted to explore the association of PPARG rs1801282 C>G polymorphism with cancer susceptibility. An extensive search of PubMed and Embase databases for all relevant publications was carried out. A total of 38 publications with 16,844 cancer cases and 23,736 controls for PPARG rs1801282 C>G polymorphism were recruited in our study. Our results indicated that PPARG rs1801282 C>G variants were associated with an increased cancer risk in Asian populations and gastric cancer. In summary, the findings suggest that PPARG rs1801282 C>G polymorphism may play a crucial role in malignant transformation and the development of cancer.

Genomic variation and DNA repair associated with soybean transgenesis: a comparison to cultivars and mutagenized plants.

PubMed

Anderson, Justin E; Michno, Jean-Michel; Kono, Thomas J Y; Stec, Adrian O; Campbell, Benjamin W; Curtin, Shaun J; Stupar, Robert M

2016-05-12

The safety of mutagenized and genetically transformed plants remains a subject of scrutiny. Data gathered and communicated on the phenotypic and molecular variation induced by gene transfer technologies will provide a scientific-based means to rationally address such concerns. In this study, genomic structural variation (e.g. large deletions and duplications) and single nucleotide polymorphism rates were assessed among a sample of soybean cultivars, fast neutron-derived mutants, and five genetically transformed plants developed through Agrobacterium based transformation methods. On average, the number of genes affected by structural variations in transgenic plants was one order of magnitude less than that of fast neutron mutants and two orders of magnitude less than the rates observed between cultivars. Structural variants in transgenic plants, while rare, occurred adjacent to the transgenes, and at unlinked loci on different chromosomes. DNA repair junctions at both transgenic and unlinked sites were consistent with sequence microhomology across breakpoints. The single nucleotide substitution rates were modest in both fast neutron and transformed plants, exhibiting fewer than 100 substitutions genome-wide, while inter-cultivar comparisons identified over one-million single nucleotide polymorphisms. Overall, these patterns provide a fresh perspective on the genomic variation associated with high-energy induced mutagenesis and genetically transformed plants. The genetic transformation process infrequently results in novel genetic variation and these rare events are analogous to genetic variants occurring spontaneously, already present in the existing germplasm, or induced through other types of mutagenesis. It remains unclear how broadly these results can be applied to other crops or transformation methods.

[Thermodynamics of drug polymorphism: domains and stability hierarchy by pressure temperature diagram. Application to the tetramorphism of fananserine].

PubMed

Toscani, S

2002-05-01

In this communication, an application of classical thermodynamics to crystalline solid state polymorphism is shown to allow stability p, T domains and stability hierarchy among crystalline phases of a polymorph to be defined by constructing the unary p, T phase diagram. The three topological rules upon which this construction is founded are presented; the first one is a straight consequence of the least vapour pressure criterion by Ostwald. Calculation of triple point co-ordinates and of two-phase equilibrium curves is based upon using both thermodynamic and crystallographic data obtained at ordinary pressure. Clapeyron equation allows the slopes of the straight lines representing equilibria between condensed phases to be calculated and, hence, triple points situated at high or negative pressure to be determined. On the other hand, the hierarchy among the thermodynamic stability degrees of the crystalline varieties may be inferred from the location of the sublimation curves, by merely acknowledging inequalities among vapour pressures at each temperature on the whole T-range. These building-up processes are pointed out by outlining the achievement of a phase diagram related to the tetramorphism of fananserine, an anxiolytic drug. Three out four crystalline forms, namely phases II, III and IV, possess their own stability domain, although those belonging to phases II and III are limited at high pressure by that of phase IV. Conversely, phase I is overall metastable and exhibits a whole monotropic behaviour.

Polymorphism of paracetamol: relative stabilities of the monoclinic and orthorhombic phases inferred from topological pressure-temperature and temperature-volume phase diagrams.

PubMed

Espeau, Philippe; Céolin, René; Tamarit, Josep-Lluis; Perrin, Marc-Antoine; Gauchi, Jean-Pierre; Leveiller, Franck

2005-03-01

The thermodynamic relationships between the two known polymorphs of paracetamol have been investigated, and the subsequent pressure-temperature and temperature-volume phase diagrams were constructed using data from crystallographic and calorimetric measurements as a function of the temperature. Irrespective of temperature, monoclinic Form I and orthorhombic Form II are stable phases at ordinary and high pressures, respectively. The I and II phase regions in the pressure-temperature diagram are bordered by the I-II equilibrium curve, for which a negative slope (dp/dT approximately -0.3 MPa x K(-1)) was determined although it was not observed experimentally. This curve goes through the I-II-liquid triple point whose coordinates (p approximately 234 MPa, T approximately 505 K) correspond to the crossing point of the melting curves, for which dp/dT values of +3.75 MPa x K(-1) (I) and +3.14 MPa x K(-1) (II) were calculated from enthalpy and volume changes upon fusion. More generally, this case exemplifies how the stability hierarchy of polymorphs may be inferred from the difference in their sublimation curves, as topologically positioned with respect to each other, using the phase rule and simple inferences resorting to Gibbs equilibrium thermodynamics. Copyright 2004 Wiley-Liss, Inc. and the American Pharmacists Association.

Lead(ii) soaps: crystal structures, polymorphism, and solid and liquid mesophases.

PubMed

Martínez-Casado, F J; Ramos-Riesco, M; Rodríguez-Cheda, J A; Redondo-Yélamos, M I; Garrido, L; Fernández-Martínez, A; García-Barriocanal, J; da Silva, I; Durán-Olivencia, M; Poulain, A

2017-07-05

The long-chain members of the lead(ii) alkanoate series or soaps, from octanoate to octadecanoate, have been thoroughly characterized by means of XRD, PDF analysis, DSC, FTIR, ssNMR and other techniques, in all their phases and mesophases. The crystal structures at room temperature of all of the members of the series are now solved, showing the existence of two polymorphic forms in the room temperature crystal phase, different to short and long-chain members. Only nonanoate and decanoate present both forms, and this polymorphism is proven to be monotropic. At higher temperature, these compounds present a solid mesophase, defined as rotator, a liquid crystal phase and a liquid phase, all of which have a similar local arrangement. Since some lead(ii) soaps appear as degradation compounds in oil paintings, the solved crystal structures of lead(ii) soaps can now be used as fingerprints for their detection using X-ray diffraction. Pair distribution function analysis on these compounds is very similar in the same phases and mesophases for the different members, showing the same short range order. This observation suggests that this technique could also be used in the detection of these compounds in disordered phases or in the initial stages of formation in paintings.

Electric-field-dependent phase volume fractions and enhanced piezoelectricity near the polymorphic phase boundary of (K0.5Na0.5)1-xLixNbO3 textured ceramics

NASA Astrophysics Data System (ADS)

Ge, Wenwei; Li, Jiefang; Viehland, D.; Chang, Yunfei; Messing, Gary L.

2011-06-01

The structure, ferroelectric and piezoelectric properties of <001> textured (K0.5Na0.5)0.98Li0.02NbO3 ceramics were investigated as a function of temperature and dc bias E. X-ray diffraction revealed an orthorhombic (O) → tetragonal (T) polymorphic phase boundary (PPB). Phase coexistence was found near the PPB over a 30 °C temperature range, where the relative phase volume fractions changed with temperature. Furthermore, increasing E applied along the <001> texture direction resulted in a notable increase in the volume fraction of the T phase at the expense of the O phase, effectively shifting the O → T boundary to lower temperature. An enhancement in the piezoelectric properties was found to accompany this increase in the T volume fraction.

Substructures of the mantle transition-zone discontinuities and compositional heterogeneities in the mid-mantle

NASA Astrophysics Data System (ADS)

Wei, S. S.; Shearer, P. M.

2017-12-01

The mantle transition-zone discontinuities are usually attributed to isochemical phase transformations of olivine and its high-pressure polymorphs. However, recent seismic observations have shown complexities in these discontinuities that cannot be explained by conventional models of thermal variations. Here we analyse SS precursor stacking results to investigate global mantle transition-zone properties. The precursor waveforms provide information on the seismic velocity and density profiles across and near the major mantle discontinuities. A sporadic low-velocity layer immediately above the 410-km discontinuity is observed worldwide, including East Asia, western North America, eastern South America, and 33-50% of the resolved Pacific Ocean. The 520-km discontinuity exhibits significant variations in its sharpness and depth, and occasionally appears to be split. Structures underlying the 660-km discontinuity show even larger complexities: a sub-discontinuity at 700-800 km depth is detected in some regions, of which some require a positive velocity gradient whereas others have a negative gradient. All of these lateral variations show no geographical correlation with discontinuity topography or tomographic models of seismic velocity, suggesting that they are not caused by regional thermal anomalies. Alternatively, our observations can be explained by compositional heterogeneities in the mid-mantle, including major minerals and volatile content, which may result in additional phase transformations and partial melting. These compositional heterogeneities should be taken into account in future geodynamic models of mantle convection and the deep water cycle.

High-pressure polymorphism of As2S3 and new AsS2 modification with layered structure

NASA Astrophysics Data System (ADS)

Bolotina, N. B.; Brazhkin, V. V.; Dyuzheva, T. I.; Katayama, Y.; Kulikova, L. F.; Lityagina, L. V.; Nikolaev, N. A.

2014-01-01

At normal pressure, the As2S3 compound is the most stable equilibrium modification with unique layered structure. The possibility of high-pressure polymorphism of this substance remains questionable. Our research showed that the As2S3 substance was metastable under pressures P > 6 GPa decomposing into two high-pressure phases: As2S3 → AsS2 + AsS. New AsS2 phase can be conserved in the single crystalline form in metastable state at room pressure up to its melting temperature (470 K). This modification has the layered structure with P1211 monoclinic symmetry group; the unit-cell values are a = 7.916(2) Å, b = 9.937(2) Å, c = 7.118(1) Å, β = 106.41° ( Z = 8, density 3.44 g/cm3). Along with the recently studied AsS high-pressure modification, the new AsS2 phase suggests that high pressure polymorphism is a very powerful tool to create new layered-structure phases with "wrong" stoichiometry.

In Situ TEM Nanoindentation Studies on Stress-Induced Phase Transformations in Metallic Materials

DOE PAGES

Liu, Y.; Wang, H.; Zhang, X.

2015-11-30

Though abundant phase transformations are in general thermally driven processes, there are many examples wherein stresses can induce phase transformations. We applied numerous in situ techniques, such as in situ x-ray diffraction and neutron diffraction in order to reveal phase transformations. Recently, an in situ nanoindentation technique coupled with transmission electron microscopy demonstrated the capability to directly correlating stresses with phase transformations and microstructural evolutions at a submicron length scale. We briefly review in situ studies on stress-induced diffusional and diffusionless phase transformations in amorphous CuZrAl alloy and NiFeGa shape memory alloy. Moreover, in the amorphous CuZrAl, in situ nanoindentationmore » studies show that the nucleation of nanocrystals (a diffusional process) occurs at ultra-low stresses manifested by a prominent stress drop. In the NiFeGa shape memory alloy, two distinctive types of martensitic (diffusionless) phase transformations accompanied by stress plateaus are observed, including a reversible gradual phase transformation at low stress levels, and an irreversible abrupt phase transition at higher stress levels.« less

Molecular nucleation mechanisms and control strategies for crystal polymorph selection

NASA Astrophysics Data System (ADS)

van Driessche, Alexander E. S.; van Gerven, Nani; Bomans, Paul H. H.; Joosten, Rick R. M.; Friedrich, Heiner; Gil-Carton, David; Sommerdijk, Nico A. J. M.; Sleutel, Mike

2018-04-01

The formation of condensed (compacted) protein phases is associated with a wide range of human disorders, such as eye cataracts, amyotrophic lateral sclerosis, sickle cell anaemia and Alzheimer’s disease. However, condensed protein phases have their uses: as crystals, they are harnessed by structural biologists to elucidate protein structures, or are used as delivery vehicles for pharmaceutical applications. The physiochemical properties of crystals can vary substantially between different forms or structures (‘polymorphs’) of the same macromolecule, and dictate their usability in a scientific or industrial context. To gain control over an emerging polymorph, one needs a molecular-level understanding of the pathways that lead to the various macroscopic states and of the mechanisms that govern pathway selection. However, it is still not clear how the embryonic seeds of a macromolecular phase are formed, or how these nuclei affect polymorph selection. Here we use time-resolved cryo-transmission electron microscopy to image the nucleation of crystals of the protein glucose isomerase, and to uncover at molecular resolution the nucleation pathways that lead to two crystalline states and one gelled state. We show that polymorph selection takes place at the earliest stages of structure formation and is based on specific building blocks for each space group. Moreover, we demonstrate control over the system by selectively forming desired polymorphs through site-directed mutagenesis, specifically tuning intermolecular bonding or gel seeding. Our results differ from the present picture of protein nucleation, in that we do not identify a metastable dense liquid as the precursor to the crystalline state. Rather, we observe nucleation events that are driven by oriented attachments between subcritical clusters that already exhibit a degree of crystallinity. These insights suggest ways of controlling macromolecular phase transitions, aiding the development of protein-based drug-delivery systems and macromolecular crystallography.

Phase variation and microevolution at homopolymeric tracts in Bordetella pertussis

PubMed Central

Gogol, Emily B; Cummings, Craig A; Burns, Ryan C; Relman, David A

2007-01-01

Background Bordetella pertussis, the causative agent of whooping cough, is a highly clonal pathogen of the respiratory tract. Its lack of genetic diversity, relative to many bacterial pathogens, could limit its ability to adapt to a hostile and changing host environment. This limitation might be overcome by phase variation, as observed for other mucosal pathogens. One of the most common mechanisms of phase variation is reversible expansion or contraction of homopolymeric tracts (HPTs). Results The genomes of B. pertussis and the two closely related species, B. bronchiseptica and B. parapertussis, were screened for homopolymeric tracts longer than expected on the basis of chance, given their nucleotide compositions. Sixty-nine such HPTs were found in total among the three genomes, 74% of which were polymorphic among the three species. Nine HPTs were genotyped in a collection of 90 geographically and temporally diverse B. pertussis strains using the polymerase chain reaction/ligase detection reaction (PCR/LDR) assay. Six HPTs were polymorphic in this collection of B. pertussis strains. Of note, one of these polymorphic HPTs was found in the fimX promoter, where a single base insertion variant was present in seven strains, all of which were isolated prior to introduction of the pertussis vaccine. Transcript abundance of fimX was found to be 3.8-fold lower in strains carrying the longer allele. HPTs in three other genes, tcfA, bapC, and BP3651, varied widely in composition across the strain collection and displayed allelic polymorphism within single cultures. Conclusion Allelic polymorphism at homopolymeric tracts is common within the B. pertussis genome. Phase variability may be an important mechanism in B. pertussis for evasion of the immune system and adaptation to different niches in the human host. High sensitivity and specificity make the PCR/LDR assay a powerful tool for investigating allelic variation at HPTs. Using this method, allelic diversity and phase variation were demonstrated at several B. pertussis loci. PMID:17509142

Ferroelectric Phase Transformations for Energy Conversion and Storage Applications

NASA Astrophysics Data System (ADS)

Jo, Hwan Ryul

Ferroelectric materials possess a spontaneous polarization and actively respond to external mechanical, electrical, and thermal loads. Due to their coupled behavior, ferroelectric materials are used in products such as sensors, actuators, detectors, and transducers. However, most current applications rely on low-energy conversion that involves low magnitude fields. They utilize the low-field linear properties of ferroelectric materials (piezoelectric, pyroelectric) and do not take full advantage of the large-field nonlinear behavior (irreversible domain wall motion, phase transformations) that can occur in ferroelectric materials. When external fields exceed a certain critical level, a structural transformation of the crystal can occur. These phase transformations are accompanied by a much larger response than the linear piezoelectric and pyroelectric responses, by as much as a multiple of ten times in the magnitude. This makes the non-linear behavior in ferroelectric materials promising for energy harvesting and energy storage technologies which will benefit from large-energy conversion. Yet, the ferroelectric phase transformation behavior under large external fields have been less studied and only a few studies have been directed at utilizing this large material response in applications. This dissertation addresses the development ferroelectric phase transformation-based applications, with particular focus on the materials. Development of the ferroelectric phase transformation-based applications was approached in several steps. First, the phase transformation behavior was fully characterized and understood by measuring the phase transformation responses under mechanical, electrical, thermal, and combined loads. Once the behavior was well characterized, systems level applications were addressed. This required assessing the effect of the phase transformation behavior on system performance. The performance of ferroelectric devices is strongly dependent on material properties and phase transformation behavior which can be tailored by modifying the chemical composition, processing conditions, and the loading history (poling). This results in optimization of system performance by tailoring material properties and phase transformation behavior. This approach applied to three ferroelectric phase transformation-based applications: 1. Ferroelectric energy generation 2. Ferroelectric high-energy storage capacitor 3. Ferroelectric thermal energy harvesting. This dissertation has addressed tuning the large field properties for phase transformation-based systems.

Glass and liquid phase diagram of a polyamorphic monatomic system

NASA Astrophysics Data System (ADS)

Reisman, Shaina; Giovambattista, Nicolas

2013-02-01

We perform out-of-equilibrium molecular dynamics (MD) simulations of a monatomic system with Fermi-Jagla (FJ) pair potential interactions. This model system exhibits polyamorphism both in the liquid and glass state. The two liquids, low-density (LDL) and high-density liquid (HDL), are accessible in equilibrium MD simulations and can form two glasses, low-density (LDA) and high-density amorphous (HDA) solid, upon isobaric cooling. The FJ model exhibits many of the anomalous properties observed in water and other polyamorphic liquids and thus, it is an excellent model system to explore qualitatively the thermodynamic properties of such substances. The liquid phase behavior of the FJ model system has been previously characterized. In this work, we focus on the glass behavior of the FJ system. Specifically, we perform systematic isothermal compression and decompression simulations of LDA and HDA at different temperatures and determine "phase diagrams" for the glass state; these phase diagrams varying with the compression/decompression rate used. We obtain the LDA-to-HDA and HDA-to-LDA transition pressure loci, PLDA-HDA(T) and PHDA-LDA(T), respectively. In addition, the compression-induced amorphization line, at which the low-pressure crystal (LPC) transforms to HDA, PLPC-HDA(T), is determined. As originally proposed by Poole et al. [Phys. Rev. E 48, 4605 (1993)], 10.1103/PhysRevE.48.4605 simulations suggest that the PLDA-HDA(T) and PHDA-LDA(T) loci are extensions of the LDL-to-HDL and HDL-to-LDL spinodal lines into the glass domain. Interestingly, our simulations indicate that the PLPC-HDA(T) locus is an extension, into the glass domain, of the LPC metastability limit relative to the liquid. We discuss the effects of compression/decompression rates on the behavior of the PLDA-HDA(T), PHDA-LDA(T), PLPC-HDA(T) loci. The competition between glass polyamorphism and crystallization is also addressed. At our "fast rate," crystallization can be partially suppressed and the glass phase diagram can be related directly with the liquid phase diagram. However, at our "slow rate," crystallization cannot be prevented at intermediate temperatures, within the glass region. In these cases, multiple crystal-crystal transformations are found upon compression/decompression (polymorphism).

Glass and liquid phase diagram of a polyamorphic monatomic system.

PubMed

Reisman, Shaina; Giovambattista, Nicolas

2013-02-14

We perform out-of-equilibrium molecular dynamics (MD) simulations of a monatomic system with Fermi-Jagla (FJ) pair potential interactions. This model system exhibits polyamorphism both in the liquid and glass state. The two liquids, low-density (LDL) and high-density liquid (HDL), are accessible in equilibrium MD simulations and can form two glasses, low-density (LDA) and high-density amorphous (HDA) solid, upon isobaric cooling. The FJ model exhibits many of the anomalous properties observed in water and other polyamorphic liquids and thus, it is an excellent model system to explore qualitatively the thermodynamic properties of such substances. The liquid phase behavior of the FJ model system has been previously characterized. In this work, we focus on the glass behavior of the FJ system. Specifically, we perform systematic isothermal compression and decompression simulations of LDA and HDA at different temperatures and determine "phase diagrams" for the glass state; these phase diagrams varying with the compression/decompression rate used. We obtain the LDA-to-HDA and HDA-to-LDA transition pressure loci, P(LDA-HDA)(T) and P(HDA-LDA)(T), respectively. In addition, the compression-induced amorphization line, at which the low-pressure crystal (LPC) transforms to HDA, P(LPC-HDA)(T), is determined. As originally proposed by Poole et al. [Phys. Rev. E 48, 4605 (1993)] simulations suggest that the P(LDA-HDA)(T) and P(HDA-LDA)(T) loci are extensions of the LDL-to-HDL and HDL-to-LDL spinodal lines into the glass domain. Interestingly, our simulations indicate that the P(LPC-HDA)(T) locus is an extension, into the glass domain, of the LPC metastability limit relative to the liquid. We discuss the effects of compression/decompression rates on the behavior of the P(LDA-HDA)(T), P(HDA-LDA)(T), P(LPC-HDA)(T) loci. The competition between glass polyamorphism and crystallization is also addressed. At our "fast rate," crystallization can be partially suppressed and the glass phase diagram can be related directly with the liquid phase diagram. However, at our "slow rate," crystallization cannot be prevented at intermediate temperatures, within the glass region. In these cases, multiple crystal-crystal transformations are found upon compression/decompression (polymorphism).

Low- and high-frequency Raman investigations on caffeine: polymorphism, disorder and phase transformation.

PubMed

Hédoux, Alain; Decroix, Anne-Amandine; Guinet, Yannick; Paccou, Laurent; Derollez, Patrick; Descamps, Marc

2011-05-19

Raman investigations are carried out both in crystalline forms of caffeine and during the isothermal transformation of the orientationally disordered form I into the stable form II at 363 K. The time dependence of the Raman spectrum exhibits no significant change in the intramolecular regime (above 100 cm(-1)), resembling the spectrum of the liquid state. By contrast, significant changes are observed below 100 cm(-1), and the low-frequency spectra of forms I and II are observed to be different from that of the liquid. The temperature dependence of the 5-600 cm(-1) spectrum gives information on the static disorder through the analysis of collective motions, while information on dynamic disorder are obtained from the study of the 555 cm(-1) band corresponding to internal vibrations in the pyrimidine ring. This analysis indubitably reveals that form II is also orientationally disordered with a local molecular arrangement that mimics that in form I and the liquid state. The comparison of the low-frequency spectra recorded in theophylline and form II of caffeine allows one to describe the stable form of caffeine from the packing arrangement of anhydrous theophylline with the consideration of reorientational molecular disorder. © 2011 American Chemical Society

Study of liquid?liquid demixing from drug solution

NASA Astrophysics Data System (ADS)

Lafferrère, Laurent; Hoff, Christian; Veesler, Stéphane

2004-09-01

In pharmaceutical industry, a deep understanding of the phase diagram is required in design of crystallization processes. We have investigated the phase diagram of a pharmaceutical compound (C 35H 41Cl 2N 3O 2) in a mixture of ethanol/water. This phase diagram exhibits a solid-solid (polymorphism) and a liquid-liquid-phase separation (LLPS) as a function of temperature and drug substance concentration. This study focuses on the LLPS which is metastable with respect to the crystallization of the two polymorphs FI and FII of C 35H 41Cl 2N 3O 2 in an ethanol/water mixture. The LLPS is metastable towards the solubility curve on the whole solvent-solute concentrations and temperature range studied. The LLPS occurred within the metastable zone for crystallization. In our experiments the liquid-liquid-phase transition prevented the drug from crystallizing, while it changed the medium and the conditions of crystallization, which consequently affected the process. The coexistence curves for the liquid phases, also named TL-L boundary, and the spinodal line were measured for a ternary mixture of water-drug-ethanol at atmospheric pressure over a temperature range of 10-50°C. This temperature range corresponds to that used in the crystallization process. Static Light Scattering, HPLC measurements and Karl-Fischer titration were applied to investigate the drug-phase diagram. The isoplethe section of the phase diagram exhibits four regions: one homogeneous (one liquid) and three two-phases (two regions with one liquid+one solid and one region with two liquids), the two solids phases being two polymorphs.

Transforming growth factor beta-1 (TGF-β1) gene single nucleotide polymorphisms (SNPs) and susceptibility to pre-eclampsia in Iranian women: A case-control study.

PubMed

Khani, Masood; Amani, Davar; Taheripanah, Robabeh; Sanadgol, Nima; Feizollahzadeh, Sadegh; Rahmani, Zahra

2015-10-01

Pre-eclampsia (PE) is a disorder of pregnancy characterized by high blood pressure and proteinuria. Transforming growth factor beta-1 (TGF-β1) is an important replicated PE candidate gene, and few studies have evaluated the direct association of TGF-β polymorphisms and risk to PE. The aim of this study was to investigate the association between three SNPs of TGF-β1 and serum level of this cytokine in PE patients and controls. In this study the polymorphisms of the TGF-β1 gene at the coding region, and positions 29T→C (Leu 10 Pro), 74G→C (Arg 25 Pro) and 788C→T (Thr 263 Ile) were studied in 123 PE and 120 normal subjects using PCR-restriction fragment length polymorphism PCR-(RFLP) and amplification refractory mutation system (ARMS)-PCR methods. Moreover, serum TGF-β1 was determined by enzyme-linked immunosorbent assay (ELISA) technique. At positions 74G→C and 29T→C the genotypes and allele frequencies showed no significant differences between PE patients and normal controls (P=0.3 and P=0.5 respectively). While in the case of position 788C→T both genotypes and allele frequencies were significantly different between PE patients and controls (P=0.02). Haplotype analysis on three polymorphic sites showed no significant differences between PE and control individuals (P=0.8). TGC and CGC haplotypes were the most frequent in both studied groups. The mean serum TGF-β1 level was significantly higher (62.73ng/ml) in PE patients compared with pregnant (47.01ng/ml) and non-pregnant (40.68ng/ml) control groups (P=0.0001). The results of this study suggest that TGF-β1 gene 788C→T polymorphism is an important factor mediating the casual pathway of preeclampsia. Copyright © 2015 International Society for the Study of Hypertension in Pregnancy. Published by Elsevier B.V. All rights reserved.

Association between circulating transforming growth factor-β1 level and polymorphisms in systemic lupus erythematosus and rheumatoid arthritis: A meta-analysis.

PubMed

Lee, Y H; Bae, S-C

2017-02-22

This study systemically reviewed evidence regarding the relationship between circulating blood transforming growth factor-β1 (TGF-β1) levels and systemic lupus erythematous (SLE) and rheumatoid arthritis (RA), and associations between TGF-β1 polymorphisms and susceptibility to SLE and RA.  We conducted a meta-analysis on the serum/plasma TGF-β1 levels in SLE and RA patients and healthy controls, and the associations between TGF-β1 +869 T/C, +915 C/G, and -509 T/C polymorphisms and SLE or RA risk. Twenty-eight studies were considered in this meta-analysis. Circulating TGF-β1 levels were significantly lower in the SLE group than in controls (SMD = -1.164, 95% CI = -2.257 - -0.070, P = 0.037). Serum/plasma TGF-β1 levels were not significantly different between RA and control groups (SMD = 0.699, 95% CI = -0.379 - 1.717, p = 0.211). No association between TGF-β1 +869 T/C polymorphism and SLE was found. However, meta-analysis showed an association between the TGF-β1 +869 T allele and RA in all subjects (OR = 1.282, 95% CI = 1.118-1.470, P = 3.8 x 10-4). Analysis after stratification by ethnicity indicated that the T allele was significantly associated with RA in Asians and Arabs (OR = 1.429, 95% CI = 1.179-1.733, P = 2.9 x 10-4; OR = 1.352, 95% CI = 1.097-1.668, P = 0.005), but not Europeans. However, no association was found between TGF-β1 +915 G/C or -509 C/T polymorphisms and RA or SLE. Meta-analysis revealed a significantly lower circulating TGF-β1 level in SLE patients, and a significant association between TGF-β1 +869 T/C polymorphism and RA development.

[Association between Fok I vitamin D receptor (VDR) gene polymorphism and plasmatic concentrations of transforming growth factor-beta1 and interferon gamma in type 1 diabetes mellitus].

PubMed

López, Tatiana; García, Diego; Angel, Bárbara; Carrasco, Elena; Codner, Ethel; Ugarte, Francisca; Pérez-Bravo, Francisco

2008-02-02

In order to assess whether Fok I vitamin D receptor gene (VDR) polymorphism is involved in the genetic susceptibility of type 1 diabetes, a case-control study was conducted and VDR genotypes were related to serum concentrations of 25(OH) vitamin D and cytokines transforming growth factor beta1 (TGF-beta1) and interferon gamma (INF-gamma). 151 incident cases of type 1 diabetes and 182 non related healthy controls from Santiago were studied for VDR polymorphisms in peripheral blood DNA. Exon 2 (Fok I) segments were amplified by polimerase chain reaction and analyzed by means of restriction fragment length polymorphism to determine each corresponding genotype. Differences for allele, genotype and serological markers as 25(OH) vitamin D, TGF-beta1 and INF-gamma levels distribution between patients and controls were analyzed. Fok I polymorphism distribution analysis showed no differences between patients and controls. Among diabetics, higher levels of TGF-beta1 (median, 282.6 pg/ml; range, 131.8-3,031.4) were observed compared with healthy children (median, 232.2 pg/ml; range, 135.7-506.5) (p < 0.0038). Similar results were observed for INF-gamma concentrations (median, 121.1 pg/ml, and range, 5.3-228.8, in cases, and median, 89.6 pg/ml, and range, 10.9-117.2 in controls) (p < 0.0004). The diabetic carriers of the ff genotype showed low levels of 25(OH) vitamin D compared with the carriers of the F allele: mean (standard deviation), 23.1 (5.9) versus 27.9 (10.3) ng/ml (p < 0.03). A similar result was observed for TGF-beta1 concentrations in diabetic carriers of ff genotype and patients carriers of the F allele (298.5 versus 276.6; p < 0.05). Fok I polymorphism of VDR could have a marginal role in the immunologic disturbance in type 1 diabetes.

Genetic polymorphism in matrix metalloproteinase-9 and transforming growth factor-β1 and susceptibility to combined pulmonary fibrosis and emphysema in a Chinese population.

PubMed

Xu, Ling; Bian, Wei; Gu, Xiao-Hua; Shen, Ce

2017-03-01

In this study, we aimed to explore the association of genetic polymorphism in matrix metalloproteinase-9 (MMP-9) and transforming growth factor-β1 (TGF-β1) and the susceptibility to combined pulmonary fibrosis and emphysema (CPFE). We examined the polymorphisms of the MMP-9 C-1562T and TGF-β1 T869C in 38 CPFE patients, 50 pulmonary emphysema patients, and 34 idiopathic pulmonary fibrosis (IPF) patients. The frequencies of polymorphic genotypes in MMP-9 were 78.95% CC and 21.05% CT in CPFE group, 76.0% CC and 24.0% CT in emphysema group, and 100.0% CC in IPF group. There were highly statistically significant increased frequencies of the CT genotype and T allele in CPFE and emphysema groups compared with IPF group (p < 0.05). The frequencies of polymorphic genotypes in TGF-β1 were 2.63% CC, 28.95% CT, 68.42% TT in CPFE group, 4.00% CC, 16.00% CT, 80.00% TT in emphysema group, and 5.88% CC, 41.18% CT, 52.94% TT in IPF group. Significant increases in the TT genotype and T allele frequencies were observed in emphysema group compared with IPF group (p < 0.05). Our study has showed that T allele in MMP-9 (C-1562T) and T allele in TGF-β1 (T869C) are risk factors of pulmonary emphysema. The T allele in MMP-9 (C-1562T) possibly predisposes patients with pulmonary fibrosis to develop emphysema. Copyright © 2017. Published by Elsevier Taiwan.

Association of transforming growth factor-beta1 gene polymorphism in the development of Epstein-Barr virus-related hematologic diseases.

PubMed

Hatta, Kanako; Morimoto, Akira; Ishii, Eiichi; Kimura, Hiroshi; Ueda, Ikuyo; Hibi, Shigeyoshi; Todo, Shinjiro; Sugimoto, Tohru; Imashuku, Shinsaku

2007-11-01

Epstein-Barr virus (EBV) is etiologically associated with various hematologic disorders, including primary acute infectious mononucleosis (IM), hemophagocytic lymphohistiocytosis (EBV-HLH), chronic active EBV infection (CAEBV) and malignant lymphomas. Although cytokines play a central role in EBV-related immune responses, the exact mechanisms causing different clinical responses remain unclear. In this study, the pattern of cytokine gene polymorphisms was comparatively analyzed in EBV-related diseases. Eighty-nine patients with EBV-related disease were analyzed; 30 with IM, 28 with EBV-HLH and 31 with CAEBV. Eighty-one EBV-seropositive healthy adults were also used as controls. Associations with polymorphisms of various cytokines, including interleukin (IL)-1 alpha and IL-1 beta were evaluated. The gene polymorphisms were typed by polymerase chain reaction with sequence-specific primers. A significant difference of polymorphisms was found for transforming growth factor (TGF)-beta1; the frequency of TGF-beta1 codon 10 C allele was significantly higher in patients with EBV-related diseases than in controls (p<0.001). The difference was significant in patients with IM or HLH (p<0.001), but not in those with CAEBV (p=0.127), compared with controls. As regards other cytokines, the frequency of the IL-1 alpha -889 C allele was significantly lower in patients with IM than in controls (p<0.05). Our results suggests that TGF-beta1 codon 10 C allele plays a role in the development of EBV-related diseases and that the IL-1 alpha -889 C allele may be involved in response failure and sequential progression into the development of HLH.

The effects of polymorphisms in 7 candidate genes on resistance to Salmonella Enteritidis in native chickens.

PubMed

Tohidi, R; Idris, I B; Malar Panandam, J; Hair Bejo, M

2013-04-01

Salmonella enterica serovar Enteritidis infection is a common concern in poultry production for its negative effects on growth as well as food safety for humans. Identification of molecular markers that are linked to resistance to Salmonella Enteritidis may lead to appropriate solutions to control Salmonella infection in chickens. This study investigated the association of candidate genes with resistance to Salmonella Enteritidis in young chickens. Two native breeds of Malaysian chickens, namely, Village Chickens and Red Junglefowl, were evaluated for bacterial colonization after Salmonella Enteritidis inoculation. Seven candidate genes were selected on the basis of their physiological role in immune response, as determined by prior studies in other genetic lines: natural resistance-associated protein 1 (NRAMP1), transforming growth factor β3 (TGFβ3), transforming growth factor β4 (TGFβ4), inhibitor of apoptosis protein 1 (IAP1), caspase 1 (CASP1), lipopolysaccharide-induced tumor necrosis factor (TNF) α factor (LITAF), and TNF-related apoptosis-inducing ligand (TRAIL). Polymerase chain reaction-RFLP was used to identify polymorphisms in the candidate genes; all genes exhibited polymorphisms in at least one breed. The NRAMP1-SacI polymorphism correlated with the differences in Salmonella Enteritidis load in the cecum (P = 0.002) and spleen (P = 0.01) of Village Chickens. Polymorphisms in the restriction sites of TGFβ3-BsrI, TGFβ4-MboII, and TRAIL-StyI were associated with Salmonella Enteritidis burden in the cecum, spleen, and liver of Village Chickens and Red Junglefowl (P < 0.05). These results indicate that the NRAMP1, TGFβ3, TGFβ4, and TRAIL genes are potential candidates for use in selection programs for increasing genetic resistance against Salmonella Enteritidis in native Malaysian chickens.

