Heating-induced glass-glass and glass-liquid transformations in computer simulations of water

NASA Astrophysics Data System (ADS)

Chiu, Janet; Starr, Francis W.; Giovambattista, Nicolas

2014-03-01

Water exists in at least two families of glassy states, broadly categorized as the low-density (LDA) and high-density amorphous ice (HDA). Remarkably, LDA and HDA can be reversibly interconverted via appropriate thermodynamic paths, such as isothermal compression and isobaric heating, exhibiting first-order-like phase transitions. We perform out-of-equilibrium molecular dynamics simulations of glassy water using the ST2 model to study the evolution of LDA and HDA upon isobaric heating. Depending on pressure, glass-to-glass, glass-to-crystal, glass-to-vapor, as well as glass-to-liquid transformations are found. Specifically, heating LDA results in the following transformations, with increasing heating pressures: (i) LDA-to-vapor (sublimation), (ii) LDA-to-liquid (glass transition), (iii) LDA-to-HDA-to-liquid, (iv) LDA-to-HDA-to-liquid-to-crystal, and (v) LDA-to-HDA-to-crystal. Similarly, heating HDA results in the following transformations, with decreasing heating pressures: (a) HDA-to-crystal, (b) HDA-to-liquid-to-crystal, (c) HDA-to-liquid (glass transition), (d) HDA-to-LDA-to-liquid, and (e) HDA-to-LDA-to-vapor. A more complex sequence may be possible using lower heating rates. For each of these transformations, we determine the corresponding transformation temperature as function of pressure, and provide a P-T "phase diagram" for glassy water based on isobaric heating. Our results for isobaric heating dovetail with the LDA-HDA transformations reported for ST2 glassy water based on isothermal compression/decompression processes [Chiu et al., J. Chem. Phys. 139, 184504 (2013)]. The resulting phase diagram is consistent with the liquid-liquid phase transition hypothesis. At the same time, the glass phase diagram is sensitive to sample preparation, such as heating or compression rates. Interestingly, at least for the rates explored, our results suggest that the LDA-to-liquid (HDA-to-liquid) and LDA-to-HDA (HDA-to-LDA) transformation lines on heating are related, both being associated with the limit of kinetic stability of LDA (HDA).

A High-Rate, Single-Crystal Model including Phase Transformations, Plastic Slip, and Twinning

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

Addessio, Francis L.; Bronkhorst, Curt Allan; Bolme, Cynthia Anne

2016-08-09

An anisotropic, rate-­dependent, single-­crystal approach for modeling materials under the conditions of high strain rates and pressures is provided. The model includes the effects of large deformations, nonlinear elasticity, phase transformations, and plastic slip and twinning. It is envisioned that the model may be used to examine these coupled effects on the local deformation of materials that are subjected to ballistic impact or explosive loading. The model is formulated using a multiplicative decomposition of the deformation gradient. A plate impact experiment on a multi-­crystal sample of titanium was conducted. The particle velocities at the back surface of three crystal orientationsmore » relative to the direction of impact were measured. Molecular dynamics simulations were conducted to investigate the details of the high-­rate deformation and pursue issues related to the phase transformation for titanium. Simulations using the single crystal model were conducted and compared to the high-­rate experimental data for the impact loaded single crystals. The model was found to capture the features of the experiments.« less

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.

Effect of gallium alloying on the structure, the phase composition, and the thermoelastic martensitic transformations in ternary Ni-Mn-Ga alloys

NASA Astrophysics Data System (ADS)

Belosludtseva, E. S.; Kuranova, N. N.; Marchenkova, E. B.; Popov, A. G.; Pushin, V. G.

2016-04-01

The effect of gallium alloying on the structure, the phase composition, and the properties of quasibinary Ni50Mn50- z Ga z (0 ⩽ z ⩽ 25 at %) alloys is studied over a wide temperature range. The influence of the alloy composition on the type of crystal structure in high-temperature austenite and martensite and the critical martensitic transformation temperatures is analyzed. A general phase diagram of the magnetic and structural transformations in the alloys is plotted. The temperature-concentration boundaries of the B2 and L21 superstructures in the austenite field, the tetragonal L10 (2 M) martensite, and the 10 M and 14 M martensite phases with complex multilayer crystal lattices are found. The predominant morphology of martensite is shown to be determined by the hierarchy of the packets of thin coherent lamellae of nano- and submicrocrystalline crystals with planar habit plane boundaries close to {011} B2. Martensite crystals are twinned along one of the 24 24{ {011} }{< {01bar 1} rangle _{B2}} "soft" twinning shear systems, which provides coherent accommodation of the martensitic transformation-induced elastic stresses.

Investigations on solid-solid phase transformation of 5-methyl-2-[(4-methyl-2-nitrophenyl)amino]-3-thiophenecarbonitrile.

PubMed

Li, Hui; Stowell, Joseph G; He, Xiaorong; Morris, Kenneth R; Byrn, Stephen R

2007-05-01

Solid-solid transformation of 5-methyl-2-[(4-methyl-2-nitrophenyl)amino]-3-thiophenecarbonitrile from the dark-red to the red form was investigated. By controlled crystallization, the dark-red form was prepared and the crystals were sieved into fractions: coarse (>250 microm), medium (125-177 microm), and fine (<88 microm). The transformation rate order (fastest to slowest) of the different fractions is coarse > medium > fine. However, milling accelerates the transformation, that is, smaller particles generated by milling transforms faster. Furthermore, ethanol vapor annealing slows both the transformation of the coarse and medium fractions, especially the latter. Therefore, the mechanism of transformation is not directly related to the crystal-size and most likely related to the amount and activity of the defects in the crystals. The three-dimensional (3-D) Avrami-Erofe'ev model, know as "random nucleation and growth" model, fits the kinetics of coarse fraction best. Higher relative humidity accelerates the transformation dramatically even though the compound is highly-hydrophobic. With minimal hydrogen bonding interaction involved, it appears even small amounts of water can serve as a nucleation catalyst by binding to the crystal surface, especially at defect sites, thus increasing the molecular mobility of these sites, promoting the transformation to the second phase and thereby increasing the transformation rate. (c) 2007 Wiley-Liss, Inc. and the American Pharmacists Association.

Shock-Induced phase transition of single crystal copper

NASA Astrophysics Data System (ADS)

Neogi, Anupam; Mitra, Nilanjan

2017-05-01

We have carried out a series of multi-million atoms non-equilibrium molecular dynamics simulations to investigate the effect of crystal orientation over the shock induced plasticity and phase transformation in single crystal copper. Crystallographic orientation of [100], [110] and [111] has been studied for various intensity of shock ranging from 1.0 km/s to 3.0 km/s. During shock wave propagation along <100> and <110>, a FCC-to-BCC phase transformation has been observed to occur behind the shock front at higher intensity of shock. Nucleated body centered phase is identified through common neighbor analysis, polyhedral matching template method, radial distribution function and also from the energetic of the particles.

Femtosecond laser-induced phase transformations in amorphous Cu77Ni6Sn10P7 alloy

NASA Astrophysics Data System (ADS)

Zhang, Y.; Liu, L.; Zou, G.; Chen, N.; Wu, A.; Bai, H.; Zhou, Y.

2015-01-01

In this study, the femtosecond laser-induced crystallization of CuNiSnP amorphous ribbons was investigated by utilizing an amplified Ti:sapphire laser system. X-ray diffraction and scanning electronic microscope were applied to examine the phase and morphology changes of the amorphous ribbons. Micromachining without crystallization, surface patterning, and selective crystallization were successfully achieved by changing laser parameters. Obvious crystallization occurred under the condition that the laser fluence was smaller than the ablation threshold, indicating that the structural evolution of the material depends strongly on the laser parameters. Back cooling method was used to inhibit heat accumulation; a reversible transformation between the disordered amorphous and crystalline phases can be achieved by using this method.

Anisotropic lattice softening near the structural phase transition in the thermosalient crystal 1,2,4,5-tetrabromobenzene.

PubMed

Zakharov, Boris A; Michalchuk, Adam A L; Morrison, Carole A; Boldyreva, Elena V

2018-03-28

The thermosalient effect (crystal jumping on heating) attracts much attention as both an intriguing academic phenomenon and in relation to its potential for the development of molecular actuators but its mechanism remains unclear. 1,2,4,5-Tetrabromobenzene (TBB) is one of the most extensively studied thermosalient compounds that has been shown previously to undergo a phase transition on heating, accompanied by crystal jumping and cracking. The difference in the crystal structures and intermolecular interaction energies of the low- and high-temperature phases is, however, too small to account for the large stress that arises over the course of the transformation. The energy is released spontaneously, and crystals jump across distances that exceed the crystal size by orders of magnitude. In the present work, the anisotropy of lattice strain is followed across the phase transition by single-crystal X-ray diffraction, focusing on the structural evolution from 273 to 343 K. A pronounced lattice softening is observed close to the transition point, with the structure becoming more rigid immediately after the phase transition. The diffraction studies are further supported by theoretical analysis of pairwise intermolecular energies and zone-centre lattice vibrations. Only three modes are found to monotonically soften up to the phase transition, with complex behaviour exhibited by the remaining lattice modes. The thermosalient effect is delayed with respect to the structural transformation itself. This can originate from the martensitic mechanism of the transformation, and the accumulation of stress associated with vibrational switching across the phase transition. The finding of this study sheds more light on the nature of the thermosalient effect in 1,2,4,5-tetrabromobenzene and can be applicable also to other thermosalient compounds.

Phase transformations in SrAl2Si2O8 glass

NASA Technical Reports Server (NTRS)

Drummond, Charles H., III; Bansal, Narottam P.

1992-01-01

Bulk glass of SrAl2Si2O8 composition crystallized at temperatures below 1000 C into hexacelsian, a hexagonal phase which undergoes a reversible, rapid transformation to an orthorhombic phase at 758 C, and at higher temperatures crystallized as celsian, a monoclinic phase. The glass transition temperature and crystallization onset temperature were determined to be 883 C and 1086 C, respectively, from DSC at a heating rate of 20 C/min. Thermal expansion of the various phases and density and bend strengths of cold isostatically pressed glass powder bars, sintered at various temperatures, were measured. The kinetics of the hexacelsian-to-celsian transformation for SrAl2Si2O8 were studied. Hexacelsian flakes were isothermally heat treated at temperatures from 1025-1200 C for various times. Avrami plots were determined by quantitatively measuring the amount of monoclinic celsian formed at various times using x ray diffraction. The Avrami constant was determined to be 1.1, suggesting a diffusionless, one dimensional transformation mechanism. The activation energy was determined from an Arrhenius plot of 1n k vs. 1/T to be 125 kilocal/mole. This value is consistent with a mechanism which transforms the layered hexacelsian structure to a three dimensional framework celsian structure and involves the breaking of Si-O bonds.

Observing in space and time the ephemeral nucleation of liquid-to-crystal phase transitions.

PubMed

Yoo, Byung-Kuk; Kwon, Oh-Hoon; Liu, Haihua; Tang, Jau; Zewail, Ahmed H

2015-10-19

The phase transition of crystalline ordering is a general phenomenon, but its evolution in space and time requires microscopic probes for visualization. Here we report direct imaging of the transformation of amorphous titanium dioxide nanofilm, from the liquid state, passing through the nucleation step and finally to the ordered crystal phase. Single-pulse transient diffraction profiles at different times provide the structural transformation and the specific degree of crystallinity (η) in the evolution process. It is found that the temporal behaviour of η exhibits unique 'two-step' dynamics, with a robust 'plateau' that extends over a microsecond; the rate constants vary by two orders of magnitude. Such behaviour reflects the presence of intermediate structure(s) that are the precursor of the ordered crystal state. Theoretically, we extend the well-known Johnson-Mehl-Avrami-Kolmogorov equation, which describes the isothermal process with a stretched-exponential function, but here over the range of times covering the melt-to-crystal transformation.

A High-Rate, Single-Crystal Model for Cyclotrimethylene Trinitramine including Phase Transformations and Plastic Slip

DOE PAGES

Addessio, Francis L.; Luscher, Darby Jon; Cawkwell, Marc Jon; ...

2017-05-14

A continuum model for the high-rate, thermo-mechanical deformation of single-crystal cyclotrimethylene trinitramine (RDX) is developed. The model includes the effects of anisotropy, large deformations, nonlinear thermo-elasticity, phase transformations, and plastic slip. A multiplicative decomposition of the deformation gradient is used. The volumetric elastic component of the deformation is accounted for through a free-energy based equation of state for the low- (α) and high-pressure (γ) polymorphs of RDX. Crystal plasticity is addressed using a phenomenological thermal activation model. The deformation gradient for the phase transformation is based on an approach that has been applied to martensitic transformations. Simulations were conducted andmore » compared to high-rate, impact loading of oriented RDX single crystals. The simulations considered multiple orientations of the crystal relative to the direction of shock loading and multiple sample thicknesses. Thirteen slip systems, which were inferred from indentation and x-ray topography, were used to model the α-polymorph. It is shown that by increasing the number of slip systems from the previously considered number of six (6) to thirteen (13) in the α-polymorph, better comparisons with data may be obtained. Simulations of impact conditions in the vicinity of the α- to γ-polymorph transformation (3.8 GPa) are considered. Eleven of the simulations, which were at pressures below the transformation value (3.0 GPa), were compared to experimental data. Comparison of the model was also made with available data for one experiment above the transformation pressure (4.4 GPa). Also, simulations are provided for a nominal pressure of 7.5 GPa to demonstrate the effect of the transformation kinetics on the deformation of a high-rate plate impact problem.« less

A High-Rate, Single-Crystal Model for Cyclotrimethylene Trinitramine including Phase Transformations and Plastic Slip

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

Addessio, Francis L.; Luscher, Darby Jon; Cawkwell, Marc Jon

A continuum model for the high-rate, thermo-mechanical deformation of single-crystal cyclotrimethylene trinitramine (RDX) is developed. The model includes the effects of anisotropy, large deformations, nonlinear thermo-elasticity, phase transformations, and plastic slip. A multiplicative decomposition of the deformation gradient is used. The volumetric elastic component of the deformation is accounted for through a free-energy based equation of state for the low- (α) and high-pressure (γ) polymorphs of RDX. Crystal plasticity is addressed using a phenomenological thermal activation model. The deformation gradient for the phase transformation is based on an approach that has been applied to martensitic transformations. Simulations were conducted andmore » compared to high-rate, impact loading of oriented RDX single crystals. The simulations considered multiple orientations of the crystal relative to the direction of shock loading and multiple sample thicknesses. Thirteen slip systems, which were inferred from indentation and x-ray topography, were used to model the α-polymorph. It is shown that by increasing the number of slip systems from the previously considered number of six (6) to thirteen (13) in the α-polymorph, better comparisons with data may be obtained. Simulations of impact conditions in the vicinity of the α- to γ-polymorph transformation (3.8 GPa) are considered. Eleven of the simulations, which were at pressures below the transformation value (3.0 GPa), were compared to experimental data. Comparison of the model was also made with available data for one experiment above the transformation pressure (4.4 GPa). Also, simulations are provided for a nominal pressure of 7.5 GPa to demonstrate the effect of the transformation kinetics on the deformation of a high-rate plate impact problem.« less

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.

Ikaite pseudomorphs in the Zaire deep-sea fan: An intermediate between calcite and porous calcite

NASA Astrophysics Data System (ADS)

Jansen, J. H. F.; Woensdregt, C. F.; Kooistra, M. J.; van der Gaast, S. J.

1987-03-01

Translucent brown aggregates of calcium-carbonate crystals have been found in cores from the Zaire deep-sea fan (west equatorial Africa). The aggregates are well preserved but very friable. Upon storage they become yellowish white and cloudy and release water. Chemical, mineralogical (XRD), petrographical, crystal-morphological, and stable-isotope data demonstrate that the crystals have passed through three phases: (1) an authigenic carbonate phase, probably calcium carbonate, which is represented by the external habit of the present crystals; (2) a translucent brown ikaite phase (CaCO3·6H2O), unstable at temperatures above 5 °C; and (3) a phase consisting of calcite microcrystals that are poorly cemented and form a porous mass within the crystal form of the morphologically unchanged first phase. The transformation from the first phase into ikaite was probably a kinetic replacement. The transformation from ikaite into the third phase occurred because of storage at room temperature. The presence of ikaite is indicative of a low-temperature, anaerobic, organic-carbon-rich marine environment. Ikaite is probably the precursor of a great number of porous calcite pseudomorphs, and possibly also of many marine authigenic microcrystalline carbonate nodules.

Snapshots of a solid-state transformation: coexistence of three phases trapped in one crystal

DOE PAGES

Aromí, G.; Beavers, C. M.; Sánchez Costa, J.; ...

2016-01-05

Crystal-to-crystal transformations have been crucial in the understanding of solid-state processes, since these may be studied in detail by means of single crystal X-ray diffraction (SCXRD) techniques. The description of the mechanisms and potential intermediates of those processes remains very challenging. In fact, solid-state transient states have rarely been observed, at least to a sufficient level of detail. We have investigated the process of guest extrusion from the non-porous molecular material [Fe(bpp)(H 2L)](ClO 4) 2·1.5C 3H 6O (bpp = 2,6-bis(pyrazol-3-yl)pyridine; H 2L = 2,6-bis(5-(2-methoxyphenyl)-pyrazol-3-yl)pyridine; C 3H 6O = acetone), which occurs through ordered diffusion of acetone in a crystal-to-crystal manner,more » leading to dramatic structural changes. The slow kinetics of the transition allows thermal trapping of the system at various intermediate stages. The transiting single crystal can be then examined at these points through synchrotron SCXRD, offering a window upon the mechanism of the transformation at the molecular scale. These experiments have unveiled the development of an ordered intermediate phase, distinct from the initial and the final states, coexisting as the process advances with either of these two phases or, at a certain moment with both of them. The new intermediate phase has been structurally characterized in full detail by SCXRD, providing insights into the mechanism of this diffusion triggered solid-state phenomenon. Lastly, the process has been also followed by calorimetry, optical microscopy, local Raman spectroscopy and powder X-ray diffraction. The discovery and description of an intermediate ordered state in a molecular solid-state transformation is of great interest and will help to understand the mechanistic details and reaction pathways underlying these transformations.« less

Large tensile superelasticity from intermartensitic transformations in Ni49Mn28Ga23 single crystal

NASA Astrophysics Data System (ADS)

Chernenko, V. A.; Villa, E.; Salazar, D.; Barandiaran, J. M.

2016-02-01

A multistep superelastic behavior, with up to a 12% strain, is reported in a <001>P-oriented Ni49Mn28Ga23 single crystal. The observed behavior is produced by intermartensitic transformations during the tensile stress-strain measurements at temperatures between -140 °C and +60 °C. The tensile stress-temperature phase diagram and the stress dependence of the intermartensitic transformation entropies have been obtained. These results provide important input for theoretical modeling of the phase transformations in these alloys and show promising mechanical properties of the classical Ni-Mn-Ga ferromagnetic shape memory alloys.

Low-temperature phase transformations in 4-cyano-4‧-pentyl-biphenyl (5CB) filled by multiwalled carbon nanotubes

NASA Astrophysics Data System (ADS)

Lebovka, N.; Melnyk, V.; Mamunya, Ye.; Klishevich, G.; Goncharuk, A.; Pivovarova, N.

2013-08-01

The effects of multiwalled carbon nanotubes (NTs) on low-temperature phase transformations in 5CB were studied by means of differential scanning calorimetry (DSC), low-temperature photoluminescence and measurements of electrical conductivity. The concentration of NTs was varied within 0-1 wt% The experimental data, obtained for pure 5CB by DSC and measurements of photoluminescence in the heating mode, evidenced the presence of two crystallization processes at T≈229 K and T≈262 K, which correspond to C1a→C1b, and C1b→C2 phase transformations. Increase of temperature T from 10 K tо 229 K provoked the red shift of photoluminescence spectral band that was explained by flattening of 5CB molecule conformation. Moreover, the photoluminescence data allow to conclude that crystallization at T≈229 K results in conformation transition to non-planar 5CB structure characteristic to ideal crystal. The non-planar conformations were dominating in nematic phase, i.e., at T>297 K. Electrical conductivity data for 5CB-NT composites revealed supplementary anomaly inside the stable crystalline phase C2, identified earlier in the temperature range 229-296.8 K. It can reflect the influence of phase transformation of 5CB in interfacial layers on the transport of charge carriers between NTs.

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.

Generalization of soft phonon modes

NASA Astrophysics Data System (ADS)

Rudin, Sven P.

2018-04-01

Soft phonon modes describe a collective movement of atoms that transform a higher-symmetry crystal structure into a lower-symmetry crystal structure. Such structural transformations occur at finite temperatures, where the phonons (i.e., the low-temperature vibrational modes) and the static perfect crystal structures provide an incomplete picture of the dynamics. Here, principal vibrational modes (PVMs) are introduced as descriptors of the dynamics of a material system with N atoms. The PVMs represent the independent collective movements of the atoms at a given temperature. Molecular dynamics (MD) simulations, here in the form of quantum MD using density functional theory calculations, provide both the data describing the atomic motion and the data used to construct the PVMs. The leading mode, PVM0, represents the 3 N -dimensional direction in which the system moves with greatest amplitude. For structural phase transitions, PVM0 serves as a generalization of soft phonon modes. At low temperatures, PVM0 reproduces the soft phonon mode in systems where one phonon dominates the phase transformation. In general, multiple phonon modes combine to describe a transformation, in which case PVM0 culls these phonon modes. Moreover, while soft phonon modes arise in the higher-symmetry crystal structure, PVM0 can be equally well calculated on either side of the structural phase transition. Two applications demonstrate these properties: first, transitions into and out of bcc titanium, and, second, the two crystal structures proposed for the β phase of uranium, the higher-symmetry structure of which stabilizes with temperature.

Atomic Migration Induced Crystal Structure Transformation and Core-Centered Phase Transition in Single Crystal Ge2Sb2Te5 Nanowires.

PubMed

Lee, Jun-Young; Kim, Jeong-Hyeon; Jeon, Deok-Jin; Han, Jaehyun; Yeo, Jong-Souk

2016-10-12

A phase change nanowire holds a promise for nonvolatile memory applications, but its transition mechanism has remained unclear due to the analytical difficulties at atomic resolution. Here we obtain a deeper understanding on the phase transition of a single crystalline Ge 2 Sb 2 Te 5 nanowire (GST NW) using atomic scale imaging, diffraction, and chemical analysis. Our cross-sectional analysis has shown that the as-grown hexagonal close-packed structure of the single crystal GST NW transforms to a metastable face-centered cubic structure due to the atomic migration to the pre-existing vacancy layers in the hcp structure going through iterative electrical switching. We call this crystal structure transformation "metastabilization", which is also confirmed by the increase of set-resistance during the switching operation. For the set to reset transition between crystalline and amorphous phases, high-resolution imaging indicates that the longitudinal center of the nanowire mainly undergoes phase transition. According to the atomic scale analysis of the GST NW after repeated electrical switching, partial crystallites are distributed around the core-centered amorphous region of the nanowire where atomic migration is mainly induced, thus potentially leading to low power electrical switching. These results provide a novel understanding of phase change nanowires, and can be applied to enhance the design of nanowire phase change memory devices for improved electrical performance.

Remarks on the Particular Behavior in Martensitic Phase Transition in Cu-Based and Ni-Ti Shape Memory Alloys

NASA Astrophysics Data System (ADS)

Torra, Vicenç; Martorell, Ferran; Lovey, Francisco C.; Sade, Marcos

2018-05-01

Many macroscopic behaviors of the martensitic transformations are difficult to explain in the frame of the classical first-order phase transformations, without including the role of point and crystallographic defects (dislocations, stacking faults, interfaces, precipitates). A few major examples are outlined in the present study. First, the elementary reason for thermoelasticity and pseudoelasticity in single crystals of Cu-Zn-Al (β-18R transformation) arises from the interaction of a growing martensite plate with the existing dislocations in the material. Secondly, in Cu-Al-Ni, the twinned hexagonal (γ') martensite produces dislocations inhibiting this transformation and favoring the appearance of 18R in subsequent transformation cycles. Thirdly, single crystals of Cu-Al-Be visualize, via enhanced stress, a transformation primarily to 18R, a structural distortion of the 18R structure, and an additional transformation to another martensitic phase (i.e., 6R) with an increased strain. A dynamic behavior in Ni-Ti is also analyzed, where defects alter the pseudoelastic behavior after cycling.

High-pressure phase transitions, amorphization, and crystallization behaviors in Bi2Se3.

PubMed

Zhao, Jinggeng; Liu, Haozhe; Ehm, Lars; Dong, Dawei; Chen, Zhiqiang; Gu, Genda

2013-03-27

The phase transition, amorphization, and crystallization behaviors of the topological insulator bismuth selenide (Bi2Se3) were discovered by performing in situ high-pressure angle-dispersive x-ray diffraction experiments during an increasing, decreasing, and recycling pressure process. In the compression process, Bi2Se3 transforms from the original rhombohedral structure (phase I(A)) to a monoclinic structure (phase II) at about 10.4 GPa, and further to a body-centered tetragonal structure (phase III) at about 24.5 GPa. When releasing pressure to ambient conditions after the complete transformation from phase II to III, Bi2Se3 becomes an amorphous solid (AM). In the relaxation process from this amorphous state, Bi2Se3 starts crystallizing into an orthorhombic structure (phase I(B)) about five hours after releasing the pressure to ambient. A review of the pressure-induced phase transition behaviors of A2B3-type materials composed from the V and VI group elements is presented.

Influence of the chemical composition of rapidly quenched amorphous alloys (Ni, Fe, Cr)-B-Si on its crystallization process

NASA Astrophysics Data System (ADS)

Elmanov, G.; Dzhumaev, P.; Ivanitskaya, E.; Skrytnyi, V.; Ruslanov, A.

2016-04-01

This paper presents results of research of the structure and phase transformations during the multistage crystallization of the metallic glasses with the compositions Ni71,5Cr6,8Fe2,7B11,9Si7,1 and Ni63,4Cr7,4Fe4,3Mn0,8B15,6Si8,5 labeled as AWS BNi-2 according to American Welding Society. Differential scanning calorimetry (DSC), X-ray diffraction analysis (XRD), scanning electron microscopy (SEM) and energy-dispersive X-ray microanalysis (EDX) were used as experimental research methods. The influence of the alloys chemical composition (boron, manganese and iron) on the temperatures and the exothermic heat effects of phase transformations, as well as on the phase composition of alloys at three stages of crystallization was analyzed. We present a thermodynamic explanation of the observed heat effects. It has been shown that manganese has the main influence on the phase transformations temperatures and heat effects in these two alloys. It is also assumed that at the final crystallization stage simultaneously with the formation of phases Ni3B and β1-Ni3Si should occur the nucleation of borides of CrB type with high Cr and low Si content.

Transformation kinetics for the shock wave induced phase transition in cadmium sulfide crystals

NASA Astrophysics Data System (ADS)

Knudson, M. D.; Gupta, Y. M.

2002-06-01

Initial stage kinetics of the cadmium sulfide (CdS) phase transition was investigated using picosecond time-resolved electronic spectroscopy in plate-impact shock wave experiments. Real-time changes in the electronic spectra were observed, with 100 ps time resolution, in CdS single crystals shocked along a and c axes to stresses ranging between 35 and 90 kbar, which is above the phase-transition threshold stress of approximately 30 kbar. Significant difference in the transformation kinetics was observed for the two crystal orientations. At sufficiently high instantaneous stress, above approximately 60 to 70 kbar for a axis and 50 kbar for c axis, transformation to a metastable state appears to reach a constant state within the 100 ps time resolution. At lower instantaneous stresses, an incubation period on the order of several nanoseconds is observed prior to the onset of electronic changes that mark the onset of the structural change. The subsequent increase in absorbance was quite rapid, with a constant state being reached within the first few nanoseconds after the onset of the structural changes. These results suggest that the nucleation process determines the transformation rate. This insight into transformation kinetics, along with the transformation mechanism obtained from the high-stress experiments, was used to develop a phenomenological model, incorporating ideas of nucleation and growth in martensitic transformations, to simulate the time-dependent extinction of light observed in our experiments. The calculational results incorporating both extinction due to light absorption by the daughter phase volumes and scattering of light by small volumes of the daughter phase were in good agreement with experimental observations. Finally, the orientational differences observed in the transformation kinetics were interpreted in terms of the differences in the elastic-plastic response for the two orientations.

Temperature and field induced strain measurements in single crystal Gd 5Si 2Ge 2

DOE PAGES

McCall, S. K.; Nersessian, N.; Carman, G. P.; ...

2016-03-29

The first-order magneto-structural transformation that occurs in Gd 5Si 2Ge 2 near room temperature makes it a strong candidate for many energy harvesting applications. Understanding the single crystal properties is crucial for allowing simulations of device performance. In this study, magnetically and thermally induced transformation strains were measured in a single crystal of Gd 5Si 2.05Ge 1.95 as it transforms from a high-temperature monoclinic paramagnet to a lower-temperature orthorhombic ferromagnet. Thermally induced transformation strains of –8500 ppm, +960 ppm and +1800 ppm, and magnetically induced transformation strains of –8500 ppm, +900 ppm and +2300 ppm were measured along the a,more » b and c axes, respectively. Furthermore, using experimental data coupled with general thermodynamic considerations, a universal phase diagram was constructed showing the transition from the monoclinic to the orthorhombic phase as a function of temperature and magnetic field.« less

Monoclinic MB phase and phase instability in [110] field cooled Pb(Zn1/3Nb2/3)O3-4.5%PbTiO3 single crystals

NASA Astrophysics Data System (ADS)

Yao, Jianjun; Cao, Hu; Ge, Wenwei; Li, Jiefang; Viehland, D.

2009-08-01

We report the finding of a monoclinic MB phase in Pb(Zn1/3Nb2/3)O3-4.5%PbTiO3 single crystals. High precision x-ray diffraction investigations of [110] field cooled crystals have shown a transformation sequence of cubic(C)→tetragonal(T)→orthorhombic(O)→monoclinic(MB), which is different from that previously reported [A.-E. Renault et al., J. Appl. Phys. 97, 044105 (2005)]. Beginning in the zero-field-cooled condition at 383 K, a rhombohedral (R)→MB→O sequence was observed with increasing field. Coexisting MB and O phases were then found upon removal of field, which fully transformed to MB on cooling to room temperature.

Formation of the molecular crystal structure during the vacuum sublimation of paracetamol

NASA Astrophysics Data System (ADS)

Belyaev, A. P.; Rubets, V. P.; Antipov, V. V.; Bordei, N. S.

2015-04-01

The results from structural and thermal studies on the formation of molecular crystals during the vacuum sublimation of paracetamol from its vapor phase are given. It is established that the vapor-crystal phase transition proceeds in a complicated way as the superposition of two phase transitions: a first-order phase transition with a change in density, and a second-order phase transition with a change in ordering. It is shown that the latter is a smeared phase transition that proceeds with the formation of a pretransitional phase that is irreversibly dissipated during phase transformation, leading to the formation of crystals of the rhombic syngony. Data from differential scanning calorimetry and X-ray diffraction analysis are presented along with microphotographs.

[Raman spectroscopic analysis of dissolution and phase transformation of chloropinnoite in the boric acid aqueous solution].

PubMed

Li, Xiao-Ping; Gao, Shi-Yang; Liu, Zhi-Hong; Hu, Man-Cheng; Xia, Shu-Ping

2005-01-01

Raman spectroscopy of dissolution and transformation of chloropinnoite in 4.5% (w.t.%) boric acid aqueous solution at 30 degrees C has been recorded. The Raman spectra of kinetics process have been obtained. The phase transformation product is kurnakovite (2MgO x 3B2O3 x 15H2O). The main polyborate anions and their interaction in aqueous solution have been proposed according to the Raman spectrum. Some assignments were tentatively given and the relations between the existing forms of polyborate anions and the crystallizing solid phases have been gained. A mechanisms of dissolution and crystallization reactions and the formation condition of kurnakovite in Qinghai-Tibet plateau were proposed and discussed.

Crystallization Kinetics of Barium and Strontium Aluminosilicate Glasses of Feldspar Composition

NASA Technical Reports Server (NTRS)

Hyatt, Mark J.; Bansal, Narottam P.

1994-01-01

Crystallization kinetics of BaO.Al2O3.2SiO2 (BAS) and SrO.Al2O3.2SiO2 (SAS) glasses in bulk and powder forms have been studied by non-isothermal differential scanning calorimetry (DSC). The crystal growth activation energies were evaluated to be 473 and 451 kJ/mol for bulk samples and 560 and 534 kJ/mol for powder specimens in BAS and SAS glasses, respectively. Development of crystalline phases on thermal treatments of glasses at various temperatures has been followed by powder x-ray diffraction. Powder samples crystallized at lower temperatures than the bulk and the crystallization temperature was lower for SAS glass than BAS. Crystallization in both glasses appeared to be surface nucleated. The high temperature phase hexacelsian, MAl2Si2O8 (M = Ba or Sr), crystallized first by nucleating preferentially on the glass surface. Also, monoclinic celsian does not nucleate directly in the glass, but is formed at higher temperatures from the transformation of the metastable hexagonal phase. In SAS the transformation to monoclinic celsian occurred rapidly after 1 h at 1100 C. In contrast, in BAS this transformation is sluggish and difficult and did not go to completion even after 10 h heat treatment at 1400 C. The crystal growth morphologies in the glasses have been observed by optical microscopy. Some of the physical properties of the two glasses are also reported.

Generalization of soft phonon modes

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

Rudin, Sven P.

Soft phonon modes describe a collective movement of atoms that transform a higher-symmetry crystal structure into a lower-symmetry crystal structure. Such structural transformations occur at finite temperatures, where the phonons (i.e., the low-temperature vibrational modes) and the static perfect crystal structures provide an incomplete picture of the dynamics. In this paper, principal vibrational modes (PVMs) are introduced as descriptors of the dynamics of a material system withmore » $N$ atoms. The PVMs represent the independent collective movements of the atoms at a given temperature. Molecular dynamics (MD) simulations, here in the form of quantum MD using density functional theory calculations, provide both the data describing the atomic motion and the data used to construct the PVMs. The leading mode, $${\\mathrm{PVM}}_{0}$$, represents the $3N$-dimensional direction in which the system moves with greatest amplitude. For structural phase transitions, $${\\mathrm{PVM}}_{0}$$ serves as a generalization of soft phonon modes. At low temperatures, $${\\mathrm{PVM}}_{0}$$ reproduces the soft phonon mode in systems where one phonon dominates the phase transformation. In general, multiple phonon modes combine to describe a transformation, in which case $${\\mathrm{PVM}}_{0}$$ culls these phonon modes. Moreover, while soft phonon modes arise in the higher-symmetry crystal structure, $${\\mathrm{PVM}}_{0}$$ can be equally well calculated on either side of the structural phase transition. Finally, two applications demonstrate these properties: first, transitions into and out of bcc titanium, and, second, the two crystal structures proposed for the $${\\beta}$$ phase of uranium, the higher-symmetry structure of which stabilizes with temperature.« less

Generalization of soft phonon modes

DOE PAGES

Rudin, Sven P.

2018-04-27

Soft phonon modes describe a collective movement of atoms that transform a higher-symmetry crystal structure into a lower-symmetry crystal structure. Such structural transformations occur at finite temperatures, where the phonons (i.e., the low-temperature vibrational modes) and the static perfect crystal structures provide an incomplete picture of the dynamics. In this paper, principal vibrational modes (PVMs) are introduced as descriptors of the dynamics of a material system withmore » $N$ atoms. The PVMs represent the independent collective movements of the atoms at a given temperature. Molecular dynamics (MD) simulations, here in the form of quantum MD using density functional theory calculations, provide both the data describing the atomic motion and the data used to construct the PVMs. The leading mode, $${\\mathrm{PVM}}_{0}$$, represents the $3N$-dimensional direction in which the system moves with greatest amplitude. For structural phase transitions, $${\\mathrm{PVM}}_{0}$$ serves as a generalization of soft phonon modes. At low temperatures, $${\\mathrm{PVM}}_{0}$$ reproduces the soft phonon mode in systems where one phonon dominates the phase transformation. In general, multiple phonon modes combine to describe a transformation, in which case $${\\mathrm{PVM}}_{0}$$ culls these phonon modes. Moreover, while soft phonon modes arise in the higher-symmetry crystal structure, $${\\mathrm{PVM}}_{0}$$ can be equally well calculated on either side of the structural phase transition. Finally, two applications demonstrate these properties: first, transitions into and out of bcc titanium, and, second, the two crystal structures proposed for the $${\\beta}$$ phase of uranium, the higher-symmetry structure of which stabilizes with temperature.« less

The growth mechanism of grain boundary carbide in Alloy 690

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

Li, Hui, E-mail: huili@shu.edu.cn; Institute of Materials, Shanghai University, Shanghai 200072; Xia, Shuang

2013-07-15

The growth mechanism of grain boundary M{sub 23}C{sub 6} carbides in nickel base Alloy 690 after aging at 715 °C was investigated by high resolution transmission electron microscopy. The grain boundary carbides have coherent orientation relationship with only one side of the matrix. The incoherent phase interface between M{sub 23}C{sub 6} and matrix was curved, and did not lie on any specific crystal plane. The M{sub 23}C{sub 6} carbide transforms from the matrix phase directly at the incoherent interface. The flat coherent phase interface generally lies on low index crystal planes, such as (011) and (111) planes. The M{sub 23}C{submore » 6} carbide transforms from a transition phase found at curved coherent phase interface. The transition phase has a complex hexagonal crystal structure, and has coherent orientation relationship with matrix and M{sub 23}C{sub 6}: (111){sub matrix}//(0001){sub transition}//(111){sub carbide}, <112{sup ¯}>{sub matrix}//<21{sup ¯}10>{sub transition}//<112{sup ¯}>{sub carbide}. The crystal lattice constants of transition phase are c{sub transition}=√(3)×a{sub matrix} and a{sub transition}=√(6)/2×a{sub matrix}. Based on the experimental results, the growth mechanism of M{sub 23}C{sub 6} and the formation mechanism of transition phase are discussed. - Highlights: • A transition phase was observed at the coherent interfaces of M{sub 23}C{sub 6} and matrix. • The transition phase has hexagonal structure, and is coherent with matrix and M{sub 23}C{sub 6}. • The M{sub 23}C{sub 6} transforms from the matrix directly at the incoherent phase interface.« less

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

Beran, L.; Cejpek, P.; Kulda, M.

Optical and magneto-optical properties of single crystal of Ni{sub 50.1}Mn{sub 28.4}Ga{sub 21.5} magnetic shape memory alloy during its transformation from martensite to austenite phase were systematically studied. Crystal orientation was approximately along (100) planes of parent cubic austenite. X-ray reciprocal mapping confirmed modulated 10 M martensite phase. Temperature depended measurements of saturation magnetization revealed the martensitic transformation at 335 K during heating. Magneto-optical spectroscopy and spectroscopic ellipsometry were measured in the sample temperature range from 297 to 373 K and photon energy range from 1.2 to 6.5 eV. Magneto-optical spectra of polar Kerr rotation as well as the spectra of ellipsometric parameter Ψ exhibitedmore » significant changes when crossing the transformation temperature. These changes were assigned to different optical properties of Ni-Mn-Ga in martensite and austenite phases due to modification of electronic structure near the Fermi energy during martensitic transformation.« less

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.

Observation of solid–solid transitions in 3D crystals of colloidal superballs

PubMed Central

Meijer, Janne-Mieke; Pal, Antara; Ouhajji, Samia; Lekkerkerker, Henk N. W.; Philipse, Albert P.; Petukhov, Andrei V.

2017-01-01

Self-organization in anisotropic colloidal suspensions leads to a fascinating range of crystal and liquid crystal phases induced by shape alone. Simulations predict the phase behaviour of a plethora of shapes while experimental realization often lags behind. Here, we present the experimental phase behaviour of superball particles with a shape in between that of a sphere and a cube. In particular, we observe the formation of a plastic crystal phase with translational order and orientational disorder, and the subsequent transformation into rhombohedral crystals. Moreover, we uncover that the phase behaviour is richer than predicted, as we find two distinct rhombohedral crystals with different stacking variants, namely hollow-site and bridge-site stacking. In addition, for slightly softer interactions we observe a solid–solid transition between the two. Our investigation brings us one step closer to ultimately controlling the experimental self-assembly of superballs into functional materials, such as photonic crystals. PMID:28186101

Nature of metastable amorphous-to-crystalline reversible phase transformations in GaSb

NASA Astrophysics Data System (ADS)

Kalkan, B.; Edwards, T. G.; Raoux, S.; Sen, S.

2013-08-01

The structural, thermodynamic, and kinetic aspects of the transformations between the metastable amorphous and crystalline phases of GaSb are investigated as a function of pressure at ambient temperature using synchrotron x-ray diffraction experiments in a diamond anvil cell. The results are consistent with the hypothesis that the pressure induced crystallization of amorphous GaSb into the β-Sn crystal structure near ˜5 GPa is possibly a manifestation of an underlying polyamorphic phase transition between a semiconducting, low density and a metallic, high density amorphous (LDA and HDA, respectively) phases. In this scenario, the large differences in the thermal crystallization kinetics between amorphous GaSb deposited in thin film form by sputtering and that prepared by laser melt quenching may be related to the relative location of the glass transition temperature of the latter in the pressure-temperature (P-T) space with respect to the location of the critical point that terminate the LDA ↔ HDA transition. The amorphous → β-Sn phase transition is found to be hysteretically reversible as the β-Sn phase undergoes decompressive amorphization near ˜2 GPa due to the lattice instabilities that give rise to density fluctuations in the crystal upon decompression.

Optical and magneto-optical studies of martensitic transformation in Ni-Mn-Ga magnetic shape memory alloys

NASA Astrophysics Data System (ADS)

Beran, L.; Cejpek, P.; Kulda, M.; Antos, R.; Holy, V.; Veis, M.; Straka, L.; Heczko, O.

2015-05-01

Optical and magneto-optical properties of single crystal of Ni50.1Mn28.4Ga21.5 magnetic shape memory alloy during its transformation from martensite to austenite phase were systematically studied. Crystal orientation was approximately along {100} planes of parent cubic austenite. X-ray reciprocal mapping confirmed modulated 10 M martensite phase. Temperature depended measurements of saturation magnetization revealed the martensitic transformation at 335 K during heating. Magneto-optical spectroscopy and spectroscopic ellipsometry were measured in the sample temperature range from 297 to 373 K and photon energy range from 1.2 to 6.5 eV. Magneto-optical spectra of polar Kerr rotation as well as the spectra of ellipsometric parameter Ψ exhibited significant changes when crossing the transformation temperature. These changes were assigned to different optical properties of Ni-Mn-Ga in martensite and austenite phases due to modification of electronic structure near the Fermi energy during martensitic transformation.

Kinetics of phase transformation in glass forming systems

NASA Technical Reports Server (NTRS)

Ray, Chandra S.

1994-01-01

The objectives of this research were to (1) develop computer models for realistic simulations of nucleation and crystal growth in glasses, which would also have the flexibility to accomodate the different variables related to sample characteristics and experimental conditions, and (2) design and perform nucleation and crystallization experiments using calorimetric measurements, such as differential scanning calorimetry (DSC) and differential thermal analysis (DTA) to verify these models. The variables related to sample characteristics mentioned in (1) above include size of the glass particles, nucleating agents, and the relative concentration of the surface and internal nuclei. A change in any of these variables changes the mode of the transformation (crystallization) kinetics. A variation in experimental conditions includes isothermal and nonisothermal DSC/DTA measurements. This research would lead to develop improved, more realistic methods for analysis of the DSC/DTA peak profiles to determine the kinetic parameters for nucleation and crystal growth as well as to assess the relative merits and demerits of the thermoanalytical models presently used to study the phase transformation in glasses.

Characterizing new compositions of [001]C relaxor ferroelectric single crystals using a work-energy model

NASA Astrophysics Data System (ADS)

Gallagher, John A.

2016-04-01

The desired operating range of ferroelectric materials with compositions near the morphotropic phase boundary is limited by field induced phase transformations. In [001]C cut and poled relaxor ferroelectric single crystals the mechanically driven ferroelectric rhombohedral to ferroelectric orthorhombic phase transformation is hindered by antagonistic electrical loading. Instability around the phase transformation makes the current experimental technique for characterization of the large field behavior very time consuming. Characterization requires specialized equipment and involves an extensive set of measurements under combined electrical, mechanical, and thermal loads. In this work a mechanism-based model is combined with a more limited set of experiments to obtain the same results. The model utilizes a work-energy criterion that calculates the mechanical work required to induce the transformation and the required electrical work that is removed to reverse the transformation. This is done by defining energy barriers to the transformation. The results of the combined experiment and modeling approach are compared to the fully experimental approach and error is discussed. The model shows excellent predictive capability and is used to substantially reduce the total number of experiments required for characterization. This decreases the time and resources required for characterization of new compositions.

Nanotwin and phase transformation in tetragonal Pb(Fe1/2Nb1/2)1-xTixO3 single crystal

NASA Astrophysics Data System (ADS)

Tu, C.-S.; Tseng, C.-T.; Chien, R. R.; Schmidt, V. Hugo; Hsieh, C.-M.

2008-09-01

This work is a study of phase transformation in (001)-cut Pb(Fe1/2Nb1/2)1-xTixO3 (x =48%) single crystals by means of dielectric permittivity, domain structure, and in situ x-ray diffraction. A first-order T(TNT)-C(TNT) phase transition was observed at the Curie temperature TC≅518 K upon zero-field heating. T, TNT, and C are tetragonal, tetragonal nanotwin, and cubic phases, respectively. T(TNT) and C(TNT) indicate that minor TNT domains reside in the T and C matrices. Nanotwins, which can cause broad diffraction peak, remain above TC≅518 K and give an average microscopic cubic symmetry in the polarizing microscopy. Colossal dielectric permittivity (>104) was observed above room temperature with strong frequency dispersion. This study suggests that nanotwins can play an important role in relaxor ferroelectric crystals while phase transition takes place. The Fe ion is a potential candidate as a B-site dopant for enhancing dielectric permittivity.

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.

Study of polymorphic control in an ethanol-water binary solvent

NASA Astrophysics Data System (ADS)

Kitano, Hiroshi; Tanaka, Takayuki; Hirasawa, Izumi

2017-07-01

Three polymorphs of L-Citrulline crystals, anhydrate (Form α, γ and δ) and pseudo polymorph (dihydrate), were confirmed. In this study, polymorphic control of L-Citrulline was attempted by changing the ethanol concentration in ethanol-water binary solvents. First, each polymorph of L-Citrulline crystals was added to the prepared ethanol-water binary solvents and samples which were obtained chronologically were measured by XRD. Also, the crystal sizes and shapes in transformation were observed by microscope. Then, polymorphs of the crystals after transformation were determined by XRD pattern. As a result, the transformation from dihydrate to anhydrate was observed by adding dihydrate crystals to the ethanol-water binary solvent. Similarly, the transformation from anhydrate to another anhydrate was observed. Especially in the case of adding dihydrate, the existences of all polymorphs were confirmed by adjusting ethanol-water binary solvent. According to the results, it was revealed that polymorphic transformation was affected by the trace amount of water contained in ethanol-water binary solvent. Moreover, transformation from dihydrate to anhydrate was constructed with three phases, dissolution of dihydrate, nucleation and growth of anhydrate. Therefore, the solution-mediated polymorphic transformation was supposed to be a key mechanism for this transformation.

Phase transformations in 40-60-GPa shocked gneisses from the Haughton Crater (Canada): An Analytical Transmission Electron Microscopy (ATEM) study

NASA Technical Reports Server (NTRS)

Martinez, I.; Guyot, F.; Schaerer, U.

1992-01-01

In order to better understand phase transformations, chemical migration, and isotopic disequilibrium in highly shocked rocks, we have performed a microprobe and an ATEM study on gneisses shocked up to 60 GPa from the Haughton Crater. This study reveals the following chemical and structural characteristics: (1) SiO2 dominant areas are formed by a mixture of pure SiO2 polycrystalline quartz identified by electron diffraction pattern and chemical analysis and a silica-rich amorphous phase containing minor amounts of aluminium, potassium, and iron; (2) Areas with biotitelike composition are formed by less than 200-nm grains of iron-rich spinels embedded in a silica-rich amorphous phase that is very similar to the one described above; (3) Layers with feldsparlike composition are constituted by 100-200-nm-sized alumina-rich grains (the indexation of the crystalline structure is under progress) and the silica-rich amorphous phase; (4) Zones characterized by the unusual Al/Si ratio close to 1 are formed by spinel grains (200-nm-sized) embedded in the same silica-rich amorphous phase; and (5) The fracturated sillimanites contain domains with a lamellar structure, defined by the intercalation of 100-nm-wide lamellae of mullite crystals and of a silica-rich amorphous phase. These mullite crystals preserved the crystallographical orientation of the preshock sillimanite. All compositional domains, identified at the microprobe scale, can thus be explained by a mixture in different proportion between the following phases: (1) a silica-rich amorphous phase, with minor Al and K; (2) quartz crystals; (3) spinel crystals and alumina-rich crystals; (4) sillimanite; and (5) mullite. Such mixtures of amorphous phases and crystals in different proportions explain disturbed isotope systems in these rocks and chemical heterogeneities observed on the microprobe.

Practical physics behind growing crystals of biological macromolecules.

PubMed

Candoni, Nadine; Grossier, Romain; Hammadi, Zoubida; Morin, Roger; Veesler, Stéphane

2012-07-01

The aim of this review is to provide biocrystallographers who intend to tackle protein-crystallization with theory and practical examples. Crystallization involves two separate processes, nucleation and growth, which are rarely completely unconnected. Here we give theoretical background and concrete examples illustrating protein crystallization. We describe the nucleation of a new phase, solid or liquid, and the growth and transformation of existing crystals obtained by primary or secondary nucleation or by seeding. Above all, we believe that a thorough knowledge of the phase diagram is vital to the selection of starting position and path for any crystallization experiment.

Finite size effects in phase transformation kinetics in thin films and surface layers

NASA Astrophysics Data System (ADS)

Trofimov, Vladimir I.; Trofimov, Ilya V.; Kim, Jong-Il

2004-02-01

In studies of phase transformation kinetics in thin films, e.g. crystallization of amorphous films, until recent time is widely used familiar Kolmogorov-Johnson-Mehl-Avrami (KJMA) statistical model of crystallization despite it is applicable only to an infinite medium. In this paper a model of transformation kinetics in thin films based on a concept of the survival probability for randomly chosen point during transformation process is presented. Two model versions: volume induced transformation (VIT) when the second-phase grains nucleate over a whole film volume and surface induced transformation (SIT) when they form on an interface with two nucleation mode: instantaneous nucleation at transformation onset and continuous one during all the process are studied. At VIT-process due to the finite film thickness effects the transformation profile has a maximum in a film middle, whereas that of the grains population reaches a minimum inhere, the grains density is always higher than in a volume material, and the thinner film the slower it transforms. The transformation kinetics in a thin film obeys a generalized KJMA equation with parameters depending on a film thickness and in limiting cases of extremely thin and thick film it reduces to classical KJMA equation for 2D- and 3D-system, respectively.

Phase transformations, anisotropic pyroelectric energy harvesting and electrocaloric properties of (Pb,La)(Zr,Sn,Ti)O3 single crystals.

PubMed

Zhuo, Fangping; Li, Qiang; Gao, Jinghan; Yan, Qingfeng; Zhang, Yiling; Xi, Xiaoqing; Chu, Xiangcheng

2017-05-31

(Pb,La)(Zr,Sn,Ti)O 3 (PLZST) single crystals with their chemical composition located at the tetragonal antiferroelectric region are grown via the flux method in a PbO-PbF 2 -B 2 O 3 mixture. Segregation of the Ti 4+ component in the as-grown crystals is observed due to the strong affinity between the oxygen anion and Ti 4+ ions. The critical electric field of the antiferroelectric to ferroelectric phase transition is determined to be about 0.5 kV mm -1 . The electric field induced ferroelectric phase transforms back into the antiferroelectric phase at a depolarization temperature of 125 °C. Anisotropy of the harvested energy density and electrocaloric behaviors are achieved for the [100], [110] and [111]-oriented PLZST crystals. Based on the thermodynamic theory approach, all the abovementioned behaviors originate from the anisotropic total entropy change. Enhanced electrocaloric strength (0.3 K mm kV -1 ) and the harvested energy density of 0.62 J cm -3 are obtained in the [111]-oriented PLZST crystals. Our results demonstrate the competence of PLZST single crystals for cooling devices and pyroelectric energy harvesting and provide new opportunities to improve energy harvesting density and electrocaloric properties via the anisotropic structural layout, which make the PLZST crystals attractive for solid state cooling devices and energy conversion technologies.

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

Aromí, G.; Beavers, C. M.; Sánchez Costa, J.

Crystal-to-crystal transformations have been crucial in the understanding of solid-state processes, since these may be studied in detail by means of single crystal X-ray diffraction (SCXRD) techniques. The description of the mechanisms and potential intermediates of those processes remains very challenging. In fact, solid-state transient states have rarely been observed, at least to a sufficient level of detail. We have investigated the process of guest extrusion from the non-porous molecular material [Fe(bpp)(H 2L)](ClO 4) 2·1.5C 3H 6O (bpp = 2,6-bis(pyrazol-3-yl)pyridine; H 2L = 2,6-bis(5-(2-methoxyphenyl)-pyrazol-3-yl)pyridine; C 3H 6O = acetone), which occurs through ordered diffusion of acetone in a crystal-to-crystal manner,more » leading to dramatic structural changes. The slow kinetics of the transition allows thermal trapping of the system at various intermediate stages. The transiting single crystal can be then examined at these points through synchrotron SCXRD, offering a window upon the mechanism of the transformation at the molecular scale. These experiments have unveiled the development of an ordered intermediate phase, distinct from the initial and the final states, coexisting as the process advances with either of these two phases or, at a certain moment with both of them. The new intermediate phase has been structurally characterized in full detail by SCXRD, providing insights into the mechanism of this diffusion triggered solid-state phenomenon. Lastly, the process has been also followed by calorimetry, optical microscopy, local Raman spectroscopy and powder X-ray diffraction. The discovery and description of an intermediate ordered state in a molecular solid-state transformation is of great interest and will help to understand the mechanistic details and reaction pathways underlying these transformations.« less

Introduction of artificial pinning centre in {open_quotes}Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub 8}{close_quotes} ceramics

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

Majewski, P.; Aldinger, F.; Elschner, S.

1994-12-31

Considering the phase equilibrium diagram of the system Bi{sub 2}O{sub 3}-SrO-CaO-CuO, single phase {open_quotes}Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub 8}{close_quotes} ceramics have been transformed by a simple annealing procedure into multi phase samples. The transformation results in the formation of second phases and in an increase of the intra grain critical current density at 1 T of five times. This increase is believed to express improved pinning properties of the superconducting crystals. The prepared pinning centres are believed to be e.g. coherent precipitates (Guinier-Preston-zones) within the superconducting crystals.

Crystal structure and phase transformations of calcium yttrium orthophosphate, Ca 3Y(PO 4) 3

NASA Astrophysics Data System (ADS)

Fukuda, Koichiro; Iwata, Tomoyuki; Niwa, Takahiro

2006-11-01

Crystal structure and phase transformations of calcium yttrium orthophosphate Ca 3Y(PO 4) 3 were investigated by X-ray powder diffraction, selected-area electron diffraction, transmission electron microscopy and optical microscopy. The high-temperature phase is isostructural with eulytite, cubic (space group I4¯3d) with a=0.983320(5) nm, V=0.950790(8) nm 3, Z=4 and D x=3.45 Mg m -3. The crystal structure was refined with a split-atom model, in which the oxygen atoms are distributed over two partially occupied sites. Below the stable temperature range of eulytite, the crystal underwent a martensitic transformation, which is accompanied by the formation of platelike surface reliefs. The inverted crystal is triclinic (space group P1) with a=1.5726(1) nm, b=0.84267(9) nm, c=0.81244(8) nm, α=109.739(4)°, β=90.119(5)°, γ=89.908(7)°, V=1.0134(1) nm 3, Z=4 and D x=3.24 Mg m -3. The crystal grains were composed of pseudo-merohedral twins. The adjacent twin domains were related by the pseudo-symmetry mirror planes parallel to {101¯} with the composition surface {101¯}. When the eulytite was cooled relatively slowly from the stable temperature range, the decomposition reaction of Ca 3Y(PO 4) 3→ β-Ca 3(PO 4) 2+YPO 4 occurred.

Transformation of eutectic emulsion to nanosuspension fabricating with solvent evaporation and ultrasonication technique

PubMed Central

Phaechamud, Thawatchai; Tuntarawongsa, Sarun

2016-01-01

Eutectic solvent can solubilize high amount of some therapeutic compounds. Volatile eutectic solvent is interesting to be used as solvent in the preparation of nanosuspension with emulsion solvent evaporation technique. The mechanism of transformation from the eutectic emulsion to nanosuspension was investigated in this study. The 30% w/w ibuprofen eutectic solution was used as the internal phase, and the external phase is composed of Tween 80 as emulsifier. Ibuprofen nanosuspension was prepared by eutectic emulsion solvent evaporating method followed with ultrasonication. During evaporation process, the ibuprofen concentration in emulsion droplets was increased leading to a drug supersaturation but did not immediately recrystallize because of low glass transition temperature (Tg) of ibuprofen. The contact angle of the internal phase on ibuprofen was apparently lower than that of the external phase at all times of evaporation, indicating that the ibuprofen crystals were preferentially wetted by the internal phase than the external phase. From calculated dewetting value ibuprofen crystallization occurred in the droplet. Crystallization of the drug was initiated with external mechanical force, and the particle size of the drug was larger due to Ostwald ripening. Cavitation force from ultrasonication minimized the ibuprofen crystals to the nanoscale. Particle size and zeta potential of formulated ibuprofen nanosuspension were 330.87±51.49 nm and −31.1±1.6 mV, respectively, and exhibited a fast dissolution. Therefore, the combination of eutectic emulsion solvent evaporation method with ultrasonication was favorable for fabricating an ibuprofen nanosuspension, and the transformation mechanism was attained successfully. PMID:27366064

Transformation of eutectic emulsion to nanosuspension fabricating with solvent evaporation and ultrasonication technique.

PubMed

Phaechamud, Thawatchai; Tuntarawongsa, Sarun

2016-01-01

Eutectic solvent can solubilize high amount of some therapeutic compounds. Volatile eutectic solvent is interesting to be used as solvent in the preparation of nanosuspension with emulsion solvent evaporation technique. The mechanism of transformation from the eutectic emulsion to nanosuspension was investigated in this study. The 30% w/w ibuprofen eutectic solution was used as the internal phase, and the external phase is composed of Tween 80 as emulsifier. Ibuprofen nanosuspension was prepared by eutectic emulsion solvent evaporating method followed with ultrasonication. During evaporation process, the ibuprofen concentration in emulsion droplets was increased leading to a drug supersaturation but did not immediately recrystallize because of low glass transition temperature (T g) of ibuprofen. The contact angle of the internal phase on ibuprofen was apparently lower than that of the external phase at all times of evaporation, indicating that the ibuprofen crystals were preferentially wetted by the internal phase than the external phase. From calculated dewetting value ibuprofen crystallization occurred in the droplet. Crystallization of the drug was initiated with external mechanical force, and the particle size of the drug was larger due to Ostwald ripening. Cavitation force from ultrasonication minimized the ibuprofen crystals to the nanoscale. Particle size and zeta potential of formulated ibuprofen nanosuspension were 330.87±51.49 nm and -31.1±1.6 mV, respectively, and exhibited a fast dissolution. Therefore, the combination of eutectic emulsion solvent evaporation method with ultrasonication was favorable for fabricating an ibuprofen nanosuspension, and the transformation mechanism was attained successfully.

Phase transitions in mixed gas hydrates: experimental observations versus calculated data.

PubMed

Schicks, Judith M; Naumann, Rudolf; Erzinger, Jörg; Hester, Keith C; Koh, Carolyn A; Sloan, E Dendy

2006-06-15

This paper presents the phase behavior of multicomponent gas hydrate systems formed from primarily methane with small amounts of ethane and propane. Experimental conditions were typically in a pressure range between 1 and 6 MPa, and the temperature range was between 260 and 290 K. These multicomponent systems have been investigated using a variety of techniques including microscopic observations, Raman spectroscopy, and X-ray diffraction. These techniques, used in combination, allowed for measurement of the hydrate structure and composition, while observing the morphology of the hydrate crystals measured. The hydrate formed immediately below the three-phase line (V-L --> V-L-H) and contained crystals that were both light and dark in appearance. The light crystals, which visually were a single solid phase, showed a spectroscopic indication for the presence of occluded free gas in the hydrate. In contrast, the dark crystals were measured to be structure II (sII) without the presence of these occluded phases. Along with hydrate measurements near the decomposition line, an unexpected transformation process was visually observed at P-T-conditions in the stability field of the hydrates. Larger crystallites transformed into a foamy solid upon cooling over this transition line (between 5 and 10 K below the decomposition temperature). Below the transition line, a mixture of sI and sII was detected. This is the first time that these multicomponent systems have been investigated at these pressure and temperature conditions using both visual and spectroscopic techniques. These techniques enabled us to observe and measure the unexpected transformation process showing coexistence of different gas hydrate phases.

Effect of Slag Composition on the Crystallization Kinetics of Synthetic CaO-SiO2-Al2O3-MgO Slags

NASA Astrophysics Data System (ADS)

Esfahani, Shaghayegh; Barati, Mansoor

2018-04-01

The crystallization kinetics of CaO-SiO2-Al2O3-MgO (CSAM) slags was studied with the aid of single hot thermocouple technique (SHTT). Kinetic parameters such as the Avrami exponent ( n), rate coefficient ( K), and effective activation energy of crystallization ( E A ) were obtained by kinetic analysis of data obtained from in situ observation of glassy to crystalline transformation and image analysis. Also, the dependence of nucleation and growth rates of crystalline phases were quantified as a function of time, temperature, and slag basicity. Together with the observations of crystallization front, they facilitated establishing the dominant mechanisms of crystallization. In an attempt to predict crystallization rate under non-isothermal conditions, a mathematical model was developed that employs the rate data of isothermal transformation. The model was validated by reproducing an experimental continuous cooling transformation diagram purely from isothermal data.

High-quality EuO thin films the easy way via topotactic transformation

DOE PAGES

Mairoser, Thomas; Mundy, Julia A.; Melville, Alexander; ...

2015-07-16

Epitaxy is widely employed to create highly oriented crystalline films. A less appreciated, but nonetheless powerful means of creating such films is via topotactic transformation, in which a chemical reaction transforms a single crystal of one phase into a single crystal of a different phase, which inherits its orientation from the original crystal. Topotactic reactions may be applied to epitactic films to substitute, add or remove ions to yield epitactic films of different phases. Here we exploit a topotactic reduction reaction to provide a non-ultra-high vacuum (UHV) means of growing highly oriented single crystalline thin films of the easily over-oxidizedmore » half-metallic semiconductor europium monoxide (EuO) with a perfection rivalling that of the best films of the same material grown by molecular-beam epitaxy or UHV pulsed-laser deposition. Lastly, as the technique only requires high-vacuum deposition equipment, it has the potential to drastically improve the accessibility of high-quality single crystalline films of EuO as well as other difficult-to-synthesize compounds.« less

Vapor-crystal phase transition in synthesis of paracetamol films by vacuum evaporation and condensation

NASA Astrophysics Data System (ADS)

Belyaev, A. P.; Rubets, V. P.; Antipov, V. V.; Bordei, N. S.; Zarembo, V. I.

2014-03-01

We report on the structural and technological investigations of the vapor-crystal phase transition during synthesis of paracetamol films of the monoclinic system by vacuum evaporation and condensation in the temperature range 220-320 K. The complex nature of the transformation accompanied by the formation of a gel-like phase is revealed. The results are interpreted using a model according to which the vapor-crystal phase transition is not a simple first-order phase transition, but is a nonlinear superposition of two phase transitions: a first-order transition with a change in density and a second-order phase transition with a change in ordering. Micrographs of the surface of the films are obtained at different phases of formation.

Atomistic insights into the nanosecond long amorphization and crystallization cycle of nanoscale G e2S b2T e5 : An ab initio molecular dynamics study

NASA Astrophysics Data System (ADS)

Branicio, Paulo S.; Bai, Kewu; Ramanarayan, H.; Wu, David T.; Sullivan, Michael B.; Srolovitz, David J.

2018-04-01

The complete process of amorphization and crystallization of the phase-change material G e2S b2T e5 is investigated using nanosecond ab initio molecular dynamics simulations. Varying the quench rate during the amorphization phase of the cycle results in the generation of a variety of structures from entirely crystallized (-0.45 K/ps) to entirely amorphized (-16 K/ps). The 1.5-ns annealing simulations indicate that the crystallization process depends strongly on both the annealing temperature and the initial amorphous structure. The presence of crystal precursors (square rings) in the amorphous matrix enhances nucleation/crystallization kinetics. The simulation data are used to construct a combined continuous-cooling-transformation (CCT) and temperature-time-transformation (TTT) diagram. The nose of the CCT-TTT diagram corresponds to the minimum time for the onset of homogenous crystallization and is located at 600 K and 70 ps. That corresponds to a critical cooling rate for amorphization of -4.5 K/ps. The results, in excellent agreement with experimental observations, suggest that a strategy that utilizes multiple quench rates and annealing temperatures may be used to effectively optimize the reversible switching speed and enable fast and energy-efficient phase-change memories.

Phase transitions of amorphous solid acetone in confined geometry investigated by reflection absorption infrared spectroscopy.

PubMed

Shin, Sunghwan; Kang, Hani; Kim, Jun Soo; Kang, Heon

2014-11-26

We investigated the phase transformations of amorphous solid acetone under confined geometry by preparing acetone films trapped in amorphous solid water (ASW) or CCl4. Reflection absorption infrared spectroscopy (RAIRS) and temperature-programmed desorption (TPD) were used to monitor the phase changes of the acetone sample with increasing temperature. An acetone film trapped in ASW shows an abrupt change in the RAIRS features of the acetone vibrational bands during heating from 80 to 100 K, which indicates the transformation of amorphous solid acetone to a molecularly aligned crystalline phase. Further heating of the sample to 140 K produces an isotropic solid phase, and eventually a fluid phase near 157 K, at which the acetone sample is probably trapped in a pressurized, superheated condition inside the ASW matrix. Inside a CCl4 matrix, amorphous solid acetone crystallizes into a different, isotropic structure at ca. 90 K. We propose that the molecularly aligned crystalline phase formed in ASW is created by heterogeneous nucleation at the acetone-water interface, with resultant crystal growth, whereas the isotropic crystalline phase in CCl4 is formed by homogeneous crystal growth starting from the bulk region of the acetone sample.

High-pressure crystal structures of an insensitive energetic crystal: 1,1-diamino-2,2-dinitroethene

DOE PAGES

Dreger, Zbigniew A.; Stash, Adam I.; Yu, Zhi -Gang; ...

2015-12-03

Understanding the insensitivity/stability of insensitive high explosive crystals requires detailed structural information at high pressures and high temperatures of interest. Synchrotron single crystal x-ray diffraction experiments were used to determine the high-pressure structures of 1,1-diamino-2,2-dinitroethene (FOX-7), a prototypical insensitive high explosive. The phase transition around 4.5 GPa was investigated and the structures were determined at 4.27 GPa (α’-phase) and 5.9 GPa (ε-phase). The α’-phase (monoclinic, P2 1/ n), structurally indistinguishable from the ambient α-phase, transforms to the new ε-phase (triclinic, P1). The most notable features of the ε-phase, compared to the α’-phase, are: formation of planar layers and flattening ofmore » molecules. Density functional theory (DFT-D2) calculations complemented the experimental results. Furthermore, the results presented here are important for understanding the molecular and crystalline attributes governing the high-pressure insensitivity/stability of insensitive high explosive crystals.« less

High-pressure crystal structures of an insensitive energetic crystal: 1,1-diamino-2,2-dinitroethene

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

Dreger, Zbigniew A.; Stash, Adam I.; Yu, Zhi -Gang

Understanding the insensitivity/stability of insensitive high explosive crystals requires detailed structural information at high pressures and high temperatures of interest. Synchrotron single crystal x-ray diffraction experiments were used to determine the high-pressure structures of 1,1-diamino-2,2-dinitroethene (FOX-7), a prototypical insensitive high explosive. The phase transition around 4.5 GPa was investigated and the structures were determined at 4.27 GPa (α’-phase) and 5.9 GPa (ε-phase). The α’-phase (monoclinic, P2 1/ n), structurally indistinguishable from the ambient α-phase, transforms to the new ε-phase (triclinic, P1). The most notable features of the ε-phase, compared to the α’-phase, are: formation of planar layers and flattening ofmore » molecules. Density functional theory (DFT-D2) calculations complemented the experimental results. Furthermore, the results presented here are important for understanding the molecular and crystalline attributes governing the high-pressure insensitivity/stability of insensitive high explosive crystals.« less

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

NASA Astrophysics Data System (ADS)

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

2005-01-01

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

Phase field modeling of tetragonal to monoclinic phase transformation in zirconia

NASA Astrophysics Data System (ADS)

Mamivand, Mahmood

Zirconia based ceramics are strong, hard, inert, and smooth, with low thermal conductivity and good biocompatibility. Such properties made zirconia ceramics an ideal material for different applications form thermal barrier coatings (TBCs) to biomedicine applications like femoral implants and dental bridges. However, this unusual versatility of excellent properties would be mediated by the metastable tetragonal (or cubic) transformation to the stable monoclinic phase after a certain exposure at service temperatures. This transformation from tetragonal to monoclinic, known as LTD (low temperature degradation) in biomedical application, proceeds by propagation of martensite, which corresponds to transformation twinning. As such, tetragonal to monoclinic transformation is highly sensitive to mechanical and chemomechanical stresses. It is known in fact that this transformation is the source of the fracture toughening in stabilized zirconia as it occurs at the stress concentration regions ahead of the crack tip. This dissertation is an attempt to provide a kinetic-based model for tetragonal to monoclinic transformation in zirconia. We used the phase field technique to capture the temporal and spatial evolution of monoclinic phase. In addition to morphological patterns, we were able to calculate the developed internal stresses during tetragonal to monoclinic transformation. The model was started form the two dimensional single crystal then was expanded to the two dimensional polycrystalline and finally to the three dimensional single crystal. The model is able to predict the most physical properties associated with tetragonal to monoclinic transformation in zirconia including: morphological patterns, transformation toughening, shape memory effect, pseudoelasticity, surface uplift, and variants impingement. The model was benched marked with several experimental works. The good agreements between simulation results and experimental data, make the model a reliable tool for predicting tetragonal to monoclinic transformation in the cases we lack experimental observations.

Anisotropy of Single-Crystal Silicon in Nanometric Cutting.

PubMed

Wang, Zhiguo; Chen, Jiaxuan; Wang, Guilian; Bai, Qingshun; Liang, Yingchun

2017-12-01

The anisotropy exhibited by single-crystal silicon in nanometric cutting is very significant. In order to profoundly understand the effect of crystal anisotropy on cutting behaviors, a large-scale molecular dynamics model was conducted to simulate the nanometric cutting of single-crystal silicon in the (100)[0-10], (100)[0-1-1], (110)[-110], (110)[00-1], (111)[-101], and (111)[-12-1] crystal directions in this study. The simulation results show the variations of different degrees in chip, subsurface damage, cutting force, and friction coefficient with changes in crystal plane and crystal direction. Shear deformation is the formation mechanism of subsurface damage, and the direction and complexity it forms are the primary causes that result in the anisotropy of subsurface damage. Structurally, chips could be classified into completely amorphous ones and incompletely amorphous ones containing a few crystallites. The formation mechanism of the former is high-pressure phase transformation, while the latter is obtained under the combined action of high-pressure phase transformation and cleavage. Based on an analysis of the material removal mode, it can be found that compared with the other crystal direction on the same crystal plane, the (100)[0-10], (110)[-110], and (111)[-101] directions are more suitable for ductile cutting.

Controlled In Meso Phase Crystallization – A Method for the Structural Investigation of Membrane Proteins

PubMed Central

Kubicek, Jan; Schlesinger, Ramona; Baeken, Christian; Büldt, Georg; Schäfer, Frank; Labahn, Jörg

2012-01-01

We investigated in meso crystallization of membrane proteins to develop a fast screening technology which combines features of the well established classical vapor diffusion experiment with the batch meso phase crystallization, but without premixing of protein and monoolein. It inherits the advantages of both methods, namely (i) the stabilization of membrane proteins in the meso phase, (ii) the control of hydration level and additive concentration by vapor diffusion. The new technology (iii) significantly simplifies in meso crystallization experiments and allows the use of standard liquid handling robots suitable for 96 well formats. CIMP crystallization furthermore allows (iv) direct monitoring of phase transformation and crystallization events. Bacteriorhodopsin (BR) crystals of high quality and diffraction up to 1.3 Å resolution have been obtained in this approach. CIMP and the developed consumables and protocols have been successfully applied to obtain crystals of sensory rhodopsin II (SRII) from Halobacterium salinarum for the first time. PMID:22536388

Segregation and Phase Transformations Along Superlattice Intrinsic Stacking Faults in Ni-Based Superalloys

NASA Astrophysics Data System (ADS)

Smith, T. M.; Esser, B. D.; Good, B.; Hooshmand, M. S.; Viswanathan, G. B.; Rae, C. M. F.; Ghazisaeidi, M.; McComb, D. W.; Mills, M. J.

2018-06-01

In this study, local chemical and structural changes along superlattice intrinsic stacking faults combine to represent an atomic-scale phase transformation. In order to elicit stacking fault shear, creep tests of two different single crystal Ni-based superalloys, ME501 and CMSX-4, were performed near 750 °C using stresses of 552 and 750 MPa, respectively. Through high-resolution scanning transmission electron microscopy (STEM) and state-of-the-art energy dispersive X-ray spectroscopy, ordered compositional changes were measured along SISFs in both alloys. For both instances, the elemental segregation and local crystal structure present along the SISFs are consistent with a nanoscale γ' to D019 phase transformation. Other notable observations are prominent γ-rich Cottrell atmospheres and new evidence of more complex reordering processes responsible for the formation of these faults. These findings are further supported using density functional theory calculations and high-angle annular dark-field (HAADF)-STEM image simulations.

Crystal structure transformation in potassium acrylate

NASA Astrophysics Data System (ADS)

Pai Verneker, V. R.; Vasanthakumari, R.

1983-10-01

Potassium acrylate undergoes a reversible phase transformation around 335°K with an activation energy of 133 kcal/mole. Differential scanning calorimetry and high temperature X-ray powder diffraction techniques have been used to probe this phenomenon.

Orientation Dependence of Functional Properties in Heterophase Single Crystals of the Ti36.5Ni51.0Hf12.5 and Ti48.5Ni51.5 Alloys

NASA Astrophysics Data System (ADS)

Panchenko, E. Yu.; Chumlyakov, Yu. I.; Surikov, N. Yu.; Tagiltsev, A. I.; Vetoshkina, N. G.; Osipovich, K. S.; Maier, H.; Sehitoglu, H.

2016-03-01

The features of orientation dependence of stress-induced thermoelastic B2-( R)- B19'-martensitic transformations in single crystals of the Ti48.5Ni51.5 and Ni51.0Ti36.5Hf12.5 (at.%) alloys, which contain disperse particles of the Ti3Ni4 and H-phase, respectively, are revealed along with those of their shape-memory effects (SME) and superelasticity (SE). It is experimentally demonstrated that irrespective of the crystal structure of disperse particles measuring more than 100 nm, for their volume fraction f > 16% there is a weaker orientation dependence of the reversible strain in the cases of manifestation of SME and SE. In the orientations of Class I, wherein martensitic detwinning introduces a considerable contribution into transformation strain, the values of SME |ɛ SME | and SE |ɛ SE | decrease by over a factor of two compared to the theoretical lattice strain value |ɛ tr0 | for a B2- B19'-transformation and the experimental values of reversible strain for quenched TiNi crystals. In the orientations of Class 2, wherein detwinning of the martensite is suppressed as is the case in quenched single-phase single crystals, the reversible strain is maintained close to its theoretical value |ɛ tr0 |. Micromechanical models of interaction between the martensite and the disperse particles are proposed, which account for the weaker orientation dependence of |ɛ SME | and |ɛ SE | due to suppression of detwinning of the B19'-martensite crystals by the particles and a transition from a single-variant evolution of the stress-induced martensitic transformations to a multiple-variant evolution of transformations in the cases of increased size of the particles and their larger volume fractions.

Crystallization Behavior of the CaO-Al2O3-MgO System Studied with a Confocal Laser Scanning Microscope

NASA Astrophysics Data System (ADS)

Jung, Sung Suk; Sohn, Il

2012-12-01

The crystallization behavior of a calcium-aluminate system with various MgO content from 2.5 to 7.5 wt pct and CaO/Al2O3 ratios between 0.8 and 1.2 has been examined using a confocal laser scanning microscope (CLSM). CCT (continuous cooling transformation) and time temperature transformation (TTT) diagrams were constructed to identify the primary crystal phase of slag at different compositions and at cooling rates between 25 and 800 K/minutes. In the slag at a CaO/Al2O3 ratio of 1.0, crystallization temperature increased during isothermal and continuous cooling with higher MgO content, and the shortest incubation time was observed at 5 wt pct MgO. When MgO content was fixed to be 5 wt pct, crystallization temperature increased with lower CaO/Al2O3 ratio. According to the slag composition, cooling rates and temperature, the primary phase could be CA, or C5A3, or C3A, or C3MA2, or MgO, and the crystal morphology changes from dendrites to faceted crystals to columnar crystals in this composition range.

Kinetic boundaries and phase transformations of ice i at high pressure.

PubMed

Wang, Yu; Zhang, Huichao; Yang, Xue; Jiang, Shuqing; Goncharov, Alexander F

2018-01-28

Raman spectroscopy in diamond anvil cells has been employed to study phase boundaries and transformation kinetics of H 2 O ice at high pressures up to 16 GPa and temperatures down to 15 K. Ice i formed at nearly isobaric cooling of liquid water transforms on compression to high-density amorphous (HDA) ice at 1.1-3 GPa at 15-100 K and then crystallizes in ice vii with the frozen-in disorder (ice vii') which remains stable up to 14.1 GPa at 80 K and 15.9 GPa at 100 K. Unexpectedly, on decompression of ice vii', it transforms to ice viii in its domain of metastability, and then it relaxes into low-density amorphous (LDA) ice on a subsequent pressure release and warming up. On compression of ice i at 150-170 K, ice ix is crystallized and no HDA ice is found; further compression of ice ix results in the sequential phase transitions to stable ices vi and viii. Cooling ice i to 210 K at 0.3 GPa transforms it to a stable ice ii. Our extensive investigations provide previously missing information on the phase diagram of water, especially on the kinetic paths that result in formation of phases which otherwise are not accessible; these results are keys for understanding the phase relations including the formation of metastable phases. Our observations inform on the ice modifications that can occur naturally in planetary environments and are not accessible for direct observations.

Kinetic boundaries and phase transformations of ice i at high pressure

NASA Astrophysics Data System (ADS)

Wang, Yu; Zhang, Huichao; Yang, Xue; Jiang, Shuqing; Goncharov, Alexander F.

2018-01-01

Raman spectroscopy in diamond anvil cells has been employed to study phase boundaries and transformation kinetics of H2O ice at high pressures up to 16 GPa and temperatures down to 15 K. Ice i formed at nearly isobaric cooling of liquid water transforms on compression to high-density amorphous (HDA) ice at 1.1-3 GPa at 15-100 K and then crystallizes in ice vii with the frozen-in disorder (ice vii') which remains stable up to 14.1 GPa at 80 K and 15.9 GPa at 100 K. Unexpectedly, on decompression of ice vii', it transforms to ice viii in its domain of metastability, and then it relaxes into low-density amorphous (LDA) ice on a subsequent pressure release and warming up. On compression of ice i at 150-170 K, ice ix is crystallized and no HDA ice is found; further compression of ice ix results in the sequential phase transitions to stable ices vi and viii. Cooling ice i to 210 K at 0.3 GPa transforms it to a stable ice ii. Our extensive investigations provide previously missing information on the phase diagram of water, especially on the kinetic paths that result in formation of phases which otherwise are not accessible; these results are keys for understanding the phase relations including the formation of metastable phases. Our observations inform on the ice modifications that can occur naturally in planetary environments and are not accessible for direct observations.

The transformation of magnetite to hematite and its influence on the rheology of iron oxide rock

NASA Astrophysics Data System (ADS)

Lagoeiro, Leonardo; Barbosa, Paola; Goncalves, Fabio; Rodrigues, Carlos

2013-04-01

Phase transformation is an important process for strain localization after the initiation of ductile shear zones. In polyphase aggregates one important aspect to consider is likely to be the interconnectivity of weak phase after the transformation of the load-bearing framework grains. However the physical processes involved in that transition is not well understood, partially because the microstructures of the initial weakening are generally obliterated by subsequent deformation. Iron oxide-quartz rocks from paleoproterozoic Iron Formations in southern Brazil preserve microstructures that allow a good insight into the evolution of the deformation mechanisms and fabrics during the transition from a load-bearing framework (magnetite) to an interconnected weak phase (hematite). We conducted microstructural and textural analyses of aggregates of magnetite and hematite combining observations in an optical microscope and measurements in the electron back-scatter diffraction (EBSD). The samples were cut parallel to the mineral lineation (the X-axis) and perpendicular to the foliation. Our goal was to understand the evolution of fabric and texture of the iron oxide aggregates caused by the change in deformation behavior resulting from the phase transformation. The studied samples consist mainly of aggregates of magnetite and hematite in a varied proportions. Samples that preserve the early microstructures consist in aggregate of magnetite grains of varied sizes. The grains are partially transformed to hematite along {111} planes but no foliation is observed in the samples. Basically the samples consist of grains of irregular shapes and a weak or absent crystallographic preferred orientation. The newly transformed hematite crystals share the (0001) planes and directions <11-20> with planes {111} and directions <110> of magnetite grains. Other samples present relicts of initial magnetite grains surrounded by a matrix of tabular to platy hematite crystals. The matrix show a preferred orientation of hematite grains. Close to the magnetite, hematite crystals show crystallographic relationship similar to those observed inside the magnetite crystals showing a good match in crystallographic planes and directions. However away from the magnetite crystals hematite of the matrix tend to show a more independent crystallographic orientation with respect to the magnetite grains. The poles to the basal planes of hematite distributed in a small circle centered around the Z-axis and the crystallographic directions <11-20> spread in a wide angle along the foliation plane. In samples where no crystal of magnetite grains is observed only platy hematite with a strong shape preferred orientation occur. Their basal planes show a strong concentration around the foliation pole contrasting to the more dispersed distribution around the Z-axis found in the samples with magnetite relicts.The directions <11-20> also distributed along the foliation planes in platy hematite samples but with a narrower angles than those of samples with magnetite relicts. The progressive transformation of magnetite to hematite led to a change in the iron formation rock fabrics from an isotropic distribution of a load-supporting magnetite to an interconnected weak platy hematite forming a strongly anisotropic fabric. The hard magnetite behaves in a brittle manner with a very limited operation of slip along the main crystallographic planes. The microfracturing creates an easy path for oxidation and transformation of magnetite. The newly formed hematite grains behave in a ductile manner and form a matrix of strongly oriented crystals. The deformation mechanisms change from the microfracturing of the harder magnetite phase to a crystal plastic deformation of the softer hematite platy grains through slip along their basal planes.

Transient phases during crystallization of solution-processed organic thin films

NASA Astrophysics Data System (ADS)

Wan, Jing; Li, Yang; Ulbrandt, Jeffery; Smilgies, Detlef-M.; Hollin, Jonathan; Whalley, Adam; Headrick, Randall

We report an in-situ study of 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT) organic semiconductor thin film deposition from solution via hollow pen writing, which exhibits multiple transient phases during crystallization. Under high writing speed (25 mm/s) the films have an isotropic morphology, although the mobilities range up to 3.0 cm2/V.s. To understand the crystallization in this highly non-equilibrium regime, we employ in-situ microbeam grazing incidence wide-angle X-ray scattering combined with optical video microscopy at different deposition temperatures. A sequence of crystallization was observed in which a layered liquid-crystalline (LC) phase of C8-BTBT precedes inter-layer ordering. For films deposited above 80ºC, a transition from LC phase to a transient crystalline state that we denote as Cr1 occurs after a temperature-dependent incubation time, which is consistent with classical nucleation theory. After an additional ~ 0.5s, Cr1 transforms to the final stable structure Cr2. Based on these results, we demonstrate a method to produce large crystalline grain size and high carrier mobility during high-speed processing by controlling the nucleation rate during the transformation from the LC phase. Nsf DMR-1307017, NSF DMR-1332208.

Phase Separation and Crystallization of Hemoglobin C in Transgenic Mouse and Human Erythrocytes

PubMed Central

Canterino, Joseph E.; Galkin, Oleg; Vekilov, Peter G.; Hirsch, Rhoda Elison

2008-01-01

Individuals expressing hemoglobin C (β6 Glu→Lys) present red blood cells (RBC) with intraerythrocytic crystals that form when hemoglobin (Hb) is oxygenated. Our earlier in vitro liquid-liquid (L-L) phase separation studies demonstrated that liganded HbC exhibits a stronger net intermolecular attraction with a longer range than liganded HbS or HbA, and that L-L phase separation preceded and enhanced crystallization. We now present evidence for the role of phase separation in HbC crystallization in the RBC, and the role of the RBC membrane as a nucleation center. RBC obtained from both human homozygous HbC patients and transgenic mice expressing only human HbC were studied by bright-field and differential interference contrast video-enhanced microscopy. RBC were exposed to hypertonic NaCl solution (1.5–3%) to induce crystallization within an appropriate experimental time frame. L-L phase separation occurred inside the RBC, which in turn enhanced the formation of intraerythrocytic crystals. RBC L-L phase separation and crystallization comply with the thermodynamic and kinetics laws established through in vitro studies of phase transformations. This is the first report, to the best of our knowledge, to capture a temporal view of intraerythrocytic HbC phase separation, crystal formation, and dissolution. PMID:18621841

Cross-phase-modulation-induced instability in photonic-crystal fibers.

PubMed

Serebryannikov, E E; Konorov, S O; Ivanov, A A; Alfimov, M V; Scalora, M; Zheltikov, A M

2005-08-01

Cross-phase-modulation-induced instability is identified as a significant mechanism for efficient parametric four-wave-mixing frequency conversion in photonic-crystal fibers. Fundamental-wavelength femtosecond pulses of a Cr, forsterite laser are used in our experiments to transform the spectrum of copropagating second-harmonic pulses of the same laser in a photonic-crystal fiber. Efficient generation of sidebands shifted by more than 80 THz with respect to the central frequency of the second harmonic is observed in the output spectrum of the probe field.

Multiple pathways of crystal nucleation in an extremely supersaturated aqueous potassium dihydrogen phosphate (KDP) solution droplet

PubMed Central

Lee, Sooheyong; Wi, Haeng Sub; Jo, Wonhyuk; Cho, Yong Chan; Lee, Hyun Hwi; Jeong, Se-Young; Kim, Yong-Il; Lee, Geun Woo

2016-01-01

Solution studies have proposed that crystal nucleation can take more complex pathways than previously expected in classical nucleation theory, such as formation of prenucleation clusters or densified amorphous/liquid phases. These findings show that it is possible to separate fluctuations in the different order parameters governing crystal nucleation, that is, density and structure. However, a direct observation of the multipathways from aqueous solutions remains a great challenge because heterogeneous nucleation sites, such as container walls, can prevent these paths. Here, we demonstrate the existence of multiple pathways of nucleation in highly supersaturated aqueous KH2PO4 (KDP) solution using the combination of a containerless device (electrostatic levitation), and in situ micro-Raman and synchrotron X-ray scattering. Specifically, we find that, at an unprecedentedly deep level of supersaturation, a high-concentration KDP solution first transforms into a metastable crystal before reaching stability at room temperature. However, a low-concentration solution, with different local structures, directly transforms into the stable crystal phase. These apparent multiple pathways of crystallization depend on the degree of supersaturation. PMID:27791068

Multiple pathways of crystal nucleation in an extremely supersaturated aqueous potassium dihydrogen phosphate (KDP) solution droplet.

PubMed

Lee, Sooheyong; Wi, Haeng Sub; Jo, Wonhyuk; Cho, Yong Chan; Lee, Hyun Hwi; Jeong, Se-Young; Kim, Yong-Il; Lee, Geun Woo

2016-11-29

Solution studies have proposed that crystal nucleation can take more complex pathways than previously expected in classical nucleation theory, such as formation of prenucleation clusters or densified amorphous/liquid phases. These findings show that it is possible to separate fluctuations in the different order parameters governing crystal nucleation, that is, density and structure. However, a direct observation of the multipathways from aqueous solutions remains a great challenge because heterogeneous nucleation sites, such as container walls, can prevent these paths. Here, we demonstrate the existence of multiple pathways of nucleation in highly supersaturated aqueous KH 2 PO 4 (KDP) solution using the combination of a containerless device (electrostatic levitation), and in situ micro-Raman and synchrotron X-ray scattering. Specifically, we find that, at an unprecedentedly deep level of supersaturation, a high-concentration KDP solution first transforms into a metastable crystal before reaching stability at room temperature. However, a low-concentration solution, with different local structures, directly transforms into the stable crystal phase. These apparent multiple pathways of crystallization depend on the degree of supersaturation.

Pressure-induced silica quartz amorphization studied by iterative stochastic surface walking reaction sampling.

PubMed

Zhang, Xiao-Jie; Shang, Cheng; Liu, Zhi-Pan

2017-02-08

The crystal to amorphous transformation is a common phenomenon in Nature and has important impacts on material properties. Our current knowledge on such complex solid transformation processes is, however, limited because of their slow kinetics and the lack of long-range ordering in amorphous structures. To reveal the kinetics in the amorphization of solids, this work, by developing iterative reaction sampling based on the stochastic surface walking global optimization method, investigates the well-known crystal to amorphous transformation of silica (SiO 2 ) under external pressures, the mechanism of which has long been debated for its non-equilibrium, pressure-sensitive kinetics and complex product components. Here we report for the first time the global potential energy surface (PES) and the lowest energy pathways for α-quartz amorphization from first principles. We show that the pressurization at 15 GPa, the reaction condition, can lift the quartz phase energetically close to the amorphous zone, which thermodynamically initializes the amorphization. More importantly, the large flexibility of Si cation coordination (including four, five and six coordination) results in many kinetically competing routes to more stable dense forms, including the known MI, stishovite, newly-identified MII and TI phases. All these pathways have high barriers due to the local Si-O bond breaking and are mediated by amorphous structures with five-fold Si. This causes simultaneous crystal-to-crystal and crystal-to-amorphous transitions. The high barrier and the reconstructive nature of the phase transition are the key kinetics origin for silica amorphization under pressures.

Mutual transformation of light waves by reflection holograms in photorefractive crystals of the 4-bar 3m symmetry

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

Naunyka, V. N.; Shepelevich, V. V., E-mail: vasshep@inbox.ru

2011-05-15

The mutual transformation of light waves in the case of their simultaneous diffraction from a bulk reflection phase hologram, which was formed in a cubic photorefractive crystal of the 4-bar 3m symmetry class, has been studied. The indicator surfaces of the polarization-optimized values of the relative intensity of the object wave, which make it possible to determine the amplification of this wave for any crystal cut, are constructed. The linear polarization azimuths at which the energy exchange between the light waves reaches a maximum are found numerically for crystals of different cuts.

Realization of atomistic transitions with colloidal nanoparticles using an ultrafast laser

NASA Astrophysics Data System (ADS)

Akguc, Gursoy; Ilday, Serim; Ilday, Omer; Gulseren, Oguz; Makey, Ghaith; Yavuz, Koray

We report on realization of rapid atomistic transitions with colloidal nanoparticles in a setting that constitutes a dissipative far-from-equilibrium system subject to stochastic forces. Large colloidal crystals (comprising hundreds of particles) can be formed and transitions between solid-liquid-gas phases can be observed effortlessly and within seconds. Furthermore, this system allows us to form and dynamically arrest metastable phases such as glassy structures and to controllably transform a crystal pattern from square to hexagonal lattices and vice versa as well as to observe formation and propagation of crystal defects (i.e. line defects, point defects, planar defects). The mechanism largely relies on an interplay between convective forces induced by femtosecond pulses and strong Brownian motion; the former drags the colloids to form and reinforce the crystal and the latter is analogous to lattice vibrations, which makes it possible to observe phase transitions, defect formation and propagation and lattice transformation. This unique system can help us get insight into the mechanisms underlying various solid state phenomena that were previously studied under slowly evolving (within hours/days), near-equilibrium colloidal systems.

Defect-induced local variation of crystal phase transition temperature in metal-halide perovskites.

PubMed

Dobrovolsky, Alexander; Merdasa, Aboma; Unger, Eva L; Yartsev, Arkady; Scheblykin, Ivan G

2017-06-26

Solution-processed organometal halide perovskites are hybrid crystalline semiconductors highly interesting for low-cost and efficient optoelectronics. Their properties are dependent on the crystal structure. Literature shows a variety of crystal phase transition temperatures and often a spread of the transition over tens of degrees Kelvin. We explain this inconsistency by demonstrating that the temperature of the tetragonal-to-orthorhombic phase transition in methylammonium lead triiodide depends on the concentration and nature of local defects. Phase transition in individual nanowires was studied by photoluminescence microspectroscopy and super-resolution imaging. We propose that upon cooling from 160 to 140 K, domains of the crystal containing fewer defects stay in the tetragonal phase longer than highly defected domains that readily transform to the high bandgap orthorhombic phase at higher temperatures. The existence of relatively pure tetragonal domains during the phase transition leads to drastic photoluminescence enhancement, which is inhomogeneously distributed across perovskite microcrystals.Understanding crystal phase transition in materials is of fundamental importance. Using luminescence spectroscopy and super-resolution imaging, Dobrovolsky et al. study the transition from the tetragonal to orthorhombic crystal phase in methylammonium lead triiodide nanowires at low temperature.

RH-temperature phase diagrams of hydrate forming deliquescent crystalline ingredients.

PubMed

Allan, Matthew; Mauer, Lisa J

2017-12-01

Several common deliquescent crystalline food ingredients (including glucose and citric acid) are capable of forming crystal hydrate structures. The propensity of such crystals to hydrate/dehydrate or deliquesce is dependent on the environmental temperature and relative humidity (RH). As an anhydrous crystal converts to a crystal hydrate, water molecules internalize into the crystal structure resulting in different physical properties. Deliquescence is a solid-to-solution phase transformation. RH-temperature phase diagrams of the food ingredients alpha-d-glucose and citric acid, along with sodium sulfate, were produced using established and newly developed methods. Each phase diagram included hydrate and anhydrate deliquescence boundaries, the anhydrate-hydrate phase boundary, and the peritectic temperature (above which the hydrate was no longer stable). This is the first report of RH-temperature phase diagrams of glucose and citric acid, information which is beneficial for selecting storage and processing conditions to promote or avoid hydrate formation or loss and/or deliquescence. Copyright © 2017 Elsevier Ltd. All rights reserved.

Phase transformation mechanism in lithium manganese nickel oxide revealed by single-crystal hard X-ray microscopy

DOE PAGES

Kuppan, Saravanan; Xu, Yahong; Liu, Yijin; ...

2017-02-01

Understanding the reaction pathway and kinetics of solid-state phase transformation is critical in designing advanced electrode materials with better performance and stability. Despite the first-order phase transition with a large lattice mismatch between the involved phases, spinel LiMn 1.5Ni 0.5O 4 is capable of fast rate even at large particle size, presenting an enigma yet to be understood. The present study uses advanced two-dimensional and three-dimensional nano-tomography on a series of well-formed LixMn 1.5Ni 0.5O 4 (0 ≤ x ≤ 1) crystals to visualize the mesoscale phase distribution, as a function of Li content at the sub-particle level. Inhomogeneity alongmore » with the coexistence of Li-rich and Li-poor phases are broadly observed on partially delithiated crystals, providing direct evidence for a concurrent nucleation and growth process instead of a shrinking-core or a particle-by-particle process. As a result, superior kinetics of (100) facets at the vertices of truncated octahedral particles promote preferential delithiation, whereas the observation of strain-induced cracking suggests mechanical degradation in the material.« less

A unified analysis of solidification in Bridgman crystal growth

NASA Astrophysics Data System (ADS)

Lu, Ming-Fang

2012-04-01

The simulation of multiphase solidification process can be handled by combining the VOF (Volume of Fluid) transport equation, in which the continuum mechanics model is used to simulate the melt/solid interface and the conservation of mass, momentum, and energy. Because the melt phase, the solid phase, and the melt/solid interface are controlled by a single control equation; if the enthalpy model based on porosity concept represents the processing of the phase transformation range, it is possible to solve the problem of phase transformation in the same way as solving the single-phase problem. Once the energy field of enthalpy for each step in time is resolved, the position of the interface can be precisely calculated with the use of VOF equation. This type of novel VOF method can be applied to find out the conditions of vertical Bridgman crystal growing located on the earth or under microgravity.

A unified analysis of solidification in Bridgman crystal growth

NASA Astrophysics Data System (ADS)

Lu, Ming-Fang

2011-11-01

The simulation of multiphase solidification process can be handled by combining the VOF (Volume of Fluid) transport equation, in which the continuum mechanics model is used to simulate the melt/solid interface and the conservation of mass, momentum, and energy. Because the melt phase, the solid phase, and the melt/solid interface are controlled by a single control equation; if the enthalpy model based on porosity concept represents the processing of the phase transformation range, it is possible to solve the problem of phase transformation in the same way as solving the single-phase problem. Once the energy field of enthalpy for each step in time is resolved, the position of the interface can be precisely calculated with the use of VOF equation. This type of novel VOF method can be applied to find out the conditions of vertical Bridgman crystal growing located on the earth or under microgravity.

Mesoscale martensitic transformation in single crystals of topological defects

PubMed Central

Martínez-González, José A.; Ramírez-Hernández, Abelardo; Zhou, Ye; Sadati, Monirosadat; Zhang, Rui; Nealey, Paul F.; de Pablo, Juan J.

2017-01-01

Liquid-crystal blue phases (BPs) are highly ordered at two levels. Molecules exhibit orientational order at nanometer length scales, while chirality leads to ordered arrays of double-twisted cylinders over micrometer scales. Past studies of polycrystalline BPs were challenged by the existence of grain boundaries between randomly oriented crystalline nanodomains. Here, the nucleation of BPs is controlled with precision by relying on chemically nanopatterned surfaces, leading to macroscopic single-crystal BP specimens where the dynamics of mesocrystal formation can be directly observed. Theory and experiments show that transitions between two BPs having a different network structure proceed through local reorganization of the crystalline array, without diffusion of the double-twisted cylinders. In solid crystals, martensitic transformations between crystal structures involve the concerted motion of a few atoms, without diffusion. The transformation between BPs, where crystal features arise in the submicron regime, is found to be martensitic in nature when one considers the collective behavior of the double-twist cylinders. Single-crystal BPs are shown to offer fertile grounds for the study of directed crystal nucleation and the controlled growth of soft matter. PMID:28874557

Solid-state transformations in the β-form of chlorpropamide on cooling to 100 K.

PubMed

Drebushchak, Tatiana N; Drebushchak, Valeri A; Boldyreva, Elena V

2011-04-01

A single-crystal X-ray diffraction study of the effect of cooling down to 100 K on the β-form of chlorpropamide, 4-chloro-N-(propylaminocarbonyl)benzenesulfonamide, has revealed reversible phase transitions at ∼257 K and between 150 and 125 K: β (Pbcn, Z' = 1) ⇔ β(II) (P2/c, Z' = 2) ⇔ β(III) (P2/n, a' = 2a, Z' = 4); the sequence corresponds to cooling. Despite changes in the space group and number of symmetry-independent molecules, the volume per molecule changes continuously in the temperature range 100-300 K. The phase transition at ∼257 K is accompanied by non-merohedral twinning, which is preserved on further cooling and through the second phase transition, but the original single crystal does not crack. DSC (differential scanning calorimetry) and X-ray powder diffraction investigations confirm the phase transitions. Twinning disappears on heating as the reverse transformations take place. The second phase transition is related to a change in conformation of the alkyl tail from trans to gauche in 1/4 of the molecules, regularly distributed in the space. Possible reasons for the increase in Z' upon cooling are discussed in comparison to other reported examples of processes (crystallization, phase transitions) in which organic crystals with Z' > 1 have been formed. Implications for pharmaceutical applications are discussed. © 2011 International Union of Crystallography

In situ phase transformation of Laves phase from Chi-phase in Mo-containing Fe–Cr–Ni alloys

DOE PAGES

Tan, L.; Yang, Y.

2015-11-01

For an in situ phase transformation of the Chi (χ) phase to the Laves phase we observed in a Fe–Cr–Ni–Mo model alloy. The morphology, composition, and crystal structure of the χ and Laves phases, and their orientation relationship with the matrix austenite phase were investigated. The resulted Laves phase has larger lattice mismatch with the matrix phase than the χ phase, leading to the increase of local strain fields and the formation of dislocations. Moreover, this finding is helpful to understand the precipitation behavior of the intermetallic phases in the Mo-containing austenitic stainless steels.

Top-down solid-phase fabrication of nanoporous cadmium oxide architectures.

PubMed

Yu, Haidong; Wang, Deshen; Han, Ming-Yong

2007-02-28

In this article, we have demonstrated one-step solid-phase transformation from high-quality cadmium carbonate microcrystals into highly nanoporous cadmium oxide. The high crystal quality of cadmium carbonate is critical for the successful fabrication of porous nanoarchitectures with predetermined morphology and well-controlled internal structure. This novel strategy has a good potential to prepare nanoporous materials at a large scale by using perfect monolithic carbonate crystals, and it is also useful to synthesize different nanoporous materials on metal-oxide-coated substrates. Meanwhile, this simple thermal transformation of cadmium carbonate into porous structures has further been extended to convert calcium carbonate into such porous structures.

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.

Intermediate phases in [111]- and [001]-oriented PbMg1/3Nb2/3O3-29PbTiO3 single crystals

NASA Astrophysics Data System (ADS)

Kamzina, L. S.

2017-09-01

Phase transformations in [111]- and [001]-oriented PbMg1/3Nb2/3O3-29PbTiO3 single crystals have been studied using dielectric and optical measurements before and after applying an electric field. It is shown that the subsequence of phase transitions rhombohedral ( R)—tetragonal ( T)—cubic ( C) phases is observed in nonpolarized samples of both orientations as temperature increases. In the [111]-oriented crystal, an additional intermediate monoclinic phase (it is possible, M a ) is induced after preliminary polarization at room temperature and the R- M a - T- C phase transitions are observed on heating. In the [001]-oriented crystal, after its polarization, the monoclinic phase forms instead of the rhombohedral phase even at room temperature and the M a - T- C transitions occur on heating. The results are discussed from the point of view of the existence polar nanoregions with different local symmetries in a glasslike matrix.

Studies on Se75Te25-x In x chalcogenide glasses; a material for phase change memory

NASA Astrophysics Data System (ADS)

Srivastava, Archana; Tiwari, S. N.; Alvi, M. A.; Khan, Shamshad A.

2018-01-01

This research paper describes the non-isothermal crystallization during phase transformation in Se75Te25-x In x glasses synthesized by melt quenching method. For crystallization studies in these glasses, non-isothermal differential scanning calorimetry (DSC) measurements was done at constant heating rates of 5, 10, 15, 20 and 25 K min-1 in air atmosphere. The glass transition temperature (T g), on-set crystallization temperature (T c), peak crystallization temperature (T p) and melting temperatures (T m) were derived by DSC thermograms. Using various thermal parameters the activation energy of glass transition and crystallization were determined by using Kissinger, Moynihan and Ozawa approaches and found to be in good agreement. The value of the activation energy of glass transition (ΔE t) was found to be minimum for Se75Te19In6 alloys confirming its maximum probability of transition in a metastable state. Thermal stability parameters of Se75Te25-x In x were determined and found to be increased with indium content. High resolution x-ray diffraction and field emission scanning electron microscopy studies were employed for the study of phase transformation in Se75Te25-x In x glasses. The outcome of these studies shows that the investigated materials may be suitable for phase change memory devices.

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.

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

Meiser, Jerome; Urbassek, Herbert M., E-mail: urbassek@rhrk.uni-kl.de

Using classical molecular dynamics simulations and the Meyer-Entel interaction potential, we study the martensitic transformation pathway in a pure iron bi-crystal containing a symmetric tilt grain boundary. Upon cooling the system from the austenitic phase, the transformation starts with the nucleation of the martensitic phase near the grain boundary in a plate-like arrangement. The Kurdjumov-Sachs orientation relations are fulfilled at the plates. During further cooling, the plates expand and merge. In contrast to the orientation relation in the plate structure, the complete transformation proceeds via the Pitsch pathway.

Concerted ligand exchange and the roles of counter anions in the reversible structural switching of crystalline peptide metallo-macrocycles.

PubMed

Miyake, Ryosuke; Shionoya, Mitsuhiko

2014-06-02

To understand reversible structural switching in crystalline materials, we studied the mechanism of reversible crystal-to-crystal transformation of a tetranuclear Ni(II) macrocycle consisting of artificial β-dipeptides. On the basis of detailed structural analyses and thermodynamic measurements made in a comparison of pseudo-isostructural crystals (NO3 and BF4 salts), we herein discuss how ligand-exchange reactions take place in the crystal due to changes in water content and temperature. Observations of the structural transformation of NO3 salt indicated that a pseudo crystalline phase transformation takes place through concerted ligand-exchange reactions at the four Ni(II) centers of the macrocycle with hydrogen bond switching. A mechanism for this ligand exchange was supported by IR spectroscopy. Thermodynamic measurements suggested that the favorable compensation relationship of the enthalpy changes due to water uptake and structural changes are keys to the reversible structural transformation. On the basis of a comparison with the pseudo-isostructural crystals, it is apparent that the crystal packing structure and the types of counter anions are important factors for facilitating reversible ligand exchange with single crystallinity.

Tuning the frequency of ultrashort laser pulses by a cross-phase-modulation-induced shift in a photonic crystal fiber.

PubMed

Konorov, S O; Akimov, D A; Zheltikov, A M; Ivanov, A A; Alfimov, M V; Scalora, M

2005-06-15

Femtosecond pulses of fundamental Cr:forsterite laser radiation are used as a pump field to tune the frequency of copropagating second-harmonic pulses of the same laser through cross-phase modulation in a photonic crystal fiber. Sub-100-kW femtosecond pump pulses coupled into a photonic crystal fiber with an appropriate dispersion profile can shift the central frequency of the probe field by more than 100 nm, suggesting a convenient way to control propagation and spectral transformations of ultrashort laser pulses.

Crystallization control for remediation of an FetO-rich CaO-SiO2-Al2O3-MgO EAF waste slag.

PubMed

Jung, Sung Suk; Sohn, Il

2014-01-01

In this work, the crystallization behavior of synthesized FetO-rich electric arc furnace (EAF) waste slags with a basicity range of 0.7 to 1.08 was investigated. Crystal growth in the melts was observed in situ using a confocal laser scanning microscope, and a delayed crystallization for higher-basicity samples was observed in the continuous cooling transformation and time temperature transformation diagrams. This result is likely due to the polymerization of the melt structure as a result of the increased number of network-forming FeO4 and AlO4 units, as suggested by Raman analysis. The complex incorporation of Al and Fe ions in the form of AlO4 and FeO4 tetrahedral units dominant in the melt structure at a higher basicity constrained the precipitation of a magnetic, nonstoichiometric, and Fe-rich MgAlFeO4 primary phase. The growth of this spinel phase caused a clear compositional separation from amorphous phase during isothermal cooling at 1473 K leading to a clear separation between the primary and amorphous phases, allowing an efficient magnetic separation of Fe compounds from the slag for effective remediation and recycling of synthesized EAF waste slags for use in higher value-added ordinary Portland cement.

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.

Accurate control of a liquid-crystal display to produce a homogenized Fourier transform for holographic memories.

PubMed

Márquez, Andrés; Gallego, Sergi; Méndez, David; Alvarez, Mariela L; Fernández, Elena; Ortuño, Manuel; Neipp, Cristian; Beléndez, Augusto; Pascual, Inmaculada

2007-09-01

We show an accurate procedure to obtain a Fourier transform (FT) with no dc term using a commercial twisted-nematic liquid-crystal display. We focus on the application to holographic storage of binary data pages, where a drastic decrease of the dc term in the FT is highly desirable. Two different codification schemes are considered: binary pi radians phase modulation and hybrid ternary modulation. Any deviation in the values of the amplitude and phase shift generates the appearance of a strong dc term. Experimental results confirm that the calculated configurations provide a FT with no dc term, thus showing the effectiveness of the proposal.

Mechanochemical spinodal decomposition: a phenomenological theory of phase transformations in multi-component, crystalline solids

DOE PAGES

Rudraraju, Shiva; Van der Ven, Anton; Garikipati, Krishna

2016-06-10

Here, we present a phenomenological treatment of diffusion-driven martensitic phase transformations in multi-component crystalline solids that arise from non-convex free energies in mechanical and chemical variables. The treatment describes diffusional phase transformations that are accompanied by symmetry-breaking structural changes of the crystal unit cell and reveals the importance of a mechanochemical spinodal, defined as the region in strain-composition space, where the free-energy density function is non-convex. The approach is relevant to phase transformations wherein the structural order parameters can be expressed as linear combinations of strains relative to a high-symmetry reference crystal. The governing equations describing mechanochemical spinodal decomposition aremore » variationally derived from a free-energy density function that accounts for interfacial energy via gradients of the rapidly varying strain and composition fields. A robust computational framework for treating the coupled, higher-order diffusion and nonlinear strain gradient elasticity problems is presented. Because the local strains in an inhomogeneous, transforming microstructure can be finite, the elasticity problem must account for geometric nonlinearity. An evaluation of available experimental phase diagrams and first-principles free energies suggests that mechanochemical spinodal decomposition should occur in metal hydrides such as ZrH 2-2c. The rich physics that ensues is explored in several numerical examples in two and three dimensions, and the relevance of the mechanism is discussed in the context of important electrode materials for Li-ion batteries and high-temperature ceramics.« less

Structural transformations in austenitic stainless steel induced by deuterium implantation: irradiation at 100 K

NASA Astrophysics Data System (ADS)

Morozov, Oleksandr; Zhurba, Volodymyr; Neklyudov, Ivan; Mats, Oleksandr; Rud, Aleksandr; Chernyak, Nikolay; Progolaieva, Viktoria

2015-03-01

Deuterium thermal desorption spectra were investigated on the samples of austenitic stainless steel 18Cr10NiTi preimplanted at 100 K with deuterium ions in the dose range from 3 × 1015 to 5 × 1018 D/cm2. The kinetics of structural transformation development in the implantation steel layer was traced from deuterium thermodesorption spectra as a function of implanted deuterium concentration. At saturation of austenitic stainless steel 18Cr10NiTi with deuterium by means of ion implantation, structural-phase changes take place, depending on the dose of implanted deuterium. The maximum attainable concentration of deuterium in steel is C = 1 (at.D/at.met. = 1/1). The increase in the implanted dose of deuterium is accompanied by the increase in the retained deuterium content, and as soon as the deuterium concentration attains C ≈ 0.5 the process of shear martensitic structural transformation in steel takes place. It includes the formation of bands, body-centered cubic (bcc) crystal structure, and the ferromagnetic phase. Upon reaching the deuterium concentration C > 0.5, the presence of these molecules causes shear martensitic structural transformations in the steel, which include the formation of characteristic bands, bcc crystal structure, and the ferromagnetic phase. At C ≥ 0.5, two hydride phases are formed in the steel, the decay temperatures of which are 240 and 275 K. The hydride phases are formed in the bcc structure resulting from the martensitic structural transformation in steel.

Phase transformation in thiamine hydrochloride tablets: Influence on tablet microstructure, physical properties, and performance.

PubMed

Chakravarty, Paroma; Suryanarayanan, Raj; Govindarajan, Ramprakash

2012-04-01

The objective of this article was to monitor phase transformation in thiamine hydrochloride, from a nonstoichiometric hydrate (NSH) to a hemihydrate (HH), in stored tablets, prepared both by direct compression and wet granulation, and to relate the storage-induced phase transformation with changes in tablet microstructure, physical properties, and performance. Raman spectroscopy revealed complete NSH → HH transformation in tablets, within 30 h of storage at 40°C/75% relative humidity. When the tablets were prepared by wet granulation of NSH alone, there was a marked increase in both tablet volume and hardness on storage. However, when microcrystalline cellulose (MCC) was included in granulation, the resulting stored tablets also exhibited a pronounced increase in disintegration time. In contrast, tablets prepared by dry processing via compression of a NSH-MCC physical mixture did not exhibit any changes in properties, despite the in situ solid form conversion. Scanning electron microscopy revealed growth of needle-like HH crystals in all stored tablets and mercury porosimetry revealed considerable changes in the pore size distribution during storage. Longer storage led to crystal growth (Ostwald ripening), causing further gradual but less dramatic changes in properties. The phase transformation and the complex interparticulate associations in the tablet influenced the changes in tablet microstructure, compact physical properties, and product behavior. Copyright © 2011 Wiley Periodicals, Inc.

Phase transformation in rapidly quenched Fe-Cr-Co-Mo-Ti-Si-B alloys

NASA Astrophysics Data System (ADS)

Zhukov, D. G.; Shubakov, V. S.; Zhukova, E. Kh; Gorshenkov, M. V.

2018-03-01

The research results of phase transformations in Fe-24Cr-16Co-3Mo-0.2Ti-1Si-B alloys (with a boron content of 1 to 3% by mass) obtained by rapid quenching are presented. The structure formation regularities during the melt spinning and during the subsequent crystallization annealing in rapidly quenched bands of the Fe-Cr-Co-Mo-Ti-Si-B system alloys were studied. The changes in the phase composition of the rapidly quenched Fe-Cr-Co-Mo-Ti- Si-B system alloys after quenching at various quench rates and at different boron concentrations in the alloys are studied. It is shown that during crystallization from an amorphous state, at temperatures above 570 °C, in addition to the α-phase, the σ-phase appears first, followed by the γ-phase. Heat treatment of rapidly quenched bands to high-coercive state was carried out. A qualitative assessment of magnetic properties in a high-coercivity state was carried out. An evaluation of the level of magnetic properties in a high-coercivity state allows us to conclude that the application of a magnetic field during crystallization from an amorphous state leads to anisotropy of the magnetic properties, that is, an anisotropic effect of thermo-magnetic treatment is detected.

A micromechanical constitutive model for anisotropic cyclic deformation of super-elastic NiTi shape memory alloy single crystals

NASA Astrophysics Data System (ADS)

Yu, Chao; Kang, Guozheng; Kan, Qianhua

2015-09-01

Based on the experimental observations on the anisotropic cyclic deformation of super-elastic NiTi shape memory alloy single crystals done by Gall and Maier (2002), a crystal plasticity based micromechanical constitutive model is constructed to describe such anisotropic cyclic deformation. To model the internal stress caused by the unmatched inelastic deformation between the austenite and martensite phases on the plastic deformation of austenite phase, 24 induced martensite variants are assumed to be ellipsoidal inclusions with anisotropic elasticity and embedded in the austenite matrix. The homogeneous stress fields in the austenite matrix and each induced martensite variant are obtained by using the Mori-Tanaka homogenization method. Two different inelastic mechanisms, i.e., martensite transformation and transformation-induced plasticity, and their interactions are considered in the proposed model. Following the assumption of instantaneous domain growth (Cherkaoui et al., 1998), the Helmholtz free energy of a representative volume element of a NiTi shape memory single crystal is established and the thermodynamic driving forces of the internal variables are obtained from the dissipative inequalities. The capability of the proposed model to describe the anisotropic cyclic deformation of super-elastic NiTi single crystals is first verified by comparing the predicted results with the experimental ones. It is concluded that the proposed model can capture the main quantitative features observed in the experiments. And then, the proposed model is further used to predict the uniaxial and multiaxial transformation ratchetting of a NiTi single crystal.

Applied Crystallography - Proceedings of the XVth Conference

NASA Astrophysics Data System (ADS)

Morawiec, H.; Ströż, D.

1993-06-01

The Table of Contents for the full book PDF is as follows: * Foreword * The International Centre for Diffraction Data and Its Future Developments * The Rietveld Method - A Historical Perspective * Real Structure in Quantitative Powder Diffraction Phase Analysis * Neutron Focusing Optics in Applied Crystallography * The Crystal Structures of Oxygen Deficient Rare Earth Oxides * Short-Range Order in Layer-Structured Ba1-xSrxBi2Nb2O9 Ferroelectrics * Radial Distribution Function as a Tool of Structural Studies on Noncrystalline Materials * Determination of Radial Distribution Function (RDF) of Electrodeposited Cu-Cd Alloys After Annealing * Spheres Packing as a Factor Describing the Local Environment and Structure Stability * X-Ray Stress Measurement of Samples Combined with Diffraction Line Analysis * Phase Stability and Martensitic Transformation in Cu-Zn and Cu-Zn-Al Single Crystals * Order, Defects, Precipitates and the Martensitic Transformation in β Cu-Zn-Al * Effect of γ Precipitates on the Martensitic Transformation in Cu-Zn-Al Alloys * Phase Transitions and Shape Memory Effect in a Thermomechanically Treated NiTi Alloy * Structure of Martensite and Bainite in CuAlMn Alloys * Glass-Ceramics * Mechanism of Texture Formation at the Rolling of Low Stacking Fault Energy Metals and Alloys * Shear Texture of Zinc and the Conditions of Its Occuring * The Development of Texture of ZnAlMg Sheets Depending on Deformation Geometry * Texture Stability of the D.S. NiAlMoCrTi Alloy After Heat Treatment * X-Ray Diffraction Method for Controlling of Texture Evolution in Layers * Texture and Lattice Imperfections Study of Some Low Alloyed Copper Alloys * Selected Examples of the Calculation of the Orientation Distribution Function for Low Crystal and Sample Symmetries * Automatical X-Ray Quantitative Phase Analysis * Application of a PC Computer for Crystallographic Calculations * Electron Diffraction Analysis using a Personal Computer * CA.R.INE Crystallography Version 2.1-1992 * PC-MINREF: The Computer Program Package for Neutron Refinement of Incommensurate Multiphase Crystal and Magnetic Structures on IBM PC Computers * Possibilities of Deflections from Stoichiometry Investigation for Phases of b1-b37 Structure by X-Ray Method * A Computer Program: “Measurement of Elastic Constants of Phases in Nontextured Polycrystalline Materials by X-Ray Method” * Crystallite Sizes and Lattice Strains of Hydrogenatid Tungsten Carbid Powder * The Bragg-Case Images of Dislocations at Different Absorption * Extended X-Ray Bremsstrahlung Isochromat of Molybdenum * Size Distribution Determination of Heterogeneity Regions in Electrodeposited Metals by Saxs Method * The Possibility of the Application of the CH2I2 - Paraffin Oil Mixture as a Masking Liquid for Metal/Carrier Systems in Saxs Investigations * Investigation on Mechanical Alloying and Amorphisation Processes by the Rietveld Method * Growth of β' Phase Single Crystals of Sn-Sb Alloy * Effect of Oxygen Agglomeration on Structure of Annealed Cz-Si Single Crystal * X-Ray Investigation of Non-Uniform Stress Fields * Problem of Polytype Structures Series for Martensitic Phases of Metals and Alloys * Structure of Strain-Induced Martensite in β-CuZnAl Alloy * The Effect of Heat Treatment on the Phase Transitions in NiTiCo Shape Memory Alloy * 9R → 18R Phase Transformation in Cu-13Zn-8Al Alloy * Effect of Austenite Thermal Instability on Characteristics of Martensitic Transformation in Fe-Ni Alloys * Vacuum Annealing Study of Thin Ti Layers on High Carbon Steel Substrates * Vacuum Annealing Study of Thin Ta Layers on High Carbon Steel Substrates * Investigation of Speed of Ionic Sputtering of NiTi Alloys in Sea 02 Auger Spectrometer * Effect of Precipitation Hardening on Thermal Stability of Austenite in Fe-Ni Alloys * Structure of 18Cr-25Ni-Nb L Steel After Two Years Operation in Catalytic Tubes * Influence of Magnetic Field on Mechanical Barkhausen Effect Stress Dependence in Steel * Precipitation Structure in High Strength Aluminium Alloys * Morphology of Laser Treated Al-Zn and Al-Fe Alloys * Structure of Rapidly Solidified AlFe and AlFeNi Ribbons After Continuous Heating * X-Ray Diffractometric Investigations of Anatase—Rutile Titanium Dioxide Forms Transformation in the Presence of Some Additives * Investigations on Phase Transformation of Coprecipitated Iron-Magnesium Hydroxides * Determination of the Crystallinity of Polymer Blends by X-Ray Diffraction Method * XPD Study of the Selected Magnesium Compounds with the Expected Pharmacological Activity * Supermolecular Structure of the Nylon 6.10 Crystallized from the Melt and Its Changes During Heating * The Analysis of Substructural Parameters of PZT-Type Ferroelectric Ceramics

Pressure-induced transformations in computer simulations of glassy water.

PubMed

Chiu, Janet; Starr, Francis W; Giovambattista, Nicolas

2013-11-14

Glassy water occurs in at least two broad categories: low-density amorphous (LDA) and high-density amorphous (HDA) solid water. We perform out-of-equilibrium molecular dynamics simulations to study the transformations of glassy water using the ST2 model. Specifically, we study the known (i) compression-induced LDA-to-HDA, (ii) decompression-induced HDA-to-LDA, and (iii) compression-induced hexagonal ice-to-HDA transformations. We study each transformation for a broad range of compression/decompression temperatures, enabling us to construct a "P-T phase diagram" for glassy water. The resulting phase diagram shows the same qualitative features reported from experiments. While many simulations have probed the liquid-state phase behavior, comparatively little work has examined the transitions of glassy water. We examine how the glass transformations relate to the (first-order) liquid-liquid phase transition previously reported for this model. Specifically, our results support the hypothesis that the liquid-liquid spinodal lines, between a low-density and high-density liquid, are extensions of the LDA-HDA transformation lines in the limit of slow compression. Extending decompression runs to negative pressures, we locate the sublimation lines for both LDA and hyperquenched glassy water (HGW), and find that HGW is relatively more stable to the vapor. Additionally, we observe spontaneous crystallization of HDA at high pressure to ice VII. Experiments have also seen crystallization of HDA, but to ice XII. Finally, we contrast the structure of LDA and HDA for the ST2 model with experiments. We find that while the radial distribution functions (RDFs) of LDA are similar to those observed in experiments, considerable differences exist between the HDA RDFs of ST2 water and experiment. The differences in HDA structure, as well as the formation of ice VII (a tetrahedral crystal), are a consequence of ST2 overemphasizing the tetrahedral character of water.

Pressure-induced transformations in computer simulations of glassy water

NASA Astrophysics Data System (ADS)

Chiu, Janet; Starr, Francis W.; Giovambattista, Nicolas

2013-11-01

Glassy water occurs in at least two broad categories: low-density amorphous (LDA) and high-density amorphous (HDA) solid water. We perform out-of-equilibrium molecular dynamics simulations to study the transformations of glassy water using the ST2 model. Specifically, we study the known (i) compression-induced LDA-to-HDA, (ii) decompression-induced HDA-to-LDA, and (iii) compression-induced hexagonal ice-to-HDA transformations. We study each transformation for a broad range of compression/decompression temperatures, enabling us to construct a "P-T phase diagram" for glassy water. The resulting phase diagram shows the same qualitative features reported from experiments. While many simulations have probed the liquid-state phase behavior, comparatively little work has examined the transitions of glassy water. We examine how the glass transformations relate to the (first-order) liquid-liquid phase transition previously reported for this model. Specifically, our results support the hypothesis that the liquid-liquid spinodal lines, between a low-density and high-density liquid, are extensions of the LDA-HDA transformation lines in the limit of slow compression. Extending decompression runs to negative pressures, we locate the sublimation lines for both LDA and hyperquenched glassy water (HGW), and find that HGW is relatively more stable to the vapor. Additionally, we observe spontaneous crystallization of HDA at high pressure to ice VII. Experiments have also seen crystallization of HDA, but to ice XII. Finally, we contrast the structure of LDA and HDA for the ST2 model with experiments. We find that while the radial distribution functions (RDFs) of LDA are similar to those observed in experiments, considerable differences exist between the HDA RDFs of ST2 water and experiment. The differences in HDA structure, as well as the formation of ice VII (a tetrahedral crystal), are a consequence of ST2 overemphasizing the tetrahedral character of water.

Enhanced visible light activity of nano-titanium dioxide doped with multiple ions: Effect of crystal defects

NASA Astrophysics Data System (ADS)

Jaimy, Kanakkanmavudi B.; Ghosh, Swapankumar; Gopakumar Warrier, Krishna

2012-12-01

Titanium dioxide photocatalysts co-doped with iron(III) and lanthanum(III) have been prepared through a modified sol-gel method. Doping with Fe3+ resulted in a relatively lower anatase to rutile phase transformation temperature, while La3+ addition reduced the crystal growth and thus retarded the phase transformation of titania nanoparticles. The presence of Fe3+ ions shifted the absorption profile of titania to the longer wavelength side of the spectrum and enhanced the visible light activity. On the other hand, La3+ addition improved the optical absorption of titania nanoparticles. Both the dopants improved the life time of excitons by proper transferring and trapping of photoexcited charges. In the present work, considerable enhancement in photocatalytic activity under visible light was achieved through synergistic effect of optimum concentrations of the two dopants and associated crystal defects.

Phase transformation of Ca{sub 4}[Al{sub 6}O{sub 12}]SO{sub 4} and its disordered crystal structure at 1073 K

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

Kurokawa, Daisuke; R and D Center, Taiheiyo Cement Corporation, Chiba 285-8655; Takeda, Seiya

The phase transformation of Ca{sub 4}[Al{sub 6}O{sub 12}]SO{sub 4} and the crystal structure of its high-temperature phase were investigated by differential thermal analysis, temperature-dependent Raman spectroscopy and high-temperature X-ray powder diffraction (CuKα{sub 1}). We determined the starting temperature of the orthorhombic-to-cubic transformation during heating (=711 K) and that of the reverse transformation during cooling (=742 K). The thermal hysteresis was negative (=−31 K), suggesting the thermoelasticity of the transformation. The space group of the high temperature phase is I4{sup ¯}3m with the unit-cell dimensions of a=0.92426(2) nm and V=0.78955(2) nm{sup 3} (Z=2) at 1073 K. The initial structural model wasmore » derived by the direct methods and further refined by the Rietveld method. The final structural model showed the orientational disordering of SO{sub 4} tetrahedra. The maximum-entropy method-based pattern fitting method was used to confirm the validity of the split-atom model, in which conventional structure bias caused by assuming intensity partitioning was minimized. At around the transformation temperature during heating, the vibrational spectra, corresponding to the Raman-active SO{sub 4} internal stretching mode, showed the continuous and gradual change in the slope of full width at half maximum versus temperature curve. This strongly suggests that the orthorhombic-to-cubic phase transformation would be principally accompanied by the statistical disordering in orientation of the SO{sub 4} tetrahedra, without distinct dynamical reorientation. - Graphical abstract: (Left) Three-dimensional electron-density distributions of the SO{sub 4} tetrahedron with the split-atom model, and (right) a bird's eye view of electron densities on the plane parallel to (111). - Highlights: • Crystal structure of Ca{sub 4}[Al{sub 6}O{sub 12}]SO{sub 4} at 1073 K is determined by powder XRD. • The atom arrangements are represented by the split-atom model. • The MPF method is used to confirm the validity of the model. • The phase transition is accompanied by orientational disordering of SO{sub 4} tetrahedra.« less

Solvent-Induced Crystallization in Poly(Ethylene Terephthalate) during Mass Transport

NASA Astrophysics Data System (ADS)

Ouyang, Hao

2001-03-01

The solvent transport in poly(ethylene terephthalate) (PET) and related phase transformation were investigated. The data of mass sorption were analyzed according to Harmon¡¦s model for Case I (Fickian), Case II (swelling) and anomalous transport. This transport process in PET is accompanied by the induced crystallization of the original amorphous state. The transformation was studied by wide angle x-ray scattering (WAXS), small angle x-ray scattering (SAXS), Differential Scanning Calorimeter (DSC), density gradient column, and Fourier Transform Infra-Red (FTIR). During this process, the matrix is under a compressive strain that causes different kinetic path of crystallization as compared to that by thermal annealing. This state of strain will assist the development of the solvent-induced crystallization. It also can be explained in terms of the principle of Le Chatelier if the local equilibrium is assumed. The model regarding the crystallization was proposed in terms of the study of long period L, the crystal thickness lc and the thickness of amorphous layer la, obtained from the linear correlation function and interface distribution function.

Combining phase-field crystal methods with a Cahn-Hilliard model for binary alloys

NASA Astrophysics Data System (ADS)

Balakrishna, Ananya Renuka; Carter, W. Craig

2018-04-01

Diffusion-induced phase transitions typically change the lattice symmetry of the host material. In battery electrodes, for example, Li ions (diffusing species) are inserted between layers in a crystalline electrode material (host). This diffusion induces lattice distortions and defect formations in the electrode. The structural changes to the lattice symmetry affect the host material's properties. Here, we propose a 2D theoretical framework that couples a Cahn-Hilliard (CH) model, which describes the composition field of a diffusing species, with a phase-field crystal (PFC) model, which describes the host-material lattice symmetry. We couple the two continuum models via coordinate transformation coefficients. We introduce the transformation coefficients in the PFC method to describe affine lattice deformations. These transformation coefficients are modeled as functions of the composition field. Using this coupled approach, we explore the effects of coarse-grained lattice symmetry and distortions on a diffusion-induced phase transition process. In this paper, we demonstrate the working of the CH-PFC model through three representative examples: First, we describe base cases with hexagonal and square symmetries for two composition fields. Next, we illustrate how the CH-PFC method interpolates lattice symmetry across a diffuse phase boundary. Finally, we compute a Cahn-Hilliard type of diffusion and model the accompanying changes to lattice symmetry during a phase transition process.

Structural transformation in antiferroelectric PbZrO3-relaxor ferroelectric Pb(Ni1/3Nb2/3)O3 solid solution system

NASA Astrophysics Data System (ADS)

Wirunchit, S.; Vittayakorn, N.

2008-07-01

The solid solution between the antiferroelectric (AFE) PbZrO3 (PZ) and the relaxor ferroelectric (FE) Pb(Ni1/3Nb2/3)O3 (PNN) was synthesized by the columbite precursor method. The crystal structure, phase transformations, and dielectric and thermal properties of (1-x )PZ-xPNN where x =0.00-0.30 were investigated. With these data, the FE phase diagram between PZ and PNN has been established. The crystal structure data obtained from X-ray diffraction indicate that the solid solution PZ-PNN, where x =0.00-0.30, successively transforms from orthorhombic to rhombohedral symmetry with an increase in the PNN concentration. The AFE phase→FE phase transition occurs in compositions of 0.00⩽x⩽0.08. The AFE →FE phase transition shifts to lower temperatures with higher compositions of x. The FE phase temperature range width increases with increased PNN. Apparently the replacement of the Zr4+ ion by Ni2+/Nb5+ ions decreases the driving force for an antiparallel shift of Pb2+ ions because they interrupt the translational symmetry and facilitates the appearance of a rhombohedral FE phase when the amount of PNN is higher than 8mol%.