Role of valence electrons in phase transformation kinetics of thallium and its dilute alloys

NASA Technical Reports Server (NTRS)

Ahmed, R.; Ahmed, S.

1991-01-01

The kinetics of the phase transformation of thallium and its dilute alloys were investigated using XRD and calorimetry. Pure thallium exhibits a beta(bcc) to alpha(hcp) phase transformation on cooling at 508 K. With alloying additions, the crystal structure for each phase does not change, although the size of the unit cell increases. The enthalpy and the temperature of phase transformation of each alloy have been determined. The chemical free energy change associated with the phase transformation of each alloy was calculated. The valence electrons make an outstanding contribution to the chemical free energy change required for the phase change.

High pressure polymorphs and amorphization of upconversion host material NaY(WO 4) 2

DOE PAGES

Hong, Fang; Yue, Binbin; Cheng, Zhenxiang; ...

2016-07-29

The pressure effect on the structural change of upconversion host material NaY(WO 4) 2 was studied in this paper by using in-situ synchrotron X-ray diffraction. A transition from the initial scheelite phase to the M-fergusonite phase occurs near 10 GPa, and another phase transition is found near 27.5 GPa, which could be an isostructural transition without symmetry change. The sample becomes amorphous when the pressure is fully released from high pressure. Finally, this work demonstrates the possibility of synthesizing various polymorph structures for non-linear optical applications with a high pressure, chemical doping, or strained thin-film nanostructure process.

Phase Stability and Transformations in Vanadium Oxide Nanocrystals

NASA Astrophysics Data System (ADS)

Bergerud, Amy Jo

Vanadium oxides are both fascinating and complex, due in part to the many compounds and phases that can be stabilized as well as the phase transformations which occur between them. The metal to insulator transitions (MITs) that take place in vanadium oxides are particularly interesting for both fundamental and applied study as they can be induced by a variety of stimuli ( i.e., temperature, pressure, doping) and utilized in many applications (i.e., smart windows, sensors, phase change memory). Nanocrystals also tend to demonstrate interesting phase behavior, due in part to the enhanced influence of surface energy on material thermodynamics. Vanadium oxide nanocrystals are thus expected to demonstrate very interesting properties in regard to phase stability and phase transformations, although synthesizing vanadium oxides in nanocrystal form remains a challenge. Vanadium sesquioxide (V2O3) is an example of a material that undergoes a MIT. For decades, the low temperature monoclinic phase and high temperature corundum phase were the only known crystal structures of V2O3. However, in 2011, a new metastable polymorph of V2O3 was reported with a cubic, bixbyite crystal structure. In Chapter 2, a colloidal route to bixbyite V2O 3 nanocrystals is presented. In addition to being one of the first reported observations of the bixbyite phase in V2O3, it is also one of the first successful colloidal syntheses of any of the vanadium oxides. The nanocrystals possess a flower-like morphology, the size and shape of which are dependent on synthesis time and temperature, respectively. An aminolysis reaction mechanism is determined from Fourier transform infrared spectroscopy data and the bixbyite crystal structure is confirmed by Rietveld refinement of X-ray diffraction (XRD) data. Phase stability is assessed in both air and inert environments, confirming the metastable nature of the material. Upon heating in an inert atmosphere above 700°C, the nanocrystals irreversibly transform to the bulk stable corundum phase of V2O3 with concurrent particle coarsening. This, in combination with the enhanced stability of the nanocrystals over bulk, suggests that the bixbyite phase may be stabilized due to surface energy effects, a well-known phenomenon in nanocrystal research. In Chapter 3, the reversible incorporation of oxygen in bixbyite V 2O3 is reported, which can be controlled by varying temperature and oxygen partial pressure. Based on XRD and thermogravimetric analysis, it is found that oxygen occupies interstitial sites in the bixbyite lattice. Two oxygen atoms per unit cell can be incorporated rapidly and with minimal changes to the structure while the addition of three or more oxygen atoms destabilizes the structure, resulting in a phase change that can be reversed upon oxygen removal. Density functional theory (DFT) supports the reversible occupation of interstitial sites in bixbyite by oxygen and the 1.1 eV barrier to oxygen diffusion predicted by DFT matches the activation energy of the oxidation process derived from observations by in situ XRD. The observed rapid oxidation kinetics are thus facilitated by short diffusion paths through the bixbyite nanocrystals. Due to the exceptionally low temperatures of oxidation and reduction, this material, made from earth-abundant atoms, is proposed for use in oxygen storage applications, where oxygen is reversibly stored and released. Further oxidation of bixbyite V2O3 under controlled oxygen partial pressure can lead to the formation of nanocrystalline vanadium dioxide (VO2), a material that is studied for its MIT that occurs at 68 C in the bulk. This transformation is accompanied by a change in crystal structure, from monoclinic to rutile phase, and a change in optical properties, from infrared transparent to infrared blocking. Because of this, VO2 is promising for thermochromic smart window applications, where optical properties vary with temperature. Recently, alternative stimuli have been utilized to trigger MITs in VO2, including electrochemical gating. Rather than inducing the expected monoclinic to rutile phase transition as originally proposed, electrochemical gating of the insulating phase was recently shown to induce oxygen vacancy formation in VO2, thereby inducing metallization, while the characteristic V-V dimerization of the monoclinic phase was retained. In Chapter 4, the preparation and electrochemical reduction of VO2 nanocrystal films is presented. The nanocrystalline morphology allows for the study of transformations under conditions that enhance the gating effect by creating a large VO2-electrolyte interfacial area and by reducing the path length for diffusion. The resulting transitions are observed optically, from insulator to metal to insulator and back, with in situ visible-near infrared spectroelectrochemistry and correlated with structural changes monitored by Raman and X-ray absorption spectroscopies. The never-before-seen transition to an insulating phase under progressive electrochemical reduction is attributed to an oxygen defect induced phase transition to a new phase. This is likely enabled by the nanocrystalline nature of the sample, which may enhance the kinetics of oxygen diffusion, support a higher degree of lattice expansion-induced strain, or simply alter the thermodynamics of the system.

Influence of XRCC1 Genetic Polymorphisms on Ionizing Radiation-Induced DNA Damage and Repair.

PubMed

Sterpone, Silvia; Cozzi, Renata

2010-07-25

It is well known that ionizing radiation (IR) can damage DNA through a direct action, producing single- and double-strand breaks on DNA double helix, as well as an indirect effect by generating oxygen reactive species in the cells. Mammals have evolved several and distinct DNA repair pathways in order to maintain genomic stability and avoid tumour cell transformation. This review reports important data showing a huge interindividual variability on sensitivity to IR and in susceptibility to developing cancer; this variability is principally represented by genetic polymorphisms, that is, DNA repair gene polymorphisms. In particular we have focussed on single nucleotide polymorphisms (SNPs) of XRCC1, a gene that encodes for a scaffold protein involved basically in Base Excision Repair (BER). In this paper we have reported and presented recent studies that show an influence of XRCC1 variants on DNA repair capacity and susceptibility to breast cancer.

Non-rigid molecule of copper(II) diiminate Cu[CF3C(NH)C(F)C(NH)CF3]2, its conformational polymorphism in crystal and structure in solutions (Raman, UV-vis and quantum chemistry study)

NASA Astrophysics Data System (ADS)

Bukalov, Sergey S.; Aysin, Rinat R.; Leites, Larissa A.; Kurykin, Mikhail A.; Khrustalev, Victor N.

2015-10-01

Calculation of potential energy surface (PES) of isolated molecule of copper(II) diiminate Cu[CF3С(NH)C(F)C(NH)CF3]2 (1) resulted a double-well curve with the minima corresponding to equivalent screwed conformations. The low barrier leads to molecular non-rigidity which seems to be the reason of conformational polymorphism in crystals, reported in [1]. For one of newly found polymorphs, the X-ray structure was determined. The differences in the Raman and UV-vis spectra between differently colored species and their solutions were revealed, they are determined by different geometries of Cu(II) coordination polyhedron and different systems of intermolecular interactions in crystals. Transformations of the polymorphs under thermal, mechanical and photo exposures were studied.

Pressure-tuning micro-Raman spectra of artists' pigments: α- and β-copper phthalocyanine polymorphs.

PubMed

Beaulieu-Houle, Guillaume; Gilson, Denis F R; Butler, Ian S

2014-01-03

The two polymorphs of copper phthalocyanine, α- and β-CuPc, have been examined by micro-Raman spectroscopy at pressures approaching 5.0 GPa. The metastable α-polymorph does not exhibit any structural changes, while the more thermodynamically stable β-polymorph does exhibit a reversible phase transition at 2.0 GPa. The pressure dependences (dν/dP) for a selected number of vibrational modes are reported. Two regions of the Raman spectra, 800-900 cm(-1) and 1100-1200 cm(-1), are sensitive to pressure such that they can be used as indicators of the polymorphic form. Copyright © 2013 Elsevier B.V. All rights reserved.

Temperature induced phase transition of CaMn{sub 0.5}Zr{sub 1.5}(PO{sub 4}){sub 3} phosphate

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

Orlova, Maria, E-mail: maria.p.orlova@gmail.com; Perfler, Lukas; Tribus, Martina

2016-03-15

In this work we investigated the structural behaviour of a CaMn{sub 0.5}Zr{sub 1.5}(PO{sub 4}){sub 3}. Due to the presence of divalent Mn{sup 2+} cations this compound can possess interesting luminescence properties. It was recently understood that this phosphate undergoes a temperature induced irreversible phase transition in the range of 800–875 °C. It has also been shown that the 3d–3d luminescence of Mn{sup 2+} increases 10 fold for the high temperature polymorph. To determine the Mn environment structural investigations of both phases have been performed by the X-ray powder diffraction and Raman spectroscopy methods. The low temperature modification adopts the trigonalmore » NZP structure type with a slightly lower symmetry (space group R32, a=8.7850(2) Å, c=22.6496(7) Å, V=1514.8(1) Å{sup 3}). The high temperature form in turn has orthorhombic symmetry (space group Pnma, a=6.2350(3) Å, b=6.6281(3) Å, c=14.4731(6) Å, V=598.13(5) Å{sup 3}). Both structures were solved ab-initio from powder data and structural analysis was performed. In-situ and RT Raman spectra are consistent with the XRD derived structural model. Mn{sup 2+} cations occupy different types of positions in these structures and a change in Mn coordination number (6 for LT phase, 7 for HT phase) results in different Mn–O bond lengths. These differences may explain the change in the optical properties between the polymorphs. - Graphical abstract: The compound CaMn{sub 0.5}Zr{sub 1.5}(PO{sub 4}){sub 3} was synthesized in order to create a material with enhanced luminescent properties. The goal of present studies is to define Mn{sup 2+} environment and its changes due to the structural transformations of the phosphate along phase transition at the T range of 800–875 °C. It was found that LT modification adopts the trigonal NZP structure type, sp.gr. R32, the HT form in turn exhibits orthorhombic symmetry sp.gr. Pnma. Mn2+ cations occupy different types of positions in those structures and a change in coordination number of Mn (6 for LT phase, 7 for HT phase) results in a change in Mn–O bond lengths.« less

High-pressure behavior of iron-nickel-cobalt phosphides and its implications for meteorites and planetary cores

NASA Astrophysics Data System (ADS)

Dera, P.; Lavina, B.; Borkowski, L. A.; Downs, R. T.; Prewitt, C. T.; Prakapenka, V.; Rivers, M. L.; Sutton, S.; Boctor, N.

2008-12-01

Minerals with composition (Fe,Ni)xP, are rare, but important accessory phases present in iron and chondrite meteorites. The occurrence of these minerals in meteoritic samples is believed to originate either from the equilibrium condensation of protoplanetary materials taking place in solar nebulae or from crystallization processes in the cores of parent bodies. Fe-Ni phosphides are considered an important candidate for a minor phase present in Earth's core, and at least partially responsible for the observed core density deficit with respect to pure Fe. We report results of high-pressure high-temperature single-crystal X- ray diffraction experiments with end-members belonging to the (Fe,Ni,Co)2P family, including Fe2P, Ni2P and Co2P. A new phase transition to the Co2Si-type structure (allabogdanite) has been found in Fe2P barringerite at 8.0 GPa, upon heating. The high-pressure phase can be quenched metastably to ambient conditions and then, if heated again, it transforms back to barringerite. Ni2P barringerite does not undergo transformation to allabogdanite structure up to 50 GPa, but instead exhibits incongruent melting with formation of pyrite-type NiP2 and Ni-P glass. Our results indicate that the presence of allabogdanite in meteoritic samples places two important constraints on the thermodynamic history of the meteorite. First, it imposes a minimum pressure and temperature for the formation of the Fe2P, and additionally rules out any higher temperature low pressure alterations. If present in the Earth's core, Fe2P will have the allabogdanite rather than the barringerite structure. Crystal chemical trends in the compressibility of (Fe,Ni,Co)2P minerals, as well as polymorphic transition paths are analyzed in the context of Earth and planetary core composition and properties.

Flux-mediated syntheses, structural characterization and low-temperature polymorphism of the p-type semiconductor Cu2Ta4O11

NASA Astrophysics Data System (ADS)

King, Nacole; Sullivan, Ian; Watkins-Curry, Pilanda; Chan, Julia Y.; Maggard, Paul A.

2016-04-01

A new low-temperature polymorph of the copper(I)-tantalate, α-Cu2Ta4O11, has been synthesized in a molten CuCl-flux reaction at 665 °C for 1 h and characterized by powder X-ray diffraction Rietveld refinements (space group Cc (#9), a=10.734(1) Å, b = 6.2506(3) Å, c=12.887(1) Å, β = 106.070(4)°). The α-Cu2Ta4O11 phase is a lower-symmetry monoclinic polymorph of the rhombohedral Cu2Ta4O11 structure (i.e., β-Cu2Ta4O11 space group R 3 ̅ c (#167), a = 6.2190(2) Å, c=37.107(1) Å), and related crystallographically by ahex=amono/√3, bhex=bmono, and chex=3cmonosinβmono. Its structure is similar to the rhombohedral β-Cu2Ta4O11 and is composed of single layers of highly-distorted and edge-shared TaO7 and TaO6 polyhedra alternating with layers of nearly linearly-coordinated Cu(I) cations and isolated TaO6 octahedra. Temperature dependent powder X-ray diffraction data show the α-Cu2Ta4O11 phase is relatively stable under vacuum at 223 K and 298 K, but reversibly transforms to β-Cu2Ta4O11 by at least 523 K and higher temperatures. The symmetry-lowering distortions from β-Cu2Ta4O11 to α-Cu2Ta4O11 arise from the out-of-center displacements of the Ta 5d0 cations in the TaO7 pentagonal bipyramids. The UV-vis diffuse reflectance spectrum of the monoclinic α-Cu2Ta4O11 shows an indirect bandgap transition of ∼2.6 eV, with the higher-energy direct transitions starting at ∼2.7 eV. Photoelectrochemical measurements on polycrystalline films of α-Cu2Ta4O11 show strong cathodic photocurrents of ∼1.5 mA/cm2 under AM 1.5 G solar irradiation.

High pressure phase transformations revisited

NASA Astrophysics Data System (ADS)

Levitas, Valery I.

2018-04-01

High pressure phase transformations play an important role in the search for new materials and material synthesis, as well as in geophysics. However, they are poorly characterized, and phase transformation pressure and pressure hysteresis vary drastically in experiments of different researchers, with different pressure transmitting media, and with different material suppliers. Here we review the current state, challenges in studying phase transformations under high pressure, and the possible ways in overcoming the challenges. This field is critically compared with fields of phase transformations under normal pressure in steels and shape memory alloys, as well as plastic deformation of materials. The main reason for the above mentioned discrepancy is the lack of understanding that there is a fundamental difference between pressure-induced transformations under hydrostatic conditions, stress-induced transformations under nonhydrostatic conditions below yield, and strain-induced transformations during plastic flow. Each of these types of transformations has different mechanisms and requires a completely different thermodynamic and kinetic description and experimental characterization. In comparison with other fields the following challenges are indicated for high pressure phase transformation: (a) initial and evolving microstructure is not included in characterization of transformations; (b) continuum theory is poorly developed; (c) heterogeneous stress and strain fields in experiments are not determined, which leads to confusing material transformational properties with a system behavior. Some ways to advance the field of high pressure phase transformations are suggested. The key points are: (a) to take into account plastic deformations and microstructure evolution during transformations; (b) to formulate phase transformation criteria and kinetic equations in terms of stress and plastic strain tensors (instead of pressure alone); (c) to develop multiscale continuum theories, and (d) to couple experimental, theoretical, and computational studies of the behavior of a tested sample to extract information about fields of stress and strain tensors and concentration of high pressure phase, transformation criteria and kinetics. The ideal characterization should contain complete information which is required for simulation of the same experiments.

High pressure phase transformations revisited.

PubMed

Levitas, Valery I

2018-04-25

High pressure phase transformations play an important role in the search for new materials and material synthesis, as well as in geophysics. However, they are poorly characterized, and phase transformation pressure and pressure hysteresis vary drastically in experiments of different researchers, with different pressure transmitting media, and with different material suppliers. Here we review the current state, challenges in studying phase transformations under high pressure, and the possible ways in overcoming the challenges. This field is critically compared with fields of phase transformations under normal pressure in steels and shape memory alloys, as well as plastic deformation of materials. The main reason for the above mentioned discrepancy is the lack of understanding that there is a fundamental difference between pressure-induced transformations under hydrostatic conditions, stress-induced transformations under nonhydrostatic conditions below yield, and strain-induced transformations during plastic flow. Each of these types of transformations has different mechanisms and requires a completely different thermodynamic and kinetic description and experimental characterization. In comparison with other fields the following challenges are indicated for high pressure phase transformation: (a) initial and evolving microstructure is not included in characterization of transformations; (b) continuum theory is poorly developed; (c) heterogeneous stress and strain fields in experiments are not determined, which leads to confusing material transformational properties with a system behavior. Some ways to advance the field of high pressure phase transformations are suggested. The key points are: (a) to take into account plastic deformations and microstructure evolution during transformations; (b) to formulate phase transformation criteria and kinetic equations in terms of stress and plastic strain tensors (instead of pressure alone); (c) to develop multiscale continuum theories, and (d) to couple experimental, theoretical, and computational studies of the behavior of a tested sample to extract information about fields of stress and strain tensors and concentration of high pressure phase, transformation criteria and kinetics. The ideal characterization should contain complete information which is required for simulation of the same experiments.

Uncovering the intrinsic size dependence of hydriding phase transformations in nanocrystals.

PubMed

Bardhan, Rizia; Hedges, Lester O; Pint, Cary L; Javey, Ali; Whitelam, Stephen; Urban, Jeffrey J

2013-10-01

A quantitative understanding of nanocrystal phase transformations would enable more efficient energy conversion and catalysis, but has been hindered by difficulties in directly monitoring well-characterized nanoscale systems in reactive environments. We present a new in situ luminescence-based probe enabling direct quantification of nanocrystal phase transformations, applied here to the hydriding transformation of palladium nanocrystals. Our approach reveals the intrinsic kinetics and thermodynamics of nanocrystal phase transformations, eliminating complications of substrate strain, ligand effects and external signal transducers. Clear size-dependent trends emerge in nanocrystals long accepted to be bulk-like in behaviour. Statistical mechanical simulations show these trends to be a consequence of nanoconfinement of a thermally driven, first-order phase transition: near the phase boundary, critical nuclei of the new phase are comparable in size to the nanocrystal itself. Transformation rates are then unavoidably governed by nanocrystal dimensions. Our results provide a general framework for understanding how nanoconfinement fundamentally impacts broad classes of thermally driven solid-state phase transformations relevant to hydrogen storage, catalysis, batteries and fuel cells.

Novel organic NLO material bis(N-phenylbiguanidium(1+)) oxalate - A combined X-ray diffraction, DSC and vibrational spectroscopic study of its unique polymorphism

NASA Astrophysics Data System (ADS)

Matulková, Irena; Císařová, Ivana; Vaněk, Přemysl; Němec, Petr; Němec, Ivan

2017-01-01

Three polymorphic modifications of bis(N-phenylbiguanidium(1+)) oxalate are reported, and their characterization is discussed in this paper. The non-centrosymmetric bis(N-phenylbiguanidium(1+)) oxalate (I), which was obtained from an aqueous solution at 313 K, belongs to the monoclinic space group Cc (a = 6.2560(2) Å, b = 18.6920(3) Å, c = 18.2980(5) Å, β = 96.249(1)°, V = 2127.0(1) Å3, Z = 4, R = 0.0314 for 4738 observed reflections). The centrosymmetric bis(N-phenylbiguanidium(1+)) oxalate (II) was obtained from an aqueous solution at 298 K and belongs to the monoclinic space group P21/n (a = 6.1335(3) Å, b = 11.7862(6) Å, c = 14.5962(8) Å, β = 95.728(2)°, V = 1049.90(9) Å3, Z = 4, R = 0.0420 for 2396 observed reflections). The cooling of the centrosymmetric phase (II) leads to the formation of bis(N-phenylbiguanidium(1+)) oxalate (III) (a = 6.1083(2) Å, b = 11.3178(5) Å, c = 14.9947(5) Å, β = 93.151(2)°, V = 1035.05(8) Å3, Z = 4, R = 0.0345 for 2367 observed reflections and a temperature of 110 K), which also belongs to the monoclinic space group P21/n. The crystal structures of the three characterized phases are generally based on layers of isolated N-phenylbiguanidium(1 +) cations separated by oxalate anions and interconnected with them by several types of N-H...O hydrogen bonds. The observed phases generally differ not only in their crystal packing but also in the lengths and characteristics of their hydrogen bonds. The thermal behaviour of the prepared compounds was studied using the DSC method in the temperature range from 90 K up to a temperature near the melting point of each crystal. The bis(N-phenylbiguanidium(1+)) oxalate (II) crystals exhibit weak reversible thermal effects on the DSC curve at 147 K (heating run). Further investigation of this effect, which was assigned to the isostructural phase transformation, was performed using FTIR, Raman spectroscopy and X-ray diffraction analysis in a wide temperature range.

Survey and analysis of crystal polymorphism in organic structures

PubMed Central

Kaur, Ramanpreet

2018-01-01

With the intention of producing the most comprehensive treatment of the prevalence of crystal polymorphism among structurally characterized materials, all polymorphic compounds flagged as such within the Cambridge Structural Database (CSD) are analysed and a list of crystallographically characterized organic polymorphic compounds is assembled. Classifying these structures into subclasses of anhydrates, salts, hydrates, non-hydrated solvates and cocrystals reveals that there are significant variations in polymorphism prevalence as a function of crystal type, a fact which has not previously been recognized in the literature. It is also shown that, as a percentage, polymorphic entries are decreasing temporally within the CSD, with the notable exception of cocrystals, which continue to rise at a rate that is a constant fraction of the overall entries. Some phenomena identified that require additional scrutiny include the relative prevalence of temperature-induced phase transitions among organic salts and the paucity of polymorphism in crystals with three or more chemical components. PMID:29765601

Haplotype-based gene-gene interaction of bone morphogenetic protein 4 and interferon regulatory factor 6 in the etiology of non-syndromic cleft lip with or without cleft palate in a Chilean population.

PubMed

Blanco, Rafael; Colombo, Alicia; Pardo, Rosa; Suazo, José

2017-04-01

Non-syndromic cleft lip with or without cleft palate (NSCL/P) is the most common craniofacial birth defect in humans, the etiology of which can be dependent on the interactions of multiple genes. We previously reported haplotype associations for polymorphic variants of interferon regulatory factor 6 (IRF6), msh homeobox 1 (MSX1), bone morphogenetic protein 4 (BMP4), and transforming growth factor beta 3 (TGFB3) in Chile. Here, we analyzed the haplotype-based gene-gene interaction for markers of these genes and NSCL/P risk in the Chilean population. We genotyped 15 single nucleoptide polymorphisms (SNPs) in 152 Chilean patients and 164 controls. Linkage disequilibrium (LD) blocks were determined using the Haploview software, and phase reconstruction was performed by the Phase program. Haplotype-based interactions were evaluated using the multifactor dimensionality reduction (MDR) method. We detected two LD blocks composed of two SNPs from BMP4 (Block 1) and three SNPs from IRF6 (Block 2). Although MDR showed no statistical significance for the global interaction model involving these blocks, we found four combinations conferring a statistically significantly increased NSCL/P risk (Block 1-Block 2): T-T/T-G C-G-T/G-A-T; T-T/T-G C-G-C/C-G-C; T-T/T-G G-A-T/G-A-T; and T-T/C-G G-A-T/G-A-T. These findings may reflect the presence of a genomic region containing potential causal variants interacting in the etiology of NSCL/P and may contribute to disentangling the complex etiology of this birth defect. © 2017 Eur J Oral Sci.

Onset of ice VII phase during ps laser pulse propagation through liquid water

NASA Astrophysics Data System (ADS)

Kumar, V. Rakesh; Kiran, P. Prem

2017-01-01

Water dominantly present in liquid state on earth gets transformed to crystalline polymorphs under different dynamic loading conditions. Out of different crystalline phases discovered till date, ice VII is observed to be stable over wide pressure (2-63 GPa) and temperature (>273 K) ranges. The formation of ice VII crystalline structure has been vastly reported during high pressure static compression using diamond anvil cell and propagation of high energy (>50 mJ/pulse) nanosecond laser pulse induced dynamic high pressures through liquid water. We present the onset of ice VII phase at low threshold of 2 mJ/pulse during 30 ps (532 nm, 10 Hz) laser pulse induced shock propagating through liquid water. Role of input pulse energy on the evolution of Stoke's and anti-Stoke's Raman shift of the dominant A1g mode of ice VII, filamentation, free-electrons, plasma shielding is presented. The H-bond network rearrangement, electron ion energy transfer time coinciding with the excitation pulse duration supported by the filamentation and plasma shielding of the ps laser pulses reduced the threshold of ice VII structure formation. Filamentation and the plasma shielding have shown the localized creation and sustenance of ice VII structure in liquid water over 3 mm length and 50 μm area of cross-section.

Phase transformation and deformation behavior of NiTi-Nb eutectic joined NiTi wires

PubMed Central

Wang, Liqiang; Wang, Cong; Zhang, Lai-Chang; Chen, Liangyu; Lu, Weijie; Zhang, Di

2016-01-01

NiTi wires were brazed together via eutectic reaction between NiTi and Nb powder deposited at the wire contact region. Phase transformation and deformation behavior of the NiTi-Nb eutectic microstructure were investigated using transmission electron microscopy (TEM) and cyclic loading-unloading tests. Results show that R phase and B19′ martensite transformation are induced by plastic deformation. R phase transformation, which significantly contributes to superelasticity, preferentially occurs at the interfaces between NiTi and eutectic region. Round-shaped Nb-rich phase with rod-like and lamellar-type eutectics are observed in eutectic regions. These phases appear to affect the deformation behavior of the brazed NiTi-Nb region via five distinct stages in stress-strain curves: (I) R phase reorientation, (II) R phase transformation from parent phase, (III) elastic deformation of reoriented martensite accompanied by the plastic deformation of Nb-rich phase and lamellar NiTi-Nb eutectic, (IV) B19′ martensitic transformation, and (V) plastic deformation of the specimen. PMID:27049025

Thermal-induced phase transition and assembly of hexagonal metastable In 2O 3 nanocrystals: A new approach to In 2O 3 functional materials

NASA Astrophysics Data System (ADS)

Shu, Shiwen; Yu, Dabin; Wang, Yan; Wang, Feng; Wang, Zirong; Zhong, Wu

2010-10-01

This paper reports on the thermal-induced performance of hexagonal metastable In 2O 3 nanocrystals involving in phase transition and assembly, with particular emphasis on the assembly for the preparation of functional materials. For In 2O 3 nanocrystals, the metastable phase was found to be thermally unstable and transform to cubic phase when temperature was higher than 600 °C, accompanied by assembly as well as evolution of optical properties, but the two polymorphs coexisted at the temperature ranging from 600 to 900 °C, during which the content of product phase and crystal size gradually increased upon increasing temperature. The assembly of In 2O 3 nanocrystals can be developed to fabricate In 2O 3 functional materials, such as various ceramic materials, or even desired nano- or micro-structures, by using metastable In 2O 3 nanocrystals as precursors or building blocks. The electrical resistivity of In 2O 3 conductive film fabricated by a hot-pressing route was as low as 3.72×10 -3 Ω cm, close to that of In 2O 3 single crystal, which is important for In 2O 3 that is always used as conductive materials. The findings should be of importance for both the wide applications of In 2O 3 in optical and electronic devices and theoretical investigations on crystal structures.

A novel analytical method for pharmaceutical polymorphs by terahertz spectroscopy and the optimization of crystal form at the discovery stage.

PubMed

Ikeda, Yukihiro; Ishihara, Yoko; Moriwaki, Toshiya; Kato, Eiji; Terada, Katsuhide

2010-01-01

A novel analytical method for the determination of pharmaceutical polymorphs was developed using terahertz spectroscopy. It was found out that each polymorph of a substance showed a specific terahertz absorption spectrum. In particular, analysis of the second derivative spectrum was enormously beneficial in the discrimination of closely related polymorphs that were difficult to discern by powder X-ray diffractometry. Crystal forms that were obtained by crystallization from various solvents and stored under various conditions were specifically characterized by the second derivative of each terahertz spectrum. Fractional polymorphic transformation for substances stored under stressed conditions was also identified by terahertz spectroscopy during solid-state stability test, but could not be detected by powder X-ray diffractometry. Since polymorphs could be characterized clearly by terahertz spectroscopy, further physicochemical studies could be conducted in a timely manner. The development form of compound examined was determined by the results of comprehensive physicochemical studies that included thermodynamic relationships, as well as chemical and physicochemical stability. In conclusion, terahertz spectroscopy, which has unique power in the elucidation of molecular interaction within a crystal lattice, can play more important role in physicochemical research. Terahertz spectroscopy has a great potential as a tool for polymorphic determination, particularly since the second derivative of the terahertz spectrum possesses high sensitivity for pharmaceutical polymorphs.

PSSRdb: a relational database of polymorphic simple sequence repeats extracted from prokaryotic genomes.

PubMed

Kumar, Pankaj; Chaitanya, Pasumarthy S; Nagarajaram, Hampapathalu A

2011-01-01

PSSRdb (Polymorphic Simple Sequence Repeats database) (http://www.cdfd.org.in/PSSRdb/) is a relational database of polymorphic simple sequence repeats (PSSRs) extracted from 85 different species of prokaryotes. Simple sequence repeats (SSRs) are the tandem repeats of nucleotide motifs of the sizes 1-6 bp and are highly polymorphic. SSR mutations in and around coding regions affect transcription and translation of genes. Such changes underpin phase variations and antigenic variations seen in some bacteria. Although SSR-mediated phase variation and antigenic variations have been well-studied in some bacteria there seems a lot of other species of prokaryotes yet to be investigated for SSR mediated adaptive and other evolutionary advantages. As a part of our on-going studies on SSR polymorphism in prokaryotes we compared the genome sequences of various strains and isolates available for 85 different species of prokaryotes and extracted a number of SSRs showing length variations and created a relational database called PSSRdb. This database gives useful information such as location of PSSRs in genomes, length variation across genomes, the regions harboring PSSRs, etc. The information provided in this database is very useful for further research and analysis of SSRs in prokaryotes.

The role of ultrasound in controlling the liquid-liquid phase separation and nucleation of vanillin polymorphs I and II

NASA Astrophysics Data System (ADS)

Parimaladevi, P.; Supriya, S.; Srinivasan, K.

2018-02-01

The influence of ultrasound on liquid-liquid phase separation (LLPS) and polymorphism of vanillin in aqueous solution has been investigated for the first time by varying the ultrasonic parameters such as power, pulse rate and insonation time at ambient condition. Results reveal that the application of ultrasound controls the impact of LLPS and accelerates the nucleation of vanillin within a short period at lower levels of ultrasonic process parameters, and also enhances the quality of the nucleated crystals. Moreover, the application of ultrasound induces the nucleation of rare and metastable polymorph of vanillin Form II in aqueous solution. But, at higher levels of power, pulse rate and insonation time, the rate of LLPS is found increased and the quality of the crystals becomes deteriorated. Morphology of the nucleated polymorphs were identified through optical microscopy and confirmed by optical goniometry. The internal structure and thermal stability of the grown stable Form I and metastable Form II of vanillin were confirmed through powder X-ray diffraction (PXRD) and differential scanning calorimetry (DSC) analyses. Further, results suggest that the ultrasound has profound effect in controlling the LLPS and nucleation of vanillin polymorphs in aqueous solution.

Phase-controlled synthesis of polymorphic tungsten diphosphide with hybridization of monoclinic and orthorhombic phases as a novel electrocatalyst for efficient hydrogen evolution

NASA Astrophysics Data System (ADS)

Pi, Mingyu; Wu, Tianli; Guo, Weimeng; Wang, Xiaodeng; Zhang, Dingke; Wang, Shuxia; Chen, Shijian

2017-05-01

The design and development of high-efficiency and non-noble-metal hydrogen evolution reaction (HER) electrocatalysts for future clean and renewable energy system has excited significant research interests over the recent years. In this communication, the polymorphic tungsten diphosphide (p-WP2) nanoparticles with mixed monoclinic (α-) and orthorhombic (β-) phases are synthesized by phase-controlled phosphidation route via vacuum capsulation and explored as a novel efficient electrocatalyst towards HER. The p-WP2 catalyst delivers superior performance with excellent stability under both acidic and alkaline conditions over its single phases of α-WP2 and β-WP2. This finding demonstrates that a highly efficient hybrid electrocatalyst can be achieved via precise composition controlling and may open up exciting opportunities for their practical applications toward energy conversion.

Phase transformation pathways of ultrafast-laser-irradiated Ln2O3 (Ln =Er -Lu )

NASA Astrophysics Data System (ADS)

Rittman, Dylan R.; Tracy, Cameron L.; Chen, Chien-Hung; Solomon, Jonathan M.; Asta, Mark; Mao, Wendy L.; Yalisove, Steven M.; Ewing, Rodney C.