Avalanching strain dynamics during the hydriding phase transformation in individual palladium nanoparticles

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

Ulvestad, A.; Welland, M. J.; Collins, S. S. E.

2015-12-11

Phase transitions in reactive environments are crucially important in energy and information storage, catalysis and sensors. Nanostructuring active particles can yield faster charging/ discharging kinetics, increased lifespan and record catalytic activities. However, establishing the causal link between structure and function is challenging for nanoparticles, as ensemble measurements convolve intrinsic single-particle properties with sample diversity. Here we study the hydriding phase transformation in individual palladium nanocubes in situ using coherent X-ray diffractive imaging. The phase transformation dynamics, which involve the nucleation and propagation of a hydrogen-rich region, are dependent on absolute time (aging) and involve intermittent dynamics (avalanching). A hydrogen-rich surfacemore » layer dominates the crystal strain in the hydrogen-poor phase, while strain inversion occurs at the cube corners in the hydrogen-rich phase. A three-dimensional phase-field model is used to interpret the experimental results. In conclusion, our experimental and theoretical approach provides a general framework for designing and optimizing phase transformations for single nanocrystals in reactive environments.« less

Avalanching strain dynamics during the hydriding phase transformation in individual palladium nanoparticles

NASA Astrophysics Data System (ADS)

Ulvestad, A.; Welland, M. J.; Collins, S. S. E.; Harder, R.; Maxey, E.; Wingert, J.; Singer, A.; Hy, S.; Mulvaney, P.; Zapol, P.; Shpyrko, O. G.

2015-12-01

Phase transitions in reactive environments are crucially important in energy and information storage, catalysis and sensors. Nanostructuring active particles can yield faster charging/discharging kinetics, increased lifespan and record catalytic activities. However, establishing the causal link between structure and function is challenging for nanoparticles, as ensemble measurements convolve intrinsic single-particle properties with sample diversity. Here we study the hydriding phase transformation in individual palladium nanocubes in situ using coherent X-ray diffractive imaging. The phase transformation dynamics, which involve the nucleation and propagation of a hydrogen-rich region, are dependent on absolute time (aging) and involve intermittent dynamics (avalanching). A hydrogen-rich surface layer dominates the crystal strain in the hydrogen-poor phase, while strain inversion occurs at the cube corners in the hydrogen-rich phase. A three-dimensional phase-field model is used to interpret the experimental results. Our experimental and theoretical approach provides a general framework for designing and optimizing phase transformations for single nanocrystals in reactive environments.

Avalanching strain dynamics during the hydriding phase transformation in individual palladium nanoparticles

PubMed Central

Ulvestad, A.; Welland, M. J.; Collins, S. S. E.; Harder, R.; Maxey, E.; Wingert, J.; Singer, A.; Hy, S.; Mulvaney, P.; Zapol, P.; Shpyrko, O. G.

2015-01-01

Phase transitions in reactive environments are crucially important in energy and information storage, catalysis and sensors. Nanostructuring active particles can yield faster charging/discharging kinetics, increased lifespan and record catalytic activities. However, establishing the causal link between structure and function is challenging for nanoparticles, as ensemble measurements convolve intrinsic single-particle properties with sample diversity. Here we study the hydriding phase transformation in individual palladium nanocubes in situ using coherent X-ray diffractive imaging. The phase transformation dynamics, which involve the nucleation and propagation of a hydrogen-rich region, are dependent on absolute time (aging) and involve intermittent dynamics (avalanching). A hydrogen-rich surface layer dominates the crystal strain in the hydrogen-poor phase, while strain inversion occurs at the cube corners in the hydrogen-rich phase. A three-dimensional phase-field model is used to interpret the experimental results. Our experimental and theoretical approach provides a general framework for designing and optimizing phase transformations for single nanocrystals in reactive environments. PMID:26655832

Isogyres - Manifestation of Spin-orbit interaction in uniaxial crystal: A closed-fringe Fourier analysis of conoscopic interference

NASA Astrophysics Data System (ADS)

Samlan, C. T.; Naik, Dinesh N.; Viswanathan, Nirmal K.

2016-09-01

Discovered in 1813, the conoscopic interference pattern observed due to light propagating through a crystal, kept between crossed polarizers, shows isochromates and isogyres, respectively containing information about the dynamic and geometric phase acquired by the beam. We propose and demonstrate a closed-fringe Fourier analysis method to disentangle the isogyres from the isochromates, leading us to the azimuthally varying geometric phase and its manifestation as isogyres. This azimuthally varying geometric phase is shown to be the underlying mechanism for the spin-to-orbital angular momentum conversion observed in a diverging optical field propagating through a z-cut uniaxial crystal. We extend the formalism to study the optical activity mediated uniaxial-to-biaxial transformation due to a weak transverse electric field applied across the crystal. Closely associated with the phase and polarization singularities of the optical field, the formalism enables us to understand crystal optics in a new way, paving the way to anticipate several emerging phenomena.

Isogyres - Manifestation of Spin-orbit interaction in uniaxial crystal: A closed-fringe Fourier analysis of conoscopic interference.

PubMed

Samlan, C T; Naik, Dinesh N; Viswanathan, Nirmal K

2016-09-14

Discovered in 1813, the conoscopic interference pattern observed due to light propagating through a crystal, kept between crossed polarizers, shows isochromates and isogyres, respectively containing information about the dynamic and geometric phase acquired by the beam. We propose and demonstrate a closed-fringe Fourier analysis method to disentangle the isogyres from the isochromates, leading us to the azimuthally varying geometric phase and its manifestation as isogyres. This azimuthally varying geometric phase is shown to be the underlying mechanism for the spin-to-orbital angular momentum conversion observed in a diverging optical field propagating through a z-cut uniaxial crystal. We extend the formalism to study the optical activity mediated uniaxial-to-biaxial transformation due to a weak transverse electric field applied across the crystal. Closely associated with the phase and polarization singularities of the optical field, the formalism enables us to understand crystal optics in a new way, paving the way to anticipate several emerging phenomena.

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.

Direct generation of abruptly focusing vortex beams using a 3/2 radial phase-only pattern.

PubMed

Davis, Jeffrey A; Cottrell, Don M; Zinn, Jonathan M

2013-03-20

Abruptly focusing Airy beams have previously been generated using a radial cubic phase pattern that represents the Fourier transform of the Airy beam. The Fourier transform of this pattern is formed using a system length of 2f, where f is the focal length of the Fourier transform lens. In this work, we directly generate these abruptly focusing Airy beams using a 3/2 radial phase pattern encoded onto a liquid crystal display. The resulting optical system is much shorter. In addition, we can easily produce vortex patterns at the focal point of these beams. Experimental results match theoretical predictions.

In Situ Neutron Diffraction Analyzing Stress-Induced Phase Transformation and Martensite Elasticity in [001]-Oriented Co49Ni21Ga30 Shape Memory Alloy Single Crystals

NASA Astrophysics Data System (ADS)

Reul, A.; Lauhoff, C.; Krooß, P.; Gutmann, M. J.; Kadletz, P. M.; Chumlyakov, Y. I.; Niendorf, T.; Schmahl, W. W.

2018-02-01

Recent studies demonstrated excellent pseudoelastic behavior and cyclic stability under compressive loads in [001]-oriented Co-Ni-Ga high-temperature shape memory alloys (HT-SMAs). A narrow stress hysteresis was related to suppression of detwinning at RT and low defect formation during phase transformation due to the absence of a favorable slip system. Eventually, this behavior makes Co-Ni-Ga HT-SMAs promising candidates for several industrial applications. However, deformation behavior of Co-Ni-Ga has only been studied in the range of theoretical transformation strain in depth so far. Thus, the current study focuses not only on the activity of elementary deformation mechanisms in the pseudoelastic regime up to maximum theoretical transformation strains but far beyond. It is shown that the martensite phase is able to withstand about 5% elastic strain, which significantly increases the overall deformation capability of this alloy system. In situ neutron diffraction experiments were carried out using a newly installed testing setup on Co-Ni-Ga single crystals in order to reveal the nature of the stress-strain response seen in the deformation curves up to 10% macroscopic strain.

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

Crystallization Experiments in the MgO-CO2-H2O system: Role of Amorphous Magnesium Carbonate Precursors in Magnesium Carbonate Hydrated Phases and Morphologies in Low Temperature Hydrothermal Fluids

NASA Astrophysics Data System (ADS)

Giampouras, Manolis; Garcia-Ruiz, Juan Manuel; Garrido, Carlos J.

2017-04-01

Numerous forms of hydrated or basic magnesium carbonates occur in the complex MgO-CO2-H2O system. Mineral saturation states from low temperature hydrothermal fluids in Semail Ophiolite (Oman), Prony Bay (New Caledonia) and Lost City hydrothermal field (mid-Atlantic ridge) strongly indicate the presence of magnesium hydroxy-carbonate hydrates (e.g. hydromagnesite) and magnesium hydroxides (brucite). Study of formation mechanisms and morphological features of minerals forming in the MgO-CO2-H2O system could give insights into serpentinization-driven, hydrothermal, alkaline environments, which are related to early Earth conditions. Temperature, hydration degree, pH and fluid composition are crucial factors regarding the formation, coexistence and transformation of such mineral phases. The rate of supersaturation, on the other hand, is a fundamental parameter to understand nucleation and crystal growth processes. All these parameters can be examined in a solution using different crystallization techniques. In the present study, we applied different crystallization techniques to synthesize and monitor the crystallization of Mg-bearing carbonates and hydroxides under abiotic conditions. Various crystallization techniques (counter-diffusion, vapor diffusion and unseeded solution mixing) were used to screen the formation conditions of each phase, transformation processes and structural development. Mineral and textural characterization of the different synthesized phases were carried out by X-ray diffraction (XRD), Raman spectroscopy and scanning electron microscopy coupled to dispersive energy spectroscopy (FE-SEM-EDS). Experimental investigation of the effect of pH level and silica content under variable reactant concentrations revealed the importance of Amorphous Magnesium Carbonate (AMC) in the formation of hydroxy-carbonate phases (hydromagnesite and dypingite). Micro-structural resemblance between AMC precursors and later stage crystalline phases highlights the critical role of internal molecule re-organization to form crystalline structures. Aggregation of AMC spherulites triggers biomimetic morphologies forming curling laminar structures and rings. The size and number of nesquehonite (MgCO3.3H2O) crystals are controlled by pH and Mg2+ ions at pH < 9. As pH increases, nesquehonite transforms to spherical, rosette-like dypingite and/or hydromagnesite. Crystallization experiments within silica gel impedes the normal growth of prismatic nesquehonite crystals and generates peculiar dendritic crystalline structures. Finally, vapor diffusion techniques resulted in synthesis of NH4+-bearing hydrated compounds after ammonium incorporation when [NH4+]/[Mg2+] ≥ 1 and ≥ 0.5M [NH4+]. Funding: We acknowledge funding from the People programme (Marie Curie Actions - ITN) of the European Union FP7 under REA Grant Agreement n˚ 608001.

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

Quartz crystal growth

DOEpatents

Baughman, Richard J.

1992-01-01

A process for growing single crystals from an amorphous substance that can undergo phase transformation to the crystalline state in an appropriate solvent. The process is carried out in an autoclave having a lower dissolution zone and an upper crystallization zone between which a temperature differential (.DELTA.T) is maintained at all times. The apparatus loaded with the substance, solvent, and seed crystals is heated slowly maintaining a very low .DELTA.T between the warmer lower zone and cooler upper zone until the amorphous substance is transformed to the crystalline state in the lower zone. The heating rate is then increased to maintain a large .DELTA.T sufficient to increase material transport between the zones and rapid crystallization. .alpha.-Quartz single crystal can thus be made from fused quartz in caustic solvent by heating to 350.degree. C. stepwise with a .DELTA.T of 0.25.degree.-3.degree. C., increasing the .DELTA.T to about 50.degree. C. after the fused quartz has crystallized, and maintaining these conditions until crystal growth in the upper zone is completed.

Formulation and Solid State Characterization of Nicotinamide-based Co-crystals of Fenofibrate

PubMed Central

Shewale, Sheetal; Shete, A. S.; Doijad, R. C.; Kadam, S. S.; Patil, V. A.; Yadav, A. V.

2015-01-01

The present investigation deals with formulation of nicotinamide-based co-crystals of fenofibrate by different methods and solid-state characterization of the prepared co-crystals. Fenofibrate and nicotinamide as a coformer in 1:1 molar ratio were used to formulate molecular complexes by kneading, solution crystallization, antisolvent addition and solvent drop grinding methods. The prepared molecular complexes were characterized by powder X-ray diffractometry, differential scanning calorimetry, Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy and in vitro dissolution study. Considerable improvement in the dissolution rate of fenofibrate from optimized co-crystal formulation was due to an increased solubility that is attributed to the super saturation from the fine co-crystals is faster because of large specific surface area of small particles and prevention of phase transformation to pure fenofibrate. In vitro dissolution study showed that the formation of co-crystals improves the dissolution rate of fenofibrate. Nicotinamide forms the co-crystals with fenofibrate, theoretically and practically. PMID:26180279

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.

Characterization of calcium carbonate crystals in pigeon yolk sacs with different incubation times.

PubMed

Song, Juan; Cheng, Haixia; Shen, Xinyu; Hu, Jingxiao; Tong, Hua

2014-05-01

Calcium carbonate crystals are known to form in the yolk sacs of fertile pigeon eggs at late stages of incubation. The composition and structure of these crystals were investigated, the crystallization environment was inspected, and the physical chemistry constants of the yolk fluid were determined through the incubation period. Polarized light microscopy was used to observe the generation and distribution of calcium carbonate crystals in the yolk sac. In addition, X-ray diffraction was employed to analyze the composition and crystal phase of the yolk sac. A decalcification and deproteination method was established to analyze the ultrastructure and composition of the crystals, as well as the internal relationship between inorganic and organic phases of the crystals. Additionally, scanning electron microscopy, transmission electron microscopy, X-ray energy dispersive spectroscopy, and Fourier transform infrared spectroscopy were used to evaluate the characteristics of the crystals. Our results demonstrated that the calcium carbonate crystals were mainly composed of vaterite and calcite, with vaterite being the major component. Vaterite, a type of biomaterial generated by an organic template control, presented as a concentric hierarchical spherical structure. The organic nature of the biomaterial prevented vaterite from transforming into calcite, which is more thermodynamically stable than vaterite. Additionally, the configuration, size, and aggregation of vaterite were also mediated by the organic template. This bio-vaterite was found during the incubation period and is valuable in calcium transport during embryonic development. Copyright © 2014 Elsevier Ltd. All rights reserved.

Phase transition studies in barium and strontium titanates at microwave frequencies

NASA Technical Reports Server (NTRS)

Dahiya, Jai N.

1993-01-01

The objectives were the following: to understand the phase transformations in barium and strontium titanates as the crystals go from one temperature to the other; and to study the dielectric behavior of barium and strontium titanate crystals at a microwave frequency of 9.12 GHz and as a function of temperature. Phase transition studies in barium and strontium titanate are conducted using a cylindrical microwave resonant cavity as a probe. The cavity technique is quite successful in establishing the phase changes in these crystals. It appears that dipole relaxation plays an important role in the behavior of the dielectric response of the medium loading the cavity as phase change takes place within the sample. The method of a loaded resonant microwave cavity as applied in this work has proven to be sensitive enough to monitor small phase changes of the cavity medium.

The self-healing of defects induced by the hydriding phase transformation in palladium nanoparticles

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

Ulvestad, A.; Yau, A.

Nanosizing can dramatically alter material properties by enhancing surface thermodynamic contributions, shortening diffusion lengths, and increasing the number of catalytically active sites per unit volume. These mechanisms have been used to explain the improved properties of catalysts, battery materials, plasmonic materials, etc. Here we show that Pd nanoparticles also have the ability to self-heal defects in their crystal structures. Using Bragg coherent diffractive imaging, we image dislocations nucleated deep in a Pd nanoparticle during the forward hydriding phase transformation that heal during the reverse transformation, despite the region surrounding the dislocations remaining in the hydrogen-poor phase. We show that defectivemore » Pd nanoparticles exhibit sloped isotherms, indicating that defects act as additional barriers to the phase transformation. Our results resolve the formation and healing of structural defects during phase transformations at the single nanoparticle level and offer an additional perspective as to how and why nanoparticles differ from their bulk counterparts.« less

Mineralogical transformations controlling acid mine drainage chemistry

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

Peretyazhko, Tetyana; Zachara, John M.; Boily, Jean F.

2009-05-30

The role of Fe(III) minerals in controlling acid mine drainage (AMD) chemistry was studied using samples from two AMD sites [Gum Boot (GB) and Fridays-2 (FR)] located in northern Pennsylvania. Chemical extractions, X-ray diffraction (XRD), scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR) were used to identify and characterize Fe(III) phases. The mineralogical analysis revealed that schwertmannite and goethite were the principal Fe(III) phases in the sediments. Schwertmannite transformation occurred at the GB site where poorly-crystallized goethite rich in surface-bound sulfate was initially formed. In contrast, no schwertmannite transformation occurred at the FR site. The goethite in GBmore » sediments had spherical morphology due to preservation of schwertmannite structure by adsorbed sulfate. Results of chemical extractions showed that poorly-crystallized goethite was subject to further crystallization accompanied by sulfate desorption. Changes in sulfate speciation preceded its desorption, with a conversion of bidentate- to monodentate-bound sulfate surface complexes. Laboratory sediment incubation experiments were conducted to evaluate the effect of mineral transformation on water chemistry. Incubation experiments were carried out with schwertmannite-containing sediments and AMD waters with different pH and chemical composition. The pH decreased to 1.9-2.2 in all suspensions and the concentrations of dissolved Fe and S increased significantly. Regardless of differences in the initial water composition, pH, Fe and S were similar in suspensions of the same sediment. XRD measurements revealed that schwertmannite transformed into goethite in GB and FR sediments during laboratory incubation. The incubation experiment demonstrated that schwertmannite transformation controlled AMD water chemistry during “closed system” laboratory contact.« less

Investigations of kinetics and mechanism of chloropinnoite in boric acid aqueous solution at 303 K by Raman spectroscopy.

PubMed

Xiaoping, Li; Shiyang, Gao; Shuping, Xia

2004-10-01

Raman spectroscopy of dissolution and transformation of chloropinnoite in 4.5% (wt.%) boric acid aqueous solution at 303 K has been recorded. The Raman spectra of kinetics process have been obtained. The phase transformation product is 2MgO.3B2O3.15H2O (kurnakovite). The main polyborate anions and their interaction in aqueous solution have been proposed according to the Raman spectrum. Some assignments were tentatively given and the relations between the existing forms of polyborate anions and the crystallizing solid phases have been gained. A mechanism of dissolution and crystallization reactions and the formation condition of kurnakovite in Qinghai-Tibet plateau were proposed and discussed.

In situ electron microscope study of the phase transformation, structure and growth of thin Te1-xSex films

NASA Astrophysics Data System (ADS)

Vermaak, J. S.; Raubenheimer, D.

1988-01-01

An in-situ electron microscope technique was utilized to observe directly the amorphous-to-crystalline phase transformation, the isothermal growth rates, as well as the orientation and structure of the recrystallized films for the Te1-xSex alloy system for x=0.2, 0.3 and 0.4. Activation energies of E=0.91, 0.93 and 0.96 eV and crystallization temperatures of Tc=-14, 81.5 and 85°C for the three alloys, respectively, were found. In all three cases the crystallization process originated from single crystalline nuclei with a hexagonal structure and with the c-axis in general parallel to the substrate surface.

[Study of the phase transformation of TiO2 with in-situ XRD in different gas].

PubMed

Ma, Li-Jing; Guo, Lie-Jin

2011-04-01

TiO2 sample was prepared by sol-gel method from chloride titanium. The phase transformation of the prepared TiO2 sample was studied by in-situ XRD and normal XRD in different gas. The experimental results showed that the phase transformation temperatures of TiO2 were different under in-situ or normal XRD in different kinds of gas. The transformation of amorphous TiO2 to anatase was controlled by kinetics before 500 degrees C. In-situ XRD showed that the growth of anatase was inhibited, but the transformation of anatase to rutile was accelerated under inactive nitrogen in contrast to air. Also better crystal was obtained under hydrogen than in argon. These all showed that external oxygen might accelerate the growth of TiO2, but reduced gas might partly counteract the negative influence of lack of external oxygen. The mechanism of phase transformation of TiO2 was studied by in-situ XRD in order to control the structure in situ.

Real-time observation of morphological transformations in II-VI semiconducting nanobelts via environmental transmission electron microscopy

DOE PAGES

Agarwal, Rahul; Zakharov, Dmitri N.; Krook, Nadia M.; ...

2015-05-01

It has been observed that wurtzite II–VI semiconducting nanobelts transform into single-crystal, periodically branched nanostructures upon heating. The mechanism of this novel transformation has been elucidated by heating II–VI nanobelts in an environmental transmission electron microscope (ETEM) in oxidizing, reducing and inert atmospheres while observing their structural changes with high spatial resolution. The interplay of surface reconstruction of high-energy surfaces of the wurtzite phase and environment-dependent anisotropic chemical etching of certain crystal surfaces in the branching mechanism of nanobelts has been observed. Understanding of structural and chemical transformations of materials via in situ microscopy techniques and their role in designingmore » new nanostructured materials is discussed.« less

Structural transformations in austenitic stainless steel induced by deuterium implantation: irradiation at 100 K.

PubMed

Morozov, Oleksandr; Zhurba, Volodymyr; Neklyudov, Ivan; Mats, Oleksandr; Rud, Aleksandr; Chernyak, Nikolay; Progolaieva, Viktoria

2015-01-01

Deuterium thermal desorption spectra were investigated on the samples of austenitic stainless steel 18Cr10NiTi preimplanted at 100 K with deuterium ions in the dose range from 3 × 10(15) to 5 × 10(18) D/cm(2). The kinetics of structural transformation development in the implantation steel layer was traced from deuterium thermodesorption spectra as a function of implanted deuterium concentration. At saturation of austenitic stainless steel 18Cr10NiTi with deuterium by means of ion implantation, structural-phase changes take place, depending on the dose of implanted deuterium. The maximum attainable concentration of deuterium in steel is C = 1 (at.D/at.met. = 1/1). The increase in the implanted dose of deuterium is accompanied by the increase in the retained deuterium content, and as soon as the deuterium concentration attains C ≈ 0.5 the process of shear martensitic structural transformation in steel takes place. It includes the formation of bands, body-centered cubic (bcc) crystal structure, and the ferromagnetic phase. Upon reaching the deuterium concentration C > 0.5, the presence of these molecules causes shear martensitic structural transformations in the steel, which include the formation of characteristic bands, bcc crystal structure, and the ferromagnetic phase. At C ≥ 0.5, two hydride phases are formed in the steel, the decay temperatures of which are 240 and 275 K. The hydride phases are formed in the bcc structure resulting from the martensitic structural transformation in steel.

Experimental gaze at nonlinear phenomena

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

Libchaber, A.

1988-09-20

Experimental observations of nonlinear problems in physics are presented, including liquid crystal phase transformations, convection of mercury, and the transition to turbulence in helium gas thermal convection./aip/.

Mechanically controlling the reversible phase transformation from zinc blende to wurtzite in AlN

DOE PAGES

Li, Zhen; Yadav, Satyesh; Chen, Youxing; ...

2017-04-10

III–V and other binary octet semiconductors often take two phase forms—wurtzite (wz) and zinc blende (zb) crystal structures—with distinct functional performance at room temperature. Here, we investigate how to control the synthesized phase structure to either wz or zb phase by tuning the interfacial strain by taking AlN as a representative III–V compound. Furthermore, by applying in situ mechanical tests at atomic scale in a transmission electron microscope, we observed the reversible phase transformation from zb to wz, and characterized the transition path—the collective glide of Shockley partials on every two {111} planes of the zb AlN.

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.

Features of structure-phase transformations and segregation processes under irradiation of austenitic and ferritic-martensitic steels

NASA Astrophysics Data System (ADS)

Neklyudov, I. M.; Voyevodin, V. N.

1994-09-01

The difference between crystal lattices of austenitic and ferritic steels leads to distinctive features in mechanisms of physical-mechanical change. This paper presents the results of investigations of dislocation structure and phase evolution, and segregation phenomena in austenitic and ferritic-martensitic steels and alloys during irradiation with heavy ions in the ESUVI and UTI accelerators and by neutrons in fast reactors BOR-60 and BN-600. The influence of different factors (including different alloying elements) on processes of structure-phase transformation was studied.

Electro-optic imaging Fourier transform spectrometer

NASA Technical Reports Server (NTRS)

Chao, Tien-Hsin (Inventor); Znod, Hanying (Inventor)

2009-01-01

An Electro-Optic Imaging Fourier Transform Spectrometer (EOIFTS) for Hyperspectral Imaging is described. The EOIFTS includes an input polarizer, an output polarizer, and a plurality of birefringent phase elements. The relative orientations of the polarizers and birefringent phase elements can be changed mechanically or via a controller, using ferroelectric liquid crystals, to substantially measure the spectral Fourier components of light propagating through the EIOFTS. When achromatic switches are used as an integral part of the birefringent phase elements, the EIOFTS becomes suitable for broadband applications, with over 1 micron infrared bandwidth.

Behavior of Sn atoms in GeSn thin films during thermal annealing: Ex-situ and in-situ observations

NASA Astrophysics Data System (ADS)

Takase, Ryohei; Ishimaru, Manabu; Uchida, Noriyuki; Maeda, Tatsuro; Sato, Kazuhisa; Lieten, Ruben R.; Locquet, Jean-Pierre

2016-12-01

Thermally induced crystallization processes for amorphous GeSn thin films with Sn concentrations beyond the solubility limit of the bulk crystal Ge-Sn binary system have been examined by X-ray photoelectron spectroscopy, grazing incidence X-ray diffraction, and (scanning) transmission electron microscopy. We paid special attention to the behavior of Sn before and after recrystallization. In the as-deposited specimens, Sn atoms were homogeneously distributed in an amorphous matrix. Prior to crystallization, an amorphous-to-amorphous phase transformation associated with the rearrangement of Sn atoms was observed during heat treatment; this transformation is reversible with respect to temperature. Remarkable recrystallization occurred at temperatures above 400 °C, and Sn atoms were ejected from the crystallized GeSn matrix. The segregation of Sn became more pronounced with increasing annealing temperature, and the ejected Sn existed as a liquid phase. It was found that the molten Sn remains as a supercooled liquid below the eutectic temperature of the Ge-Sn binary system during the cooling process, and finally, β-Sn precipitates were formed at ambient temperature.

Orientation of liquid crystalline blue phases on unidirectionally orienting surfaces

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

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.

Aluminate effect on desilication product phase transformation

NASA Astrophysics Data System (ADS)

Peng, Hong; Vaughan, James

2018-06-01

It remains a grand challenge in the treatment of bauxite residue to physically separate zeolite (also known as the DeSilication Product, DSP) from other unleached mineral phases owing to their fine sizes, typically less than 2 μm in diameter. In this study, the effect of aluminate concentration on DSP phase transformation was investigated from synthetic NaOH-NaAl(OH)4-Na2SiO3-H2O solution at 90 °C. The results show how at relatively low aluminate concentrations of 0.125 and 0.25 M NaAl(OH)4(aq), larger zeolite crystals of up to 60 μm in diameter are formed during homogenous precipitation from aqueous solution. The precipitation process involves the conversion of zeolite LTA to sodalite via the formation of an intermediate phase, octahedral LTN. Initial amorphous solids precipitate as aggregates in which cubic zeolite LTA nucleation occurs. As the reaction proceeds, truncated octahedral LTN appears with the cubic zeolite LTA and finally sodalite crystallizes on the LTA-LTN aggregates resulting in coarsened particles.

Heavy ion irradiation-induced microstructural evolution in pyrochlore Lu{sub 2}Ti{sub 2}O{sub 7} at room temperature and 723 K

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

Xie, Q.R.; Zhang, J., E-mail: zhangjian@xmu.edu.cn; Dong, X.N.

Polycrystalline pyrochlore Lu{sub 2}Ti{sub 2}O{sub 7} pellets were irradiated with 600 keV Kr{sup 3+} at room temperature and 723 K to a fluence of 4×10{sup 15} ions/cm{sup 2}, corresponding to an average ballistic damage dose of 10 displacements per atom in the peak damage region. Irradiation-induced microstructural evolution was examined by grazing incidence X-ray diffraction, and cross-sectional transmission electron microscopy. Incomplete amorphization was observed in the sample irradiated at room temperature due to the formation of nano-crystal which has the identical structure of pyrochlore, and the formation of nano-crystal is attributed to the mechanism of epitaxial recrystallization. However, an orderedmore » pyrochlore phase to a swelling disordered fluorite phase transformation is occurred for the Lu{sub 2}Ti{sub 2}O{sub 7} sample irradiated at 723 K, which is due to the disordering of metal cations and anion vacancies. - Graphical Abstract: Polycrystalline pyrochlore Lu{sub 2}Ti{sub 2}O{sub 7} pellets were irradiated with 600 keV Kr{sup 3+} to a fluence of 4×10{sup 15} ions/cm{sup 2} at room temperature and 723 K, Incomplete amorphization was observed in the sample irradiated at room temperature due to the formation of nano-crystal. However, an ordered pyrochlore phase to a swelling disordered fluorite phase transformation is occurred for the Lu{sub 2}Ti{sub 2}O{sub 7} sample irradiated at 723 K, which is due to the disordering of metal cations and anion vacancies. - Highlights: Pyrochlore Lu{sub 2}Ti{sub 2}O{sub 7} pellets were irradiated by heavy ions at RT and 723 K. At RT irradiation, ~75% of amorphization was achieved. The nano-crystals were formed in the damage layer at RT irradiation. The formed nano-crystals enhanced the radiation tolerance of Lu{sub 2}Ti{sub 2}O{sub 7}. A pyrochlore to fluorite phase transformation was observed at 723 K irradiation.« less

Pressure-induced structural phase transformation and superconducting properties of titanium mononitride

NASA Astrophysics Data System (ADS)

Li, Qian; Guo, Yanan; Zhang, Miao; Ge, Xinlei

2018-03-01

In this work, we have systematically performed the first-principles structure search on titanium mononitride (TiN) within Crystal Structure AnaLYsis by Particle Swarm Optimization (CALYPSO) methodology at high pressures. Here, we have confirmed a phase transition from cubic rock-salt (fcc) phase to CsCl (bcc) phase of TiN at ∼348 GPa. Further simulations reveal that the bcc phase is dynamically stable, and could be synthesized experimentally in principle. The calculated elastic anisotropy decreases with the phase transformation from fcc to bcc structure under high pressures, and the material changes from ductile to brittle simultaneously. Moreover, we found that both structures are superconductive with the superconducting critical temperature of 2-12 K.

Control of composition and crystallinity in hydroxyapatite films deposited by electron cyclotron resonance plasma sputtering

NASA Astrophysics Data System (ADS)

Akazawa, Housei; Ueno, Yuko

2014-01-01

Hydroxyapatite (HAp) films were deposited by electron cyclotron resonance plasma sputtering under a simultaneous flow of H2O vapor gas. Crystallization during sputter-deposition at elevated temperatures and solid-phase crystallization of amorphous films were compared in terms of film properties. When HAp films were deposited with Ar sputtering gas at temperatures above 460 °C, CaO byproducts precipitated with HAp crystallites. Using Xe instead of Ar resolved the compositional problem, yielding a single HAp phase. Preferentially c-axis-oriented HAp films were obtained at substrate temperatures between 460 and 500 °C and H2O pressures higher than 1×10-2 Pa. The absorption signal of the asymmetric stretching mode of the PO43- unit (ν3) in the Fourier-transform infrared absorption (FT-IR) spectra was the narrowest for films as-crystallized during deposition with Xe, but widest for solid-phase crystallized films. While the symmetric stretching mode of PO43- (ν1) is theoretically IR-inactive, this signal emerged in the FT-IR spectra of solid-phase crystallized films, but was absent for as-crystallized films, indicating superior crystallinity for the latter. The Raman scattering signal corresponding to ν1 PO43- sensitively reflected this crystallinity. The surface hardness of as-crystallized films evaluated by a pencil hardness test was higher than that of solid-phase crystallized films.

Demonstration of single crystal growth via solid-solid transformation of a glass

DOE PAGES

Savytskii, Dmytro; Knorr, Brian; Dierolf, Volkmar; ...

2016-03-18

Many advanced technologies have relied on the availability of single crystals of appropriate material such as silicon for microelectronics or superalloys for turbine blades. Similarly, many promising materials could unleash their full potential if they were available in a single crystal form. However, the current methods are unsuitable for growing single crystals of these oftentimes incongruently melting, unstable or metastable materials. Here we demonstrate a strategy to overcome this hurdle by avoiding the gaseous or liquid phase, and directly converting glass into a single crystal. Specifically, Sb 2S 3 single crystals are grown in Sb-S-I glasses as an example ofmore » this approach. In this first unambiguous demonstration of an all-solid-state glass → crystal transformation, extraneous nucleation is avoided relative to crystal growth via spatially localized laser heating and inclusion of a suitable glass former in the composition. Lastly, the ability to fabricate patterned single-crystal architecture on a glass surface is demonstrated, providing a new class of micro-structured substrate for low cost epitaxial growth, active planar devices, etc.« less

Synthesis, crystal growth and characterization of a phase matchable nonlinear optical single crystal: p-chloro dibenzylideneacetone

NASA Astrophysics Data System (ADS)

Ravindra, H. J.; John Kiran, A.; Nooji, Satheesha Rai; Dharmaprakash, S. M.; Chandrasekharan, K.; Kalluraya, Balakrishna; Rotermund, Fabian

2008-05-01

Good quality single crystals of p-chloro dibenzylideneacetone (CDBA) of size 13 mm×8 mm×2 mm were grown by slow evaporation solution growth technique. The grown crystals were confirmed by elemental analysis, Fourier transform infrared (FTIR) analysis and single crystal X-ray diffraction techniques. From the thermo gravimetric/differential thermal (TG/DT) analysis, the CDBA was found to be thermally stable up to 250 °C. The mechanical stability of the crystal is comparable with that of the other reported chalcones. The lower optical cut-off wavelength for this crystal was observed at 440 nm. The laser damage threshold of the crystal was 0.6 GW/cm 2 at 532 nm. The second harmonic generation conversion efficiency of the powder sample of CDBA was found to be 4.5 times greater than that of urea. We also demonstrate the existence of the phase matching property in this crystal using Kurtz powder technique.

Phase transformations in amorphous fullerite C60 under high pressure and high temperature

NASA Astrophysics Data System (ADS)

Borisova, P. A.; Blanter, M. S.; Brazhkin, V. V.; Somenkov, V. A.; Filonenko, V. P.

2015-08-01

First phase transformations of amorphous fullerite C60 at high temperatures (up to 1800 K) and high pressures (up to 8 GPa) have been investigated and compared with the previous studies on the crystalline fullerite. The study was conducted using neutron diffraction and Raman spectroscopy. The amorphous fullerite was obtained by ball-milling. We have shown that under thermobaric treatment no crystallization of amorphous fullerite into С60 molecular modification is observed, and it transforms into amorphous-like or crystalline graphite. A kinetic diagram of phase transformation of amorphous fullerite in temperature-pressure coordinates was constructed for the first time. Unlike in crystalline fullerite, no crystalline polymerized phases were formed under thermobaric treatment on amorphous fullerite. We found that amorphous fullerite turned out to be less resistant to thermobaric treatment, and amorphous-like or crystalline graphite were formed at lower temperatures than in crystalline fullerite.

Fast Atomic-Scale Chemical Imaging of Crystalline Materials and Dynamic Phase Transformations

DOE PAGES

Lu, Ping; Yuan, Ren Liang; Ihlefeld, Jon F.; ...

2016-03-04

Chemical imaging at the atomic-scale provides a useful real-space approach to chemically investigate solid crystal structures, and has been recently demonstrated in aberration corrected scanning transmission electron microscopy (STEM). Atomic-scale chemical imaging by STEM using energy-dispersive X-ray spectroscopy (EDS) offers easy data interpretation with a one-to-one correspondence between image and structure but has a severe shortcoming due to the poor efficiency of X-ray generation and collection. As a result, it requires a long acquisition time of typical > few 100 seconds, limiting its potential applications. Here we describe the development of an atomic-scale STEM EDS chemical imaging technique that cutsmore » the acquisition time to one or a few seconds, efficiently reducing the acquisition time by more than 100 times. This method was demonstrated using LaAlO 3 (LAO) as a model crystal. Applying this method to the study of phase transformation induced by electron-beam radiation in a layered lithium transition-metal (TM) oxide, i.e., Li[Li 0.2Ni 0.2Mn 0.6]O 2 (LNMO), a cathode materials for lithium-ion batteries, we obtained a time-series of the atomic-scale chemical imaging, showing the transformation progressing by preferably jumping of Ni atoms from the TM layers into the Li-layers. The new capability offers an opportunity for temporal, atomic-scale chemical mapping of crystal structures for the investigation of materials susceptible to electron irradiation as well as phase transformation and dynamics at the atomic-scale.« less

Multiple pathways in pressure-induced phase transition of coesite

NASA Astrophysics Data System (ADS)

Liu, Wei; Wu, Xuebang; Liang, Yunfeng; Liu, Changsong; Miranda, Caetano R.; Scandolo, Sandro

2017-12-01

High-pressure single-crystal X-ray diffraction method with precise control of hydrostatic conditions, typically with helium or neon as the pressure-transmitting medium, has significantly changed our view on what happens with low-density silica phases under pressure. Coesite is a prototype material for pressure-induced amorphization. However, it was found to transform into a high-pressure octahedral (HPO) phase, or coesite-II and coesite-III. Given that the pressure is believed to be hydrostatic in two recent experiments, the different transformation pathways are striking. Based on molecular dynamic simulations with an ab initio parameterized potential, we reproduced all of the above experiments in three transformation pathways, including the one leading to an HPO phase. This octahedral phase has an oxygen hcp sublattice featuring 2 × 2 zigzag octahedral edge-sharing chains, however with some broken points (i.e., point defects). It transforms into α-PbO2 phase when it is relaxed under further compression. We show that the HPO phase forms through a continuous rearrangement of the oxygen sublattice toward hcp arrangement. The high-pressure amorphous phases can be described by an fcc and hcp sublattice mixture.

Two-dimensional lithium diffusion behavior and probable hybrid phase transformation kinetics in olivine lithium iron phosphate

DOE PAGES

Hong, Liang; Li, Linsen; Chen-Wiegart, Yuchen-Karen; ...

2017-10-30

Olivine lithium iron phosphate is a technologically important electrode material for lithium-ion batteries and a model system for studying electrochemically driven phase transformations. Despite extensive studies, many aspects of the phase transformation and lithium transport in this material are still not well understood. Here we combine operando hard X-ray spectroscopic imaging and phase-field modeling to elucidate the delithiation dynamics of single-crystal lithium iron phosphate microrods with long-axis along the [010] direction. Lithium diffusivity is found to be two-dimensional in microsized particles containing ~3%lithium-iron anti-site defects. Our study provides direct evidence for the previously predicted surface reaction-limited phase-boundary migration mechanism andmore » the potential operation of a hybrid mode of phase growth, in which phase-boundary movement is controlled by surface reaction or lithium diffusion in different crystallographic directions. These findings uncover the rich phase-transformation behaviors in lithium iron phosphate and intercalation com-pounds in general and can help guide the design of better electrodes.« less

Two-dimensional lithium diffusion behavior and probable hybrid phase transformation kinetics in olivine lithium iron phosphate

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

Hong, Liang; Li, Linsen; Chen-Wiegart, Yuchen-Karen

Olivine lithium iron phosphate is a technologically important electrode material for lithium-ion batteries and a model system for studying electrochemically driven phase transformations. Despite extensive studies, many aspects of the phase transformation and lithium transport in this material are still not well understood. Here we combine operando hard X-ray spectroscopic imaging and phase-field modeling to elucidate the delithiation dynamics of single-crystal lithium iron phosphate microrods with long-axis along the [010] direction. Lithium diffusivity is found to be two-dimensional in microsized particles containing ~3%lithium-iron anti-site defects. Our study provides direct evidence for the previously predicted surface reaction-limited phase-boundary migration mechanism andmore » the potential operation of a hybrid mode of phase growth, in which phase-boundary movement is controlled by surface reaction or lithium diffusion in different crystallographic directions. These findings uncover the rich phase-transformation behaviors in lithium iron phosphate and intercalation com-pounds in general and can help guide the design of better electrodes.« less

Two-dimensional lithium diffusion behavior and probable hybrid phase transformation kinetics in olivine lithium iron phosphate

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

Hong, Liang; Chen-Wiegart, Yu-Chen K.

2017-10-30

Olivine lithium iron phosphate is a technologically important electrode material for lithium-ion batteries and a model system for studying electrochemically driven phase transformations. Despite extensive studies, many aspects of the phase transformation and lithium transport in this material are still not well understood. Here we combine operando hard X-ray spectroscopic imaging and phase-field modeling to elucidate the delithiation dynamics of single-crystal lithium iron phosphate microrods with long-axis along the [010] direction. Lithium diffusivity is found to be two-dimensional in microsized particles containing ~3%lithium-iron anti-site defects. Our study provides direct evidence for the previously predicted surface reaction-limited phase-boundary migration mechanism andmore » the potential operation of a hybrid mode of phase growth, in which phase-boundary movement is controlled by surface reaction or lithium diffusion in different crystallographic directions. These findings uncover the rich phase-transformation behaviors in lithium iron phosphate and intercalation com-pounds in general and can help guide the design of better electrodes.« less

Crystal and Morphological Phase Transformation of Pb(II) to Pb(IV) in Chlorinated Water

EPA Science Inventory

Herein, we show that an important transformation of Pb(II) to Pb(IV) under laboratory conditions which is intended to represent in real water flowing system in lead pipes. These results will give an insight in understanding the scale formation in lead pipes and dissolution of lea...

Synthesis of a mesoporous single crystal Ga2O3 nanoplate with improved photoluminescence and high sensitivity in detecting CO.

PubMed

Yan, Shicheng; Wan, Lijuan; Li, Zhaosheng; Zhou, Yong; Zou, Zhigang

2010-09-14

A new approach is proposed to synthesize a mesoporous single crystal Ga(2)O(3) nanoplate by heating a single crystal nanoplate of GaOOH, which involves an ion exchange between KGaO(2) and CH(3)COOH at room temperature for the formation of GaOOH and pseudomorphic and topotactic phase transformation from GaOOH to Ga(2)O(3).

Phase transformations in ion-irradiated silicides

NASA Technical Reports Server (NTRS)

Hewett, C. A.; Lau, S. S.; Suni, I.; Hung, L. S.

1985-01-01

The present investigation has three objectives. The first is concerned with the phase transformation of CoSi2 under ion implantation and the subsequent crystallization characteristics during annealing, taking into account epitaxial and nonepitaxial recrystallization behavior. The second objective is related to a study of the general trend of implantation-induced damage and crystallization behavior for a number of commonly used silicides. The last objective involves a comparison of the recrystallization behavior of cosputtered refractory silicides with that of the ion-implanted silicides. It was found that epitaxial regrowth of ion-irradiated CoSi2 occurred for samples with an epitaxial seed left at the Si/CoSi2 interface. A structural investigation of CoSi2 involving transmission electron microscopy (TEM) showed that after high-dose implantation CoSi2 is amorphous.

Theoretical calculations of high-pressure phases of NiF2: An ab initio constant-pressure study

NASA Astrophysics Data System (ADS)

Kürkçü, Cihan; Merdan, Ziya; Öztürk, Hülya

2016-12-01

We have studied the structural properties of the antiferromagnetic NiF2 tetragonal structure with P42/ mnm symmetry using density functional theory (DFT) under rapid hydrostatic pressure up to 400 GPa. For the exchange correlation energy we used the local density approximation (LDA) of Ceperley and Alder (CA). Two phase transformations are successfully observed through the simulations. The structures of XF2-type compounds crystallize in rutile-type structure. NiF2 undergoes phase transformations from the tetragonal rutile-type structure with space group P42/ mnm to orthorhombic CaCl2-type structure with space group Pnnm and from this orthorhombic phase to monoclinic structure with space group C2/ m at 152 GPa and 360 GPa, respectively. These phase changes are also studied by total energy and enthalpy calculations. According to these calculations, we perdict these phase transformations at about 1.85 and 30 GPa.

Sign reversal of transformation entropy change in Co{sub 2}Cr(Ga,Si) shape memory alloys

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

Xu, Xiao, E-mail: xu@material.tohoku.ac.jp; Omori, Toshihiro; Kainuma, Ryosuke

2015-11-02

In situ X-ray diffraction (XRD) measurements and compression tests were performed on Co{sub 2}Cr(Ga,Si) shape memory alloys. The reentrant martensitic transformation behavior was directly observed during the in situ XRD measurements. The high-temperature parent phase and low-temperature reentrant parent phase were found to have a continuous temperature dependence of lattice parameter, therefore suggesting that they are the same phase in nature. Moreover, compression tests were performed on a parent-phase single crystal sample; an evolution from normal to inverse temperature dependence of critical stress for martensitic transformation was directly observed. Based on the Clausius-Clapeyron analysis, a sign reversal of entropy changemore » can be expected on the same alloy.« less

Improving the efficiency of molecular replacement by utilizing a new iterative transform phasing algorithm

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

He, Hongxing; Fang, Hengrui; Miller, Mitchell D.

2016-07-15

An iterative transform algorithm is proposed to improve the conventional molecular-replacement method for solving the phase problem in X-ray crystallography. Several examples of successful trial calculations carried out with real diffraction data are presented. An iterative transform method proposed previously for direct phasing of high-solvent-content protein crystals is employed for enhancing the molecular-replacement (MR) algorithm in protein crystallography. Target structures that are resistant to conventional MR due to insufficient similarity between the template and target structures might be tractable with this modified phasing method. Trial calculations involving three different structures are described to test and illustrate the methodology. The relationshipmore » of the approach to PHENIX Phaser-MR and MR-Rosetta is discussed.« less

Mechanisms for pressure-induced crystal-crystal transition, amorphization, and devitrification of SnI{sub 4}

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

Liu, H.; Tse, J. S., E-mail: john.tse@usask.ca; Hu, M. Y.

2015-10-28

The pressure-induced amorphization and subsequent recrystallization of SnI{sub 4} have been investigated using first principles molecular dynamics calculations together with high-pressure {sup 119}Sn nuclear resonant inelastic x-ray scattering measurements. Above ∼8 GPa, we observe a transformation from an ambient crystalline phase to an intermediate crystal structure and a subsequent recrystallization into a cubic phase at ∼64 GPa. The crystalline-to-amorphous transition was identified on the basis of elastic compatibility criteria. The measured tin vibrational density of states shows large amplitude librations of SnI{sub 4} under ambient conditions. Although high pressure structures of SnI{sub 4} were thought to be determined by randommore » packing of equal-sized spheres, we detected electron charge transfer in each phase. This charge transfer results in a crystal structure packing determined by larger than expected iodine atoms.« less

Mechanisms for pressure-induced crystal-crystal transition, amorphization, and devitrification of Snl 4

DOE PAGES

Liu, Hanyu; Tse, John S.; Hu, Michael Y.; ...

2015-10-27

The pressure-induced amorphization and subsequent recrystallization of SnI 4 have been investigated using first principles molecular dynamics calculations together with high-pressure 119Sn nuclear resonant inelastic x-ray scattering measurements. Above ~8 GPa, we observe a transformation from an ambient crystalline phase to an intermediate crystal structure and a subsequent recrystallization into a cubic phase at ~64 GPa. The crystalline-to-amorphous transition was identified on the basis of elastic compatibility criteria. The measured tin vibrational density of states shows large amplitude librations of SnI 4 under ambient conditions. Although high pressure structures of SnI 4 were thought to be determined by random packingmore » of equal-sized spheres, we detected electron charge transfer in each phase. As a result, this charge transfer results in a crystal structure packing determined by larger than expected iodine atoms. (C) 2015 AIP Publishing LLC.« less

Mechanisms for pressure-induced crystal-crystal transition, amorphization, and devitrification of SnI4.

PubMed

Liu, H; Tse, J S; Hu, M Y; Bi, W; Zhao, J; Alp, E E; Pasternak, M; Taylor, R D; Lashley, J C

2015-10-28

The pressure-induced amorphization and subsequent recrystallization of SnI4 have been investigated using first principles molecular dynamics calculations together with high-pressure (119)Sn nuclear resonant inelastic x-ray scattering measurements. Above ∼8 GPa, we observe a transformation from an ambient crystalline phase to an intermediate crystal structure and a subsequent recrystallization into a cubic phase at ∼64 GPa. The crystalline-to-amorphous transition was identified on the basis of elastic compatibility criteria. The measured tin vibrational density of states shows large amplitude librations of SnI4 under ambient conditions. Although high pressure structures of SnI4 were thought to be determined by random packing of equal-sized spheres, we detected electron charge transfer in each phase. This charge transfer results in a crystal structure packing determined by larger than expected iodine atoms.

Temperature induced phase transformations and negative electrocaloric effect in (Pb,La)(Zr,Sn,Ti)O3 antiferroelectric single crystal

NASA Astrophysics Data System (ADS)

Zhuo, Fangping; Li, Qiang; Yan, Qingfeng; Zhang, Yiling; Wu, Hong-Hui; Xi, Xiaoqing; Chu, Xiangcheng; Cao, Wenwu

2017-10-01

Temperature induced phase transitions and electrocaloric effect (ECE) of (Pb,La)(Zr,Sn,Ti)O3 (PLZST) single crystals have been comprehensively studied. Based on the in situ evolution of domain structures and dielectric properties of the PLZST crystals, the phase transitions during heating are in the sequence of orthorhombic antiferroelectric → rhombohedral ferroelectric → cubic paraelectric. Coexistence of the negative and positive ECEs has been achieved in the PLZST single crystals. A negative ECE value of -1.26 °C and enhanced electrocaloric strength of -0.21 K mm/kV near the Curie temperature have been obtained. A modified Landau model gives a satisfactory description of the experimentally observed unusual ECE. Moreover, a temperature-electric field phase diagram is also established based on theoretical analysis. Our results will help people understand better the electrocaloric family, particularly on the negative and/or positive effect in antiferroelectrics and ferroelectrics.

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

Liu, J. P.; Wang, Y. D.; Hao, Y. L.

Two main explanations exist for the deformation mechanisms in Ti-Nb-based gum metals, i.e. the formation of reversible nanodisturbance and reversible stress-induced martensitic transformation. In this work, we used the in situ synchrotron-based high-energy X-ray diffuse-scattering technique to reveal the existence of a specific deformation mechanism, i.e. deformation-induced spatially confined martensitic transformations, in Ti-24Nb-4Zr-8Sn-0.10O single crystals with cubic 13 parent phase, which explains well some anomalous mechanical properties of the alloy such as low elastic modulus and nonlinear superelasticity. Two kinds of nanosized martensites with different crystal structures were found during uniaxial tensile loading along the [11 0](beta) axis at roommore » temperature and 190 K, respectively. The detailed changes in the martensitic phase transformation characteristics and the transformation kinetics were experimentally observed at different temperatures. The domain switch from non-modulated martensite to a modulated one occurred at 190 K, with its physical origin attributed to the heterogeneity of local phonon softening depending on temperature and inhomogeneous composition in the parent phase. An in-depth understanding of the formation of stress-induced spatially confined nanosized martensites with a large gradient in chemical composition may benefit designs of high-strength and high-ductility alloys. (C) 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.« less

Evolution of molecular crystal optical phonons near structural phase transitions

NASA Astrophysics Data System (ADS)

Michki, Nigel; Niessen, Katherine; Xu, Mengyang; Markelz, Andrea

Molecular crystals are increasingly important photonic and electronic materials. For example organic semiconductors are lightweight compared to inorganic semiconductors and have inexpensive scale up processing with roll to roll printing. However their implementation is limited by their environmental sensitivity, in part arising from the weak intermolecular interactions of the crystal. These weak interactions result in optical phonons in the terahertz frequency range. We examine the evolution of intermolecular interactions near structural phase transitions by measuring the optical phonons as a function of temperature and crystal orientation using terahertz time-domain spectroscopy. The measured orientation dependence of the resonances provides an additional constraint for comparison of the observed spectra with the density functional calculations, enabling us to follow specific phonon modes. We observe crystal reorganization near 350 K for oxalic acid as it transforms from dihydrate to anhydrous form. We also report the first THz spectra for the molecular crystal fructose through its melting point.

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

Ma, Xiang; Zhang, Shuai; Jiao, Fang

Two-step nucleation pathways in which disordered, amorphous, or dense liquid states precede appearance of crystalline phases have been reported for a wide range of materials, but the dynamics of such pathways are poorly understood. Moreover, whether these pathways are general features of crystallizing systems or a consequence of system-specific structural details that select for direct vs two-step processes is unknown. Using atomic force microscopy to directly observe crystallization of sequence-defined polymers, we show that crystallization pathways are indeed sequence dependent. When a short hydrophobic region is added to a sequence that directly forms crystalline particles, crystallization instead follows a two-stepmore » pathway that begins with creation of disordered clusters of 10-20 molecules and is characterized by highly non-linear crystallization kinetics in which clusters transform into ordered structures that then enter the growth phase. The results shed new light on non-classical crystallization mechanisms and have implications for design of self-assembling polymer systems.« less

Spatially resolved observation of crystal-face-dependent catalysis by single turnover counting

NASA Astrophysics Data System (ADS)

Roeffaers, Maarten B. J.; Sels, Bert F.; Uji-I, Hiroshi; de Schryver, Frans C.; Jacobs, Pierre A.; de Vos, Dirk E.; Hofkens, Johan

2006-02-01

Catalytic processes on surfaces have long been studied by probing model reactions on single-crystal metal surfaces under high vacuum conditions. Yet the vast majority of industrial heterogeneous catalysis occurs at ambient or elevated pressures using complex materials with crystal faces, edges and defects differing in their catalytic activity. Clearly, if new or improved catalysts are to be rationally designed, we require quantitative correlations between surface features and catalytic activity-ideally obtained under realistic reaction conditions. Transmission electron microscopy and scanning tunnelling microscopy have allowed in situ characterization of catalyst surfaces with atomic resolution, but are limited by the need for low-pressure conditions and conductive surfaces, respectively. Sum frequency generation spectroscopy can identify vibrations of adsorbed reactants and products in both gaseous and condensed phases, but so far lacks sensitivity down to the single molecule level. Here we adapt real-time monitoring of the chemical transformation of individual organic molecules by fluorescence microscopy to monitor reactions catalysed by crystals of a layered double hydroxide immersed in reagent solution. By using a wide field microscope, we are able to map the spatial distribution of catalytic activity over the entire crystal by counting single turnover events. We find that ester hydrolysis proceeds on the lateral {1010} crystal faces, while transesterification occurs on the entire outer crystal surface. Because the method operates at ambient temperature and pressure and in a condensed phase, it can be applied to the growing number of liquid-phase industrial organic transformations to localize catalytic activity on and in inorganic solids. An exciting opportunity is the use of probe molecules with different size and functionality, which should provide insight into shape-selective or structure-sensitive catalysis and thus help with the rational design of new or more productive heterogeneous catalysts.

Time temperature transformation diagram for secondary crystal products of Co-based Co-Fe-B-Si-Nb-Mn soft magnetic nanocomposite

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

DeGeorge, V., E-mail: vdegeorge@cmu.edu; Zoghlin, E.; Keylin, V.

2015-05-07

Secondary crystallization is the subject of much investigation in magnetic amorphous and nanocomposites (MANCs) as it limits the long term and thermal stability of their operation in device applications, including power electronics, sensors, and electric motors. Secondary crystal products [Blazquez et al., Philos. Mag. Lett. 82(7), 409–417 (2002); Ohodnicki et al., Phys. Rev. B 78, 144414 (2008); Willard et al., Metall. Mater. Trans. A 38, 725 (2007)], nanostructure and crystallization kinetics [Hsiao et al., IEEE Trans. Magn. 38(5), 3039 (2002); McHenry et al., Scr. Mater. 48(7), 881 (2003)], and onset temperatures and activation energies [Ohodnicki et al., Acta. Mater. 57,more » 87 (2009); Long et al., J. Appl. Phys. 101, 09N114 (2007)] at constant heating have been reported for similar alloys. However, a time-temperature-transformation (TTT) diagram for isothermal crystallization, more typical of application environments, has not been reported in literature. Here, a TTT diagram for the Co based, Co-Fe-Si-Nb-B-Mn MANC system is presented, along with a method for determining such. The method accounts for the presence of primary crystal phases and yields crystal fraction of secondary phase(s) by using a novel four stage heating profile. The diagram, affirmed by Kissinger activation energy analysis, reports thermal stability of the MANC for millennia at conventional device operating temperatures, and stability limits less than a minute at elevated temperatures. Both extremes are necessary to be able to avoid secondary crystalline products and establish operating limits for this mechanically attractive, high induction soft magnetic nanocomposite.« less

Phase transitions in orthopyroxene (En 90) to 49GPa from single-crystal X-ray diffraction

DOE PAGES

Finkelstein, Gregory J.; Dera, Przemyslaw K.; Duffy, Thomas S.

2014-10-29

Synchrotron-based high-pressure single-crystal X-ray diffraction experiments were conducted on ~Mg 0.9Fe 0.1SiO 3 (En 90) orthopyroxene crystals at room temperature to a maximum pressure of 48.5 GPa. The sample was compressed in a diamond anvil cell with a neon pressure medium and a gold pressure calibrant. In addition to the previously described orthopyroxene to β-opx transition (designated HPCEN2 in previous studies), we observe two further phase transitions at 29.9 GPa and 40.3 GPa. However, we do not observe the γ-opx phase recently described in an Fe-rich orthopyroxene composition. The structures of both of the new phases were solved in spacemore » group Pca21. While their Mg-O layers remain pyroxene-like, their Si-O layers transform in a stepwise fashion to akimotoite-like sheets, with sites in 4-, 5-, or 6-fold coordination, depending on the specific structure and layer. Due to the increased Si-O coordination number, we designate the new structures α- and β-post-orthopyroxene (α-popx and β-popx). α-popx has one Si-O layer that is entirely tetrahedral, and one layer that contains both tetrahedra and 5-coordinated Si in distorted square pyramids. β-popx retains the mixed 4- and 5-coordinated Si layer found in α-popx, while the other Si layer adopts fully octahedral coordination. The α- and β-popx structures show a progressive transformation towards the arrangement of Si layers found in akimotoite, a potentially important phase in the earth’s transition zone. Metastable transformations in pyroxenes are of interest for understanding possible metastability in geological environments such as subducting slabs and meteorite impacts« less

Phase transitions in orthopyroxene (En 90) to 49GPa from single-crystal X-ray diffraction

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

Finkelstein, Gregory J.; Dera, Przemyslaw K.; Duffy, Thomas S.

Synchrotron-based high-pressure single-crystal X-ray diffraction experiments were conducted on ~Mg 0.9Fe 0.1SiO 3 (En 90) orthopyroxene crystals at room temperature to a maximum pressure of 48.5 GPa. The sample was compressed in a diamond anvil cell with a neon pressure medium and a gold pressure calibrant. In addition to the previously described orthopyroxene to β-opx transition (designated HPCEN2 in previous studies), we observe two further phase transitions at 29.9 GPa and 40.3 GPa. However, we do not observe the γ-opx phase recently described in an Fe-rich orthopyroxene composition. The structures of both of the new phases were solved in spacemore » group Pca21. While their Mg-O layers remain pyroxene-like, their Si-O layers transform in a stepwise fashion to akimotoite-like sheets, with sites in 4-, 5-, or 6-fold coordination, depending on the specific structure and layer. Due to the increased Si-O coordination number, we designate the new structures α- and β-post-orthopyroxene (α-popx and β-popx). α-popx has one Si-O layer that is entirely tetrahedral, and one layer that contains both tetrahedra and 5-coordinated Si in distorted square pyramids. β-popx retains the mixed 4- and 5-coordinated Si layer found in α-popx, while the other Si layer adopts fully octahedral coordination. The α- and β-popx structures show a progressive transformation towards the arrangement of Si layers found in akimotoite, a potentially important phase in the earth’s transition zone. Metastable transformations in pyroxenes are of interest for understanding possible metastability in geological environments such as subducting slabs and meteorite impacts« less

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.

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

Li, Xiao; Martínez-González, José A.; Hernández-Ortiz, Juan P.

Liquid crystal blue phases (BPs) are highly ordered at two levels. Molecules exhibit orientational order at nanometer length scales, while chirality leads to ordered arrays of doubletwisted cylinders over micrometer scales. Past studies of polycrystalline BPs were challenged by grain boundaries between randomly oriented crystalline nanodomains. Here, the nucleation of BPs is controlled with considerable precision by relying on chemically nano-patterned surfaces, leading to macroscopic single-crystal BP specimens where the dynamics of meso-crystal formation can be directly observed. Theory and experiments show that transitions between two BPs having a different network structure proceed through local re-organization of the crystalline array,more » without diffusion of the double twisted cylinders. In solid crystals, martensitic transformations between crystal structures involve the concerted motion of a few atoms, without diffusion. The transformation between BPs, where crystal features arise in the sub-micron regime, is found to be martensitic in nature, with the diffusion-less feature associated to the collective behavior of the double twist cylinders. Single-crystal BPs are shown to offer fertile grounds for the study of directed crystal-nucleation and the controlled growth of soft matter.« less

Limit of validity of Ostwald's rule of stages in a statistical mechanical model of crystallization.

PubMed

Hedges, Lester O; Whitelam, Stephen

2011-10-28

We have only rules of thumb with which to predict how a material will crystallize, chief among which is Ostwald's rule of stages. It states that the first phase to appear upon transformation of a parent phase is the one closest to it in free energy. Although sometimes upheld, the rule is without theoretical foundation and is not universally obeyed, highlighting the need for microscopic understanding of crystallization controls. Here we study in detail the crystallization pathways of a prototypical model of patchy particles. The range of crystallization pathways it exhibits is richer than can be predicted by Ostwald's rule, but a combination of simulation and analytic theory reveals clearly how these pathways are selected by microscopic parameters. Our results suggest strategies for controlling self-assembly pathways in simulation and experiment.

Martensitic Transformation in a β-Type Mg-Sc Alloy

NASA Astrophysics Data System (ADS)

Ogawa, Yukiko; Ando, Daisuke; Sutou, Yuji; Somekawa, Hidetoshi; Koike, Junichi

2018-03-01

Recently, we found that a Mg-Sc alloy with a bcc (β) phase exhibits superelasticity and a shape memory effect at low temperature. In this work, we examined the stress-induced and thermally induced martensitic transformation of the β-type Mg-Sc alloy and investigated the crystal structure of the thermally induced martensite phase based on in situ X-ray diffraction (XRD) measurements. The lattice constants of the martensite phase were calculated to be a = 0.3285 nm, b = 0.5544 nm, and c = 0.5223 nm when we assumed that the martensite phase has an orthorhombic structure (Cmcm). Based on the lattice correspondence between a bcc and an orthorhombic structures such as that in the case of β-Ti shape memory alloys, we estimated the transformation strain of the β Mg-Sc alloy. As a result, the transformation strains along the 001, 011, and 111 directions in the β phase were calculated to be + 5.7, + 8.8, and + 3.3%, respectively.

Chirality Switching by Martensitic Transformation in Protein Cylindrical Crystals: Application to Bacterial Flagella

NASA Astrophysics Data System (ADS)

Komai, Ricardo Kiyohiro

Martensitic transformations provide unique engineering properties that, when designed properly, become important parts of new technology. Martensitic transformations have been studied for many years in traditional alloys (iron, steel, titanium, etc.), however there is still much to be learned in regards to these transformations in biological materials. Olson and Hartman showed in 1982 that these transformations are also observed in bacterial flagella and T4 bacteriophage viral sheaths, allowing for propulsion of bacteria in a fluid environment and, for the virus, is responsible for the infection mechanism. This work demonstrates, using the bacterial flagella as an example, that these transformations can be modelled using thermodynamic methods that are also used to model the transformations in alloys. This thesis work attempts to explain the transformations that occur in bacterial flagella, which are capable of small strain, highly reversible martensitic transformations. The first stress/temperature phase diagrams of these flagella were created by adding the mechanical energy of the transformation of the flagella to limited chemical thermodynamics information of the transformation. Mechanical energy is critical to the transformation process because the bacterial body applies a torque to the radius of the flagella. Finally, work has begun and will be completed in regards to understanding the kinetics of the transformation of the flagella. The motion of the transformation interface can be predicted by using a Landau-Ginzburg model. The crystallography of the transformation in bacterial flagella is also being computed to determine the invariant lines of transformation that occur within this cylindrical crystal. This work has shown that it is possible to treat proteins in a similar manner that alloys are treated when using thermodynamic modelling. Much can be learned from translating what is known regarding phase transformations in hard material systems to soft, organic systems.