2018-01-01

Ultrafast laser irradiation causes intense electronic excitations in materials, leading to transient high temperatures and pressures. Here, we show that ultrafast laser irradiation drives an irreversible cubic-to-monoclinic phase transformation in Ln2O3 (Ln =Er -Lu ), and explore the mechanism by which the phase transformation occurs. A combination of grazing incidence x-ray diffraction and transmission electron microscopy are used to determine the magnitude and depth-dependence of the phase transformation, respectively. Although all compositions undergo the same transformation, their transformation mechanisms differ. The transformation is pressure-driven for Ln =Tm -Lu , consistent with the material's phase behavior under equilibrium conditions. However, the transformation is thermally driven for Ln =Er , revealing that the nonequilibrium conditions of ultrafast laser irradiation can lead to novel transformation pathways. Ab initio molecular-dynamics simulations are used to examine the atomic-scale effects of electronic excitation, showing the production of oxygen Frenkel pairs and the migration of interstitial oxygen to tetrahedrally coordinated constitutional vacancy sites, the first step in a defect-driven phase transformation.

Phase transformation pathways of ultrafast-laser-irradiated Ln 2 O 3 ( Ln = Er – Lu )

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

Rittman, Dylan R.; Tracy, Cameron L.; Chen, Chien-Hung

Ultrafast laser irradiation causes intense electronic excitations in materials, leading to transient high temperatures and pressures. Here, we show that ultrafast laser irradiation drives an irreversible cubic-to-monoclinic phase transformation in Ln 2O 3 ( Ln = Er – Lu ) , and explore the mechanism by which the phase transformation occurs. A combination of grazing incidence x-ray diffraction and transmission electron microscopy are used to determine the magnitude and depth-dependence of the phase transformation, respectively. Although all compositions undergo the same transformation, their transformation mechanisms differ. The transformation is pressure-driven for Ln = Tm – Lu , consistent with themore » material's phase behavior under equilibrium conditions. However, the transformation is thermally driven for Ln = Er , revealing that the nonequilibrium conditions of ultrafast laser irradiation can lead to novel transformation pathways. Ab initio molecular-dynamics simulations are used to examine the atomic-scale effects of electronic excitation, showing the production of oxygen Frenkel pairs and the migration of interstitial oxygen to tetrahedrally coordinated constitutional vacancy sites, the first step in a defect-driven phase transformation.« less

Phase transformation pathways of ultrafast-laser-irradiated Ln 2 O 3 ( Ln = Er – Lu )

DOE PAGES

Rittman, Dylan R.; Tracy, Cameron L.; Chen, Chien-Hung; ...

2018-01-10

Ultrafast laser irradiation causes intense electronic excitations in materials, leading to transient high temperatures and pressures. Here, we show that ultrafast laser irradiation drives an irreversible cubic-to-monoclinic phase transformation in Ln 2O 3 ( Ln = Er – Lu ) , and explore the mechanism by which the phase transformation occurs. A combination of grazing incidence x-ray diffraction and transmission electron microscopy are used to determine the magnitude and depth-dependence of the phase transformation, respectively. Although all compositions undergo the same transformation, their transformation mechanisms differ. The transformation is pressure-driven for Ln = Tm – Lu , consistent with themore » material's phase behavior under equilibrium conditions. However, the transformation is thermally driven for Ln = Er , revealing that the nonequilibrium conditions of ultrafast laser irradiation can lead to novel transformation pathways. Ab initio molecular-dynamics simulations are used to examine the atomic-scale effects of electronic excitation, showing the production of oxygen Frenkel pairs and the migration of interstitial oxygen to tetrahedrally coordinated constitutional vacancy sites, the first step in a defect-driven phase transformation.« less

Transforming Growth Factor-β1 Gene Polymorphism (T29C) in Egyptian Patients with Hepatitis B Virus Infection: A Preliminary Study

PubMed Central

Talaat, Roba M.; Dondeti, Mahmoud F.; El-Shenawy, Soha Z.; Khamiss, Omaima A.

2013-01-01

The interindividual variations in the capacity of transforming growth factor-β1 (TGF-β1) production have been ascribed to genetic polymorphisms in TGF-β1 gene. As pathogenesis of HBV has a genetic background, this preliminary study was designed to assess the impact of TGF-β1 (T29C) on the susceptibility of Egyptians to HBV infection. Genotyping was performed using single stranded polymorphism-polymerase chain reaction (SSP-PCR) in 65 Egyptian hepatitis B patients and 50 healthy controls. TGF-β1 plasma levels were measured using Enzyme-linked immunosorbent assay (ELISA). The frequency of CC genotype was significantly higher (P < 0.05) in HBV patients compared to controls. On the contrary, TC genotype did not show significant difference in both groups. TT genotype was significantly higher (P < 0.01) in controls than HBV patients. Our current preliminary data revealed that the frequency of the genotypes in the controls were within Hardy-Weinberg equilibrium (HWE) while the patients group was out of HWE (P < 0.01). TGF-β1 was significantly (r = −0.684; P < 0.001) deceased in the sera of patients as compared to normal subjects. Depending on our preliminary work, CC genotype may act as a host genetic factor in the susceptibility to HBV infection in Egyptians. Taken together, the current data pointed to the importance of polymorphism of TGF-β1 gene (T29C) in HBV infection. PMID:24455227

Phase transformation dependence on initial plastic deformation mode in Si via nanoindentation

DOE PAGES

Wong, Sherman; Haberl, Bianca; Williams, James S.; ...

2016-09-30

Silicon in its diamond-cubic phase is known to phase transform to a technologically interesting mixture of the body-centred cubic and rhombohedral phases under nanoindentation pressure. In this study, we demonstrate that during plastic deformation the sample can traverse two distinct pathways, one that initially nucleates a phase transformation while the other initially nucleates crystalline defects. These two pathways remain distinct even after sufficient pressure is applied such that both deformation mechanisms are present within the sample. Here, it is further shown that the indents that initially nucleate a phase transformation generate larger, more uniform volumes of the phase transformed materialmore » than indents that initially nucleate crystalline defects.« less

Leu72Met408 Polymorphism of the Ghrelin Gene Is Associated With Early Phase of Gastric Emptying in the Patients With Functional Dyspepsia in Japan

PubMed Central

Yamawaki, Hiroshi; Futagami, Seiji; Shimpuku, Mayumi; Shindo, Tomotaka; Maruki, Yuuta; Nagoya, Hiroyuki; Kodaka, Yasuhiro; Sato, Hitomi; Gudis, Katya; Kawagoe, Tetsuro; Sakamoto, Choitsu

2015-01-01

Background/Aims There are no available data about the relationship between ghrelin gene genotypes and early phase of gastric emptying in functional dyspepsia (FD) as defined by Rome III classification. Methods We enrolled 74 patients presenting with typical symptoms of FD and 64 healthy volunteers. Gastric motility was evaluated using the 13C-acetate breath test. We used Rome III criteria to evaluate upper abdominal symptoms and self-rating questionnaires for depression (SRQ-D) scores to determine status of depression. The Arg51Gln (346G>A), preproghrelin (3056T>C), Leu72Met (408C>A), Gln90Leu (3412T>A) and G-protein β3 (825C>T) polymorphisms were analyzed in the DNA from blood samples of enrolled subjects. Genotyping was performed by polymerase chain reaction. Results There was a significant relationship between the Gln90Leu3412 genotype and SRQ-D score in FD patients (P = 0.009). Area under the curve at 15 minutes (AUC15) value was significantly associated with the Leu72Met408 genotype (P = 0.015) but not with entire gastric emptying. Conclusions The Leu72Met (408C>A) single nucleotide polymorphism was significantly associated with early phase of gastric emptying in FD patients. Further studies will be necessary to clarify the association between ghrelin gene single nucleotide polymorphisms and early phase of gastric emptying in FD patients. PMID:25540946

Leu72Met408 Polymorphism of the Ghrelin Gene Is Associated With Early Phase of Gastric Emptying in the Patients With Functional Dyspepsia in Japan.

PubMed

Yamawaki, Hiroshi; Futagami, Seiji; Shimpuku, Mayumi; Shindo, Tomotaka; Maruki, Yuuta; Nagoya, Hiroyuki; Kodaka, Yasuhiro; Sato, Hitomi; Gudis, Katya; Kawagoe, Tetsuro; Sakamoto, Choitsu

2015-01-01

There are no available data about the relationship between ghrelin gene genotypes and early phase of gastric emptying in functional dyspepsia (FD) as defined by Rome III classification. We enrolled 74 patients presenting with typical symptoms of FD and 64 healthy volunteers. Gastric motility was evaluated using the 13C-acetate breath test. We used Rome III criteria to evaluate upper abdominal symptoms and self-rating questionnaires for depression (SRQ-D) scores to determine status of depression. The Arg51Gln (346G->A), preproghrelin (3056T->C), Leu72Met (408C->A), Gln90Leu (3412T->A) and G-protein 3 (825C->T) polymorphisms were analyzed in the DNA from blood samples of enrolled subjects. Genotyping was performed by polymerase chain reaction. There was a significant relationship between the Gln90Leu3412 genotype and SRQ-D score in FD patients (P = 0.009). Area under the curve at 15 minutes (AUC15) value was significantly associated with the Leu72Met408 genotype (P = 0.015) but not with entire gastric emptying. The Leu72Met (408C->A) single nucleotide polymorphism was significantly associated with early phase of gastric emptying in FD patients. Further studies will be necessary to clarify the association between ghrelin gene single nucleotide polymorphisms and early phase of gastric emptying in FD patients.

TGF-β Polymorphisms Are a Risk Factor for Chagas Disease

PubMed Central

Ferreira, Roberto Rodrigues; Madeira, Fabiana da Silva; Alves, Gabriel Farias; Chambela, Mayara da Costa; Curvo, Eduardo de Oliveira Vaz; Moreira, Aline dos Santos; Almeida de Sá, Renata; Cabello, Pedro Hernan; Bailly, Sabine; Araujo-Jorge, Tania Cremonini; Saraiva, Roberto Magalhães

2018-01-01

Transforming growth factor β1 (TGF-β1) is an important mediator in Chagas disease. Furthermore, patients with higher TGF-β1 serum levels show a worse clinical outcome. Gene polymorphism may account for differences in cytokine production during infectious diseases. We tested whether TGFB1 polymorphisms could be associated with Chagas disease susceptibility and severity in a Brazilian population. We investigated five single-nucleotide polymorphisms (−800 G>A, −509 C>T, +10 T>C, +25 G>C, and +263 C>T). 152 patients with Chagas disease (53 with the indeterminate form and 99 with the cardiac form) and 48 noninfected subjects were included. Genotypes CT and TT at position −509 of the TGFB1 gene were more frequent in Chagas disease patients than in noninfected subjects. Genotypes TC and CC at codon +10 of the TGFB1 gene were also more frequent in Chagas disease patients than in noninfected subjects. We found no significant differences in the distribution of the studied TGFB1 polymorphisms between patients with the indeterminate or cardiac form of Chagas disease. Therefore, −509 C>T and +10 T>C TGFB1 polymorphisms are associated with Chagas disease susceptibility in a Brazilian population. PMID:29670670

TGF-β Polymorphisms Are a Risk Factor for Chagas Disease.

PubMed

Ferreira, Roberto Rodrigues; Madeira, Fabiana da Silva; Alves, Gabriel Farias; Chambela, Mayara da Costa; Curvo, Eduardo de Oliveira Vaz; Moreira, Aline Dos Santos; Almeida de Sá, Renata; Mendonça-Lima, Leila; Cabello, Pedro Hernan; Bailly, Sabine; Feige, Jean-Jacques; Araujo-Jorge, Tania Cremonini; Saraiva, Roberto Magalhães; Waghabi, Mariana Caldas

2018-01-01

Transforming growth factor β 1 (TGF- β 1) is an important mediator in Chagas disease. Furthermore, patients with higher TGF- β 1 serum levels show a worse clinical outcome. Gene polymorphism may account for differences in cytokine production during infectious diseases. We tested whether TGFB1 polymorphisms could be associated with Chagas disease susceptibility and severity in a Brazilian population. We investigated five single-nucleotide polymorphisms (-800 G>A, -509 C>T, +10 T>C, +25 G>C, and +263 C>T). 152 patients with Chagas disease (53 with the indeterminate form and 99 with the cardiac form) and 48 noninfected subjects were included. Genotypes CT and TT at position -509 of the TGFB1 gene were more frequent in Chagas disease patients than in noninfected subjects. Genotypes TC and CC at codon +10 of the TGFB1 gene were also more frequent in Chagas disease patients than in noninfected subjects. We found no significant differences in the distribution of the studied TGFB1 polymorphisms between patients with the indeterminate or cardiac form of Chagas disease. Therefore, -509 C>T and +10 T>C TGFB1 polymorphisms are associated with Chagas disease susceptibility in a Brazilian population.

Comparing photoelectrochemical water oxidation, recombination kinetics and charge trapping in the three polymorphs of TiO2.

PubMed

Moss, Benjamin; Lim, Kee Kean; Beltram, Alessandro; Moniz, Savio; Tang, Junwang; Fornasiero, Paolo; Barnes, Piers; Durrant, James; Kafizas, Andreas

2017-06-07

In this article we present the first comparative study of the transient decay dynamics of photo-generated charges for the three polymorphs of TiO 2 . To our knowledge, this is the first such study of the brookite phase of TiO 2 over timescales relevant to the kinetics of water splitting. We find that the behavior of brookite, both in the dynamics of relaxation of photo-generated charges and in energetic distribution, is similar to the anatase phase of TiO 2 . Moreover, links between the rate of recombination of charge carriers, their energetic distribution and the mode of transport are made in light of our findings and used to account for the differences in water splitting efficiency observed across the three polymorphs.

Microscopic origin of entropy-driven polymorphism in hybrid organic-inorganic perovskite materials

NASA Astrophysics Data System (ADS)

Butler, Keith T.; Svane, Katrine; Kieslich, Gregor; Cheetham, Anthony K.; Walsh, Aron

2016-11-01

Entropy is a critical, but often overlooked, factor in determining the relative stabilities of crystal phases. The importance of entropy is most pronounced in softer materials, where small changes in free energy can drive phase transitions, which has recently been demonstrated in the case of organic-inorganic hybrid-formate perovskites. In this Rapid Communication we demonstrate the interplay between composition and crystal structure that is responsible for the particularly pronounced role of entropy in determining polymorphism in hybrid organic-inorganic materials. Using ab initio based lattice dynamics, we probe the origins and effects of vibrational entropy of four archetype perovskite (A B X3 ) structures. We consider an inorganic material (SrTiO3), an A -site hybrid-halide material (CH3NH3) PbI3 , a X -site hybrid material KSr (BH4)3 , and a mixed A - and X -site hybrid-formate material (N2H5) Zn (HCO2)3 , comparing the differences in entropy between two common polymorphs. The results demonstrate the importance of low-frequency intermolecular modes in determining the phase stability in these materials. The understanding gained allows us to propose a general principle for the relative stability of different polymorphs of hybrid materials as temperature is increased.

Three-dimensional imaging of dislocation dynamics during the hydriding phase transformation

NASA Astrophysics Data System (ADS)

Ulvestad, A.; Welland, M. J.; Cha, W.; Liu, Y.; Kim, J. W.; Harder, R.; Maxey, E.; Clark, J. N.; Highland, M. J.; You, H.; Zapol, P.; Hruszkewycz, S. O.; Stephenson, G. B.

2017-05-01

Crystallographic imperfections significantly alter material properties and their response to external stimuli, including solute-induced phase transformations. Despite recent progress in imaging defects using electron and X-ray techniques, in situ three-dimensional imaging of defect dynamics remains challenging. Here, we use Bragg coherent diffractive imaging to image defects during the hydriding phase transformation of palladium nanocrystals. During constant-pressure experiments we observe that the phase transformation begins after dislocation nucleation close to the phase boundary in particles larger than 300 nm. The three-dimensional phase morphology suggests that the hydrogen-rich phase is more similar to a spherical cap on the hydrogen-poor phase than to the core-shell model commonly assumed. We substantiate this using three-dimensional phase field modelling, demonstrating how phase morphology affects the critical size for dislocation nucleation. Our results reveal how particle size and phase morphology affects transformations in the PdH system.

Reduced sediment melting at 7.5-12 GPa: phase relations, geochemical signals and diamond nucleation

NASA Astrophysics Data System (ADS)

Brey, G. P.; Girnis, A. V.; Bulatov, V. K.; Höfer, H. E.; Gerdes, A.; Woodland, A. B.

2015-08-01

Melting of carbonated sediment in the presence of graphite or diamond was experimentally investigated at 7.5-12 GPa and 800-1600 °C in a multianvil apparatus. Two starting materials similar to GLOSS of Plank and Langmuir (Chem Geol 145:325-394, 1998) were prepared from oxides, carbonates, hydroxides and graphite. One mixture (Na-gloss) was identical in major element composition to GLOSS, and the other was poorer in Na and richer in K (K-gloss). Both starting mixtures contained ~6 wt% CO2 and 7 wt% H2O and were doped at a ~100 ppm level with a number of trace elements, including REE, LILE and HFSE. The near-solidus mineral assemblage contained a silica polymorph (coesite or stishovite), garnet, kyanite, clinopyroxene, carbonates (aragonite and magnesite-siderite solid solution), zircon, rutile, bearthite and hydrous phases (phengite and lawsonite at <9 GPa and the hydrous aluminosilicates topaz-OH and phase egg at >10 GPa). Hydrous phases disappear at ~900 °C, and carbonates persist up to 1000-1100 °C. At temperatures >1200 °C, the mineral assemblage consists of coesite or stishovite, kyanite and garnet. Clinopyroxene stability depends strongly on the Na content in the starting mixture; it remains in the Na-gloss composition up to 1600 °C at 12 GPa, but was not observed in K-gloss experiments above 1200 °C. The composition of melt or fluid changes gradually with increasing temperature from hydrous carbonate-rich (<10 wt% SiO2) at 800-1000 °C to volatile-rich silicate liquids (up to 40 wt% SiO2) at high temperatures. Trace elements were analyzed in melts and crystalline phases by LA ICP MS. The garnet-melt and clinopyroxene-melt partition coefficients are in general consistent with results from the literature for volatile-free systems and silicocarbonate melts derived by melting carbonated peridotites. Most trace elements are strongly incompatible in kyanite and silica polymorphs ( D < 0.01), except for V, Cr and Ni, which are slightly compatible in kyanite ( D > 1). Aragonite and Fe-Mg carbonate have very different REE partition coefficients ( D Mst-Sd/L ~ 0.01 and D Arg/L ~ 1). Nb, Ta, Zr and Hf are strongly incompatible in both carbonates. The bearthite/melt partition coefficients are very high for LREE (>10) and decrease to ~1 for HREE. All HFSE are strongly incompatible in bearthite. In contrast, Ta, Nb, Zr and Hf are moderately to strongly compatible in ZrSiO4 and TiO2 phases. Based on the obtained partition coefficients, the composition of a mobile phase derived by sediment melting in deep subduction zones was calculated. This phase is strongly enriched in incompatible elements and displays a pronounced negative Ta-Nb anomaly but no Zr-Hf anomaly. Although all experiments were conducted in the diamond stability field, only graphite was observed in low-temperature experiments. Spontaneous diamond nucleation and the complete transformation of graphite to diamond were observed at temperatures above 1200-1300 °C. We speculate that the observed character of graphite-diamond transformation is controlled by relationships between the kinetics of metastable graphite dissolution and diamond nucleation in a hydrous silicocarbonate melt that is oversaturated in C.

Solvent induced modifications to fiber nanostructure and morphology for 12HSA molecular gels

NASA Astrophysics Data System (ADS)

Gao, Jie

Molecular organogels are thermo reversible quasi-solid materials, which are formed by low molecular weight organogelators (LMOGs) undergoing supramolecular aggregation via non-covalent interactions, forming a three-dimensional fibrillar network. Numerous applications of molecular organogels are been investigated as edible oils, drug release matrices and personal care products. The chemistry of the organic phase (i.e., solvent) influences every level of structure in organogels. Different solvents induce LMOG to assemble into "crystal like" fibers, which have more than one crystal form, lamellar arrangement and domain size. Differences in these solid states are known to affect the macroscopic properties of the gel, including critical gelator concentration (CGC), melting point, melting enthalpy and opacity.12-hydroxystearic acid (12HSA) was examined in several classes of organic solvents with different function groups. These gels, sols or precipitates were analyzed using a series of techniques including: powder x-ray diffraction (XRD), differential scanning calorimetry (DSC), fourier-transform infrared spectroscopy (FT-IR), pulsed nuclear magnetic resonance spectroscopy (pNMR) and microscopy. Specifically, certain solvents caused 12HSA to self-assemble into a triclinic parallel polymorphic form with subcell spacing of ~4.6, 3.9, and 3.8 A and an interdigitated unit cell with a lamellar arrangement (38~44 A). This polymorphic form corresponded to a less effective sphereultic supramolecular crystalline network, which immobilizes solvents at CGC greater than 1.5 wt %. The other group of solvents induce a hexagonal subcell spacing (i.e., unit sub cell spacing ~4.1 A) and are arranged in a multi lamellar fashion with a unit cell greater than the bimolecular length of 12HSA (~54 A).This polymorphic form corresponds to fibrillar aggregates with a CGC less than 1 wt %.

A bacterial model for expression of mutations in the human ornithine transcarbamylase (OTC) gene

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

Tuchman, M.; McCann, M.T.; Qureshi, A.A.

1994-09-01

OTC is a mitochondrial enzyme catalyzing the formation of citrulline from carbamyl phosphate and ornithine. X-linked deficiency of OTC is the most prevalent genetic defect of ureagenesis. Mutations and polymorphisms in the OTC gene identified in deficient patients have indicated the occurrence of many family-specific, unique alleles. Due to the low frequency of recurrent mutations, distinguishing between deleterious mutations and polymorphisms is difficult. Using a human OTC gene containing plasmid driven by a tac promoter, we have devised a simple and efficient method for expressing mutations in the mature human OTC enzyme. To demonstrate this method, PCR engineered site-directed mutagenesismore » was employed to generated cDNA fragments which contained either the R151Q or R277W known mutations found in patients with neonatal and late-onset OTC deficiency, respectively. The normal allele for each mutation was also generated by an identical PCR procedure. Digestion with Bgl II- and Sty I-generated mutant and normal replacement cassettes containing the respective mutant and wild type sequences. Upon transformation of JM109 E.coli cells, OTC enzymatic activity was measured at log and stationary phases of growth using a radiochromatographic method. The R141Q mutation abolished enzymatic activity (<0.02% of normal), whereas the R277W mutation expressed partial activity (2.3% of normal). In addition, a PCR-generated mutation, A280V, resulted in 73% loss of catalytic activity. This OTC expression system is clinically applicable for distinguishing between mutations and polymorphisms, and it can be used to investigate the effects of mutations on various domains of the OTC gene.« less

Effect of silk sericin on morphology and structure of calcium carbonate crystal

NASA Astrophysics Data System (ADS)

Zhao, Rui-Bo; Han, Hua-Feng; Ding, Shao; Li, Ze-Hao; Kong, Xiang-Dong

2013-06-01

In this paper, silk sericin was employed to regulate the mineralization of calcium carbonate (CaCO3). CaCO3 composite particles were prepared by the precipitation reaction of sodium carbonate with calcium chloride solution in the presence of silk sericin. The as-prepared samples were collected at different reaction time to study the crystallization process of CaCO3 by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and X-ray diffraction (XRD). The results showed that silk sericin significantly affected the morphology and crystallographic polymorph of CaCO3. With increasing the reaction time, the crystal phase of CaCO3 transferred from calcite dominated to vaterite dominated mixtures, while the morphology of CaCO3 changed from disk-like calcite crystal to spherical vaterite crystal. These studies showed the potential of silk sericin used as a template molecule to control the growth of inorganic crystal.

Vibrational Spectroscopic Studies of Reduced-Sensitivity RDX under Static Compression

NASA Astrophysics Data System (ADS)

Wong, Chak P.; Gump, Jared C.

2006-07-01

Explosive formulations with reduced-sensitivity RDX showed reduced shock sensitivity using Naval Ordnance Laboratory (NOL) Large Scale Gap Test, compared with similar formulations using standard RDX. Molecular processes responsible for the reduction of sensitivity are unknown and are crucial for formulation development. Vibrational spectroscopy at static high pressure may shed light on the mechanisms responsible for the reduced shock sensitivity as shown by the NOL Large Scale Gap Test. I-RDX®, a form of reduced- sensitivity RDX was subjected to static compression at ambient temperature in a Merrill-Bassett sapphire cell from ambient to about 6 GPa. The spectroscopic techniques used were Raman and Fourier-Transform IR (FTIR). The pressure dependence of the Raman mode frequencies of I-RDX® was determined and compared with that of standard RDX. The behavior of I-RDX® near the pressure at which standard RDX, at ambient temperature, undergoes a phase transition from the α to the γ polymorph is presented.

Rapid hydrothermal synthesis of VO2 (B) and its conversion to thermochromic VO2 (M1).

PubMed

Popuri, Srinivasa Rao; Miclau, Marinela; Artemenko, Alla; Labrugere, Christine; Villesuzanne, Antoine; Pollet, Michaël

2013-05-06

The present study provides a rapid way to obtain VO2 (B) under economical and environmentally friendly conditions. VO2 (B) is one of the well-known polymorphs of vanadium dioxide and is a promising cathode material for aqueous lithium ion batteries. VO2 (B) was successfully synthesized by rapid single-step hydrothermal process using V2O5 and citric acid as precursors. The present study shows that phase-pure VO2 (B) polytype can be easily obtained at 180 °C for 2 h and 220 °C for 1 h, that is, the lowest combination of temperature and duration reported so far. The obtained VO2 (B) is characterized by X-ray powder diffraction, high-resolution scanning electron microscopy, and Fourier transform infrared spectroscopy. In addition, we present an indirect way to obtain VO2 (M1) by annealing VO2 (B) under vacuum for 1 h.

Microbial diversity of landslide soils assessed by RFLP and SSCP fingerprints.

PubMed

Guida, Marco; Cannavacciuolo, Paolo Losanno; Cesarano, Mara; Borra, Marco; Biffali, Elio; D'Alessandro, Raffaella; De Felice, Bruna

2014-08-01

Landslides are a significant component of natural disasters in most countries around the world. Understanding these destructive phenomena through the analysis of possible correlations between microbial communities and the alteration of the soil responsible for landslides is important in order to reduce their negative consequences. To address this issue, bacterial and fungal communities in soils triggering landslides in Termini-Nerano and Massa Lubrense-Nerano (Naples, Italy) were analysed by genetic profiling techniques. Fingerprints were generated by single-strand conformation polymorphisms (SSCP) and random amplified polymorphic DNA (RAPD). The microbial community in both soil types was enriched in species which could contribute to the degradation process occurring during landslides, forming biofilms and leading to the transformation or the formation of minerals. Indeed, some of the identified bacteria were found to favour the transformation of clay minerals. These findings suggest a possible relationship between bacterial and fungal community-colonising soils and the occurrence of landslides.

Phase I study of combined therapy with vorinostat and gefitinib to treat BIM deletion polymorphism-associated resistance in EGFR-mutant lung cancer (VICTROY-J): a study protocol.

PubMed

Takeuchi, Shinji; Yoshimura, Kenichi; Fujiwara, Tadami; Ando, Masahiko; Shimizu, Shinobu; Nagase, Katsuhiko; Hasegawa, Yoshinori; Takahashi, Toshiaki; Katakami, Nobuyuki; Inoue, Akira; Yano, Seiji

2017-01-01

The BIM deletion polymorphism is reported to be associated with poor outcomes of epidermal growth factor receptor (EGFR)-mutant non-small cell lung cancer (NSCLC) treated with EGFR-TKIs, including gefitinib. We have shown that a histone deacetylase inhibitor, vorinostat, can epigenetically restore BIM function and apoptosis sensitivity to EGFR-TKIs in EGFR-mutant NSCLC cells with BIM deletion polymorphisms. The purpose of this study is to determine the feasibility of combined treatment of vorinostat with gefitinib in BIM deletion polymorphism positive EGFR-mutant NSCLC patients. BIM deletion polymorphism positive EGFR-mutant NSCLC patients treated with at least one EGFR-TKI and one regimen of chemotherapy are being recruited to this study. Vorinostat (200-400 mg) will be administered orally once daily on days 1-7, and gefitinib 250 mg orally once daily on days 1-14. With a fixed dose of gefitinib, the dose of vorinostat will be escalated following a conventional 3+3 design. The primary endpoint is to define the maximum tolerated dose (MTD) of vorinostat combined with 250 mg of gefitinib. This is the first phase I study of combined therapy with vorinostat and gefitinib for NSCLC patients double selected for an EGFR mutation and BIM deletion polymorphism. J. Med. Invest. 64: 321-325, August, 2017.

Lubricating and waxy esters, I. Synthesis, crystallization, and melt behavior of linear monoesters.

PubMed

Bouzidi, Laziz; Li, Shaojun; Di Biase, Steve; Rizvi, Syed Q; Narine, Suresh S

2012-01-01

Four pure jojoba wax-like esters (JLEs), having carbon chain length of 36, 40 (two isomers) and 44, were prepared by Steglish esterification of fatty acids (or acid chlorides) with fatty alcohols at room temperature. Calorimetric and diffraction data was used to elucidate the phase behavior of the esters. The primary thermal parameters (crystallization and melting temperatures) obtained from the DSC of the symmetrical molecules correspond well with the carbon numbers of the JLEs. However, the data also suggests that carbon number is not the only factor since the symmetry of the molecule also plays a significant role in the phase behavior. Overall, the JLEs show very little polymorphic activity at the experimental conditions used, suggesting that they are likely to transform the same way during melting as well as crystallization, a characteristic which may be useful in designing new waxes and lubricants. The XRD data clearly show that the solid phase in all samples consists of a mixture of a β-phase and a β'-phase; fully distinguishable by their characteristic diffraction peaks. Subtle differences between the subcell patterns and phase development of the samples were observed. Different layering of the samples was also observed, understandably because of the chain length differences between the compounds. The long spacings were perfectly linearly proportional to the number of carbon atoms. The length of the ester layers with n carbon atoms can be calculated by a formula similar to that used for the layers in linear alkane molecules. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

[Study on once sampling quantitation based on information entropy of ISSR amplified bands of Houttuynia cordata].

PubMed

Wang, Haiqin; Liu, Wenlong; He, Fuyuan; Chen, Zuohong; Zhang, Xili; Xie, Xianggui; Zeng, Jiaoli; Duan, Xiaopeng

2012-02-01

To explore the once sampling quantitation of Houttuynia cordata through its DNA polymorphic bands that carried information entropy, from other form that the expression of traditional Chinese medicine polymorphism, genetic polymorphism, of traditional Chinese medicine. The technique of inter simple sequence repeat (ISSR) was applied to analyze genetic polymorphism of H. cordata samples from the same GAP producing area, the DNA genetic bands were transformed its into the information entropy, and the minimum once sampling quantitation with the mathematical mode was measured. One hundred and thirty-four DNA bands were obtained by using 9 screened ISSR primers to amplify from 46 strains DNA samples of H. cordata from the same GAP, the information entropy was H=0.365 6-0.978 6, and RSD was 14.75%. The once sampling quantitation was W=11.22 kg (863 strains). The "once minimum sampling quantitation" were calculated from the angle of the genetic polymorphism of H. cordata, and a great differences between this volume and the amount from the angle of fingerprint were found.

High pressure polymorphs and amorphization of upconversion host material NaY(WO{sub 4}){sub 2}

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

Hong, Fang; Yue, Binbin, E-mail: yuebb@hpstar.ac.cn, E-mail: chenbin@hpstar.ac.cn; The Advanced Light Source, Lawrence Berkeley National Laboratory, 1 Cyclotron Rd, Berkeley, California 94720

2016-07-25

The pressure effect on the structural change of upconversion host material NaY(WO{sub 4}){sub 2} was studied by using in-situ synchrotron X-ray diffraction. A transition from the initial scheelite phase to the M-fergusonite phase occurs near 10 GPa, and another phase transition is found near 27.5 GPa, which could be an isostructural transition without symmetry change. The sample becomes amorphous when the pressure is fully released from high pressure. This work demonstrates the possibility of synthesizing various polymorph structures for non-linear optical applications with a high pressure, chemical doping, or strained thin-film nanostructure process.

Navigating at Will on the Water Phase Diagram

NASA Astrophysics Data System (ADS)

Pipolo, S.; Salanne, M.; Ferlat, G.; Klotz, S.; Saitta, A. M.; Pietrucci, F.

2017-12-01

Despite the simplicity of its molecular unit, water is a challenging system because of its uniquely rich polymorphism and predicted but yet unconfirmed features. Introducing a novel space of generalized coordinates that capture changes in the topology of the interatomic network, we are able to systematically track transitions among liquid, amorphous, and crystalline forms throughout the whole phase diagram of water, including the nucleation of crystals above and below the melting point. Our approach, based on molecular dynamics and enhanced sampling or free energy calculation techniques, is not specific to water and could be applied to very different structural phase transitions, paving the way towards the prediction of kinetic routes connecting polymorphic structures in a range of materials.

Pressure, temperature, and electric field dependence of phase transformations in niobium modified 95/5 lead zirconate titanate

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

Dong, Wen D.; Carlos Valadez, J.; Gallagher, John A.

2015-06-28

Ceramic niobium modified 95/5 lead zirconate-lead titanate (PZT) undergoes a pressure induced ferroelectric to antiferroelectric phase transformation accompanied by an elimination of polarization and a volume reduction. Electric field and temperature drive the reverse transformation from the antiferroelectric to ferroelectric phase. The phase transformation was monitored under pressure, temperature, and electric field loading. Pressures and temperatures were varied in discrete steps from 0 MPa to 500 MPa and 25 °C to 125 °C, respectively. Cyclic bipolar electric fields were applied with peak amplitudes of up to 6 MV m{sup −1} at each pressure and temperature combination. The resulting electric displacement–electric field hysteresis loops weremore » open “D” shaped at low pressure, characteristic of soft ferroelectric PZT. Just below the phase transformation pressure, the hysteresis loops took on an “S” shape, which split into a double hysteresis loop just above the phase transformation pressure. Far above the phase transformation pressure, when the applied electric field is insufficient to drive an antiferroelectric to ferroelectric phase transformation, the hysteresis loops collapse to linear dielectric behavior. Phase stability maps were generated from the experimental data at each of the temperature steps and used to form a three dimensional pressure–temperature–electric field phase diagram.« less

Comparison of the quench and fault current limiting characteristics of the flux-coupling type SFCL with single and three-phase transformer

NASA Astrophysics Data System (ADS)

Jung, Byung Ik; Cho, Yong Sun; Park, Hyoung Min; Chung, Dong Chul; Choi, Hyo Sang

2013-01-01

The South Korean power grid has a network structure for the flexible operation of the system. The continuously increasing power demand necessitated the increase of power facilities, which decreased the impedance in the power system. As a result, the size of the fault current in the event of a system fault increased. As this increased fault current size is threatening the breaking capacity of the circuit breaker, the main protective device, a solution to this problem is needed. The superconducting fault current limiter (SFCL) has been designed to address this problem. SFCL supports the stable operation of the circuit breaker through its excellent fault-current-limiting operation [1-5]. In this paper, the quench and fault current limiting characteristics of the flux-coupling-type SFCL with one three-phase transformer were compared with those of the same SFCL type but with three single-phase transformers. In the case of the three-phase transformers, both the superconducting elements of the fault and sound phases were quenched, whereas in the case of the single-phase transformer, only that of the fault phase was quenched. For the fault current limiting rate, both cases showed similar rates for the single line-to-ground fault, but for the three-wire earth fault, the fault current limiting rate of the single-phase transformer was over 90% whereas that of the three-phase transformer was about 60%. It appears that when the three-phase transformer was used, the limiting rate decreased because the fluxes by the fault current of each phase were linked in one core. When the power loads of the superconducting elements were compared by fault type, the initial (half-cycle) load was great when the single-phase transformer was applied, whereas for the three-phase transformer, its power load was slightly lower at the initial stage but became greater after the half fault cycle.

Reverse Shape Memory Effect Related to α → γ Transformation in a Fe-Mn-Al-Ni Shape Memory Alloy

NASA Astrophysics Data System (ADS)

Peng, Huabei; Huang, Pan; Zhou, Tiannan; Wang, Shanling; Wen, Yuhua

2017-05-01

In this study, we investigated the shape memory behavior and phase transformations of solution-treated Fe43.61Mn34.74Al13.38Ni8.27 alloy between room temperature and 1173 K (900 °C). This alloy exhibits the reverse shape memory effect resulting from the phase transformation of α (bcc) → γ (fcc) between 673 K and 1073 K (400 °C and 800 °C) in addition to the shape memory effect resulting from the martensitic reverse transformation of γ' (fcc) → α (bcc) below 673 K (400 °C). There is a high density of hairpin-shaped dislocations in the α phase undergoing the martensitic reverse transformation of γ' → α. The lath γ phase, which preferentially nucleates and grows in the reversed α phase, has the same crystal orientation with the reverse-transformed γ' martensite. However, the vermiculate γ phase, which is precipitated in the α phase between lath γ phase, has different crystal orientations. The lath γ phase is beneficial to attaining better reverse shape memory effect than the vermiculate γ phase.

Transformation of the θ-phase in Mg-Li-Al alloys: a density functional theory study.

PubMed

Zhang, Caili; Han, Peide; Zhang, Zhuxia; Dong, Minghui; Zhang, Lili; Gu, Xiangyang; Yang, Yanqing; Xu, Bingshe

2012-03-01

In Mg-Li-Al alloys, θ-phase MgAlLi(2) is a strengthening and metastable phase which is liable to be transformed to the equilibrium phase AlLi on overaging. While the structural details of the θ-phase MgAlLi(2) and the microscopic transformation are still unknown. In this paper, the structure of MgAlLi(2) unit cell was determined through X-ray powder diffraction simulation. Microscopic transformation process of θ-phase MgAlLi(2) was discussed in detail using first principles method.

Analysis of Transformation Plasticity in Steel Using a Finite Element Method Coupled with a Phase Field Model

PubMed Central

Cho, Yi-Gil; Kim, Jin-You; Cho, Hoon-Hwe; Cha, Pil-Ryung; Suh, Dong-Woo; Lee, Jae Kon; Han, Heung Nam

2012-01-01

An implicit finite element model was developed to analyze the deformation behavior of low carbon steel during phase transformation. The finite element model was coupled hierarchically with a phase field model that could simulate the kinetics and micro-structural evolution during the austenite-to-ferrite transformation of low carbon steel. Thermo-elastic-plastic constitutive equations for each phase were adopted to confirm the transformation plasticity due to the weaker phase yielding that was proposed by Greenwood and Johnson. From the simulations under various possible plastic properties of each phase, a more quantitative understanding of the origin of transformation plasticity was attempted by a comparison with the experimental observation. PMID:22558295

Three-dimensional imaging of dislocation dynamics during the hydriding phase transformation

DOE PAGES

Ulvestad, A.; Welland, M. J.; Cha, W.; ...

2017-01-16

Crystallographic imperfections can significantly alter material properties and responses to external stimuli, including solute induced phase transformations and crystal growth and dissolution . Despite recent progress in imaging defects using both electron and x-ray techniques, in situ three-dimensional imaging studies of defect dynamics, necessary to understand and engineer nanoscale processes, remains challenging. Here, we report in situ three-dimensional imaging of defect dynamics during the hydriding phase transformation of individual palladium nanocrystals by Bragg Coherent Diffractive Imaging (BCDI) . During constant pressure experiments, we observed that the phase transformation begins after the nucleation of dislocations in large (300 nm) particles. Themore » 3D dislocation network shows that dislocations are close to the phase boundary. The 3D phase morphology resolved by BCDI suggests that the hydrogen-rich phase is more similar to a spherical cap on the hydrogen-poor phase than the core-shell model commonly assumed. We substantiate this conclusion using 3D phase field modeling and demonstrate how phase morphology affects the critical size for dislocation nucleation. We determine the size dependence of the transformation pressure for large (150-300 nm) palladium nanocrystals using variable pressure experiments. Our results reveal a pathway for solute induced structural phase transformations in nanocrystals and demonstrate BCDI as a novel method for understanding dislocation dynamics in phase transforming systems at the nanoscale.« less

Single crystal growth in spin-coated films of polymorphic phthalocyanine derivative under solvent vapor

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

Higashi, T.; Ohmori, M.; Ramananarivo, M. F.

2015-12-01

The effects of solvent vapor on spin-coated films of a polymorphic phthalocyanine derivative were investigated. Growth of single crystal films via redissolving organic films under solvent vapor was revealed by in situ microscopic observations of the films. X-ray diffraction measurement of the films after exposing to solvent vapor revealed the phase transition of polymorphs under solvent vapor. The direction of crystal growth was clarified by measuring the crystal orientation in a grown monodomain film. The mechanism of crystal growth based on redissolving organic films under solvent vapor was discussed in terms of the different solubilities of the polymorphs.

Phase transformation in the alumina-titania system during flash sintering experiments

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

Jha, S. K.; Lebrun, J. M.; Raj, R.

2016-02-01

We show that phase transformation in the alumina–titania system, which produces aluminum-titanate, follows an unusual trajectory during flash sintering. The experiments begin with mixed powders of alumina–titania and end in dense microstructures that are transformed into aluminum-titanate. The sintering and the phase transformation are separated in time, with the sintering occurs during Stage II, and phase transformation during Stage III of the flash sintering experiment. Stage III is the steady-state condition of flash activated state that is established under current control, while Stage II is the period of transition from voltage to current control. The extent of phase transformation increasesmore » with the current density and the hold time in Stage III.« less

Color image encryption based on gyrator transform and Arnold transform

NASA Astrophysics Data System (ADS)

Sui, Liansheng; Gao, Bo

2013-06-01

A color image encryption scheme using gyrator transform and Arnold transform is proposed, which has two security levels. In the first level, the color image is separated into three components: red, green and blue, which are normalized and scrambled using the Arnold transform. The green component is combined with the first random phase mask and transformed to an interim using the gyrator transform. The first random phase mask is generated with the sum of the blue component and a logistic map. Similarly, the red component is combined with the second random phase mask and transformed to three-channel-related data. The second random phase mask is generated with the sum of the phase of the interim and an asymmetrical tent map. In the second level, the three-channel-related data are scrambled again and combined with the third random phase mask generated with the sum of the previous chaotic maps, and then encrypted into a gray scale ciphertext. The encryption result has stationary white noise distribution and camouflage property to some extent. In the process of encryption and decryption, the rotation angle of gyrator transform, the iterative numbers of Arnold transform, the parameters of the chaotic map and generated accompanied phase function serve as encryption keys, and hence enhance the security of the system. Simulation results and security analysis are presented to confirm the security, validity and feasibility of the proposed scheme.

Martensitic transformation and phase diagram in ternary Co-V-Ga Heusler alloys

NASA Astrophysics Data System (ADS)

Xu, Xiao; Nagashima, Akihide; Nagasako, Makoto; Omori, Toshihiro; Kanomata, Takeshi; Kainuma, Ryosuke

2017-03-01

We report the martensitic transformation behavior in Co-V-Ga Heusler alloys. Thermoanalysis and thermomagnetization measurements were conducted to observe the martensitic transformation. By using a transmission electron microscope and an in situ X-ray diffractometer, martensitic transformation was found to occur from the L21 Heusler parent phase to the D022 martensite phase. Phase diagrams were determined for two pseudo-binary sections where martensitic transformation was detected. Magnetic properties, including the Curie temperatures and spontaneous magnetization of the parent phase, were also investigated. The magnetic properties showing behaviors different from those of NiMn-based alloys were found.

Use of glancing angle X-ray powder diffractometry to depth-profile phase transformations during dissolution of indomethacin and theophylline tablets.

PubMed

Debnath, Smita; Predecki, Paul; Suryanarayanan, Raj

2004-01-01

The purpose of this study was (i) to develop glancing angle x-ray powder diffractometry (XRD) as a method for profiling phase transformations as a function of tablet depth; and (ii) to apply this technique to (a) study indomethacin crystallization during dissolution of partially amorphous indomethacin tablets and to (b) profile anhydrate --> hydrate transformations during dissolution of theophylline tablets. The intrinsic dissolution rates of indomethacin and theophylline were determined after different pharmaceutical processing steps. Phase transformations during dissolution were evaluated by various techniques. Transformation in the bulk and on the tablet surface was characterized by conventional XRD and scanning electron microscopy, respectively. Glancing angle XRD enabled us to profile these transformations as a function of depth from the tablet surface. Pharmaceutical processing resulted in a decrease in crystallinity of both indomethacin and theophylline. When placed in contact with the dissolution medium, while indomethacin recrystallized, theophylline anhydrate rapidly converted to theophylline monohydrate. Due to intimate contact with the dissolution medium, drug transformation occurred to a greater extent at or near the tablet surface. Glancing angle XRD enabled us to depth profile the extent of phase transformations as a function of the distance from the tablet surface. The processed sample (both indomethacin and theophylline) transformed more rapidly than did the corresponding unprocessed drug. Several challenges associated with the glancing angle technique, that is, the effects of sorbed water, phase transformations during the experimental timescale, and the influence of phase transformation on penetration depth, were addressed. Increased solubility, and consequently dissolution rate, is one of the potential advantages of metastable phases. This advantage is negated if, during dissolution, the metastable to stable transformation rate > dissolution rate. Glancing angle XRD enabled us to quantify and thereby profile phase transformations as a function of compact depth. The technique has potential utility in monitoring surface reactions, both chemical decomposition and physical transformations, in pharmaceutical systems.

Mercury sulphide dimorphism in glasses

DOE PAGES

Kassem, Mohammad; Sokolov, Anton; Cuisset, Arnault; ...

2016-05-23

Crystals usually exist in several polymorphic forms in different domains of the P,T-diagram. Glasses and liquids also reveal density- or entropy-driven polyamorphism when e.g. an amorphous molecular solid or liquid transforms into a network polymorph. Using pulsed neutron and high-energy X-ray diffraction, we show that mercury sulphide exists simultaneously in two polymorphic modifications in a glass network forming chain-like and tetrahedral motifs. DFT simulations of 4-fold coordinated mercury species and RMC modelling of high-resolution diffraction data provide additional details on local Hg environment and connectivity implying the (HgS2/2)m oligomeric chains (1 m 6) are acting as a network former whilemore » the HgS4/4-related mixed agglomerated units behave as a modifier« less

Cytokine gene polymorphisms in Italian preterm infants: association between interleukin-10 -1082 G/A polymorphism and respiratory distress syndrome.

PubMed

Capasso, Mario; Avvisati, Rosa Anna; Piscopo, Carmelo; Laforgia, Nicola; Raimondi, Francesco; de Angelis, Filomena; Iolascon, Achille

2007-03-01

In this study, we determined the genotype frequencies of polymorphisms of cytokine genes and investigated their association with the risk of respiratory distress syndrome (RDS) in preterm infants. Genetic polymorphisms in the cytokines interleukin (IL)-10, IL-8, and tumor necrosis factor (TNF) alpha, were studied in 342 white Italian newborns (112 without RDS, 66 prematurely born with RDS, and 164 infants born at term who were included as healthy controls). The polymorphisms were analyzed by polymerase chain reaction (PCR) restriction fragment length polymorphism (RFLP). The IL-10 mRNA levels were analyzed according to genotype by quantitative real-time PCR (QRT-PCR) in Epstein-Barr virus-transformed lymphoblastoid cell lines (EBV-LCLs) of 42 full-term healthy infants. Logistic regression analysis demonstrated the risk of RDS to be significantly lower in preterm infants with an IL-10 -1082 GG/GA genotype than in those with an AA genotype [odds ratio (OR) = 0.48, 95% confidence interval (CI): 0.24-0.95, p = 0.03]. QRT-PCR analyses showed that the IL-10 mRNA levels were significantly higher in 27 IL-10 -1082 GG/GA carriers compared with 15 IL-10 -1082 AA carriers (p = 0.03). We conclude that the IL-10 -1082 GG/GA polymorphism may have a role in RDS development in premature infants.

Application of a novel combination of near-infrared spectroscopy and a humidity-controlled 96-well plate to the characterization of the polymorphism of imidafenacin.

PubMed

Uchida, Hiroshi; Yoshinaga, Tokuji; Mori, Hirotoshi; Otsuka, Makoto

2010-11-01

This study aimed to apply a currently available chemometric near-infrared spectroscopy technique to the characterization of the polymorphic properties of drug candidates. The technique requires only small quantities of samples and is therefore applicable to drugs in the early stages of development. The combination of near-infrared spectroscopy and a patented 96-well plate divided into 32 individual, humidity-controlled, three-well compartments was used in the characterization of a hygroscopic drug, imidafenacin, which has two polymorphs and one pseudo-polymorph. Characterization was also conducted with powder X-ray diffraction and thermal analysis. The results were compared with those from routinely used conventional analyses. Both the microanalysis and conventional analysis successfully characterised the substance (transformation and relative stability among the two polymorphs and a pseudo-polymorph) depending on the storage conditions. Near-infrared spectroscopic analyses utilizing a humidity-controlled 96-well plate required only small amounts of the sample for characterization under the various conditions of relative humidity. Near-infrared microanalysis can be applied to polymorphic studies of small quantities of a drug candidate. The results also suggest that the method will predict the behaviors of a hygroscopic candidate in solid pharmaceutical preparations at the early stages of drug development. © 2010 The Authors. JPP © 2010 Royal Pharmaceutical Society of Great Britain.

Length-Scale-Dependent Phase Transformation of LiFePO4 : An In situ and Operando Study Using Micro-Raman Spectroscopy and XRD.

PubMed

Siddique, N A; Salehi, Amir; Wei, Zi; Liu, Dong; Sajjad, Syed D; Liu, Fuqiang

2015-08-03

The charge and discharge of lithium ion batteries are often accompanied by electrochemically driven phase-transformation processes. In this work, two in situ and operando methods, that is, micro-Raman spectroscopy and X-ray diffraction (XRD), have been combined to study the phase-transformation process in LiFePO4 at two distinct length scales, namely, particle-level scale (∼1 μm) and macroscopic scale (∼several cm). In situ Raman studies revealed a discrete mode of phase transformation at the particle level. Besides, the preferred electrochemical transport network, particularly the carbon content, was found to govern the sequence of phase transformation among particles. In contrast, at the macroscopic level, studies conducted at four different discharge rates showed a continuous but delayed phase transformation. These findings uncovered the intricate phase transformation in LiFePO4 and potentially offer valuable insights into optimizing the length-scale-dependent properties of battery materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Acquisition of plumage polymorphism in white-throated sparrows

Treesearch

Carter T. Atkinson; C. John Ralph

1980-01-01

The White-throated Sparrow (Zonotrichia albicollis) was thought to be polymorphic in breeding plumage, having distinct white and tan phases that are bimodal in distribution and independent of sex. Vardy (1971), however, submitted evidence that plumage type is determined primarily by age, sex, and molt cycle. We reexamined this question by measuring plumage...

Phase transformations involving the [alpha][sub 2] and O phases in Ti-Al-Nb alloys. [Ti-28. 5Al-13Nb

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

Muraleedharan, K.; Banerjee, D.

1993-08-15

An orthorhombic (O) phase with Cmcm space group and Ti[sub 2]AlNb composition has ben established in the Ti-Al-Nb system. Efforts to develop alloys with this orthorhombic phase as a major phase, in place of the [alpha][sub 2] (Ti[sub 3]Al) phase, resulted in compositions with superior combinations of strength and toughness. The determination of phase diagrams for the Ti-Al-Nb system is a continuing effort. Bendersky et al. considered possible transformation paths and the hierarchy of structures in going from the [beta] phase to [alpha][sub 2] or O phases through displacive or replacive reactions. Microstructures predicted by these considerations have been documentedmore » in the particularly well investigated [beta]-->O transformation. Very little work has however been carried out on the [alpha][sub 2]-->O phase transformation. In this paper, the authors report preliminary results of isothermal aging study of this transformation.« less

Anagostic interactions in chiral separation. Polymorphism in a [Co(II)(L)] complex: Crystallographic and theoretical studies

NASA Astrophysics Data System (ADS)

Awwadi, Firas F.; Hodali, Hamdallah A.

2018-02-01

Syntheses and crystal structures of two polymorphs of the complex [Co(II)(L)], where H2L = 2,2'-[cis-1,2-diaminocyclohexanediylbis (nitrilo-methylidyne)]bis (5-dimethyl-amino]phenol, have been studied. The two polymorphs concomitantly crystallized by vapour diffusion of solvent. The first polymorph (I) crystallized as a racemate in the centrosymmetric tetragonal I41/a space group. The second polymorph (II) crystallized in the chiral orthorhombic space group P212121. The chiral conformers of symmetrical cis-1,2-disubstituted cyclohexane molecules cannot be resolved in the liquid or gas phases, due to the rapid ring inversion. In the present study, the two chiral conformers are present in crystals of polymorph I, whereas, only one chiral conformer is present in crystals of polymorph II. Crystal structure analysis indicated that the formation of two different polymorphs of [Co(II)(L)] complex can be rationalized based on Csbnd H⋯Co anagostic interactions. Density Functional Theory (DFT) calculations indicated that Csbnd H⋯Co interactions are due to HOMO-LUMO interactions.

Stress-Induced Cubic-to-Hexagonal Phase Transformation in Perovskite Nanothin Films.

PubMed

Cao, Shi-Gu; Li, Yunsong; Wu, Hong-Hui; Wang, Jie; Huang, Baoling; Zhang, Tong-Yi

2017-08-09

The strong coupling between crystal structure and mechanical deformation can stabilize low-symmetry phases from high-symmetry phases or induce novel phase transformation in oxide thin films. Stress-induced structural phase transformation in oxide thin films has drawn more and more attention due to its significant influence on the functionalities of the materials. Here, we discovered experimentally a novel stress-induced cubic-to-hexagonal phase transformation in the perovskite nanothin films of barium titanate (BaTiO 3 ) with a special thermomechanical treatment (TMT), where BaTiO 3 nanothin films under various stresses are annealed at temperature of 575 °C. Both high-resolution transmission electron microscopy and Raman spectroscopy show a higher density of hexagonal phase in the perovskite thin film under higher tensile stress. Both X-ray photoelectron spectroscopy and electron energy loss spectroscopy does not detect any change in the valence state of Ti atoms, thereby excluding the mechanism of oxygen vacancy induced cubic-to-hexagonal (c-to-h) phase transformation. First-principles calculations show that the c-to-h phase transformation can be completed by lattice shear at elevated temperature, which is consistent with the experimental observation. The applied bending plus the residual tensile stress produces shear stress in the nanothin film. The thermal energy at the elevated temperature assists the shear stress to overcome the energy barriers during the c-to-h phase transformation. The stress-induced phase transformation in perovskite nanothin films with TMT provides materials scientists and engineers a novel approach to tailor nano/microstructures and properties of ferroelectric materials.

Fundamental Studies on Phase Transformations and Mechanical Properties of Fusion Welds in Advanced Naval Steels

DTIC Science & Technology

2017-07-31

Studies on Phase Transformations and Mechanical Properties of Fusion Welds in Advanced Naval Steels Sb. GRANT NUMBER N00014-12-1-0475 Sc. PROGRAM...naval and structural applications. However, prior to this research project, a fundamental understanding of the phase transformation behavior under the...Steel, Phase Transformations 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF 18. NUMBER a. REPORT b.ABSTRACT c. THIS PAGE ABSTRACT OF PAGES u u

Phase Stability and Stress-Induced Transformations in Beta Titanium Alloys

NASA Astrophysics Data System (ADS)

Kolli, R. Prakash; Joost, William J.; Ankem, Sreeramamurthy

2015-06-01

In this article, we provide a brief review of the recent developments related to the relationship between phase stability and stress-induced transformations in metastable body-centered-cubic β-phase titanium alloys. Stress-induced transformations occur during tensile, compressive, and creep loading and influence the mechanical response. These transformations are not fully understood and increased understanding of these mechanisms will permit future development of improved alloys for aerospace, biomedical, and energy applications. In the first part of this article, we review phase stability and discuss a few recent developments. In the second section, we discuss the current status of understanding stress-induced transformations and several areas that require further study. We also provide our perspective on the direction of future research efforts. Additionally, we address the occurrence of the hcp ω-phase and the orthorhombic α″-martensite phase stress-induced transformations.

Molecular and immunological characterisation of Theileria parva stocks which are components of the 'Muguga cocktail' used for vaccination against East Coast fever in cattle.

PubMed

Bishop, R; Geysen, D; Spooner, P; Skilton, R; Nene, V; Dolan, T; Morzaria, S

2001-01-20

The 'Muguga cocktail' which is composed of three Theileria parva stocks Muguga, Kiambu 5 and Serengeti-transformed has been used extensively for live vaccination against East Coast fever in cattle in eastern, central and southern Africa. Herein we describe the molecular characterisation of the T. parva vaccine stocks using three techniques, an indirect fluorescent antibody test with a panel of anti-schizont monoclonal antibodies (MAb), Southern blotting with four T. parva repetitive DNA probes and polymerase chain reaction (PCR)-based assays detecting polymorphism within four single copy loci encoding antigen genes. The Muguga and Serengeti-transformed stocks exhibited no obvious differences in their reactivity with the panel of MAbs, whereas Kiambu 5 differed with several MAbs. Kiambu 5 DNA was very distinct from the Muguga and Serengeti-transformed isolates in the hybridisation pattern with all four nucleic acid probes, whereas Muguga and Serengeti-transformed isolates exhibited minor differences and could not be discriminated with one of the probes. PCR amplification in combination with restriction fragment length polymorphism analysis indicated that Kiambu 5 was also markedly divergent from the Muguga and Serengeti-transformed stocks within two of the four antigen coding genes. The T. parva Serengeti-transformed stock did not contain a 130 base pair insert within the p67 sporozoite antigen gene, which has been observed previously in most T. parva parasites isolated from buffalo, and could not be discriminated from T. parva Muguga at any of the four single copy loci. Collectively the data indicate that two of the cocktail components T. parva Serengeti-transformed and Muguga are genetically closely related, while the third component Kiambu 5 is quite distinct. Based on the findings, there may be a need to include only one of the T. parva Muguga and Serengeti-transformed components in the immunising cocktail. The study demonstrates the value of molecular characterisation data for monitoring of live vaccines.

Studies of phase transitions in the aripiprazole solid dosage form.

PubMed

Łaszcz, Marta; Witkowska, Anna

2016-01-05

Studies of the phase transitions in an active substance contained in a solid dosage form are very complicated but essential, especially if an active substance is classified as a BCS Class IV drug. The purpose of this work was the development of sensitive methods for the detection of the phase transitions in the aripiprazole tablets containing initially its form III. Aripiprazole exhibits polymorphism and pseudopolymorphism. Powder diffraction, Raman spectroscopy and differential scanning calorimetry methods were developed for the detection of the polymorphic transition between forms III and I as well as the phase transition of form III into aripiprazole monohydrate in tablets. The study involved the initial 10 mg and 30 mg tablets, as well as those stored in Al/Al blisters, a triplex blister pack and HDPE bottles (with and without desiccant) under accelerated and long term conditions. The polymorphic transition was not observed in the initial and stored tablets but it was visible on the DSC curve of the Abilify(®) 10 mg reference tablets. The formation of the monohydrate was observed in the diffractograms and Raman spectra in the tablets stored under accelerated conditions. The monohydrate phase was not detected in the tablets stored in the Al/Al blisters under long term conditions. The results showed that the Al/Al blisters can be recommended as the packaging of the aripiprazole tablets containing form III. Copyright © 2015 Elsevier B.V. All rights reserved.

Methylenetetrahydrofolate reductase C677T polymorphism: association with risk for childhood acute lymphoblastic leukemia and response during the initial phase of chemotherapy in greek patients.

PubMed

Chatzidakis, Konstantinos; Goulas, Antonis; Athanassiadou-Piperopoulou, Fani; Fidani, Liana; Koliouskas, Dimitrios; Mirtsou, Vassiliki

2006-08-01

As of late, a number of studies have focused on the association of the gene for methyletetrahydrofolate reductase (MTHFR) with risk for acute lymphoblastic leukemia (ALL) in children and in adults, as well as with response to chemotherapy. The degree of this association may vary according to the ethnic background and geographic localization of the population under study, or the phase of treatment when response to chemotherapy is concerned. We have analyzed the MTHFR C677T polymorphism in 52 patients and 88 control individuals, all ethnic Greek residents of northern Greece, and examined the association of this polymorphism with (a) susceptibility to childhood ALL and (b) the distribution of average plasma alanine aminotransferase (ALT) levels, white blood cell counts (WBC), and hemoglobin levels (Hb) during the induction and consolidation phases of treatment. We were able to detect a statistically significant protective effect, with respect to ALL, associated with carriage of the MTHFR 677T allele [OR = 0.387 (95% CI = 0.193-0.776)]. In addition, we observed a general tendency towards lower values in all three parameters studied, associated with the MTHFR 677CC genotype, which was more evident in the transition from the induction to the consolidation phase, indicating that MTHFR genotyping may be of prognostic value in the early phase of treatment for childhood ALL, in our population.

A first-principles study on new high-pressure metastable polymorphs of MoO{sub 2}

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

Becker, Nils; Dronskowski, Richard; Jülich-Aachen Research Alliance

The pressure-dependence of the stabilities of several MoO{sub 2} phases has been investigated by density-functional theory (GGA/PBE/PAW). Out of a set of 15 MX{sub 2} structures, the [SnO{sub 2}(II)], [α-PbO{sub 2}], and a modified rutile structure type were identified as possible metastable MoO{sub 2} polymorphs based on the analysis of thermodynamic properties and dynamic stability. High-pressure calculations suggest an orthorhombic TiO{sub 2} structure, dubbed [ortho-TiO{sub 2}], as a high-pressure polymorph at around 25 GPa. Furthermore, we find that the previously reported rutile-type MoO{sub 2} may be understood as a modified rutile type similar to the [VO{sub 2}] structure. - Graphicalmore » abstract: First-principles electronic structure and thermochemical calculations reveal four structure candidates as possible metastable polymorphs of MoO{sub 2}. Most promising is a distorted rutile-type similar to the known [VO{sub 2}] structure. An orthorhombic polymorph is proposed as a high-pressure polymorph. Display Omitted - Highlights: • Three possible metastable structure candidates for MoO{sub 2}. • Undistorted rutile type is improbable, a new distorted rutile-type MoO{sub 2} was suggested. • Orthorhombic phase of MoO{sub 2} (ortho-TiO{sub 2} type) should form at 25 GPa. • ab initio thermochemical data provided for MoO{sub 2}.« less

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.

Moisture induced polymorphic transition of mannitol and its morphological transformation.

PubMed

Yoshinari, Tomohiro; Forbes, Robert T; York, Peter; Kawashima, Yoshiaki

2002-10-24

The effects of moisture on the polymorphic transition of crystalline mannitol were investigated. Mannitol has three polymorphic forms, and was classified as alpha, beta, and delta form, respectively, by Walter-Lévy (C.R. Acad. Sc. Paris Ser. C (1968) 267, 1779). The water uptake of delta form crystalline was greater than that of the beta form when each crystalline form was stored at 97%RH (25 degrees C). The different powder X-ray diffraction patterns obtained before and after humidification confirmed that a moisture induced polymorphic transition from the delta to beta form had occurred. Morphological changes were also observed with an increase in the specific surface area of the delta sample from 0.4 to 2.3 m(2)/g being found on exposure to humidity. Thus it was suggested that the observed higher hygroscopicity of the newly formed beta form arose from the gradual increase in the surface area with the polymorphic transition from the delta to beta form. When considering the mechanism of this polymorphic transition, the results from molecular modelling, cross-polarisation/magic angle spinning (CP/MAS) solid-state NMR spectra and scanning electron-micrographs suggest that water molecules act as a molecular loosener to facilitate conversion from delta to the beta form as a result of multi-nucleation. Copyright 2002 Elsevier Science B.V.

Deformation mode and strain path dependence of martensite phase transformation in a medium manganese TRIP steel

DOE PAGES

Wu, Wei; Wang, Yu-wei; Makrygiannis, Panagiotis; ...

2017-11-06

The martensite phase transformation dependence upon deformation modes and strain paths in a medium manganese (10 wt%) TRIP steel stamped into a T-shape panel was quantified through combination of 3D digital image correlation and synchrotron X-ray diffraction. The T-shape emulates a portion of a common anti-intrusion component. The stamping speed was kept intentionally slow (1 mm/s) so as to avoid excessive heat generation. The steel, which belongs to the third generation advanced high strength steel (3GAHSS) family, was chosen for two reasons: (1) it is two-phase, i.e. austenite and ferrite, with martensite resulting from deformation-induced phase transformation; (2) the 66more » vol.% initial retained austenite volume fraction (RAVF) enabled a thorough examination of the martensite phase transformation at large deformation levels without exhaustion. Strain fields were coupled with measured RAVF values of small specimens extracted from specific locations on a formed T-shape panel. This enabled an exploration of the effects of linear, bilinear, and non-linear strain paths as well as deformation modes such as tension, plane strain, biaxial tension, and equibiaxial tension. Results suggest a significant martensite phase transformation dependence on deformation mode and strain path in the absence of fracture and when martensite phase transformation is unaffected by heat generated during forming. In general, the uniaxial and biaxial tension deformation modes facilitate the martensite phase transformation, while the smallest amount of martensite phase transformation occurs under plane strain. Some discussion as to further application of the experimental methods detailed in this study to other 3GAHSS and the effects of fracture on martensite phase transformation is provided.« less

Deformation mode and strain path dependence of martensite phase transformation in a medium manganese TRIP steel

DOE PAGES

Wu, Wei; Wang, Yu -Wei; Makrygiannis, Panagiotis; ...

2017-11-06

The martensite phase transformation dependence upon deformation modes and strain paths in a medium manganese (10 wt%) TRIP steel stamped into a T-shape panel was quantified through combination of 3D digital image correlation and synchrotron X-ray diffraction. The T-shape emulates a portion of a common anti-intrusion component. The stamping speed was kept intentionally slow (1 mm/s) so as to avoid excessive heat generation. The steel, which belongs to the third generation advanced high strength steel (3GAHSS) family, was chosen for two reasons: (1) it is two-phase, i.e. austenite and ferrite, with martensite resulting from deformation-induced phase transformation; (2) the 66more » vol.% initial retained austenite volume fraction (RAVF) enabled a thorough examination of the martensite phase transformation at large deformation levels without exhaustion. Strain fields were coupled with measured RAVF values of small specimens extracted from specific locations on a formed T-shape panel. This enabled an exploration of the effects of linear, bilinear, and non-linear strain paths as well as deformation modes such as tension, plane strain, biaxial tension, and equibiaxial tension. Results suggest a significant martensite phase transformation dependence on deformation mode and strain path in the absence of fracture and when martensite phase transformation is unaffected by heat generated during forming. In general, the uniaxial and biaxial tension deformation modes facilitate the martensite phase transformation, while the smallest amount of martensite phase transformation occurs under plane strain. In conclusion, some discussion as to further application of the experimental methods detailed in this study to other 3GAHSS and the effects of fracture on martensite phase transformation is provided.« less

Deformation mode and strain path dependence of martensite phase transformation in a medium manganese TRIP steel

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

Wu, Wei; Wang, Yu -Wei; Makrygiannis, Panagiotis

The martensite phase transformation dependence upon deformation modes and strain paths in a medium manganese (10 wt%) TRIP steel stamped into a T-shape panel was quantified through combination of 3D digital image correlation and synchrotron X-ray diffraction. The T-shape emulates a portion of a common anti-intrusion component. The stamping speed was kept intentionally slow (1 mm/s) so as to avoid excessive heat generation. The steel, which belongs to the third generation advanced high strength steel (3GAHSS) family, was chosen for two reasons: (1) it is two-phase, i.e. austenite and ferrite, with martensite resulting from deformation-induced phase transformation; (2) the 66more » vol.% initial retained austenite volume fraction (RAVF) enabled a thorough examination of the martensite phase transformation at large deformation levels without exhaustion. Strain fields were coupled with measured RAVF values of small specimens extracted from specific locations on a formed T-shape panel. This enabled an exploration of the effects of linear, bilinear, and non-linear strain paths as well as deformation modes such as tension, plane strain, biaxial tension, and equibiaxial tension. Results suggest a significant martensite phase transformation dependence on deformation mode and strain path in the absence of fracture and when martensite phase transformation is unaffected by heat generated during forming. In general, the uniaxial and biaxial tension deformation modes facilitate the martensite phase transformation, while the smallest amount of martensite phase transformation occurs under plane strain. In conclusion, some discussion as to further application of the experimental methods detailed in this study to other 3GAHSS and the effects of fracture on martensite phase transformation is provided.« less

Deformation mode and strain path dependence of martensite phase transformation in a medium manganese TRIP steel

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

Wu, Wei; Wang, Yu-wei; Makrygiannis, Panagiotis

The martensite phase transformation dependence upon deformation modes and strain paths in a medium manganese (10 wt%) TRIP steel stamped into a T-shape panel was quantified through combination of 3D digital image correlation and synchrotron X-ray diffraction. The T-shape emulates a portion of a common anti-intrusion component. The stamping speed was kept intentionally slow (1 mm/s) so as to avoid excessive heat generation. The steel, which belongs to the third generation advanced high strength steel (3GAHSS) family, was chosen for two reasons: (1) it is two-phase, i.e. austenite and ferrite, with martensite resulting from deformation-induced phase transformation; (2) the 66more » vol.% initial retained austenite volume fraction (RAVF) enabled a thorough examination of the martensite phase transformation at large deformation levels without exhaustion. Strain fields were coupled with measured RAVF values of small specimens extracted from specific locations on a formed T-shape panel. This enabled an exploration of the effects of linear, bilinear, and non-linear strain paths as well as deformation modes such as tension, plane strain, biaxial tension, and equibiaxial tension. Results suggest a significant martensite phase transformation dependence on deformation mode and strain path in the absence of fracture and when martensite phase transformation is unaffected by heat generated during forming. In general, the uniaxial and biaxial tension deformation modes facilitate the martensite phase transformation, while the smallest amount of martensite phase transformation occurs under plane strain. Some discussion as to further application of the experimental methods detailed in this study to other 3GAHSS and the effects of fracture on martensite phase transformation is provided.« less

In- Situ Synchrotron Diffraction Studies on Transformation Strain Development in a High-Strength Quenched and Tempered Structural Steel—Part II. Martensitic Transformation

NASA Astrophysics Data System (ADS)

Dutta, R. K.; Huizenga, R. M.; Petrov, R. H.; Amirthalingam, M.; King, A.; Gao, H.; Hermans, M. J. M.; Richardson, I. M.