Ion-beam-induced magnetic transformation of CO-stabilized fcc Fe films on Cu(100)

NASA Astrophysics Data System (ADS)

Shah Zaman, Sameena; Oßmer, Hinnerk; Jonner, Jakub; Novotný, Zbyněk; Buchsbaum, Andreas; Schmid, Michael; Varga, Peter

2010-12-01

We have grown 22-ML-thick Fe films on a Cu(100) single crystal. The films were stabilized in the face-centered-cubic (fcc) γ phase by adsorption of carbon monoxide during growth, preventing the transformation to the body-centered-cubic (bcc) α phase. A structural transformation of these films from fcc to bcc can be induced by Ar+ ion irradiation. Scanning-tunneling microscopy images show the nucleation of bcc crystallites, which grow with increasing Ar+ ion dose and eventually result in complete transformation of the film to bcc. Surface magneto-optic Kerr effect measurements confirm the transformation of the Fe film from paramagnetic (fcc) to ferromagnetic (bcc) with an in-plane easy axis. The transformation can also be observed by low-energy electron diffraction. We find only very few nucleation sites of the bcc phase and argue that nucleation of the bcc phase happens under special circumstances during resolidification of the molten iron in the thermal spike after ion impact. Intermixing with the Cu substrate impedes the transformation. We also demonstrate the transformation of films coated with Au to protect them from oxidation at ambient conditions.

Phase transformation as the single-mode mechanical deformation of silicon

DOE PAGES

Wong, Sherman; Haberl, Bianca; Williams, James S.; ...

2015-06-25

The mixture of the metastable body-centered cubic (bc8) and rhombohedral (r8) phases of silicon that is formed via nanoindentation of diamond cubic (dc) silicon exhibits properties that are of scientifc and technological interest. This letter demonstrates that large regions of this mixed phase can be formed in crystalline Si via nanoindentation without signifcant damage to the surrounding crystal. Cross-sectional transmission electron microscopy is used to show that volumes 6 μm wide and up to 650 nm deep can be generated in this way using a spherical tip of ~21.5 μm diameter. The phase transformed region is characterised using both Ramanmore » microspectroscopy and transmission electron microscopy. It is found that uniform loading using large spherical indenters can favor phase transformation as the sole deformation mechanism as long as the maximum load is below a critical level. We suggest that the sluggish nature of the transformation from the dc-Si phase to the metallic (b-Sn) phase normally results in competing deformation mechanisms such as slip and cracking but these can be suppressed by controlled loading conditions.« less

Nanoclusters first: a hierarchical phase transformation in a novel Mg alloy

NASA Astrophysics Data System (ADS)

Okuda, Hiroshi; Yamasaki, Michiaki; Kawamura, Yoshihito; Tabuchi, Masao; Kimizuka, Hajime

2015-09-01

The Mg-Y-Zn ternary alloy system contains a series of novel structures known as long-period stacking ordered (LPSO) structures. The formation process and its key concept from a viewpoint of phase transition are not yet clear. The current study reveals that the phase transformation process is not a traditional spinodal decomposition or structural transformation but, rather a novel hierarchical phase transformation. In this transformation, clustering occurs first, and the spatial rearrangement of the clusters induce a secondary phase transformation that eventually lead to two-dimensional ordering of the clusters. The formation process was examined using in situ synchrotron radiation small-angle X-ray scattering (SAXS). Rapid quenching from liquid alloy into thin ribbons yielded strongly supersaturated amorphous samples. The samples were heated at a constant rate of 10 K/min. and the scattering patterns were acquired. The SAXS analysis indicated that small clusters grew to sizes of 0.2 nm after they crystallized. The clusters distributed randomly in space grew and eventually transformed into a microstructure with two well-defined cluster-cluster distances, one for the segregation periodicity of LPSO and the other for the in-plane ordering in segregated layer. This transformation into the LPSO structure concomitantly introduces the periodical stacking fault required for the 18R structures.

From Modeling of Plasticity in Single-Crystal Superalloys to High-Resolution X-rays Three-Crystal Diffractometer Peaks Simulation

NASA Astrophysics Data System (ADS)

Jacques, Alain

2016-12-01

The dislocation-based modeling of the high-temperature creep of two-phased single-crystal superalloys requires input data beyond strain vs time curves. This may be obtained by use of in situ experiments combining high-temperature creep tests with high-resolution synchrotron three-crystal diffractometry. Such tests give access to changes in phase volume fractions and to the average components of the stress tensor in each phase as well as the plastic strain of each phase. Further progress may be obtained by a new method making intensive use of the Fast Fourier Transform, and first modeling the behavior of a representative volume of material (stress fields, plastic strain, dislocation densities…), then simulating directly the corresponding diffraction peaks, taking into account the displacement field within the material, chemical variations, and beam coherence. Initial tests indicate that the simulated peak shapes are close to the experimental ones and are quite sensitive to the details of the microstructure and to dislocation densities at interfaces and within the soft γ phase.

Polymorphic phase transitions: Macroscopic theory and molecular simulation.

PubMed

Anwar, Jamshed; Zahn, Dirk

2017-08-01

Transformations in the solid state are of considerable interest, both for fundamental reasons and because they underpin important technological applications. The interest spans a wide spectrum of disciplines and application domains. For pharmaceuticals, a common issue is unexpected polymorphic transformation of the drug or excipient during processing or on storage, which can result in product failure. A more ambitious goal is that of exploiting the advantages of metastable polymorphs (e.g. higher solubility and dissolution rate) while ensuring their stability with respect to solid state transformation. To address these issues and to advance technology, there is an urgent need for significant insights that can only come from a detailed molecular level understanding of the involved processes. Whilst experimental approaches at best yield time- and space-averaged structural information, molecular simulation offers unprecedented, time-resolved molecular-level resolution of the processes taking place. This review aims to provide a comprehensive and critical account of state-of-the-art methods for modelling polymorph stability and transitions between solid phases. This is flanked by revisiting the associated macroscopic theoretical framework for phase transitions, including their classification, proposed molecular mechanisms, and kinetics. The simulation methods are presented in tutorial form, focusing on their application to phase transition phenomena. We describe molecular simulation studies for crystal structure prediction and polymorph screening, phase coexistence and phase diagrams, simulations of crystal-crystal transitions of various types (displacive/martensitic, reconstructive and diffusive), effects of defects, and phase stability and transitions at the nanoscale. Our selection of literature is intended to illustrate significant insights, concepts and understanding, as well as the current scope of using molecular simulations for understanding polymorphic transitions in an accessible way, rather than claiming completeness. With exciting prospects in both simulation methods development and enhancements in computer hardware, we are on the verge of accessing an unprecedented capability for designing and developing dosage forms and drug delivery systems in silico, including tackling challenges in polymorph control on a rational basis. Copyright © 2017 Elsevier B.V. All rights reserved.

Inhibition of the solid state transformation of carbamazepine in aqueous solution: impact of polymeric properties.

PubMed

Gift, Alan D; Hettenbaugh, Jacob A; Quandahl, Rachel A; Mapes, Madison

2017-11-06

The effects of polymers on the anhydrate-to-hydrate transformation of carbamazepine (CBZ) was investigated. The three types of polymers studied were polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA) and substituted celluloses which included hydroxypropyl methylcellulose (HPMC) and methylcellulose (MC). Anhydrous CBZ was added to dilute aqueous polymer solutions and Raman spectroscopy measurements were collected to monitor the kinetics of the solution-mediated transformation to CBZ dihydrate. Polymers exhibiting the greatest inhibition were able to reduce the growth phase of the solution-mediated transformation and change the habit of the hydrate crystal indicating polymer adsorption to the hydrate crystal surface as the mechanism of inhibition. The results of the various polymers showed that short chain substituted celluloses (HPMC and MC) inhibited the CBZ transformation to a much greater extent than longer chains. The same trend was observed for PVP and PVA, but to a lesser extent. These chain length effects were attributed to changes in polymer confirmation when adsorbed on the crystal surface. Additionally, decreasing the percentage of hydroxyl groups on the PVA polymer backbone reduced the ability of the polymer to inhibit the transformation and changing the degree of substitutions of methyl and hydroxypropyl groups on the cellulosic polymer backbone had no effect on the transformation.

Structural phase transition of gold under uniaxial, tensile, and triaxial stresses: An ab initio study

NASA Astrophysics Data System (ADS)

Durandurdu, Murat

2007-07-01

The behavior of gold crystal under uniaxial, tensile, and three different triaxial stresses is studied using an ab initio constant pressure technique within a generalized gradient approximation. Gold undergoes a phase transformation from the face-centered-cubic structure (fcc) to a body-centered-tetragonal (bct) structure having the space group of I4/mmm with the application of uniaxial stress, while it transforms to a face-centered-tetragonal (fct) phase within I4/mmm symmetry under uniaxial tensile loading. Further uniaxial compression of the bct phase results in a symmetry change from I4/mmm to P1 at high stresses and ultimately structural failure around 200.0GPa . For the case of triaxial stresses, gold also converts into a bct state. The critical stress for the fcc-to-bct transformation increases as the ratio of the triaxial stress increases. Both fct and bct phases are elastically unstable.

Observation of a re-entrant phase transition in the molecular complex tris(μ 2-3,5-diisopropyl-1,2,4-triazolato-κ 2 N 1: N 2)trigold(I) under high pressure

DOE PAGES

Woodall, Christopher H.; Christensen, Jeppe; Skelton, Jonathan M.; ...

2016-08-18

We report a molecular crystal that exhibits four successive phase transitions under hydro­static pressure, driven by aurophilic interactions, with the ground-state structure re-emerging at high pressure. The effect of pressure on two polytypes of tris(μ 2-3,5-diiso­propyl-1,2,4-triazolato-κ 2 N 1: N 2)trigold(I) (denoted Form-I and Form-II) has been analysed using luminescence spectroscopy, single-crystal X-ray diffraction and first-principles computation. A unique phase behaviour was observed in Form-I, with a complex sequence of phase transitions between 1 and 3.5 GPa. The ambient C2/c mother cell transforms to a P2 1/n phase above 1 GPa, followed by a P2 1/a phase above 2 GPamore » and a large-volume C2/c supercell at 2.70 GPa, with the previously observed P2 1/n phase then reappearing at higher pressure. The observation of crystallographically identical low- and high-pressure P2 1/n phases makes this a rare example of a re-entrant phase transformation. The phase behaviour has been characterized using detailed crystallographic theory and modelling, and rationalized in terms of molecular structural distortions. The dramatic changes in conformation are correlated with shifts of the luminescence maxima, from a band maximum at 14040 cm –1 at 2.40 GPa, decreasing steeply to 13550 cm –1 at 3 GPa. A similar study of Form-II displays more conventional crystallographic behaviour, indicating that the complex behaviour observed in Form-I is likely to be a direct consequence of the differences in crystal packing between the two polytypes.« less

Observation of a re-entrant phase transition in the molecular complex tris(μ 2-3,5-diisopropyl-1,2,4-triazolato-κ 2 N 1: N 2)trigold(I) under high pressure

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

Woodall, Christopher H.; Christensen, Jeppe; Skelton, Jonathan M.

We report a molecular crystal that exhibits four successive phase transitions under hydro­static pressure, driven by aurophilic interactions, with the ground-state structure re-emerging at high pressure. The effect of pressure on two polytypes of tris(μ 2-3,5-diiso­propyl-1,2,4-triazolato-κ 2 N 1: N 2)trigold(I) (denoted Form-I and Form-II) has been analysed using luminescence spectroscopy, single-crystal X-ray diffraction and first-principles computation. A unique phase behaviour was observed in Form-I, with a complex sequence of phase transitions between 1 and 3.5 GPa. The ambient C2/c mother cell transforms to a P2 1/n phase above 1 GPa, followed by a P2 1/a phase above 2 GPamore » and a large-volume C2/c supercell at 2.70 GPa, with the previously observed P2 1/n phase then reappearing at higher pressure. The observation of crystallographically identical low- and high-pressure P2 1/n phases makes this a rare example of a re-entrant phase transformation. The phase behaviour has been characterized using detailed crystallographic theory and modelling, and rationalized in terms of molecular structural distortions. The dramatic changes in conformation are correlated with shifts of the luminescence maxima, from a band maximum at 14040 cm –1 at 2.40 GPa, decreasing steeply to 13550 cm –1 at 3 GPa. A similar study of Form-II displays more conventional crystallographic behaviour, indicating that the complex behaviour observed in Form-I is likely to be a direct consequence of the differences in crystal packing between the two polytypes.« less

Polymorphism in phenobarbital: discovery of a new polymorph and crystal structure of elusive form V.

PubMed

Roy, Saikat; Goud, N Rajesh; Matzger, Adam J

2016-03-21

This report highlights the discovery of a new polymorph of the anticonvulsant drug phenobarbital (PB) using polymer-induced heteronucleation (PIHn) and unravelling the crystal structure of the elusive form V. Both forms are characterized by structural, thermal and VT-Raman spectroscopy methods to elucidate phase transformation behavior and shed light on stability relationships.

Study of a splat cooled Cu-Zr-noncrystalline phase.

NASA Technical Reports Server (NTRS)

Revcolevschi, A.; Grant, N. J.

1972-01-01

By rapid quenching from the melt, using the splat forming gun technique, a noncrystalline phase has been obtained in a Cu-Zr alloy containing 60 at. % Cu. Upon heating, rapid crystallization of the samples takes place at 477 C with a heat release of about 700 cal per mol. The variation of the electrical resistivity of the samples with temperature confirms the transformation. Very high resolution electron microscopy studies of the structural changes of the samples upon heating are presented and show the gradual crystallization of the amorphous structure.

Preparation of α-alumina nanoparticles with various shapes via hydrothermal phase transformation under supercritical water conditions

NASA Astrophysics Data System (ADS)

Hakuta, Y.; Nagai, N.; Suzuki, Y.-H.; Kodaira, T.; Bando, K. K.; Takashima, H.; Mizukami, F.

2013-12-01

Alumina (Al2O3) fine particles are widely used as industrial materials including fillers for metal or plastics, paints, polisher, cosmetics and electric substrates, due to its high hardness, chemical stability, and high thermal conductivity. The performance of those industrial products is closely related to the particle size or shape of the alumina particles used, and thus a new synthetic method to control size, shape, and crystal structure of the aluminum oxide is desired for the improvement of the performance. Hydrothermal phase transformation using various aluminum compounds such as oxide, hydroxide, and salt as a staring material, is known as one of the synthetic methods for producing alumina fine particles; however, the influence about the size and shape of the starting aluminum compounds has been little mentioned, although they strongly affect the size and shape of the final products. In this study, we investigated the influence of the shape, size and crystal structure of the starting aluminum compounds on those of the products, and newly succeeded in the production of rod-like α-Al2O3 nanoparticles from fibrous boehmite nanoparticles using hydrothermal phase transformation under supercritical water conditions.

Time and metamorphic petrology: Calcite to aragonite experiments

USGS Publications Warehouse

Hacker, B.R.; Kirby, S.H.; Bohlen, S.R.

1992-01-01

Although the equilibrium phase relations of many mineral systems are generally well established, the rates of transformations, particularly in polycrystalline rocks, are not. The results of experiments on the calcite to aragonite transformation in polycrystalline marble are different from those for earlier experiments on powdered and single-crystal calcite. The transformation in the polycrystalline samples occurs by different mechanisms, with a different temperature dependence, and at a markedly slower rate. This work demonstrates the importance of kinetic studies on fully dense polycrystalline aggregates for understanding mineralogic phase changes in nature. Extrapolation of these results to geological time scales suggests that transformation of calcite to aragonite does not occur in the absence of volatiles at temperatures below 200??C. Kinetic hindrance is likely to extend to higher temperatures in more complex transformations.

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).

The Effect of Acidity Coefficient on Crystallization Behavior of Blast Furnace Slag Fibers

NASA Astrophysics Data System (ADS)

Tian, Tie-Lei; Zhang, Yu-Zhu; Xing, Hong-wei; Li, Jie; Zhang, Zun-Qian

2018-01-01

The chemical structure of mineral wool fiber was investigated by using Fourier Transform Infrared Spectroscopy (FTIR). Next, the glass transition temperature and the crystallization temperature of the fibers were studied. Finally, the crystallization kinetics of fiber was studied. The results show that the chemical bond structure of fibers gets more random with the increase of acidity coefficient. The crystallization phases of the fibers are mainly melilites, and also a few anorthites and diopsides. The growth mechanism of the crystals is three dimensional. The fibers with acidity coefficient of 1.2 exhibit the best thermal stability and is hard to crystallize as it has the maximum aviation energy of crystallization kinetics.

Magneto-optical spectroscopy of ferromagnetic shape-memory Ni-Mn-Ga alloy

NASA Astrophysics Data System (ADS)

Veis, M.; Beran, L.; Zahradnik, M.; Antos, R.; Straka, L.; Kopecek, J.; Fekete, L.; Heczko, O.

2014-05-01

Magneto-optical properties of single crystal of Ni50.1Mn28.4Ga21.5 magnetic shape memory alloy in martensite and austenite phase were systematically studied. Crystal orientation was approximately along {100} planes of parent cubic austenite. At room temperature, the sample was in modulated 10M martensite phase and transformed to cubic austenite at 323 K. Spectral dependence of polar magneto-optical Kerr effect was obtained by generalized magneto-optical ellipsometry with rotating analyzer in the photon energy range from 1.2 to 4 eV, and from room temperature to temperature above the Curie point. The Kerr rotation spectra exhibit prominent features typical for complexes containing Mn atoms. Significant spectral changes during transformation to austenite can be explained by different optical properties caused by changes in density of states near the Fermi energy.

Zeroth-order phase-contrast technique.

PubMed

Pizolato, José Carlos; Cirino, Giuseppe Antonio; Gonçalves, Cristhiane; Neto, Luiz Gonçalves

2007-11-01

What we believe to be a new phase-contrast technique is proposed to recover intensity distributions from phase distributions modulated by spatial light modulators (SLMs) and binary diffractive optical elements (DOEs). The phase distribution is directly transformed into intensity distributions using a 4f optical correlator and an iris centered in the frequency plane as a spatial filter. No phase-changing plates or phase dielectric dots are used as a filter. This method allows the use of twisted nematic liquid-crystal televisions (LCTVs) operating in the real-time phase-mostly regime mode between 0 and p to generate high-intensity multiple beams for optical trap applications. It is also possible to use these LCTVs as input SLMs for optical correlators to obtain high-intensity Fourier transform distributions of input amplitude objects.

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.

In situ crystallization and transformation kinetics of polymorphic forms of saturated-unsaturated-unsaturated triacylglycerols: 1-palmitoyl-2,3-dioleoyl glycerol, 1-stearoyl-2,3-dioleoyl glycerol, and 1-palmitoyl-2-oleoyl-3-linoleoyl glycerol.

PubMed

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

2016-07-01

We examined the influence of dynamic thermal treatment (variation of cooling/heating rates) on the polymorphic crystallization and transformation pathways of 1-palmitoyl-2,3-dioleoyl glycerol (POO), 1-stearoyl-2,3-dioleoyl glycerol (SOO), and 1-palmitoyl-2-oleoyl-3-linoleoyl glycerol (POL), which are major saturated-unsaturated-unsaturated (SUU) triacylglycerols (TAGs) of vegetable oils and animal fats (e.g., palm oil, olive oil, and Iberian ham fat). Using mainly a combination of differential scanning calorimetry (DSC) and synchrotron radiation X-ray diffraction (SR-XRD), we analyzed the polymorphic behavior of TAGs when high (15°Cmin -1 ), intermediate (2°Cmin -1 ), and low (0.5°Cmin -1 ) cooling and heating rates were applied. Multiple polymorphic forms were detected in POO, SOO, and POL (sub-α, α, β' 2 , and β' 1 ). Transient disordered phases, defined as kinetic liquid crystal (KLC) phases, were determined in POO and SOO for the first time. The results demonstrated that more stable forms were directly obtained from the melt by decreasing the cooling rates, whereas less stable forms predominated at high cooling rates, as confirmed in our previous work. Regarding heating rate variation, we confirmed that the nature of the polymorphic transformations observed (solid-state, transformation through KLC phase, or melt-mediation) depended largely on the heating rate. These results were discussed considering the activation energies involved in each process and compared with previous studies on TAGs with different saturated-unsaturated structures (1,3-dioleoyl-2-palmitoylglycerol, 1,3-dipalmitoyl-2-oleoyl-glycerol, trioleoyl glycerol, and 1,2-dioleoyl-3-linoleoyl glycerol). Copyright © 2016 Elsevier Ltd. All rights reserved.

A Kinetic Study of the Effect of Basicity on the Mold Fluxes Crystallization

NASA Astrophysics Data System (ADS)

Zhou, Lejun; Wang, Wanlin; Ma, Fanjun; Li, Jin; Wei, Juan; Matsuura, Hiroyuki; Tsukihashi, Fumitaka

2012-04-01

The effect of basicity on the mold fluxes crystallization was investigated in this article. The time-temperature-transformation (TTT) diagrams and continuous-cooling-transformation (CCT) diagrams of mold fluxes with different basicity were constructed by using single, hot thermocouple technology (SHTT). The results showed that with the increase of basicity, the incubation time of isothermal crystallization became shorter, the crystallization temperature was getting higher, and the critical cooling rate of continuous cooling crystallization became faster. The X-ray diffraction analysis suggested that calcium silicate (CaO·SiO2) was precipitated at the upper part of the TTT diagram and cuspidine (Ca4Si2O7F2) was formed at the lower part, when the basicity of mold fluxes was within 1.0 to 1.2. However, when basicity was 0.8, only the cuspidine phase was formed. A kinetic study of isothermal crystallization process indicated that the increase of the basicity tended to enhance the mold flux crystallization, and the crystallization activation energy became smaller. The crystallization mechanism of cupsidine was changing from one-dimensional growth to three-dimensional growth with a constant number of nuclei, when the basicity of mold fluxes varied from 0.8 to 1.2.

Transformation Paths from Cubic to Low-Symmetry Structures in Heusler Ni2MnGa Compound.

PubMed

Zelený, Martin; Straka, Ladislav; Sozinov, Alexei; Heczko, Oleg

2018-05-08

In order to explain the formation of low-temperature phases in stoichiometric Ni 2 MnGa magnetic shape memory alloy, we investigate the phase transformation paths from cubic austenite with Heusler structure to low-symmetry martensitic structures. We used ab initio calculations combined with the generalized solid state nudged elastic band method to determine the minimum energy path and corresponding changes in crystal lattice. The four-, five-, and seven-layered modulated phases of martensite (4O, 10M, and 14M) are built as the relaxed nanotwinned non-modulated (NM) phase. Despite having a total energy larger than the other martensitic phases, the 10M phase will spontaneously form at 0 K, because there is no energy barrier on the path and the energy decreases with a large negative slope. Moreover, a similar negative slope in the beginning of path is found also for the transformation to the 6M premartensite, which appears as a local minimum on the path leading further to 10M martensite. Transformation paths to other structures exhibit more or less significant barriers in the beginning hindering such a transformation from austenite. These findings correspond to experiment and demonstrates that the kinetics of the transformation is decisive for the selection of the particular low-symmetry structure.

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.

Structural Transformation in Fe73.5Nb3Cu1Si15.5B7 Amorphous Alloy Induced by Laser Heating

NASA Astrophysics Data System (ADS)

Nykyruy, Yu. S.; Mudry, S. I.; Kulyk, Yu. O.; Zhovneruk, S. V.

2018-03-01

The effect of continuous laser irradiation (λ = 1.06 μm) with laser power of 45 W on the structure of Fe73.5Nb3Cu1Si15.5B7 amorphous alloy has been studied using X-ray diffraction and SEM methods. The sample of the ribbon has been placed at a distance from the focal plane of the lens, so a laser beam has been defocused and the diameter of laser spot on the ribbon surface has been about 10 mm. An exposure time τ varied within interval 0.25-0.70 s. Under such conditions structural transformation processes, which depend on the exposure time, have occurred in an irradiated zone. Crystallization process has started at τ = 0.35 s with the formation of α-Fe(Si) nanocrystalline phase, while complete crystallization has occurred at τ = 0.55 s with formation of two nanocrystalline phases: α-Fe(Si) and a hexagonal H-phase.

High Pressure Phase Transformations in Heavy Rare Earth Metals and Connections to Actinide Crystal Structures

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

Vohra, Yogesh K.; Sangala, Bagvanth Reddy; Stemshorn, Andrew K.

2008-07-01

High-pressure studies have been performed on heavy rare earth metals Terbium (Tb) to 155 GPa and Holmium (Ho) to 134 GPa in a diamond anvil cell at room temperature. The following crystal structure sequence was observed in both metals hcp {yields} Sm-type {yields} dhcp {yields} distorted fcc (hR-24) {yields} monoclinic (C2/m) with increasing pressure. The last transformation to a low symmetry monoclinic phase is accompanied by a volume collapse of 5 % for Tb at 51 GPa and a volume collapse of 3 % for Ho at 103 GPa. This volume collapse under high pressure is reminiscent of f-shell delocalizationmore » in light rare earth metal Cerium (Ce), Praseodymium (Pr), and heavy actinide metals Americium (Am) and Curium (Cm). The orthorhombic Pnma phase that has been reported in Am and Cm after f-shell delocalization is not observed in heavy rare earth metals under high pressures. (authors)« less

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.

Fast Atomic-Scale Chemical Imaging of Crystalline Materials and Dynamic Phase Transformations.

PubMed

Lu, Ping; Yuan, Ren Liang; Ihlefeld, Jon F; Spoerke, Erik David; Pan, Wei; Zuo, Jian Min

2016-04-13

Atomic-scale phenomena fundamentally influence materials form and function that makes the ability to locally probe and study these processes critical to advancing our understanding and development of materials. Atomic-scale chemical imaging by scanning transmission electron microscopy (STEM) using energy-dispersive X-ray spectroscopy (EDS) is a powerful approach to investigate solid crystal structures. Inefficient X-ray emission and collection, however, require long acquisition times (typically hundreds of seconds), making the technique incompatible with electron-beam sensitive materials and study of dynamic material phenomena. Here we describe an atomic-scale STEM-EDS chemical imaging technique that decreases the acquisition time to as little as one second, a reduction of more than 100 times. We demonstrate this new approach using LaAlO3 single crystal and study dynamic phase transformation in beam-sensitive Li[Li0.2Ni0.2Mn0.6]O2 (LNMO) lithium ion battery cathode material. By capturing a series of time-lapsed chemical maps, we show for the first time clear atomic-scale evidence of preferred Ni-mobility in LNMO transformation, revealing new kinetic mechanisms. These examples highlight the potential of this approach toward temporal, atomic-scale mapping of crystal structure and chemistry for investigating dynamic material phenomena.

Enhancing Entropy and Enthalpy Fluctuations to Drive Crystallization in Atomistic Simulations.

PubMed

Piaggi, Pablo M; Valsson, Omar; Parrinello, Michele

2017-07-07

Crystallization is a process of great practical relevance in which rare but crucial fluctuations lead to the formation of a solid phase starting from the liquid. As in all first order first transitions, there is an interplay between enthalpy and entropy. Based on this idea, in order to drive crystallization in molecular simulations, we introduce two collective variables, one enthalpic and the other entropic. Defined in this way, these collective variables do not prejudge the structure into which the system is going to crystallize. We show the usefulness of this approach by studying the cases of sodium and aluminum that crystallize in the bcc and fcc crystalline structures, respectively. Using these two generic collective variables, we perform variationally enhanced sampling and well tempered metadynamics simulations and find that the systems transform spontaneously and reversibly between the liquid and the solid phases.

Measurement of Body-Centered-Cubic Aluminum at 475 GPa [Observation of Body-Centered-Cubic Aluminum at 475 GPa

DOE PAGES

Polsin, D. N.; Fratanduono, D. E.; Rygg, J. R.; ...

2017-10-27

Nanosecond in situ x-ray diffraction and simultaneous velocimetry measurements were used to determine the crystal structure and pressure, respectively, of ramp compressed aluminum at stress states between 111 and 475 GPa. The solid-solid Al phase transformations, fcc-hcp and hcp-bcc, are observed at 216 ± 9 GPa and 321 ± 12 GPa, respectively, with the bcc phase persisting to 475 GPa. Here, this is the first in situ observation of the high-pressure bcc phase of Al. High-pressure texture of the hcp and bcc phases suggests close-packed or nearly close-packed lattice planes remain parallel through both transformations.

Measurement of Body-Centered-Cubic Aluminum at 475 GPa [Observation of Body-Centered-Cubic Aluminum at 475 GPa

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

Polsin, D. N.; Fratanduono, D. E.; Rygg, J. R.

Nanosecond in situ x-ray diffraction and simultaneous velocimetry measurements were used to determine the crystal structure and pressure, respectively, of ramp compressed aluminum at stress states between 111 and 475 GPa. The solid-solid Al phase transformations, fcc-hcp and hcp-bcc, are observed at 216 ± 9 GPa and 321 ± 12 GPa, respectively, with the bcc phase persisting to 475 GPa. Here, this is the first in situ observation of the high-pressure bcc phase of Al. High-pressure texture of the hcp and bcc phases suggests close-packed or nearly close-packed lattice planes remain parallel through both transformations.

Identification and characterization of the intermediate phase in hybrid organic-inorganic MAPbI3 perovskite.

PubMed

Guo, Xin; McCleese, Christopher; Kolodziej, Charles; Samia, Anna C S; Zhao, Yixin; Burda, Clemens

2016-03-07

Perovskite films were prepared using single step solution deposition at different annealing temperatures and annealing times. The crystal structure, phases and grain size were investigated with XRD, XPS and SEM/EDX. The prepared films show a typical orientation of tetragonal perovskite phase and a gradual transition at room temperature from the yellow intermediate phase to the black perovskite phase. Films with high purity were obtained by sintering at 100 °C. In addition, the chemical composition and crystal structure of intermediate phase were investigated in detail. FTIR, UV-vis and NMR spectra revealed the occurance of DMF complexes. Interestingly, the intermediate phase could be transformed to the black perovskite phase upon X-ray irradiation. In addition, the recovery of the aged perovskite films from a yellow intermediate phase back to the black perovskite was shown to be viable via heating and X-ray irradiation.

Growth and characterization of metal halide perovskite crystals: Benzyltributyl ammonium tetrachloro manganate(II) monohydrate

NASA Astrophysics Data System (ADS)

Dhandapani, M.; Sugandhi, K.; Nithya, S.; Muthuraja, P.; Balachandar, S.; Aranganayagam, K. R.

2018-05-01

The perovskite type organic-inorganic hybrid benzyltributyl ammoniumtetrachloro manganate (II) monohydrates (BTBA-Mn) are synthesized and the single crystals are grown by slow evaporation solution growth technique. The structure of the grown crystals are confirmed by using X-ray diffraction (XRD), unit cell parameter analysis, Fourier transform Infrared (FTIR), elemental analysis and 13C-NMR spectral studies. Thermogravimetry (TG), differential thermal analysis (DTA) and differential scanning colorimetric (DSC) analysis were carried out to understand thermal stability and occurrence of phase transition.

Multiple pathways in pressure-induced phase transition of coesite

PubMed Central

Liu, Wei; Wu, Xuebang; Liu, Changsong; Miranda, Caetano R.; Scandolo, Sandro

2017-01-01

High-pressure single-crystal X-ray diffraction method with precise control of hydrostatic conditions, typically with helium or neon as the pressure-transmitting medium, has significantly changed our view on what happens with low-density silica phases under pressure. Coesite is a prototype material for pressure-induced amorphization. However, it was found to transform into a high-pressure octahedral (HPO) phase, or coesite-II and coesite-III. Given that the pressure is believed to be hydrostatic in two recent experiments, the different transformation pathways are striking. Based on molecular dynamic simulations with an ab initio parameterized potential, we reproduced all of the above experiments in three transformation pathways, including the one leading to an HPO phase. This octahedral phase has an oxygen hcp sublattice featuring 2 × 2 zigzag octahedral edge-sharing chains, however with some broken points (i.e., point defects). It transforms into α-PbO2 phase when it is relaxed under further compression. We show that the HPO phase forms through a continuous rearrangement of the oxygen sublattice toward hcp arrangement. The high-pressure amorphous phases can be described by an fcc and hcp sublattice mixture. PMID:29162690

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

Femtosecond laser pulse induced phase transition of Cr-doped Sb2Te1 films studied with a pump-probe system

NASA Astrophysics Data System (ADS)

Jiang, Minghui; Wang, Qing; Lei, Kai; Wang, Yang; Liu, Bo; Song, Zhitang

2016-10-01

The Femtosecond laser pulse induced phase transition dynamics of Cr-doped Sb2Te1 films was studied by real-time reflectivity measurements with a pump-probe system. It was found that crystallization of the as-deposited CrxSb2Te1 phase-change thin films exhibits a multi-stage process lasting for about 40ns.The time required for the multi-stage process seems to be not related to the contents of Cr element. The durations of the crystallization and amorphization processes are approximately the same. Doping Cr into Sb2Te1 thin film can improve its photo-thermal stability without obvious change in the crystallization rate. Optical images and image intensity cross sections are used to visualize the transformed regions. This work may provide further insight into the phase-change mechanism of CrxSb2Te1 under extra-non-equilibrium conditions and aid to develop new ultrafast phase-change memory materials.

Ultrafast diffraction conoscopy of the structural phase transition in VO2: Evidence of two lattice distortions

NASA Astrophysics Data System (ADS)

Kumar, Nardeep; Rúa, Armando; Fernández, Félix E.; Lysenko, Sergiy

2017-06-01

Photoinduced phase transitions in complex correlated systems occur very rapidly and involve the interplay between various electronic and lattice degrees of freedom. For these materials to be considered for practical applications, it is important to discover how their phase transitions take place. Here we use a novel ultrafast diffraction conoscopy technique to study the evolution of vanadium dioxide (VO2) from biaxial to uniaxial symmetry. A key finding in this study is an additional relaxation process through which the phase transition takes place. Our results show that the biaxial monoclinic crystal initially, within the first 100-300 fs, transforms to a transient biaxial crystal, and within the next 300-400 fs converts into a uniaxial rutile crystal. The characteristic times for these transitions depend on film morphology and are presumably altered by misfit strain. We take advantage of Landau phenomenology to describe the complex dynamics of VO2 phase transition in the femtosecond regime.

Calculations of single crystal elastic constants for yttria partially stabilised zirconia from powder diffraction data

NASA Astrophysics Data System (ADS)

Lunt, A. J. G.; Xie, M. Y.; Baimpas, N.; Zhang, S. Y.; Kabra, S.; Kelleher, J.; Neo, T. K.; Korsunsky, A. M.

2014-08-01

Yttria Stabilised Zirconia (YSZ) is a tough, phase-transforming ceramic that finds use in a wide range of commercial applications from dental prostheses to thermal barrier coatings. Micromechanical modelling of phase transformation can deliver reliable predictions in terms of the influence of temperature and stress. However, models must rely on the accurate knowledge of single crystal elastic stiffness constants. Some techniques for elastic stiffness determination are well-established. The most popular of these involve exploiting frequency shifts and phase velocities of acoustic waves. However, the application of these techniques to YSZ can be problematic due to the micro-twinning observed in larger crystals. Here, we propose an alternative approach based on selective elastic strain sampling (e.g., by diffraction) of grain ensembles sharing certain orientation, and the prediction of the same quantities by polycrystalline modelling, for example, the Reuss or Voigt average. The inverse problem arises consisting of adjusting the single crystal stiffness matrix to match the polycrystal predictions to observations. In the present model-matching study, we sought to determine the single crystal stiffness matrix of tetragonal YSZ using the results of time-of-flight neutron diffraction obtained from an in situ compression experiment and Finite Element modelling of the deformation of polycrystalline tetragonal YSZ. The best match between the model predictions and observations was obtained for the optimized stiffness values of C11 = 451, C33 = 302, C44 = 39, C66 = 82, C12 = 240, and C13 = 50 (units: GPa). Considering the significant amount of scatter in the published literature data, our result appears reasonably consistent.

Crystal structure stability and electronic properties of the layered nickelate La4Ni3O10

NASA Astrophysics Data System (ADS)

Puggioni, Danilo; Rondinelli, James M.

2018-03-01

We investigate the crystal structure and the electronic properties of the trilayer nickelate La4Ni3O10 by means of quantum-mechanical calculations in the framework of the density-functional theory. We find that, at low temperature, La4Ni3O10 undergoes a hitherto unreported structural phase transition and transforms to a new monoclinic P 21/a phase. This phase exhibits electronic properties in agreement with recent angle-resolved photoemission spectroscopy data reported in H. Li et al., [Nat. Commun. 8, 704 (2017), 10.1038/s41467-017-00777-0] and should be considered in models focused on explaining the observed ˜140 K metal-to-metal phase transition.

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.

Crystallization Kinetics in Fluorochloroziroconate Glass-Ceramics

NASA Astrophysics Data System (ADS)

Alvarez, Carlos J.

Annealing fluorochlorozirconate (FCZ) glasses nucleates BaCl2 nanocrystals in the glass matrix, resulting in a nanocomposite glass-ceramic that has optical properties suitable for use as a medical X-ray imaging plate. Understanding the way in which the BaCl¬2 nanocrystal nucleation, growth and phase transformation processes proceed is critical to controlling the optical behavior. However, there is a very limited amount of information about the formation, morphology, and distribution of the nanocrystalline particles in FCZ glass-ceramics. In this thesis, the correlation between the microstructure and the crystallization kinetics of FCZ glass-ceramics, are studied in detail. In situ X-ray diffraction and transmission electron microscopy annealing experiments are used to analyze the crystal structure, size and distribution of BaCl 2 nanocrystals in FCZ glass-ceramics as a function of annealing rate and temperature. Microstructural analysis of the early stages on nucleation identified the formation of both BaCl2 and BaF2 nanocrystals. Annealing FCZ glass-ceramics above 280°C can cause the formation of additional glass matrix phase crystals, their microstructure and the annealing parameters required for their growth are identified. As the crystalline phases grow directly from the glass, small variations in processing of the glass can have a profound influence on the crystallization process. The information obtained from these experiments improves the understanding of the nucleation, growth and phase transformation process of the BaCl¬2 nanocrystals and additional crystalline phases that form in FCZ glass-ceramics, and may help expedite the implementation of FCZ glass-ceramics as next-generation X-ray detectors. Lastly, as these glass-ceramics may one day be commercialized, an investigation into their degradation in different environmental conditions was also performed. The effects of direct contact with water or prolonged exposure to humid environments on the microstructure and the optical properties for FCZ glasses and glass-ceramics was explored.

Anion Exchange in II-VI Semiconducting Nanostructures via Atomic Templating.

PubMed

Agarwal, Rahul; Krook, Nadia M; Ren, Ming-Liang; Tan, Liang Z; Liu, Wenjing; Rappe, Andrew M; Agarwal, Ritesh

2018-03-14

Controlled chemical transformation of nanostructures is a promising technique to obtain precisely designed novel materials, which are difficult to synthesize otherwise. We report high-temperature vapor-phase anion-exchange reactions to chemically transform II-VI semiconductor nanostructures (100-300 nm length scale) while retaining the single crystallinity, crystal structure, morphology, and even defect distribution of the parent material via atomic templating. The concept of atomic templating is employed to obtain kinetically controlled, thermodynamically metastable structural phases such as zincblende CdSe and CdS from zincblende CdTe upon complete chemical replacement of Te with Se or S. The underlying transformation mechanisms are explained through first-principles density functional theory calculations. Atomic templating is a unique path to independently tune materials' phase and composition at the nanoscale, allowing the synthesis of novel materials.

Complete stress-induced depolarization of relaxor ferroelectric crystals without transition through a non-polar phase

NASA Astrophysics Data System (ADS)

Shkuratov, Sergey I.; Baird, Jason; Antipov, Vladimir G.; Hackenberger, Wesley; Luo, Jun; Zhang, Shujun; Lynch, Christopher S.; Chase, Jay B.; Jo, Hwan R.; Roberts, Christopher C.

2018-03-01

The development of relaxor ferroelectric single crystal technology is driven by the ability to tailor ferroelectric properties through domain engineering not achievable in polycrystalline materials. In this study, three types of domain-engineered rhombohedral Pb(In1/2Nb1/2)O3-Pb(Mg1/3Nb2/3)O3-PbTiO3 crystals were subjected to transverse high strain rate loading. The experimental results indicate that the domain configuration has a significant effect on the stress-induced depolarization and the associated charge released. A complete depolarization of the single-domain crystals with 3m symmetry is observed, while multidomain crystals with 4mm and mm2 symmetries retain a fraction of their initial remanent polarization. The complete depolarization of single-domain crystals is unique without transition to a non-polar phase, with a stress-induced charge density of 0.48 C/m2. This is up to three times higher than that of the multidomain crystals and PbZrxTi1-xO3 ferroelectric ceramics that are critical for ultrahigh-power transducer applications. The main offering of this work is to propose a detailed mechanism for complete stress-induced depolarization in ferroelectric crystals which does not involve an intermediate transformation to a non-polar phase.

Optical simulation of quantum algorithms using programmable liquid-crystal displays

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

Puentes, Graciana; La Mela, Cecilia; Ledesma, Silvia

2004-04-01

We present a scheme to perform an all optical simulation of quantum algorithms and maps. The main components are lenses to efficiently implement the Fourier transform and programmable liquid-crystal displays to introduce space dependent phase changes on a classical optical beam. We show how to simulate Deutsch-Jozsa and Grover's quantum algorithms using essentially the same optical array programmed in two different ways.

2D-1D structural phase transformation of Co(II) 3,5-pyridinedicarboxylate frameworks with chromotropism.

PubMed

Cheansirisomboon, Achareeya; Pakawatchai, Chaveng; Youngme, Sujittra

2012-09-21

Two new metal-organic frameworks [Co(pydc)(H(2)O)(2)](n) (1) and [Co(pydc)(H(2)O)(4)](n)(H(2)O)(n) (2), (pydc = 3,5-pyridinedicarboxylate) have been synthesized by a diffusion method and characterized by single-crystal X-ray diffraction. The structure of 1 reveals an infinite 2D layer with honeycomb-like cavities in which each pydc ligand bridges three Co(II) ions. The adjacent 2D layers are orderly packed in an ABAB-type array via intermolecular interactions of the combined π-π stacking and hydrogen bonds to form a 3D supramolecular architecture. Interestingly, compound 1 exhibits a water induced crystal-to-amorphous transformation with chromotropism confirmed by spectroscopic techniques, elemental analysis, TGA and XRPD. When this amorphous phase (1A) was exposed to water vapor, it was readily converted into the second crystalline phase 1B with a color change. Moreover, a reversible process between 1A and 1B was performed. In the case of compound 2, pydc acts as didentate bridging ligand connecting two Co(II) ions, leading to a 1D zig-zag chain. Guest water molecules fill the gaps in between chains and form hydrogen bonds with the host chains stabilizing the 3D network of 2. Additionally, compound 2 also exhibits a water induced crystal-to-amorphous transformation with chromotropism and the reversible process was also performed between the dehydrated (2A) and rehydrated (2') forms. Surprisingly, the IR and UV-vis spectra, elemental analysis, TGA curve and XRPD pattern of the rehydrated second phase 1B are found to be identical to that of 2 and 2', these results confirm that 2, 2' and 1B are the same compound.

Nanosecond electrical and optical pulses and self phase conjugation from photorefractive lithium niobate fibers and crystals

NASA Astrophysics Data System (ADS)

Kukhtarev, N.; Kukhtareva, T.; Curley, M.; Jaenisch, H. M.; Edwards, M. E.; Gu, M.; Zhou, Z.; Guo, R.

2007-09-01

We have observed nanosecond electrical and optical pulsations from photorefractive lithium-niobate optical fibers using CW green and blue low-power lasers. Fourier spectra of the pulsations have a maximum at ~900 MHz with peaks separated by ~30MHz. We consider free-space and fiber supported illumination of the fiber crystal. Strong nonlinear enhanced backscattering with phase conjugation was observed from bulk crystals and crystal fibers along the C-axis. Model of transformation of CW laser irradiation of ferroelectric crystals into periodic nanosecond electrical and optical pulsations is suggested. This model includes combinations of photorefractive, pyroelectric, piezoelectric, and photogalvanic mechanisms of the holographic grating formation and crystal electrical charging. Possible applications of these short photo-induced electrical pulses for modulation of holographic beam coupling, pulsed electrolysis, electrophoresis, focused electron beams, X-ray and neutron generation, and hand-held micro X-ray devices for localized oncology imaging and treatment based on our advanced sensor work are discussed.

Indium hydroxide to oxide decomposition observed in one nanocrystal during in situ transmission electron microscopy studies

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

Miehe, Gerhard; Lauterbach, Stefan; Kleebe, Hans-Joachim

The high-resolution transmission electron microscopy (HR-TEM) is used to study, in situ, spatially resolved decomposition in individual nanocrystals of metal hydroxides and oxyhydroxides. This case study reports on the decomposition of indium hydroxide (c-In(OH){sub 3}) to bixbyite-type indium oxide (c-In{sub 2}O{sub 3}). The electron beam is focused onto a single cube-shaped In(OH){sub 3} crystal of {l_brace}100{r_brace} morphology with ca. 35 nm edge length and a sequence of HR-TEM images was recorded during electron beam irradiation. The frame-by-frame analysis of video sequences allows for the in situ, time-resolved observation of the shape and orientation of the transformed crystals, which in turnmore » enables the evaluation of the kinetics of c-In{sub 2}O{sub 3} crystallization. Supplementary material (video of the transformation) related to this article can be found online at (10.1016/j.jssc.2012.09.022). After irradiation the shape of the parent cube-shaped crystal is preserved, however, its linear dimension (edge) is reduced by the factor 1.20. The corresponding spotted selected area electron diffraction (SAED) pattern representing zone [001] of c-In(OH){sub 3} is transformed to a diffuse strongly textured ring-like pattern of c-In{sub 2}O{sub 3} that indicates the transformed cube is no longer a single crystal but is disintegrated into individual c-In{sub 2}O{sub 3} domains with the size of about 5-10 nm. The induction time of approximately 15 s is estimated from the time-resolved Fourier transforms. The volume fraction of the transformed phase (c-In{sub 2}O{sub 3}), calculated from the shrinkage of the parent c-In(OH){sub 3} crystal in the recorded HR-TEM images, is used as a measure of the kinetics of c-In{sub 2}O{sub 3} crystallization within the framework of Avrami-Erofeev formalism. The Avrami exponent of {approx}3 is characteristic for a reaction mechanism with fast nucleation at the beginning of the reaction and subsequent three-dimensional growth of nuclei with a constant growth rate. The structural transformation path in reconstructive decomposition of c-In(OH){sub 3} to c-In{sub 2}O{sub 3} is discussed in terms of (i) the displacement of hydrogen atoms that lead to breaking the hydrogen bond between OH groups of [In(OH){sub 6}] octahedra and finally to their destabilization and (ii) transformation of the vertices-shared indium-oxygen octahedra in c-In(OH){sub 3} to vertices- and edge-shared octahedra in c-In{sub 2}O{sub 3}. - Graphical abstract: Frame-by-frame analysis of video sequences recorded of HR-TEM images reveals that a single cube-shaped In(OH){sub 3} nanocrystal with {l_brace}100{r_brace} morphology decomposes into bixbyite-type In{sub 2}O{sub 3} domains while being imaged. The mechanism of this decomposition is evaluated through the analysis of the structural relationship between initial (c-In(OH){sub 3}) and transformed (c-In{sub 2}O{sub 3}) phases and though the kinetics of the decomposition followed via the time-resolved shrinkage of the initial crystal of indium hydroxide. Highlights: Black-Right-Pointing-Pointer In-situ time-resolved High Resolution Transmission Electron Microscopy. Black-Right-Pointing-Pointer Crystallographic transformation path. Black-Right-Pointing-Pointer Kinetics of the decomposition in one nanocrystal.« less

Crystallization of heavy metal fluoride glasses

NASA Technical Reports Server (NTRS)

Bansal, Narottam P.; Bruce, Allan J.; Doremus, R. H.; Moynihan, C. T.

1984-01-01

The kinetics of crystallization of a number of fluorozirconate glasses were studied using isothermal and dynamic differential scanning calorimetry and X-ray diffraction. The addition of the fluorides LiF, NaF, AlF3, LaF3 to a base glass composition of ZrF4-BaF2 reduced the tendency to crystallize, probably by modifying the viscosity-temperature relation. ZrF4-BaF2-LaF3-AlF3-NaF glass was the most stable against devitrification and perhaps is the best composition for optical fibers with low scattering loss. Some glasses first crystallize out into metastable beta-BaZr2F10 and beta-BaZrF6 phases, which transform into the most stable alpha-phases when heated to higher temperatures. The size of the crystallites was estimated to be about 600 A from X-ray diffraction.

Investigating Li 2NiO 2–Li 2CuO 2 Solid Solutions as High-Capacity Cathode Materials for Li-Ion Batteries

DOE PAGES

Xu, Jing; Renfrew, Sara; Marcus, Matthew A.; ...

2017-05-11

Li 2Ni 1–xCu xO 2 solid solutions were prepared by a solid-state method to study the correlation between composition and electrochemical performance. Cu incorporation improved the phase purity of Li 2Ni 1–xCu xO 2 with orthorhombic Immm structure, resulting in enhanced capacity. However, the electrochemical profiles suggested Cu incorporation did not prevent irreversible phase transformation during the electrochemical process, instead, it likely influenced the phase transformation upon lithium removal. By combining ex situ X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), and differential electrochemical mass spectrometry (DEMS) measurements, this study elucidates the relevant phase transformation (e.g., crystal structure, local environment, andmore » charge compensation) and participation of electrons from lattice oxygen during the first cycle in these complex oxides.« less

Structural analysis and martensitic transformation in equiatomic HfPd alloy

NASA Astrophysics Data System (ADS)

Hisada, S.; Matsuda, M.; Takashima, K.; Yamabe-Mitarai, Y.

2018-02-01

We investigated the crystal structure and the martensitic transformation in equiatomic HfPd alloy. The analysis of the crystal structure by electron diffraction and Rietveld refinement using X-ray diffraction data indicates that the space group of the martensitic phase is Cmcm, and the lattice parameters are a = 0.329 nm, b = 1.021 nm, and c = 0.438 nm. Martensitic variants are composed of the plate-like morphology of several hundred nm, and the boundaries between the variants have (021)Cmcm twin relations. This (021)Cmcm twin boundary seems to be sharp without ledge and steps. Differential scanning calorimetry measurement indicates that each martensitic transformation temperature is determined to be Ms = 819 K, Mf = 794 K, As = 928 K, and Af = 954 K. Based on the dimension change using a thermo-mechanical analyzer, the expansion and shrinkage of the sample occurred with the forward and reverse martensitic transformation, respectively.

Study of a structural phase transition by two dimensional Fourier transform NMR method

NASA Astrophysics Data System (ADS)

Trokiner, A.; Man, P. P.; Théveneau, H.; Papon, P.

1985-09-01

The fluoroperovskite RbCaF 3 undergoes a structural phase transition at 195.5 K, from a cubic phase where the 87Rb nuclei have no quadrupolar interaction ( ωQ= 0) to a tetragonal phase where ω Q ≠ O. The transition is weakly first-order. A two-dimensional FT NMR experiment has been performed on 87Rb ( I = {3}/{2}) in a single crystal in both phases and in the vicinity of the phase transition. Our results show the coexistence of the two phases at the phase transition.

In-situ neutron diffraction and crystal plasticity finite element modeling to study the kinematic stability of retained austenite in bearing steels

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

Voothaluru, Rohit; Bedekar, Vikram; Xie, Qingge

This work integrates in-situ neutron diffraction and crystal plasticity finite element modeling to study the kinematic stability of retained austenite in high carbon bearing steels. The presence of a kinematically metastable retained austenite in bearing steels can significantly affect the macro-mechanical and micro-mechanical material response. Mechanical characterization of metastable austenite is a critical component in accurately capturing the micro-mechanical behavior under typical application loads. Traditional mechanical characterization techniques are unable to discretely quantify the micro-mechanical response of the austenite, and as a result, the computational predictions rely heavily on trial and error or qualitative descriptions of the austenite phase. Inmore » order to overcome this, in the present work, we use in-situ neutron diffraction of a uniaxial tension test of an A485 Grade 1 bearing steel specimen. The mechanical response determined from the neutron diffraction analysis was incorporated into a hybrid crystal plasticity finite element model that accounts for the martensite's crystal plasticity and the stress-assisted transformation from austenite to martensite in bearing steels. Here, the modeling response was used to estimate the single crystal elastic constants of the austenite and martensite phases. Finally, the results show that using in-situ neutron diffraction, coupled with a crystal plasticity model, can successfully predict both the micro-mechanical and macro-mechanical responses of bearing steels while accounting for the martensitic transformation of the retained austenite.« less

In-situ neutron diffraction and crystal plasticity finite element modeling to study the kinematic stability of retained austenite in bearing steels

DOE PAGES

Voothaluru, Rohit; Bedekar, Vikram; Xie, Qingge; ...

2018-11-21

This work integrates in-situ neutron diffraction and crystal plasticity finite element modeling to study the kinematic stability of retained austenite in high carbon bearing steels. The presence of a kinematically metastable retained austenite in bearing steels can significantly affect the macro-mechanical and micro-mechanical material response. Mechanical characterization of metastable austenite is a critical component in accurately capturing the micro-mechanical behavior under typical application loads. Traditional mechanical characterization techniques are unable to discretely quantify the micro-mechanical response of the austenite, and as a result, the computational predictions rely heavily on trial and error or qualitative descriptions of the austenite phase. Inmore » order to overcome this, in the present work, we use in-situ neutron diffraction of a uniaxial tension test of an A485 Grade 1 bearing steel specimen. The mechanical response determined from the neutron diffraction analysis was incorporated into a hybrid crystal plasticity finite element model that accounts for the martensite's crystal plasticity and the stress-assisted transformation from austenite to martensite in bearing steels. Here, the modeling response was used to estimate the single crystal elastic constants of the austenite and martensite phases. Finally, the results show that using in-situ neutron diffraction, coupled with a crystal plasticity model, can successfully predict both the micro-mechanical and macro-mechanical responses of bearing steels while accounting for the martensitic transformation of the retained austenite.« less

Method for making glass-ceramic articles exhibiting high frangibility

DOEpatents

Beall, George H.; Brydges, III., William T.; Ference, Joseph; Kozlowski, Theodore R.

1976-02-03

This invention is concerned with glass-ceramic articles having compositions within a very narrowly-delimited area of the MgO-Al.sub.2 O.sub.3 -B.sub.2 O.sub.3 -SiO.sub.2 field and having alpha-quartz and sapphirine as the principal crystal phases, resulting from nucleation through a combination of TiO.sub.2 and ZrO.sub.2. Upon contacting such articles with lithium ions at an elevated temperature, said lithium ions will replace magnesium ions on a two Li.sup.+-for-one Mg.sup..sup.+2 basis within the crystal structures, thereby providing a unitary glass-ceramic article having an integral surface layer wherein the principal crystal phase is a lithium-stuffed beta-quartz solid solution. That transformation of crystal phases results in compressive stresses being set up within the surface layer as the articles are cooled. Through the careful control of composition, crystallization treatment, and the parameters of the replacement reaction in the crystal structures, a tremendous degree of stored elastic energy can be developed within the articles such that they will demonstrate frangibility when fractured but will not exhibit undesirable spontaneous breakage and/or spalling.

Magnesium-aspartate-based crystallization switch inspired from shell molt of crustacean

PubMed Central

Tao, Jinhui; Zhou, Dongming; Zhang, Zhisen; Xu, Xurong; Tang, Ruikang

2009-01-01

Many animals such as crustacean periodically undergo cyclic molt of the exoskeleton. During this process, amorphous calcium mineral phases are biologically stabilized by magnesium and are reserved for the subsequent rapid formation of new shell tissue. However, it is a mystery how living organisms can regulate the transition of the precursor phases precisely. We reveal that the shell mineralization from the magnesium stabilized precursors is associated with the presence of Asp-rich proteins. It is suggested that a cooperative effect of magnesium and Asp-rich compound can result into a crystallization switch in biomineralization. Our in vitro experiments confirm that magnesium increases the lifetime of amorphous calcium carbonate and calcium phosphate in solution so that the crystallization can be temporarily switched off. Although Asp monomer alone inhibits the crystallization of pure amorphous calcium minerals, it actually reduces the stability of the magnesium-stabilized precursors to switch on the transformation from the amorphous to crystallized phases. These modification effects on crystallization kinetics can be understood by an Asp-enhanced magnesium desolvation model. The interesting magnesium-Asp-based switch is a biologically inspired lesson from nature, which can be developed into an advanced strategy to control material fabrications. PMID:20007788

Magnesium-aspartate-based crystallization switch inspired from shell molt of crustacean.

PubMed

Tao, Jinhui; Zhou, Dongming; Zhang, Zhisen; Xu, Xurong; Tang, Ruikang

2009-12-29

Many animals such as crustacean periodically undergo cyclic molt of the exoskeleton. During this process, amorphous calcium mineral phases are biologically stabilized by magnesium and are reserved for the subsequent rapid formation of new shell tissue. However, it is a mystery how living organisms can regulate the transition of the precursor phases precisely. We reveal that the shell mineralization from the magnesium stabilized precursors is associated with the presence of Asp-rich proteins. It is suggested that a cooperative effect of magnesium and Asp-rich compound can result into a crystallization switch in biomineralization. Our in vitro experiments confirm that magnesium increases the lifetime of amorphous calcium carbonate and calcium phosphate in solution so that the crystallization can be temporarily switched off. Although Asp monomer alone inhibits the crystallization of pure amorphous calcium minerals, it actually reduces the stability of the magnesium-stabilized precursors to switch on the transformation from the amorphous to crystallized phases. These modification effects on crystallization kinetics can be understood by an Asp-enhanced magnesium desolvation model. The interesting magnesium-Asp-based switch is a biologically inspired lesson from nature, which can be developed into an advanced strategy to control material fabrications.

NIR‐Triggered Crystal Phase Transformation of NiTi‐Layered Double Hydroxides Films for Localized Chemothermal Tumor Therapy

PubMed Central

Wang, Donghui; Ge, Naijian; Yang, Tingting; Peng, Feng; Qiao, Yuqin; Li, Qianwen

2018-01-01

Abstract Construction of localized drug‐eluting systems with synergistic chemothermal tumor‐killing abilities is promising for biomedical implants directly contacting with tumor tissues. In this study, an intelligent and biocompatible drug‐loading platform, based on a gold nanorods‐modified butyrate‐inserted NiTi‐layered double hydroxides film (Au@LDH/B), is prepared on the surface of nitinol alloy. The prepared films function as drug‐loading “sponges,” which pump butyrate out under near‐infrared (NIR) irradiation and resorb drugs in water when the NIR laser is shut off. The stimuli‐responsive release of butyrate is verified to be related with the NIR‐triggered crystal phase transformation of Au@LDH/B. In vitro and in vivo studies reveal that the prepared films possess excellent biosafety and high efficiency in synergistic thermochemo tumor therapy, showing a promising application in the construction of localized stimuli‐responsive drug‐delivery systems. PMID:29721424

Shape Memory effect and Superelasticity in the [001] Single crystals of a FeNiCoAlTa Alloy with γ-α'-Thermoelastic Martensitic Transformations

NASA Astrophysics Data System (ADS)

Chumlyakov, Yu. I.; Kireeva, I. V.; Kretinina, I. V.; Keinikh, K. S.; Kuts, O. A.; Kirillov, V. A.; Karaman, I.; Maier, H.

2013-12-01

Using single crystals of a Fe - 28% Ni - 17% Co - 11.5% Al - 25% Ta (аt.%) alloy, oriented for tensile loading along the [001] direction, the shape-memory (SME) and superelasticity (SE) effects caused by reversible thermoelastic martensitic transformations (MTs) from a high-temperature fcc-phase into a bctmartensite are investigated. It is demonstrated that the conditions necessary for the thermoelastic MTs to occur are achieved by aging at 973 K within the time interval (t) from 0.5 to 7.0 hours, which is accompanied by precipitation of the γ'-phase particles, (FeNiCo)3(AlTa), whose d < 8-12 nm. When the size of the γ'-precipitates becomes as large as d ≥ 8-12 nm, the MT becomes partially reversible. The physical causes underlying the kinetics of thermoelstic reversible fcc-bct MTs are discussed.

High pressure-high temperature phase diagram of an energetic crystal: Dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate (TKX-50)

DOE PAGES

Dreger, Z. A.; Breshike, C. J.; Gupta, Y. M.

2017-05-08

Raman spectroscopy was used to examine the high pressure-high temperature structural and chemical stability of an insensitive, high-performance energetic crystal – dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate (TKX-50). The phase diagram was determined over 8 GPa and (293-760) K. Under isobaric heating, the melting/decomposition of TKX-50 is preceded by a transformation to two consecutive high-temperature intermediates; a lower-temperature intermediate – diammonium 5,5’-bistetrazole-1,1'-diolate, and a higher-temperature intermediate – dihydroxylammonium 5,5'-bistetrazolate and/or diammonium 5,5'-bistetrazolate. Pressure strongly increases the transition temperatures for these transformations and subsequent decomposition. As a result, significant increase in the chemical stability of TKX-50 and intermediates with pressure was attributed to a suppressionmore » of hydrogen-transfer.« less

Melting of superheated molecular crystals

NASA Astrophysics Data System (ADS)

Cubeta, Ulyana; Bhattacharya, Deepanjan; Sadtchenko, Vlad

2017-07-01

Melting dynamics of micrometer scale, polycrystalline samples of isobutane, dimethyl ether, methyl benzene, and 2-propanol were investigated by fast scanning calorimetry. When films are superheated with rates in excess of 105 K s-1, the melting process follows zero-order, Arrhenius-like kinetics until approximately half of the sample has transformed. Such kinetics strongly imply that melting progresses into the bulk via a rapidly moving solid-liquid interface that is likely to originate at the sample's surface. Remarkably, the apparent activation energies for the phase transformation are large; all exceed the enthalpy of vaporization of each compound and some exceed it by an order of magnitude. In fact, we find that the crystalline melting kinetics are comparable to the kinetics of dielectric α-relaxation in deeply supercooled liquids. Based on these observations, we conclude that the rate of non-isothermal melting for superheated, low-molecular-weight crystals is limited by constituent diffusion into an abnormally dense, glass-like, non-crystalline phase.

Magneto-optical spectroscopy of ferromagnetic shape-memory Ni-Mn-Ga alloy

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

Veis, M., E-mail: veis@karlov.mff.cuni.cz; Beran, L.; Zahradnik, M.

2014-05-07

Magneto-optical properties of single crystal of Ni{sub 50.1}Mn{sub 28.4}Ga{sub 21.5} magnetic shape memory alloy in martensite and austenite phase were systematically studied. Crystal orientation was approximately along (100) planes of parent cubic austenite. At room temperature, the sample was in modulated 10M martensite phase and transformed to cubic austenite at 323 K. Spectral dependence of polar magneto-optical Kerr effect was obtained by generalized magneto-optical ellipsometry with rotating analyzer in the photon energy range from 1.2 to 4 eV, and from room temperature to temperature above the Curie point. The Kerr rotation spectra exhibit prominent features typical for complexes containing Mn atoms. Significantmore » spectral changes during transformation to austenite can be explained by different optical properties caused by changes in density of states near the Fermi energy.« less

Crystal structure of simple metals at high pressures

NASA Astrophysics Data System (ADS)

Degtyareva, Olga

2010-09-01

The effects of pressure on the crystal structure of simple (or sp-) elements are analysed in terms of changes in coordination number, packing density, and interatomic distances, and general rules are established. In the polyvalent elements from groups 14-17, the covalently bonded structures tend to transform to metallic phases with a gradual increase in coordination number and packing density, a behaviour normally expected under pressure. Group 1 and 2 metallic elements, however, show a reverse trend towards structures with low packing density due to intricate changes in their electronic structure. Complex crystal structures such as host-guest and incommensurately modulated structures found in these elements are given special attention in this review in an attempt to determine their role in the observed phase-transition sequences.

Shape memory behavior of single and polycrystalline nickel rich nickel titanium alloys

NASA Astrophysics Data System (ADS)

Kaya, Irfan

NiTi is the most commonly used shape memory alloy (SMA) and has been widely used for bio-medical, electrical and mechanical applications. Nickel rich NiTi shape memory alloys are coming into prominence due to their distinct superelasticity and shape memory properties as compared to near equi-atomic NiTi shape memory alloys. Besides, their lower density and higher work output than steels makes these alloys an excellent candidate for aerospace and automotive industry. Shape memory properties and phase transformation behavior of high Ni-rich Ni54Ti46 (at.%) polycrystals and Ni-rich Ni 51Ti49 (at.%) single-crystals are determined. Their properties are sensitive to heat treatments that affect the phase transformation behavior of these alloys. Phase transformation properties and microstructure were investigated in aged Ni54Ti46 alloys with differential scanning calorimetry (DSC) and transmission electron microscopy (TEM) to reveal the precipitation characteristics and R-phase formation. It was found that Ni54Ti46 has the ability to exhibit perfect superelasticity under high stress levels (~2 GPa) with 4% total strain after 550°C-3h aging. Stress independent R-phase transformation was found to be responsible for the change in shape memory behavior with stress. The shape memory responses of [001], [011] and [111] oriented Ni 51Ti49 single-crystals alloy were reported under compression to reveal the orientation dependence of their shape memory behavior. It has been found that transformation strain, temperatures and hysteresis, Classius-Clapeyron slopes, critical stress for plastic deformation are highly orientation dependent. The effects of precipitation formation and compressive loading at selected temperatures on the two-way shape memory effect (TWSME) properties of a [111]- oriented Ni51Ti49 shape memory alloy were revealed. Additionally, aligned Ni4Ti3 precipitates were formed in a single crystal of Ni51Ti49 alloy by aging under applied compression stress along the [111] direction. Formation of a single family of Ni4Ti3 precipitates were exhibited significant TWSME without any training or deformation. When the homogenized and aged specimens were loaded in martensite, positive TWSME was observed. After loading at high temperature in austenite, the homogenized specimen did not show TWSME while the aged specimen revealed negative TWSME.

Solid-solid phase transformation via internal stress-induced virtual melting, significantly below the melting temperature. Application to HMX energetic crystal.

PubMed

Levitas, Valery I; Henson, Bryan F; Smilowitz, Laura B; Asay, Blaine W

2006-05-25

We theoretically predict a new phenomenon, namely, that a solid-solid phase transformation (PT) with a large transformation strain can occur via internal stress-induced virtual melting along the interface at temperatures significantly (more than 100 K) below the melting temperature. We show that the energy of elastic stresses, induced by transformation strain, increases the driving force for melting and reduces the melting temperature. Immediately after melting, stresses relax and the unstable melt solidifies. Fast solidification in a thin layer leads to nanoscale cracking which does not affect the thermodynamics or kinetics of the solid-solid transformation. Thus, virtual melting represents a new mechanism of solid-solid PT, stress relaxation, and loss of coherence at a moving solid-solid interface. It also removes the athermal interface friction and deletes the thermomechanical memory of preceding cycles of the direct-reverse transformation. It is also found that nonhydrostatic compressive internal stresses promote melting in contrast to hydrostatic pressure. Sixteen theoretical predictions are in qualitative and quantitative agreement with experiments conducted on the PTs in the energetic crystal HMX. In particular, (a) the energy of internal stresses is sufficient to reduce the melting temperature from 551 to 430 K for the delta phase during the beta --> delta PT and from 520 to 400 K for the beta phase during the delta --> beta PT; (b) predicted activation energies for direct and reverse PTs coincide with corresponding melting energies of the beta and delta phases and with the experimental values; (c) the temperature dependence of the rate constant is determined by the heat of fusion, for both direct and reverse PTs; results b and c are obtained both for overall kinetics and for interface propagation; (d) considerable nanocracking, homogeneously distributed in the transformed material, accompanies the PT, as predicted by theory; (e) the nanocracking does not change the PT thermodynamics or kinetics appreciably for the first and the second PT beta <--> delta cycles, as predicted by theory; (f) beta <--> delta PTs start at a very small driving force (in contrast to all known solid-solid transformations with large transformation strain), that is, elastic energy and athermal interface friction must be negligible; (g) beta --> alpha and alpha --> beta PTs, which are thermodynamically possible in the temperature range 382.4 < theta < 430 K and below 382.4 K, respectively, do not occur.

Synthesis and characterization of β-Sialon powders from Si, halloysite clay and AlN powders

NASA Astrophysics Data System (ADS)

Yin, Li; Jones, Mark Ian

2017-07-01

Two β-Sialons, with z-values of 1 and 4, respectively, were successfully synthesized by silicothermal reduction and nitridation method under 0.4 MPa nitrogen pressure. The effect of firing temperatures on the phase transformations and morphologies of β-Sialons were analyzed by XRD and SEM. For β-Sialons (z = 1), the product was finally composed of targeted β-Sialon (z = 1) and secondary phase α-Si3N4; for z = 4, β-Sialon (z = 4) was the main phase, and 15R-Sialon and α-Al2O3 co-existed as secondary phases. A higher firing temperature is more beneficial for the phase transformations and crystal growth of β-Sialons, however, the most suitable firing temperature was 1400∘C.

Effect of annealing temperature on titania nanoparticles

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

Manikandan, K., E-mail: sanjaymani367@gmail.com; Arumugam, S., E-mail: sanjaymani367@gmail.com; Chandrasekaran, G.

2014-04-24

Titania polycrystalline samples are prepared by using sol-gel route hydrolyzing a alkoxide titanium precursor under acidic conditions. The as prepared samples are treated with different calcination temperatures. The anatase phase of titania forms when treated below 600°C, above that temperature the anatase phase tends to transform into the rutile phase of titania. The experimental determination of average grain size, phase formation, lattice parameters and the crystal structures of titania samples at different calcinations is done using X-ray diffraction (XRD). Fourier Transform Infra-red Spectroscopy (FTIR), UV-vis-NIR spectroscopy and Scanning Electron Microscopy (SEM) and Energy Dispersive Analysis X-ray are used to characterizemore » the samples to bring impact on the respective properties.« less

Asymmetric flavone-based liquid crystals: synthesis and properties

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

Timmons, Daren J.; Jordan, Abraham J.; Kirchon, Angelo A.

2017-02-01

A series of flavones (n-F) substituted at the 4', and 6 positions was prepared, characterised by NMR (1H,13C), HRMS, and studied for liquid crystal properties. The 4'-alkoxy,6-methoxyflavones (4-F–16-F) exhibit varying ranges of nematic and smectic A phases as evidenced by polarised optical microscopy and differential scanning calorimetry (DSC). As the tail length is increased, the smectic phase becomes more prevalent. Smectic phases for (8-F–16-F) were further analysed by powder X-ray diffraction (XRD), and the rate of structural transformations was explored by combined DSC/XRD studies. Flavonol 6-F–OH was also prepared but no mesogenic behaviour was observed. The molecular structures of 6-Fmore » and 6-F–OH were determined by single-crystal XRD and help to explain the differences in material properties. Additionally, fluorescence and electrochemical studies were conducted on solutions of n-F.« less

Phase diagram calculations and high pressure Raman spectroscopy studies of organic "plastic crystal" thermal energy storage materials

NASA Astrophysics Data System (ADS)

Chellappa, Raja S.

This dissertation presents the phase diagram calculations and high pressure Raman spectroscopy studies on organic "plastic crystal" thermal storage materials. The organic "plastic crystals" that were studied include pentaerythritol [PE:C(CH 2OH)4], neopentylglycol [NPG:(CH3)2C(CH 2OH)2], tris(hydroxymethyl)-aminomethane [TRIS:(NH2 )C(CH2OH)3], and 2-amino-2-methyl-1,3-propanediol [AMPL: (NH2)(CH3)C(CH2OH)2]. Thermodynamic optimization of the experimental data of AMPL-NPG and PE-AMPL binary system was performed and the calculated phase diagrams are presented. A preliminary calculated phase diagram of the TRIS-NPG binary system is also presented. A thorough reevaluation of the existing calorimetric and x-ray diffraction data of the PE-AMPL binary system is also presented. This analysis resulted in the correct interpretation of the phase boundaries and a revised phase diagram has been drawn. The results of high pressure Raman spectroscopy experiments on neopentylglycol and pentaerythritol presented. The phase transformation pressures were determined by analyzing the frequency shifts as a function of pressure as well as the changes in the internal modes of vibration for these compounds. A simplified assignment of the vibrational modes for NPG at ambient pressure is presented. The results indicate experiments were carried out using Diamond Anvil Cell (DAC) and the pressure induced transformations were studied by Raman spectroscopy. In NPG, a phase transition occurs at ˜3.6 GPa from Phase I (Monoclinic) to Phase II (unknown structure). In PE, the proposed phase transformation pressures are ˜4.8 GPa (Phase I to Phase II), ˜6.9 GPa (Phase II to Phase III), ˜9.5 GPa (Phase III to Phase IV), and ˜15 GPa (Phase IV to Amorphous). The results of a critical assessment of the vapor pressure data of solid metal carbonyls. The vapor pressure data of Chromium Carbonyl (Cr(CO)6), Tungsten Carbonyl (W(CO)6 ), Osmium Carbonyl (Os3(CO)12), Molybdenum Carbonyl (MO(CO)6). Rhenium Carbonyl (Re2(CO)10), and Manganese Carbonyl (Mn(CO)5) were assessed using the "Oonk Methodology". The sublimation properties using the assessed data (Delta subGo,DeltasubH o and Deltasub Cop,m ) of these compounds have been evaluated and a discussion on the mutual consistency of various data sets for each compound over a wide range of temperature is also presented.

Mesomorphic behaviors of a series of heterocyclic thiophene-imine-ester-based liquid crystals

NASA Astrophysics Data System (ADS)

Foo, K.-L.; Ha, S.-T.; Yeap, G. Y.; Lee, S. L.

2018-05-01

The synthesis and characterization of a series of heterocyclic liquid crystal, 4-{[(thiophen-2-yl)methylidene]amino}phenyl 4-alkoxybenzoates possessing even number of carbon atoms at the alkoxy chain (CnH2n+1O-, n = 6, 8, 10, 12, 14, 16, 18) are reported. The molecular structures of title compounds were elucidated using Fourier-transform infrared spectroscopy (FTIR) and Nuclear Magnetic Resonance (NMR) spectroscopic techniques along with mass spectrometric analysis. The phase behavior of these compounds was characterized and studied by differential scanning calorimetry and polarizing optical microscopy. All members exhibited enantiotropic nematic phase except for the highest member (n = 18) which is a non-mesogen. Influence of alkoxy chain length on the transition temperatures of crystal-to-nematic (melting point) and nematic-to-isotropic (clearing point) was studied. Nematic phase range was found to increase from n = 6 to n = 10, then it started to descend from n = 12 to n = 16 and finally the nematic phase disappeared when n changed to 18.

Fast Crystallization of the Phase Change Compound GeTe by Large-Scale Molecular Dynamics Simulations.

PubMed

Sosso, Gabriele C; Miceli, Giacomo; Caravati, Sebastiano; Giberti, Federico; Behler, Jörg; Bernasconi, Marco

2013-12-19

Phase change materials are of great interest as active layers in rewritable optical disks and novel electronic nonvolatile memories. These applications rest on a fast and reversible transformation between the amorphous and crystalline phases upon heating, taking place on the nanosecond time scale. In this work, we investigate the microscopic origin of the fast crystallization process by means of large-scale molecular dynamics simulations of the phase change compound GeTe. To this end, we use an interatomic potential generated from a Neural Network fitting of a large database of ab initio energies. We demonstrate that in the temperature range of the programming protocols of the electronic memories (500-700 K), nucleation of the crystal in the supercooled liquid is not rate-limiting. In this temperature range, the growth of supercritical nuclei is very fast because of a large atomic mobility, which is, in turn, the consequence of the high fragility of the supercooled liquid and the associated breakdown of the Stokes-Einstein relation between viscosity and diffusivity.

Making Diamond in the Laboratory

ERIC Educational Resources Information Center

Strong, Herbert

1975-01-01

Discusses the graphite to diamond transformation and a phase diagram for carbon. Describes high temperature-higher pressure experimental apparatus and growth of diamonds from seed crystals. Reviews properties of the diamond which suggest uses for the synthetic product. Illustrations with text. (GH)

Effect of phase composition on crystal texture formation in hot deformed nanocrystalline SmCo5 magnets

NASA Astrophysics Data System (ADS)

Ma, Qiang; Yue, Ming; Xu, Xiaochang; Zhang, Hongguo; Zhang, Dongtao; Zhang, Xuefeng; Zhang, Jiuxing

2018-05-01

In the present study, bulk anisotropic nanocrystalline SmCo5 magnets were prepared by hot press and subsequent hot deformation method. Effect of phase composition on texture and magnetic properties are presented, based on which the mechanism of plastic deformation and texture formation during the hot deformation process is discussed. The SmCo5 magnets were prepared by hot deformation, excessive Sm of 2.5 wt% and 10 wt% was added to compensate the weight loss due to Sm evaporation. Our analyses reveal that the phase composition is one of the most important parameters that determine the texture of SmCo5 magnets. It is therefore suggested that the existence of 2:17 phase and its phase transformation undermined the crystal texture formation as well as the magnetic properties of nanocrystalline SmCo5 magnets.

New Density Functional Approach for Solid-Liquid-Vapor Transitions in Pure Materials

NASA Astrophysics Data System (ADS)

Kocher, Gabriel; Provatas, Nikolas

2015-04-01

A new phase field crystal (PFC) type theory is presented, which accounts for the full spectrum of solid-liquid-vapor phase transitions within the framework of a single density order parameter. Its equilibrium properties show the most quantitative features to date in PFC modeling of pure substances, and full consistency with thermodynamics in pressure-volume-temperature space is demonstrated. A method to control either the volume or the pressure of the system is also introduced. Nonequilibrium simulations show that 2- and 3-phase growth of solid, vapor, and liquid can be achieved, while our formalism also allows for a full range of pressure-induced transformations. This model opens up a new window for the study of pressure driven interactions of condensed phases with vapor, an experimentally relevant paradigm previously missing from phase field crystal theories.

Influence of Hydrogen Bond on Thermal and Phase Transitions of Binary Complex Liquid Crystals

NASA Astrophysics Data System (ADS)

Vijayakumar, V. N.; Rajasekaran, T. R.; Baskar, K.

2017-12-01

A novel supramolecular liquid crystal (LC) is synthesized from the binary complex of 4-decyloxy benzoic acid and cholesteryl acetate. Fourier transform infrared (FTIR) spectroscopic study confirms the formation of intermolecular hydrogen bond between the mesogens. Various mesophases and corresponding textural changes in the complex are observed by comparing with its constituents through polarizing optical microscopic (POM) studies. The thermal stability factor of smectic phase for present complex is calculated. An interesting observation of present work is that investigation of extended thermal span of mesomorphic phases, decreased enthalpy, a nematic phase with a high clearing point and a low melting point. This is due to an arrangement of molecular reorientations and the development of new associations by hydrogen bonding. Optical tilt angle for smectic C phase is determined and the same is fitted to a power law.

Polarization-phase diagnostics of latent course of cholelithiasis in patients with chronic cholecystitis combined with diabetes mellitus type 2

NASA Astrophysics Data System (ADS)

Fediv, O. I.; Ivashchuk, O. I.; Marchuk, Yu. F.; Andriychuk, D. R.

2011-09-01

The principles of optical model of human bile polycrystalline structure are described. The three optical levels - isotropic, liquid-crystal and solid-crystal have been proposed. It has been introduced and proposed the scenarios of phase distribution formation in the boundary field of laser radiation, transformed by bile layers. The experimental scheme of direct measurement of coordinate phase distributions has been presented. The results of investigating the interrelation between the values of correlation and fractal parameters are presented. They characterize the coordinate distributions of phase shifts between the orthogonal components of the amplitude in the points of laser images of bile smears of cholelithiasis patients in combination with other pathologies. The diagnostic criteria of the cholelithiasis nascency and its severity degree differentiation are determined.

Direct Laser Writing of δ- to α-Phase Transformation in Formamidinium Lead Iodide

PubMed Central

2017-01-01

Organolead halide perovskites are increasingly considered for applications well beyond photovoltaics, for example, as the active regions within photonic devices. Herein, we report the direct laser writing (DLW: 458 nm cw-laser) of the formamidinium lead iodide (FAPbI3) yellow δ-phase into its high-temperature luminescent black α-phase, a remarkably easy and scalable approach that takes advantage of the material’s susceptibility to transition under ambient conditions. Through the DLW of α-FAPbI3 tracks on δ-FAPbI3 single-crystal surfaces, the controlled and rapid microfabrication of highly luminescent structures exhibiting long-term phase stability is detailed, offering an avenue toward the prototyping of complex perovskite-based optical devices. The dynamics and kinetics of laser-induced δ- to α-phase transformations are investigated in situ by Raman microprobe analysis, as a function of irradiation power, time, temperature, and atmospheric conditions, revealing an interesting connection between oxygen intercalation at the surface and the δ- to α-phase transformation dynamics, an insight that will find application within the wider context of FAPbI3 thermal phase relations. PMID:28763617

Selective Precipitation and Concentrating of Perovskite Crystals from Titanium-Bearing Slag Melt in Supergravity Field

NASA Astrophysics Data System (ADS)

Gao, Jintao; Zhong, Yiwei; Guo, Zhancheng

2016-08-01

Selective precipitation and concentrating of perovskite crystals from titanium-bearing slag melt in the supergravity field was investigated in this study. Since perovskite was the first precipitated phase from the slag melt during the cooling process, and a greater precipitation quantity and larger crystal sizes of perovskite were obtained at 1593 K to 1563 K (1320 °C to 1290 °C), concentrating of perovskite crystals from the slag melt was carried out at this temperature range in the supergravity field, at which the perovskite transforms into solid particles while the other minerals remain in the liquid melt. The layered structures appeared significantly in the sample obtained by supergravity treatment, and all the perovskite crystals moved along the supergravity direction and concentrated as the perovskite-rich phase in the bottom area, whereas the molten slag concentrated in the upper area along the opposite direction, in which it was impossible to find any perovskite crystals. With the gravity coefficient of G = 750, the mass fraction of TiO2 in the perovskite-rich phase was up to 34.65 wt pct, whereas that of the slag phase was decreased to 12.23 wt pct, and the recovery ratio of Ti in the perovskite-rich phase was up to 75.28 pct. On this basis, an amplification experimental centrifugal apparatus was exploited and the continuous experiment with larger scale was further carried out, the results confirming that selective precipitation and concentrating of perovskite crystals from the titanium-bearing slag melt by supergravity was a feasible method.

Mesoscale modeling of strain induced solid state amorphization in crystalline materials

NASA Astrophysics Data System (ADS)

Lei, Lei

Solid state amorphization, and in particular crystalline to amorphous transformation, can be observed in metallic alloys, semiconductors, intermetallics, minerals, and also molecular crystals when they undergo irradiation, hydrogen gas dissolution, thermal interdiffusion, mechanical alloying, or mechanical milling. Although the amorphization mechanisms may be different, the transformation occurs due to the high level of disorder introduced into the material. Milling induced solid state amorphization is proposed to be the result of accumulation of crystal defects, specifically dislocations, as the material is subjected to large deformations during the high energy process. Thus, understanding the deformation mechanisms of crystalline materials will be the first step in studying solid state amorphization in crystalline materials, which not only has scientific contributions, but also technical consequences. A phase field dislocation dynamics (PFDD) approach is employed in this work to simulate plastic deformation of molecular crystals. This PFDD model has the advantage of tracking all of the dislocations in a material simultaneously. The model takes into account the elastic interaction between dislocations, the lattice resistance to dislocation motion, and the elastic interaction of dislocations with an external stress field. The PFDD model is employed to describe the deformation of molecular crystals with pharmaceutical applications, namely, single crystal sucrose, acetaminophen, gamma-indomethacin, and aspirin. Stress-strain curves are produced that result in expected anisotropic material response due to the activation of different slip systems and yield stresses that agree well with those from experiments. The PFDD model is coupled to a phase transformation model to study the relation between plastic deformation and the solid state amorphization of crystals that undergo milling. This model predicts the amorphous volume fraction in excellent agreement with experimental observation. Finally, we incorporate the effect of stress free surfaces to model the behavior of dislocations close to these surfaces and in the presence of voids.

α″ Martensite and Amorphous Phase Transformation Mechanism in TiNbTaZr Alloy Incorporated with TiO2 Particles During Friction Stir Processing

NASA Astrophysics Data System (ADS)

Ran, Ruoshi; Liu, Yiwei; Wang, Liqiang; Lu, Eryi; Xie, Lechun; Lu, Weijie; Wang, Kuaishe; Zhang, Lai-Chang

2018-03-01

This work studied the formation of the α″ martensite and amorphous phases of TiNbTaZr alloy incorporated with TiO2 particles during friction stir processing. Formation of the amorphous phase in the top surface mainly results from the dissolution of oxygen, rearrangement of the lattice structure, and dislocations. High-stress stemming caused by dislocations and high-stress concentrations at crystal-amorphous interfaces promote the formation of α″ martensite. Meanwhile, an α″ martensitic transformation is hindered by oxygen diffusion from TiO2 to the matrix, thereby increasing resistance to shear.

Shock induced polymorphic transition in quartz, carbon, and boron nitride

NASA Technical Reports Server (NTRS)

Tan, Hua; Ahrens, Thomas J.

1990-01-01

The model proposed by Ahrens (1988) to explain the mechanism of the polymorphism in silicates is revised, and the revised model is applied to the quartz/stishovite, graphite/diamond, and graphite-boron nitride (g-BN) phase transformations. In this model, a key assumption is that transformation to a high-density amorphous or possibly liquid phase which rapidly crystallized to the high-pressure phase is triggered by the high temperatures in the shear band and upon crossing the metastable extension of a melting curve. Good agreement between the calcualted results and published data is obtained. The present theory predicts the standard entropy for cubic BN to be 0.4-0.5 J/g K.

α″ Martensite and Amorphous Phase Transformation Mechanism in TiNbTaZr Alloy Incorporated with TiO2 Particles During Friction Stir Processing

NASA Astrophysics Data System (ADS)

Ran, Ruoshi; Liu, Yiwei; Wang, Liqiang; Lu, Eryi; Xie, Lechun; Lu, Weijie; Wang, Kuaishe; Zhang, Lai-Chang

2018-06-01

This work studied the formation of the α″ martensite and amorphous phases of TiNbTaZr alloy incorporated with TiO2 particles during friction stir processing. Formation of the amorphous phase in the top surface mainly results from the dissolution of oxygen, rearrangement of the lattice structure, and dislocations. High-stress stemming caused by dislocations and high-stress concentrations at crystal-amorphous interfaces promote the formation of α″ martensite. Meanwhile, an α″ martensitic transformation is hindered by oxygen diffusion from TiO2 to the matrix, thereby increasing resistance to shear.

Calculations of single crystal elastic constants for yttria partially stabilised zirconia from powder diffraction data

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

Lunt, A. J. G., E-mail: alexander.lunt@eng.ox.ac.uk; Xie, M. Y.; Baimpas, N.

2014-08-07

Yttria Stabilised Zirconia (YSZ) is a tough, phase-transforming ceramic that finds use in a wide range of commercial applications from dental prostheses to thermal barrier coatings. Micromechanical modelling of phase transformation can deliver reliable predictions in terms of the influence of temperature and stress. However, models must rely on the accurate knowledge of single crystal elastic stiffness constants. Some techniques for elastic stiffness determination are well-established. The most popular of these involve exploiting frequency shifts and phase velocities of acoustic waves. However, the application of these techniques to YSZ can be problematic due to the micro-twinning observed in larger crystals.more » Here, we propose an alternative approach based on selective elastic strain sampling (e.g., by diffraction) of grain ensembles sharing certain orientation, and the prediction of the same quantities by polycrystalline modelling, for example, the Reuss or Voigt average. The inverse problem arises consisting of adjusting the single crystal stiffness matrix to match the polycrystal predictions to observations. In the present model-matching study, we sought to determine the single crystal stiffness matrix of tetragonal YSZ using the results of time-of-flight neutron diffraction obtained from an in situ compression experiment and Finite Element modelling of the deformation of polycrystalline tetragonal YSZ. The best match between the model predictions and observations was obtained for the optimized stiffness values of C11 = 451, C33 = 302, C44 = 39, C66 = 82, C12 = 240, and C13 = 50 (units: GPa). Considering the significant amount of scatter in the published literature data, our result appears reasonably consistent.« less

Influence of phase transformation on stress evolution during growth of metal thin films on silicon.

PubMed

Fillon, A; Abadias, G; Michel, A; Jaouen, C; Villechaise, P

2010-03-05

In situ stress measurements during two-dimensional growth of low mobility metal films on amorphous Si were used to demonstrate the impact of interface reactivity and phase transformation on stress evolution. Using Mo1-xSix films as examples, the results show that the tensile stress rise, which develops after the film has become crystalline, is correlated with an increase in lateral grain size. The origin of the tensile stress is attributed to the volume change resulting from the alloy crystallization, which occurs at a concentration-dependent critical thickness.

Phase competition in the growth of SrCoOx/LaAlO3 thin films

NASA Astrophysics Data System (ADS)

Zhang, Jie; Meng, Dechao; Huang, Haoliang; Cai, Honglei; Huang, Qiuping; Wang, Jianlin; Yang, Yuanjun; Zhai, Xiaofang; Fu, Zhengping; Lu, Yalin

2018-02-01

The reversible topotactic phase transformation between brownmillerite SrCoO2.5 to perovskite SrCoO3 has attracted more and more attention for potential applications as solid oxide fuels and electrolysis cells. However, the relatively easy transformation result from small thermal stable energy barriers between the two phases leads to unstable the structures. In the paper, amounts of SrCoO3-δ films have been prepared by pulsed laser deposition at optimized growth conditions with the temperature range of 590-720°C. The X-ray diffraction (XRD) results demonstrated that a phase competition emerged around 650°C. The Gibbs free energies of two phases at high temperature revealed the difference of stability of these two phases under different growth temperature. The optical spectroscopies and X-ray photoelectron spectroscopies were used to verify the electronic structure and chemical state differences between the two phases with distinct crystal structures.

Kinetics and pathways for crystallization of amorphous mullite and YAG

NASA Astrophysics Data System (ADS)

Johnson, Bradley Richard

The crystallization behavior of quenched mullite (3Al2O 3•2SiO2) and YAG (Y3Al5O 12) composition glasses (made using containerless methods) were characterized with the ultimate goal of producing single crystal, structural, ceramic oxide fibers from these materials. The kinetics for crystallization were determined from thermal analysis experiments. From the results, time-temperature-transformation (TTT) curves were calculated. The crystallization pathways were determined by examining the crystal structure, microstructure, and chemical composition of heat treated specimens using x-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). A machine was also designed and built to facilitate controlled crystallization of amorphous fibers. Quenched, Y3Al5O12 composition beads crystallized at temperatures as low as 840°C. The as-received specimens contained a few, small YAG crystals, in addition to a mixture of different amorphous phases. The coexistence of two different amorphous phases of the same composition, but having different densities is termed polyamorphism, and this has been reported to occur in Y3Al5O12 composition quenched melts. Although various crystallization pathways have been reported for chemically synthesized YAG precursors, these specimens crystallized directly into YAG, which was the only phase formed. Quenched, 3Al2O3•2SiO2 composition mullite beads and fibers crystallized at temperatures as low as 920°C. Due to phase separation in the quenched melts, multiple phases with slightly different compositions and different crystallization activation energies crystallized. These phases were not equilibrium, 3:2 mullite, but metastable, alumina-rich, pseudotetragonal mullite. The residual, amorphous, silica-rich phase existed as numerous, 7--10 nm sized inclusions embedded within pseudotetragonal mullite. A large amount of internal strain was detected in pseudotetragonal mullite, and the source of this strain was suggested to be the embedded, silica-rich inclusions. Pseudotetragonal mullite gradually converted to equilibrium, orthorhombic, 3:2 mullite between 1000--1400°C. This was characterized by assimilation of the embedded, silica-rich inclusions and the elimination of internal strain. Additionally, recrystallization of numerous, small, strain- and inclusion-free, 3:2 mullite grains was observed to occur as the process proceeded to completion.

Overview: Experimental studies of crystal nucleation: Metals and colloids.

PubMed

Herlach, Dieter M; Palberg, Thomas; Klassen, Ina; Klein, Stefan; Kobold, Raphael

2016-12-07

Crystallization is one of the most important phase transformations of first order. In the case of metals and alloys, the liquid phase is the parent phase of materials production. The conditions of the crystallization process control the as-solidified material in its chemical and physical properties. Nucleation initiates the crystallization of a liquid. It selects the crystallographic phase, stable or meta-stable. Its detailed knowledge is therefore mandatory for the design of materials. We present techniques of containerless processing for nucleation studies of metals and alloys. Experimental results demonstrate the power of these methods not only for crystal nucleation of stable solids but in particular also for investigations of crystal nucleation of metastable solids at extreme undercooling. This concerns the physical nature of heterogeneous versus homogeneous nucleation and nucleation of phases nucleated under non-equilibrium conditions. The results are analyzed within classical nucleation theory that defines the activation energy of homogeneous nucleation in terms of the interfacial energy and the difference of Gibbs free energies of solid and liquid. The interfacial energy acts as barrier for the nucleation process. Its experimental determination is difficult in the case of metals. In the second part of this work we therefore explore the potential of colloidal suspensions as model systems for the crystallization process. The nucleation process of colloids is observed in situ by optical observation and ultra-small angle X-ray diffraction using high intensity synchrotron radiation. It allows an unambiguous discrimination of homogeneous and heterogeneous nucleation as well as the determination of the interfacial free energy of the solid-liquid interface. Our results are used to construct Turnbull plots of colloids, which are discussed in relation to Turnbull plots of metals and support the hypothesis that colloids are useful model systems to investigate crystal nucleation.

Crystal structure, equation of state, and elasticity of phase H (MgSiO4H2) at Earth's lower mantle pressures.

PubMed

Tsuchiya, Jun; Mookherjee, Mainak

2015-10-23

Dense hydrous magnesium silicate (DHMS) phases play a crucial role in transporting water in to the Earth's interior. A newly discovered DHMS, phase H (MgSiO4H2), is stable at Earth's lower mantle, i.e., at pressures greater than 30 GPa. Here we report the crystal structure and elasticity of phase H and its evolution upon compression. Using first principles simulations, we have explored the relative energetics of the candidate crystal structures with ordered and disordered configurations of magnesium and silicon atoms in the octahedral sites. At conditions relevant to Earth's lower mantle, it is likely that phase H is able to incorporate a significant amount of aluminum, which may enhance the thermodynamic stability of phase H. The sound wave velocities of phase H are ~2-4% smaller than those of isostructural δ-AlOOH. The shear wave impedance contrast due to the transformation of phase D to a mixture of phase H and stishovite at pressures relevant to the upper part of the lower mantle could partly explain the geophysical observations. The calculated elastic wave velocities and anisotropies indicate that phase H can be a source of significant seismic anisotropy in the lower mantle.

Grain growth and phase transformations induced by shock waves on alpha-GeO2 powder

NASA Astrophysics Data System (ADS)

Rosales, Ivonne; Thions-Renero, Claude; Martinez, Erendira; Bucio, Lauro; Orozco, Eligio

2011-09-01

An impact experiment on a mixture of water and microcrystalline alpha-GeO2 powder was performed with a single-stage gas gun. The recovered sample contained micrometer-scale crystals of different sizes and morphologies that correspond to 88% of alpha-GeO2, 6.0% of monoclinic phase (P21/c, space group No. 14), 4.9% of orthorhombic phase (Pnnm, space group No. 58) and 1.1% of rutile-type phase.

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

Wan, Li; Thompson, Gregory, E-mail: gthompson@eng.ua.edu

A series of 40–2 nm bilayer spacing Ti/Fe multilayers were sputter-deposited. As the length scale of individual Ti layers equaled to 2 nm, Ti phase transforms from a hexagonal close packed (hcp)-to-body centered cubic (bcc) crystal structures for equal layer thicknesses in Ti/Fe multilayers. Further equal reductions in bilayer spacing to less than 1 nm resulted in an additional transformation from a crystalline to amorphous structure. Atom probe tomography reveals significant intermixing between layers which contributes to the observed phase transformations. Real-time, intrinsic growth stress measurements were also performed to relate the adatom mobility to these phase transformations. For the hcp Ti/bcc Femore » multilayers of equivalent volume fractions, the multilayers undergo an overall tensile stress state to a compressive stress state with decreasing bilayer thickness for the multilayers. When the above phase transformations occurred, a modest reduction in the overall compressive stress of the multilayer was noted. Depending on the Fe thickness, the Ti growth was observed to be a tensile to compressive growth change to a purely compressive growth for thinner bilayer spacing. Fe retained a tensile growth stress regardless of the bilayer spacing studied.« less

Crystal structure of simple metals at high pressures

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

Degtyareva, Olga

2010-10-22

The effects of pressure on the crystal structure of simple (or sp-) elements are analysed in terms of changes in coordination number, packing density, and interatomic distances, and general rules are established. In the polyvalent elements from groups 14-17, the covalently bonded structures tend to transform to metallic phases with a gradual increase in coordination number and packing density, a behaviour normally expected under pressure. Group 1 and 2 metallic elements, however, show a reverse trend towards structures with low packing density due to intricate changes in their electronic structure. Complex crystal structures such as host-guest and incommensurately modulated structuresmore » found in these elements are given special attention in this review in an attempt to determine their role in the observed phase-transition sequences.« less

Earth physics and phase transformations program: A concept and proposal

NASA Technical Reports Server (NTRS)

Bonavito, N. L.; Tanaka, T.

1971-01-01

A program to study the geophysical characteristics of the earth is presented as an integration of the different disciplines that constitute the earth sciences, through the foundation of a generalized geodynamic theory of earth physics. A program is considered for defining the physical constants of the earth's material which parametrize the hydrodynamic equation in the microscopic solid state behavior of the crystals of the lithosphere. In addition, in order to lay the foundation for a generalized theory in earth physics, specific research areas are considered, such as the nature of the kinetics of the phase transitions in mineral assemblages, the equilibrium thermodynamic properties of crystals which are major constituents of mineral assemblages, and the transport properties of pure crystals which are major constituents of mineral assemblages.

Cyclic stability of superelasticity in the aged [ {bar{1}}23 ]-oriented Ni49Fe18Ga27Co6 single crystals

NASA Astrophysics Data System (ADS)

Panchenko, E. Yu.; Chumlyakov, Yu. I.; Timofeeva, E. E.; Vetoshkina, N. G.; Maier, H.

2013-02-01

The results of investigation of the effect of precipitates of different sizes, from 5 to 300 nm, on the character of stress-induced martensitic transformations, the value of stress hysteresis and cyclic stability of superelasticity in Ni49Fe18Ga27Со6 (at.%) ferromagnetic single crystals oriented along the [ {bar{1}}23 ] axis are presented. It is shown that a martensitic transformation in single crystals of Ni49Fe18Ga27Со6 containing dispersed particles of the γ- and γ'-phases measuring up to 30 nm (ageing at 673 K for 1 and 4 hours) is characterized by storing considerable elastic energy. It is revealed that these single crystals exhibit higher cyclic stability of superelasticity and a narrower stress hysteresis compared to those in the initial state and aged at 823 K for 0.5 hour, the latter containing much larger (150-300 nm) particles.

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.

CO oxidation studies over supported noble metal catalysts and single crystals: A review

NASA Technical Reports Server (NTRS)

Boecker, Dirk; Gonzalez, Richard D.

1987-01-01

The catalytic oxidation of CO over noble metal catalysts is reviewed. Results obtained on supported noble metal catalysts and single crystals both at high pressures and under UHV conditions are compared. The underlying causes which result in surface instabilities and multiple steady-state oscillations are considered, in particular, the occurrence of hot spots. CO islands of reactivity, surface oxide formation and phase transformations under oscillatory conditions are discussed.

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.

Ni-Mn-Ga Single Crystal Exhibiting Multiple Magnetic Shape Memory Effects

NASA Astrophysics Data System (ADS)

Heczko, Oleg; Veřtát, Petr; Vronka, Marek; Kopecky, Vít; Perevertov, Oleksiy

2016-09-01

Both magnetically induced phase transformation and magnetically induced reorientation (MIR) effects were observed in one Ni50Mn28Ga22 single crystal sample by direct measurement of the magnetic field-induced strain. We investigated various twinning microstructures ranged from single twin interface to fine twinning and crossing twins to evaluate what controls the apparent twinning stress crucial for MIR. The main challenges for the applications of these effects are outlined.

Mechanisms of the Wurtzite to Rocksalt Transformation in CdSe Nanocrystals

NASA Astrophysics Data System (ADS)

Grünwald, Michael; Rabani, Eran; Dellago, Christoph

2006-06-01

We study the pressure-driven phase transition from the four-coordinate wurtzite to the six-coordinate rocksalt structure in CdSe nanocrystals with molecular dynamics computer simulations. With an ideal gas as the pressure medium, we apply hydrostatic pressure to spherical and faceted nanocrystals ranging in diameter from 25 to 62 Å. In spherical crystals, the main mechanism of the transformation involves the sliding of (100) planes, but depending on the specific surface structure we also observe a second mechanism proceeding through the flattening of (100) planes. In faceted crystals, the transition proceeds via a five-coordinated hexagonal structure, which is stabilized at intermediate pressures due to dominant surface energetics.

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.

Investigation of the Nd-rich phases in the Nd-Fe-B system

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

Tang, W.; Zhou, S.; Wang, R.

1988-11-15

The crystal structures and the compositions of the Nd-rich phases in the Nd-Fe-B system have been investigated by means of transmission electron microscopy, x-ray diffraction, and Auger spectroscopy techniques. It has been observed that there are two kinds of Nd-rich phases with different structures and compositions. Most of the Nd-rich phases will undergo a phase transformation when the powder is sintered at high temperatures. This phase transformation is accompanied by the introduction of oxygen into the alloy which will change from a ternary system into a quaternary one. Both of the two Nd-rich phases are stable phases in this latermore » system. With the aid of the EDX and the Auger spectroscope, the compositions of the dhcp and the fcc Nd-rich phases have been determined. The Nd contents of the two phases are about 90 and 70 at. %, respectively, with the later phase containing about 15 at. % of oxygen.« less

Kinetic transition in the order-disorder transformation at a solid/liquid interface

NASA Astrophysics Data System (ADS)

Galenko, P. K.; Nizovtseva, I. G.; Reuther, K.; Rettenmayr, M.

2018-01-01

Phase-field analysis for the kinetic transition in an ordered crystal structure growing from an undercooled liquid is carried out. The results are interpreted on the basis of analytical and numerical solutions of equations describing the dynamics of the phase field, the long-range order parameter as well as the atomic diffusion within the crystal/liquid interface and in the bulk crystal. As an example, the growth of a binary A50B50 crystal is described, and critical undercoolings at characteristic changes of growth velocity and the long-range order parameter are defined. For rapidly growing crystals, analogies and qualitative differences are found in comparison with known non-equilibrium effects, particularly solute trapping and disorder trapping. The results and model predictions are compared qualitatively with results of the theory of kinetic phase transitions (Chernov 1968 Sov. Phys. JETP 26, 1182-1190) and with experimental data obtained for rapid dendritic solidification of congruently melting alloy with order-disorder transition (Hartmann et al. 2009 Europhys. Lett. 87, 40007 (doi:10.1209/0295-5075/87/40007)). This article is part of the theme issue `From atomistic interfaces to dendritic patterns'.

The nature of the mineral component of bone and the mechanism of calcification.

PubMed

Glimcher, M J

1987-01-01

From the physical chemical standpoint, the formation of a solid phase of Ca-P in bone represents a phase transformation, a process exemplified by the formation of ice from water. Considering the structural complexity and abundance of highly organized macromolecules in the cells and extracellular tissue spaces of mineralized tissues generally and in bone particularly, it is inconceivable that this phase transformation occurs by homogeneous nucleation, i.e., without the active participation of an organic component acting as a nucleator. This is almost surely true in biologic mineralization in general. Electron micrographs and low-angle neutron and X-ray diffraction studies clearly show that calcification of collagen fibrils occurs in an extremely intimate and highly organized fashion: initiation of crystal formation within the collagen fibrils in the hole zone region, with the long axes (c-axis) of the crystals aligned roughly parallel to the long axis of the fibril within which they are located. Crystals are initially formed in hole zone regions within individual fibrils separated by unmineralized regions. Calcification is initiated in spatially distinct nucleation sites. This indicates that such regions within a single, undirectional fibril represents independent sites for heterogeneous nucleation. Clearly, sites where mineralization is initiated in adjacent collagen fibrils are even further separated, emphasizing even more clearly that the process of progressive calcification of the collagen fibrils and therefore of the tissue is characterized principally by the presence of increasing numbers of independent nucleation sites within additional hole zone regions of the collagen fibrils. The increase in the mass of Ca-P apatite accrues principally by multiplication of more crystals, mostly by secondary nucleation from the crystals initially deposited in the hole zone region. Very little additional growth of the crystals occurs with time, the additional increase in mineral mass being principally the result of increase in the number of crystals (multiplication), not size of the crystals (crystal growth). The crystals within the collagen fibers grow in number and possibly in size to extend into the overlap zone of the collagen fibrils ("pores") so that all of the available space within the fibrils, which has possibly expanded in volume from its uncalcified level, is eventually occupied by the mineral crystals. It must be recognized that the calcification of separate tissue components and compartments (collagen, mitochondria, matrix vesicles) must be an independent physical chemical event.(ABSTRACT TRUNCATED AT 400 WORDS)

Effects of high pressure on microstructure evolution and crystallization mechanisms during solidification of nickel

NASA Astrophysics Data System (ADS)

Zhang, Hai-Tao; Mo, Yun-Fei; Liu, Rang-Su; Tian, Ze-An; Liu, Hai-Rong; Hou, Zhao-Yang; Zhou, Li-Li; Liang, Yong-Chao; Peng, Ping

2018-03-01

To deeply understand the effects of high pressure on microstructural evolutions and crystallization mechanisms of liquid metal Ni during solidification process, MD simulation studies have been performed under 7 pressures of 0 ˜ 30 GPa, at cooling rate of 1.0 × 1011 K s-1. Adopting several microstructural analyzing methods, especially the cluster-type index method (CTIM-2) to analyze the local microstructures in the system. It is found that the pressure has important influence on the formation and evolution of microstructures, especially of the main basic clusters in the system. All the simulation systems are directly solidified into crystal structures, and the 1421, 1422, 1441 and 1661 bond-types, as well the FCC (12 0 0 0 12 0), HCP (12 0 0 0 6 6) and BCC (14 6 0 8 0 0) clusters play a key role in the microstructure transitions from liquid to crystal structures. The crystallization temperature T c is enhanced almost linearly with the increase of pressure. Highly interesting, it is found for the first time that there is an important phase transformation point from FCC to BCC structures between 20 ˜ 22.5 GPa during the solidification processes from the same initial liquid system at the same cooling rate. And the effect of increasing pressure is similar to that of decreasing cooling rate for the phase transformation of microstructures during solidification process of liquid metal Ni system, though they have different concrete effecting mechanisms.

Thermal annealing studies of GeTe-Sb2Te3 alloys with multiple interfaces

NASA Astrophysics Data System (ADS)

Bragaglia, Valeria; Mio, Antonio M.; Calarco, Raffaella

2017-08-01

A high degree of vacancy ordering is obtained by annealing amorphous GeTe-Sb2Te3 (GST) alloys deposited on a crystalline substrate, which acts as a template for the crystallization. Under annealing the material evolves from amorphous to disordered rocksalt, to ordered rocksalt with vacancies arranged into (111) oriented layers, and finally converts into the stable trigonal phase. The role of the interface in respect to the formation of an ordered crystalline phase is studied by comparing the transformation stages of crystalline GST with and without a capping layer. The capping layer offers another crystallization interface, which harms the overall crystalline quality.

Phase transformations and equation of state of praseodymium metal to 103 GPa

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

Chesnut, Gary N.; Vohra, Yogesh K.

2000-08-01

Pressure-induced structural phase transformations in a trivalent rare-earth metal praseodymium (Pr) were studied at room temperature in a diamond anvil cell to 103 GPa by energy dispersive x-ray diffraction using a synchrotron source. Our x-ray diffraction studies document the following crystal structure sequence: dhcp{yields}fcc{yields}distorted fcc(hR24 type){yields}monoclinic(C2/m){yields}{alpha}-uranium with increasing pressure. We measure a 16.7% volume collapse at the transition to the {alpha}-uranium phase at 20 GPa. The high-pressure {alpha}-uranium phase in Pr was found to be stable to the highest pressure of 103 GPa, which corresponds to a volume compression V/V{sub 0}=0.407. (c) 2000 The American Physical Society.

Engineering the Structural and Electronic Phases of MoTe 2 through W Substitution

DOE PAGES

Rhodes, D.; Chenet, D. A.; Janicek, B. E.; ...

2017-02-01

MoTe 2 is an exfoliable transition metal dichalcogenide (TMD) that crystallizes in three symmetries: the semiconducting trigonal-prismatic 2H- or α-phase, the semimetallic and monoclinic 1T'- or β-phase, and the semimetallic orthorhombic γ-structure. The 2H-phase displays a band gap of ~1 eV making it appealing for flexible and transparent optoelectronics. The γ-phase is predicted to possess unique topological properties that might lead to topologically protected nondissipative transport channels. Recently, it was argued that it is possible to locally induce phase-transformations in TMDs, through chemical doping, local heating, or electric-field to achieve ohmic contacts or to induce useful functionalities such as electronicmore » phase-change memory elements. The combination of semiconducting and topological elements based upon the same compound might produce a new generation of high performance, low dissipation optoelectronic elements. Here, we show that it is possible to engineer the phases of MoTe2 through W substitution by unveiling the phase-diagram of the Mo 1–xW xTe 2 solid solution, which displays a semiconducting to semimetallic transition as a function of x. We find that a small critical W concentration xc ~ 8% stabilizes the γ-phase at room temperature. Lastly, this suggests that crystals with x close to xc might be particularly susceptible to phase transformations induced by an external perturbation, for example, an electric field. Photoemission spectroscopy, indicates that the γ-phase possesses a Fermi surface akin to that of WTe 2.« less

In situ observation of quasimelting of diamond and reversible graphite-diamond phase transformations.

PubMed

Huang, J Y

2007-08-01

Because of technique difficulties in achieving the extreme high-pressure and high-temperature (HPHT) simultaneously, direct observation of the structures of carbon at extreme HPHT conditions has not been possible. Banhart and Ajayan discovered remarkably that carbon onions can act as nanoscopic pressure cells to generate high pressures. By heating carbon onions to approximately 700 degrees C and under electron beam irradiation, the graphite-to-diamond transformation was observed in situ by transmission electron microscopy (TEM). However, the highest achievable temperature in a TEM heating holder is less than 1000 degrees C. Here we report that, by using carbon nanotubes as heaters and carbon onions as high-pressure cells, temperatures higher than 2000 degrees C and pressures higher than 40 GPa were achieved simultaneously in carbon onions. At such HPHT conditions and facilitated by electron beam irradiation, the diamond formed in the carbon onion cores frequently changed its shape, size, orientation, and internal structure and moved like a fluid, implying that it was in a quasimelting state. The fluctuation between the solid phase of diamond and the fluid/amorphous phase of diamond-like carbon, and the changes of the shape, size, and orientation of the solid diamond, were attributed to the dynamic crystallization of diamond crystal from the quasimolten state and the dynamic graphite-diamond phase transformations. Our discovery offers unprecedented opportunities to studying the nanostructures of carbon at extreme conditions in situ and at an atomic scale.

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.

Effect of high-energy electron irradiation in an electron microscope column on fluorides of alkaline earth elements (CaF2, SrF2, and BaF2)

NASA Astrophysics Data System (ADS)

Nikolaichik, V. I.; Sobolev, B. P.; Zaporozhets, M. A.; Avilov, A. S.

2012-03-01

The effect of high-energy (150 eV) electron irradiation in an electron microscope column on crystals of fluorides of alkaline earth elements CaF2, SrF2, and BaF2 is studied. During structural investigations by electron diffraction and electron microscopy, the electron irradiation causes chemical changes in MF2 crystals such as the desorption of fluorine and the accumulation of oxygen in the irradiated area with the formation of oxide MO. The fluorine desorption rate increases significantly when the electron-beam density exceeds the threshold value of ˜2 × 103 pA/cm2). In BaF2 samples, the transformation of BaO into Ba(OH)2 was observed when irradiation stopped. The renewal of irradiation is accompanied by the inverse transformation of Ba(OH)2 into BaO. In the initial stage of irradiation of all MF2 compounds, the oxide phase is in the single-crystal state with a lattice highly matched with the MF2 matrix. When the irradiation dose is increased, the oxide phase passes to the polycrystalline phase. Gaseous products of MF2 destruction (in the form of bubbles several nanometers in diameter) form a rectangular array with a period of ˜20 nm in the sample.

Final Report, Fundamental Mechanisms of Transient States in Materials Quantified by DTEM

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

Campbell, G. H.; McKeown, J. T.

At the project’s inception, there was growing evidence that the time domain for in situ observations of material evolution held great promise for allowing measurements to be made in never previously contemplated regimes. Also, central to the development of the project was the knowledge that phase transformations are of central importance to the development of materials microstructure and hence properties. We addressed this opportunity by developing a transmission electron microscope that could be operated in the pulsed mode (DTEM), with exposure times down to 20 ns and interframe times down to 20 ns in the nine-frame movie mode, designed withmore » the intent of performing in situ experiments. This unprecedented capability allowed us to investigate structural phase transformations, intermetallic formation reactions, crystallization from the amorphous phase, rapid solidification of liquid metals, transformations in phase change materials, and catalyst nanoparticles. The ability of the electron microscope to create images with high spatial resolution allows for the accurate measurement of position. Common to all of the transformations mentioned above is the presence of a distinct interface between the old phase and the growing new phase. Measuring the position of the interface as a function of time, combined with the ability to count nucleation sites as a function of time, allowed for the exceptionally accurate measure of transformation kinetics. These measurements were used to guide and constrain the development of models and simulation methods for the classes of transformations studied.« less

Micromechanics of plastic deformation and phase transformation in a three-phase TRIP-assisted advanced high strength steel: Experiments and modeling

NASA Astrophysics Data System (ADS)

Srivastava, Ankit; Ghassemi-Armaki, Hassan; Sung, Hyokyung; Chen, Peng; Kumar, Sharvan; Bower, Allan F.

2015-05-01

The micromechanics of plastic deformation and phase transformation in a three-phase advanced high strength steel are analyzed both experimentally and by microstructure-based simulations. The steel examined is a three-phase (ferrite, martensite and retained austenite) quenched and partitioned sheet steel with a tensile strength of 980 MPa. The macroscopic flow behavior and the volume fraction of martensite resulting from the austenite-martensite transformation during deformation were measured. In addition, micropillar compression specimens were extracted from the individual ferrite grains and the martensite particles, and using a flat-punch nanoindenter, stress-strain curves were obtained. Finite element simulations idealize the microstructure as a composite that contains ferrite, martensite and retained austenite. All three phases are discretely modeled using appropriate crystal plasticity based constitutive relations. Material parameters for ferrite and martensite are determined by fitting numerical predictions to the micropillar data. The constitutive relation for retained austenite takes into account contributions to the strain rate from the austenite-martensite transformation, as well as slip in both the untransformed austenite and product martensite. Parameters for the retained austenite are then determined by fitting the predicted flow stress and transformed austenite volume fraction in a 3D microstructure to experimental measurements. Simulations are used to probe the role of the retained austenite in controlling the strain hardening behavior as well as internal stress and strain distributions in the microstructure.

Microfluidic sorting of protein nanocrystals by size for X-ray free-electron laser diffraction

PubMed Central

Abdallah, Bahige G.; Zatsepin, Nadia A.; Roy-Chowdhury, Shatabdi; Coe, Jesse; Conrad, Chelsie E.; Dörner, Katerina; Sierra, Raymond G.; Stevenson, Hilary P.; Camacho-Alanis, Fernanda; Grant, Thomas D.; Nelson, Garrett; James, Daniel; Calero, Guillermo; Wachter, Rebekka M.; Spence, John C. H.; Weierstall, Uwe; Fromme, Petra; Ros, Alexandra

2015-01-01

The advent and application of the X-ray free-electron laser (XFEL) has uncovered the structures of proteins that could not previously be solved using traditional crystallography. While this new technology is powerful, optimization of the process is still needed to improve data quality and analysis efficiency. One area is sample heterogeneity, where variations in crystal size (among other factors) lead to the requirement of large data sets (and thus 10–100 mg of protein) for determining accurate structure factors. To decrease sample dispersity, we developed a high-throughput microfluidic sorter operating on the principle of dielectrophoresis, whereby polydisperse particles can be transported into various fluid streams for size fractionation. Using this microsorter, we isolated several milliliters of photosystem I nanocrystal fractions ranging from 200 to 600 nm in size as characterized by dynamic light scattering, nanoparticle tracking, and electron microscopy. Sorted nanocrystals were delivered in a liquid jet via the gas dynamic virtual nozzle into the path of the XFEL at the Linac Coherent Light Source. We obtained diffraction to ∼4 Å resolution, indicating that the small crystals were not damaged by the sorting process. We also observed the shape transforms of photosystem I nanocrystals, demonstrating that our device can optimize data collection for the shape transform-based phasing method. Using simulations, we show that narrow crystal size distributions can significantly improve merged data quality in serial crystallography. From this proof-of-concept work, we expect that the automated size-sorting of protein crystals will become an important step for sample production by reducing the amount of protein needed for a high quality final structure and the development of novel phasing methods that exploit inter-Bragg reflection intensities or use variations in beam intensity for radiation damage-induced phasing. This method will also permit an analysis of the dependence of crystal quality on crystal size. PMID:26798818

Microfluidic sorting of protein nanocrystals by size for X-ray free-electron laser diffraction

DOE PAGES

Abdallah, Bahige G.; Zatsepin, Nadia A.; Roy-Chowdhury, Shatabdi; ...

2015-08-19

We report that the advent and application of the X-ray free-electron laser (XFEL) has uncovered the structures of proteins that could not previously be solved using traditional crystallography. While this new technology is powerful, optimization of the process is still needed to improve data quality and analysis efficiency. One area is sample heterogeneity, where variations in crystal size (among other factors) lead to the requirement of large data sets (and thus 10–100 mg of protein) for determining accurate structure factors. To decrease sample dispersity, we developed a high-throughput microfluidic sorter operating on the principle of dielectrophoresis, whereby polydisperse particles canmore » be transported into various fluid streams for size fractionation. Using this microsorter, we isolated several milliliters of photosystem I nanocrystal fractions ranging from 200 to 600 nm in size as characterized by dynamic light scattering, nanoparticle tracking, and electron microscopy. Sorted nanocrystals were delivered in a liquid jet via the gas dynamic virtual nozzle into the path of the XFEL at the Linac Coherent Light Source. We obtained diffraction to ~4 Å resolution, indicating that the small crystals were not damaged by the sorting process. We also observed the shape transforms of photosystem I nanocrystals, demonstrating that our device can optimize data collection for the shape transform-based phasing method. Using simulations, we show that narrow crystal size distributions can significantly improve merged data quality in serial crystallography. From this proof-of-concept work, we expect that the automated size-sorting of protein crystals will become an important step for sample production by reducing the amount of protein needed for a high quality final structure and the development of novel phasing methods that exploit inter-Bragg reflection intensities or use variations in beam intensity for radiation damage-induced phasing. Ultimately, this method will also permit an analysis of the dependence of crystal quality on crystal size.« less

Structural, magnetothermal, and magnetotransport properties of single crystal terbium silicon germanide and spontaneous generation of voltage in single crystal gadolinium silicon germanide and gadolinium

NASA Astrophysics Data System (ADS)

Zou, Min

A systematic study of single crystalline Tb5Si2.2Ge1.8, including magnetic field induced crystallographic and magnetic phase transformations, magnetocaloric effect, ferromagnetic short-range correlations, electrical resistivity, magnetoresistance, and spontaneous generation of voltage (SGV) has been presented. A study of SGV in single crystalline Gd5Si2Ge2 and Gd has also been included. The metamagnetic-like transitions and giant magnetocaloric effect were observed with the magnetic field applied parallel to the a- and c-axes, but not the b-axis in a Tb5Si 2.2Ge1.8 single crystal. The in-situ x-ray powder diffraction study indicates that these metamagnetic-like transitions are coupled to a crystallographic phase transformation occurring via strong magnetoelastic interactions. The magnetocrystalline anisotropy plays an important role in this system. Magnetic fields less than 40 kOe can not drive either the magnetic or the crystallographic phase transition to completion for Tb5Si2.2Ge1.8 powder due to the strong single ion anisotropy of Tb. Magnetic field dependencies of the critical temperatures of magnetic phase transitions of Tb5Si2.2Ge1.8 are highly anisotropic for both the main magnetic ordering process occurring around 120 K and a spin reorientation transition at ~70 K. Magnetic-field-induced phase transitions occur with the magnetic field applied isothermally along the a-and b-axes (but not along the c-axis) between 1.8 and 70 K in fields below 70 kOe. Strongly anisotropic thermal irreversibility is observed in the Griffiths phase regime between 120 and 200 K with applied fields ranging from 10 to 1000 Oe. Our data: (1) show that the magnetic and structural phase transitions around 120 K are narrowly decoupled; (2) uncover the anisotropy of ferromagnetic short-range order in the Griffiths phase; and (3) reveal some unusual magnetic domain effects in the long-range ordered state of the Tb5Si2.2Ge1.8 compound. The temperature-magnetic field phase diagrams with field applied along the three major crystallographic directions have been constructed. The positive colossal magnetoresistance (CMR) with a magnitude of ~150% was observed with the magnetic field applied parallel to the a-axis, but not the b- and c-axes in Tb5Si 2.2Ge1.8 single crystals. The electrical resistivity shows a low-temperature high-resistivity behavior (i.e. the resistivity at low temperature is higher after the transformation to the low temperature phase than the resistivity of the phase before the transition) along the a-axis, contrary to those along the b- and c-axes. The positive CMR effect originates from an intrinsic crystallographic phase coexistence state frozen below the Curie Temperature (TC). The differences in the temperature dependencies of electrical resistivities and longitudinal magnetoresistance along the a-axis and those along the b- and c-axes can be explained by the geometry of the phase boundaries at low temperatures, and the inability of the external magnetic field to induce the crystallographic phase transformation along the b- and c-axes. Temperature-induced SGVs were observed along all three principal crystallographic axes of Tb5Si2.2Ge1.8, but not in Gd. Field-induced SGVs were observed with magnetic fields less than 40 kOe applied along the a-axis of Tb5Si2.2Ge1.8, and the c-axis of Gd. The absence of the temperature induced SGV in Gd indicates the key role first-order phase transformations play in the appearance of the effect when temperature varies. The anisotropy of magnetic field induced SGV in Tb5Si2.2Ge1.8 and the existence of field induced SGV in Gd, highlight the importance of the magnetocaloric effect in bringing about the SGV. In single crystal and polycrystalline Gd5Si 2Ge2 during the coupled magneto-structural transformations, reversible and repeatable SGV responses of the materials to the temperature and magnetic field have been observed. The parameters of the response and the magnitude of the signal are anisotropic and rate dependent. The magnitude of the SGV signal, and the critical temperatures and critical magnetic fields at which the SGV occurs vary with the rate of temperature and magnetic field changes.

Testing the Crystalline Integrity of Baddeleyite: A Systematic EBSD and Confocal Laser-Raman Spectroscopy Study

NASA Astrophysics Data System (ADS)

DesOrmeau, J. W.; Ibanez-Mejia, M.; Lafuente Valverde, B.; Eddy, M. P.; Trail, D.; Wang, Y.

2017-12-01

The accessory mineral baddeleyite (monoclinic ZrO2) has great potential as a high-precision U-Pb geochronometer in silica-undersaturated rocks. However, due to a lack of understanding of alpha-recoil damage to the crystal structure and the influences on chemical diffusion properties and closed-system behavior, limitations still exist. Studies have shown phase transformations in baddeleyite (monoclinic to tetragonal) resulting from radiation damage due to ion bombardment [e.g., 1], but the effects of self-irradiation on the baddeleyite crystal structure over geologic timescales remain poorly understood. A recent study reported confocal laser-Raman spectra suggesting the presence of a tetragonal phase in a Phalaborwa baddeleyite [2], which has crucial implications for Pb mobility and high-precision U-Pb results. To better understand the physical effects of self-irradiation in baddeleyite over geologic timescales, samples of various ages (ca. 2060-32 Ma) and calculated alpha-doses (0.001-0.901 x 1016 α/mg) were imaged by cathodoluminescence (CL) and subsequently analyzed via electron backscatter diffraction (EBSD) and confocal laser-Raman spectroscopy. Synthetic baddeleyite grown in a one-atmosphere furnace was also analyzed to allow a comparison of EBSD and Raman results of the pure monoclinic phase and the natural unknown samples. Whole grain EBSD maps (n=75) of baddeleyite from the Phalabowra and Kovdor carbonatites, the Ammänpelto sill, and the Duluth, Ogden and Yinmawanshan gabbros show complex twinning that is loosely correlated to CL zoning and identification of the monoclinic phase only, suggesting no evidence for phase transformations within grains of contrasting age and amounts of alpha-doses. Preliminary Raman results show evidence of systematic shifts in the vibrational modes of Phalabowra baddeleyite with respect to the younger crystals, which may be the result of radiation-induced damage accumulation rather than phase transformation. These results aim to better characterize the poorly known effects of radiation damage in natural baddeleyite and assist in improving methods for high-precision U-Pb dating of mafic systems on Earth and other planetary bodies. [1] Valdez et al. (2008), J. Nucl. Mater. 381, pp. 259-266. [2[ Schaltegger and Davies (2017), RIMG 83, pp.297-328.

Evidence for a New Intermediate Phase in a Strongly Correlated 2D System near Wigner Crystallization

NASA Astrophysics Data System (ADS)

Gao, Xuan; Qiu, Richard; Goble, Nicholas; Serafin, Alex; Yin, Liang; Xia, Jian-Sheng; Sullivan, Neil; Pfeiffer, Loren; West, Ken

How the two dimensional (2D) quantum Wigner crystal (WC) transforms into the metallic liquid phase remains an outstanding problem in physics. In theories considering the 2D WC to liquid transition in the clean limit, it was suggested that a number of intermediate phases might exist. We have studied the transformation between the metallic fluid phase and the low magnetic field reentrant insulating phase (RIP) which was interpreted as due to the WC [Qiu et al., PRL 108, 106404 (2012)], in a strongly correlated 2D hole system in GaAs quantum well with large interaction parameter rs (~20-30) and high mobility. Instead of a sharp transition, we found that increasing density (or lowering rs) drives the RIP into a state where the incipient RIP coexists with Fermi liquid. This apparent mixture phase intermediate between Fermi liquid and WC also exhibits a non-trivial temperature dependent resistivity behavior which can be qualitatively understood by the reversed melting of WC in the mixture, in analogy to the Pomeranchuk effect in the solid-liquid mixture of Helium-3. X.G. thanks NSF (DMR-0906415) for supporting work at CWRU. Experiments at the NHMFL High B/T Facility were supported by NSF Grant 0654118 and the State of Florida. L.P. thanks the Gordon and Betty Moore Foundation and NSF MRSEC (DMR-0819860) for support.

Crystallization of Synthetic Blast Furnace Slags Pertaining to Heat Recovery

NASA Astrophysics Data System (ADS)

Esfahani, Shaghayegh

Heat recovery from blast furnace slags is often contradicted by another requirement, to generate amorphous slag for its use in cement production. As both the rate and extent of heat recovery and slag structure are determined by its cooling rate, a relation between the crystallization kinetics and the cooling conditions is highly desired. In this study, CaO-SiO2-Al2O3-MgO (CSAM) slags with different basicities were studied by Single Hot Thermocouple Technique (SHTT) during isothermal treatment and non-isothermal cooling. Their time-temperature-transformation (TTT) and continuous-cooling-transformation (CCT) diagrams were plotted and compared with each other. Furthermore, kinetic parameters such as the Avrami exponent (n), rate coefficient (K) and effective activation energy of crystallization (EA) were found by analysis of data obtained from in-situ observation of glassy to crystalline transformation and image analysis. Also, the dependence of nucleation and growth rates of crystalline phases were quantified as a function of time, temperature, and slag basicity. Together with the observations of crystallization front, they facilitated establishing the dominant mechanisms of crystallization. In addition to the experimental work, a mathematical model was developed and validated that predicts the amount of crystallization during cooling. A second mathematical model that calculates temperature history of slag during its cooling was coupled with the above model, to allow studying the effect of parameters such as the slag/air ratio and granule size on the heat recovery and glass content of slag.

Low temperature structural transformation in T[Ni(CN){sub 4}].xpyz with x=1,2; T=Mn,Co,Ni,Zn,Cd; pyz=pyrazine

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

Rodriguez-Hernandez, J.; Instituto de Ciencia y Tecnologia de Materiales, Universidad de La Habana; Lemus-Santana, A.A.

2010-01-15

The materials under study are pillared solids T[Ni(CN){sub 4}].xpyz with one and two (x=1,2) pyrazine (pyz) molecules and where T=Mn, Co, Ni, Zn, Cd. Stimulated by their structural features and potential role as prototype of porous solids for hydrogen storage, the structural stability under cryogenic conditions for this series of pillared solids was studied. At low temperature, in the 100-200 K range, the occurrence of a reversible structural transformation was found. For T=Mn, Co, Zn, Cd, with x=2, the structural transformation was observed to occur around 185 K, and the low temperature phase crystallizes with a monoclinic unit cell (spacemore » group Pc). This structure change results from certain charge redistribution on cooling within the involved ligands. For T=Ni with x=1, both the low and high temperature phases crystallize with unit cells of tetragonal symmetry, within the same space group but with a different unit cell volume. In this case the structure change is observed around 120 K. Above that temperature the rotational states for the pyrazine molecule are thermally excited and all the pyrazine molecules in the structure become equivalent. Under this condition the material structure is described using a smaller structural unit. The structural study using X-ray powder diffraction data was complemented with calorimetric and Raman spectroscopy measurements. For the low temperature phases the crystal structures were solved from Patterson methods and then refined using the Rietveld method. - Graphical abstract: Low temperature ordered structure for pyrazine in T[Ni(CN){sub 4}].pyz.« 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.

Surface or internal nucleation and crystallization of glass-ceramics

NASA Astrophysics Data System (ADS)

Höland, W.; Rheinberger, V. M.; Ritzberger, C.; Apel, E.

2013-07-01

Fluoroapatite (Ca5(PO4)3F) was precipitated in glass-ceramics via internal crystallization of base glasses. The crystals grew with a needle-like morphology in the direction of the crystallographic c-axis. Two different reaction mechanisms were analyzed: precipitation via a disordered primary apatite crystals and a solid state parallel reaction to rhenanite (NaCaPO4) precipitation. In contrast to the internal nucleation used in the formation of fluoroapatite, surface crystallization was induced to precipitate a phosphate-free oxyapatite of NaY9(SiO4)6O2-type. Internal nucleation and crystallization have been shown to be a very useful tool for developing high-strength lithium disilicate (Li2Si2O5) glass-ceramics. A very controlled process was conducted to transform the lithium metasilicate glass-ceramic precursor material into the final product of the lithium disilicate glass-ceramic without the major phase of the precursor material. The combination of all these methods allowed the driving forces of the internal nucleation and crystallization mechanisms to be explained. An amorphous phosphate primary phase was discovered in the process. Nucleation started at the interface between the amorphous phosphate phase and the glass matrix. The final products of all these glass-ceramics are biomaterials for dental restoration showing special optical properties, e.g. translucence and color close to dental teeth.