2014-01-01

In-situ synchrotron diffraction studies on the kinetics of phase transformation and transformation strain development during bainitic transformation were presented in part I of the current article. In the current article, in-situ phase transformation behavior of a high-strength (830 MPa yield stress) quenched and tempered S690QL1 [Fe-0.16C-0.2Si-0.87Mn-0.33Cr-0.21Mo (wt. pct)] structural steel, during continuous cooling and under different mechanical loading conditions to promote martensitic transformation, has been studied. Time-temperature-load resolved 2D synchrotron diffraction patterns were recorded and used to calculate the phase fractions and lattice parameters of the phases during heating and cooling cycles under different loading conditions. In addition to the thermal expansion behavior, the effects of the applied stress on the elastic strains during the martensitic transformation were calculated. The results show that small tensile stresses applied at the transformation temperature do not change the kinetics of the phase transformation. The start temperature for the martensitic transformation increases with the increasing applied tensile stress. The elastic strains are not affected significantly with the increasing tensile stress. The variant selection during martensitic transformation under small applied loads (in the elastic region) is weak.

A polymorphism in the glucocorticoid receptor gene is associated with refractory hypotension in premature infants.

PubMed

Ogasawara, Kei; Sato, Maki; Hashimoto, Koichi; Imamura, Takashi; Go, Hayato; Hosoya, Mitsuaki

2018-06-01

Glucocorticoids play an important role in endocrine control. The association of glucocorticoid receptor (GR) gene polymorphisms with altered sensitivity to glucocorticoid therapy has been reported in adults. However, there are few such reports in infants. The present study analyzed the prevalence of four GR polymorphisms in preterm infants born before 30 weeks of gestation and determined the associations between these polymorphisms and clinical outcomes in the infants. Totally, 41 preterm infants born at two hospitals in Fukushima were retrospectively screened for the presence of four GR gene polymorphisms, using a TaqMan single-nucleotide polymorphism genotyping assay. The effect of GR gene polymorphisms on clinical outcomes during hospitalization was evaluated. The following primary clinical outcomes were assessed: refractory hypotension in the acute phase and/or severe bronchopulmonary dysplasia, maximum dopamine and dobutamine doses administered, and total hydrocortisone dose administered in the first 48 h of life. Multivariate analysis with logistic regression was used to assess the association between clinical factors and refractory hypotension. Of the four GR polymorphisms, only the BclI polymorphism was detected. The genotype distribution was as follows: C/C, 33; C/G, 8; and G/G, 0 infants. Significant differences were observed between the C/C and C/G genotypes with respect to the following variables: refractory hypotension (6% vs. 50%), dopamine dose [3.0 (2.0-4.0) vs. 4.8 (4.0-7.5) μg/kg/min], dobutamine dose [2.4 (0.0-3.6) vs. 4.0 (0-10.0) μg/kg/min], and total hydrocortisone dose administered in the first 48 h of life [2.0 (0-10.0) vs. 6.0 (0-12.0) mg/kg]. Multivariate analysis showed that the BclI genotype (C/C) was significantly less associated with refractory hypotension in the acute phase (odds ratio, 0.008; 95% confidence interval, 0.000-0.371; p = 0.013). The incidence of refractory hypotension in infants with the C/C genotype was initially expected to be higher than that in infants with the C/G genotype. However, the results of this study were rather different from what we originally expected. The suppressive effect of antenatal steroid use on the HPA axis of the preterm infants with the BclI variant may be associated with refractory hypotension in the acute phase. Copyright © 2017. Published by Elsevier B.V.

Tunable arbitrary unitary transformer based on multiple sections of multicore fibers with phase control.

PubMed

Zhou, Junhe; Wu, Jianjie; Hu, Qinsong

2018-02-05

In this paper, we propose a novel tunable unitary transformer, which can achieve arbitrary discrete unitary transforms. The unitary transformer is composed of multiple sections of multi-core fibers with closely aligned coupled cores. Phase shifters are inserted before and after the sections to control the phases of the waves in the cores. A simple algorithm is proposed to find the optimal phase setup for the phase shifters to realize the desired unitary transforms. The proposed device is fiber based and is particularly suitable for the mode division multiplexing systems. A tunable mode MUX/DEMUX for a three-mode fiber is designed based on the proposed structure.

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

Ulvestad, A.; Welland, M. J.; Cha, W.

Crystallographic imperfections can significantly alter material properties and responses to external stimuli, including solute induced phase transformations and crystal growth and dissolution . Despite recent progress in imaging defects using both electron and x-ray techniques, in situ three-dimensional imaging studies of defect dynamics, necessary to understand and engineer nanoscale processes, remains challenging. Here, we report in situ three-dimensional imaging of defect dynamics during the hydriding phase transformation of individual palladium nanocrystals by Bragg Coherent Diffractive Imaging (BCDI) . During constant pressure experiments, we observed that the phase transformation begins after the nucleation of dislocations in large (300 nm) particles. Themore » 3D dislocation network shows that dislocations are close to the phase boundary. The 3D phase morphology resolved by BCDI suggests that the hydrogen-rich phase is more similar to a spherical cap on the hydrogen-poor phase than the core-shell model commonly assumed. We substantiate this conclusion using 3D phase field modeling and demonstrate how phase morphology affects the critical size for dislocation nucleation. We determine the size dependence of the transformation pressure for large (150-300 nm) palladium nanocrystals using variable pressure experiments. Our results reveal a pathway for solute induced structural phase transformations in nanocrystals and demonstrate BCDI as a novel method for understanding dislocation dynamics in phase transforming systems at the nanoscale.« less

Crystal structure, chemical expansion and phase stability of HoMnO{sub 3} at high temperature

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

Selbach, Sverre M., E-mail: selbach@material.ntnu.no; Nordli Lovik, Amund; Bergum, Kristin

Anisotropic thermal and chemical expansion of hexagonal HoMnO{sub 3} was investigated by high temperature X-ray diffraction in inert (N{sub 2}) and oxidizing (air) atmospheres up to 1623 K. A second order structural phase transition directly from P6{sub 3}cm to P6{sub 3}/mmc was found at 1298{+-}4 K in N{sub 2} atmosphere, and 1318{+-}4 K in air. For the low temperature polymorph P6{sub 3}cm the contraction of the c-axis was more rapid in inert than in oxidizing atmosphere. The c-axis of the P6{sub 3}/mmc polymorph of HoMnO{sub 3} displayed anomalously high expansion above 1400 K, which is discussed in relation to chemicalmore » expansion caused by point defects. The a-axis expanded stronger in inert than oxidizing atmosphere. Anisotropic chemical and thermal expansion of the P6{sub 3}cm phase of YMnO{sub 3} in N{sub 2}, air and O{sub 2} atmospheres was found to be qualitatively similar to that of HoMnO{sub 3}. Decomposition of hexagonal HoMnO{sub 3} by two different processes occurs in oxidizing atmosphere above {approx}1200 K followed by nucleation and growth of the perovskite polymorph of HoMnO{sub 3}. A rapid, reconstructive transition from the perovskite back to the hexagonal polymorph was observed in situ at 1623 K upon reduction of the partial pressure of oxygen. A phase stability diagram of the hexagonal and orthorhombic polymorphs is proposed. Finally, distinctly non-linear electrical conductivity was observed for both HoMnO{sub 3} and YMnO{sub 3} in oxidizing atmosphere between 555 and 630 K, and shown to be associated with excess oxygen. - Graphical abstract: Chemical expansion of hexagonal HoMnO{sub 3} is observed during HTXRD in different pO{sub 2}. Oxidizing atmosphere favors the competing perovskite polymorph. Electrical conductivity anomalies related to excess oxygen are found at 550-630 K. Highlights: Black-Right-Pointing-Pointer Thermal evolution of crystal structure of HoMnO{sub 3} studied up to 1623 K in air and N{sub 2}. Black-Right-Pointing-Pointer Anisotropic chemical expansion of HoMnO{sub 3} and YMnO{sub 3} in N{sub 2}, air and O{sub 2}. Black-Right-Pointing-Pointer Hexagonal phase destabilized with respect to perovskite in oxidizing atmosphere. Black-Right-Pointing-Pointer Crystal structure and phase stability discussed in terms of point defect chemistry. Black-Right-Pointing-Pointer Electrical conductivity anomalies associated with excess oxygen at 550-630 K.« less

BDNF Polymorphism Predicts General Intelligence after Penetrating Traumatic Brain Injury

PubMed Central

Rostami, Elham; Krueger, Frank; Zoubak, Serguei; Dal Monte, Olga; Raymont, Vanessa; Pardini, Matteo; Hodgkinson, Colin A.; Goldman, David; Risling, Mårten; Grafman, Jordan

2011-01-01

Neuronal plasticity is a fundamental factor in cognitive outcome following traumatic brain injury. Brain-derived neurotrophic factor (BDNF), a member of the neurotrophin family, plays an important role in this process. While there are many ways to measure cognitive outcome, general cognitive intelligence is a strong predictor of everyday decision-making, occupational attainment, social mobility and job performance. Thus it is an excellent measure of cognitive outcome following traumatic brain injury (TBI). Although the importance of the single-nucleotide polymorphisms polymorphism on cognitive function has been previously addressed, its role in recovery of general intelligence following TBI is unknown. We genotyped male Caucasian Vietnam combat veterans with focal penetrating TBI (pTBI) (n = 109) and non-head injured controls (n = 38) for 7 BDNF single-nucleotide polymorphisms. Subjects were administrated the Armed Forces Qualification Test (AFQT) at three different time periods: pre-injury on induction into the military, Phase II (10–15 years post-injury, and Phase III (30–35 years post-injury). Two single-nucleotide polymorphisms, rs7124442 and rs1519480, were significantly associated with post-injury recovery of general cognitive intelligence with the most pronounced effect at the Phase II time point, indicating lesion-induced plasticity. The genotypes accounted for 5% of the variance of the AFQT scores, independently of other significant predictors such as pre-injury intelligence and percentage of brain volume loss. These data indicate that genetic variations in BDNF play a significant role in lesion-induced recovery following pTBI. Identifying the underlying mechanism of this brain-derived neurotrophic factor effect could provide insight into an important aspect of post-traumatic cognitive recovery. PMID:22087305

The 3111 Clock gene polymorphism is not associated with sleep and circadian rhythmicity in phenotypically characterized human subjects.

PubMed

Robilliard, Donna L; Archer, Simon N; Arendt, Josephine; Lockley, Steven W; Hack, Lisa M; English, Judie; Leger, Damien; Smits, Marcel G; Williams, Adrian; Skene, Debra J; Von Schantz, Malcolm

2002-12-01

Mutations in clock genes are associated with abnormal circadian parameters, including sleep. An association has been reported previously between a polymorphism (3111C), situated in the 3'-untranslated region (3'-UTR) of the circadian gene Clock and evening preference. In the present study, this polymorphism was assessed in: (1) 105 control subjects with defined diurnal preference, (2) 26 blind subjects with free-running circadian rhythms and characterized with regard to circadian period (tau) and (3) 16 delayed sleep phase syndrome patients. The control group was chosen from a larger population (n = 484) by Horne-Ostberg questionnaire analysis, from which three subgroups were selected (evening, intermediate and morning preference). Data from sleep diaries completed by 90% of these subjects showed a strong correlation between preferred and estimated timings of sleep and wake. The mean timings of activities for the evening group were at least 2 h later than the morning group. Genetic analysis showed that, in contrast with the previously published finding, there was no association between 3111C and eveningness. Neither was there an association between 3111C and tau, nor a significant difference in 3111C frequency between the normal and delayed sleep phase syndrome groups. To assess the effect of this polymorphism on messenger RNA (mRNA) translatability, luciferase reporter gene constructs containing the two Clock polymorphic variants in their 3'-UTR were transfected into COS-1 cells and luciferase activity measured. No significant difference was observed between the two variants. These results do not support Clock 3111C as a marker for diurnal preference, tau, or delayed sleep phase syndrome in humans.

Massively parallel haplotyping on microscopic beads for the high-throughput phase analysis of single molecules.

PubMed

Boulanger, Jérôme; Muresan, Leila; Tiemann-Boege, Irene

2012-01-01

In spite of the many advances in haplotyping methods, it is still very difficult to characterize rare haplotypes in tissues and different environmental samples or to accurately assess the haplotype diversity in large mixtures. This would require a haplotyping method capable of analyzing the phase of single molecules with an unprecedented throughput. Here we describe such a haplotyping method capable of analyzing in parallel hundreds of thousands single molecules in one experiment. In this method, multiple PCR reactions amplify different polymorphic regions of a single DNA molecule on a magnetic bead compartmentalized in an emulsion drop. The allelic states of the amplified polymorphisms are identified with fluorescently labeled probes that are then decoded from images taken of the arrayed beads by a microscope. This method can evaluate the phase of up to 3 polymorphisms separated by up to 5 kilobases in hundreds of thousands single molecules. We tested the sensitivity of the method by measuring the number of mutant haplotypes synthesized by four different commercially available enzymes: Phusion, Platinum Taq, Titanium Taq, and Phire. The digital nature of the method makes it highly sensitive to detecting haplotype ratios of less than 1:10,000. We also accurately quantified chimera formation during the exponential phase of PCR by different DNA polymerases.

An Experiment in Physical Chemistry: Polymorphism and Phase Stability in Acetaminophen (Paracetamol)

ERIC Educational Resources Information Center

Myrick, Michael L.; Baranowski, Megan; Profeta, Luisa T. M.

2010-01-01

Differential scanning calorimetry analyses of two easily prepared polymorphs of acetaminophen (also known as paracetamol) are recorded. The density of the forms can be found in the literature. Rules for heats of transition, heats of fusion, and density, as well as methods for determining the solid-solid transition temperature between the forms,…

Modeling and simulation, and their validation of three-phase transformers with three legs under DC bias

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

Fuchs, E.F.; You, Y.; Roesler, D.J.

This paper proposes a new model for three-phase transformers with three legs with and without tank under DC bias based on electric and magnetic circuit theory. For the calculation of the nonsinusoidal no-load currents, a combination of time and frequency domains is used. The analysis shows that (1) asymmetric three-phase transformers with three legs generate magnetizing currents with triplen harmonics not being of the zero-sequence type. (2) The wave shapes of the three magnetizing currents of (asymmetric) transformers are dependent on the phase sequence. (3) The magnetic history of transformer magnetization -- due to residual magnetization and hysteresis of themore » tank -- cannot be ignored if a DC bias is present and the magnetic influence of the tank is relatively strong, e.g., for oil-cooled transformers. (4) Symmetric three-phase transformers with three legs generate no-load currents without triplen harmonics. (5) The effects of DC bias currents (e.g., reactive power demand, harmonic distortion) can be suppressed employing symmetric three-phase transformers with three legs including tank. Measurements corroborate computational results; thus this nonlinear model is valid and accurate.« less

Statistics on gene-based laser speckles with a small number of scatterers: implications for the detection of polymorphism in the Chlamydia trachomatis omp1 gene

NASA Astrophysics Data System (ADS)

Ulyanov, Sergey S.; Ulianova, Onega V.; Zaytsev, Sergey S.; Saltykov, Yury V.; Feodorova, Valentina A.

2018-04-01

The transformation mechanism for a nucleotide sequence of the Chlamydia trachomatis gene into a speckle pattern has been considered. The first and second-order statistics of gene-based speckles have been analyzed. It has been demonstrated that gene-based speckles do not obey Gaussian statistics and belong to the class of speckles with a small number of scatterers. It has been shown that gene polymorphism can be easily detected through analysis of the statistical characteristics of gene-based speckles.

Room-Temperature Deformation and Martensitic Transformation of Two Co-Cr-Based Alloys

NASA Astrophysics Data System (ADS)

Cai, S.; Schaffer, J. E.; Huang, D.; Gao, J.; Ren, Y.

2018-05-01

Deformation of two Co-Cr alloys was studied by in situ synchrotron X-ray diffraction. Both alloys show stress-induced martensite transformation, which is affected by phase stabilities and transformation strains. Crystal structure of WC in Co-20Cr-15W-10Ni is identified. Compared with other phases present, it is elastically isotropic, exhibits high strength, and can elastically withstand strains exceeding 1 pct. Texture change during phase transformation is explained based on the crystal orientation relationship between γ- and ɛ-phases.

Room-Temperature Deformation and Martensitic Transformation of Two Co-Cr-Based Alloys

NASA Astrophysics Data System (ADS)

Cai, S.; Schaffer, J. E.; Huang, D.; Gao, J.; Ren, Y.

2018-07-01

Deformation of two Co-Cr alloys was studied by in situ synchrotron X-ray diffraction. Both alloys show stress-induced martensite transformation, which is affected by phase stabilities and transformation strains. Crystal structure of WC in Co-20Cr-15W-10Ni is identified. Compared with other phases present, it is elastically isotropic, exhibits high strength, and can elastically withstand strains exceeding 1 pct. Texture change during phase transformation is explained based on the crystal orientation relationship between γ- and ɛ-phases.

Structures of dolomite at ultrahigh pressure and their influence on the deep carbon cycle

PubMed Central

Merlini, Marco; Crichton, Wilson A.; Hanfland, Michael; Gemmi, Mauro; Müller, Harald; Kupenko, Ilya; Dubrovinsky, Leonid

2012-01-01

Carbon-bearing solids, fluids, and melts in the Earth's deep interior may play an important role in the long-term carbon cycle. Here we apply synchrotron X-ray single crystal micro-diffraction techniques to identify and characterize the high-pressure polymorphs of dolomite. Dolomite-II, observed above 17 GPa, is triclinic, and its structure is topologically related to CaCO3-II. It transforms above 35 GPa to dolomite-III, also triclinic, which features carbon in [3 + 1] coordination at the highest pressures investigated (60 GPa). The structure is therefore representative of an intermediate between the low-pressure carbonates and the predicted ultra-high pressure carbonates, with carbon in tetrahedral coordination. Dolomite-III does not decompose up to the melting point (2,600 K at 43 GPa) and its thermodynamic stability demonstrates that this complex phase can transport carbon to depths of at least up to 1,700 km. Dolomite-III, therefore, is a likely occurring phase in areas containing recycled crustal slabs, which are more oxidized and Ca-enriched than the primitive lower mantle. Indeed, these phases may play an important role as carbon carriers in the whole mantle carbon cycling. As such, they are expected to participate in the fundamental petrological processes which, through carbon-bearing fluids and carbonate melts, will return carbon back to the Earth’s surface. PMID:22869705

Evaluating structure selection in the hydrothermal growth of FeS 2 pyrite and marcasite

DOE PAGES

Kitchaev, Daniil A.; Ceder, Gerbrand

2016-12-14

While the ab initio prediction of the properties of solids and their optimization towards new proposed materials is becoming established, little predictive theory exists as to which metastable materials can be made and how, impeding their experimental realization. Here we propose a quasi-thermodynamic framework for predicting the hydrothermal synthetic accessibility of metastable materials and apply this model to understanding the phase selection between the pyrite and marcasite polymorphs of FeS 2. We demonstrate that phase selection in this system can be explained by the surface stability of the two phases as a function of ambient pH within nano-size regimes relevantmore » to nucleation. This result suggests that a first-principles understanding of nano-size phase stability in realistic synthesis environments can serve to explain or predict the synthetic accessibility of structural polymorphs, providing a guideline to experimental synthesis via efficient computational materials design.« less

High-pressure/high-temperature polymorphs of energetic materials by first-principles simulations

NASA Astrophysics Data System (ADS)

Le, Nam; Schweigert, Igor

2017-06-01

Energetic molecular crystals exhibit complex phase diagrams that include solid-solid phase transitions, melting, and decomposition. Sorescu and Rice have recently demonstrated that first-principles molecular dynamics (MD) simulations based on dispersion-corrected density functional theory (DFT) can capture the α to γ phase transition in hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) on time scales of several picoseconds. Motivated by their work, we are using DFT-based MD to model the relative stability of solid phases in several molecular crystals. In this presentation, we report simulations of pentaerythritol tetranitrate (PETN) and 2,4,6-trinitrotoluene (TNT) under high pressures and temperatures and compare them with experimentally observed polymorphs. This work was supported by the U.S. Naval Research Laboratory via the National Research Council and by the Office of Naval Research through the U.S. Naval Research Laboratory.

Binary Phase Behavior of Saturated-Unsaturated Mixed-Acid Triacylglycerols-A Review.

PubMed

Zhang, Lu; Ueno, Satoru; Sato, Kiyotaka

2018-06-01

Most natural lipids contain a complex mixture of individual triacylglycerols (TAGs). An in-depth knowledge of the mixing behavior of TAGs is necessary for the rational design and engineering of food materials. The binary phase diagram of TAGs is a simplified model that can be explored to help foster an understanding of the phase behavior of complex fats and oils. This article reviews recent research on the binary phase behavior of saturated-unsaturated mixed-acid TAGs, with special emphasis on the stearicunsaturated and palmitic-unsaturated diacid TAGs. The occurrence of polymorphic forms and mutual solubility of TAG mixtures are strongly related to the glycerol conformation of the saturated-oleic diacid TAGs; it appears to be most influenced by the chain-length mismatch in saturated-elaidic diacid TAGs. In addition, the polymorphism of pure enantiomers and racemic mixture of chiral TAGs was also reviewed, while the effect of chirality on mixing behavior was discussed.

Visualization of anisotropic-isotropic phase transformation dynamics in battery electrode particles

DOE PAGES

Wang, Jiajun; Karen Chen-Wiegart, Yu-chen; Eng, Christopher; ...

2016-08-12

Anisotropy, or alternatively, isotropy of phase transformations extensively exist in a number of solid-state materials, with performance depending on the three-dimensional transformation features. Fundamental insights into internal chemical phase evolution allow manipulating materials with desired functionalities, and can be developed via real-time multi-dimensional imaging methods. In this paper, we report a five-dimensional imaging method to track phase transformation as a function of charging time in individual lithium iron phosphate battery cathode particles during delithiation. The electrochemically driven phase transformation is initially anisotropic with a preferred boundary migration direction, but becomes isotropic as delithiation proceeds further. We also observe the expectedmore » two-phase coexistence throughout the entire charging process. Finally, we expect this five-dimensional imaging method to be broadly applicable to problems in energy, materials, environmental and life sciences.« less

Amyloid Hydrogen Bonding Polymorphism Evaluated by (15)N{(17)O}REAPDOR Solid-State NMR and Ultra-High Resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry.

PubMed

Wei, Juan; Antzutkin, Oleg N; Filippov, Andrei V; Iuga, Dinu; Lam, Pui Yiu; Barrow, Mark P; Dupree, Ray; Brown, Steven P; O'Connor, Peter B

2016-04-12

A combined approach, using Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) and solid-state NMR (Nuclear Magnetic Resonance), shows a high degree of polymorphism exhibited by Aβ species in forming hydrogen-bonded networks. Two Alzheimer's Aβ peptides, Ac-Aβ(16-22)-NH2 and Aβ(11-25), selectively labeled with (17)O and (15)N at specific amino acid residues were investigated. The total amount of peptides labeled with (17)O as measured by FTICR-MS enabled the interpretation of dephasing observed in (15)N{(17)O}REAPDOR solid-state NMR experiments. Specifically, about one-third of the Aβ peptides were found to be involved in the formation of a specific >C═(17)O···H-(15)N hydrogen bond with their neighbor peptide molecules, and we hypothesize that the rest of the molecules undergo ± n off-registry shifts in their hydrogen bonding networks.

The swimming of a perfect deforming helix

NASA Astrophysics Data System (ADS)

Koens, Lyndon; Zhang, Hang; Mourran, Ahmed; Lauga, Eric

2017-11-01

Many bacteria rotate helical flagellar filaments in order to swim. When at rest or rotated counter-clockwise these flagella are left handed helices but they undergo polymorphic transformations to right-handed helices when the motor is reversed. These helical deformations themselves can generate motion, with for example Rhodobacter sphaeroides using the polymorphic transformation of the flagellum to generate rotation, or Spiroplasma propagating a change of helix handedness across its body's length to generate forward motion. Recent experiments reported on an artificial helical microswimmer generating motion without a propagating change in handedness. Made of a temperature sensitive gel, these swimmers moved by changing the dimensions of the helix in a non-reciprocal way. Inspired by these results and helix's ubiquitous presence in the bacterial world, we investigate how a deforming helix moves within a viscous fluid. Maintaining a single handedness along its entire length, we discuss how a perfect deforming helix can create a non-reciprocal swimming stroke, identify its principle directions of motion, and calculate the swimming kinematics asymptotically.

Assessment of genetic stability and instability of tissue culture-propagated plantlets of Aloe vera L. by RAPD and ISSR markers.

PubMed

Rathore, Mangal Singh; Chikara, J; Mastan, Shaik G; Rahman, H; Anand, K G V; Shekhawat, N S

2011-11-01

Efficient plantlet regeneration with and without intermediate callus phase was achieved for a selected genotype of Aloe vera L. which is sweet in test and used as a vegetable and source of food. Random amplified polymorphic DNA (RAPD) and inter simple sequence repeats (ISSR) marker assays were employed to evaluate genetic stability of plantlets and validate the most reliable method for true-to-type propagation of sweet aloe, among two regeneration systems developed so far. Despite phenotypic similarities in plantlets produced through both regeneration systems, the differences in genomic constituents of plantlets produced through intermediate callus phase using soft base of inflorescence have been effectively distinguished by RAPD and ISSR markers. No polymorphism was observed in regenerants produced following direct regeneration of axillary buds, whereas 80% and 73.3% of polymorphism were observed in RAPD and ISSR, respectively, in the regenerants produced indirectly from base of the inflorescence axis via an intermediate callus phase. Overall, 86.6% of variations were observed in the plantlets produced via an intermediate callus phase. The occurrence of genetic polymorphism is associated with choice of explants and method used for plantlet regeneration. This confirms that clonal propagation of sweet aloe using axillary shoot buds can be used for commercial exploitation of the selected genotype where a high degree of fidelity is an essential prerequisite. On the other hand, a high degree of variations were observed in plantlets obtained through indirect regeneration and thus cannot be used for the mass multiplication of the genotype; however, it can be used for crop improvement through induction of somaclonal variations and genetic manipulations.

Dynamically fluctuating electric dipole moments in fullerene-based magnets.

PubMed

Kambe, Takashi; Oshima, Kokichi

2014-09-19

We report here the direct evidence of the existence of a permanent electric dipole moment in both crystal phases of a fullerene-based magnet--the ferromagnetic α-phase and the antiferromagnetic α'-phase of tetra-kis-(dimethylamino)-ethylene-C60 (TDAE-C60)--as determined by dielectric measurements. We propose that the permanent electric dipole originates from the pairing of a TDAE molecule with surrounding C60 molecules. The two polymorphs exhibit clear differences in their dielectric responses at room temperature and during the freezing process with dynamically fluctuating electric dipole moments, although no difference in their room-temperature structures has been previously observed. This result implies that two polymorphs have different local environment around the molecules. In particular, the ferromagnetism of the α-phase is founded on the homogeneous molecule displacement and orientational ordering. The formation of the different phases with respect to the different rotational states in the Jahn-Teller distorted C60s is also discussed.

Dynamically fluctuating electric dipole moments in fullerene-based magnets

PubMed Central

Kambe, Takashi; Oshima, Kokichi

2014-01-01

We report here the direct evidence of the existence of a permanent electric dipole moment in both crystal phases of a fullerene-based magnet—the ferromagnetic α-phase and the antiferromagnetic α′-phase of tetra-kis-(dimethylamino)-ethylene-C60 (TDAE-C60)—as determined by dielectric measurements. We propose that the permanent electric dipole originates from the pairing of a TDAE molecule with surrounding C60 molecules. The two polymorphs exhibit clear differences in their dielectric responses at room temperature and during the freezing process with dynamically fluctuating electric dipole moments, although no difference in their room-temperature structures has been previously observed. This result implies that two polymorphs have different local environment around the molecules. In particular, the ferromagnetism of the α-phase is founded on the homogeneous molecule displacement and orientational ordering. The formation of the different phases with respect to the different rotational states in the Jahn–Teller distorted C60s is also discussed. PMID:25236361

New metastable form of glibenclamide prepared by redispersion from ternary solid dispersions containing polyvinylpyrrolidone-K30 and sodium lauryl sulfate.

PubMed

Thongnopkoon, Thanu; Puttipipatkhachorn, Satit

2016-01-01

Modification of polymorphic forms of poorly water-soluble drugs is one way to achieve the desirable properties. In this study, glibenclamide (GBM) particles with different polymorphic forms, including a new metastable form, were obtained from redispersion of ternary solid dispersion systems. The ternary solid dispersion systems, consisting of GBM, polyvinylpyrrolidone-K30 (PVP-K30) and sodium lauryl sulfate (SLS), were prepared by solvent evaporation method and subsequently redispersed in deionized water. The precipitated drug particles were then collected at a given time period. The drug particles with different polymorphic forms could be achieved depending on the polymer/surfactant ratio. Amorphous drug nanoparticles could be obtained by using a high polymer/surfactant ratio, whereas two different crystalline forms were obtained from the systems containing low polymer/surfactant ratios. Interestingly, a new metastable form IV of GBM with improved dissolution behavior could be obtained from the system of GBM:PVP-K30:SLS with the weight ratio of 2:2:4. This new polymorphic form IV of GBM was confirmed by differential scanning calorimetry (DSC), Fourier transform infrared (FT-IR) spectroscopy, powder X-ray diffractometry (PXRD) and solid state 13 C nuclear magnetic resonance (NMR) spectroscopy. The molecular arrangement of the new polymorphic form IV of GBM was proposed. The GBM particles with polymorphic form IV also showed an improved dissolution behavior. In addition, it was found that the formation of the new polymorphic form IV of GBM by this process was reproducible.

Genetic Contributions to Age-Related Decline in Executive Function: A 10-Year Longitudinal Study of COMT and BDNF Polymorphisms

PubMed Central

Erickson, Kirk I.; Kim, Jennifer S.; Suever, Barbara L.; Voss, Michelle W.; Francis, B. Magnus; Kramer, Arthur F.

2008-01-01

Genetic variability in the dopaminergic and neurotrophic systems could contribute to age-related impairments in executive control and memory function. In this study we examined whether genetic polymorphisms for catechol-O-methyltransferase (COMT) and brain-derived neurotrophic factor (BDNF) were related to the trajectory of cognitive decline occurring over a 10-year period in older adults. A single nucleotide polymorphism in the COMT (Val158/108Met) gene affects the concentration of dopamine in the prefrontal cortex. In addition, a Val/Met substitution in the pro-domain for BDNF (Val66Met) affects the regulated secretion and trafficking of BDNF with Met carriers showing reduced secretion and poorer cognitive function. We found that impairments over the 10-year span on a task-switching paradigm did not vary as a function of the COMT polymorphism. However, for the BDNF polymorphism the Met carriers performed worse than Val homozygotes at the first testing session but only the Val homozygotes demonstrated a significant reduction in performance over the 10-year span. Our results argue that the COMT polymorphism does not affect the trajectory of age-related executive control decline, whereas the Val/Val polymorphism for BDNF may promote faster rates of cognitive decay in old age. These results are discussed in relation to the role of BDNF in senescence and the transforming impact of the Met allele on cognitive function in old age. PMID:18958211

Probing the Pathways and Interactions Controlling Crystallization by Particle Attachment

NASA Astrophysics Data System (ADS)

De Yoreo, J. J.; Li, D.; Chun, J.; Schenter, G.; Mundy, C.; Rosso, K. M.

2016-12-01

Crystallization by particle attachment appears to be a widespread mechanism of mineralization. Yet many long-standing questions surrounding nucleation and assembly of precursor particles remain unanswered, due in part to a lack of tools to probe mineralization dynamics with adequate spatial and temporal resolution. Here we report results of liquid phase TEM studies of nucleation and particle assembly in a number of mineral systems. We interpret the results within a framework that considers the impact of both the complexity of free energy landscapes and kinetic factors associated with high supersaturation or slow dynamics. In the calcium carbonate system, the need for high supersturations to overcome the high barrier to nucleation of calcite leads to simultaneous occurrence of multiple pathways, including direct formation of all the common ploymorphs, as well as two-step pathways through which initial precursors, particularly ACC, undergo a direct transformation to a more stable phase. Introduction of highly charged polymers that bind calcium inhibits nucleation, but directs the pathway to a metastable amorphous phase that no longer transforms to more stable polymorphs. Experiments in the iron oxide and oxyhydroxide systems show that, when high supersaturations lead to nucleation of many nanoprticles, further growth occurs through a combination of particle aggregation events and Ostwald ripening. In some cases, aggregation occurs only through oriented attachment on lattice matched faces, leading to single crystals with complex topologies and internal twin boundaries, while in others aggregation results initially in poor co-alignment, but over time the particles undergo atomic rearrangements to achieve a single crystal structure. AFM-based measurements of forces between phyllosilicate surfaces reveal the importance of long-range dispersion interactions in driving alignment, as well as the impact of electrolyte concentration and temperature on the competition of those attractive forces with repulsive electrostatic interactions. Taken together, the results help to define an emerging framework for understanding crystallization by particle attachment.

Selecting the spin crossover profile with controlled crystallization of mononuclear Fe(iii) polymorphs.

PubMed

Vicente, Ana I; Ferreira, Liliana P; Carvalho, Maria de Deus; Rodrigues, Vítor H N; Dîrtu, Marinela M; Garcia, Yann; Calhorda, Maria José; Martinho, Paulo N

2018-05-08

Two polymorphic species of the [Fe(5-Br-salEen)2]ClO4 compound were obtained, each of them being selectively recovered after evaporation of the solvent at a controlled rate. While polymorph 1a is formed during slow evaporation, fast evaporation favors polymorph 1b. The importance of the evaporation rate was recognized after detailed studies of the reaction temperature, solvent evaporation rate and crystallization temperature effects. The complex in the new polymorphic form 1a showed an abrupt spin crossover at 172 K with a small 1 K hysteresis window and over a narrow 10 K range. 57Fe Mössbauer spectroscopy and differential scanning calorimetry, complemented by X-ray studies for both the high-spin and low-spin forms, were used to further characterize the new polymorphic phase 1a. Both polymorphs are based on the same Fe(iii) complex cation hydrogen bonded to the perchlorate anion. These units are loosely bound in the crystals via weak interactions. In the new polymorph 1a, the hydrogen bonds are stronger, while the weak hydrogen and halogen bonds, as well as π-π stacking, create a cooperative network, not present in 1b, responsible for the spin transition profile.