In Situ X-Ray Studies of Crystallization Kinetics and Ordering in Functional Organic and Hybrid Materials

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

Yang, Bin; Keum, Jong K.; Geohegan, David B.

In-Situ and time-resolved X-ray scattering and diffraction is dedicated to yielding the change of structural information as the materials are processed or grown in a controlled environment. In this chapter, we introduce the use of in situ and time-resolved X-ray techniques to understand molecular packing, crystal orientation, and phase transformation during the synthesis and processing of functional organic semiconductors, organic nanowires, and hybrid perovskite materials.

Effect of SiO2/B2O3 Ratio on the Crystallization Behavior and Dielectric Properties of Barium Strontium Titanate Glass-Ceramics Prepared by Sol-Gel Process

NASA Astrophysics Data System (ADS)

Chen, Yongzhou; Zhang, Yong; Song, Xiaozhen; Shen, Ziqin; Zhang, Tianyuan

2018-05-01

Ferroelectric glass-ceramics, with a basic composition 90 wt.% (Ba0.65Sr0.35)TiO3-10 wt.% (B2O3-nSiO2) (n = 0.5, 1, 3, 5) were synthesized by the sol-gel method and their phase development and dielectric properties were investigated by differential thermal analysis, x-ray diffraction, field emission scanning electron microscopy, dielectric temperature curves and impedance spectroscopy. From the differential thermal analysis, glass transition and crystallization behavior can be observed. From the x-ray diffraction study, two crystalline phases (Ba,Sr)TiO3 and Ba2TiSi2O8 were formed over the entire composition range of the glass-ceramics. In addition, the main crystal phase has undergone a transformation from (Ba,Sr)TiO3 to Ba2TiSi2O8 with the increase of n. A typical structure in which the crystal phase was surrounded by a glassy matrix has been observed in the scanning electron microscope images. As a result of temperature dependent dielectric property measurements, the dielectric constant increased obviously with the increase of n from 0.5 to 1. Further increasing n led to a reduction of the dielectric constant, which is in coincidence with the variation of the intensity of (Ba,Sr)TiO3 phase with n. According to the impedance spectroscopy analysis and the activation energy calculation, the relaxation peak in both Z″ and M″ data should be attributed to the crystal-glass interface, and the change of conduction mechanism with the increase of SiO2/B2O3 ratio may be attributed to the corresponding transition of the main crystal phase.

Temperature and electric-field induced phase transitions, and full tensor properties of [011] C-poled domain-engineered tetragonal 0 .63 Pb (M g1 /3N b2 /3) -0 .37 PbTi O3 single crystals

NASA Astrophysics Data System (ADS)

Zheng, Limei; Jing, Yujia; Lu, Xiaoyan; Wang, Ruixue; Liu, Gang; Lü, Weiming; Zhang, Rui; Cao, Wenwu

2016-03-01

The phase-transition sequence of 0.67 Pb (M g1 /3N b2 /3)- 0.37 PbTi O3 (PMN-0.37PT) single crystals driven by the electric (E ) field and temperature is comprehensively studied. Based on the strain-E field loop, polarization-E field loop, and the evolution of domain configurations, the E field along the [011] C induced phase transitions have been confirmed to be as follows: tetragonal (T ) → monoclinic (MC)→ single domain orthorhombic (O ) phase. As the E field decreases, the induced O phase cannot be maintained and transformed to the MC phase, then to the coexistence state of MC and T phases. In addition, the complete sets of dielectric, piezoelectric, and elastic constants for the [011] C-poled domain-engineered PMN-0.37PT single crystal were measured at room temperature, which show high longitudinal dielectric, piezoelectric, and electromechanical properties (ɛ33T=10 661 ,d33=1052 pC /N , and k33= 0.766 ). Our results revealed that the MC phase plays an important role in the high electromechanical properties of this domain-engineered single crystal. The temperature dependence of the domain configuration revealed that the volume fraction of the MC phase decreases with temperature accompanied by the reduction of ɛ33T,d31, and k31 due to the substantially smaller intrinsic properties of the T phase.

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

78 FR 64916 - Application(s) for Duty-Free Entry of Scientific Instruments

Federal Register 2010, 2011, 2012, 2013, 2014

2013-10-30

...., light to heat), crystallization, melting, phase transformations, fracture, and other dynamic events. The... Sciences University, 1120 15th Street, Augusta, GA 30912. Instrument: Imaging System/Digital Microscope... the instrument include fast wavelength change, a dichromotome system, and two different light sources...

Thermomechanical behavior of shape memory elastomeric composites

NASA Astrophysics Data System (ADS)

Ge, Qi; Luo, Xiaofan; Rodriguez, Erika D.; Zhang, Xiao; Mather, Patrick T.; Dunn, Martin L.; Qi, H. Jerry

2012-01-01

Shape memory polymers (SMPs) can fix a temporary shape and recover their permanent shape in response to environmental stimuli such as heat, electricity, or irradiation. Most thermally activated SMPs use the macromolecular chain mobility change around the glass transition temperature ( Tg) to achieve the shape memory (SM) effects. During this process, the stiffness of the material typically changes by three orders of magnitude. Recently, a composite materials approach was developed to achieve thermally activated shape memory effect where the material exhibits elastomeric response in both the temporary and the recovered configurations. These shape memory elastomeric composites (SMECs) consist of an elastomeric matrix reinforced by a semicrystalline polymer fiber network. The matrix provides background rubber elasticity while the fiber network can transform between solid crystals and melt phases over the operative temperature range. As such it serves as a reversible "switching phase" that enables shape fixing and recovery. Shape memory elastomeric composites provide a new paradigm for the development of a wide array of active polymer composites that utilize the melt-crystal transition to achieve the shape memory effect. This potentially allows for material systems with much simpler chemistries than most shape memory polymers and thus can facilitate more rapid material development and insertion. It is therefore important to understand the thermomechanical behavior and to develop corresponding material models. In this paper, a 3D finite-deformation constitutive modeling framework was developed to describe the thermomechanical behavior of SMEC. The model is phenomenological, although inspired by micromechanical considerations of load transfer between the matrix and fiber phases of a composite system. It treats the matrix as an elastomer and the fibers as a complex solid that itself is an aggregate of melt and crystal phases that evolve from one to the other during a temperature change. As such, the composite consists of an elastomer reinforced by a soft liquid at high temperature and a stiff solid at low temperature. The model includes a kinetic description of the non-isothermal crystallization and melting of the fibers during a temperature change. As the fibers transform from melt to crystal during cooling it is assumed that new crystals are formed in an undeformed state, which requires careful tracking of the kinematics of the evolving phases which comes at a significant computational cost. In order to improve the computational efficiency, an effective phase model (EPM) is adopted to treat the evolving crystal phases as an effective medium. A suite of careful thermomechanical experiments with a SMEC was carried out to calibrate various model parameters, and then to demonstrate the ability of the model to accurately capture the shape memory behavior of the SMEC system during complex thermomechanical loading scenarios. The model also identifies the effects of microstructural design parameters such as the fiber volume fraction.

Length scale effects and multiscale modeling of thermally induced phase transformation kinetics in NiTi SMA

NASA Astrophysics Data System (ADS)

Frantziskonis, George N.; Gur, Sourav

2017-06-01

Thermally induced phase transformation in NiTi shape memory alloys (SMAs) shows strong size and shape, collectively termed length scale effects, at the nano to micrometer scales, and that has important implications for the design and use of devices and structures at such scales. This paper, based on a recently developed multiscale model that utilizes molecular dynamics (MDs) simulations at small scales and MD-verified phase field (PhF) simulations at larger scales, reports results on specific length scale effects, i.e. length scale effects in martensite phase fraction (MPF) evolution, transformation temperatures (martensite and austenite start and finish) and in the thermally cyclic transformation between austenitic and martensitic phase. The multiscale study identifies saturation points for length scale effects and studies, for the first time, the length scale effect on the kinetics (i.e. developed internal strains) in the B19‧ phase during phase transformation. The major part of the work addresses small scale single crystals in specific orientations. However, the multiscale method is used in a unique and novel way to indirectly study length scale and grain size effects on evolution kinetics in polycrystalline NiTi, and to compare the simulation results to experiments. The interplay of the grain size and the length scale effect on the thermally induced MPF evolution is also shown in this present study. Finally, the multiscale coupling results are employed to improve phenomenological material models for NiTi SMA.

Co-crystallization phase transformations in all π-conjugated block copolymers with different main-chain moieties.

PubMed

Lee, Yi-Huan; Chen, Wei-Chih; Yang, Yi-Lung; Chiang, Chi-Ju; Yokozawa, Tsutomu; Dai, Chi-An

2014-05-21

Driven by molecular affinity and balance in the crystallization kinetics, the ability to co-crystallize dissimilar yet self-crystallizable blocks of a block copolymer (BCP) into a uniform domain may strongly affect its phase diagram. In this study, we synthesize a new series of crystalline and monodisperse all-π-conjugated poly(2,5-dihexyloxy-p-phenylene)-b-poly(3-(2-ethylhexyl)thiophene) (PPP-P3EHT) BCPs and investigate this multi-crystallization effect. Despite vastly different side-chain and main-chain structures, PPP and P3EHT blocks are able to co-crystallize into a single uniform domain comprising PPP and P3EHT main-chains with mutually interdigitated side-chains spaced in-between. With increasing P3EHT fraction, PPP-P3EHTs undergo sequential phase transitions and form hierarchical superstructures including predominately PPP nanofibrils, co-crystalline nanofibrils, a bilayer co-crystalline/pure P3EHT lamellar structure, a microphase-separated bilayer PPP-P3EHT lamellar structure, and finally P3EHT nanofibrils. In particular, the presence of the new co-crystalline lamellar structure is the manifestation of the interaction balance between self-crystallization and co-crystallization of the dissimilar polymers on the resulting nanostructure of the BCP. The current study demonstrates the co-crystallization nature of all-conjugated BCPs with different main-chain moieties and may provide new guidelines for the organization of π-conjugated BCPs for future optoelectronic applications.

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

PubMed Central

Liu, Jie; Lu, Xiaolong; Wu, Chunrui

2013-01-01

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

Microstructure and electrical properties of Sb2Te phase-change material

NASA Astrophysics Data System (ADS)

Liu, Guangyu; Wu, Liangcai; Li, Tao; Rao, Feng; Song, Sannian; Liu, Bo; Song, Zhitang

2016-10-01

Phase Change Memory (PCM) has great potential for commercial applications of next generation non-volatile memory (NVM) due to its high operation speed, high endurance and low power consumption. Sb2Te (ST) is a common phase-change material and has fast crystallization speed, while thermal stability is relatively poor and its crystallization temperature is about 142°C. According to the Arrhenius law, the extrapolated failure temperature is about 55°C for ten years. When heated above the crystallization temperature while below the melting point, its structure can be transformed from amorphous phase to hexagonal phase. Due to the growth-dominated crystallization mechanism, the grain size of ST film is large and the diameter of about 300 nm is too large compared with Ge2Sb2Te5 (GST), which may deteriorate the device performance. High resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED) were employed to study the microstructures and the results indicate that the crystal plane is {110}. In addition, device cells were manufactured and their current-voltage (I-V) and resistance-voltage characteristics were tested, and the results reveal that the threshold voltage (Vth) of ST film is 0.87 V. By researching the basic properties of ST, we can understand its disadvantages and manage to improve its performance by doping or other proper methods. Finally, the improved ST can be a candidate for optical discs and PCM.

Time Dependent Structural Evolution of Porous Organic Cage CC3

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

Lucero, Jolie; Elsaidi, Sameh; Anderson, Ryther

Porous organic cage compounds are emerged with remarkable structural diversity and functionality that have applications in gas separation, catalysis and energy storage. Fundamental understanding of nucleation and growth of such materials have significant implications for understanding molecularly directed self-assembly phenomena. Herein we followed the structural evolution of a prototypical type of porous organic cage, CC3 as a function of synthesis time. Three distinctive crystal formation stages were identified: at short synthesis times, a rapid crystal growth stage in which amorphous agglomerates transformed into larger irregular particles was observed. At intermediate synthesis times, a decrease in crystal size over time wasmore » observed presumably due to crystal fragmentation, redissolution and/or homogeneous nucleation led. Finally, at longer synthesis times, a regrowth process was observed in which particles coalesced through Ostwald ripening leading to a continuous increase in crystal size. Molecular simulation studies, based on the construction of in silico CC3 models and simulation of XRD patterns and nitrogen isotherms, confirm the samples at different synthesis times to be a mixture of CC3α and CC3 amorphous phases. The CC3α phase is found to contract at different synthesis times, and the amorphous phase is found to essentially disappear at the longest synthesis time. Nitrogen and carbon dioxide adsorption properties of these CC3 phases were evaluated, and were highly dependent on synthesis time.« less

Indium hydroxide to oxide decomposition observed in one nanocrystal during in situ transmission electron microscopy studies

NASA Astrophysics Data System (ADS)

Miehe, Gerhard; Lauterbach, Stefan; Kleebe, Hans-Joachim; Gurlo, Aleksander

2013-02-01

The high-resolution transmission electron microscopy (HR-TEM) is used to study, in situ, spatially resolved decomposition in individual nanocrystals of metal hydroxides and oxyhydroxides. This case study reports on the decomposition of indium hydroxide (c-In(OH)3) to bixbyite-type indium oxide (c-In2O3). The electron beam is focused onto a single cube-shaped In(OH)3 crystal of {100} morphology with ca. 35 nm edge length and a sequence of HR-TEM images was recorded during electron beam irradiation. The frame-by-frame analysis of video sequences allows for the in situ, time-resolved observation of the shape and orientation of the transformed crystals, which in turn enables the evaluation of the kinetics of c-In2O3 crystallization. Supplementary material (video of the transformation) related to this article can be found online at 10.1016/j.jssc.2012.09.022. After irradiation the shape of the parent cube-shaped crystal is preserved, however, its linear dimension (edge) is reduced by the factor 1.20. The corresponding spotted selected area electron diffraction (SAED) pattern representing zone [001] of c-In(OH)3 is transformed to a diffuse strongly textured ring-like pattern of c-In2O3 that indicates the transformed cube is no longer a single crystal but is disintegrated into individual c-In2O3 domains with the size of about 5-10 nm. The induction time of approximately 15 s is estimated from the time-resolved Fourier transforms. The volume fraction of the transformed phase (c-In2O3), calculated from the shrinkage of the parent c-In(OH)3 crystal in the recorded HR-TEM images, is used as a measure of the kinetics of c-In2O3 crystallization within the framework of Avrami-Erofeev formalism. The Avrami exponent of ˜3 is characteristic for a reaction mechanism with fast nucleation at the beginning of the reaction and subsequent three-dimensional growth of nuclei with a constant growth rate. The structural transformation path in reconstructive decomposition of c-In(OH)3 to c-In2O3 is discussed in terms of (i) the displacement of hydrogen atoms that lead to breaking the hydrogen bond between OH groups of [In(OH)6] octahedra and finally to their destabilization and (ii) transformation of the vertices-shared indium-oxygen octahedra in c-In(OH)3 to vertices- and edge-shared octahedra in c-In2O3.

Cryo-quenched Fe-Ni-Cr alloy single crystals: A new decorative steel

DOE PAGES

Boatner, Lynn A.; Kolopus, James A.; Lavrik, Nicolay V.; ...

2016-08-31

In this paper, a decorative steel is described that is formed by a process that is unlike that of the fabrication methods utilized in making the original Damascus steels over 2000 years ago. The decorative aspect of the steel arises from a three-dimensional surface pattern that results from cryogenically quenching polished austenitic alloy single crystals into the martensitic phase that is present below 190 K. No forging operations are involved – the mechanism is entirely based on the metallurgical phase properties of the ternary alloy. The symmetry of the decorative pattern is determined and controlled by the crystallographic orientation andmore » symmetry of the 70%Fe,15%Ni,15%Cr alloy single crystals. Finally, in addition to using “cuts” made along principal crystallographic surface directions, an effectively infinite number of other random-orientation “cuts” can be utilized to produce decorative patterns where each pattern is unique after the austenitic-to-martensitic phase transformation.« less

The composite structure of mixed τ-(Ag, Cu)xV2O5 bronzes—Evidence for T dependant guest-species ordering and mobility

NASA Astrophysics Data System (ADS)

Hermes, Wilfred; Dollé, Mickaël; Rozier, Patrick; Lidin, Sven

2013-03-01

The complex structural behavior of τ-[AgCu]˜0.92V4O10 has been elucidated by single crystal X-ray diffraction and thermal analysis. The τ-phase region is apparently composed of several distinct phases and this study identifies at least three: τ1rt, τ2rt and τlt. τ1rt and τ2rt have slightly different compositions and crystal habits. Both phases transform to τlt at low temperature. The room temperature modification τ1rt crystallizes in an incommensurately modulated structure with monoclinic symmetry C2(0β1/2) [equivalent to no 5.4, B2(01/2γ) in the Intnl. Tables for Crystallography, Volume C] and the cell parameters a=11.757(4) Å, b=3.6942(5) Å c=9.463(2) Å β=114.62(2)° and the q-vector (0 0.92 1/2), but it is more convenient to transform this to a setting with a non-standard centering X=(1/2 1/2 0 0; 0 0 1/2 1/2; 1/2 1/2 1/2 1/2;) and an axial q vector (0 0.92 0). The structure features a vanadate host lattice with Cu and Ag guests forming an incommensurate composite. The structural data indicates perfect Ag/Cu ordering. At low temperature this modification is replaced by a triclinic phase characterized by two independent q-vectors. The τ2rt phase is similar to the low temperature modification τlt but the satellite reflections are generally more diffuse.

Pathways for Metastable Carbonate Synthesis

NASA Astrophysics Data System (ADS)

Whittaker, Michael L.

Carbonate minerals are integral to life on earth, as reservoirs for CO 2 in the earth's natural carbon cycle and as the skeletal elements of abundant organisms like corals and plankton. Because of its relevance, availability, and low toxicity, calcium carbonate is also an important model system for phase transformations in aqueous solutions. However, it often does not conform to classical theories of nucleation, prompting a critical reevaluation of both the pathways of carbonate mineralization and the theories that describe them. Most importantly, it has been shown that amorphous calcium carbonate (ACC) is frequently a precursor to crystalline calcium carbonate during precipitation, in both biological and inorganic systems. Amorphous precursors influence phase transformations in several ways, including decoupling densification of ions in solution from their arrangement on a crystalline lattice, altering solution thermodynamics, creating new interfaces, and changing kinetic barriers. To exert control over these processes in vivo, organisms generally confine precipitation reactions to small volumes, often within lipid membrane vesicles. Herein, I describe in vitro model systems designed to elucidate and replicate biological mineralization pathways. Giant unilamellar vesicles are shown to slow the rate of crystallization of ACC by excluding nucleation accelerants, and by preserving the high kinetic barriers to lower energy phases that result. Phosphatidylcholine, one of the most abundant natural lipids, does not interact strongly with ACC, but the interfacial chemistry canbe tuned by changing the lipid charge or reducing steric shielding. Microfluidically produced water-in-oil emulsions were used as liposome analogs to study crystallization kinetics. In ensembles of hundreds of emulsion drops, we show that vaterite forms from ACC via a classical, two-step nucleation process. We also extend the classical theory of nucleation to highly confined aqueous systems, where the formation of a nucleus changes the system composition. In systems chemically similar to ACC, amorphous strontium carbonate (ASC) is also observed in liposomes, but crystallizes rapidly, while amorphous barium carbonate (ABC) is not. We show that ACC can be made with over 50% barium, forming ACBC, but crystallizes at a dramatically faster rate with increasing barium. I demonstrate that this process dramatically departs from the classical description applied to ACC crystallization. It can be explained by the increasing short- and mid-range order in ACBC with increasing barium, which resembles that of crystalline Ca1-xBaxCO3 and selectively lowers the barrier to its formation relative to lower-energy structures. This Ca1-xBaxCO3 phase has been misidentified as calcite in the literature, but we solve the structure, assign the new spacegroup R3m, and call it balcite. Balcite is only thermodynamically stable above 525°C, and is over 30% harder than calcite. In the absence of calcium, I show that ABC is a highly transient precursor to a previously uncharacterized BaCO3·H2 O phase. This phase forms as very thin (10 nm) and extremely anisotropic platelets, which themselves recrystallize rapidly into witherite (BaCO 3). These examples demonstrate the power of amorphous precursors to enable metastable crystalline materials through thermodynamically downhill transformations, and the ability of confined volumes to reduce the rate of these transformations and enable their quantification.

Microstructural Formations and Phase Transformation Pathways in Hot Isostatically Pressed Tantalum Carbides

DTIC Science & Technology

2012-01-01

and wear-resistant brake liners. The phase diagram for the tantalum–carbon system [5] is shown in Fig. 1a with corresponding crystal structures shown... structure ), with carbon atoms occupying the octahe- dral interstitial sites in a tantalum face-centered cubic (fcc) lattice [2,7]. The carbon-deficient...carbon sublattice. The allotropic phase trans- formation temperature between a-Ta2C (CdI2 antitype structure ) and b (L’3 structure ) is 2300 K [1,7]. In

The Influence of Alloying and Processing on the Microstructure and Properties of Beta-NiAl.

DTIC Science & Technology

1998-09-30

transformation , such as the Heusler alloys .’J. 9 ] It is the purpose of this article to report crystal structure of the parent and martensite phases and...additions, thermal and constitutional vacancies, deviations from stoichiometry, processing defects/inhomogeneities and precipitate phases on both the low ...Mn-Al Heusler alloys aged at phase , in the Ni-Al-Mn alloys quenched from high tern- low temperatures. peratures over 1000 °C.t41 In these specimens

Direct Observation of the Thickness-Induced Crystallization and Stress Build-Up during Sputter-Deposition of Nanoscale Silicide Films.

PubMed

Krause, Bärbel; Abadias, Gregory; Michel, Anny; Wochner, Peter; Ibrahimkutty, Shyjumon; Baumbach, Tilo

2016-12-21

The kinetics of phase transitions during formation of small-scale systems are essential for many applications. However, their experimental observation remains challenging, making it difficult to elucidate the underlying fundamental mechanisms. Here, we combine in situ and real-time synchrotron X-ray diffraction (XRD) and X-ray reflectivity (XRR) experiments with substrate curvature measurements during deposition of nanoscale Mo and Mo 1-x Si x films on amorphous Si (a-Si). The simultaneous measurements provide direct evidence of a spontaneous, thickness-dependent amorphous-to-crystalline (a-c) phase transition, associated with tensile stress build-up and surface roughening. This phase transformation is thermodynamically driven, the metastable amorphous layer being initially stabilized by the contributions of surface and interface energies. A quantitative analysis of the XRD data, complemented by simulations of the transformation kinetics, unveils an interface-controlled crystallization process. This a-c phase transition is also dominating the stress evolution. While stress build-up can significantly limit the performance of devices based on nanostructures and thin films, it can also trigger the formation of these structures. The simultaneous in situ access to the stress signal itself, and to its microstructural origins during structure formation, opens new design routes for tailoring nanoscale devices.

In situ X-ray diffraction strain-controlled study of Ti–Nb–Zr and Ti–Nb–Ta shape memory alloys: crystal lattice and transformation features

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

Dubinskiy, S.; National University of Science and Technology “MISIS”, 4, Leninskiy prosp., Moscow 119049; Prokoshkin, S.

2014-02-15

Phase and structure transformations in biomedical Ti–21.8Nb–6.0Zr (TNZ) and Ti–19.7Nb–5.8Ta (TNT) shape memory alloys (at.%) under and without load in the − 150 to 100 °S temperature range are studied in situ using an original tensile module for a low-temperature chamber of an X-ray diffractometer. Alpha″- and beta-phase lattice parameters, the crystallographic resource of recovery strain, phase and structure transformation sequences, and microstress appearance and disappearance are examined, compared and discussed. For both alloys, the crystallographic resource of recovery strain decreases with temperature increase to become 4.5% for TNZ and 2.5% for TNT alloy (at RT). Loading at low temperaturesmore » leads to additional α″-phase formation and reorientation. Heating under load, as compared to strain-free heating, affects the reverse transformation sequence of both alloys in different ways. For TNZ alloy, strain-free heating results in simultaneous ω→β and α″→β transformations, whereas during heating under stress, they are sequential: β + ω→α″ precedes α″→β. For TNT alloy, strain-free heating results in reverse α″→β transformation, whereas during heating under stress, α″→β transformation is preceded by α″-phase reorientation. - Highlights: • Comparative in situ XRD analysis of Ti–Nb–Zr(Ta) shape memory alloys is realized. • Lattice parameters of β- and α″-phases are calculated in the − 150 to + 100 °C range. • The higher the temperature, the lower the α″→β transformation strain. • Loading at low temperatures results in α″-phase formation and reorientation. • Transformation sequences upon heating with and without loading are different.« less

Kinetics and mechanism of the pressure-induced lamellar order/disorder transition in phosphatidylethanolamine: a time-resolved X-ray diffraction study.

PubMed

Mencke, A P; Caffrey, M

1991-03-05

By using synchrotron radiation, a movie was made of the X-ray scattering pattern from a biological liquid crystal undergoing a phase transition induced by a pressure jump. The system studied includes the fully hydrated phospholipid dihexadecylphosphatidylethanolamine in the lamellar gel (L beta') phase at a temperature of 68 degrees C and a pressure of 9.7 MPa (1400 psig). Following the rapid release of pressure to atmospheric the L beta' phase transforms slowly into the lamellar liquid crystal (L alpha) phase. The pressure perturbation is applied with the intention of producing a sudden phase disequilibrium followed by monitoring the system as it relaxes to its new equilibrium condition. Remarkably, the proportion of sample in the L alpha phase grows linearly with time, taking 37 s to totally consume the L beta' phase. The time dependencies of radius, peak intensity, and width of the powder diffraction ring of the low-angle (001) lamellar reflections were obtained from the movie by image processing. The concept of an "effective pressure" is introduced to account for the temperature variations that accompany the phase transition and to establish that the observed large transit time is indeed intrinsic to the sample and not due to heat exchange with the environment. The reverse transformation, L alpha to L beta', induced by a sudden jump from atmospheric pressure to 9.7 MPa, is complete in less than 13 s. These measurements represent a new approach for studying the kinetics of lipid phase transitions and for gaining insights into the mechanism of the lamellar order/disorder transition.

Dielectric properties and phase transition behaviors in (1-x)PbZrO3-xPb(Mg1/2W1/2)O3 ceramics

NASA Astrophysics Data System (ADS)

Vittayakorn, Naratip; Charoonsuk, Piyanut; Kasiansin, Panisara; Wirunchit, Supamas; Boonchom, Banjong

2009-09-01

The solid solution of lead zirconate [PbZrO3 (PZ)] and lead magnesium tungstate [Pb(Mg1/2W1/2)O3 (PMW)] has been synthesized by the wolframite precursor method. The crystal structure, phase transformations, dielectric and thermal properties of (1-x)PZ-xPMW, where x =0.00-0.10, were investigated. The crystal structure of sintered ceramics was analyzed by x-ray diffraction. Phase-pure perovskite was obtained for all compositions. Furthermore, a change from orthorhombic to rhombohedral symmetry was observed as the mole fraction of increased PMW. As a result, it was found that PbZrO3-Pb(Mg1/2W1/2)O3 undergoes successive transitions from the antiferroelectric phase to the ferroelectric phase to the paraelectric state. The coexistence of orthorhombic and rhombohedral phases in this binary system is located near the composition x =0.1.

Nonlinear unitary transformations of space-variant polarized light fields from self-induced geometric-phase optical elements

NASA Astrophysics Data System (ADS)

Kravets, Nina; Brasselet, Etienne

2018-01-01

We propose to couple the optical orientational nonlinearities of liquid crystals with their ability to self-organize to tailor them to control space-variant-polarized optical fields in a nonlinear manner. Experimental demonstration is made using a liquid crystal light valve that behaves like a light-driven geometric phase optical element. We also unveil two original nonlinear optical processes, namely self-induced separability and nonseparability. These results contribute to the advancement of nonlinear singular optics that is still in its infancy despite 25 years of effort, which may foster the development of nonlinear protocols to manipulate high-dimensional optical information both in the classical and quantum regimes.

Selective and reusable iron(II)-based molecular sensor for the vapor-phase detection of alcohols.

PubMed

Naik, Anil D; Robeyns, Koen; Meunier, Christophe F; Léonard, Alexandre F; Rotaru, Aurelian; Tinant, Bernard; Filinchuk, Yaroslav; Su, Bao Lian; Garcia, Yann

2014-02-03

A mononuclear iron(II) neutral complex (1) is screened for sensing abilities for a wide spectrum of chemicals and to evaluate the response function toward physical perturbation like temperature and mechanical stress. Interestingly, 1 precisely detects methanol among an alcohol series. The sensing process is visually detectable, fatigue-resistant, highly selective, and reusable. The sensing ability is attributed to molecular sieving and subsequent spin-state change of iron centers, after a crystal-to-crystal transformation.

The behavior of commensurate-incommensurate transitions using the phase field crystal model

NASA Astrophysics Data System (ADS)

Zhang, Tinghui; Lu, Yanli; Chen, Zheng

2018-02-01

We study the behavior of the commensurate-incommensurate (CI) transitions by using a phase field crystal model. The model is capable of modeling both elastic and plastic deformation and can simulate the evolution of the microstructure of the material at the atomic scale and the diffusive time scale, such as for adsorbed monolayer. Specifically, we study the behavior of the CI transitions as a function of lattice mismatch and the amplitude of substrate pinning potential. The behavior of CI phase transitions is revealed with the increase of the amplitude of pinning potential in some certain lattice mismatches. We find that for the negative lattice mismatch absorbed monolayer undergoes division, reorganization and displacement as increasing the amplitude of substrate pinning potential. In addition, for the positive mismatch absorbed monolayer undergoes a progress of phase transformation after a complete grain is split. Our results accord with simulations for atomic models of absorbed monolayer on a substrate surface.

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

Epitaxial growth of three dimensionally structured III-V photonic crystal via hydride vapor phase epitaxy

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

Zheng, Qiye; Kim, Honggyu; Zhang, Runyu

2015-12-14

Three-dimensional (3D) photonic crystals are one class of materials where epitaxy, and the resultant attractive electronic properties, would enable new functionalities for optoelectronic devices. Here we utilize self-assembled colloidal templates to fabricate epitaxially grown single crystal 3D mesostructured GaxIn1-xP (GaInP) semiconductor photonic crystals using hydride vapor phase epitaxy (HVPE). The epitaxial relationship between the 3D GaInP and the substrate is preserved during the growth through the complex geometry of the template as confirmed by X-ray diffraction (XRD) and high resolution transmission electron microscopy. XRD reciprocal space mapping of the 3D epitaxial layer further demonstrates the film to be nearly fullymore » relaxed with a negligible strain gradient. Fourier transform infrared spectroscopy reflection measurement indicates the optical properties of the photonic crystal which agree with finite difference time domain simulations. This work extends the scope of the very few known methods for the fabrication of epitaxial III-V 3D mesostructured materials to the well-developed HVPE technique.« less

Epitaxial growth of three dimensionally structured III-V photonic crystal via hydride vapor phase epitaxy

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

Zheng, Qiye; Kim, Honggyu; Zhang, Runyu

2015-12-14

Three-dimensional (3D) photonic crystals are one class of materials where epitaxy, and the resultant attractive electronic properties, would enable new functionalities for optoelectronic devices. Here we utilize self-assembled colloidal templates to fabricate epitaxially grown single crystal 3D mesostructured Ga{sub x}In{sub 1−x}P (GaInP) semiconductor photonic crystals using hydride vapor phase epitaxy (HVPE). The epitaxial relationship between the 3D GaInP and the substrate is preserved during the growth through the complex geometry of the template as confirmed by X-ray diffraction (XRD) and high resolution transmission electron microscopy. XRD reciprocal space mapping of the 3D epitaxial layer further demonstrates the film to bemore » nearly fully relaxed with a negligible strain gradient. Fourier transform infrared spectroscopy reflection measurement indicates the optical properties of the photonic crystal which agree with finite difference time domain simulations. This work extends the scope of the very few known methods for the fabrication of epitaxial III-V 3D mesostructured materials to the well-developed HVPE technique.« less

On the existence of declared 9R phase in Fe–Ni invar alloy

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

Kabanova, I. G.; Sagaradze, V. V., E-mail: vsagaradze@imp.uran.ru; Kataeva, N. V.

2016-07-15

An analysis of recently reported electron diffraction patterns suggests that metastable austenitic Fe–32Ni alloy subjected to α → γ transformation upon slow heating does not exhibit any signs of formation of the 9R phase; the conventional nanocrystalline γ phase with an fcc lattice is formed instead. Extended lamellae with a layered structure, erroneously identified as a new phase of the (3R + 9R) type in Fe–32Ni alloy, are conventional twinning (midrib) regions of each initial α crystal, in which γ-phase twin nanolamellae are formed upon heating.

A stress-induced phase transition model for semi-crystallize shape memory polymer

NASA Astrophysics Data System (ADS)

Guo, Xiaogang; Zhou, Bo; Liu, Liwu; Liu, Yanju; Leng, Jinsong

2014-03-01

The developments of constitutive models for shape memory polymer (SMP) have been motivated by its increasing applications. During cooling or heating process, the phase transition which is a continuous time-dependent process happens in semi-crystallize SMP and the various individual phases form at different temperature and in different configuration. Then, the transformation between these phases occurred and shape memory effect will emerge. In addition, stress applied on SMP is an important factor for crystal melting during phase transition. In this theory, an ideal phase transition model considering stress or pre-strain is the key to describe the behaviors of shape memory effect. So a normal distributed model was established in this research to characterize the volume fraction of each phase in SMP during phase transition. Generally, the experiment results are partly backward (in heating process) or forward (in cooling process) compared with the ideal situation considering delay effect during phase transition. So, a correction on the normal distributed model is needed. Furthermore, a nonlinear relationship between stress and phase transition temperature Tg is also taken into account for establishing an accurately normal distributed phase transition model. Finally, the constitutive model which taking the stress as an influence factor on phase transition was also established. Compared with the other expressions, this new-type model possesses less parameter and is more accurate. For the sake of verifying the rationality and accuracy of new phase transition and constitutive model, the comparisons between the simulated and experimental results were carried out.

Structures, Phase Transitions and Tricritical Behavior of the Hybrid Perovskite Methyl Ammonium Lead Iodide

DOE PAGES

Whitfield, P. S.; Herron, N.; Guise, W. E.; ...

2016-10-21

Here, we examine the crystal structures and structural phase transitions of the deuterated, partially deuterated and hydrogenous organic-inorganic hybrid perovskite methyl ammonium lead iodide (MAPbI 3) using time-of-flight neutron and synchrotron X-ray powder diffraction. Near 330 K the high temperature cubic phases transformed to a body-centered tetragonal phase. The variation of the order parameter Q for this transition scaled with temperature T as Q (T c-T) , where T c is the critical temperature and the exponent was close to , as predicted for a tricritical phase transition. We also observed coexistence of the cubic and tetragonal phases over amore » range of temperature in all cases, demonstrating that the phase transition was in fact first-order, although still very close to tricritical. Upon cooling further, all the tetragonal phases transformed into a low temperature orthorhombic phase around 160 K, again via a first-order phase transition. Finally, based upon these results, we discuss the impact of the structural phase transitions upon photovoltaic performance of MAPbI 3 based solar cells.« less

A level set approach for shock-induced α-γ phase transition of RDX

NASA Astrophysics Data System (ADS)

Josyula, Kartik; Rahul; De, Suvranu

2018-02-01

We present a thermodynamically consistent level sets approach based on regularization energy functional which can be directly incorporated into a Galerkin finite element framework to model interface motion. The regularization energy leads to a diffusive form of flux that is embedded within the level sets evolution equation which maintains the signed distance property of the level set function. The scheme is shown to compare well with the velocity extension method in capturing the interface position. The proposed level sets approach is employed to study the α-γphase transformation in RDX single crystal shocked along the (100) plane. Example problems in one and three dimensions are presented. We observe smooth evolution of the phase interface along the shock direction in both models. There is no diffusion of the interface during the zero level set evolution in the three dimensional model. The level sets approach is shown to capture the characteristics of the shock-induced α-γ phase transformation such as stress relaxation behind the phase interface and the finite time required for the phase transformation to complete. The regularization energy based level sets approach is efficient, robust, and easy to implement.

Discovery of carbon-vacancy ordering in Nb4AlC3–x under the guidance of first-principles calculations

PubMed Central

Zhang, Hui; Hu, Tao; Wang, Xiaohui; Li, Zhaojin; Hu, Minmin; Wu, Erdong; Zhou, Yanchun

2015-01-01

The conventional wisdom to tailor the properties of binary transition metal carbides by order-disorder phase transformation has been inapplicable for the machinable ternary carbides (MTCs) due to the absence of ordered phase in bulk sample. Here, the presence of an ordered phase with structural carbon vacancies in Nb4AlC3–x (x ≈ 0.3) ternary carbide is predicted by first-principles calculations, and experimentally identified for the first time by transmission electron microscopy and micro-Raman spectroscopy. Consistent with the first-principles prediction, the ordered phase, o-Nb4AlC3, crystalizes in P63/mcm with a = 5.423 Å, c = 24.146 Å. Coexistence of ordered (o-Nb4AlC3) and disordered (Nb4AlC3–x) phase brings about abundant domains with irregular shape in the bulk sample. Both heating and electron irradiation can induce the transformation from o-Nb4AlC3 to Nb4AlC3–x. Our findings may offer substantial insights into the roles of carbon vacancies in the structure stability and order-disorder phase transformation in MTCs. PMID:26388153

Glass formation and crystallization in the alumina-silica-lanthanum phosphate system for ceramics composites

NASA Astrophysics Data System (ADS)

Guo, Shuling

The formation, structure, and dynamics of glasses in the alumina-silica-lanthanum phosphate system and their crystallization were investigated as a function of composition. These are of interest because of their potential as precursors for synthesizing ceramic-matrix-composites via co-crystallization of lanthanum monazite and either mullite or alumina into finely mixed microstructures. The glasses were characterized by X-Ray Diffraction (XRD), Raman spectroscopy, Differential Scanning Calorimetry (DSC), Nuclear Magnetic Resonance (NMR), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), and Electron Energy Loss Spectrometry (EELS). Glass formation from rapidly quenched liquids was easiest and most consistent for compositions containing silica, such as for mullitemonazite compositions, and more difficult for alumina-monazite compositions. For mullite-monazite glasses, the glass transition temperatures increased linearly from 845°C to 906°C with increasing mullite content. An analysis of the glass structure indicated a network consisting of corner-linked aluminate, silicate and phosphate tetrahedra where aluminum played a central role of separating silicon and phosphorous. It was hypothesized that the glass network consisted of domains of aluminum silicate network edged by phosphate tetrahedra. A maximum in the crystallization temperature was attributed to the complexity of the glass network. At relatively mullite-rich compositions, simultaneous and cooperative crystallization of lanthanum phosphate and mullite correlated with the highest crystallization temperatures, and the lowest activation energies of crystallization. This was preceded by amorphous phase segregation in the glass at lower temperatures. An intermediate phase of lanthanum phosphate was discovered with an orthorhombic unit cell. For compositions of high phosphate contents, lanthanum phosphate precipitated first at about 900°C leaving an essentially pure mullite glass. Mullite crystallized at about 1000°C, matching the conditions for crystallizing pure mullite glass. The phosphate phase transformed to monazite at even higher temperatures. No amorphous phase segregation was observed in these cases. Microstructures were correlated with nucleation and growth conditions such that the continuous and isolated phases could be manipulated. Optimum nucleation temperatures were close to the glass transition temperature. Conditions were identified for forming a continuous boundary phase of monazite that isolated mullite grains, which is desired for fabricating ceramic-matrix-composites.

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.

CRYSTAL AND MORPHOLOGICAL PHASE TRANSFORMATION OF LEAD IN THE PRESENCE OF ORTHOPHOSPHATE

EPA Science Inventory

The use of phosphates in the drinking water industry is well known. Orthophosphate is used to reduce lead levels at the consumer’s tap by forming a relatively insoluble divalent lead orthophosphate compounds on the surface of the lead source (e.g., lead service line, brass fixtur...

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.

Vapor-phase hydrothermal transformation of HTiOF3 intermediates into {001} faceted anatase single-crystalline nanosheets.

PubMed

Liu, Porun; Wang, Yun; Zhang, Haimin; An, Taicheng; Yang, Huagui; Tang, Zhiyong; Cai, Weiping; Zhao, Huijun

2012-12-07

For the first time, a facile, one-pot hydrofluoric acid vapor-phase hydrothermal (HF-VPH) method is demonstrated to directly grow single-crystalline anatase TiO(2) nanosheets with 98.2% of exposed {001} faceted surfaces on the Ti substrate via a distinctive two-stage formation mechanism. The first stage produces a new intermediate crystal (orthorhombic HTiOF(3) ) that is transformed into anatase TiO(2) nanosheets during the second stage. The findings reveal that the HF-VPH reaction environment is unique and differs remarkably from that of liquid-phase hydrothermal processes. The uniqueness of the HF-VPH conditions can be readily used to effectively control the nanostructure growth. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Retrieving cirrus microphysical properties from stellar aureoles

NASA Astrophysics Data System (ADS)

DeVore, J. G.; Kristl, J. A.; Rappaport, S. A.

2013-06-01

The aureoles around stars caused by thin cirrus limit nighttime measurement opportunities for ground-based astronomy, but can provide information on high-altitude ice crystals for climate research. In this paper we attempt to demonstrate quantitatively how this works. Aureole profiles can be followed out to ~0.2° from stars and ~0.5° from Jupiter. Interpretation of diffracted starlight is similar to that for sunlight, but emphasizes larger particles. Stellar diffraction profiles are very distinctive, typically being approximately flat out to a critical angle followed by gradually steepening power-law falloff with slope less steep than -3. Using the relationship between the phase function for diffraction and the average Fourier transform of the projected area of complex ice crystals, we show that defining particle size in terms of average projected area normal to the propagation direction of the starlight leads to a simple, analytic approximation representing large-particle diffraction that is nearly independent of crystal habit. A similar analytic approximation for the diffraction aureole allows it to be separated from the point spread function and the sky background. Multiple scattering is deconvolved using the Hankel transform leading to the diffraction phase function. Application of constrained numerical inversion to the phase function then yields a solution for the particle size distribution in the range between ~50 μm and ~400 μm. Stellar aureole measurements can provide one of the very few, as well as least expensive, methods for retrieving cirrus microphysical properties from ground-based observations.

Vibrational properties of Ni-Mn-Ga shape memory alloy in the martensite phases

NASA Astrophysics Data System (ADS)

Ener, Semih; Mehaddene, Tarik; Pedersen, Björn; Leitner, Michael; Neuhaus, Jürgen; Petry, Winfried

2013-12-01

Studying the phonon dispersion of the ferromagnetic shape memory alloy system Ni-Mn-Ga gives insight into the mechanism of the martensite transition and the forces driving the transition. Transformation of austenite single crystals under uniaxial stress results in the coexistence of two martensitic variants with perpendicular modulation vector. Here we report on inelastic neutron scattering studies of martensite crystals with off-stoichiometric compositions, varying from non-modulated (NM) to five- (5M) and seven- (7M) layer modulated martensite phases. Both the 5M and 7M crystals show fully commensurate satellite peaks along [\\xi \\bar {\\xi } 0], corresponding to the five- and seven-layer modulation. These superstructure peaks become Γ-points of the modulated structure. Due to the coexistence of two variants within the (001) plane, both new acoustic phonons reflecting the modulation vector [\\xi \\bar {\\xi } 0] and acoustic TA2[ξξ0] phonons corresponding to the non-modulated direction are observed. The latter display a pronounced softening around ξ = 0.2-0.4 when approaching the martensite-austenite transition from above and below, i.e. this soft mode has lowest frequency at the transition temperature. Overall the phonon dispersion of the austenite and martensite phase resemble each other very much. The coexistence of two martensitic variants after uniaxial transformation explains the particular behaviour of the low-energy excitations, in contrast to previous interpretations involving charge-density waves and associated phason modes.

500 keV Ar2+ ion irradiation induced anatase to brookite phase transformation and ferromagnetism at room temperature in TiO2 thin films

NASA Astrophysics Data System (ADS)

Bharati, B.; Mishra, N. C.; Kanjilal, D.; Rath, Chandana

2018-01-01

In our earlier report, where we have demonstrated ferromagnetic behavior at room temperature (RT) in TiO2 thin films deposited through electron beam evaporation technique followed by annealing either in Ar or O2 atmosphere [Mohanty et al., Journal of Magnetism and Magnetic Materials 355 (2014) 240-245], here we have studied the evolution of structure and magnetic properties after irradiating the TiO2 thin films with 500 keV Ar2+ ions. The pristine film while exhibits anatase phase, the films become amorphous after irradiating at fluence in the range 1 × 1014 to 1 × 1016 ions/cm2. Increasing the fluence up to 5 × 1016 ions/cm2, amorphous to crystalline phase transformation occurs and the structure becomes brookite. Although anatase to rutile phase transformation is usually reported in literatures, anatase to brookite phase transformation is an unusual feature which we have reported here for the first time. Such anatase to brookite phase transformation is accompanied with grain growth without showing any change in film thickness evidenced from Rutherford's Back Scattering (RBS) measurement. From scanning probe micrographs (SPM), roughness is found to be more in amorphous films than in the crystalline ones. Anatase to brookite phase transformation could be realized by considering the importance of intermediate amorphous phase. Because due to amorphous phase, heat deposited by energetic ions are localized as dissipation of heat is less and as a result, the localized region crystallizes in brookite phase followed by grain growth as observed in highest fluence. Further, we have demonstrated ferromagnetic behavior at RT in irradiated films similar to pristine one, irrespective of their phase and crystallinity. Origin for room temperature ferromagnetism (RTFM) is attributed to the presence of oxygen vacancies which is confirmed by carrying out XPS measurement.

Crystallization and properties of Sr-Ba aluminosilicate glass-ceramic matrices

NASA Technical Reports Server (NTRS)

Bansal, Narottam P.; Hyatt, Mark J.; Drummond, Charles H., III

1991-01-01

Powders of roller quenched (Sr,Ba)O-Al2O3-2SiO2 glasses of various compositions were uniaxially pressed into bars and hot isostatically pressed at 1350 C for 4 hours or cold isostatically pressed and sintered at different temperatures between 800 to 1500 C for 10 or 20 hours. Densities, flexural strengths, and linear thermal expansion were measured for three compositions. The glass transition and crystallization temperatures were determined by Differential Scanning Calorimetry (DSC). The liquidus and crystallization temperature from the melt were measured using high temperature Differential Thermal Analysis (DTA). Crystalline phases formed on heat treatment of the glasses were identified by powder X ray diffraction. In Sr containing glasses, the monoclinic celsian phase always crystallized at temperatures above 1000 C. At lower temperatures, the hexagonal analog formed. The temperature for orthorhombic to hexagonal structural transformation increased monotonically with SrO content, from 327 C for BaO-Al2O3-2SiO2 to 758 C for SrO-Al2O3-2SiO2. These glass powders can be sintered to almost full densities and monoclinic celsian phase at a relatively low temperature of 1100 C.

Crystallization and properties of Sr-Ba aluminosilicate glass-ceramic matrices

NASA Technical Reports Server (NTRS)

Bansal, Narottam P.; Hyatt, Mark J.; Drummond, Charles H., III

1991-01-01

Powders of roller quenched (Sr,Ba)O-Al2O3-2SiO2 glasses of various compositions were uniaxially pressed into bars and hot isostatically pressed at 1350 C for 4 hours or cold isostatically pressed and sintered at different temperatures between 800 to 1500 C for 10 or 20 hours. Densities, flexural strengths, and linear thermal expansion were measured for three compositions. The glasss transition and crystallization temperatures were determined by Differential Scanning Calorimetry (DSC). The liquidus and crystallization temperature from the melt were measured using high temperature Differential Thermal Analysis (DTA). Crystalline phases formed on heat treatment of the glasses were identified by powder x ray diffraction. In Sr containing glasses, the monoclinic celsian phase always crystallized at temperatures above 1000 C. At lower temperatures, the hexagonal analog formed. The temperature for orthorhombic to hexagonal structure transformation increased monotonically with SrO content, from 327 C for BaO-Al2O3-2SiO2 to 758 C for SrO-Al2O3-2SiO2. These glass powders can be sintered to almost full densities and monoclinic celsian phase at a relatively low temperature of 1100 C.

Sculpting Nanoscale Functional Channels in Complex Oxides Using Energetic Ions and Electrons

DOE PAGES

Sachan, Ritesh; Zarkadoula, Eva; Ou, Xin; ...

2018-04-26

The formation of metastable phases has attracted significant attention because of their unique properties and potential functionalities. In the present study, we demonstrate the phase conversion of energetic-ion-induced amorphous nanochannels/tracks into a metastable defect fluorite in A 2B 2O 7 structured complex oxides by electron irradiation. Through in situ electron irradiation experiments in a scanning transmission electron microscope, we observe electron-induced epitaxial crystallization of the amorphous nanochannels in Yb 2Ti 2O 7 into the defect fluorite. This energetic-electron-induced phase transformation is attributed to the coupled effect of ionization-induced electronic excitations and local heating, along with subthreshold elastic energy transfers. Wemore » also show the role of ionic radii of A-site cations (A = Yb, Gd, and Sm) and B-site cations (Ti and Zr) in facilitating the electron-beam-induced crystallization of the amorphous phase to the defect-fluorite structure. The formation of the defect-fluorite structure is eased by the decrease in the difference between ionic radii of A- and B-site cations in the lattice. Molecular dynamics simulations of thermal annealing of the amorphous phase nanochannels in A 2B 2O 7 draw parallels to the electron-irradiation-induced crystallization and confirm the role of ionic radii in lowering the barrier for crystallization. Furthermore, these results suggest that employing guided electron irradiation with atomic precision is a useful technique for selected area phase formation in nanoscale printed devices.« less

Sculpting Nanoscale Functional Channels in Complex Oxides Using Energetic Ions and Electrons

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

Sachan, Ritesh; Zarkadoula, Eva; Ou, Xin

The formation of metastable phases has attracted significant attention because of their unique properties and potential functionalities. In the present study, we demonstrate the phase conversion of energetic-ion-induced amorphous nanochannels/tracks into a metastable defect fluorite in A 2B 2O 7 structured complex oxides by electron irradiation. Through in situ electron irradiation experiments in a scanning transmission electron microscope, we observe electron-induced epitaxial crystallization of the amorphous nanochannels in Yb 2Ti 2O 7 into the defect fluorite. This energetic-electron-induced phase transformation is attributed to the coupled effect of ionization-induced electronic excitations and local heating, along with subthreshold elastic energy transfers. Wemore » also show the role of ionic radii of A-site cations (A = Yb, Gd, and Sm) and B-site cations (Ti and Zr) in facilitating the electron-beam-induced crystallization of the amorphous phase to the defect-fluorite structure. The formation of the defect-fluorite structure is eased by the decrease in the difference between ionic radii of A- and B-site cations in the lattice. Molecular dynamics simulations of thermal annealing of the amorphous phase nanochannels in A 2B 2O 7 draw parallels to the electron-irradiation-induced crystallization and confirm the role of ionic radii in lowering the barrier for crystallization. Furthermore, these results suggest that employing guided electron irradiation with atomic precision is a useful technique for selected area phase formation in nanoscale printed devices.« less

Generalized Finsler geometric continuum physics with applications in fracture and phase transformations

NASA Astrophysics Data System (ADS)

Clayton, J. D.

2017-02-01

A theory of deformation of continuous media based on concepts from Finsler differential geometry is presented. The general theory accounts for finite deformations, nonlinear elasticity, and changes in internal state of the material, the latter represented by elements of a state vector of generalized Finsler space whose entries consist of one or more order parameter(s). Two descriptive representations of the deformation gradient are considered. The first invokes an additive decomposition and is applied to problems involving localized inelastic deformation mechanisms such as fracture. The second invokes a multiplicative decomposition and is applied to problems involving distributed deformation mechanisms such as phase transformations or twinning. Appropriate free energy functions are posited for each case, and Euler-Lagrange equations of equilibrium are derived. Solutions are obtained for specific problems of tensile fracture of an elastic cylinder and for amorphization of a crystal under spherical and uniaxial compression. The Finsler-based approach is demonstrated to be more general and potentially more physically descriptive than existing hyperelasticity models couched in Riemannian geometry or Euclidean space, without incorporation of supplementary ad hoc equations or spurious fitting parameters. Predictions for single crystals of boron carbide ceramic agree qualitatively, and in many instances quantitatively, with results from physical experiments and atomic simulations involving structural collapse and failure of the crystal along its c-axis.

Organic alloy systems suitable for the investigation of regular binary and ternary eutectic growth

NASA Astrophysics Data System (ADS)

Sturz, L.; Witusiewicz, V. T.; Hecht, U.; Rex, S.

2004-09-01

Transparent organic alloys showing a plastic crystal phase were investigated experimentally using differential scanning calorimetry and directional solidification with respect to find a suitable model system for regular ternary eutectic growth. The temperature, enthalpy and entropy of phase transitions have been determined for a number of pure substances. A distinction of substances with and without plastic crystal phases was made from their entropy of melting. Binary phase diagrams were determined for selected plastic crystal alloys with the aim to identify eutectic reactions. Examples for lamellar and rod-like eutectic solidification microstructures in binary systems are given. The system (D)Camphor-Neopentylglycol-Succinonitrile is identified as a system that exhibits, among others, univariant and a nonvariant eutectic reaction. The ternary eutectic alloy close to the nonvariant eutectic composition solidifies with a partially faceted solid-liquid interface. However, by adding a small amount of Amino-Methyl-Propanediol (AMPD), the temperature of the nonvariant eutectic reaction and of the solid state transformation from plastic to crystalline state are shifted such, that regular eutectic growth with three distinct nonfaceted phases is observed in univariant eutectic reaction for the first time. The ternary phase diagram and examples for eutectic microstructures in the ternary and the quaternary eutectic alloy are given.

Diffusion paths formation for Cu + ions in superionic Cu 6PS 5I single crystals studied in terms of structural phase transition

NASA Astrophysics Data System (ADS)

Gągor, A.; Pietraszko, A.; Kaynts, D.

2005-11-01

In order to understand the structural transformations leading to high ionic conductivity of Cu + ions in Cu 6PS 5I argyrodite compound, the detailed structure analysis based on single-crystal X-ray diffraction has been performed. Below the phase transition at T=(144-169) K Cu 6PS 5I belongs to monoclinic, ferroelastic phase (space group Cc) with ordered copper sublattice. Above Tc delocalization of copper ions begins and crystal changes the symmetry to cubic superstructure with space group F-43 c ( a'=19.528 Å, z=32). Finally, above T1=274 K increasing disordering of the Cu + ions heightens the symmetry to F-43 m ( a=9.794 Å, z=4). In this work, the final structural model of two cubic phases is presented including the detailed temperature evolution of positions and site occupation factors of copper ions ( R1=0.0397 for F-43 c phase, and 0.0245 for F-43 m phase). Possible diffusion paths for the copper ions are represented by means of the atomic displacement factors and split model. The structural results coincide well with the previously reported non-Arrhenius behavior of conductivity and indicate significant change in conduction mechanism.

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

PubMed

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

2011-08-10

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

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

NASA Astrophysics Data System (ADS)

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

2011-08-01

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

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.

Reaction-diffusion-induced explosive crystallization in a metal-selenium nanometer film structure

NASA Astrophysics Data System (ADS)

Kogai, V. Ya.

2016-03-01

Experimental data for reaction-diffusion-induced explosive crystallization in a nanodimensional metal (Cu, Ag)/selenium structure are presented. It is found that after the metal layer has completely diffused into the amorphous Se film, the electrical potential rises from 0.14 to 1.21 V in the Cu(30 nm)/Se(140 nm) heterolayer and from 0.01 to 1.17 V in the Ag(30 nm)/Se(140 nm) heterolayer. The metals diffusing into the amorphous Se layer interact with Se, forming nuclei of a new phase (CuSe or Ag2Se). The intense growth of the CuSe and Ag2Se crystallization centers results in a considerable liberation of latent energy in the form of phase transformation heat and in explosive growth of CuSe and Ag2Se nanocrystalline particles. The mean size of CuSe and Ag2Se crystallites equals 25 and 50 nm, respectively.

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.

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

NASA Astrophysics Data System (ADS)

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

2016-08-01

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

Interaction between Convection and Heat Transfer in Crystal Growth

NASA Technical Reports Server (NTRS)

1998-01-01

Crystals are integral components in some of our most sophisticated and rapidly developing industries. Single crystals are solids with the most uniform structures that can be obtained on an atomic scale. Because of their structural uniformity, crystals can transmit acoustic and electromagnetic waves and charged particles with essentially no scattering or interferences. This transparency, which can be selectively modified by controlled additions of impurities known as dopants, is the foundation of modern electronic industry. It has brought about widespread application of crystals in transistors, lasers, microwave devices, infrared detectors, magnetic memory devices, and many other magnets and electro-optic components. The performance of a crystal depends strongly on its compositional homogeneity. For instance, in modern microcircuitry, compositional variations of a few percent (down to a submicron length scale) can seriously jeopardize predicted yields. Since crystals are grown by carefully controlled phase transformations, the compositional adjustment in the solid is often made during growth from the nutrient. Hence, a detailed understanding of mass transfer in the nutrient is essential. Moreover, since mass transfer is often the slowest process during growth, it is usually the rate limiting mechanism. Crystal growth processes are usually classified according to the nature of the parent phase. Nevertheless, whether the growth occurs by solidification from a melt (melt growth), nucleation from a solution (solution growth), condensation from a vapor (physical vapor transport) or chemical reaction of gases (chemical vapor deposition), the parent phase is a fluid. As is with most non-equilibrium processes involving fluids, liquid or vapor, fluid motion plays an important role, affecting both the concentration and temperature gradients at the soli-liquid interface.

Why do ultrasoft repulsive particles cluster and crystallize? Analytical results from density-functional theory.

PubMed

Likos, Christos N; Mladek, Bianca M; Gottwald, Dieter; Kahl, Gerhard

2007-06-14

We demonstrate the accuracy of the hypernetted chain closure and of the mean-field approximation for the calculation of the fluid-state properties of systems interacting by means of bounded and positive pair potentials with oscillating Fourier transforms. Subsequently, we prove the validity of a bilinear, random-phase density functional for arbitrary inhomogeneous phases of the same systems. On the basis of this functional, we calculate analytically the freezing parameters of the latter. We demonstrate explicitly that the stable crystals feature a lattice constant that is independent of density and whose value is dictated by the position of the negative minimum of the Fourier transform of the pair potential. This property is equivalent with the existence of clusters, whose population scales proportionally to the density. We establish that regardless of the form of the interaction potential and of the location on the freezing line, all cluster crystals have a universal Lindemann ratio Lf=0.189 at freezing. We further make an explicit link between the aforementioned density functional and the harmonic theory of crystals. This allows us to establish an equivalence between the emergence of clusters and the existence of negative Fourier components of the interaction potential. Finally, we make a connection between the class of models at hand and the system of infinite-dimensional hard spheres, when the limits of interaction steepness and space dimension are both taken to infinity in a particularly described fashion.

Amorphous calcium carbonate transforms into calcite during sea urchin larval spicule growth

PubMed Central

Beniash, E.; Aizenberg, J.; Addadi, L.; Weiner, S.

1997-01-01

Sea urchin larvae form an endoskeleton composed of a pair of spicules. For more than a century it has been stated that each spicule comprises a single crystal of the CaCO3 mineral, calcite. We show that an additional mineral phase, amorphous calcium carbonate, is present in the sea urchin larval spicule, and that this inherently unstable mineral transforms into calcite with time. This observation significantly changes our concepts of mineral formation in this well-studied organism.

Antiferroelectric-ferroelectric phase transition in lead zinc niobate modified lead zirconate ceramics: crystal studies, microstructure, thermal and electrical properties

NASA Astrophysics Data System (ADS)

Sukkha, Usa; Muanghlua, Rangson; Niemcharoen, Surasak; Boonchoma, Banjong; Vittayakorn, Naratip

2010-08-01

The combination of antiferroelectric PbZrO3 (PZ) and relaxor ferroelectric Pb(Zn1/3Nb2/3)O3 was prepared via the columbite precursor method. The basic characterizations were performed using X-ray diffraction (XRD), scanning electron microscopy (SEM), linear thermal expansion, differential scanning calorimetry (DSC) techniques, dielectric spectroscopy, and hysteresis measurement. The XRD result indicated that the solid solubility limit of the (1- x)PZ- xPZN system was about x=0.40. The crystal structure of (1- x)PZ- xPZN transformed from orthorhombic to rhombohedral symmetry when the concentration of PZN was increased. A ferroelectric intermediate phase began to appear between the paraelectric and antiferroelectric phases of pure PZ, with increasing PZN content. In addition, the temperature range of the ferroelectric phase increased with increasing PZN concentration. The morphotropic phase boundary (MPB) in this system was located close to the composition, x=0.20.

Hollow Gaussian beam generated by beam shaping with phase-only liquid crystal spatial light modulator

NASA Astrophysics Data System (ADS)

Nie, Yongming; Li, Xiujian; Qi, Junli; Ma, Haotong; Liao, Jiali; Yang, Jiankun; Hu, Wenhua

2012-03-01

Based on the refractive beam shaping system, the transformation of a quasi-Gaussian beam into a dark hollow Gaussian beam by a phase-only liquid crystal spatial light modulator (LC-SLM) is proposed. According to the energy conservation and constant optical path principle, the phase distribution of the aspheric lens and the phase-only LC-SLM can modulate the wave-front properly to generate the hollow beam. The numerical simulation results indicate that, the dark hollow intensity distribution of the output shaped beam can be maintained well for a certain propagation distance during which the dark region will not decrease whereas the ideal hollow Gaussian beam will do. By designing the phase modulation profile, which loaded into the LC-SLM carefully, the experimental results indicate that the dark hollow intensity distribution of the output shaped beam can be maintained well even at a distance much more than 550 mm from the LC-SLM, which agree with the numerical simulation results.

Pressure-Induced Phase Transitions in the Cd-Yb Periodic Approximant to a Quasicrystal

NASA Astrophysics Data System (ADS)

Watanuki, Tetsu; Machida, Akihiko; Ikeda, Tomohiro; Aoki, Katsutoshi; Kaneko, Hiroshi; Shobu, Takahisa; Sato, Taku J.; Tsai, An Pang

2006-03-01

The phase study of a Cd-Yb 1/1 approximant crystal over a wide pressure and temperature range is crucial for the comparison study between periodic and quasiperiodic crystals. The Cd4 tetrahedra, the most inner part of the atomic clusters, exhibited various structural ordering in the orientation sensitive to pressure and temperature. Five ordered phases appeared in a P-T span up to 5.2 GPa and down to 10 K. The propagation direction of ordering alternated from [110] to ⟨111⟩ at about 1.0 GPa and again to [110] at 3.5 4.3 GPa. The primarily ordered phases that appeared by cooling to 210 250 K between 1.0 5.2 GPa further transformed to finely ordered ones at 120 155 K. Besides the original short-range type interaction, a long-range type interaction was likely developed under pressure to lead to the primary ordering of Cd4 tetrahedra. Coexistence of these interactions is responsible for the complicated phase behavior.

Low temperature synthesis of monolithic transparent Ta2O5 gels from hydrolysis of metal alkoxide

NASA Technical Reports Server (NTRS)

Bansal, Narottam P.

1993-01-01

Tantalum oxide gels in the form of transparent monoliths and powder were prepared from hydrolysis of tantalum pentaethoxide under controlled conditions using different mole ratios of Ta(OC2H5)5:C2H50H:H20:HCl. Alcohol acts as the mutual solvent and HCl as the deflocculating agent. For a fixed alkoxide:water:HCl ratio, time of gel formation increased with the alcohol to alkoxide mole ratio. Thermal evolution of the physical and structural changes in the gel was monitored by differential thermal analysis, thermogravimetric analysis, x-ray diffraction, and infrared spectroscopy. On heating to approximately 400 C, the amorphous gel crystallized into the low temperature orthorhombic phase Beta-Ta2O5, which transformed into the high temperature tetragonal phase Alpha-Ta2O5 when further heated to approximately 1450 C. The volume fraction of the crystalline phase increased with the firing temperature. The Alpha-Ta205 converted back into the low temperature phase, Beta-Ta2O5, on slow cooling through the transformation temperature of 1360 C indicating a slow but reversible transformation.

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

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

Somrani, Saida; Banu, Mihai; Jemal, Mohamed

2005-05-15

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

Microstructural Evolution of Dy2O3-TiO2 Powder Mixtures during Ball Milling and Post-Milled Annealing

PubMed Central

Huang, Jinhua; Ran, Guang; Lin, Jianxin; Shen, Qiang; Lei, Penghui; Wang, Xina; Li, Ning

2016-01-01

The microstructural evolution of Dy2O3-TiO2 powder mixtures during ball milling and post-milled annealing was investigated using XRD, SEM, TEM, and DSC. At high ball-milling rotation speeds, the mixtures were fined, homogenized, nanocrystallized, and later completely amorphized, and the transformation of Dy2O3 from the cubic to the monoclinic crystal structure was observed. The amorphous transformation resulted from monoclinic Dy2O3, not from cubic Dy2O3. However, at low ball-milling rotation speeds, the mixtures were only fined and homogenized. An intermediate phase with a similar crystal structure to that of cubic Dy2TiO5 was detected in the amorphous mixtures annealed from 800 to 1000 °C, which was a metastable phase that transformed to orthorhombic Dy2TiO5 when the annealing temperature was above 1050 °C. However, at the same annealing temperatures, pyrochlore Dy2Ti2O7 initially formed and subsequently reacted with the remaining Dy2O3 to form orthorhombic Dy2TiO5 in the homogenous mixtures. The evolutionary mechanism of powder mixtures during ball milling and subsequent annealing was analyzed. PMID:28772375

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.