Synchrotron X-ray diffuse scattering from a stable polymorphic material: terephthalic acid, C 8 H 6 O 4

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

Goossens, D. J.; Chan, E. J.

Terephthalic acid (TPA, C 8H 6O 4) is an industrially important chemical, one that shows polymorphism and disorder. Three polymorphs are known, two triclinic [(I) and (II)] and one monoclinic (III). Of the two triclinic polymorphs, (II) has been shown to be more stable in ambient conditions. This paper presents models of the local order of polymorphs (I) and (II), and compares the single-crystal diffuse scattering (SCDS) computed from the models with that observed from real crystals. TPA shows relatively weak and less-structured diffuse scattering than some other polymorphic materials, but it does appear that the SCDS is less wellmore » modelled by a purely harmonic model in polymorph (I) than in polymorph (II), according to the idea that the diffuse scattering is sensitive to anharmonicity that presages a structural phase transition. The work here verifies that displacive correlations are strong along the molecular chains and weak laterally, and that it is not necessary to allow the —COOH groups to librate to successfully model the diffuse scattering – keeping in mind that the data are from X-ray diffraction and not directly sensitive to H atoms.« less

Shock-induced deformation of Shergottites: Shock-pressures and perturbations of magmatic ages on Mars

NASA Astrophysics Data System (ADS)

El Goresy, Ahmed; Gillet, Ph.; Miyahara, M.; Ohtani, E.; Ozawa, S.; Beck, P.; Montagnac, G.

2013-01-01

Shergottites and Chassignites practiced major deformation effects whose nature, magnitude and relevance were controversially evaluated and disputatively debated. Our studies of many shocked shergottites present, contrary to numerous previous reports, ample evidence for pervasive shock-induced melting amounting of at least 23 vol.% of the shergottite consisting of maskelynite and pyrrhotite, partial melting of pyroxene, titanomagnetite, ilmenite and finding of several high-pressure polymorphs and pressure-induced dissociation reactions. Our results cast considerable doubt on using the refractive index (RI) or cathodoluminescence (CL) spectra of maskelynite, in estimating the magnitudes of peak-shock pressure in both shergottites and ordinary chondrites. RI of maskelynite was set after quenching of the feldspar liquid before decompression to maskelynite glass followed by glass relaxation after decompression at the closure temperature of relaxation. The RI procedure widely practiced in the past 38 years revealed unrealistic very high-pressure estimates discrepant with the high-pressure mineral inventory in shocked shergottites and ordinary chondrites and with results obtained by robust laboratory static experiments. Shergottites contain the silica high-pressure polymorphs: the scrutinyite-structured polymorph seifertite, a monoclinic ultra dense polymorph of silica with ZrO2-structure, stishovite, a dense liquidus assemblage consisting of stishovite + Na-hexa-aluminosilicate (Na-CAS) and both K-lingunite and Ca-lingunite. Applying individual high-pressure silica polymorphs alone like stishovite, to estimate the equilibrium shock pressure, is inadequate due to the considerable shift of their nominal upper pressure bounds intrinsically induced by spatially variable absorptions of minor oxides like Al2O3, Na2O, FeO, MgO and TiO2. This practice revealed variable pressure estimates even within the same shergottite subjected to the same peak-shock pressure. Occurrence of Na-CAS + stishovite, lack of the NaAlSiO4 Ca-ferrite structured polymorph or jadeite indicates that the peak-shock pressures barely exceeded 22 GPa. We present convincing and ample evidence refuting the claim that the shock-induced high-pressure inventory in shergottites and ordinary chondrites are disequilibrium assemblages resulted from local pressure spikes in excess of 80 GPa and during the decompression stage. Such scenario calls for a series of incomplete and quenched retrograde reactions starting with the crystallization of Mg-silicate perovskite + magnesiowüstite, if the claimed peak-shock pressure was in excess of 80 GPa. This would be followed by replacement of this pair by majorite-pyropess + magnesiowüstite or akimotoite + magnesiowüstite below 23 GPa and 2000 °C, polycrystalline ringwoodite above 16 GPa, respectively and finally replacement by polycrystalline olivine below 16 GPa. Such incomplete retrograde reactions were never encountered in any shergottite, chassignite or shocked ordinary chondrite so far. Olivine-ringwoodite phase transformation in the L6 Y-791384 commences with the coherent mechanism producing ringwoodite lamellae with their (1 1 1) planes parallel to the (1 0 0) of olivine followed by the incoherent mechanism due to build up of strain in the parental olivine. This is in accord with the olivine-ringwoodite settings produced in static laboratory experiments in a multi-anvil device. Olivine-ringwoodite phase transitions were also encountered in comparable settings in the shergottite NWA 1068. Application of experimentally obtained kinetic parameters of the olivine-ringwoodite phase transitions reveals possible duration of the natural dynamic events up to few seconds thus unambiguously refuting the claimed disequilibrium decompression mechanism. The shock-induced pervasive melting of labradorite, pyrrhotite, titanomagnetite, ilmenite and partial melting of clinopyroxene strongly suggests shock-induced partial to complete resetting of the Ar-Ar, Rb-Sr, Sm-Nd, Re-Os, U-Pb and Lu-Hf radiometric systems. This also casts considerable doubt on the radiometric ages shorter than 575 Ma reported in the past 38 years to allegedly be the igneous crystallization ages. These short ages probably resulted from partial or total shock-induced age resetting.

Thermodynamics of HMX Polymorphs and HMX/RDX Mixtures

DOE PAGES

Myint, Philip C.; Nichols, Albert L.

2016-12-09

In this paper, we present thermodynamic models for the five most commonly studied phases of the energetic material octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX): liquid HMX and four solid polymorphs (α-, β-, γ-, and δ-HMX). We show results for the density, heat capacity, bulk modulus, and sound speed, as well as a phase diagram that illustrates the temperature and pressure regions over which the various HMX phases are most thermodynamically stable. The models are based on the same equation of state presented in our recently published paper [Myint et al., Ind. Eng. Chem. Res., 2016, 55, 2252] on another energetic material, hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). Wemore » combine our HMX and RDX models together so that the equation of state can also be applied to liquid and solid mixtures of HMX/RDX. This allows us to generate an HMX/RDX phase diagram and calculate the enthalpy change associated with a few different kinds of phase transitions that these mixtures may undergo. Our paper is the first to present a single equation of state that is capable of modeling both pure HMX and HMX/RDX mixtures. A distinct feature of HMX is the strongly metastable nature of its polymorphs. This has caused some ambiguity in the literature regarding the thermodynamic stability of α-HMX. Finally, by examining possible arrangements for the relative order of the six different solid-solid transition (α–β, α–γ, α–δ, β–γ, β–δ, and γ–δ) temperatures, we conclude that α-HMX must be thermodynamically stable so that the HMX phase diagram must have an α phase region.« less

Design of electromagnetic refractor and phase transformer using coordinate transformation theory.

PubMed

Lin, Lan; Wang, Wei; Cui, Jianhua; Du, Chunlei; Luo, Xiangang

2008-05-12

We designed an electromagnetic refractor and a phase transformer using form-invariant coordinate transformation of Maxwell's equations. The propagation direction of electromagnetic energy in these devices can be modulated as desired. Unlike the conventional dielectric refractor, electromagnetic fields at our refraction boundary do not conform to the Snell's law in isotropic materials and the impedance at this boundary is matched which makes the reflection extremely low; and the transformation of the wave front from cylindrical to plane can be realized in the phase transformer with a slab structure. Two dimensional finite-element simulations were performed to confirm the theoretical results.

Polymorphs of Theophylline Characterized by DNP Enhanced Solid-State NMR

PubMed Central

2015-01-01

We show how dynamic nuclear polarization (DNP) enhanced solid-state NMR spectroscopy can be used to characterize polymorphs and solvates of organic solids. We applied DNP to three polymorphs and one hydrated form of the asthma drug molecule theophylline. For some forms of theophylline, sample grinding and impregnation with the radical-containing solution, which are necessary to prepare the samples for DNP, were found to induce polymorphic transitions or desolvation between some forms. We present protocols for sample preparation for solid-state magic-angle spinning (MAS) DNP experiments that avoid the polymorphic phase transitions in theophylline. These protocols include cryogrinding, grinding under inert atmosphere, and the appropriate choice of the impregnating liquid. By applying these procedures, we subsequently demonstrate that two-dimensional correlation experiments, such as 1H–13C and 1H–15N HETCOR or 13C–13C INADEQUATE, can be obtained at natural isotopic abundance in reasonable times, thus enabling more advanced structural characterization of polymorphs. PMID:26393368

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

Devaraj, Arun; Jana, Saumyadeep; McInnis, Colleen A.

During eutectoid transformation of U-10Mo alloy, uniform metastable γ UMo phase is expected to transform to a mixture of α-U and γ’-U 2Mo phase. The presence of transformation products in final U-10Mo fuel, especially the α phase is considered detrimental for fuel irradiation performance, so it is critical to accurately evaluate the extent of transformation in the final U-10Mo alloy. This phase transformation can cause a volume change that induces a density change in final alloy. To understand this density and volume change, we developed a theoretical model to calculate the volume expansion and resultant density change of U-10Mo alloymore » as a function of the extent of eutectoid transformation. Based on the theoretically calculated density change for 0 to 100% transformation, we conclude that an experimental density measurement system will be challenging to employ to reliably detect and quantify the extent of transformation. Subsequently, to assess the ability of various methods to detect the transformation in U-10Mo, we annealed U-10Mo alloy samples at 500°C for various times to achieve in low, medium, and high extent of transformation. After the heat treatment at 500°C, the samples were metallographically polished and subjected to optical microscopy and x-ray diffraction (XRD) methods. Based on our assessment, optical microscopy and image processing can be used to determine the transformed area fraction, which can then be correlated with the α phase volume fraction measured by XRD analysis. XRD analysis of U-10Mo aged at 500°C detected only α phase and no γ’ was detected. To further validate the XRD results, atom probe tomography (APT) was used to understand the composition of transformed regions in U-10Mo alloys aged at 500°C for 10 hours. Based on the APT results, the lamellar transformation product was found to comprise α phase with close to 0 at% Mo and γ phase with 28–32 at% Mo, and the Mo concentration was highest at the α/γ interface.« less

Photochemical solution processing of films of metastable phases for flexible devices: the β-Bi2O3 polymorph

PubMed Central

Pérez-Mezcua, Dulce; Bretos, Iñigo; Jiménez, Ricardo; Ricote, Jesús; Jiménez-Rioboó, Rafael J.; da Silva, Cosmelina Gonçalves; Chateigner, Daniel; Fuentes-Cobas, Luis; Sirera, Rafael; Calzada, M. Lourdes

2016-01-01

The potential of UV-light for the photochemical synthesis and stabilization of non-equilibrium crystalline phases in thin films is demonstrated for the β-Bi2O3 polymorph. The pure β-Bi2O3 phase is thermodynamically stable at high temperature (450–667 °C), which limits its applications in devices. Here, a tailored UV-absorbing bismuth(III)-N-methyldiethanolamine complex is selected as an ideal precursor for this phase, in order to induce under UV-light the formation of a –Bi–O–Bi– continuous network in the deposited layers and the further conversion into the β-Bi2O3 polymorph at a temperature as low as 250 °C. The stabilization of the β-Bi2O3 films is confirmed by their conductivity behavior and a thorough characterization of their crystal structure. This is also supported by their remarkable photocatalytic activity. Besides, this processing method has allowed us for the first time the preparation of β-Bi2O3 films on flexible plastic substrates, which opens new opportunities for using these materials in potential applications not available until now (e.g., flexible photocatalytic reactors, self-cleaning surfaces or wearable antimicrobial fabrics). Therefore, photochemical solution deposition (PCSD) demonstrates to be not only an efficient approach for the low temperature processing of oxide films, but also an excellent alternative for the stabilization of metastable phases. PMID:27996042

Personalized tacrolimus doses determined by CYP3A5 genotype for induction and maintenance phases of kidney transplantation.

PubMed

Vannaprasaht, Suda; Reungjui, Sirirat; Supanya, Darika; Sirivongs, Dhavee; Pongskul, Cholatip; Avihingsanon, Yingyos; Tassaneeyakul, Wichittra

2013-11-01

Cytochrome P450 (CYP) 3A4 and 3A5 are major isoforms involved in the metabolism of tacrolimus, with the CYP3A5 gene being more polymorphic. It is hypothesized that individual variation in the metabolism of tacrolimus drug may result from genetic polymorphism of CYP3A5. It has been reported that the clearance of tacrolimus in patients with the CYP3A5*1 allele was ~2.5-fold greater than that in those with the CYP3A5*3/*3 genotype. Recent data have also shown that polymorphism in exon 26 (C3435T) of the multidrug resistance gene (MDR1) was correlated with the expression level and function of P-glycoprotein in the lower duodenum, making the relationship between polymorphism of MDR1 and the effective dose of tacrolimus a source of controversy. This study investigated the influence of genetic polymorphisms of CYP3A5 and MDR1 on the dose requirements for the induction and maintenance phases of tacrolimus therapy in kidney transplant recipients. Sixty-eight kidney transplant recipients were enrolled, and their clinical and laboratory data were retrospectively reviewed after 6 months of tacrolimus administration. Genotypes of CYP3A5*1 and CYP3A5*3 and exon 26 of MDR1 (C3435T) were determined by the single-nucleotide polymorphism genotyping method. The frequencies of CYP3A5*3/*3, CYP3A5*1/*3, and CYP3A5*1/*1 were 44.1%, 35.3%, and 20.6%, respectively. The mean dose of tacrolimus required for the induction phase was significantly greater in the CYP3A5*1/*1 group (0.142 [0.050] mg/kg/d) than that required in the CYP3A5*1/*3 group (0.097 [0.040] mg/kg/d; P = 0.072) and in the CYP3A5*3/*3 group (0.077 [0.020] mg/kg/d; P = 0.005). The maintenance dose of tacrolimus required in the CYP3A5*1/*1 group (0.12 [0.03] mg/kg/d) was 1.3-fold higher than that in the CYP3A5*1/*3 group (0.09 [0.03] mg/kg/d; P = 0.018) and 2.4-fold higher than in the CYP3A5*3/*3 group (0.05 [0.02] mg/kg/d; P < 0.0001). No statistically significant relationship was observed between the doses of tacrolimus required for the induction and maintenance phases and MDR1 polymorphism. Determination of the CYP3A5 genotype would be helpful in the design of adequate immunosuppressive treatment and in lowering toxicity by predicting the doses of tacrolimus required for the induction and maintenance phases in individual kidney transplant recipients. © 2013 Elsevier HS Journals, Inc. All rights reserved.

Rheo-NMR Measurements of Cocoa Butter Crystallized Under

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

Mudge, E.; Mazzanti, G

2009-01-01

Modifications of a benchtop NMR instrument were made to apply temperature control to a shearing NMR cell. This has enabled the determination in situ of the solid fat content (SFC) of cocoa butter under shearing conditions. The cocoa butter was cooled at 3 C/min to three final temperatures of 17.5, 20.0, and 22.5 C with applied shear rates between 45 and 720 s-1. Polymorphic transitions of the cocoa butter were determined using synchrotron X-ray diffraction with an identical shearing system constructed of Lexan. Sheared samples were shown to have accelerated phase transitions compared to static experiments. In experiments where formmore » V was confirmed to be the dominant polymorph, the final SFC averaged around 50%. However, when other polymorphic forms were formed, a lower SFC was measured because the final temperature was within the melting range of that polymorph and only partial crystallization happened. A shear rate of 720 s-1 delayed phase transitions, likely due to viscous heating of the sample. Pulsed NMR is an invaluable tool for determining the crystalline fraction in hydrogen containing materials, yet its use for fundamental and industrial research on fat or alkanes crystallization under shear has only recently been developed.« less

Martensitelike spontaneous relaxor-normal ferroelectric transformation in Pb(Zn1/3Nb2/3)O3-PbLa(ZrTi)O3 system

NASA Astrophysics Data System (ADS)

Deng, Guochu; Ding, Aili; Li, Guorong; Zheng, Xinsen; Cheng, Wenxiu; Qiu, Pingsun; Yin, Qingrui

2005-11-01

The spontaneous relaxor-normal ferroelectric transformation was found in the tetragonal composition of Pb(Zn1/3Nb2/3)O3-PbLa(ZrTi)O3 (0.3PZN-0.7PLZT) complex ABO3 system. The corresponding dielectric permittivities and losses of different compositions located near the morphotrophic phase boundary were analyzed. By reviewing all of the results about this type of transformation in previous references, the electric, compositional, structural, and thermodynamic characteristics of the spontaneous relaxor-normal transformation were proposed. Additionally, the adaptive phase model for martensite transformation proposed by Khachaturyan et al. [Phys. Rev. B 43, 10832 (1991)] was introduced into this ferroelectric transformation to explain the unique transformation pathway and associated features such as the tweedlike domain patterns and the dielectric dispersion under the critical transition temperature. Due to the critical compositions near the MPB, the ferroelectric materials just fulfill the condition, in which the adaptive phases can form in the transformation procedure. The formation of the adaptive phases, which are composed of stress-accommodating twinned domains, makes the system bypass the energy barrier encountered in conventional martensite transformations. The twinned adaptive phase corresponds to the tweedlike domain pattern under a transmission electronic microscope. At lower temperature, these precursor phases transform into the conventional ferroelectric state with macrodomains by the movement of domain walls, which causes a weak dispersion in dielectric permittivity.

Phase transformations at interfaces: Observations from atomistic modeling

DOE PAGES

Frolov, T.; Asta, M.; Mishin, Y.

2016-10-01

Here, we review the recent progress in theoretical understanding and atomistic computer simulations of phase transformations in materials interfaces, focusing on grain boundaries (GBs) in metallic systems. Recently developed simulation approaches enable the search and structural characterization of GB phases in single-component metals and binary alloys, calculation of thermodynamic properties of individual GB phases, and modeling of the effect of the GB phase transformations on GB kinetics. Atomistic simulations demonstrate that the GB transformations can be induced by varying the temperature, loading the GB with point defects, or varying the amount of solute segregation. The atomic-level understanding obtained from suchmore » simulations can provide input for further development of thermodynamics theories and continuous models of interface phase transformations while simultaneously serving as a testing ground for validation of theories and models. They can also help interpret and guide experimental work in this field.« less

Transforming growth factor beta-3 and environmental factors and cleft lip with/without cleft palate.

PubMed

Guo, Zeqiang; Huang, Chengle; Ding, Kaihong; Lin, Jianyan; Gong, Binzhong

2010-07-01

To identify the interactions among two loci (C641A and G15572-) of transforming growth factor beta 3 (TGFbeta3), and exposures in pregnancy with cleft lip with/without cleft palate (CL/P), a hospital-based case-control study was conducted. Associations among offspring polymorphisms of TGFbeta3 C641A and G15572-, paternal smoking, paternal high-risk drinking, maternal passive smoking, and maternal multivitamin supplement with CL/P were analyzed by logistic regression analysis, and the results showed that maternal passive smoking exposures and maternal multivitamin use were associated with the risk of CL/P but offspring polymorphisms of TGFbeta3 C641A and G15572-, paternal smoking, and paternal high-risk drinking were not. Interactions among these variables were analyzed using the multifactor dimensionality reduction method, and the results showed that the two-factor model, including maternal passive smoking and TGFbeta3 C641A, among all models evaluated had the best ability to predict CL/P risk with a maximum cross-validation consistency (9/10) and a maximum average testing accuracy (0.5892; p = 0.0010). These findings suggested that maternal passive smoking exposure is a risk factor for CL/P, whereas maternal multivitamin supplement is a protective factor. The polymorphism of TGFbeta3 C641A participates in interaction effect for CL/P with environmental exposures, although the polymorphism was not associated with CL/P in single-locus analysis, and synergistic effect of TGFbeta3 C641A and maternal passive smoking could provide a new tool for identifying high-risk individuals of CL/P and also an additional evidence that CL/P is determined by both genetic and environmental factors.

An optical Fourier transform coprocessor with direct phase determination.

PubMed

Macfaden, Alexander J; Gordon, George S D; Wilkinson, Timothy D

2017-10-20

The Fourier transform is a ubiquitous mathematical operation which arises naturally in optics. We propose and demonstrate a practical method to optically evaluate a complex-to-complex discrete Fourier transform. By implementing the Fourier transform optically we can overcome the limiting O(nlogn) complexity of fast Fourier transform algorithms. Efficiently extracting the phase from the well-known optical Fourier transform is challenging. By appropriately decomposing the input and exploiting symmetries of the Fourier transform we are able to determine the phase directly from straightforward intensity measurements, creating an optical Fourier transform with O(n) apparent complexity. Performing larger optical Fourier transforms requires higher resolution spatial light modulators, but the execution time remains unchanged. This method could unlock the potential of the optical Fourier transform to permit 2D complex-to-complex discrete Fourier transforms with a performance that is currently untenable, with applications across information processing and computational physics.

Association of REL Polymorphism with Cow's Milk Proteins Allergy in Pediatric Algerian Population.

PubMed

Rahmoun, Nesrine; El Mecherfi, Kamel Eddine; Bouchetara, Assia; Lardjem Hetraf, Sara; Dahmani Amira, Chahinez; Adda Neggaz, Leila; Boudjema, Abdallah; Zemani-Fodil, Faouzia; Kheroua, Omar

2018-02-01

Cow's milk proteins allergy (CMPA) pathogenesis involves complex immunological mechanisms with the participation of several cells and molecules involved in food allergy. The association of polymorphisms in the interleukin 4, Forkhead box P3 and the avian reticuloendotheliosis genes was investigated in an infant population with CMPA of Western Algeria. We obtained DNA and clinical data from milk allergic subjects during active phase and from a group of non-atopic control subjects. Our findings showed that the allele G of the cRel gene intronic polymorphism at +7883 positions was significantly higher among cow's milk proteins allergic patients compared to control subjects. The results of this study suggest a possible association of CMPA with cRel G+7883T polymorphism.

Phase transition kinetics in DIET of vanadium pentoxide. I. Experimental results

NASA Astrophysics Data System (ADS)

Ai, R.; Fan, H.-J.; Marks, L. D.

1993-01-01

Experimental results of the kinetics of phase transformation in vanadium pentoxide during surface loss of oxygen from electron irradiation are described. Phase transformations under three different regimes were examined: (a) low flux; (b) intermediate flux and (c) high flux. Different phase transformation routes were observed under different fluxes. In a companion paper, numerical calculations are presented demonstrating that these results are due to a mixed interface/diffusion controlled phase transition pumped by surface oxygen loss.

Influence of Temperature on Fatigue-Induced Martensitic Phase Transformation in a Metastable CrMnNi-Steel

NASA Astrophysics Data System (ADS)

Biermann, Horst; Glage, Alexander; Droste, Matthias

2016-01-01

Metastable austenitic steels can exhibit a fatigue-induced martensitic phase transformation during cyclic loading. It is generally agreed that a certain strain amplitude and a threshold of the cumulated plastic strain must be exceeded to trigger martensitic phase transformation under cyclic loading. With respect to monotonic loading, the martensitic phase transformation takes place up to a critical temperature—the so-called M d temperature. The goal of the present investigation is to determine an M d,c temperature which would be the highest temperature at which a fatigue-induced martensitic phase transformation can take place. For this purpose, fatigue tests controlled by the total strain were performed at different temperatures. The material investigated was a high-alloy metastable austenitic steel X3CrMnNi16.7.7 (16.3Cr-7.2Mn-6.6Ni-0.03C-0.09N-1.0Si) produced using the hot pressing technique. The temperatures were set in the range of 283 K (10 °C) ≤ T ≤ 473 K (200 °C). Depending on the temperature and strain amplitude, the onset of the martensitic phase transformation shifted to different values of the cumulated plastic strain, or was inhibited completely. Moreover, it is known that metastable austenitic CrMnNi steels with higher nickel contents can exhibit the deformation-induced twinning effect. Thus, at higher temperatures and strain amplitudes, a transition from the deformation-induced martensitic transformation to deformation-induced twinning takes place. The fatigue-induced martensitic phase transformation was monitored during cyclic loading using a ferrite sensor. The microstructure after the fatigue tests was examined using the back-scattered electrons, the electron channeling contrast imaging and the electron backscatter diffraction techniques to study the temperature-dependent dislocation structures and phase transformations.

Solvent Vapor Annealing of Amorphous Carbamazepine Films for Fast Polymorph Screening and Dissolution Alteration.

PubMed

Schrode, Benedikt; Bodak, Brigitta; Riegler, Hans; Zimmer, Andreas; Christian, Paul; Werzer, Oliver

2017-09-30

Solubility enhancement and thus higher bioavailability are of great importance and a constant challenge in pharmaceutical research whereby polymorph screening and selection is one of the most important tasks. A very promising approach for polymorph screening is solvent vapor annealing where a sample is exposed to an atmosphere saturated with molecules of a specific chemical/solvent. In this work, amorphous carbamazepine thin films were prepared by spin coating, and the transformation into crystalline forms under exposure to solvent vapors was investigated. Employing grazing incidence X-ray diffraction, four distinct carbamazepine polymorphs, a solvate, and hydrates could be identified, while optical microscopy showed mainly spherulitic morphologies. In vitro dissolution experiments revealed different carbamazepine release from the various thin-film samples containing distinct polymorphic compositions: heat treatment of amorphous samples at 80 °C results in an immediate release; samples exposed to EtOH vapors show a drug release about 5 times slower than this immediate one; and all the others had intermediate release profiles. Noteworthy, even the sample of slowest release has a manifold faster release compared to a standard powder sample demonstrating the capabilities of thin-film preparation for faster drug release in general. Despite the small number of samples in this screening experiment, the results clearly show how solvent vapor annealing can assist in identifying potential polymorphs and allows for estimating their impact on properties like bioavailability.

Association of transforming growth-factor alpha gene polymorphisms with nonsyndromic cleft palate only (CPO)

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

Shiang, R.; Lidral, A.C.; Ardinger, H.H.

1993-10-01

Genetic analysis and tissue-specific expression studies support a role for transforming growth-factor alpha (TGFA) in craniofacial development. Previous studies have confirmed an association of alleles for TGFA with nonsyndromic cleft lip with or without cleft palate (CL/P) in humans. The authors carried out a retrospective association study to determine whether specific allelic variants of the TGFA gene are also associated with cleft palate only (CPO). The PCR products from 12 overlapping sets of primers to the TGFA cDNA were examined by using single-strand conformational polymorphism analysis. Four DNA polymorphic sites for TGFA were identified in the 3[prime] untranslated region ofmore » the TGFA gene. These variants, as well as previously identified RFLPs for TGFA, were characterized in case and control populations for CPO by using X[sup 2] analysis. A significant association between alleles of TGFA and CPO was identified which further supports a role for this gene as one of the genetic determinants of craniofacial development. Sequence analysis of the variants disclosed a cluster of three variable sites within 30 bp of each other in the 3[prime] untranslated region previously associated with an antisense transcript. These studies extend the role for TGFA in craniofacial morphogenesis and support an interrelated mechanism underlying nonsyndromic forms of CL/P. 46 refs., 3 figs., 3 tabs.« less

An NQR Study of TNT Characteristics.

DTIC Science & Technology

1977-09-01

RDX , HMX , a r d some of t he heavy me t al 3~~: id~.s h~~’n for rn.nn ye.~rs been use d as rn~~lit~~ry nii p lns i n’t-~~~~, Thr p h y s i c a l...ambient temperatures of more than one coexisting crystal phase. This polymorphism is known to occur in TNT , HMX and PbN3, and is responsible for a...specific problems of TNT polymorphism and phase transitions were researched . This is one of the problems which is relevant to present day concerns . The

The polymorphic and mesomorphic behavior of four esters of cholesterol.

NASA Technical Reports Server (NTRS)

Merritt, W. G.; Cole, G. D.; Walker, W. W.

1971-01-01

The techniques of differential scanning calorimetry, X-ray powder diffractometry, and positron annihilation have been used to study the polymorphic and mesomorphic behavior of the following esters of cholesterol: cholesteryl formate, cholesteryl butyrate, cholesteryl benzoate, and cholesteryl cinnamate. Each of these compounds exhibits a single mesophase of the cholesteric type. The solid phase formed from the melt for each ester was observed to be structurally different from the solid phase obtained from solution. Solvents from which the solution-grown samples were crystallized were as follows: cholesteryl formate and cholesteryl butyrate from acetone, cholesteryl benzoate from benzene, and cholesteryl cinnamate from 2-butanone.

In situ Observation of Phase Transformation in MnAl(C) Magnetic Materials

PubMed Central

Si, Ping-Zhan; Qian, Hui-Dong; Choi, Chul-Jin; Park, Jihoon; Han, Sangho; Ge, Hong-Liang; Shinde, Kiran P.

2017-01-01

The phase transformation in two modes, including both displacive and massive growth of τ-phase from ε-MnAl(C), was observed by in situ transmission electron microscopy. The exact temperature range for different phase transformation modes was determined by magnetic measurements. The displacive growth of ε→τ in Mn54Al46 (or Mn54Al46C2.44) occurs at temperatures below 650 K (or 766 K), above which both modes coexist. One-third or less of the ε-phase can be transformed into τ-phase via displacive mode while the remaining two-thirds or more via massive mode. In bulk τ-phase, most τ-nanocrystals formed via displacive mode are distributed in the matrix of large τ-grains that formed via massive mode. The typical massive growth rate of the τ-phase is 8–60 nm/s, while the displacive growth rate is low. A more complete understanding of the ε→τ phase transformations in the MnAl-based magnets was provided in this work, based on which the annealing process for ε→τ was optimized and thus high purity τ-phase with high saturation magnetization was obtained. PMID:28858231

Nanoscale multiphase phase field approach for stress- and temperature-induced martensitic phase transformations with interfacial stresses at finite strains

NASA Astrophysics Data System (ADS)

Basak, Anup; Levitas, Valery I.

2018-04-01

A thermodynamically consistent, novel multiphase phase field approach for stress- and temperature-induced martensitic phase transformations at finite strains and with interfacial stresses has been developed. The model considers a single order parameter to describe the austenite↔martensitic transformations, and another N order parameters describing N variants and constrained to a plane in an N-dimensional order parameter space. In the free energy model coexistence of three or more phases at a single material point (multiphase junction), and deviation of each variant-variant transformation path from a straight line have been penalized. Some shortcomings of the existing models are resolved. Three different kinematic models (KMs) for the transformation deformation gradient tensors are assumed: (i) In KM-I the transformation deformation gradient tensor is a linear function of the Bain tensors for the variants. (ii) In KM-II the natural logarithms of the transformation deformation gradient is taken as a linear combination of the natural logarithm of the Bain tensors multiplied with the interpolation functions. (iii) In KM-III it is derived using the twinning equation from the crystallographic theory. The instability criteria for all the phase transformations have been derived for all the kinematic models, and their comparative study is presented. A large strain finite element procedure has been developed and used for studying the evolution of some complex microstructures in nanoscale samples under various loading conditions. Also, the stresses within variant-variant boundaries, the sample size effect, effect of penalizing the triple junctions, and twinned microstructures have been studied. The present approach can be extended for studying grain growth, solidifications, para↔ferro electric transformations, and diffusive phase transformations.

Polymorphism of the bivalent metal vanadates MeV 2O 6 ( Me = Mg, Ca, Mn, Co, Ni, Cu, Zn, Cd)

NASA Astrophysics Data System (ADS)

Mocała, Krzysztof; Ziółkowski, Jacek

1987-08-01

Based on the literature data, our former findings and additional DTA and high-temperature X-ray studies performed for CdV 2O 6, MgV 2O 6, and MnV 2O 6, a consistent scheme of the phase transformations of the MeV 2O 6 ( Me = Mg, Ca, Mn, Co, Ni, Cu, Zn, Cd) metavanadates is constructed at normal pressure between room temperature and melting points. Three types of structures exist for the considered compounds: brannerite type (B), pseudobrannerite type (P), and NiV 2O 6 type (N). The following phase transformations have been observed: Me = Mg, B → P at 535°C; Me = Mn, B → P at 540°C; Me = Co, N → B at 660°C; Me = Cu, B (with triclinic distortion) → B at 625°C (secondary order); and Me = Cd, B → P at 170°. CaV 2O 6P, NiV 2O 6N, and ZnV 2O 6B exist in unique form in the entire temperature range. P-form seems to be favored by Me of larger ionic radii. N-form seems to appear at a peculiar d-shell structure and small Me size. Preliminary explanation of the dependence of the structure type on Me size is offered. New X-ray data are given for CdV 2O 6B, CdV 2O 6P, MgV 2O 6B, MgV 2O 6P, and MnV 2O 6P.

Deformation and Failure Mechanisms of Shape Memory Alloys

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

Daly, Samantha Hayes

2015-04-15

The goal of this research was to understand the fundamental mechanics that drive the deformation and failure of shape memory alloys (SMAs). SMAs are difficult materials to characterize because of the complex phase transformations that give rise to their unique properties, including shape memory and superelasticity. These phase transformations occur across multiple length scales (one example being the martensite-austenite twinning that underlies macroscopic strain localization) and result in a large hysteresis. In order to optimize the use of this hysteretic behavior in energy storage and damping applications, we must first have a quantitative understanding of this transformation behavior. Prior resultsmore » on shape memory alloys have been largely qualitative (i.e., mapping phase transformations through cracked oxide coatings or surface morphology). The PI developed and utilized new approaches to provide a quantitative, full-field characterization of phase transformation, conducting a comprehensive suite of experiments across multiple length scales and tying these results to theoretical and computational analysis. The research funded by this award utilized new combinations of scanning electron microscopy, diffraction, digital image correlation, and custom testing equipment and procedures to study phase transformation processes at a wide range of length scales, with a focus at small length scales with spatial resolution on the order of 1 nanometer. These experiments probe the basic connections between length scales during phase transformation. In addition to the insights gained on the fundamental mechanisms driving transformations in shape memory alloys, the unique experimental methodologies developed under this award are applicable to a wide range of solid-to-solid phase transformations and other strain localization mechanisms.« less

Pressure-induced transformations in amorphous silicon: A computational study

NASA Astrophysics Data System (ADS)

Garcez, K. M. S.; Antonelli, A.

2014-02-01

We study the transformations between amorphous phases of Si through molecular simulations using the environment dependent interatomic potential (EDIP) for Si. Our results show that upon pressure, the material undergoes a transformation from the low density amorphous (LDA) Si to the high density amorphous (HDA) Si. This transformation can be reversed by decompressing the material. This process, however, exhibits clear hysteresis, suggesting that the transformation LDA ↔ HDA is first-order like. The HDA phase is predominantly five-fold coordinated, whereas the LDA phase is the normal tetrahedrally bonded amorphous Si. The HDA phase at 400 K and 20 GPa was submitted to an isobaric annealing up to 800 K, resulting in a denser amorphous phase, which is structurally distinct from the HDA phase. Our results also show that the atomic volume and structure of this new amorphous phase are identical to those of the glass obtained by an isobaric quenching of the liquid in equilibrium at 2000 K and 20 GPa down to 400 K. The similarities between our results and those for amorphous ices suggest that this new phase is the very high density amorphous Si.