Tuning upconversion luminescence of LiYF4:Yb3+,Er3+/Tm3+/Ho3+ microcrystals synthesized through a molten salt process.

PubMed

Niu, Na; He, Fei; Wang, Liuzhen; Wang, Lin; Wang, Yan; Gai, Shili; Yang, Piaoping

2014-05-01

In this paper, well-defined tetragonal-phase LiYF4:Yb3+,Er3+/Tm3+/Ho3+ micro-crystals with octahedral morphology were successfully prepared through a surfactant-free molten salt process for the first time. By gradually increasing the LiF content in the NaNO3-KNO3 reaction medium, the crystal phase transforms from a mixture of YF3 and LiYF4 to pure tetragonal-phase LiYF4. The possible formation process for the phase and morphology evolution is also presented. Moreover, upon 980 nm laser diode (LD) excitation, the lanthanide ions (Yb3+, Er3+/Tm3+/Ho3+) doped LiYF4 crystals exhibit intense upconversion emission lights. By tuning the sensitizer concentrations of Yb3+ ions in LiYF4:Yb3+,Er3+, the relative intensities of green and red emissions can be precisely adjusted under single wavelength excitation. Consequently, multicolor upconversion emissions can be obtained. On the other hand, UC mechanisms were also given based on the emission spectra and the plot of luminescence intensity to pump power.

Analytical ultrasonics for characterization of metallurgical microstructures and transformations

NASA Technical Reports Server (NTRS)

Rosen, M.

1986-01-01

The application of contact (piezoelectric) and noncontact (laser generation and detection) ultrasonic techniques for dynamic investigation of precipitation hardening processes in aluminum alloys, as well as crystallization and phase transformation in rapidly solidified amorphous and microcrystalline alloys is discussed. From the variations of the sound velocity and attenuation the precipitation mechanism and kinetics were determined. In addition, a correlation was established between the observed changes in the velocity and attenuation and the mechanical properties of age-hardenable aluminum alloys. The behavior of the elastic moduli, determined ultrasonically, were found to be sensitive to relaxation, crystallization and phase decomposition phenomena in rapidly solidified metallic glasses. Analytical ultrasonics enables determination of the activation energies and growth parameters of the reactions. Therefrom theoretical models can be constructed to explain the changes in mechanical and physical properties upon heat treatment of glassy alloys. The composition dependence of the elastic moduli in amorphous Cu-Zr alloys was found to be related to the glass transition temperature, and consequently to the glass forming ability of these alloys. Dynamic ultrasonic analysis was found to be feasible for on-line, real-time, monitoring of metallurgical processes.

THE ROLE OF METASTABLE STATES IN POLYMER PHASE TRANSITIONS: Concepts, Principles, and Experimental Observations

NASA Astrophysics Data System (ADS)

Cheng, Stephen Z. D.; Keller, Andrew

1998-08-01

Polymer phases can be described in the same way as phases in other condensed matter using a number density operator and its correlation functions. This description requires the understanding of symmetry operations and order at different atomic and molecular levels. Statistical mechanics provides a link between the microscopic description of the structure and motion and the macroscopic thermodynamic properties. Within the limits of the laws of thermodynamics, polymers exhibit a rich variety of phase transition behaviors. By definition, a first-order phase transition describes a transformation that involves a sudden change of thermodynamic properties at its transition temperature, whereas higher-order phase transitions are classified as critical phenomena. Of special interest is the role of metastability in phase and phase transition behaviors. Although a metastable state possesses a local free energy minimum, it is not at the global equilibrium. Furthermore, metastable states can also be associated with phase sizes. Metastable behavior is also observed in phase transformations that are impeded by kinetic limitations along the pathway to thermodynamic equilibrium. This is illustrated in structural and morphological investigations of crystallization and mesophase transitions, liquid-liquid phase separation, vitrification, and gel formation, as well as combinations of transformation processes. In these cases, the metastable state often becomes the dominant state for the entire system and is observed over a range of time and size scales. This review describes the general principles of metastability in polymer phases and phase transitions and provides illustrations from current experimental works in selected areas.

Resistivity changes of some amorphous alloys undergoing nanocrystallization

NASA Astrophysics Data System (ADS)

Barandiarán, J. M.; Fernández Barquín, L.; Sal, J. C. Gómez; Gorría, P.; Hernando, A.

1993-10-01

The electrical resistivity of amorphous alloys with compositions: Fe 73.5Nb 3Cu 1Si 13.5B 9, Fe 86Zr 7Cu 1B 6 and Co 80Nb 8B 12 has been studied in the temperature range from 300 to 1100 K, where crystallization occurs. The products of crystallization and the grain size have been studied by X-ray diffraction. In a first step, all the alloys crystallize with small grains of a few nanometers in diameter (nanocrystalline state), and the resistivity behavior at this process accounts for the difference between the amorphous and nanocrystalline phases. The nanocrystalline phases are: α-Fe-Si, α-Fe and fcc Co for the three compounds studied respectively. A second process, at which grain growth and precipitation of intermetallic compounds and borides takes place, has been found for all the alloys. The resistivity is sensitive, not only to the total transformed sample amount, but to the topological distribution of the crystalline phases, and therefore shows a more complex behavior than other well established techniques, as differential scanning calorimetry. This supplementary information given by the resistivity is also discussed.

Quantum Hooke's Law to classify pulse laser induced ultrafast melting

DOE PAGES

Hu, Hao; Ding, Hepeng; Liu, Feng

2015-02-03

Ultrafast crystal-to-liquid phase transition induced by femtosecond pulse laser excitation is an interesting material's behavior manifesting the complexity of light-matter interaction. There exist two types of such phase transitions: one occurs at a time scale shorter than a picosecond via a nonthermal process mediated by electron-hole plasma formation; the other at a longer time scale via a thermal melting process mediated by electron-phonon interaction. However, it remains unclear what material would undergo which process and why? Here, by exploiting the property of quantum electronic stress (QES) governed by quantum Hooke's law, we classify the transitions by two distinct classes ofmore » materials: the faster nonthermal process can only occur in materials like ice having an anomalous phase diagram characterized with dT m/dP < 0, where T m is the melting temperature and P is pressure, above a high threshold laser fluence; while the slower thermal process may occur in all materials. Especially, the nonthermal transition is shown to be induced by the QES, acting like a negative internal pressure, which drives the crystal into a “super pressing” state to spontaneously transform into a higher-density liquid phase. Our findings significantly advance fundamental understanding of ultrafast crystal-to-liquid phase transitions, enabling quantitative a priori predictions.« less

Quantum Hooke's Law to Classify Pulse Laser Induced Ultrafast Melting

NASA Astrophysics Data System (ADS)

Hu, Hao; Ding, Hepeng; Liu, Feng

2015-02-01

Ultrafast crystal-to-liquid phase transition induced by femtosecond pulse laser excitation is an interesting material's behavior manifesting the complexity of light-matter interaction. There exist two types of such phase transitions: one occurs at a time scale shorter than a picosecond via a nonthermal process mediated by electron-hole plasma formation; the other at a longer time scale via a thermal melting process mediated by electron-phonon interaction. However, it remains unclear what material would undergo which process and why? Here, by exploiting the property of quantum electronic stress (QES) governed by quantum Hooke's law, we classify the transitions by two distinct classes of materials: the faster nonthermal process can only occur in materials like ice having an anomalous phase diagram characterized with dTm/dP < 0, where Tm is the melting temperature and P is pressure, above a high threshold laser fluence; while the slower thermal process may occur in all materials. Especially, the nonthermal transition is shown to be induced by the QES, acting like a negative internal pressure, which drives the crystal into a ``super pressing'' state to spontaneously transform into a higher-density liquid phase. Our findings significantly advance fundamental understanding of ultrafast crystal-to-liquid phase transitions, enabling quantitative a priori predictions.

Quantum Hooke's Law to Classify Pulse Laser Induced Ultrafast Melting

PubMed Central

Hu, Hao; Ding, Hepeng; Liu, Feng

2015-01-01

Ultrafast crystal-to-liquid phase transition induced by femtosecond pulse laser excitation is an interesting material's behavior manifesting the complexity of light-matter interaction. There exist two types of such phase transitions: one occurs at a time scale shorter than a picosecond via a nonthermal process mediated by electron-hole plasma formation; the other at a longer time scale via a thermal melting process mediated by electron-phonon interaction. However, it remains unclear what material would undergo which process and why? Here, by exploiting the property of quantum electronic stress (QES) governed by quantum Hooke's law, we classify the transitions by two distinct classes of materials: the faster nonthermal process can only occur in materials like ice having an anomalous phase diagram characterized with dTm/dP < 0, where Tm is the melting temperature and P is pressure, above a high threshold laser fluence; while the slower thermal process may occur in all materials. Especially, the nonthermal transition is shown to be induced by the QES, acting like a negative internal pressure, which drives the crystal into a “super pressing” state to spontaneously transform into a higher-density liquid phase. Our findings significantly advance fundamental understanding of ultrafast crystal-to-liquid phase transitions, enabling quantitative a priori predictions. PMID:25645258

Quantum Hooke's law to classify pulse laser induced ultrafast melting.

PubMed

Hu, Hao; Ding, Hepeng; Liu, Feng

2015-02-03

Ultrafast crystal-to-liquid phase transition induced by femtosecond pulse laser excitation is an interesting material's behavior manifesting the complexity of light-matter interaction. There exist two types of such phase transitions: one occurs at a time scale shorter than a picosecond via a nonthermal process mediated by electron-hole plasma formation; the other at a longer time scale via a thermal melting process mediated by electron-phonon interaction. However, it remains unclear what material would undergo which process and why? Here, by exploiting the property of quantum electronic stress (QES) governed by quantum Hooke's law, we classify the transitions by two distinct classes of materials: the faster nonthermal process can only occur in materials like ice having an anomalous phase diagram characterized with dTm/dP < 0, where Tm is the melting temperature and P is pressure, above a high threshold laser fluence; while the slower thermal process may occur in all materials. Especially, the nonthermal transition is shown to be induced by the QES, acting like a negative internal pressure, which drives the crystal into a "super pressing" state to spontaneously transform into a higher-density liquid phase. Our findings significantly advance fundamental understanding of ultrafast crystal-to-liquid phase transitions, enabling quantitative a priori predictions.

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

X Li; Y Mao; H Ma

An ionic liquid (IL) 1-docosanyl-3-methylimidazolium bromide was incorporated into ultra-high molecular weight polyethylene (UHMWPE) and formed IL/UHMWPE blends by solution mixing. The structure evolution of these blends during uniaxial stretching was followed by in-situ synchrotron wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) techniques. During deformation at room temperature, deformation-induced phase transformation from orthorhombic to monoclinic phase was observed in both IL/UHMWPE blends and neat UHMWPE. The elongation-to-break ratios of IL/UHMWPE blends were found to increase by 2-3 times compared with that of pure UHMWPE, while the tensile strength remained about the same. In contrast, during deformation at highmore » temperature (120 C), no phase transformation was observed. However, the blend samples showed much better toughness, higher crystal orientation and higher tilting extent of lamellar structure at high strains.« less

Observation of a New High-Pressure Solid Phase in Dynamically Compressed Aluminum

NASA Astrophysics Data System (ADS)

Polsin, D. N.

2017-10-01

Aluminum is ideal for testing theoretical first-principles calculations because of the relative simplicity of its atomic structure. Density functional theory (DFT) calculations predict that Al transforms from an ambient-pressure, face-centered-cubic (fcc) crystal to the hexagonal close-packed (hcp) and body-centered-cubic (bcc) structures as it is compressed. Laser-driven experiments performed at the University of Rochester's Laboratory for Laser Energetics and the National Ignition Facility (NIF) ramp compressed Al samples to pressures up to 540 GPa without melting. Nanosecond in-situ x-ray diffraction was used to directly measure the crystal structure at pressures where the solid-solid phase transformations of Al are predicted to occur. Laser velocimetry provided the pressure in the Al. Our results show clear evidence of the fcc-hcp and hpc-bcc transformations at 216 +/- 9 GPa and 321 +/- 12 GPa, respectively. This is the first experimental in-situ observation of the bcc phase in compressed Al and a confirmation of the fcc-hcp transition previously observed under static compression at 217 GPa. The observations indicate these solid-solid phase transitions occur on the order of tens of nanoseconds time scales. In the fcc-hcp transition we find the original texture of the sample is preserved; however, the hcp-bcc transition diminishes that texture producing a structure that is more polycrystalline. The importance of this dynamic is discussed. The NIF results are the first demonstration of x-ray diffraction measurements at two different pressures in a single laser shot. This material is based upon work supported by the Department of Energy National Nuclear Security Administration under Award Number DE-NA0001944.

Structural transformations of 3-fluoro and 3-fluoro-4-methoxy benzaldehydes under cryogenic conditions: A computational and low temperature infrared spectroscopy investigation

NASA Astrophysics Data System (ADS)

Ogruc Ildiz, G.; Konarska, J.; Fausto, R.

2018-05-01

Structural transformations of 3-fluorobenzaldehyde (C7H5FO; 3FBA) and 3-fluoro-4-methoxybenzaldehyde (C8H7FO2; 3F4MBA), taking place in different solid phase environments and at low temperature, were investigated by infrared spectroscopy, complemented by quantum chemistry calculations undertaken at the DFT(B3LYP)/6-311++G(d,p) level of approximation. The studied compounds were isolated from gas phase into cryogenic inert matrices (Ar, Xe), allowing to characterize their equilibrium conformational composition in gas-phase at room temperature. In both cases, two conformers differing by the orientation of the aldehyde moiety (with the carbonyl aldehyde bond cis or trans in relation to the aromatic ring fluorine substituent) were found to coexist, with the cis conformer being slightly more populated than the trans form. In situ narrowband UV irradiation of the as-deposited matrices led either to preferential isomerization of the cis conformer into the trans form or decarbonylation of both conformers, depending on the used excitation wavelength. Deposition of the vapours of 3F4MBA only, onto the cold (15 K) substrate, produced an amorphous solid containing also both the cis and trans conformers of the compound. Subsequent heating of the amorphous phase up to 268 K led to crystallization of the compound, which is accompanied by conformational selection, the cis form being the single species present in the crystal. The experimentally observed transformations of the studied compounds, together with the structural and vibrational results obtained from the performed quantum chemical calculations, allowed a detailed structural and vibrational characterization of the individual conformers.

Kinetics of transformation of deformation processed gold-matrix composite

NASA Astrophysics Data System (ADS)

Wongpreedee, Kageeporn

Gold matrix Ḏeformation-processed M&barbelow;etal M&barbelow;etal C&barbelow;omposites (DMMC) have been developed that have better strength and conductivity than conventional gold alloys. However, DMMC possess metastable two-phase microstructures, and their strength and conductivity decrease after prolonged exposure to elevated temperatures. The kinetics of the transformation from the metastable two-phase microstructure to the equilibrium single-phase solid solution is of interest. This document describes a study of the elevated temperature stability of Au DMMC's and the relationship between microstructure and resistivity of three compositions: Au-7 vol %Ag, Au-14 vol %Ag, and Au-vol 7%Pt. DMMC samples were prepared by a powder metallurgy technique and mechanical processes. The smallest final diameter of these wires was 120 mum. Avrami and Arrhenius relations were used to evaluate the kinetic transformation. The extensive deformation used to produce these composites reshaped the initially equi-axed powder particles into a nanofilamentary composite. Electrical resistivity measurements were used to determine the degree of transformation from the initial metastable nano-filamentary composite to the equilibrium solid solution condition. These measurements indicated that this transformation in Au-14 at%Ag, Au-7 at %Ag Au and Au-7 at %Pt DMMC wires proceeded with activation energies of 141, 156, and 167 kJ/mol, respectively. It is thought that these empirically determined activation energies differ from those determined in single crystal, planar interface Au-Ag and Au-Pt diffusion couples due to chemical potential, surface curvature, and strain effects. The DMMC systems reach the equilibrium solid solution condition faster than single crystal, planar interface systems for two reasons: (1) far more defects (dislocations, grain boundaries, vacancies from non-conservative dislocation motion, etc.) are present in the Au-Ag and Au-Pt DMMC composites, and (2) the small radius of curvature of the Ag and Pt filaments increases the chemical potential for diffusion in the DMMC.

Micro-Raman scattering and dielectric investigations of phase transitions behavior in the PbHf0.7Sn0.3O3 single crystal

NASA Astrophysics Data System (ADS)

Jankowska-Sumara, Irena; Ko, Jae-Hyeon; Podgórna, Maria; Oh, Soo Han; Majchrowski, Andrzej

2017-09-01

Raman light scattering was used to detect the sequence of transitions in a PbHf1-xSnxO3 (PHS) single crystal with x = 0.30 in a temperature range of 77-873 K. Changes of Raman spectra were observed in the vicinity of structural phase transitions: between the antiferroelectric (AFE1)-antiferroelectric (AFE2)—intermediate—paraelectric phases. Light scattering and dielectric investigations were used to find out the nature and sequence of the phase transition, as well as the large dielectric permittivity values measured at the phase transition, by searching for the soft-phonon-mode behavior. The experimentally recorded spectra were analyzed in terms of the damped-harmonic oscillator model for the phonon bands. It is demonstrated that the structural phase transformations in PHS can be considered as the result of softening of many modes, not only the ferroelectric one. It was also proved that locally broken symmetry effects are present at temperatures far above the Curie temperature and are connected with the softening of two optic modes of different nature.

Electrical resistance of single-crystal magnetite (Fe 3 O 4 ) under quasi-hydrostatic pressures up to 100 GPa

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

Muramatsu, Takaki; Gasparov, Lev V.; Berger, Helmuth

2016-04-07

We measured the pressure dependence of electrical resistance of single-crystal magnetite (Fe 3O 4) under quasi-hydrostatic conditions to 100 GPa using low-temperature, megabar diamond-anvil cell techniques in order to gain insight into the anomalous behavior of this material that has been reported over the years in different high-pressure experiments. The measurements under nearly hydrostatic pressure conditions allowed us to detect the clear Verwey transition and the high-pressure structural phase. Furthermore, the appearance of a metallic ground state after the suppression of the Verwey transition around 20 GPa and the concomitant enhancement of electrical resistance caused by the structural transformation tomore » the high-pressure phase form reentrant semiconducting-metallic-semiconducting behavior, though the appearance of the metallic phase is highly sensitive to stress conditions and details of the measurement technique.« less

Sequence of phase transitions in (NH4)3SiF7.

PubMed

Mel'nikova, S V; Molokeev, M S; Laptash, N M; Pogoreltsev, E I; Misyul, S V; Flerov, I N

2017-02-21

Single crystals of silicon double salt (NH 4 ) 3 SiF 7 = (NH 4 ) 2 SiF 6 ·NH 4 F = (NH 4 ) 3 [SiF 6 ]F were grown and studied by the methods of polarization optics, X-ray diffraction and calorimetry. A sequence of symmetry transformations with the temperature change was established: P4/mbm (Z = 2) (G 1 ) ↔ Pbam (Z = 4) (G 2 ) ↔ P2 1 /c (Z = 4) (G 3 ) ↔ P1[combining macron] (Z = 4) (G 4 ) ↔ P2 1 /c (Z = 8) (G 5 ). Crystal structures of different phases were determined. The experimental data were also interpreted by a group-theoretical analysis of the complete condensate of order parameters taking into account critical and noncritical atomic displacements. Strengthening of the N-HF hydrogen bonds can be a driving force of the observed phase transitions.

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

Aronhime, Natan; Zoghlin, Eli; Keylin, Vladimir

Fe-Ni based metal amorphous nanocomposites (MANCs) are investigated in the pseudo-binary alloys (Fe 100–xNi x) 80Nb 4Si 2B 14. To optimize the soft magnetic properties of the nanocomposites, primary and secondary crystallization kinetics must be understood. As such, primary and secondary crystallization temperatures are determined by differential scanning calorimetry, and activation energies are calculated, along with the resulting crystalline phases. Time-temperature-transformation diagrams for primary and secondary crystallization in (Fe 70Ni 30) 80Nb 4Si 2B 14 are presented. Saturation magnetization and Curie temperature are determined. In conclusion, the shape of magnetization vs. time curves for (Fe 30Ni 70) 80Nb 4Si 2Bmore » 14 at various temperatures suggest that the secondary crystal product often consumes some of the primary crystalline product.« less

High-temperature ultrasonic characterization of the mechanical and microstructural behavior of a fibrous composite with a magnesium lithium aluminum silicate glass-ceramic matrix

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

Cutard, T.; Huger, M.; Fargeot, D.

The mechanical behavior and the microstructural modifications of a SiC-fiber-reinforced magnesium lithium aluminum silicate glass-ceramic (SiC/MASL) have been characterized by ultrasonic measurement of uniaxial Young`s modulus at high temperature. Under vacuum, long isothermal agings in the 750--1,000 C temperature range have shown matrix modifications in terms of crystallization of residual glassy phases, and of phase transformations in the Li{sub 2}O-Al{sub 2}O{sub 3}-SiO{sub 2} system. In air, long isothermal agings performed under the same conditions have led to the same matrix transformations but in competition with oxidation mechanisms of the carbon fiber-matrix interphase. All of these matrix and/or interface transformations havemore » been confirmed by X-ray diffraction analysis, scanning electron microscopy, scanning acoustic microscopy, and microindentation tests.« less

High-pressure polymorphism of acetylsalicylic acid (aspirin): Raman spectroscopy

NASA Astrophysics Data System (ADS)

Crowell, Ethan L.; Dreger, Zbigniew A.; Gupta, Yogendra M.

2015-02-01

Micro-Raman spectroscopy was used to elucidate the high-pressure polymorphic behavior of acetylsalicylic acid (ASA), an important pharmaceutical compound known as aspirin. Using a diamond anvil cell (DAC), single crystals of the two polymorphic phases of aspirin existing at ambient conditions (ASA-I and ASA-II) were compressed to 10 GPa. We found that ASA-I does not transform to ASA-II, but instead transforms to a new phase (ASA-III) above ∼2 GPa. It is demonstrated that this transformation primarily introduces structural changes in the bonding and arrangement of the acetyl groups and is reversible upon the release of pressure. In contrast, a less dense ASA-II shows no transition in the pressure range studied, though it appears to exhibit a disordered structure above 7 GPa. Our results suggest that ASA-III is the most stable polymorph of aspirin at high pressures.

Electron-electron correlations in Raman spectra of VO2

NASA Astrophysics Data System (ADS)

Goncharuk, I. N.; Ilinskiy, A. V.; Kvashenkina, O. E.; Shadrin, E. B.

2013-01-01

It has been shown that, in single crystals and films of a strongly correlated material, namely, vanadium dioxide, upon a thermally stimulated phase transition from the low-temperature monoclinic phase to the high-temperature tetragonal phase, the narrow-line Raman spectrum of the insulating (monoclinic) phase transforms into the broad-band Raman spectrum, which contains two peaks at 500 and 5000 cm-1 with widths of 400 and 3500 cm-1, respectively. It has been found that, as the temperature of the monoclinic phase approaches the structural phase transition temperature (340 K), the line profile of soft-mode phonons at a frequency of 149 cm-1 with A g symmetry and the line profile of phonons at a frequency of 201 cm-1 with A g symmetry acquire an asymmetric shape with a Fano antiresonance that is characteristic of the interaction of a single phonon vibration with a continuum of strongly correlated electrons. It has been demonstrated that the thermal transformation of peaks in the Raman spectra of the VO2 metallic phase is in quantitative agreement with the theory of Raman scattering in strongly correlated materials.

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

NASA Astrophysics Data System (ADS)

Perfit, Michael R.; Fornari, Daniel J.

1983-12-01

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

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

Zheligovskaya, E. A., E-mail: lmm@phyche.ac.ru

Structural mechanisms are proposed for experimentally observed phase transitions between crystalline modifications of aqueous ice, Ih and II, as well as II and Ic. It is known that the Ih–II transition occurs with the conservation of large structural units (hexagonal channels) common for these ices. It is shown that the Ih → II transition may occur with the conservation of 5/6 of all hydrogen bonds in crystal, including all hydrogen bonds in the retained channels (3/4 of the total number of bonds in crystal) and 1/3 of the bonds between these channels (1/12 of the total number). The transformation ofmore » other hydrogen bonds between the retained channels leads to the occurrence of proton order in ice II. A structural mechanism is proposed to explain the transformation of single crystals of ice Ih either into single crystals of ice II or into crystalline twins of ice II with c axes rotated by 180° with respect to each other, which is often observed at the Ih → II transition. It is established that up to 7/12 of all hydrogen bonds are retained at the irreversible cooperative II → Ic transition.« less

Rate constants and mechanisms for the crystallization of Al nano-goethite under environmentally relevant conditions

NASA Astrophysics Data System (ADS)

Bazilevskaya, Ekaterina; Archibald, Douglas D.; Martínez, Carmen Enid

2012-07-01

Mobile inorganic and organic nanocolloidal particles originate-from and interact-with bulk solid phases in soil and sediment environments, and as such, they contribute to the dynamic properties of environmental systems. In particular, ferrihydrite and (nano)goethite are the most abundant of nanocolloidal Fe oxy(hydr)oxides in these environments. We therefore investigated the ferrihydrite to goethite phase transformation using experimental reaction conditions that mimicked environmental conditions where the formation of nanocolloidal Fe oxy(hydr)oxides may occur: slow titration of dilute solutions to pH 5 at 25 °C with and without 2 mol% Al. Subsequently, the rate constants from 54-d nano-goethite aging/crystallization experiments at 50 °C were determined using aliquots pulled for vibrational spectroscopy (including multivariate curve resolution, MCR, analyses of infrared spectra) and synchrotron-based X-ray diffraction (XRD). We also present a mechanistic model that accounts for the nano-goethite crystallization observed by the aforementioned techniques, and particle structural characteristics observed by dynamic light scattering (DLS) and transmission electron microscopy (TEM). In contrast to the common assumption that metastable ferrihydrite precipitates first, before it transforms to goethite, the presence of characteristic infrared bands in freshly synthesized nanoparticle suspensions indicate goethite can precipitate directly from solution under environmentally relevant conditions: low Fe concentration, ambient temperature, and pH maintained at 5. However, the presence of 2 mol% Al prevented direct goethite precipitation. Rate constants obtained by fitting the contributions from the MCR-derived goethite-like component to the OH-stretching region were (7.4 ± 1.1) × 10-7 s-1 for 0% Al and (4.2 ± 0.4) × 10-7 s-1 for 2 mol% Al suspensions. Rate constants derived from intensities of OH-bending infrared vibrations (795 and 895 cm-1) showed similar values, within error, for both 0 and 2 mol% Al nanoparticle suspensions. Thus, the presence of 2 mol% Al decreased the rate constants determined from analyses of infrared OH-stretching and OH-bending vibrations by 43-57%. We postulate that dissolution re-precipitation reactions are accelerated in aggregate microenvironments by locally increased supersaturation, yielding the dominant mechanism for transformation of ferrihydrite to goethite and goethite crystal growth when bulk ion concentrations are low. Although we did observe growth of a population of prismatic goethite single crystals by TEM, there was more substantial growth of a population of polycrystalline goethite needles that appeared to retain some defects from a preceding aggregation step that we detected with DLS. Since the presence of Al hinders the dissolution of ferrihydrite, it too reduces the rate of crystallization to goethite and its crystal growth. As exemplified in this nano-particle crystallization study, the combination of advanced spectral-curve-resolution algorithms and sensitive and quantitative infrared sampling techniques opens future opportunities for the quantification of mineral phase dynamics in nanocolloidal suspensions, which is important for many aspects of environmental studies.

Diffusion paths formation for Cu{sup +} ions in superionic Cu{sub 6}PS{sub 5}I single crystals studied in terms of structural phase transition

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

Gagor, A.; Pietraszko, A.; Kaynts, D.

2005-11-15

In order to understand the structural transformations leading to high ionic conductivity of Cu{sup +} ions in Cu{sub 6}PS{sub 5}I argyrodite compound, the detailed structure analysis based on single-crystal X-ray diffraction has been performed. Below the phase transition at T{sub c}=(144-169)K Cu{sub 6}PS{sub 5}I belongs to monoclinic, ferroelastic phase (space group Cc) with ordered copper sublattice. Above T{sub c} delocalization of copper ions begins and crystal changes the symmetry to cubic superstructure with space group F-43c (a{sup '}=19.528A, z=32). Finally, above T{sub 1}=274K increasing disordering of the Cu{sup +} ions heightens the symmetry to F-43m (a=9.794A, z=4). In this work,more » the final structural model of two cubic phases is presented including the detailed temperature evolution of positions and site occupation factors of copper ions (R{sub 1}=0.0397 for F-43c phase, and 0.0245 for F-43m phase). Possible diffusion paths for the copper ions are represented by means of the atomic displacement factors and split model. The structural results coincide well with the previously reported non-Arrhenius behavior of conductivity and indicate significant change in conduction mechanism.« less

Ion Conduction Path and Low-Temperature Form:. Argyrodite-Type Superionic Conductors

NASA Astrophysics Data System (ADS)

Onoda, M.; Wada, H.; Sato, A.; Ishii, M.

2007-01-01

The structures of the orthorhombic room-temperature phase of Cu8GeS6 (phase II) and the monoclinic low-temperature phase of Ag7TaS6 (phase II) have been successfully refined based on X-ray diffraction data from 12-fold twinned (Cu8GeS6 II) and 24-fold twinned (Ag7TaS6 II) crystals. Respectively among 6 major and 6 minor twin domains of Cu8GeS6 II, or among 12 major and 12 minor twin domains of Ag7TaS6 II, the argyrodite-type frameworks, GeS6 or TaS6, can be superposed to each other in principle, and only Cu-Cu or Ag-Ag network directions differ. At higher temperature, the crystals were considered to be 2-fold twinned crystals of superionic-conductor phase I with a space group F 43m. On cooling, each domain transforms into 6 domains of orthorhombic Cu8GeS6 II or 12 domains of monoclinic Ag7TaS6 II. Superposed projections along 6 directions of the structure of Cu8GeS6 II and along 12 directions of the structure of Ag7TaS6 II seem to show approximate expressions for Cu-ion and Ag-ion conduction paths in superionic-conductor phases, Cu8GeS6 I and Ag7TaS6I.

Precise calibration of spatial phase response nonuniformity arising in liquid crystal on silicon.

PubMed

Xu, Jingquan; Qin, SiYi; Liu, Chen; Fu, Songnian; Liu, Deming

2018-06-15

In order to calibrate the spatial phase response nonuniformity of liquid crystal on silicon (LCoS), we propose to use a Twyman-Green interferometer to characterize the wavefront distortion, due to the inherent curvature of the device. During the characterization, both the residual carrier frequency introduced by the Fourier transform evaluation method and the lens aberration are error sources. For the tilted phase error introduced by residual carrier frequency, the least mean square fitting method is used to obtain the tilted phase error. Meanwhile, we use Zernike polynomials fitting based on plane mirror calibration to mitigate the lens aberration. For a typical LCoS with 1×12,288 pixels after calibration, the peak-to-valley value of the inherent wavefront distortion is approximately 0.25λ at 1550 nm, leading to a half-suppression of wavefront distortion. All efforts can suppress the root mean squares value of the inherent wavefront distortion to approximately λ/34.

Liquid phase heteroepitaxial growth on convex substrate using binary phase field crystal model

NASA Astrophysics Data System (ADS)

Lu, Yanli; Zhang, Tinghui; Chen, Zheng

2018-06-01

The liquid phase heteroepitaxial growth on convex substrate is investigated with the binary phase field crystal (PFC) model. The paper aims to focus on the transformation of the morphology of epitaxial films on convex substrate with two different radiuses of curvature (Ω) as well as influences of substrate vicinal angles on films growth. It is found that films growth experience different stages on convex substrate with different radiuses of curvature (Ω). For Ω = 512 Δx , the process of epitaxial film growth includes four stages: island coupled with layer-by-layer growth, layer-by-layer growth, island coupled with layer-by-layer growth, layer-by-layer growth. For Ω = 1024 Δx , film growth only experience islands growth and layer-by-layer growth. Also, substrate vicinal angle (π) is an important parameter for epitaxial film growth. We find the film can grow well when π = 2° for Ω = 512 Δx , while the optimized film can be obtained when π = 4° for Ω = 512 Δx .

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.

The Morse code effect: A crystal-crystal transformation observed in gel-grown lead (II) oxalate crystals

NASA Astrophysics Data System (ADS)

Lisgarten, J. N.; Marks, J. A.

2018-05-01

This paper reports on an unusual crystal-crystal transformation phenomenon, which we have called the Morse Code Effect, based on the change in appearance of lead(II) oxalate crystals grown in agarose gels.

High-pressure phase transitions in rare earth metal thulium to 195 GPa.

PubMed

Montgomery, Jeffrey M; Samudrala, Gopi K; Tsoi, Georgiy M; Vohra, Yogesh K

2011-04-20

We have performed image plate x-ray diffraction studies on a heavy rare earth metal, thulium (Tm), in a diamond anvil cell to a pressure of 195 GPa and volume compression V/V₀ = 0.38 at room temperature. The rare earth crystal structure sequence, hcp →Sm-type→ dhcp →fcc → distorted fcc, is observed in Tm below 70 GPa with the exception of a pure fcc phase. The focus of our study is on the ultrahigh-pressure phase transition and Rietveld refinement of crystal structures in the pressure range between 70 and 195 GPa. The hexagonal hR-24 phase is seen to describe the distorted fcc phase between 70 and 124 GPa. Above 124 ± 4 GPa, a structural transformation from hR 24 phase to a monoclinic C 2/m phase is observed with a volume change of -1.5%. The equation of state data shows rapid stiffening above the phase transition at 124 GPa and is indicative of participation of f-electrons in bonding. We compare the behavior of Tm to other heavy rare-earths and heavy actinide metals under extreme conditions of pressure.

High-pressure phase transitions in rare earth metal thulium to 195 GPa

NASA Astrophysics Data System (ADS)

Montgomery, Jeffrey M.; Samudrala, Gopi K.; Tsoi, Georgiy M.; Vohra, Yogesh K.

2011-04-01

We have performed image plate x-ray diffraction studies on a heavy rare earth metal, thulium (Tm), in a diamond anvil cell to a pressure of 195 GPa and volume compression V/Vo = 0.38 at room temperature. The rare earth crystal structure sequence, {hcp}\\to {Sm {-}type} \\to {dhcp} \\to {fcc} \\to distorted fcc, is observed in Tm below 70 GPa with the exception of a pure fcc phase. The focus of our study is on the ultrahigh-pressure phase transition and Rietveld refinement of crystal structures in the pressure range between 70 and 195 GPa. The hexagonal hR- 24 phase is seen to describe the distorted fcc phase between 70 and 124 GPa. Above 124 ± 4 GPa, a structural transformation from hR 24 phase to a monoclinic C 2/m phase is observed with a volume change of - 1.5%. The equation of state data shows rapid stiffening above the phase transition at 124 GPa and is indicative of participation of f-electrons in bonding. We compare the behavior of Tm to other heavy rare-earths and heavy actinide metals under extreme conditions of pressure.

Ferroelasticity in the LnNbO/sub 4/-type rare earth niobates

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

Brixner, L.H.; Whitney, J.F.; Zumsteg, F.C.

1977-01-01

The previously reported phase transitions for the isostructural rare earth niobates between 500/sup 0/C and 850/sup 0/C correspond to a point group transformation 4/mF2/m, which is purely ferroelastic. The correct room temperature point group for all LnNbO/sub 4/ compounds is 2/m. Crystal growth and domain wall behavior is discussed for LaNbO/sub 4/. The high temperature phase transition is described for YbNbO/sub 4/.

Proceedings of the 12th Army Symposium on Solid Mechanics, ’Synergism of Mechanics Mathematics and Materials’ 4-7 November 1991, Plymouth, Massachusetts.

DTIC Science & Technology

1991-11-07

proposed that a phase transformation to untempered martensite (via austenite) occurred within the shear band [9]. Wittman et al used TEM observations to...porous materials is used to simulate the plate impact experiment. 1. Introduction While second phase precipitates or particles greatly enhance the...34Dispersed Particle Hard- ening of Aluminum- Copper Alloy Single Crystals", Acta Metall., Vol. 8, March, pp. 147-155. [2] Meiklejohn, W. H. and Skoda

Vitrification of incinerated tannery sludge in silicate matrices for chromium stabilization.

PubMed

Varitis, S; Kavouras, P; Pavlidou, E; Pantazopoulou, E; Vourlias, G; Chrissafis, K; Zouboulis, A I; Karakostas, Th; Komninou, Ph

2017-01-01

The vitrification process was applied for the stabilization and solidification of a rich in chromium ash that was the by-product of incineration of tannery sludge. Six different batch compositions were produced, based on silica as the glass former and sodium and calcium oxides as flux agents. As-vitrified products (monoliths) were either composed of silicate matrices with separated from the melt Eskolaite (Cr 2 O 3 ) crystallites or were homogeneous glasses (in one case). All as-vitrified products were thermally treated in order to transform them to partially crystallized, i.e. devitrified products. Devitrification is an important part of the work since studying the transformation of the initial as-vitrified products into glass-ceramics with better properties could result to stabilized products with potential added value. The devitrified products were diversified by the effective crystallization mode and separated crystal phase composition. These variations originated from differences in: (a) batch composition of the initial as-vitrified products and (b) thermal treatment conditions. In devitrified products crystallization led to the separation of Devitrite (Na 2 Ca 3 Si 6 O 16 ), Combeite (Na 4 Ca 4 Si 6 O 18 ) and Wollastonite (CaSiO 3 ) crystalline phases, while Eskolaite crystallites were not affected by thermal treatment. Leaching test results revealed that chromium was successfully stabilized inside the as-vitrified monoliths. Devitrification impairs chromium stabilization, only in the case where the initial as-vitrified product was a homogeneous glass. In all other cases, devitrification did not affect successful chromium stabilization. Copyright © 2016 Elsevier Ltd. All rights reserved.

Sealing glass-ceramics with near-linear thermal strain, Part II: Sequence of crystallization and phase stability

DOE PAGES

Rodriguez, Mark A.; Griego, James J. M.; Dai, Steve

2016-08-22

The sequence of crystallization in a recrystallizable lithium silicate sealing glass-ceramic Li 2O–SiO 2–Al 2O 3–K 2O–B 2O 3–P 2O 5–ZnO was analyzed by in situ high-temperature X-ray diffraction (HTXRD). Glass-ceramic specimens have been subjected to a two-stage heat-treatment schedule, including rapid cooling from sealing temperature to a first hold temperature 650°C, followed by heating to a second hold temperature of 810°C. Notable growth and saturation of Quartz was observed at 650°C (first hold). Cristobalite crystallized at the second hold temperature of 810°C, growing from the residual glass rather than converting from the Quartz. The coexistence of quartz and cristobalitemore » resulted in a glass-ceramic having a near-linear thermal strain, as opposed to the highly nonlinear glass-ceramic where the cristobalite is the dominant silica crystalline phase. HTXRD was also performed to analyze the inversion and phase stability of the two types of fully crystallized glass-ceramics. While the inversion in cristobalite resembles the character of a first-order displacive phase transformation, i.e., step changes in lattice parameters and thermal hysteresis in the transition temperature, the inversion in quartz appears more diffuse and occurs over a much broader temperature range. Furthermore, localized tensile stresses on quartz and possible solid-solution effects have been attributed to the transition behavior of quartz crystals embedded in the glass-ceramics.« less

Magnetic properties and crystallization kinetics of (Fe 100–xNi x) 80Nb 4Si 2B 14 metal amorphous nanocomposites

DOE PAGES

Aronhime, Natan; Zoghlin, Eli; Keylin, Vladimir; ...

2017-09-26

Fe-Ni based metal amorphous nanocomposites (MANCs) are investigated in the pseudo-binary alloys (Fe 100–xNi x) 80Nb 4Si 2B 14. To optimize the soft magnetic properties of the nanocomposites, primary and secondary crystallization kinetics must be understood. As such, primary and secondary crystallization temperatures are determined by differential scanning calorimetry, and activation energies are calculated, along with the resulting crystalline phases. Time-temperature-transformation diagrams for primary and secondary crystallization in (Fe 70Ni 30) 80Nb 4Si 2B 14 are presented. Saturation magnetization and Curie temperature are determined. In conclusion, the shape of magnetization vs. time curves for (Fe 30Ni 70) 80Nb 4Si 2Bmore » 14 at various temperatures suggest that the secondary crystal product often consumes some of the primary crystalline product.« less

An Optically Isotropic Antiferroelectric Liquid Crystal (OI-AFLC) Display Mode Operating over a Wide Temperature Range using Ternary Bent-Core Liquid Crystal Mixtures

DOE PAGES

Bergquist, Leah; Zhang, Cuiyu; Ribeiro de Almeida, Roberta R.; ...

2017-02-07

Here, we report on the synthesis and characterization of bent-core liquid crystal (LC) compounds and the preparation of mixtures that provide an optically isotropic antiferroelectric (OI-AFLC) liquid crystal display mode over a very wide temperature interval and well below room temperature. From the collection of compounds synthesized during this study, we recognized that several ternary mixtures displayed a modulated SmC aP A phase down to below -40 °C and up to about 100 °C on both heating and cooling, as well as optical tilt angles in the transformed state of approximately 45° (optically isotropic state). The materials were fully characterizedmore » and their liquid crystal as well as electro-optical properties analyzed by polarized optical microscopy, differential scanning calorimetry, synchrotron X-ray diffraction, dielectric spectroscopy, and electro-optical tests.« less

An Optically Isotropic Antiferroelectric Liquid Crystal (OI-AFLC) Display Mode Operating over a Wide Temperature Range using Ternary Bent-Core Liquid Crystal Mixtures

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

Bergquist, Leah; Zhang, Cuiyu; Ribeiro de Almeida, Roberta R.

Here, we report on the synthesis and characterization of bent-core liquid crystal (LC) compounds and the preparation of mixtures that provide an optically isotropic antiferroelectric (OI-AFLC) liquid crystal display mode over a very wide temperature interval and well below room temperature. From the collection of compounds synthesized during this study, we recognized that several ternary mixtures displayed a modulated SmC aP A phase down to below -40 °C and up to about 100 °C on both heating and cooling, as well as optical tilt angles in the transformed state of approximately 45° (optically isotropic state). The materials were fully characterizedmore » and their liquid crystal as well as electro-optical properties analyzed by polarized optical microscopy, differential scanning calorimetry, synchrotron X-ray diffraction, dielectric spectroscopy, and electro-optical tests.« less

Imperfection and radiation damage in protein crystals studied with coherent radiation

PubMed Central

Nave, Colin; Sutton, Geoff; Evans, Gwyndaf; Owen, Robin; Rau, Christoph; Robinson, Ian; Stuart, David Ian

2016-01-01

Fringes and speckles occur within diffraction spots when a crystal is illuminated with coherent radiation during X-ray diffraction. The additional information in these features provides insight into the imperfections in the crystal at the sub-micrometre scale. In addition, these features can provide more accurate intensity measurements (e.g. by model-based profile fitting), detwinning (by distinguishing the various components), phasing (by exploiting sampling of the molecular transform) and refinement (by distinguishing regions with different unit-cell parameters). In order to exploit these potential benefits, the features due to coherent diffraction have to be recorded and any change due to radiation damage properly modelled. Initial results from recording coherent diffraction at cryotemperatures from polyhedrin crystals of approximately 2 µm in size are described. These measurements allowed information about the type of crystal imperfections to be obtained at the sub-micrometre level, together with the changes due to radiation damage. PMID:26698068

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

DOE PAGES

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

2016-07-20

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

Study of the transformation sequence on a high temperature martensitic transformation Ni-Mn-Ga-Co shape memory alloy

NASA Astrophysics Data System (ADS)

Recarte, V.; Pérez-Landazábal, J. I.; Sánchez-Alarcos, V.; Rodríguez-Velamazán, J. A.

2014-11-01

Ni-Mn-Ga alloys show the highest magnetic-field-induced strain among ferromagnetic shape memory alloys. A great effort is being done in this alloy system to increase the application temperature range. In this sense, the addition of small amounts of Cobalt to NiMnGa alloys has been proved to increase the MT temperatures through the increase of the electron per atom relation (e/a). In this work, the analysis of the crystal structure of the present phases and the phase transformations has been performed on a Ni-Mn-Ga-Co alloy by neutron diffraction measurements from 10 K to 673 K. The study has been completed by means of calorimetric and magnetic measurements. On cooling the alloy undergoes a martensitic transformation from a face centered cubic structure to a nonmodulated tetragonal martensite. The appearance of intermartensite transformations can be disregarded in the whole temperature range below the martensitic transformation. However, a jump in the unit-cell volume of the tetragonal martensite has been observed at 325 K. Since this temperature is close to the Curie temperature of the alloy both, the structural and magnetic contributions are taken into account to explain the results.

Spontaneous Phase Transformation and Exfoliation of Rectangular Single-Crystal Zinc Hydroxy Dodecylsulfate Nanomembranes

Treesearch

Fei Wang; Joseph E. Jakes; Dalong Geng; Xudong Wang

2013-01-01

Free-standing two-dimensional (2D) nanostructures, exemplified by graphene and semiconductor nanomembranes, exhibit exotic electrical and mechanical properties and have great potential in electronic applications where devices need to be flexible or conformal to nonplanar surfaces. Based on our previous development of a substrate-free synthesis of large-area, free-...

Crystallographic phases in heavy rare earth metals under megabar pressures

NASA Astrophysics Data System (ADS)

Samudrala, G. K.; Vohra, Y. K.

2012-07-01

Experiments aimed at understanding the crystallographic phases of heavy rare earth metals were carried out in a diamond anvil cell at the Advanced Photon Source, Argonne National Laboratory. Heavy rare earth metals dysprosium (Dy), holmium (Ho), erbium (Er) and thulium (Tm) were compressed to multi-megabar pressures. The rare earth crystal sequence hcp→Sm-type→dhcp→distorted-fcc (dfcc) is observed in all four elements. Upon further compression, a structural transformation to a monoclinic C2/m phase has been observed. We summarize the results from these experiments and present Rietveld structural refinements on high pressure phases for the specific case of dysprosium.

Application of the windowed-Fourier-transform-based fringe analysis technique for investigating temperature and concentration fields in fluids.

PubMed

Mohanan, Sharika; Srivastava, Atul

2014-04-10

The present work is concerned with the development and application of a novel fringe analysis technique based on the principles of the windowed-Fourier-transform (WFT) for the determination of temperature and concentration fields from interferometric images for a range of heat and mass transfer applications. Based on the extent of the noise level associated with the experimental data, the technique has been coupled with two different phase unwrapping methods: the Itoh algorithm and the quality guided phase unwrapping technique for phase extraction. In order to generate the experimental data, a range of experiments have been carried out which include cooling of a vertical flat plate in free convection conditions, combustion of mono-propellant flames, and growth of organic as well as inorganic crystals from their aqueous solutions. The flat plate and combustion experiments are modeled as heat transfer applications wherein the interest is to determine the whole-field temperature distribution. Aqueous-solution-based crystal growth experiments are performed to simulate the mass transfer phenomena and the interest is to determine the two-dimensional solute concentration field around the growing crystal. A Mach-Zehnder interferometer has been employed to record the path-integrated quantity of interest (temperature and/or concentration) in the form of interferometric images in the experiments. The potential of the WFT method has also been demonstrated on numerically simulated phase data for varying noise levels, and the accuracy in phase extraction have been quantified in terms of the root mean square errors. Three levels of noise, i.e., 0%, 10%, and 20% have been considered. Results of the present study show that the WFT technique allows an accurate extraction of phase values that can subsequently be converted into two-dimensional temperature and/or concentration distribution fields. Moreover, since WFT is a local processing technique, speckle patterns and the inherent noise in the interferometric data do not affect the resultant phase values. Brief comparisons of the accuracy of the WFT with other standard techniques such as conventional Fourier-filtering methods are also presented.

The Phase Transformation and Crystal Structure Studies of Strontium Substituted Barium Monoferrite

NASA Astrophysics Data System (ADS)

Mulyawan, A.; Adi, W. A.; Mustofa, S.; Fisli, A.

2017-03-01

Unlike other AFe2O4 ferrite materials, Barium Monoferrite (BaFe2O4) have an orthorhombic structure which is very interesting to further study the crystal structure and phase formation. In this study, Strontium substituted Barium Monoferrite in the form of Ba(1-x)Sr(x)Fe2O4 has successfully been synthesized through solid state reaction method which includes BaCO3, SrCO3, and Fe2O3 as starting materials. Ba(1-x)Sr(x)Fe2O4 was made by varying the dopant composition of Strontium (Sr2+) from x = 0, 0.1, 0.3, and 0.5. Each composition was assisted by ethanol and continued to the milling process for 5 hours then followed by sintering process at 900 °C for 5 hours. The phase transformation was studied by using X-ray diffractometer (XRD) and Rietveld refinement using General Structure Analysis System (GSAS) also 3D crystal visualization using VESTA. Referring to the refinement results, a single phase of BaFe2O4 was formed in x = 0 and 0.1. The composition has orthorhombic structure, space group B b21m, and lattice parameters of a = 19.0229, b = 5.3814 c = 8.4524 Å, α = β = γ = 90° and a = 18.9978, b = 5.3802 c = 8.4385 Å, α = β = γ = 90° respectively. In the composition of x = 0.3 it was found that the phase of BaSrFe4O8 begin to form due to the overload expansion of the Sr2+ occupancy which made the distortion of the initial lattice parameters and finally in the x = 0.5 composition the single phase of BaSrFe4O8 was clearly formed. Energy Dispersive Spectroscopy (EDS) was used to confirm the change of the material structure by measuring the elemental compound composition ratio. The result of EDS spectra clearly exhibited the dominant elements were Barium (Ba), Strontium (Sr), Iron (Fe), and Oxygen (O) with the compound ratio (Atomic percentage and mass percentage) correspond to the BaFe2O4 and BaSrFe4O8 phase.

Nanoindentation of silicon implanted with hydrogen: effect of implantation dose on silicon’s mechanical properties and nanoindentation-induced phase transformation

NASA Astrophysics Data System (ADS)

Jelenković, Emil V.; To, Suet; Goncharova, Lyudmila V.; Wong, Sing Fai

2017-07-01

Implantation of hydrogen in single-crystal silicon (c-Si) is known to affect its machining. However, very little is reported on the material and mechanical properties of hydrogen-implanted silicon (Si). In this article, near-surface regions (~0-500 nm) of lightly doped (1 0 0) Si were modified by varying the hydrogen concentration using ion implantation. The maximum hydrogen concentration was varied from ~4  ×  1020 to ~3.2  ×  1021 cm-3. The implanted Si was investigated by nanoindentation. From the dynamic nanoindentation test, it was found that in hydrogen-implanted Si hardness is increased significantly, while the elastic modulus is reduced. The nanoindentation-induced Si phase transformation was studied under different load/unload rates and loads. Raman spectroscopy revealed that the hydrogen implantation tends to suppress Si-XII and Si-III phases and facilitates amorphous Si formation during the unloading stage of nanoindentation. Both the mechanical properties and phase transformations were qualitatively related not only to the hydrogen concentration, but also to the implantation-generated defects and strain.

First-principles screening of structural properties of intermetallic compounds on martensitic transformation

NASA Astrophysics Data System (ADS)

Lee, Joohwi; Ikeda, Yuji; Tanaka, Isao

2017-11-01

Martensitic transformation with good structural compatibility between parent and martensitic phases are required for shape memory alloys (SMAs) in terms of functional stability. In this study, first-principles-based materials screening is systematically performed to investigate the intermetallic compounds with the martensitic phases by focusing on energetic and dynamical stabilities as well as structural compatibility with the parent phase. The B2, D03, and L21 crystal structures are considered as the parent phases, and the 2H and 6M structures are considered as the martensitic phases. In total, 3384 binary and 3243 ternary alloys with stoichiometric composition ratios are investigated. It is found that 187 alloys survive after the screening. Some of the surviving alloys are constituted by the chemical elements already widely used in SMAs, but other various metallic elements are also found in the surviving alloys. The energetic stability of the surviving alloys is further analyzed by comparison with the data in Materials Project Database (MPD) to examine the alloys whose martensitic structures may cause further phase separation or transition to the other structures.

Research opportunities in salt hydrates for thermal energy storage

NASA Astrophysics Data System (ADS)

Braunstein, J.

1983-11-01

The state of the art of salt hydrates as phase change materials for low temperature thermal energy storage is reviewed. Phase equilibria, nucleation behavior and melting kinetics of the commonly used hydrate are summarized. The development of efficient, reliable inexpensive systems based on phase change materials, especially salt hydrates for the storage (and retrieval) of thermal energy for residential heating is outlined. The use of phase change material thermal energy storage systems is not yet widespread. Additional basic research is needed in the areas of crystallization and melting kinetics, prediction of phase behavior in ternary systems, thermal diffusion in salt hydrate systems, and in the physical properties pertinent to nonequilibrium and equilibrium transformations in these systems.

Pressure-induced amorphization in orthorhombic Ta{sub 2}O{sub 5}: An intrinsic character of crystal

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

Li, Quanjun; Zhang, Huafang; Cheng, Benyuan

2014-05-21

The phase transition of orthorhombic Ta{sub 2}O{sub 5} was investigated by in situ synchrotron X-ray diffraction and Raman spectroscopy. The orthorhombic phase transforms into an amorphous form completely at 24.7 GPa. A bulk modulus B{sub 0} = 139 (9) GPa for the orthorhombic Ta{sub 2}O{sub 5} is derived from the P-V data. We suggest that the pressure-induced amorphization (PIA) in Ta{sub 2}O{sub 5} can be attributed to the unstability of the a axis under high pressure leads to the connections of polyhedral breaking down and even triggers disorder of the whole crystal frame. These results demonstrate that the PIA is an intrinsic charactermore » of Ta{sub 2}O{sub 5} which depends on its orthorhombic crystal structure rather than nanosize effects. This study provides a new kind of bulk material for investigating PIA in metal oxides.« less

Pressure evolution of electrical transport in the 3D topological insulator (Bi,Sb) 2 (Se,Te) 3

DOE PAGES

Jeffries, J. R.; Butch, N. P.; Vohra, Y. K.; ...

2015-03-18

The group V-VI compounds|like Bi 2Se 3, Sb 2Te 3, or Bi 2Te 3|have been widely studied in recent years for their bulk topological properties. The high-Z members of this series form with the same crystal structure, and are therefore amenable to isostructural substitution studies. It is possible to tune the Bi-Sb and Te-Se ratios such that the material exhibits insulating behavior, thus providing an excellent platform for understanding how a topological insulator evolves with applied pressure. We report our observations of the pressure-dependent electrical transport and crystal structure of a pseudobinary (Bi,Sb) 2(Te,Se) 3 compound. Similar to some ofmore » its sister compounds, the (Bi,Sb) 2(Te,Se) 3 pseudobinary compound undergoes multiple, pressure-induced phase transformations that result in metallization, the onset of a close-packed crystal structure, and the development of distinct superconducting phases.« less

Hydroxyapatite: Vibrational spectra and monoclinic to hexagonal phase transition

NASA Astrophysics Data System (ADS)

Slepko, Alexander; Demkov, Alexander A.

2015-02-01

Fundamental studies of biomaterials are necessary to deepen our understanding of their degradation and to develop cure for related illnesses. Biomineral hydroxyapatite Ca10(PO4)6(OH)2 is the main mineral constituent of mammal bone, and its synthetic analogues are used in biomedical applications. The mineral can be found in either hexagonal or monoclinic form. The transformation between these two phases is poorly understood, but knowing its mechanism may be critical to reversing processes in bone related to aging. Using density functional theory, we investigate the mechanisms of the phase transformation and estimate the transition temperature to be 680 K in fair agreement with the experimental temperature of 470 K. We also report the heat capacity of hydroxyapatite and a peculiarity in its phonon dispersion that might allow for non-destructive measurements of the crystal composition with applications in preventive medical screening for bone mineral loss.

Influence of Al content on non-equilibrium solidification behavior of Ni-Al-Ta model single crystal alloys

NASA Astrophysics Data System (ADS)

Ai, Cheng; Zhou, Jian; Zhang, Heng; Zhao, Xinbao; Pei, Yanling; Li, Shusuo; Gong, Shengkai

2016-01-01

The non-equilibrium solidification behaviors of five Ni-Al-Ta ternary model single crystal alloys with different Al contents were investigated by experimental analysis and theoretical calculation (by JMatPro) in this study. These model alloys respectively represented the γ' phase with various volume fractions (100%, 75%, 50%, 25% and 0%) at 900 °C. It was found that with decreasing Al content, liquidus temperature of experimental alloys first decreased and then increased. Meanwhile, the solidification range showed a continued downward trend. In addition, with decreasing Al content, the primary phases of non-equilibrium solidified model alloys gradually transformed from γ' phase to γ phase, and the area fraction of which first decreased and then increased. Moreover, the interdendritic/intercellular precipitation of model alloys changed from β phase (for 100% γ') to (γ+γ')Eutectic (for 75% γ'), (γ+γ')Eutectic+γ' (for 50% γ' and 25% γ') and none interdendritic precipitation (for 0% γ'), and the last stage non-equilibrium solidification sequence of model alloys was determined by the nominal Al content and different microsegregation behaviors of Al element.

VO{sub 2} (A): Reinvestigation of crystal structure, phase transition and crystal growth mechanisms

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

Rao Popuri, Srinivasa; University of Bordeaux, ICMCB, UPR 9048, F-33608 Pessac; National Institute for Research and Development in Electrochemistry and Condensed Matter, Timisoara, Plautius Andronescu Str. No. 1, 300224 Timisoara

2014-05-01

Well crystallized VO{sub 2} (A) microrods were grown via a single step hydrothermal reaction in the presence of V{sub 2}O{sub 5} and oxalic acid. With the advantage of high crystalline samples, we propose P4/ncc as an appropriate space group at room temperature. From morphological studies, we found that the oriented attachment and layer by layer growth mechanisms are responsible for the formation of VO{sub 2} (A) micro rods. The structural and electronic transitions in VO{sub 2} (A) are strongly first order in nature, and a marked difference between the structural transition temperatures and electronic transitions temperature was evidenced. The reversiblemore » intra- (LTP-A to HTP-A) and irreversible inter- (HTP-A to VO{sub 2} (M1)) structural phase transformations were studied by in-situ powder X-ray diffraction. Attempts to increase the size of the VO{sub 2} (A) microrods are presented and the possible formation steps for the flower-like morphologies of VO{sub 2} (M1) are described. - Graphical abstract: Using a single step and template free hydrothermal synthesis, well crystallized VO{sub 2} (A) microrods were prepared and the P4/ncc space group was assigned to the room temperature crystal structure. Reversible and irreversible phase transitions among different VO{sub 2} polymorphs were identified and their progressive nature was highlighted. Attempts to increase the microrods size, involving layer by layer formation mechanisms, are presented. - Highlights: • Highly crystallized VO{sub 2} (A) microrods were grown via a single step hydrothermal process. • The P4/ncc space group was determined for VO{sub 2} (A) at room temperature. • The electronic structure and progressive nature of the structural phase transition were investigated. • A weak coupling between structural and electronic phase transitions was identified. • Different crystallite morphologies were discussed in relation with growth mechanisms.« less

Elastic excitations in BaTiO3 single crystals and ceramics: Mobile domain boundaries and polar nanoregions observed by resonant ultrasonic spectroscopy

NASA Astrophysics Data System (ADS)

Salje, Ekhard K. H.; Carpenter, Michael A.; Nataf, Guillaume F.; Picht, Gunnar; Webber, Kyle; Weerasinghe, Jeevaka; Lisenkov, S.; Bellaiche, L.

2013-01-01

The dynamic properties of elastic domain walls in BaTiO3 were investigated using resonance ultrasonic spectroscopy (RUS). The sequence of phase transitions is characterized by minima in the temperature dependence of RUS resonance frequencies and changes in Q factors (resonance damping). Damping is related to the friction of mobile twin boundaries (90° ferroelectric walls) and distorted polar nanoregions (PNRs) in the cubic phase. Damping is largest in the tetragonal phase of ceramic materials but very low in single crystals. Damping is also small in the low-temperature phases of the ceramic sample and slightly increases with decreasing temperature in the single crystal. The phase angle between the real and imaginary part of the dynamic response function changes drastically in the cubic and tetragonal phases and remains constant in the orthorhombic phase. Other phases show a moderate dependence of the phase angle on temperature showing systematic changes of twin microstructures. Mobile twin boundaries (or sections of twin boundaries such as kinks inside twin walls) contribute strongly to the energy dissipation of the forced oscillation while the reduction in effective modulus due to relaxing twin domains is weak. Single crystals and ceramics show strong precursor softening in the cubic phase related to polar nanoregions (PNRs). The effective modulus decreases when the transition point of the cubic-tetragonal transformation is approached from above. The precursor softening follows temperature dependence very similar to recent results from Brillouin scattering. Between the Burns temperature (≈586 K) and Tc at 405 K, we found a good fit of the squared RUS frequency [˜Δ (C11-C12)] to a Vogel-Fulcher process with an activation energy of ˜0.2 eV. Finally, some first-principles-based effective Hamiltonian computations were carried out in BaTiO3 single domains to explain some of these observations in terms of the dynamics of the soft mode and central mode.

Magnetic properties and phase transformations of iron sulfides synthesized under the hydrothermal method

NASA Astrophysics Data System (ADS)

Li, S. H.; Chen, Y. H.

2016-12-01

The iron sulfide nano-minerals possess advantages of high abundance, low cost, and low toxicity. These advantages make them be competitive in the magnetic, electronic, and photoelectric applications. Mackinawite can be used in soil or water remediations. Greigite is very important for paleomagnetic and geochemical environment studies and the anode materials for lithium ion batteries. Besides, greigite is also utilized for hyperthermia and biomedicine. Pyrrhotite can be applied as geothermometry. Due to the above-mentioned reasons, iron sulfide minerals have specific significances and they must be further investigated, like their phase transformations, magnetic properties, and etc. In this study, the iron sulfide minerals were synthesized by using a hydrothermal method. The ex-situ and in-situ X-ray diffraction (XRD) was used to examine the crystal structure and phase transformation of iron sulfide minerals. The Transmission electron microscopy (TEM) and superconducting quantum interference device (SQUID) were carried out to investigate their morphology and magnetic properties, respectively. The results suggested that the phase transformation sequence was followed the order: mackinawite → greigite → (smythite) → pyrrhotite. Two pure mineral phases of greigite and pyrrhotite were obtained under the hydrothermal conditions. The morphology of the pure greigite is granular aggregates with a particle size of approximately 30 nm and pyrrhotite presented a hexagonal sheet stacking with a particle size of thousands nanometers. The greigite had a ferri-magnetic behavior and pyrrhotite was weak ferro-magnetic. Both of them had a pseudo-single magnetic domain (PSD) based on the Day's plot from SQUID data. The complete phase-transformation pathways and high magnetization of iron sulfide minerals are observed in this study and these kind of iron sulfide minerals are worthy to further study.

A novel laser-based method for controlled crystallization in dental prosthesis materials

NASA Astrophysics Data System (ADS)

Cam, Peter; Neuenschwander, Beat; Schwaller, Patrick; Köhli, Benjamin; Lüscher, Beat; Senn, Florian; Kounga, Alain; Appert, Christoph

2015-02-01

Glass-ceramic materials are increasingly becoming the material of choice in the field of dental prosthetics, as they can feature both high strength and very good aesthetics. It is believed that their color, microstructure and mechanical properties can be tuned such as to achieve an optimal lifelike performance. In order to reach that ultimate perfection a controlled arrangement of amorphous and crystalline phases in the material is required. A phase transformation from amorphous to crystalline is achieved by a heat treatment at defined temperature levels. The traditional approach is to perform the heat treatment in a furnace. This, however, only allows a homogeneous degree of crystallization over the whole volume of the parent glass material. Here a novel approach using a local heat treatment by laser irradiation is presented. To investigate the potential of this approach the crystallization process of SiO2-Li2O-Al2O3-based glass has been studied with laser systems (pulsed and continuous wave) operating at different wavelengths. Our results show the feasibility of gradual and partial crystallization of the base material using continuous laser irradiation. A dental prosthesis machined from an amorphous glassy state can be effectively treated with laser irradiation and crystallized within a confined region of a few millimeters starting from the body surface. Very good aesthetics have been achieved. Preliminary investigation with pulsed nanosecond lasers of a few hundreds nanoseconds pulse width has enabled more refinement of crystallization and possibility to place start of phase change within the material bulk.