Low Temperature Phase Transformations in Copper-Quenched Ti-44.5Al-8Nb-2.5V Alloy

PubMed Central

Cao, Shouzhen; Xiao, Shulong; Chen, Yuyong; Xu, Lijuan; Wang, Xiaopeng; Han, Jianchao

2017-01-01

In this study, an easily controlled transformation similar to the β + α → β + α + γ and the analysis of metastable phases in a β solidifying Ti-44.5Al-8Nb-2.5V alloy were investigated. Therefore, a liquid alloy copper-quenching followed by annealing at an application temperature (850 °C) has been carried out. Following quenching, a microstructure composed of several supersaturated phases—the basket-weave β0 (βbv) phase, the plate-like α2 (αp) phase and the stripe-like γ (γs) phase—was obtained. In the annealing processes, phase transformations in the prior βbv and αp phases domain corresponded nicely to the β + α → β + α + γ transformation during solidification. Also, in the annealed γs phase, the kinetics of the phase transformations involving the metastable L12 phase was firstly detected by transmission electron microscopy (TEM). The L12 phase had a lattice structure similar to the γ phase, whereas the composition of the phase was similar to the α2 phase. The formation of the γ pre-twin phase with an anti-phase boundary (APB) was detected in the γs phase of the matrix. The orientation relationships between the γs and precipitated: γ (γp) phase are <101]γs//<114]γp, (101¯)γs//(1¯10)γp and (01¯0)γs//(221¯)γp. PMID:28772561

Solid-state transformation of Fe-rich intermetallic phases in Al–5.0Cu–0.6Mn squeeze cast alloy with variable Fe contents during solution heat treatment

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

Lin, Bo; School of Mechanical Engineering, Gui Zhou University, Guiyang 550000; Zhang, Weiwen, E-mail: mewzhang@scut.edu.cn

2015-06-15

The Al–5.0 wt.% Cu–0.6 wt.% Mn alloys with a variable Fe content were prepared by squeeze casting. Optical microscopy (OM), Deep etching technique, scanning electron microscopy(SEM), X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used to examine the solid-state transformation of Fe-rich intermetallics during the solution heat treatment. The results showed that the Chinese script-like α-Fe, Al{sub 6}(FeMn) and needle-like Al{sub 3}(FeMn) phases transform to a new Cu-rich β-Fe (Al{sub 7}Cu{sub 2}(FeMn)) phase during solution heat treatment. The possible reaction and overall transformation kinetics of the solid-state phase transformation for the Fe-rich intermetallics were investigated. - Graphical abstract: Displaymore » Omitted - Highlights: • The α-Fe, Al{sub 6}(FeMn) and Al{sub 3}(FeMn) phases change to the β-Fe phases. • Possible reactions of Fe phases during solution heat treatment are discussed. • The overall fractional transformation rate follows an Avrami curve.« less

Hugoniot equation of state and dynamic strength of boron carbide

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

Grady, Dennis E.

Boron carbide ceramics have been particularly problematic in attempts to develop adequate constitutive model descriptions for purposes of analysis of dynamic response in the shock and impact environment. Dynamic strength properties of boron carbide ceramic differ uniquely from comparable ceramics. Furthermore, boron carbide is suspected, but not definitely shown, to undergoing polymorphic phase transformation under shock compression. In the present paper, shock-wave compression measurements conducted over the past 40 years are assessed for the purpose of achieving improved understanding of the dynamic equation of state and strength of boron carbide. In particular, attention is focused on the often ignored Losmore » Alamos National Laboratory (LANL) Hugoniot measurements performed on porous sintered boron carbide ceramic. The LANL data are shown to exhibit two compression anomalies on the shock Hugoniot within the range of 20–60 GPa that may relate to crystallographic structure transitions. More recent molecular dynamics simulations on the compressibility of the boron carbide crystal lattice reveal compression transitions that bear similarities to the LANL Hugoniot results. The same Hugoniot data are complemented with dynamic isentropic compression data for boron carbide extracted from Hugoniot measurements on boron carbide and copper granular mixtures. Other Hugoniot measurements, however, performed on near-full-density boron carbide ceramic differ markedly from the LANL Hugoniot data. These later data exhibit markedly less compressibility and tend not to show comparable anomalies in compressibility. Alternative Hugoniot anomalies, however, are exhibited by the near-full-density data. Experimental uncertainty, Hugoniot strength, and phase transformation physics are all possible explanations for the observed discrepancies. It is reasoned that experimental uncertainty and Hugoniot strength are not likely explanations for the observed differences. The notable mechanistic difference in the processes of shock compression between the LANL data and that of the other studies is the markedly larger inelastic deformation and dissipation experienced in the shock event brought about by compaction of the substantially larger porosity LANL test ceramics. High-pressure diamond anvil cell experiments reveal extensive amorphization, reasoned to be a reversion product of a higher-pressure crystallographic phase, which is a consequence of application of both high pressure and shear deformation to the boron carbide crystal structure. A dependence of shock-induced high-pressure phase transformation in boron carbide on the extent of shear deformation experienced in the shock process offers a plausible explanation for the differences observed in the LANL Hugoniot data on porous ceramic and that of other shock data on near-full-density boron carbide.« less

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

Holt, Allison M; Standaert, Robert F; Jubb, Aaron M

Biological membranes, formed primarily by the self-assembly of complex mixtures of phospholipids, provide a structured scaffold for compartmentalization and structural processes in living cells. The specific physical properties of phospholipid species present in a given membrane play a key role in mediating these processes. Phosphatidylethanolamine (PE), a zwitterionic lipid present in bacterial, yeast, and mammalian cell membranes, is exceptional. In addition to undergoing the standard lipid polymorphic transition between the gel and liquid-crystalline phase, it can also assume an unusual polymorphic state, the inverse hexagonal phase (HII). Divalent cations are among the factors that drive the formation of the HIImore » phase, wherein the lipid molecules form stacked tubular structures by burying the hydrophilic head groups and exposing the hydrophobic tails to the bulk solvent. Most biological membranes contain a lipid species capable of forming the HII state suggesting that such lipid polymorphic structural states play an important role in structural biological processes such as membrane fusion. In this study, the interactions between Mg2+ and biomimetic bacterial cell membranes composed of PE and phosphatidylglycerol (PG) were probed using differential scanning calorimetry (DSC), small-angle x-ray scattering (SAXS), and fluorescence spectroscopy. The lipid phase transitions were examined at varying ratios of PE to PG and upon exposure to physiologically relevant concentrations of Mg2+. An understanding of these basic interactions enhances our understanding of membrane dynamics and how membrane-mediated structural changes may occur in vivo.« less

Phase transitions of sodium niobate powder and ceramics, prepared by solid state synthesis

NASA Astrophysics Data System (ADS)

Koruza, J.; Tellier, J.; Malič, B.; Bobnar, V.; Kosec, M.

2010-12-01

Phase transitions of sodium niobate, prepared by the solid state synthesis method, were examined using dielectric measurements, differential scanning calorimetry, and high temperature x-ray diffraction, in order to contribute to the clarification of its structural behavior below 400 °C. Four phase transitions were detected in the ceramic sample using dielectric measurements and differential scanning calorimetry and the obtained temperatures were in a good agreement with previous reports for the transitions of the P polymorph. The anomaly observed by dielectric measurements in the vicinity of 150 °C was frequency dependent and could be related to the dynamics of the ferroelectric nanoregions. The phase transitions of the as-synthesized NaNbO3 powder were investigated using differential scanning calorimetry and high temperature x-ray diffraction. The results show the existence of the Q polymorph at room temperature, not previously reported for the powder, which undergoes a transition to the R polymorph upon heating through a temperature region between 265 and 326.5 °C. This transition is mainly related to the displacement of Na into a more symmetric position and a minor change in the tilting system. The structures at room temperature, 250, 300, and 420 °C were refined by the Rietveld method and the evolution of the tilting system of the octahedral network and cationic displacement are reported.

Preliminary Reports, Memoranda and Technical Notes of the Materials Research Council Summer Conference La Jolla, California,

DTIC Science & Technology

1980-07-01

are many possible sources of acoustic emission. Some examples are, fracture of brittle particles , martensitic phase transformations , twinning, grain...Model for Some Martensitic Phase Transformations B. Budiansky .............. ........ . .... 374 ! TITLE PAGE S Fracture Toughness and Tensile Strength...the stress-induced phase transformation of a second phase of embedded particles such as zirconia. In a way which is not clearly understood, the zone of

Relationships Between the Phase Transformation Kinetics, Texture Evolution, and Microstructure Development in a 304L Stainless Steel Under Biaxial Loading Conditions: Synchrotron X-ray and Electron Backscatter Diffraction Studies

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

Cakmak, Ercan; Choo, Hahn; Kang, Jun-Yun

2015-02-11

The relationships between the martensitic phase transformation kinetics, texture evolution, and the microstructure development in the parent austenite phase were studied for a 304L stainless steel that exhibits the transformation-induced plasticity effect under biaxial loading conditions at ambient temperature. The applied loading paths included: pure torsion, simultaneous biaxial torsion/tension, simultaneous biaxial torsion/compression, and stepwise loading of tension followed by torsion (i.e., first loading by uniaxial tension and then by pure torsion in sequence). Synchrotron X-ray and electron backscatter diffraction techniques were used to measure the evolution of the phase fractions, textures, and microstructures as a function of the applied strains.more » The influence of loading character and path on the changes in martensitic phase transformation kinetics is discussed in the context of (1) texture-transformation relationship and the preferred transformation of grains belonging to certain texture components over the others, (2) effects of axial strains on shear band evolutions, and (3) volume changes associated with martensitic transformation.« less

Pressure-Induced Polymerization of LiN(CN) 2

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

Keefer, Derek W.; Gou, Huiyang; Purdy, Andrew P.

The high-pressure behavior of lithium dicyanamide (LiN(CN) 2) was studied with in situ Raman and infrared (IR) spectroscopies, and synchrotron angle-dispersive powder X-ray diffraction (PXRD) in a diamond anvil cell (DAC) to 22 GPa. The fundamental vibrational modes associated with molecular units were assigned using a combination of experimental data and density functional perturbation theory. Some low-frequency modes were observed for the first time. On the basis of spectroscopic and diffraction data, we suggest a polymorphic phase transformation at ~8 GPa, wherein dicyanamide ions remain as discrete molecular species. Above ca. 18 GPa, dicyanamide units polymerize, forming a largely disorderedmore » network, and the extent of polymerization may be increased by annealing at elevated temperature. The polymerized product consists of tricyanomelaminate-like groups containing sp 2-hybidized carbon–nitrogen bonds and exhibits a visible absorption edge near 540 nm. The product is recoverable to ambient conditions but is not stable in air/moisture.« less

High-pressure minerals in shocked meteorites

NASA Astrophysics Data System (ADS)

Tomioka, Naotaka; Miyahara, Masaaki

2017-09-01

Heavily shocked meteorites contain various types of high-pressure polymorphs of major minerals (olivine, pyroxene, feldspar, and quartz) and accessory minerals (chromite and Ca phosphate). These high-pressure minerals are micron to submicron sized and occur within and in the vicinity of shock-induced melt veins and melt pockets in chondrites and lunar, howardite-eucrite-diogenite (HED), and Martian meteorites. Their occurrence suggests two types of formation mechanisms (1) solid-state high-pressure transformation of the host-rock minerals into monomineralic polycrystalline aggregates, and (2) crystallization of chondritic or monomineralic melts under high pressure. Based on experimentally determined phase relations, their formation pressures are limited to the pressure range up to 25 GPa. Textural, crystallographic, and chemical characteristics of high-pressure minerals provide clues about the impact events of meteorite parent bodies, including their size and mutual collision velocities and about the mineralogy of deep planetary interiors. The aim of this article is to review and summarize the findings on natural high-pressure minerals in shocked meteorites that have been reported over the past 50 years.

Vibrational Spectroscopic Studies of Reduced-Sensitivity RDX under Static Compression

NASA Astrophysics Data System (ADS)

Wong, Chak

2005-07-01

Explosives formulations with Reduced- Sensitivity RDX showed reduced shock sensitivity using NOL Large Scale Gap Test, compared with similar formulations using normal RDX. Molecular processes responsible for the reduction of sensitivity are unknown and are crucial for formulation development. Vibrational spectroscopy at static high pressure may shed light to the mechanisms responsible for the reduced shock sensitivity as shown by the NOL Large Scale Gap Test. SIRDX, a form of Reduced- Sensitivity RDX, was subjected to static compression at ambient temperature in a Merrill-Bassett sapphire cell from ambient to about 6 GPa. The spectroscopic techniques used were Raman and Fourier-Transformed IR (FTIR). The pressure dependence of the Raman mode frequencies of SIRDX was determined and compared with that of normal RDX. The behavior of SIRDX near the pressure at which normal RDX, at ambient temperature, undergoes a phase transition from the α to the γ polymorph will be presented. Implications to the reduction in sensitivity will be discussed.

MC3, Version 1

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

Cawkwell, Marc Jon

2016-09-09

The MC3 code is used to perform Monte Carlo simulations in the isothermal-isobaric ensemble (constant number of particles, temperature, and pressure) on molecular crystals. The molecules within the periodic simulation cell are treated as rigid bodies, alleviating the requirement for a complex interatomic potential. Intermolecular interactions are described using generic, atom-centered pair potentials whose parameterization is taken from the literature [D. E. Williams, J. Comput. Chem., 22, 1154 (2001)] and electrostatic interactions arising from atom-centered, fixed, point partial charges. The primary uses of the MC3 code are the computation of i) the temperature and pressure dependence of lattice parameters andmore » thermal expansion coefficients, ii) tensors of elastic constants and compliances via the Parrinello and Rahman’s fluctuation formula [M. Parrinello and A. Rahman, J. Chem. Phys., 76, 2662 (1982)], and iii) the investigation of polymorphic phase transformations. The MC3 code is written in Fortran90 and requires LAPACK and BLAS linear algebra libraries to be linked during compilation. Computationally expensive loops are accelerated using OpenMP.« less

Polyamorphism of D-mannitol

NASA Astrophysics Data System (ADS)

Zhu, Men; Yu, Lian

2017-06-01

Polymorphism is common in the crystalline state but rare and even controversial in the liquid or glassy state. Among molecular substances, only two are major contenders for materials that exhibit the phenomenon, including the famous case of water with its low- and high-density amorphous (LDA and HDA) ices . We report that the same phenomenon exists in another extensively hydrogen-bonded system, D-mannitol. Under the ambient pressure, D-mannitol's supercooled liquid spontaneously transforms to another amorphous phase of lower energy, larger volume (2.1%), and stronger hydrogen bonds. This transition is similar to water's HDA to LDA transition and shows the same anomaly of heat release coupled with volume expansion. In both systems, polyamorphism appears to arise from the competing demands of hydrogen bonds (loose packing) and van der Waals forces (close packing). D-mannitol is expected to play an important role as a new system for investigating polyamorphic transitions and suggests a more general occurrence of the phenomenon than the current literature indicates in systems with extensive hydrogen bonds (network bonds in general).

Study on stress-strain response of multi-phase TRIP steel under cyclic loading

NASA Astrophysics Data System (ADS)

Dan, W. J.; Hu, Z. G.; Zhang, W. G.; Li, S. H.; Lin, Z. Q.

2013-12-01

The stress-strain response of multi-phase TRIP590 sheet steel is studied in cyclic loading condition at room temperature based on a cyclic phase transformation model and a multi-phase mixed kinematic hardening model. The cyclic martensite transformation model is proposed based on the shear-band intersection, where the repeat number, strain amplitude and cyclic frequency are used to control the phase transformation process. The multi-phase mixed kinematic hardening model is developed based on the non-linear kinematic hardening rule of per-phase. The parameters of transformation model are identified with the relationship between the austenite volume fraction and the repeat number. The parameters in Kinematic hardening model are confirmed by the experimental hysteresis loops in different strain amplitude conditions. The responses of hysteresis loop and stress amplitude are evaluated by tension-compression data.

Investigation of the Formation Process of Two Piracetam Cocrystals during Grinding

PubMed Central

Rehder, Sönke; Klukkert, Marten; Löbmann, Korbinian A. M.; Strachan, Clare J.; Sakmann, Albrecht; Gordon, Keith; Rades, Thomas; Leopold, Claudia S.

2011-01-01

Cocrystal formation rates during dry grinding and liquid-assisted grinding were investigated by X-ray powder diffractometry and Raman spectroscopy. Two polymorphic forms of piracetam were used to prepare known piracetam cocrystals as model substances, i.e., piracetam-citric acid and piracetam-tartaric acid cocrystals. Raman spectroscopy in combination with principal component analysis was used to visualize the cocrystal formation pathways. During dry grinding, cocrystal formation appeared to progress via an amorphous intermediate stage, which was more evident for the piracetam-citric acid than for the piracetam-tartaric acid cocrystal. It was shown that liquid-assisted grinding led to faster cocrystal formation than dry grinding, which may be explained by the higher transformation rate due to the presence of liquid. The cocrystal formation rate did not depend on the applied polymorphic form of the piracetam and no polymorphic cocrystals were obtained. PMID:24309304

Evaluation of Potential Energy Loss Reduction and Savings for U. S. Army Electrical Distribution Systems

DTIC Science & Technology

1993-09-01

Different Size Transformers (Per Transformer ) 41 15 Additional Energy Losses for Mis-Sized Transformers (Per Transformer ) 42 16 Power System ...directly affects the amount of neutral line power loss in the system . Since most Army three-phase loads are distribution transformers spread out over a...61 Balancing Three-Phase Loads Balancing Feeder Circuit Loads Power Factor Correction Optimal Transformer Sizing Conductor Sizing Combined

Holotransformations of bacterial colonies and genome cybernetics

NASA Astrophysics Data System (ADS)

Ben-Jacob, Eshel; Tenenbaum, Adam; Shochet, Ofer; Avidan, Orna

1994-01-01

We present a study of colony transformations during growth of Bacillus subtilis under adverse environmental conditions. It is a continuation of our pilot study of “Adaptive self-organization during growth of bacterial colonies” (Physica A 187 (1992) 378). First we identify and describe the transformations pathway, i.e. the excitation of the branching modes from Bacillus subtilis 168 (grown under diffusion limited conditions) and the phase transformations between the tip-splitting phase (phase T) and the chiral phase (phase C) which belong to the same mode. This pathway shows the evolution of complexity as the bacteria are exposed to adverse growth conditions. We present the morphology diagram of phases T and C as a function of agar concentration and pepton level. As expected, the growth of phase T is ramified (fractal-like or DLA-like) at low pepton level (about 1 g/1) and turns compact at high pepton level (about 10 g/1). The growth of phase C is also ramified at low pepton level and turns denser and finally compact as the pepton level increases. Generally speaking, the colonies develop more complex patterns and higher micro-level organization for more adverse environments. We use the growth velocity as a response function to describe the growth. At low agar concentration (and low pepton level) phase C grows faster than phase T, and for a high agar concentration (about 2%) phase T grows faster. We observe colony transformations between the two phases (phase transformations). They are found to be consistent with the “fastest growing morphology” selection principle adopted from azoic systems. The transformations are always from the slower phase to the faster one. Hence, we observe T→ C transformations at low agar concentrations and C→ T transformations at high agar concentrations. We have observed both localized and extended transformations. Usually, the transformations are localized for more adverse growth conditions, and extended for growth conditions close to the boundaries between morphologies. We have observed also transformations between different branching modes, as well as transformations via virtual states. Motivated by the contemporary knowledge about phages and plasmids, we postulate a theoretical framework to comply with our experimental findings. We explain our observations using these assumptions as well as our proposal of co-mutations and auto-catalytic mutations as presented in the above mentioned pilot paper. This theoretical framework is a part of the new evolving picture of genome cybernetics. We also discuss the concept of adaptive genome changes which are based on pre-existing knowledge as well as the concept of genetic learning. i.e. changes (in response to a new problem) which develop the potential for adaptive genome changes. These concepts follow naturally if the picture of genome cybernetics is accepted. We conclude with a discussion of the implications and with further predictions (to be tested experimentally) derived from our assumptions.

Electron backscatter diffraction studies of focused ion beam induced phase transformation in cobalt

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

Jones, H.G., E-mail: helen.jones@npl.co.uk

A focused ion beam microscope was used to induce cubic to hexagonal phase transformation in a cobalt alloy, of similar composition to that of the binder phase in a hardmetal, in a controlled manner at 0°, 45° and 80° ion incident angles. The cobalt had an average grain size of ~ 20 μm, allowing multiple orientations to be studied, exposed to a range of doses between 6 × 10{sup 7} and 2 × 10{sup 10} ions/μm{sup 2}. Electron backscatter diffraction (EBSD) was used to determine the original and induced phase orientations, and area fractions, before and after the ion beammore » exposure. On average, less phase transformation was observed at higher incident angles and after lower ion doses. However there was an orientation effect where grains with an orientation close to (111) planes were most susceptible to phase transformation, and (101) the least, where grains partially and fully transformed at varying ion doses. - Highlights: •Ion-induced phase change in FCC cobalt was observed at multiple incidence angles. •EBSD was used to study the relationship between grain orientation and transformation. •Custom software analysed ion dose and phase change with respect to grain orientation. •A predictive capability of ion-induced phase change in cobalt was enabled.« less

Interleukin-1 gene polymorphisms in chronic gastritis patients infected with Helicobacter pylori as risk factors of gastric cancer development.

PubMed

Hnatyszyn, Andrzej; Wielgus, Karolina; Kaczmarek-Rys, Marta; Skrzypczak-Zielinska, Marzena; Szalata, Marlena; Mikolajczyk-Stecyna, Joanna; Stanczyk, Jerzy; Dziuba, Ireneusz; Mikstacki, Adam; Slomski, Ryszard

2013-12-01

Epidemiological investigations indicated association of the Helicobacter pylori infections with the occurrence of inflammatory conditions of the gastric mucosa and development of chronic gastritis and intestinal type of gastric cancer. IL1A and IL1B genes have been proposed as key factors in determining risk of gastritis and malignant transformation. The aim of this paper was to evaluate association of interleukin-1 gene polymorphisms with chronic gastritis, atrophy, intestinal metaplasia, dysplasia and intestinal type of gastric cancer in H. pylori-infected patients. Patients subjected to analysis represent group of 144 consecutive cases that suffered from dyspepsia with coexisting infection of H. pylori and chronic gastritis, chronic atrophic gastritis, intestinal metaplasia, dysplasia or gastric cancer. Molecular studies involved analysis of -889C>T polymorphism of IL1A gene and +3954C>T polymorphism of IL1B gene. Statistical analysis of association of polymorphism -889C>T of gene IL1A with changes in gastric mucosa showed lack of significance, whereas +3954C>T polymorphism of IL1B gene showed significant association. Frequency of allele T of +3954C>T polymorphism of IL1B gene was higher in group of patients with chronic gastritis, atrophy, intestinal metaplasia, dysplasia or intestinal type of gastric cancer (32.1 %) as compared with population group (23 %), χ(2) = 4.61 and p = 0.03. This corresponds to odds ratio: 1.58, 95 % CI: 1.04-2.4. Our results indicate that +3954C>T polymorphism of IL1B gene increase susceptibility to inflammatory response of gastric mucosa H. pylori-infected patients and plays a significant role in the development of chronic gastritis, atrophy, intestinal metaplasia, dysplasia and the initiation of carcinogenesis.

Self-Limited Growth in Pentacene Thin Films

PubMed Central

2017-01-01

Pentacene is one of the most studied organic semiconducting materials. While many aspects of the film formation have already been identified in very thin films, this study provides new insight into the transition from the metastable thin-film phase to bulk phase polymorphs. This study focuses on the growth behavior of pentacene within thin films as a function of film thickness ranging from 20 to 300 nm. By employing various X-ray diffraction methods, combined with supporting atomic force microscopy investigations, one crystalline orientation for the thin-film phase is observed, while three differently tilted bulk phase orientations are found. First, bulk phase crystallites grow with their 00L planes parallel to the substrate surface; second, however, crystallites tilted by 0.75° with respect to the substrate are found, which clearly dominate the former in ratio; third, a different bulk phase polymorph with crystallites tilted by 21° is found. The transition from the thin-film phase to the bulk phase is rationalized by the nucleation of the latter at crystal facets of the thin-film-phase crystallites. This leads to a self-limiting growth of the thin-film phase and explains the thickness-dependent phase behavior observed in pentacene thin films, showing that a large amount of material is present in the bulk phase much earlier during the film growth than previously thought. PMID:28287698

Self-Limited Growth in Pentacene Thin Films.

PubMed

Pachmajer, Stefan; Jones, Andrew O F; Truger, Magdalena; Röthel, Christian; Salzmann, Ingo; Werzer, Oliver; Resel, Roland

2017-04-05

Pentacene is one of the most studied organic semiconducting materials. While many aspects of the film formation have already been identified in very thin films, this study provides new insight into the transition from the metastable thin-film phase to bulk phase polymorphs. This study focuses on the growth behavior of pentacene within thin films as a function of film thickness ranging from 20 to 300 nm. By employing various X-ray diffraction methods, combined with supporting atomic force microscopy investigations, one crystalline orientation for the thin-film phase is observed, while three differently tilted bulk phase orientations are found. First, bulk phase crystallites grow with their 00L planes parallel to the substrate surface; second, however, crystallites tilted by 0.75° with respect to the substrate are found, which clearly dominate the former in ratio; third, a different bulk phase polymorph with crystallites tilted by 21° is found. The transition from the thin-film phase to the bulk phase is rationalized by the nucleation of the latter at crystal facets of the thin-film-phase crystallites. This leads to a self-limiting growth of the thin-film phase and explains the thickness-dependent phase behavior observed in pentacene thin films, showing that a large amount of material is present in the bulk phase much earlier during the film growth than previously thought.

Self-assembly of hard helices: a rich and unconventional polymorphism.

PubMed

Kolli, Hima Bindu; Frezza, Elisa; Cinacchi, Giorgio; Ferrarini, Alberta; Giacometti, Achille; Hudson, Toby S; De Michele, Cristiano; Sciortino, Francesco

2014-11-07

Hard helices can be regarded as a paradigmatic elementary model for a number of natural and synthetic soft matter systems, all featuring the helix as their basic structural unit, from natural polynucleotides and polypeptides to synthetic helical polymers, and from bacterial flagella to colloidal helices. Here we present an extensive investigation of the phase diagram of hard helices using a variety of methods. Isobaric Monte Carlo numerical simulations are used to trace the phase diagram; on going from the low-density isotropic to the high-density compact phases a rich polymorphism is observed, exhibiting a special chiral screw-like nematic phase and a number of chiral and/or polar smectic phases. We present full characterization of the latter, showing that they have unconventional features, ascribable to the helical shape of the constituent particles. Equal area construction is used to locate the isotropic-to-nematic phase transition, and the results are compared with those stemming from an Onsager-like theory. Density functional theory is also used to study the nematic-to-screw-nematic phase transition; within the simplifying assumption of perfectly parallel helices, we compare different levels of approximation, that is second- and third-virial expansions and a Parsons-Lee correction.

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

Weese, R K; Burnham, A K; Maienschein, J L

Dimensional changes related to temperature cycling of the beta and delta polymorphs of HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) are important for a variety of applications. The coefficient of thermal expansion (CTE) of the beta and delta phases are measured and reported in this work over a temperature range of -20 C to 215 C. In addition, dimensional changes associated with the phase transition were measured, both through the transition and back down. Initially, differential scanning calorimetry (DSC) was used to investigate back conversion of the delta phase to the beta phase polymorph. The most successful approach was first to measure the amount ofmore » the beta to delta conversion, then after a given cooling period a repeat analysis, to measure the heat consumed by a second pass through the beta to delta phase transition. In addition, TMA is used to measure the dimensional change of a 0.20-gram sample of HMX during its initial heating and then three days later during a 2nd heating. This HMX shows the beta to delta phase transition a second time, thereby confirming the back conversion from delta to beta phase HMX.« less

The correlation of local deformation and stress-assisted local phase transformations in MMC foams

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

Berek, H., E-mail: harry.berek@ikgb.tu-freiberg.de; Ballaschk, U.; Aneziris, C.G.

2015-09-15

Cellular structures are of growing interest for industry, and are of particular importance for lightweight applications. In this paper, a special case of metal matrix composite foams (MMCs) is investigated. The investigated foams are composed of austenitic steel exhibiting transformation induced plasticity (TRIP) and magnesia partially stabilized zirconia (Mg-PSZ). Both components exhibit martensitic phase transformation during deformation, thus generating the potential for improved mechanical properties such as strength, ductility, and energy absorption capability. The aim of these investigations was to show that stress-assisted phase transformations within the ceramic reinforcement correspond to strong local deformation, and to determine whether they canmore » trigger martensitic phase transformations in the steel matrix. To this end, in situ interrupted compression experiments were performed in an X-ray computed tomography device (XCT). By using a recently developed registration algorithm, local deformation could be calculated and regions of interest could be defined. Corresponding cross sections were prepared and used to analyze the local phase composition by electron backscatter diffraction (EBSD). The results show a strong correlation between local deformation and phase transformation. - Graphical abstract: Display Omitted - Highlights: • In situ compressive deformation on MMC foams was performed in an XCT. • Local deformation fields and their gradient amplitudes were estimated. • Cross sections were manufactured containing defined regions of interest. • Local EBSD phase analysis was performed. • Local deformation and local phase transformation are correlated.« less

Combined Determination of Elastic Properties and Structure of Coesite under Simulated Mantle Conditions

NASA Astrophysics Data System (ADS)

Mueller, H. J.; Schilling, F. R.; Lauterjung, J.; Lathe, C.

2001-12-01

The high pressure SiO2-polymorph coesite seems to be an important mineral in the subduction process including crustal material (Chopin, 1984; Schreyer, 1995). The quartz to coesite transition is thus of fundamental importance to understand the processes within a subducting crust. Furthermore, the nature of the quartz to coesite transition is discussed controversially, because high pressure XRD-studies suggest an intermediate phase during the transformation process (Zinn et al., 1997). For the combined determination of elastic properties and structure a cubic multi-anvil high pressure apparatus (MAX80) was used. For the maximum sample volume of 20 mm3 the pressure limit is about 7GPa. The pressure is measured by use of NaCl as an internal pressure marker with calibrated PVT-data. The maximum temperature of about 2,000K is generated by an internal graphite heater and controlled by a thermocouple. The synchrotron beam (100x100 microns) is guided by a collimator through the sample between the anvils. For energy-dispersive X-ray diffraction, a Ge-solid state detector analyses the diffracted white beam at a fixed angle. The compressional and shear wave velocities were determined simultaneously by ultrasonic interferometry inside MAX80. Two of the six anvils are equipped with overtone polished lithium niobate transducers at their rear side, outside the volume under pressure, for generation and detection of ultrasonic waves between 10 and 60 MHz. Different buffer - reflector combinations and transducer arrangements were used to optimize the critical interference between both sample echoes. Therefore MAX80 is equipped for asymmetrical and symmetrical interferometric set-ups, i.e. compressional and shear waves are generated from the same or from two anvils, opposite to each other. We used for our transient measurements 3 natural fine-grained quartzites from Turkey and Germany. As a first step the pressure was increased gradually up to 4GPa at ambient temperature. At each pressure Vp and Vs was measured by ultrasonic interferometry. After reaching a given pressure, temperature was increased. At 4.5GPa and 800\\deg C the phase transition to coesite took place in less than 2 minutes. The fast kinetic of transformation was observed by synchrotron radiation. The compressional wave velocity increased by 30% and the shear wave velocity by 10% during the phase transition. The kinetic of the transition was varied by choosing different pressure and temperature conditions. The transformation with lower kinetic was studied in detail by XRD and ultrasonic interferometry. At 4.2 GPa the transformation could not be observed even above 950\\deg C. At 4.5 GPa and 750\\deg C the transition stopped at about 50% transformation, but transforms complete while increasing temperature to 800\\deg C. After the phase transition monitored by X-ray scattering the sample was quenched and Vp and Vs of coesite was measured at ambient temperatures up to the maximum pressure. Small differences in grain size, shape and in minor graphite contents did not change systematically the PT-conditions and kinetics. In addition to the kinetic and change of elastic properties the pressure and temperature derivatives of elastic properties of coesite will be presented.\\Chopin, C., Contr. Min. Petrol., 86 (1984), 107-118\\Schreyer, W., J. Geophys. Res., 100 (1995), 8,353-8,366\\Zinn P., Lauterjung J., Wirth R. & Hinze E. Zeitschrift für Kristallographie, 212 (1997), 691-698.

Nature and composition of fat bloom from palm kernel stearin and hydrogenated palm kernel stearin compound chocolates.

PubMed

Smith, Kevin W; Cain, Fred W; Talbot, Geoff

2004-08-25

Palm kernel stearin and hydrogenated palm kernel stearin can be used to prepare compound chocolate bars or coatings. The objective of this study was to characterize the chemical composition, polymorphism, and melting behavior of the bloom that develops on bars of compound chocolate prepared using these fats. Bars were stored for 1 year at 15, 20, or 25 degrees C. At 15 and 20 degrees C the bloom was enriched in cocoa butter triacylglycerols, with respect to the main fat phase, whereas at 25 degrees C the enrichment was with palm kernel triacylglycerols. The bloom consisted principally of solid fat and was sharper melting than was the fat in the chocolate. Polymorphic transitions from the initial beta' phase to the beta phase accompanied the formation of bloom at all temperatures.

Probing microstructure and phase evolution of α-MoO 3 nanobelts for sodium-ion batteries by in situ transmission electron microscopy

DOE PAGES

Xia, Weiwei; Xu, Feng; Zhu, Chongyang; ...

2016-07-15

The fundamental electrochemical reaction mechanisms and the phase transformation pathways of layer-structured α-MoO 3 nanobelt during the sodiation/desodiation process to date remain largely unknown. In this study, to observe the real-time sodiation/desodiaton behaviors of α-MoO 3 during electrochemical cycling, we construct a MoO 3 anode sodium-ion battery inside a transmission electron microscope (TEM). Utilizing in situ TEM and electron diffraction pattern (EDP) observation, α-MoO 3 nanobelts are found to undergo a unique multi-step phase transformation. Upon the first sodiation, α-MoO 3 nanobelts initially form amorphous Na xMoO3 phase and are subsequently sodiated into intermediate phase of crystalline NaMoO 2, finallymore » resulting in the crystallized Mo nanograins embedded within the Na 2O matrix. During the first desodiation process, Mo nanograins are firstly re-oxidized into intermediate phase NaMoO 2 that is further transformed into amorphous Na 2MoO 3, resulting in an irreversible phase transformation. Upon subsequent sodiation/desodiation cycles, however, a stable and reversible phase transformation between crystalline Mo and amorphous Na2MoO 3 phases has been revealed. In conclusion, our work provides an in-deepth understanding of the phase transformation pathways of α-MoO 3 nanobelts upon electrochemical sodiation/desodiation processes, with the hope of assistance in designing sodium-ion batteries with enhanced performance.« less

Transformation mechanism of amorphous calcium carbonate into calcite in the sea urchin larval spicule.

PubMed

Politi, Yael; Metzler, Rebecca A; Abrecht, Mike; Gilbert, Benjamin; Wilt, Fred H; Sagi, Irit; Addadi, Lia; Weiner, Steve; Gilbert, P U P A; Gilbert, Pupa

2008-11-11

Sea urchin larval spicules transform amorphous calcium carbonate (ACC) into calcite single crystals. The mechanism of transformation is enigmatic: the transforming spicule displays both amorphous and crystalline properties, with no defined crystallization front. Here, we use X-ray photoelectron emission spectromicroscopy with probing size of 40-200 nm. We resolve 3 distinct mineral phases: An initial short-lived, presumably hydrated ACC phase, followed by an intermediate transient form of ACC, and finally the biogenic crystalline calcite phase. The amorphous and crystalline phases are juxtaposed, often appearing in adjacent sites at a scale of tens of nanometers. We propose that the amorphous-crystal transformation propagates in a tortuous path through preexisting 40- to 100-nm amorphous units, via a secondary nucleation mechanism.

Temperature dependent polymorphism of pyrazinamide: An in situ Raman and DFT study

NASA Astrophysics Data System (ADS)

Sharma, Poornima; Nandi, Rajib; Gangopadhyay, Debraj; Singh, Anurag; Singh, Ranjan K.

2018-02-01

The α and γ polymorphs of drug pyrazinamide have been detected with the help of temperature dependent Raman spectroscopic technique. Pyrazinamide is a very useful drug used for the treatment of tuberculosis (TB) and plays a significant role in destroying the dormant tubercle bacilli which are not destroyed by other common TB drugs. Temperature dependent Raman spectra suggest polymorphic phase change from α → γ form of pyrazinamide between 145 and 146 °C. In situ Raman spectra of pyrazinamide between 145 and 146 °C show the conversion of α → γ form by the shift in Cdbnd O stretching vibration accompanied by several other changes. The phase change is characterized by the breaking of two linear Nsbnd H ⋯ O type hydrogen bonds associated with Cdbnd O stretching vibration in α dimer and formation of one linear Nsbnd H ⋯ N type hydrogen bond along with a weak intramolecular Csbnd H ⋯ O type hydrogen bond in the γ dimer.

Controlling the selective formation of calcium sulfate polymorphs at room temperature.

PubMed

Tritschler, Ulrich; Van Driessche, Alexander E S; Kempter, Andreas; Kellermeier, Matthias; Cölfen, Helmut

2015-03-23

Calcium sulfate is a naturally abundant and technologically important mineral with a broad scope of applications. However, controlling CaSO4 polymorphism and, with it, its final material properties still represents a major challenge, and to date there is no universal method for the selective production of the different hydrated and anhydrous forms under mild conditions. Herein we report the first successful synthesis of pure anhydrite from solution at room temperature. We precipitated calcium sulfate in alcoholic media at low water contents. Moreover, by adjusting the amount of water in the syntheses, we can switch between the distinct polymorphs and fine-tune the outcome of the reaction, yielding either any desired CaSO4 phase in pure state or binary mixtures with predefined compositions. This concept provides full control over phase selection in CaSO4 mineralization and may allow for the targeted fabrication of corresponding materials for use in various areas. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Atomistic to Continuum Multiscale and Multiphysics Simulation of NiTi Shape Memory Alloy

NASA Astrophysics Data System (ADS)

Gur, Sourav

Shape memory alloys (SMAs) are materials that show reversible, thermo-elastic, diffusionless, displacive (solid to solid) phase transformation, due to the application of temperature and/ or stress (/strain). Among different SMAs, NiTi is a popular one. NiTi shows reversible phase transformation, the shape memory effect (SME), where irreversible deformations are recovered upon heating, and superelasticity (SE), where large strains imposed at high enough temperatures are fully recovered. Phase transformation process in NiTi SMA is a very complex process that involves the competition between developed internal strain and phonon dispersion instability. In NiTi SMA, phase transformation occurs over a wide range of temperature and/ or stress (strain) which involves, evolution of different crystalline phases (cubic austenite i.e. B2, different monoclinic variant of martensite i.e. B19', and orthorhombic B19 or BCO structures). Further, it is observed from experimental and computational studies that the evolution kinetics and growth rate of different phases in NiTi SMA vary significantly over a wide spectrum of spatio-temporal scales, especially with length scales. At nano-meter length scale, phase transformation temperatures, critical transformation stress (or strain) and phase fraction evolution change significantly with sample or simulation cell size and grain size. Even, below a critical length scale, the phase transformation process stops. All these aspects make NiTi SMA very interesting to the science and engineering research community and in this context, the present focuses on the following aspects. At first this study address the stability, evolution and growth kinetics of different phases (B2 and variants of B19'), at different length scales, starting from the atomic level and ending at the continuum macroscopic level. The effects of simulation cell size, grain size, and presence of free surface and grain boundary on the phase transformation process (transformation temperature, phase fraction evolution kinetics due to temperature) are also demonstrated herein. Next, to couple and transfer the statistical information of length scale dependent phase transformation process, multiscale/ multiphysics methods are used. Here, the computational difficulty from the fact that the representative governing equations (i.e. different sub-methods such as molecular dynamics simulations, phase field simulations and continuum level constitutive/ material models) are only valid or can be implemented over a range of spatiotemporal scales. Therefore, in the present study, a wavelet based multiscale coupling method is used, where simulation results (phase fraction evolution kinetics) from different sub-methods are linked via concurrent multiscale coupling fashion. Finally, these multiscale/ multiphysics simulation results are used to develop/ modify the macro/ continuum scale thermo-mechanical constitutive relations for NiTi SMA. Finally, the improved material model is used to model new devices, such as thermal diodes and smart dampers.

Solid state characterization and crystal structure from X-ray powder diffraction of two polymorphic forms of ranitidine base.

PubMed

de Armas, Héctor Novoa; Peeters, Oswald M; Blaton, Norbert; Van Gyseghem, Elke; Martens, Johan; Van Haele, Gerrit; Van Den Mooter, Guy

2009-01-01

Ranitidine hydrochloride (RAN-HCl), a known anti-ulcer drug, is the product of reaction between HCl and ranitidine base (RAN-B). RAN-HCl has been extensively studied; however this is not the case of the RAN-B. The solid state characterization of RAN-B polymorphs has been carried out using different analytical techniques (microscopy, thermal analysis, Fourier transform infrared spectrometry in the attenuated total reflection mode, (13)C-CPMAS-NMR spectroscopy and X-ray powder diffraction). The crystal structures of RAN-B form I and form II have been determined using conventional X-ray powder diffraction in combination with simulated annealing and whole profile pattern matching, and refined using rigid-body Rietveld refinement. RAN-B form I is a monoclinic polymorph with cell parameters: a = 7.317(2), b = 9.021(2), c = 25.098(6) A, beta = 95.690(1) degrees and space group P2(1)/c. The form II is orthorhombic: a = 31.252(4), b = 13.052(2), c = 8.0892(11) A with space group Pbca. In RAN-B polymorphs, the nitro group is involved in a strong intramolecular hydrogen bond responsible for the existence of a Z configuration in the enamine portion of the molecules. A tail to tail packing motif can be denoted via intermolecular hydrogen bonds. The crystal structures of RAN-B forms are compared to those of RAN-HCl polymorphs. RAN-B polymorphs are monotropic polymorphic pairs. (c) 2008 Wiley-Liss, Inc. and the American Pharmacists Association

Thermodynamic Stability Analysis of Tolbutamide Polymorphs and Solubility in Organic Solvents.

PubMed

Svärd, Michael; Valavi, Masood; Khamar, Dikshitkumar; Kuhs, Manuel; Rasmuson, Åke C

2016-06-01

Melting temperatures and enthalpies of fusion have been determined by differential scanning calorimetry (DSC) for 2 polymorphs of the drug tolbutamide: FI(H) and FV. Heat capacities have been determined by temperature-modulated DSC for 4 polymorphs: FI(L), FI(H), FII, FV, and for the supercooled melt. The enthalpy of fusion of FII at its melting point has been estimated from the enthalpy of transition of FII into FI(H) through a thermodynamic cycle. Calorimetric data have been used to derive a quantitative polymorphic stability relationship between these 4 polymorphs, showing that FII is the stable polymorph below approximately 333 K, above which temperature FI(H) is the stable form up to its melting point. The relative stability of FV is well below the other polymorphs. The previously reported kinetic reversibility of the transformation between FI(L) and FI(H) has been verified using in situ Raman spectroscopy. The solid-liquid solubility of FII has been gravimetrically determined in 5 pure organic solvents (methanol, 1-propanol, ethyl acetate, acetonitrile, and toluene) over the temperature range 278 to 323 K. The ideal solubility has been estimated from calorimetric data, and solution activity coefficients at saturation in the 5 solvents determined. All solutions show positive deviation from Raoult's law, and all van't Hoff plots of solubility data are nonlinear. The solubility in toluene is well below that observed in the other investigated solvents. Solubility data have been correlated and extrapolated to the melting point using a semiempirical regression model. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Transformation-Induced Diffraction Peak Broadening During Bainitic and Martensitic Transformations Under Small External Loads in a Quenched and Tempered High Strength Steel

NASA Astrophysics Data System (ADS)

Dutta, R. K.; Huizenga, R. M.; Amirthalingam, M.; Hermans, M. J. M.; King, A.; Richardson, I. M.

2013-09-01

In situ phase transformation behavior of a high strength S690QL1 steel during continuous cooling under different mechanical loading conditions has been used to investigate the effect of small external loads on the transformation-induced plasticity during bainitic and martensitic transformations. The results show that during phase transformations, the untransformed austenite undergoes plastic deformation, thereby retarding further transformation to bainite/martensite. This occurs independent of external load.

Polymorphism in the PER3 promoter associates with diurnal preference and delayed sleep phase disorder.

PubMed

Archer, Simon N; Carpen, Jayshan D; Gibson, Mark; Lim, Gim Hui; Johnston, Jonathan D; Skene, Debra J; von Schantz, Malcolm

2010-05-01

To screen the PER3 promoter for polymorphisms and investigate the phenotypic associations of these polymorphisms with diurnal preference, delayed sleep phase disorder/syndrome (DSPD/DSPS), and their effects on reporter gene expression. Interspecific comparison was used to define the approximate extent of the PER3 promoter as the region between the transcriptional start site and nucleotide position -874. This region was screened in DNA pools using PCR and direct sequencing, which was also used to screen DNA from individual participants. The different promoter alleles were cloned into a luciferase expression vector and a deletion library created. Promoter activation was measured by chemiluminescence. N/A. DNA samples were obtained from volunteers with defined diurnal preference (3 x 80, selected from a pool of 1,590), and DSPD patients (n=23). N/A. We verified three single nucleotide polymorphisms (G -320T, C -319A, G -294A), and found a novel variable number tandem repeat (VNTR) polymorphism (-318 1/2 VNTR). The -320T and -319A alleles occurred more frequently in DSPD compared to morning (P = 0.042 for each) or evening types (P = 0.006 and 0.033). The allele combination TA2G was more prevalent in DSPD compared to morning (P 0.033) or evening types (P = 0.002). Luciferase expression driven by the TA2G combination was greater than for the more common GC2A (P < 0.05) and the rarer TA1G (P < 0.001) combinations. Deletion reporter constructs identified two enhancer regions (-703 to -605, and -283 to -80). Polymorphisms in the PER3 promoter could affect its expression, leading to potential differences in the observed functions of PER3.

Switching to nilotinib in patients with chronic myeloid leukemia in chronic phase with molecular suboptimal response to frontline imatinib: SENSOR final results and BIM polymorphism substudy.

PubMed

Miyamura, Koichi; Miyamoto, Toshihiro; Tanimoto, Mitsune; Yamamoto, Kazuhito; Kimura, Shinya; Kawaguchi, Tatsuya; Matsumura, Itaru; Hata, Tomoko; Tsurumi, Hisashi; Saito, Shigeki; Hino, Masayuki; Tadokoro, Seiji; Meguro, Kuniaki; Hyodo, Hideo; Yamamoto, Masahide; Kubo, Kohmei; Tsukada, Junichi; Kondo, Midori; Aoki, Makoto; Okada, Hikaru; Yanada, Masamitsu; Ohyashiki, Kazuma; Taniwaki, Masafumi

2016-12-01

Optimal management of patients with chronic myeloid leukemia in chronic phase with suboptimal molecular response (MR) to frontline imatinib is undefined. We report final results from SENSOR, which evaluated efficacy/safety of nilotinib in this setting. A substudy assessed whether BIM polymorphisms impacted response to nilotinib. In this single-arm, multicenter study, Japanese patients with suboptimal MR per European LeukemiaNet 2009 criteria (complete cytogenetic response, but not major MR [MMR]) after ≥18 months of frontline imatinib received nilotinib 400mg twice daily for 24 months. MR, BCR-ABL1 mutations/variants, and BIM polymorphisms were evaluated in a central laboratory. Primary endpoint was the MMR rate at 12 months (null hypothesis of 40%). Of 45 patients (median exposure, 22.08 months), 39 completed the study and six discontinued. At 12 and 24 months, 51.1% (95% CI, 35.8%-66.3%) and 66.7% (95% CI, 51.0%-80.0%) achieved MMR, respectively. Cumulative MMR incidence by 24 months was 75.6%. Of 40 patients analyzed, 10 of 12 (83.3%) with and 17 of 28 (60.7%) without BIM polymorphisms achieved MMR at 24 months. The safety profile was manageable with dose reductions and interruptions. Nilotinib provided clinical benefit for patients with suboptimal response to imatinib, and BIM polymorphisms did not influence MMR achievement. ClinicalTrials.gov: NCT01043874. Copyright © 2016 Elsevier Ltd. All rights reserved.

Rationale for the crystallization of titania polymorphs in solution

NASA Astrophysics Data System (ADS)

Kränzlin, N.; Staniuk, M.; Heiligtag, F. J.; Luo, L.; Emerich, H.; van Beek, W.; Niederberger, M.; Koziej, D.

2014-11-01

We use in situ X-ray absorption and diffraction studies to directly monitor the crystallization of different titania polymorphs in one and the same solution. We find that, despite the commonly accepted polymorphic-crossover from anatase to rutile triggered by the critical size of nanoparticles, in the solution their respective nucleation and growth are independent processes. Moreover, we find that 5.9 nm rutile nanoparticles are formed prior to the formation of 8.4 nm anatase nanoparticles. Our results suggest that the origins of this crystallization mechanism lie in the formation of an intermediate non-crystalline phase and in time-dependent changes in the chemical environment.We use in situ X-ray absorption and diffraction studies to directly monitor the crystallization of different titania polymorphs in one and the same solution. We find that, despite the commonly accepted polymorphic-crossover from anatase to rutile triggered by the critical size of nanoparticles, in the solution their respective nucleation and growth are independent processes. Moreover, we find that 5.9 nm rutile nanoparticles are formed prior to the formation of 8.4 nm anatase nanoparticles. Our results suggest that the origins of this crystallization mechanism lie in the formation of an intermediate non-crystalline phase and in time-dependent changes in the chemical environment. Electronic supplementary information (ESI) available: Detailed instructions on the experimental part including set-up, recorded XAS and PXRD raw data and their details. See DOI: 10.1039/c4nr04346d

Impurities block the alpha to omega martensitic transformation in titanium.

PubMed

Hennig, Richard G; Trinkle, Dallas R; Bouchet, Johann; Srinivasan, Srivilliputhur G; Albers, Robert C; Wilkins, John W

2005-02-01

Impurities control phase stability and phase transformations in natural and man-made materials, from shape-memory alloys to steel to planetary cores. Experiments and empirical databases are still central to tuning the impurity effects. What is missing is a broad theoretical underpinning. Consider, for example, the titanium martensitic transformations: diffusionless structural transformations proceeding near the speed of sound. Pure titanium transforms from ductile alpha to brittle omega at 9 GPa, creating serious technological problems for beta-stabilized titanium alloys. Impurities in the titanium alloys A-70 and Ti-6Al-4V (wt%) suppress the transformation up to at least 35 GPa, increasing their technological utility as lightweight materials in aerospace applications. These and other empirical discoveries in technological materials call for broad theoretical understanding. Impurities pose two theoretical challenges: the effect on the relative phase stability, and the energy barrier of the transformation. Ab initio methods calculate both changes due to impurities. We show that interstitial oxygen, nitrogen and carbon retard the transformation whereas substitutional aluminium and vanadium influence the transformation by changing the d-electron concentration. The resulting microscopic picture explains the suppression of the transformation in commercial A-70 and Ti-6Al-4V alloys. In general, the effect of impurities on relative energies and energy barriers is central to understanding structural phase transformations.

Isotropic scalar image visualization of vector differential image data using the inverse Riesz transform.

PubMed

Larkin, Kieran G; Fletcher, Peter A

2014-03-01

X-ray Talbot moiré interferometers can now simultaneously generate two differential phase images of a specimen. The conventional approach to integrating differential phase is unstable and often leads to images with loss of visible detail. We propose a new reconstruction method based on the inverse Riesz transform. The Riesz approach is stable and the final image retains visibility of high resolution detail without directional bias. The outline Riesz theory is developed and an experimentally acquired X-ray differential phase data set is presented for qualitative visual appraisal. The inverse Riesz phase image is compared with two alternatives: the integrated (quantitative) phase and the modulus of the gradient of the phase. The inverse Riesz transform has the computational advantages of a unitary linear operator, and is implemented directly as a complex multiplication in the Fourier domain also known as the spiral phase transform.

Isotropic scalar image visualization of vector differential image data using the inverse Riesz transform

PubMed Central

Larkin, Kieran G.; Fletcher, Peter A.

2014-01-01

X-ray Talbot moiré interferometers can now simultaneously generate two differential phase images of a specimen. The conventional approach to integrating differential phase is unstable and often leads to images with loss of visible detail. We propose a new reconstruction method based on the inverse Riesz transform. The Riesz approach is stable and the final image retains visibility of high resolution detail without directional bias. The outline Riesz theory is developed and an experimentally acquired X-ray differential phase data set is presented for qualitative visual appraisal. The inverse Riesz phase image is compared with two alternatives: the integrated (quantitative) phase and the modulus of the gradient of the phase. The inverse Riesz transform has the computational advantages of a unitary linear operator, and is implemented directly as a complex multiplication in the Fourier domain also known as the spiral phase transform. PMID:24688823

Association of gene polymorphism with serum levels of inflammatory and angiogenic factors in Pakistani patients with age-related macular degeneration.

PubMed

Ambreen, Fareeha; Ismail, Muhammad; Qureshi, Irfan Zia

2015-01-01

To study the association of serum levels of inflammatory mediators and angiogenic factors with genetic polymorphism in Pakistani age-related macular degeneration (AMD) patients. This was a cross-sectional and case-control study that included 90 AMD patients diagnosed through slit-lamp examination, fundoscopy, and ocular coherence tomography. For reference and comparison purposes, 100 healthy age-matched subjects (controls) were also recruited. IL-6, IL-8, VEGF, and CRP levels were estimated in the serum samples of patients and control subjects. Using restriction fragment length polymorphism, single nucleotide polymorphisms were studied in IL-6 (rs1800795, rs1800796, rs1800797), IL-8 (rs4073, rs2227306, rs2227543), VEGF (rs3025039, rs699947), and CRP genes (rs1205, rs1130864). Since the data were obtained from a sample population, the Box-Cox transformation algorithm was applied to reduce heterogeneity of error. Multivariate analyses of variance (M-ANOVA) were applied on the transformed data to investigate the association of serum levels of IL-6, IL-8, VEGF, and CRP with AMD. Genotype and allele frequencies were compared through χ(2) tests applying Hardy-Weinberg equilibrium. The serum concentrations of IL-6 and IL-8, VEGF, and CRP between homozygotes and heterozygotes were compared through one-way ANOVA. Significance level was p<0.05. Compared to control subjects, serum IL-6 (p<0.0001), IL-8 (p<0.0001), VEGF (p<0.0001), and CRP (p<0.0001) levels were significantly elevated in the AMD patients. For rs1800795, patients with the GG genotype showed significantly raised levels of IL-6 compared to those with GC and CC genotypes (p<0.0001). Serum IL-8 levels were significantly higher in patients with the GG genotype compared to the GC and CC genotypes for the single nucleotide polymorphism (SNP) rs2227543 (p<0.002). Similarly, significantly higher VEGF levels were detected for genotype TT for rs3025039 SNP (p<0.038). However, no significant alteration in serum CRP levels was detected in hetero- or homozygotes for rs1205 and rs1130864 SNPs. Serum IL-6, IL-8, and VEGF levels are substantially increased in AMD, and the levels coincide with polymorphism in the respective gene. No such relationship appears to exist with regard to SNPs of CRP.

Analytical Study on the Saturated Polarization Under Electric Field and Phase Equilibrium of Three-Phase Polycrystalline Ferroelectrics by Using the Generalized Inverse-Pole-Figure Model

NASA Astrophysics Data System (ADS)

Ju, Kyong-Sik; Ryo, Hyok-Su; Pak, Sung-Nam; Pak, Chang-Su; Ri, Sung-Guk; Ri, Dok-Hwan

2018-07-01

By using the generalized inverse-pole-figure model, the numbers of crystalline particles involved in different domain-switching near the triple tetragonal-rhombohedral-orthorhombic (T-R-O) points of three-phase polycrystalline ferroelectrics have been analytically calculated and domain-switching which can bring out phase transformations has been considered. Through polarization by an electric field, different numbers of crystalline particles can be involved in different phase transformations. According to the phase equilibrium conditions, the phase equilibrium compositions of the three phases coexisting near the T-R-O triple point have been evaluated from the results of the numbers of crystalline particles involved in different phase transformations.

Structure and Stability of High-Pressure Dolomite with Implications for the Earth's Deep Carbon Cycle

NASA Astrophysics Data System (ADS)

Solomatova, N. V.; Asimow, P. D.

2014-12-01

Carbon is subducted into the mantle primarily in the form of metasomatically calcium-enriched basaltic rock, calcified serpentinites and carbonaceous ooze. The fate of these carbonates in subduction zones is not well understood. End-member CaMg(CO3)2 dolomite typically breaks down into two carbonates at 2-7 GPa, which may further decompose to oxides and CO2-bearing fluid. However, high-pressure X-ray diffraction experiments have recently shown that the presence of iron may be sufficient to stabilize dolomite I to high pressures, allowing the transformation to dolomite II at 17 GPa and subsequently to dolomite III at 35 GPa [1][2]. Such phases may be a principal host for deeply subducted carbon. The structure and equation of state of these high-pressure phases is debated and the effect of varying concentrations of iron is unknown, creating a need for theoretical calculations. Here we compare calculated dolomite structures to experimentally observed phases. Using the Vienna ab-initio simulation package (VASP) interfaced with a genetic algorithm that predicts crystal structures (USPEX), a monoclinic phase with space group 5 ("dolomite sg5") was found for pure end-member dolomite. Dolomite sg5 has a lower energy than reported dolomite structures and an equation of state that resembles that of dolomite III. It is possible that dolomite sg5 is not achieved experimentally due to a large energy barrier and a correspondingly large required volume drop, resulting in the transformation to metastable dolomite II. Due to the complex energy landscape for candidate high-pressure dolomite structures, it is likely that several competing polymorphs exist. Determining the behavior of high-pressure Ca-Mg-Fe(-Mn) dolomite phases in subduction environments is critical for our understanding of the Earth's deep carbon cycle and supercell calculations with Fe substitution are in progress. [1] Mao, Z., Armentrout, M., Rainey, E., Manning, C. E., Dera, P., Prakapenka, V. B., and Kavner, A. (2011). Dolomite III: A new candidate lower mantle carbonate. Geophy. Res. Lett., 38(22). [2] Merlini, M., Crichton, W. A., Hanfland, M., Gemmi, M., Müller, H., Kupenko, I., and Dubrovinsky, L. (2012). Structures of dolomite at ultrahigh pressure and their influence on the deep carbon cycle. Proc. Nat. Acad. Sci., 109(34), 13509-13514.

Determination of the continuous cooling transformation diagram of a high strength low alloyed steel

NASA Astrophysics Data System (ADS)

Kang, Hun Chul; Park, Bong June; Jang, Ji Hun; Jang, Kwang Soon; Lee, Kyung Jong

2016-11-01

The continuous cooling transformation diagram of a high strength low alloyed steel was determined by a dilatometer and microscopic analysis (OM, SEM) as well as thermodynamic analysis. As expected, Widmanstätten ferrite, bainite and martensite coexisted for most cooling rates, which made it difficult to determine the transformation kinetics of individual phases. However, peaks were clearly observed in the dilatometric {d( {LVDT} )}/{dT} curves. By overlapping the {d( {LVDT} )}/{dT} curves, which were determined using various cooling rates, peaks were separated and the peak rate temperatures, as well as the temperature at the start of transformation (5%) and the end of transformation (95%) of an individual phase, were determined. A SEM analysis was also conducted to identify which phase existed and to quantify the volume fraction of each phase. It was confirmed that the additional {d( {LVDT} )}/{dT} curve analysis described the transformation behavior more precisely than the conventional continuous cooling transformation diagram, as determined by the volume measured from the microstructure analysis.

Crystallization kinetics of BaO-Al2O3-SiO2 glasses

NASA Technical Reports Server (NTRS)

Bansal, Narottam P.; Hyatt, Mark J.

1989-01-01

Barium aluminosilicate glasses are being investigated as matrix materials in high-temperature ceramic composites for structural applications. Kinetics of crystallization of two refractory glass compositions in the barium aluminosilicate system were studied by differential thermal analysis (DTA), X-ray diffraction (XRD), and scanning electron microscopy (SEM). From variable heating rate DTA, the crystallization activation energies for glass compositions (wt percent) 10BaO-38Al2O3-51SiO2-1MoO3 (glass A) and 39BaO-25Al2O3-35SiO2-1MoO3 (glass B) were determined to be 553 and 558 kJ/mol, respectively. On thermal treatment, the crystalline phases in glasses A and B were identified as mullite (3Al2O3-2SiO2) and hexacelsian (BaO-Al2O3-2SiO2), respectively. Hexacelsian is a high-temperature polymorph which is metastable below 1590 C. It undergoes structural transformation into the orthorhombic form at approximately 300 C accompanied by a large volume change which is undesirable for structural applications. A process needs to be developed where stable monoclinic celsian, rather than hexacelsian, precipitates out as the crystal phase in glass B.

Crystallization kinetics of BaO-Al2O3-SiO2 glasses

NASA Technical Reports Server (NTRS)

Bansal, Narottam P.; Hyatt, Mark J.

1988-01-01

Barium aluminosilicate glasses are being investigated as matrix materials in high-temperature ceramic composites for structural applications. Kinetics of crystallization of two refractory glass compositions in the barium aluminosilicate system were studied by differential thermal analysis (DTA), X-ray diffraction (XRD), and scanning electron microscopy (SEM). From variable heating rate DTA, the crystallization activation energies for glass compositions (wt percent) 10BaO-38Al2O3-51SiO2-1MoO3 (glass A) and 39BaO-25Al2O3-35SiO2-1MoO3 (glass B) were determined to be 553 and 558 kJ/mol, respectively. On thermal treatment, the crystalline phases in glasses A and B were identified as mullite (3Al2O3-2SiO2) and hexacelsian (BaO-Al2O3-2SiO2), respectively. Hexacelsian is a high-temperature polymorph which is metastable below 1590 C. It undergoes structural transformation into the orthorhombic form at approximately 300 C accompanied by a large volume change which is undesirable for structural applications. A process needs to be developed where stable monoclinic celsian, rather than hexacelsian, precipitates out as the crystal phase in glass B.

Fresnel transform phase retrieval from magnitude.

PubMed

Pitts, Todd A; Greenleaf, James F

2003-08-01

This report presents a generalized projection method for recovering the phase of a finite support, two-dimensional signal from knowledge of its magnitude in the spatial position and Fresnel transform domains. We establish the uniqueness of sampled monochromatic scalar field phase given Fresnel transform magnitude and finite region of support constraints for complex signals. We derive an optimally relaxed version of the algorithm resulting in a significant reduction in the number of iterations needed to obtain useful results. An advantage of using the Fresnel transform (as opposed to Fourier) for measurement is that the shift-invariance of the transform operator implies retention of object location information in the transformed image magnitude. As a practical application in the context of ultrasound beam measurement we discuss the determination of small optical phase shifts from near field optical intensity distributions. Experimental data are used to reconstruct the phase shape of an optical field immediately after propagating through a wide bandwidth ultrasonic pulse. The phase of each point on the optical wavefront is proportional to the ray sum of pressure through the ultrasound pulse (assuming low ultrasonic intensity). An entire pressure field was reconstructed in three dimensions and compared with a calibrated hydrophone measurement. The comparison is excellent, demonstrating that the phase retrieval is quantitative.

Nano-scale phase transformation in Ti-implanted austenitic 301 stainless steel.

PubMed

Gustiono, Dwi; Sakaguchi, Norihito; Shibayama, Tamaki; Kinoshita, Hiroshi; Takahashi, Heishichiro

2003-01-01

Phase-transformation behaviours were investigated for austenitic 301 stainless steel during implantation at room temperature with 300 keV Ti ions to fluences of 8 x 10(19) to approximately 3 x 10(21) ions m(-2) by means of transmission electron microscopy. The cross-sectional specimen was prepared using a focused ion beam. Plan observation of the implanted specimen showed that phase transformation from gamma-phase to alpha-phase was induced by implantation to a fluence of 3 x 10(20) Ti ions m(-2). The nucleation of the irradiation (implantation)-induced phase increased with the increase of the dose. The orientation relationship between the gamma matrix and the induced alpha martensitic phase was identified as (011)alpha//(111)gamma and [11-1]alpha//[10-1], close to the Kurdjumov-Sachs relationship. Cross-sectional observation after implantation to a fluence of 5 x 10(20) ions m(-2) showed that phase transformation mostly nucleated near the surface and occurred in the higher the concentration gradient of the implanted ion, i.e. a higher stress concentration takes place and this stress introduced by the implanted ions acts as a driving force for the transformation.

Polymorphism in molecular solids: an extraordinary system of red, orange, and yellow crystals.

PubMed

Yu, Lian

2010-09-21

Diamond and graphite are polymorphs of each other: they have the same composition but different structures and properties. Many other substances exhibit polymorphism: inorganic and organic, natural and manmade. Polymorphs are encountered in studies of crystallization, phase transition, materials synthesis, and biomineralization and in the manufacture of specialty chemicals. Polymorphs can provide valuable insights into crystal packing and structure-property relationships. 5-Methyl-2-[(2-nitrophenyl)amino]-3-thiophenecarbonitrile, known as ROY for its red, orange, and yellow crystals, has seven polymorphs with solved structures, the largest number in the Cambridge Structural Database. First synthesized by medicinal chemists, ROY has attracted attention from solid-state chemists because it demonstrates the remarkable diversity possible in organic solids. Many structures of ROY polymorphs and their thermodynamic properties are known, making ROY an important model system for testing computational models. Though not the most polymorphic substance on record, ROY is extraordinary in that many of its polymorphs can crystallize simultaneously from the same liquid and are kinetically stable under the same conditions. Studies of ROY polymorphs have revealed a new crystallization mechanism that invalidates the common view that nucleation defines the polymorph of crystallization. A slow-nucleating polymorph can still dominate the product if it grows rapidly and nucleates on another polymorph. Studies of ROY have also helped understand a new, surprisingly fast mode of crystal growth in organic liquids cooled to the glass transition temperature. This growth mode exists only for those polymorphs that have more isotropic, and perhaps more liquid-like, packing. The rich polymorphism of ROY results from a combination of favorable thermodynamics and kinetics. Not only must there be many polymorphs of comparable energies or free energies, many polymorphs must be kinetically stable and crystallize at comparable rates to be observed. This system demonstrates the unique insights that polymorphism provides into solid-state structures and properties, as well as the inadequacy of our current understanding of the phenomenon. Despite many studies of ROY, it is still impossible to predict the next molecule that is equally or more polymorphic. ROY is a lucky gift from medicinal chemists.

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

Cong, Daoyong; Rule, Kirrily Clair; Li, Wen-Hsien

Here we describe insights into the phase transformation kinetics and lattice dynamics associated with the newly discovered confined martensitic transformation, which are of great significance to the in-depth understanding of the phase transformation behavior responsible for the rich new physical phenomena in shape memory alloys and could shed light on the design of novel multifunctional properties through tuning the confined martensitic transformation.

Genetic variation in eleven phase I drug metabolism genes in an ethnically diverse population.

PubMed

Solus, Joseph F; Arietta, Brenda J; Harris, James R; Sexton, David P; Steward, John Q; McMunn, Chara; Ihrie, Patrick; Mehall, Janelle M; Edwards, Todd L; Dawson, Elliott P

2004-10-01

The extent of genetic variation found in drug metabolism genes and its contribution to interindividual variation in response to medication remains incompletely understood. To better determine the identity and frequency of variation in 11 phase I drug metabolism genes, the exons and flanking intronic regions of the cytochrome P450 (CYP) isoenzyme genes CYP1A1, CYP1A2, CYP2A6, CYP2B6, CYP2C8, CYP2C9, CYP2C19, CYP2D6, CYP2E1, CYP3A4 and CYP3A5 were amplified from genomic DNA and sequenced. A total of 60 kb of bi-directional sequence was generated from each of 93 human DNAs, which included Caucasian, African-American and Asian samples. There were 388 different polymorphisms identified. These included 269 non-coding, 45 synonymous and 74 non-synonymous polymorphisms. Of these, 54% were novel and included 176 non-coding, 14 synonymous and 21 non-synonymous polymorphisms. Of the novel variants observed, 85 were represented by single occurrences of the minor allele in the sample set. Much of the variation observed was from low-frequency alleles. Comparatively, these genes are variation-rich. Calculations measuring genetic diversity revealed that while the values for the individual genes are widely variable, the overall nucleotide diversity of 7.7 x 10(-4) and polymorphism parameter of 11.5 x 10(-4) are higher than those previously reported for other gene sets. Several independent measurements indicate that these genes are under selective pressure, particularly for polymorphisms corresponding to non-synonymous amino acid changes. There is relatively little difference in measurements of diversity among the ethnic groups, but there are large differences among the genes and gene subfamilies themselves. Of the three CYP subfamilies involved in phase I drug metabolism (1, 2, and 3), subfamily 2 displays the highest levels of genetic diversity.