Predicting kinetics of polymorphic transformations from structure mapping and coordination analysis

NASA Astrophysics Data System (ADS)

Stevanović, Vladan; Trottier, Ryan; Musgrave, Charles; Therrien, Félix; Holder, Aaron; Graf, Peter

2018-03-01

To extend materials design and discovery into the space of metastable polymorphs, rapid and reliable assessment of transformation kinetics to lower energy structures is essential. Herein we focus on diffusionless polymorphic transformations and investigate routes to assess their kinetics using solely crystallographic arguments. As part of this investigation we developed a general algorithm to map crystal structures onto each other, and ascertain the low-energy (fast-kinetics) transformation pathways between them. Pathways with minimal dissociation of chemical bonds, along which the number of bonds (in ionic systems the first-shell coordination) does not decrease below that in the end structures, are shown to always be the fast-kinetics pathways. These findings enable the rapid assessment of the kinetics of polymorphic transformation and the identification of long-lived metastable structures. The utility is demonstrated on a number of transformations including those between high-pressure SnO2 phases, which lack a detailed atomic-level understanding.

Giant Magnetoelectric Energy Conversion Utilizing Inter-Ferroelectric Phase Transformations in Ferroics

NASA Astrophysics Data System (ADS)

Finkel, Peter; Staruch, Margo

Phase transition-based electromechanical transduction permits achieving a non-resonant broadband mechanical energy conversion see (Finkel et al Actuators, 5 [1] 2. (2015)) , the idea is based on generation high energy density per cycle , at least 100x of magnitude larger than linear piezoelectric type generators in stress biased [011]cut relaxor ferroelectric Pb(In1/2Nb1/2)O3-Pb(Mg1/3Nb2/3)O3-PbTiO3 (PIN-PMN-PT) single crystal can generate reversible strain >0.35% at remarkably low fields (0.1 MV/m) for tens of millions of cycles. Recently we demonstrated that large strain and polarization rotation can be generated for over 40 x 106cycles with little fatigue by realization of reversible ferroelectric-ferroelectric phase transition in [011] cut PIN-PMN-PT relaxor ferroelectric single crystal while sweeping through the transition with a low applied electric field <0.18 MV/m under mechanical stress. This methodology was extended in the present work to propose magnetoelectric (ME) composite hybrid system comprised of highly magnetostrictive alloymFe81.4Ga18.6 (Galfenol), and lead indium niobate-lead magnesium niobate-lead titanate (PIN-PMN-PT) domain engineered relaxor ferroelectric single crystal. A small time-varying magnetic field applied to this system causes the magnetostrictive element to expand, and the resulting stress forces the phase change in the relaxor ferroelectric single crystal. ME coupling coefficient was fond to achieve 80 V/cm Oe near the FR-FO phase transition that is at least 100X of magnitude higher than any currently reported values.

High-Pressure Phase Relations and Crystal Structures of Postspinel Phases in MgV2O4, FeV2O4, and MnCr2O4: Crystal Chemistry of AB2O4 Postspinel Compounds.

PubMed

Ishii, Takayuki; Sakai, Tsubasa; Kojitani, Hiroshi; Mori, Daisuke; Inaguma, Yoshiyuki; Matsushita, Yoshitaka; Yamaura, Kazunari; Akaogi, Masaki

2018-06-04

We have investigated high-pressure, high-temperature phase transitions of spinel (Sp)-type MgV 2 O 4 , FeV 2 O 4 , and MnCr 2 O 4 . At 1200-1800 °C, MgV 2 O 4 Sp decomposes at 4-7 GPa into a phase assemblage of MgO periclase + corundum (Cor)-type V 2 O 3 , and they react at 10-15 GPa to form a phase with a calcium titanite (CT)-type structure. FeV 2 O 4 Sp transforms to CT-type FeV 2 O 4 at 12 GPa via decomposition phases of FeO wüstite + Cor-type V 2 O 3 . MnCr 2 O 4 Sp directly transforms to the calcium ferrite (CF)-structured phase at 10 GPa and 1000-1400 °C. Rietveld refinements of CT-type MgV 2 O 4 and FeV 2 O 4 and CF-type MnCr 2 O 4 confirm that both the CT- and CF-type structures have frameworks formed by double chains of edge-shared B 3+ O 6 octahedra (B 3+ = V 3+ and Cr 3+ ) running parallel to one of orthorhombic cell axes. A relatively large A 2+ cation (A 2+ = Mg 2+ , Fe 2+ , and Mn 2+ ) occupies a tunnel-shaped space formed by corner-sharing of four double chains. Effective coordination numbers calculated from eight neighboring oxygen-A 2+ cation distances of CT-type MgV 2 O 4 and FeV 2 O 4 and CF-type MnCr 2 O 4 are 5.50, 5.16, and 7.52, respectively. This implies that the CT- and CF-type structures practically have trigonal prism (six-coordinated) and bicapped trigonal prism (eight-coordinated) sites for the A 2+ cations, respectively. A relationship between cation sizes of VIII A 2+ and VI B 3+ and crystal structures (CF- and CT-types) of A 2+ B 2 3+ O 4 is discussed using the above new data and available previous data of the postspinel phases. We found that CF-type A 2+ B 2 3+ O 4 crystallize in wide ionic radius ranges of 0.9-1.4 Å for VIII A 2+ and 0.55-1.1 Å for VI B 3+ , whereas CT-type phases crystallize in very narrow ionic radius ranges of ∼0.9 Å for VIII A 2+ and 0.6-0.65 Å for VI B 3+ . This would be attributed to the fact that the tunnel space of CT-type structure is geometrically less flexible due to the smaller coordination number for A 2+ cation than that of CF-type.

Structural complexity of simple Fe 2O 3 at high pressures and temperatures

DOE PAGES

Bykova, Elena; Dubrovinsky, L.; Dubrovinskaia, N.; ...

2016-02-11

Although chemically very simple, Fe 2O 3 is known to undergo a series of enigmatic structural, electronic and magnetic transformations at high pressures and high temperatures. So far, these transformations have neither been correctly described nor understood because of the lack of structural data. Here we report a systematic investigation of the behaviour of Fe 2O 3 at pressures over 100 GPa and temperatures above 2,500 K employing single crystal X-ray diffraction and synchrotron Mössbauer source spectroscopy. Crystal chemical analysis of structures presented here and known Fe(II, III) oxides shows their fundamental relationships and that they can be described bymore » the homologous series nFeO·mFe 2O 3. Decomposition of Fe 2O 3 and Fe 3O 4 observed at pressures above 60 GPa and temperatures of 2,000 K leads to crystallization of unusual Fe 5O 7 and Fe 25O 32 phases with release of oxygen. Lastly, our findings suggest that mixed-valence iron oxides may play a significant role in oxygen cycling between earth reservoirs.« less

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.

Acanthite–argentite transformation in nanocrystalline silver sulfide and the Ag{sub 2}S/Ag nanoheterostructure

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

Gusev, A. I., E-mail: gusev@ihim.uran.ru; Sadovnikov, S. I.

Nanocrystalline acanthite-structured silver sulfide of the monoclinic structure and a Ag{sub 2}S/Ag nanoheterostructure are produced. The high-temperature X-ray diffraction technique is applied to the in situ study of the (acanthite α-Ag{sub 2}S)–(argentite β-Ag{sub 2}S) phase transformation in nanocrystalline silver sulfide. The crystal structure of argentite is refined, and it is found that the content of vacant sites in the metal sublattice of argentite exceeds 92%. A model of a resistive switch, whose operation is based on the reversible acanthite–argentite transformation in a Ag{sub 2}S/Ag heterostructure, is considered.

Enhanced ferroelectric properties and thermal stability of nonstoichiometric 0.92(Na0.5Bi0.5)TiO3-0.08(K0.5Bi0.5)TiO3 single crystals

NASA Astrophysics Data System (ADS)

Zhang, Haiwu; Chen, Chao; Zhao, Xiangyong; Deng, Hao; Li, Long; Lin, Di; Li, Xiaobing; Ren, Bo; Luo, Haosu; Yan, Jun

2013-11-01

Bi deficient, Mn doped 0.92(Na0.5Bi0.5)TiO3-0.08(K0.5Bi0.5)TiO3 single crystals were grown by carefully controlled top-seeded solution growth method. Local structures were investigated by transmission electron microscopy. The site occupation and valence state of manganese were characterized by electron paramagnetic resonance spectrum. The leakage current density in the as-grown single crystals is effectively depressed. The introduced defect complexes suppress the temperature induced phase transformation, increasing the depolarization temperature (165 °C) and thermal stability of ferroelectric properties.

Nanoplate-like tungsten trioxide (hydrate) films prepared by crystal-seed-assisted hydrothermal reaction

NASA Astrophysics Data System (ADS)

Wang, P.; Yang, L.; Dai, B.; Yang, Z.; Guo, S.; Zhu, J.

2017-07-01

Vertically-aligned WO3 nanoplates on transparent conducting fluorine-doped tin oxide (FTO) glass were prepared by a facile template-free crystal-seed-assisted hydrothermal method. The effects of the hydrothermal temperature and reaction time on the crystal structure and morphology of the products were investigated by XRD and SEM. The XRD results showed that the as-prepared thin films obtained below 150∘C comprised orthorhombic WO3 ṡ H2O and completely converted to monoclinic WO3 at 180∘C. It was also noted that there was a phase transformation from orthorhombic to monoclinic by increasing the reaction time from 1 to 12 h. SEM analysis revealed that WO3 thin films are composed of plate-like nanostructures.

Phase transformations and phase equilibria in the Co–Sn–Ti system in the crystallization interval

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

Fartushna, Iu.; Bulanova, M.; National Technical University of Ukraine, Kiev Polytechnical Institute, Kiev

2016-12-15

The Co–Sn–Ti system was studied in the crystallization interval (below ~50 at% Sn) by the methods of Scanning Electron Microscopy, microprobe analysis, Differential Thermal Analysis, X-ray diffraction. The liquidus and solidus projections and the melting diagram were constructed. Only Co{sub 2}TiSn(τ1) ternary compound (Heusler phase-L1{sub 2}) was found in equilibria with the liquid in the concentration interval studied. Taking into account our recent data, the liquidus projection is characterized by the fields of primary crystallization of (βTi), (Co), binary-based phases Ti{sub 3}Sn, Ti{sub 2}Sn, Ti{sub 5}Sn{sub 3}, Ti{sub 6}Sn{sub 5}, Ti{sub 2}Co, TiCo, TiCo{sub 2} (c), TiCo{sub 2} (h), TiCo{submore » 3}, βCo{sub 3}Sn{sub 2}, CoSn and ternary τ1. The solidus projection is characterized by thirteen three-phase fields, which result from invariant four-phase equilibria, five are of eutectic type (E) and eight of transition type (U) and the existence of one more region Ti{sub 2}Sn{sub 3}+βCoSn{sub 3}+(Sn) in the solidus projection is discussed. - Graphical abstract: Liquidus projection of the Ti–РЎРѕ –Sn system. Fields of crystallization, isotherms and monovariant lines. - Highlights: • The Ti–Co–Sn system is first studied in the composition range up to 50% of Sn. • Liquidus and solidus projections, melting diagram and reaction scheme are constructed. • One ternary compound form in the studied temperature interval: (Co{sub 2}TiSn(τ1)).« less

Fourier transform-infrared studies of thin H2SO4/H2O films: Formation, water uptake, and solid-liquid phase changes

NASA Technical Reports Server (NTRS)

Middlebrook, Ann M.; Iraci, Laura T.; Mcneill, Laurie S.; Koehler, Birgit G.; Wilson, Margaret A.; Saastad, Ole W.; Tolbert, Margaret A.; Hanson, David R.

1993-01-01

Fourier transform-infrared (FTIR) spectroscopy was used to examine films representative of stratospheric sulfuric acid aerosols. Thin films of sulfuric acid were formed in situ by the condensed phase reaction of SO3 with H2O. FTIR spectra show that the sulfuric acid films absorb water while cooling in the presence of water vapor. Using stratospheric water pressures, the most dilute solutions observed were greater than 40 wt % before simultaneous ice formation and sulfuric acid freezing occurred. FTIR spectra also revealed that the sulfuric acid films crystallized mainly as sulfuric acid tetrahydrate (SAT). Crystallization occurred either when the composition was about 60 wt% H2SO4 or after ice formed on the films at temperatures 1-4 K below the ice frost point. Finally, we determined that the melting point for SAT depended on the background water pressure and was 216-219 K in the presence of 4 x 10(exp -4) Torr H2O. Our results suggest that once frozen, sulfuric acid aerosols in the stratosphere are likely to melt at these temperatures, 30 K colder than previously thought.

MaRIE first experiments summaries version: May 9, 2010

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

Sarrao, John L

2010-01-01

A predictive understanding of microstructure-based heterogeneity and its consequences for materials damage & failure and phase transformation initiation is presently lacking. Most metallic materials used in applications are polycrystalline aggregates - individual single crystals separated by grain boundaries. Most of these materials are either metallic alloys or contain impurities. In either case, there is spatial variability in their chemical composition. These materials also contain dislocations which will be distributed in some way throughout the individual grains and increase in density with deformation and typically form dislocation sub-cell arrangements - producing spatial distribution in dislocation density. Many materials also produce twinmore » or slip band structures with deformation which produce further heterogeneity within individual crystals. The objective of this first experiment is to probe the physics of dynamic solid-solid phase transformation and damage at length scales approaching those at which they nucleate in order to gain a detailed understanding of this process and the influence real material microstructure has on these events. These experiments would simultaneously be simulated by the appropriate modeling tools to further develop these predictive tools and to assist in our interpretation of experimental results.« less

Diffusive, Displacive Deformations and Local Phase Transformation Govern the Mechanics of Layered Crystals: The Case Study of Tobermorite.

PubMed

Tao, Lei; Shahsavari, Rouzbeh

2017-07-19

Understanding the deformation mechanisms underlying the mechanical behavior of materials is the key to fundamental and engineering advances in materials' performance. Herein, we focus on crystalline calcium-silicate-hydrates (C-S-H) as a model system with applications in cementitious materials, bone-tissue engineering, drug delivery and refractory materials, and use molecular dynamics simulation to investigate its loading geometry dependent mechanical properties. By comparing various conventional (e.g. shear, compression and tension) and nano-indentation loading geometries, our findings demonstrate that the former loading leads to size-independent mechanical properties while the latter results in size-dependent mechanical properties at the nanometer scales. We found three key mechanisms govern the deformation and thus mechanics of the layered C-S-H: diffusive-controlled and displacive-controlled deformation mechanisms, and strain gradient with local phase transformations. Together, these elaborately classified mechanisms provide deep fundamental understanding and new insights on the relationship between the macro-scale mechanical properties and underlying molecular deformations, providing new opportunities to control and tune the mechanics of layered crystals and other complex materials such as glassy C-S-H, natural composite structures, and manmade laminated structures.

Transformation twinning of Ni-Mn-Ga characterized with temperature-controlled atomic force microscopy.

PubMed

Reinhold, Matthew; Watson, Chad; Knowlton, William B; Müllner, Peter

2010-06-01

The magnetomechanical properties of ferromagnetic shape memory alloy Ni-Mn-Ga single crystals depend strongly on the twin microstructure, which can be modified through thermomagnetomechanical training. Atomic force microscopy (AFM) and magnetic force microscopy (MFM) were used to characterize the evolution of twin microstructures during thermomechanical training of a Ni-Mn-Ga single crystal. Experiments were performed in the martensite phase at 25 degrees C and in the austenite phase at 55 degrees C. Two distinct twinning surface reliefs were observed at room temperature. At elevated temperature (55 degrees C), the surface relief of one twinning mode disappeared while the other relief remained unchanged. When cooled back to 25 degrees C, the twin surface relief recovered. The relief persisting at elevated temperature specifies the positions of twin boundaries that were present when the sample was polished prior to surface characterization. AFM and MFM following thermomechanical treatment provide a nondestructive method to identify the crystallographic orientation of each twin and of each twin boundary plane. Temperature dependent AFM and MFM experiments reveal the twinning history thereby establishing the technique as a unique predictive tool for revealing the path of the martensitic and reverse transformations of magnetic shape memory alloys.

Transformation twinning of Ni–Mn–Ga characterized with temperature-controlled atomic force microscopy

PubMed Central

Reinhold, Matthew; Watson, Chad; Knowlton, William B.; Müllner, Peter

2010-01-01

The magnetomechanical properties of ferromagnetic shape memory alloy Ni–Mn–Ga single crystals depend strongly on the twin microstructure, which can be modified through thermomagnetomechanical training. Atomic force microscopy (AFM) and magnetic force microscopy (MFM) were used to characterize the evolution of twin microstructures during thermomechanical training of a Ni–Mn–Ga single crystal. Experiments were performed in the martensite phase at 25 °C and in the austenite phase at 55 °C. Two distinct twinning surface reliefs were observed at room temperature. At elevated temperature (55 °C), the surface relief of one twinning mode disappeared while the other relief remained unchanged. When cooled back to 25 °C, the twin surface relief recovered. The relief persisting at elevated temperature specifies the positions of twin boundaries that were present when the sample was polished prior to surface characterization. AFM and MFM following thermomechanical treatment provide a nondestructive method to identify the crystallographic orientation of each twin and of each twin boundary plane. Temperature dependent AFM and MFM experiments reveal the twinning history thereby establishing the technique as a unique predictive tool for revealing the path of the martensitic and reverse transformations of magnetic shape memory alloys. PMID:20589105

Humidity induced phase transformation of poloxamer 188 and its effect on physical stability of amorphous solid dispersion of AMG 579, a PDE10A inhibitor.

PubMed

Wu, Qiong; Kennedy, Michael T; Nagapudi, Karthik; Kiang, Y-H

2017-04-15

Poloxamer 188, a commonly used emulsifying and solubilizing agent, was found to be the cause of crystallization of an investigational drug, AMG 579, from its amorphous solid dispersion at accelerated storage conditions. Investigation of this physical stability issue included thorough characterization of poloxamer 188 at non-ambient conditions. At 40°C, poloxamer 188 becomes deliquescent above relative humidity of 75%. Upon returning to ambient conditions, the deliquescent poloxamer 188 loses water and re-solidifies. The reversible phase transformation of poloxamer 188 may cause physical and chemical stability issues and this risk should be assessed when selecting it as an excipient for formulation development. Copyright © 2017 Elsevier B.V. All rights reserved.

Escape of carbon element in surface ablation of cobalt cemented tungsten carbide with pulsed UV laser

NASA Astrophysics Data System (ADS)

Li, Tiejun; Lou, Qihong; Dong, Jingxing; Wei, Yunrong; Liu, Jingru

2001-03-01

Surface ablation of cobalt cemented tungsten carbide hardmetal has been carried out in this work using a 308 nm, 30 ns XeCl excimer laser. The surface phase transformation on different pulse number of laser shots has been investigated by means of XRD and microphotography as well as AES at laser fluence of 2.5 J/cm 2. The experimental results showed that the phase structure of irradiated area has partly transformed from original WC to β-WC 1- x, then to α-W 2C and CW 3, and finally to W crystal. It is suggested that the formation of non-stoichiometric tungsten carbide should result from the escaping of carbon element due to accumulated heating of surface by pulsed laser irradiation.

The deviations of the Al6Li3Cu quasicrystal from icosahedral symmetry : a reminiscence of a cubic crystal

NASA Astrophysics Data System (ADS)

Donnadieu, Patricia

1994-05-01

The (Al6Li3Cu) (T2) quasicrystals are known to exhibit large deviations from the icosahedral symmetry. Series of electron diffraction patterns are used to investigate these imperfections in as-cast T, samples. A detailed analysis of the 5-fold and 3-fold symmetry diffraction patterns shows that they are compatible with the m3 point group instead of the m35 icosahedral group. This symmetry reduction is interprétéd as reminiscent of the cubic approximant phase (R-Al5Li3Cu) rather than of higher order approximant phases. This interpretation is supported by previous observations on crystal/quasicrystal phase transformation in the AlLiCu system. Les quasicristaux de phase T2(Al6Li3Cu) montrent d'importantes déviations à la symétrie icosaédrique. Ces imperfections sont mises en évidence par diffraction électronique dans des échantillons de phase T2 brut de coulée. Un examen détaillé des diagrammes de diffraction de symétrie d'ordre 3 et 5 révèle qu'ils sont compatibles avec le groupe ponctuel m3 au lieu du groupe de l'icosaèdre (m35). Cette réduction de symétrie est interprétée comme une réminiscence de la phase cubique approximante (R-Al5Li3Cu) et non l'apparition d'approximant d'ordre plus élevé. Cette interprétation est suggérée par des observations antérieures sur la transformation cristal/quasicristal dans le système AlLiCu.

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.

Crystallization kinetics of orthorhombic paracetamol from supercooled melts studied by non-isothermal DSC.

PubMed

Nikolakakis, Ioannis; Kachrimanis, Kyriakos

2017-02-01

A simple and highly reproducible procedure was established for the study of orthorhombic paracetamol crystallization kinetics, comprising melting, quench-cooling of the melt and scanning the formed glass by DSC at different heating rates. Results were analyzed on the basis of the mean as well as local values of the Avrami exponent, n, the energy of activation, as well as the Šesták-Berggren two-parameter autocatalytic kinetic model. The mean value of the Avrami kinetic exponent, n, ranged between 3 and 5, indicating deviation from the nucleation and growth mechanism underlying the Johnson-Mehl, Avrami-Kolmogorov (JMAK) model. To verify the extent of the deviation, local values of the Avrami exponent as a function of the volume fraction transformed were calculated. Inspection of the local exponent values indicates that the crystallization mechanism changes over time, possibly reflecting the uncertainty of crystallization onset, instability of nucleation due to an autocatalytic effect of the crystalline phase, and growth anisotropy due to impingement of spherulites in the last stages of crystallization. The apparent energy of activation, E a , has a rather low mean value, close to 81 kJ/mol, which is in agreement with the observed instability of glassy-state paracetamol. Isoconversional methods revealed that E a tends to decrease with the volume fraction transformed, possibly because of the different energy demands of nucleation and growth. The exponents of the Šesták-Berggren two-parameter model showed that the crystallized fraction influences the process, confirming the complexity of the crystallization mechanism.

Structure and reactions in some amphiphilic association systems

NASA Astrophysics Data System (ADS)

Guo, Rong

1999-06-01

The partial determinations of phase diagrams for some typical surfactants, such as SDS, CTAB and Triton X-100, give the basic aggregated states of the surfactant systems. In the micellar solutions, the diffusion coefficients of some surfactant association systems are determined by the cyclic voltammetry without any probe and used to describe the phase structure. (1) The first CMC, which represents the formation of spherical micelles, and the second CMC, which represents the transformation from spherical to rod-like micelles, are measured. The first and the second CMC are 8.0 x 10-3 mol. L -1 and 5.6 x 10-3 mol. L-1 for SDS, 8.9 x 10-4 mol. L-1 and 2.1 x 10-2 mol. L-1 for CTAB, and 3.2 x 10 -4 mol. L-1 and 1.3 x 10-3 mol. L-1 for Triton X-100, respectively. (2) The addition of polar additives, such as ethanol and benzyl alcohol (BA) in SDS micelles, or hexanol in Triton X-100 micelles, increases the diffusion coefficients and diffusion activation energy, decreases the micropolarity of the micelles with different shape, and causes the transformation from rod-like micelles to spherical ones or from spherical micelles to bicontinuous structure. (3) The isotropic region, which connects to the water comer in the phase diagram, is probably not an area of a single O/W structure, but an area with three different structures---the rod structure, spherical structure and the bicontinuous one. In the lyotropic liquid crystalline phase, the measurements of the small angle X-ray diffraction indicate that the structure parameters, such as interlayer spacing and water penetration, are related to the compositions of the surfactant association systems. The lamellar liquid crystal has a high water penetration but the hexagonal liquid crystal only has a water penetration about 0.05. Some surfactant association systems have been applied in the hydrotrope action of vitamin C (VC) and preparation of nanoparticles, respectively. Vitamin C (VC) can be used as hydrotrope agent in the cationic surfactant CTAB system with various co-surfactants: n-pentanol, n-octanol, n-valeric acid, and n-caproic acid, but not in SDS or Triton X-100 systems. Presence of VC stabilizes both W/O and O/W microemulsions but destabilizes the lamellar liquid crystalline phase. Hence, the "phase transition" from the lamellar liquid crystalline phase to the isotropic phase of O/W, W/O and bicontinuous structure phase occurs with the addition of VC. The hydrotropic action of VC has been used in sunscreens to increase the solubility of sunscreen E 557. The UV absorption spectra of E557 in various media surprisingly had a dependence on the colloid structure. A new method, the preparation of water-soluble nanoparticles, has been found by employing the effect of the penetration of solvent from water layer to amphiphilic layer in lamellar liquid crystals on the solubility of inorganic salts. Water-insoluble nanoparticles have been synthesized by the reaction of two water-soluble inorganic salts in the lamellar liquid crystal. The particle size is less than 10nm and can be controlled by the thickness of the solvent layer in the lamellar liquid crystal. The lamellar liquid crystalline phase of the Triton X-100/decanol/water system has been chosen as a medium because of its large lamellar liquid crystal region and its stability when inorganic salts are added.

Stability of Ni-bsed bulk metallic glasses

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

Tokarz, Michelle L; Speakman, Scott A; Porter, Wallace D

Several ternary (Ni{sub x}Nb{sub y}Sn{sub z}) refractory alloy glasses (RAGs) were studied at elevated temperatures in order to assess the stability of the amorphous state, i.e. devitrification, and to identify subsequent phase transformations in these materials. differential scanning calorimetry (DSC) experiments indicated a complex phase transformation sequence with several distinct crystallization and melting events being recorded above the glass transition temperature, T{sub g}. Below T{sub g} the RAG samples were studied with an in situ environmental X-ray furnace facility, which allowed step-wise isothermal ramping experiments commencing at a temperature below the reduced temperature of T/T{sub g} {approx} 0.80. Distinct crystallinemore » phases were observed when T/T{sub g} {approx} 0.84 for ternary RAG alloys, while similar experiments on Zr-based Vit 106 glass alloys did not reveal any apparent phase separation until T/T{sub g} {approx} 0.96. The phase separation kinetics followed an Arrhenius type of relationship with Ni{sub 3}Sn, and Nb{sub 2}O{sub 5} being the principle crystalline precipitates.« less

Preparation and characterization of Phase change material microcapsules by a core-shell-like emulsion polymerization method

NASA Astrophysics Data System (ADS)

Ding, Li-ming; Pei, Guang-ling

2015-07-01

Phase change material microcapsules (MicroPCMs) were synthesized by a coreshell-like emulsion polymerization method. Styrene and methylacrylic acid copolymer (PS- MAA) was used as a wall material, and paraffin was used as a core material in order to prepare spherical, high resistance and high enthalpy MicroPCMs. Scanning Electron Microscope (SEM), laser particle size analyzer, Fourier Transform Infrared Spectroscopy (FTIR), Thermogravimetry (TG) and Differential Scanning Calorimeter (DSC) were employed to characterize the MicroPCMs. The results indicated that the average particle size of MicroPCMs was 42.29 μm, and the content of paraffin within microcapsules was 57.6%. The melting temperature and crystallization temperature were 30.7°C and 25.2°C.The melting enthalpy and crystallization enthalpy were -84.1 J/g and 91.3 J/g, respectively.

Serial Femtosecond Crystallography Opens New Avenues for Structural Biology

PubMed Central

Coe, Jesse; Fromme, Petra

2016-01-01

Free electron lasers (FELs) provide X-ray pulses in the femtosecond time domain with up to 1012 higher photon flux than synchrotrons and open new avenues for the determination of difficult to crystallize proteins, like large complexes and human membrane proteins. While the X-ray pulses are so strong that they destroy any solid material, the crystals diffract before they are destroyed. The most successful application of FELs for biology has been the method of serial femtosecond crystallography (SFX) where nano or microcrystals are delivered to the FEL beam in a stream of their mother liquid at room temperature, which ensures the replenishment of the sample before the next X-ray pulse arrives. New injector technology allows also for the delivery of crystal in lipidic cubic phases or agarose, which reduces the sample amounts for an SFX data set by two orders of magnitude. Time-resolved SFX also allows for analysis of the dynamics of biomolecules, the proof of principle being recently shown for light-induced reactions in photosystem II and photoactive yellow protein. An SFX data sets consist of thousands of single crystal snapshots in random orientations, which can be analyzed now “on the fly” by data analysis programs specifically developed for SFX, but de-novo phasing is still a challenge, that might be overcome by two-color experiments or phasing by shape transforms. PMID:26786767

High-Temperature Stable Anatase Titanium Oxide Nanofibers for Lithium-Ion Battery Anodes.

PubMed

Lee, Sangkyu; Eom, Wonsik; Park, Hun; Han, Tae Hee

2017-08-02

Control of the crystal structure of electrochemically active materials is an important approach to fabricating high-performance electrodes for lithium-ion batteries (LIBs). Here, we report a methodology for controlling the crystal structure of TiO 2 nanofibers by adding aluminum isopropoxide to a common sol-gel precursor solution utilized to create TiO 2 nanofibers. The introduction of aluminum cations impedes the phase transformation of electrospun TiO 2 nanofibers from the anatase to the rutile phase, which inevitably occurs in the typical annealing process utilized for the formation of TiO 2 crystals. As a result, high-temperature stable anatase TiO 2 nanofibers were created in which the crystal structure was well-maintained even at high annealing temperatures of up to 700 °C. Finally, the resulting anatase TiO 2 nanofibers were utilized to prepare LIB anodes, and their electrochemical performance was compared to pristine TiO 2 nanofibers that contain both anatase and rutile phases. Compared to the electrode prepared with pristine TiO 2 nanofibers, the electrode prepared with anatase TiO 2 nanofibers exhibited excellent electrochemical performances such as an initial Coulombic efficiency of 83.9%, a capacity retention of 89.5% after 100 cycles, and a rate capability of 48.5% at a current density of 10 C (1 C = 200 mA g -1 ).

The effect of crystal structure of TiO2 nanotubes on the formation of calcium phosphate coatings during biomimetic deposition

NASA Astrophysics Data System (ADS)

Liu, Yi; Kim, Sun; McLeod, John A.; Li, Jun; Guo, Xiaoxuan; Sham, Tsun-Kong; Liu, Lijia

2017-02-01

The crystallization process of bioactive calcium phosphate (CaP) species via biomimetic deposition onto anodic TiO2 nanotubes is investigated. The porous surface of nanostructured TiO2 provides an ideal substrate for CaP crystallization. The compositions of CaP coatings are studied using X-ray absorption near-edge structures (XANES) at the Ca K-edge. Using detection modes with different probing depths, both the surface of the CaP coating and the CaP-TiO2 interface are simultaneously analyzed. Calcium phosphate (CaP) species, such as hydroxyapatite (HAp), octacalcium phosphate (Ca8(HPO4)2(PO4)4·5H2O, OCP), brushite (CaHPO4·2H2O, DCPD), and amorphous calcium phosphate (ACP), are found in the CaP coatings. TiO2 nanotubes of amorphous and anatase phases are comparatively studied to determine their effect on the efficiency of CaP formation and the phase transformation among CaP species in prolonged deposition time. It is found the composition of CaP coating has a strong dependency on the crystal structure of TiO2 substrate and the kinetics (deposition time).

Single-pass, efficient type-I phase-matched frequency doubling of high-power ultrashort-pulse Yb-fiber laser using LiB_3O_5

NASA Astrophysics Data System (ADS)

Shukla, Mukesh Kumar; Kumar, Samir; Das, Ritwick

2016-05-01

We report 48 % efficient single-pass second harmonic generation of high-power ultrashort-pulse ({≈ }250 fs) Yb-fiber laser by utilizing type-I phase matching in LiB_3O_5 (LBO) crystal. The choice of LBO among other borate crystals for high-power frequency doubling is essentially motivated by large thermal conductivity, low birefringence and weak group velocity dispersion. By optimally focussing the beam in a 4-mm-long LBO crystal, we have generated about 2.3 W of average power at 532 nm using 4.8 W of available pump power at 1064 nm. The ultrashort green pulses were found out to be near-transform limited sech^2 pulses with a pulse width of Δ τ ≈ 150 fs and being delivered at 78 MHz repetition rate. Due to appreciably low spatial walk-off angle for LBO ({≈ }0.4°), we obtain M^2<1.26 for the SH beam which signifies marginal distortion in comparison with the pump beam (M^2<1.15). We also discuss the impact of third-order optical nonlinearity of the LBO crystal on the generated ultrashort SH pulses.

Snapshots of crystal growth: Nanoclusters of organic conductors on Au(111) surfaces

NASA Astrophysics Data System (ADS)

Schott, J. H.; Ward, M. D.

1994-06-01

Mono- and multilayer crystalline nanoclusters of tetra-hiafulvalene-tetracyanoquinodimethane ((TTF) (TCNO)), a low-dimensional organic conductor in the bulk form, can be formed readily on Au(111) surfaces by vapor phase sublimation under ambient conditions. Scanning tunneling microscopy of monolayer (TTF)(TCNQ) films reveals a two-dimensional density of states (DOS) that is consistent with the arrangement of TTF and TCNO molecules in the ac face of bulk (TTF)(TCNO), in which the molecular planes are nearly parallel to the Au(111) substrate. In contrast, clusters with thicknesses corresponding to two or three molecular layers exhibit a transformation to a highly anisotropic DOS that can be attributed to interlayer molecular overlap in segregated TTF and TCNQ molecular chains along the c-axis, which can be described as 'molecular wires'. The orientation of the crystalline (TTF)(TCNO) clusters is preserved throughout the crystal growth sequence, leading to meso- and macroscopic (TTF)(TCNO) needles that are oriented perpendicular to the Au(111) substrate. These studies provide visualization of crystal growth from the initial stages of nucleation to macroscopic crystals, and a revealing example of the changes in electronic structure that occur during the evolution of molecular (TTF)(TCNQ) nuclei into a bulk crystalline phase.

Synthesis of iron oxide nanorods via chemical scavenging and phase transformations of intermediates at ambient conditions

NASA Astrophysics Data System (ADS)

Deshmukh, Ruchi; Mehra, Anurag; Thaokar, Rochish

2017-01-01

Chemically induced shape transformations of isotropic seeds, comprised of iron oxyhydroxides and iron oxide borate into nanorods, is reported. Transient growth studies show that the nanorods are formed via phase transformation and aggregation of various metastable species. Addition of tetra- methyl-ammonium hydroxide (TMAH) to the in situ synthesized seeds ensures a typical reaction pathway that favors formation of magnetite (Fe 3 O 4) via the steps of chemical etching, phase transformation of intermediates, and crystal consolidation. Whereas, with addition of sodium hydroxide (NaOH), either magnetite (Fe 3 O 4) or a mixture of ( γ-Fe 2 O 3 + α-FeOOH) is obtained. The shape with both the additives is always that of nanorods. When the seeds treated with TMAH were aged in an ultrasonication bath, rods with almost twice the length and diameter (length = 2800 nm, diameter = 345 nm) are obtained as compared to the sample aged without ultrasonication (length = 1535 nm, diameter = 172 nm). The morphology of nanostructures depending upon other experimental conditions such as, aging the sample at 60 ∘C, seeds synthesized under ultrasonication/ stirring or externally added are also examined and discussed in detail. All the samples show high coercivity and strong ferromagnetic behavior at room temperature and should be promising candidates as ferro-fluids for various applications.

Temperature-mediated phase transformation, pore geometry and pore hysteresis transformation of borohydride derived in-born porous zirconium hydroxide nanopowders

PubMed Central

Nayak, Nadiya B.; Nayak, Bibhuti B.

2016-01-01

Development of in-born porous nature of zirconium hydroxide nanopowders through a facile hydrogen (H2) gas-bubbles assisted borohydride synthesis route using sodium borohydride (NaBH4) and novel information on the temperature-mediated phase transformation, pore geometry as well as pore hysteresis transformation of in-born porous zirconium hydroxide nanopowders with the help of X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) isotherm and Transmission Electron Microscopy (TEM) images are the main theme of this research work. Without any surfactants or pore forming agents, the borohydride derived amorphous nature of porous powders was stable up to 500 °C and then the seed crystals start to develop within the loose amorphous matrix and trapping the inter-particulate voids, which led to develop the porous nature of tetragonal zirconium oxide at 600 °C and further sustain this porous nature as well as tetragonal phase of zirconium oxide up to 800 °C. The novel hydrogen (H2) gas-bubbles assisted borohydride synthesis route led to develop thermally stable porous zirconium hydroxide/oxide nanopowders with an adequate pore size, pore volume, and surface area and thus these porous materials are further suggested for promising use in different areas of applications. PMID:27198738

Dynamic compression of minerals in the magnesium oxide-iron oxide-silicon dioxide system

NASA Astrophysics Data System (ADS)

Akins, Joseph A.

The first shock wave experiments performed on silicate materials were reported for quartz in 1962. The intervening forty years have allowed for extensive investigation of SiO2 by dynamic, static and theoretical means. Previous studies have concluded that quartz transforms completely to stishovite at ˜40 GPa and melts at ˜115 GPa along its Hugoniot. Recent discoveries that SiO2 transforms to phases slightly more dense than stishovite have led to a reexamination of the dynamic compression of SiO2 in this thesis. Based on comparing calculated Hugoniots to data for multiple initial SiO2 phases, it is proposed that, in addition to the stishovite and melt transitions, quartz is completely transformed to the CaCl2 structure at ˜70 GPa. Coesite shows evidence of complete transformation to stishovite at ˜50 GPa, and to the CaCl 2 structure at ˜65 GPa. Due to the higher temperature achieved in the quartz samples the slope of the stishovite-CaCl2 phase boundary is constrained to be ˜180 K/GPa. From a similar analysis of Hugoniot data collected for high quality MgSiO 3 natural crystal and synthetic glass in this study, and existing data, it is concluded that along the crystal Hugoniot akimotoite is attained at ˜70 GPa, perovskite structure at ˜110 GPa and melt at ˜170 GPa. It is found that the melt is 2--3% denser than the solid at pressures greater than 100 GPa, after correcting for thermal differences in the two regimes. An important implication is a negative Clapeyron slope, leading to a decreasing melting temperature with increasing pressure, above ˜100 GPa. These observations increase the possibility of the existence of a significant amount of partial melt in the lowermost mantle, e.g., the ultra low velocity zone.

The compressibility of cubic white and orthorhombic, rhombohedral, and simple cubic black phosphorus

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

Clark, Simon M; Zaug, Joseph

2010-03-10

The effect of pressure on the crystal structure of white phosphorus has been studied up to 22.4 GPa. The ?alpha phase was found to transform into the alpha' phase at 0.87 +- 0.04 GPa with a volume change of 0.1 +- 0.3 cc/mol. A fit of a second order Birch- Murnaghan equation to the data gave Vo = 16.94 ? 0.08 cc/mol and Ko = 6.7 +- 0.5 GPa for the alpha phase and Vo = 16.4 +- 0.1 cc/mol and Ko = 9.1 +- 0.3 GPa for the alpha' phase. The alpha' phase was found to transform to themore » A17 phase of black phosphorus at 2.68 +- 0.34 GPa and then with increasing pressure to the A7 and then simple cubic phase of black phosphorus. A fit of a second order Birch-Murnaghan equation to our data combined with previous measurements gave Vo = 11.43 +- 0.05 cc/mol and Ko = 34.7 +- 0.5 GPa for the A17 phase, Vo = 9.62 +- 0.01 cc/mol and Ko = 65.0 +- 0.6 GPa for the A7 phase and , Vo = 9.23 +- 0.01 cc/mol and Ko = 72.5 +- 0.3 GPa for the simple cubic phase.« less

High-resolution 2-D Bragg diffraction reveal heterogeneous domain transformation behavior in a bulk relaxor ferroelectric

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

Pramanick, Abhijit, E-mail: apramani@cityu.edu.hk; Stoica, Alexandru D.; An, Ke

2016-08-29

In-situ measurement of fine-structure of neutron Bragg diffraction peaks from a relaxor single-crystal using a time-of-flight instrument reveals highly heterogeneous mesoscale domain transformation behavior under applied electric fields. It is observed that only ∼25% of domains undergo reorientation or phase transition contributing to large average strains, while at least 40% remain invariant and exhibit microstrains. Such insights could be central for designing new relaxor materials with better performance and longevity. The current experimental technique can also be applied to resolve complex mesoscale phenomena in other functional materials.

High-resolution 2-D Bragg diffraction reveal heterogeneous domain transformation behavior in a bulk relaxor ferroelectric

DOE PAGES

Pramanick, Abhijit; Stoica, Alexandru D.; An, Ke

2016-09-02

In-situ measurement of fine-structure of neutron Bragg diffraction peaks from a relaxor single-crystal using a time-of-flight instrument reveals highly heterogeneous mesoscale domain transformation behavior under applied electric fields. We observed that only 25% of domains undergo reorienta- tion or phase transition contributing to large average strains, while at least 40% remain invariant and exhibit microstrains. Such insights could be central for designing new relaxor materials with better performance and longevity. The current experimental technique can also be applied to resolve com- plex mesoscale phenomena in other functional materials.

Characterization of the calcification of cardiac valve bioprostheses by environmental scanning electron microscopy and vibrational spectroscopy.

PubMed

Delogne, Christophe; Lawford, Patricia V; Habesch, Steven M; Carolan, Vikki A

2007-10-01

Bioprosthetic heart valve tissue and associated calcification were studied in their natural state, using environmental scanning electron microscopy (ESEM). Energy dispersive X-ray micro-analysis, X-ray diffraction, Fourier-transform infrared and Raman spectroscopy were used to characterize the various calcific deposits observed with ESEM. The major elements present in calcified valves were also analyzed by inductively coupled plasma-optical emission spectroscopy. To better understand the precursor formation of the calcific deposits, results from the elemental analyses were statistically correlated. ESEM revealed the presence of four broad types of calcium phosphate crystal morphology. In addition, two main patterns of organization of calcific deposits were observed associated with the collagen fibres. Energy dispersive X-ray micro-analysis identified the crystals observed by ESEM as salts containing mainly calcium and phosphate with ratios from 1.340 (possibly octacalcium phosphate, which has a Ca/P ratio of 1.336) to 2.045 (possibly hydroxyapatite with incorporation of carbonate and metal ion contaminants, such as silicon and magnesium, in the crystal lattice). Raman and fourier-transform infrared spectroscopy also identified the presence of carbonate and the analyses showed spectral features very similar to a crystalline hydroxyapatite spectrum, also refuting the presence of precursor phases such as beta-tricalcium phosphate, octacalcium phosphate and dicalcium phosphate dihydrate. The results of this study raised the possibility of the presence of precursor phases associated with the early stages of calcification.

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.

Rotator Phases of n-Heptane under High Pressure: Raman Scattering and X-ray Diffraction Studies

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

C Ma; Q Zhou; F Li

2011-12-31

We performed high-pressure Raman scattering and angle-dispersive synchrotron X-ray diffraction measurements on n-heptane at room temperature. It has been found that n-heptane undergoes a liquid to rotator phase III (R{sub III}) transition at 1.2 GPa and then transforms into another rotator phase R{sub IV} at about 3 GPa. As the pressure reaches 7.5 GPa, a transition from an orientationally disordered R{sub IV} phase to an ordered crystalline state starts and is completed around 14.5 GPa. Our results clearly present the high-pressure phase transition sequence (liquid-R{sub III}-R{sub IV}-crystal) of n-heptane, similar to that of normal alkanes.

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.

Mold Flux Crystallization and Mold Thermal Behavior

NASA Astrophysics Data System (ADS)

Peterson, Elizabeth Irene

Mold flux plays a small but critical role in the continuous casting of steel. The carbon-coated powder is added at the top of the water-cooled copper mold, over time it melts and infiltrates the gap between the copper mold and the solidifying steel strand. Mold powders serve five primary functions: (1) chemical insulation, (2) thermal insulation, (3) lubrication between the steel strand and mold, (4) absorption of inclusions, and (5) promotion of even heat flux. All five functions are critical to slab casting, but surface defect prevention is primarily controlled through even heat flux. Glassy fluxes have high heat transfer and result in a thicker steel shell. Steels with large volumetric shrinkage on cooling must have a crystalline flux to reduce the radiative heat transfer and avoid the formation of cracks in the shell. Crystallinity plays a critical role in steel shell formation, therefore it is important to study the thermal conditions that promote each phase and its morphology. Laboratory tests were performed to generate continuous cooling transformation (CCT) and time-temperature-transformation (TTT) diagrams. Continuous cooling transformation tests were performed in an instrumented eight cell step chill mold. Results showed that cuspidine was the only phase formed in conventional fluxes and all observed structures were dendritic. An isothermal tin bath quench method was also developed to isothermally age glassy samples. Isothermal tests yielded different microstructures and different phases than those observed by continuous cooling. Comparison of aged tests with industrial flux films indicates similar faceted structures along the mold wall, suggesting that mold flux first solidifies as a glass along the mold wall, but the elevated temperature devitrifies the glassy structure forming crystals that cannot form by continuous cooling.

Characterising laser beams with liquid crystal displays

NASA Astrophysics Data System (ADS)

Dudley, Angela; Naidoo, Darryl; Forbes, Andrew

2016-02-01

We show how one can determine the various properties of light, from the modal content of laser beams to decoding the information stored in optical fields carrying orbital angular momentum, by performing a modal decomposition. Although the modal decomposition of light has been known for a long time, applied mostly to pattern recognition, we illustrate how this technique can be implemented with the use of liquid-crystal displays. We show experimentally how liquid crystal displays can be used to infer the intensity, phase, wavefront, Poynting vector, and orbital angular momentum density of unknown optical fields. This measurement technique makes use of a single spatial light modulator (liquid crystal display), a Fourier transforming lens and detector (CCD or photo-diode). Such a diagnostic tool is extremely relevant to the real-time analysis of solid-state and fibre laser systems as well as mode division multiplexing as an emerging technology in optical communication.

Growth of tungsten oxide nanostructures by chemical solution deposition

NASA Astrophysics Data System (ADS)

Jin, L. H.; Bai, Y.; Li, C. S.; Wang, Y.; Feng, J. Q.; Lei, L.; Zhao, G. Y.; Zhang, P. X.

2018-05-01

Tungsten oxide nanostructures were fabricated on LaAlO3 (00l) substrates by a simple chemical solution deposition. The decomposition behavior and phase formation of ammonium tungstate precursor were characterized by thermal analysis and X-ray diffraction. Moreover, the morphology and chemical state of nanostructures were analyzed by scanning electron microscopy, atomic force microscopy and X-ray photoelectron spectra. The effects of crystallization temperature on the formation of nanodots and nanowires were investigated. The results indicated that the change of nanostructures had close relationship with the crystallization temperature during the chemical solution deposition process. Under higher crystallization temperature, the square-like dots transformed into the dome-like nanodots and nanowires. Moreover high density well-ordered nanodots could be obtained on the substrate with the further increase of crystallization temperature. It also suggested that this simple chemical solution process could be used to adjust the nanostructures of tungsten oxide compounds on substrate.

Acoustic Emission from Organic Martensites.

PubMed

Panda, Manas K; Etter, Martin; Dinnebier, Robert E; Naumov, Panče

2017-07-03

In salient effects, still crystals of solids that switch between phases acquire a momentum and are autonomously propelled because of rapid release of elastic energy accrued during a latent structural transition induced by heat, light, or mechanical stimulation. When mechanical reconfiguration is induced by change of temperature in thermosalient crystals, bursts of detectable acoustic waves are generated prior to self-actuation. These observations provide compelling evidence that the thermosalient transitions in organic and organic-containing crystals are molecular analogues of the martensitic transitions in some metals, and metal alloys such as steel and shape-memory alloys. Within a broader context, these results reveal that, akin to metallic bonding, the intermolecular interactions in molecular solids are capable of gradual accrual and sudden release of a substantial amount of strain during anisotropic thermal expansion, followed by a rapid transformation of the crystal packing in a diffusionless, non-displacive transition. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quasi-equilibrium size distribution of subcritical nuclei in amorphous phase change AgIn-Sb2Te

NASA Astrophysics Data System (ADS)

Darmawikarta, Kristof; Lee, Bong-Sub; Shelby, Robert M.; Raoux, Simone; Bishop, Stephen G.; Abelson, John R.

2013-07-01

We investigate the effect of low temperature annealing or of extended storage at room temperature on the subsequent nucleation behavior of amorphous AgIn-incorporated Sb2Te (AIST), a material for phase change memories. Time-resolved reflectivity measurements during pulsed laser crystallization reveal the rates of solid-phase transformation, while fluctuation transmission electron microscopy detects the nanoscale order in the amorphous phase prior to crystallization. The nanoscale order is postulated to consist of subcritical nuclei that coarsen upon annealing at temperatures ranging from 25 °C (for months) or 100 °C (for hours). Samples that have been annealed remain fully amorphous as evaluated by conventional diffraction experiments. Shorter nucleation times are consistently associated with the observation of increased nanoscale order. The effect of annealing is observed to saturate: there is no further reduction in nucleation time or increase in nanoscale order for annealing at 100 °C beyond three hours. This result supports the general prediction of classical nucleation theory that the size distribution of subcritical nuclei increases from the as-deposited state to a quasi-equilibrium.

Raman study of TiO2 role in SiO2-Al2O3-MgO-TiO2-ZnO glass crystallization.

PubMed

Furić, Kresimir; Stoch, Leszek; Dutkiewicz, Jan

2005-05-01

Tough glass-ceramic material of special mechanical properties with nanosize crystal phases formed by appropriately controlled crystallization was studied by Raman spectroscopy. It was obtained by TiO2 activated crystallization of Mg-aluminosilicate glass of SiO2-Al2O3-MgO-TiO2-ZnO composition. Crystallization was preceded by a change in the TiO2 structural position and state, which is manifested by a changed color of glass from yellow into blue shortly before the glass transformation (Tg) temperature. Raman spectroscopy was applied to explain the mechanism of this process and to establish the role of TiO2 in the early stage of glass crystallization that precedes a complete crystal phase formation. The starting glasses were found in almost complete disorder, since all bands were weak, broad and dominated by a Bose band at about 90 cm-1. After the sample annealing all bands turned out better resolved and the Bose band practically disappeared, both confirming the amorphous structure reorganization process. A multiplet observed in the vicinity of 150 cm-1 we assigned to the anatase and other titania structures that can be considered prime centers of crystallization. Finally, in the closest neighborhood of the Rayleigh line the low frequency mode characterizing nanoparticles was observed. According to this band theory, the mean size of initial titania crystallites is about 10nm for all samples, but the size distribution varies within factor two among them.

Raman study of TiO 2 role in SiO 2-Al 2O 3-MgO-TiO 2-ZnO glass crystallization

NASA Astrophysics Data System (ADS)

Furić, Krešimir; Stoch, Leszek; Dutkiewicz, Jan

2005-05-01

Tough glass-ceramic material of special mechanical properties with nanosize crystal phases formed by appropriately controlled crystallization was studied by Raman spectroscopy. It was obtained by TiO 2 activated crystallization of Mg-aluminosilicate glass of SiO 2-Al 2O 3-MgO-TiO 2-ZnO composition. Crystallization was preceded by a change in the TiO 2 structural position and state, which is manifested by a changed color of glass from yellow into blue shortly before the glass transformation ( Tg) temperature. Raman spectroscopy was applied to explain the mechanism of this process and to establish the role of TiO 2 in the early stage of glass crystallization that precedes a complete crystal phase formation. The starting glasses were found in almost complete disorder, since all bands were weak, broad and dominated by a Bose band at about 90 cm -1. After the sample annealing all bands turned out better resolved and the Bose band practically disappeared, both confirming the amorphous structure reorganization process. A multiplet observed in the vicinity of 150 cm -1 we assigned to the anatase and other titania structures that can be considered prime centers of crystallization. Finally, in the closest neighborhood of the Rayleigh line the low frequency mode characterizing nanoparticles was observed. According to this band theory, the mean size of initial titania crystallites is about 10 nm for all samples, but the size distribution varies within factor two among them.

On the nature of the reversibility of hydration-dehydration on the crystal structure and magnetism of the ferrimagnet [MnII(enH)(H2O)][CrIII(CN)6].H2O.

PubMed

Yoshida, Yusuke; Inoue, Katsuya; Kurmoo, Mohamedally

2009-01-05

We report the synthesis, crystal structure, and thermal and magnetic properties of the two-dimensional achiral soft ferrimagnet [Mn(II)(enH)(H(2)O)][Cr(III)(CN)(6)].H(2)O (1), en = 1,2-diaminoethane, as well as the recyclability of the dehydration and rehydration and their influence on the crystal structure and its magnetic properties. Unlike [Mn(S-pnH)(H(2)O)][Cr(CN)(6)].H(2)O (2S, pn = 1,2-diaminopropane), which is a chiral (P2(1)2(1)2(1)) enantiopure ferrimagnet (T(C) = 38 K), 1 crystallizes in the achiral orthorhombic Pcmn space group, having a similar two-dimensional square network of Mn-Cr with bridging cyanide, and 1 behaves also as a soft ferrimagnet (T(C) = 42 K). X-ray diffraction experiments on a single crystal of 1 indicate a transformation from a single crystal to an amorphous phase upon dehydrataion and partial recovery of its crystallinity upon rehydration. The dehydrated phase 1-DP exhibits long-range ordering at 75 K to a ferrimagnetic state and coercive field at 2 K of 100 Oe, which are a higher critical temperature and coercive field than for the virgin sample (H(C) = 60 Oe). Thermogravimetric analyses indicate that the crystallinity deteriorates upon hydration-dehydration cycling, with persistence toward the amorphous phase, as also seen by magnetization measurements. This effect is associated with an increase of statistical disorder inherent in the dehydration-rehydration process. X-ray powder diffraction suggests that 1-DP may retain order within the layers but loses coherence in the stacking of the layers.

Variation in the Helical Structure of Native Collagen

DTIC Science & Technology

2014-02-24

unsampled molecular transform of the sample (non-crystalline diffraction arising from the helical symmetry), these patterns also contain Bragg peaks...tissues may be treated as analogous to that from a single macromolecular crystal. Except that it arises from many fibrils within the sample , giving rise...density maps, constructed from experimentally determined phases and observed amplitudes, showed good agreement. The observed diffraction and the simulated

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

Imaging the Hydrogen Absorption Dynamics of Individual Grains in Polycrystalline Palladium Thin Films in 3D

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

Yau, Allison; Harder, Ross J.; Kanan, Matthew W.

Defects such as dislocations and grain boundaries often control the properties of polycrystalline materials. In nanocrystalline materials, investigating this structure-function relationship while preserving the sample remains challenging because of the short length scales and buried interfaces involved. Here we use Bragg coherent diffractive imaging to investigate the role of structural inhomogeneity on the hydriding phase transformation dynamics of individual Pd grains in polycrystalline films in three-dimensional detail. In contrast to previous reports on single- and polycrystalline nanoparticles, we observe no evidence of a hydrogen-rich surface layer and consequently no size dependence in the hydriding phase transformation pressure over a 125-325more » nm size range. We do observe interesting grain boundary dynamics, including reversible rotations of grain lattices while the material remains in the hydrogen-poor phase. The mobility of the grain boundaries, combined with the lack of a hydrogen-rich surface layer, suggests that the grain boundaries are acting as fast diffusion sites for the hydrogen atoms. Such hydrogen-enhanced plasticity in the hydrogen poor phase provides insight into the switch from the size-dependent behavior of single-crystal nanoparticles to the lower transformation pressures of polycrystalline materials and may play a role in hydrogen embrittlement.« less

Application of the fractional Fourier transform to the design of LCOS based optical interconnects and fiber switches.

PubMed

Robertson, Brian; Zhang, Zichen; Yang, Haining; Redmond, Maura M; Collings, Neil; Liu, Jinsong; Lin, Ruisheng; Jeziorska-Chapman, Anna M; Moore, John R; Crossland, William A; Chu, D P

2012-04-20

It is shown that reflective liquid crystal on silicon (LCOS) spatial light modulator (SLM) based interconnects or fiber switches that use defocus to reduce crosstalk can be evaluated and optimized using a fractional Fourier transform if certain optical symmetry conditions are met. Theoretically the maximum allowable linear hologram phase error compared to a Fourier switch is increased by a factor of six before the target crosstalk for telecom applications of -40 dB is exceeded. A Gerchberg-Saxton algorithm incorporating a fractional Fourier transform modified for use with a reflective LCOS SLM is used to optimize multi-casting holograms in a prototype telecom switch. Experiments are in close agreement to predicted performance.

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.

Vortex Airy beams directly generated via liquid crystal q-Airy-plates

NASA Astrophysics Data System (ADS)

Wei, Bing-Yan; Liu, Sheng; Chen, Peng; Qi, Shu-Xia; Zhang, Yi; Hu, Wei; Lu, Yan-Qing; Zhao, Jian-Lin

2018-03-01

Liquid crystal q-Airy-plates with director distributions integrated by q-plates and polarization Airy masks are proposed and demonstrated via the photoalignment technique. Single/dual vortex Airy beams of opposite topological charges and orthogonal circular polarizations are directly generated with polarization-controllable characteristic. The singular phase of the vortex part is verified by both astigmatic transformation and digital holography. The trajectory of vortex Airy beams is investigated, manifesting separate propagation dynamics of optical vortices and Airy beams. Meanwhile, Airy beams still keep their intrinsic transverse acceleration, self-healing, and nondiffraction features. This work provides a versatile candidate for generating high-quality vortex Airy beams.

Microstructural changes in Beta-silicon nitride grains upon crystallizing the grain-boundary glass

NASA Technical Reports Server (NTRS)

Lee, William E.; Hilmas, Gregory E.; Lange, F. F. (Editor)

1991-01-01

Crystallizing the grain boundary glass of a liquid phase sintered Si3N4 ceramic for 2 h or less at 1500 C led to formation of gamma Y2Si2O7. After 5 h at 1500 C, the gamma Y2Si2O7 had transformed to beta Y2Si2O7 with a concurrent dramatic increase in dislocation density within beta Si3N4 grains. Reasons for the increased dislocation density is discussed. Annealing for 20 h at 1500 C reduced dislocation densities to the levels found in as-sintered materials.

Science Using an Electrostatic Levitation Furnace in the MUCAT Sector at the APS

NASA Technical Reports Server (NTRS)

Goldman, A.; Kelton, K. F.; Rogers, J. R.

2004-01-01

The original motivation for the construction of the BESL prototype was to obtain the first proof of a 50-year-old hypothesis regarding the solidification of liquid metals. Since the 1950s it has been known that under proper conditions liquid metals can be cooled below their melting temperature (undercooled) without crystallizing to the stable solid phase. In 1952 Frank proposed that this was because the atoms in the metallic liquid were arranged with the symmetry of an icosahedron, a Platonic solid consisting of 20 tetrahedra (4-sided pyramid-shaped polyhedra) arranged around a common center. Since this local atomic order is incompatible with the long-range translational periodicity of crystal phases, a barrier is formed to the formation of small regions of the crystal phase, the nucleation barrier. A proof of Frank's hypothesis required a direct correlation between measured icosahedral order in the undercooled liquid and the nucleation barrier. The tendency of sample containers to catalyze nucleation obscured this relation, requiring containerless techniques. Combining containerless processing techniques for electrostatically levitated droplets (ESL) with x-ray synchrotron methods, a team from Washington University, St. Louis, MO, NASA Marshall Space Flight Center, and MUCAT at the APS demonstrated an increasing icosahedral order in TiZrNi liquids with decreasing temperature below the melting temperature. The increased icosahedral order caused the transformation of the liquid to a metastable icosahedral quasicrystal phase, instead of the stable tetrahedrally-coordinated crystal intermetallic, giving the first clear demonstration of the connection between the nucleation barrier and the local structure of the liquid, verifying Frank's hypothesis for this alloy.

Phase transition analysis of V-shaped liquid crystal: Combined temperature-dependent FTIR and density functional theory approach

NASA Astrophysics Data System (ADS)

Singh, Swapnil; Singh, Harshita; Karthick, T.; Tandon, Poonam; Prasad, Veena

2018-01-01

Temperature-dependent Fourier transform infrared spectroscopy (FTIR) combined with density functional theory (DFT) is employed to study the mechanism of phase transitions of V-shaped bent-core liquid crystal. Since it has a large number of flexible bonds, one-dimensional potential energy scan (PES) was performed on the flexible bonds and predicted the most stable conformer I. A detailed analysis of vibrational normal modes of conformer I have been done on the basis of potential energy distribution. The good agreement between the calculated spectrum of conformer I and observed FTIR spectrum at room temperature validates our theoretical structure model. Furthermore, the prominent changes observed in the stretching vibrational bands of CH3/CH2, Cdbnd O, ring CC, ring CO, ring CH in-plane bending, and ring CH out-of-plane bending at Iso → nematic phase transition (at 155 °C) have been illustrated. However, the minor changes in the spectral features observed for the other phase transitions might be due to the shape or bulkiness of molecules. Combined FTIR and PES study beautifully explained the dynamics of the molecules, molecular realignment, H-bonding, and conformational changes at the phase transitions.

Phase Transformations and Metallization of Magnesium Oxide at High Pressure and Temperature

NASA Astrophysics Data System (ADS)

McWilliams, R. Stewart; Spaulding, Dylan K.; Eggert, Jon H.; Celliers, Peter M.; Hicks, Damien G.; Smith, Raymond F.; Collins, Gilbert W.; Jeanloz, Raymond

2012-12-01

Magnesium oxide (MgO) is representative of the rocky materials comprising the mantles of terrestrial planets, such that its properties at high temperatures and pressures reflect the nature of planetary interiors. Shock-compression experiments on MgO to pressures of 1.4 terapascals (TPa) reveal a sequence of two phase transformations: from B1 (sodium chloride) to B2 (cesium chloride) crystal structures above 0.36 TPa, and from electrically insulating solid to metallic liquid above 0.60 TPa. The transitions exhibit large latent heats that are likely to affect the structure and evolution of super-Earths. Together with data on other oxide liquids, we conclude that magmas deep inside terrestrial planets can be electrically conductive, enabling magnetic field-producing dynamo action within oxide-rich regions and blurring the distinction between planetary mantles and cores.

Dehydration of Uranyl Nitrate Hexahydrate to Uranyl Nitrate Trihydrate under Ambient Conditions as Observed via Dynamic Infrared Reflectance Spectroscopy

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

Johnson, Timothy J.; Sweet, Lucas E.; Meier, David E.

2015-05-22

the hexahydrate [UO 2(NO 3) 2(H 2O) 6] (UNH) and the trihydrate [UO 2(NO 3) 2(H 2O) 3] (UNT) forms. Their stabilities depend on both relative humidity and temperature. Both phases have previously been studied by infrared transmission spectroscopy, but the data were limited by both instrumental resolution and the ability to prepare the samples as pellets without desiccating them. We report time-resolved infrared (IR) measurements using an integrating sphere that allow us to observe the transformation from the hexahydrate to the trihydrate simply by flowing dry nitrogen gas over the sample. Hexahydrate samples were prepared and confirmed via knownmore » XRD patterns, then measured in reflectance mode. The hexahydrate has a distinct uranyl asymmetric stretch band at 949.0 cm -1 that shifts to shorter wavelengths and broadens as the sample dehydrates and recrystallizes to the trihydrate, first as a blue edge shoulder but ultimately resulting in a doublet band with reflectance peaks at 966 and 957 cm -1. The data are consistent with transformation from UNH to UNT since UNT has two non-equivalent UO 2 2+ sites. The dehydration of UO 2(NO 3) 2(H 2O) 6 to UO 2(NO 3) 2(H 2O) 3 is both a morphological and structural change that has the lustrous lime green crystals changing to the dull greenish yellow of the trihydrate. Crystal structures and phase transformation were confirmed theoretically using DFT calculations and experimentally via microscopy methods. Both methods showed a transformation with two distinct sites for the uranyl cation in the trihydrate, as opposed to a single crystallographic site in the hexahydrate.« less

Microstructure, Thermal, Mechanical, and Dielectric Properties of BaO-CaO-Al2O3-B2O3-SiO2 Glass-Ceramics

NASA Astrophysics Data System (ADS)

Li, Bo; Bian, Haibo; Fang, Yi

2017-12-01

BaO-CaO-Al2O3-B2O3-SiO2 (BCABS) glass-ceramics were prepared via the method of controlled crystallization. The effect of CaO modification on the microstructure, phase evolution, as well as thermal, mechanical, and dielectric properties was investigated. XRD identified that quartz is the major crystal phase; cristobalite and bazirite are the minor crystal phases. Moreover, the increase of CaO could inhibit the phase transformation from quartz to cristobalite, but excessive CaO would increase the porosity of the ceramics. Additionally, with increasing the amount of CaO, the thermal expansion curve tends to be linear, and subsequently the CTE value decreases gradually, which is attributed to the decrease of cristobalite with high CTE and the formation of CaSiO3 with low CTE. The results indicated that a moderate amount of CaO helps attaining excellent mechanical, thermal, and dielectric properties, that is, the specimen with 9 wt% CaO sintered at 950 °C has a high CTE value (11.5 × 10-6/°C), a high flexural strength (165.7 MPa), and good dielectric properties (ɛr = 6.2, tanδ = 1.8 × 10-4, ρ = 4.6 × 1011 Ω•cm).

High-Pressure High-Temperature Phase Diagram of the Organic Crystal Paracetamol

NASA Astrophysics Data System (ADS)

Smith, Spencer; Montgomery, Jeffrey; Vohra, Yogesh

High-pressure high-temperature (HPHT) Raman spectroscopy studies have been performed on the organic crystal paracetamol in a diamond anvil cell utilizing boron-doped diamond as heating anvil. The HPHT data obtained from boron-doped diamond heater is cross-checked with data obtained using a standard block heater diamond anvil cell. Isobaric measurements were conducted at pressures up to 8.5 GPa and temperature up to 520 K in a number of different experiments. Solid state phase transitions from monoclinic Form I --> orthorhombic Form II were observed at various pressures and temperatures as well as transitions from Form II --> unknown Form IV. The melting temperature for paracetamol was observed to increase with increasing pressures to 8.5 GPa. Our previous angle dispersive x-ray diffraction studies at the Advanced Photon Source has confirmed the existence of two unknown crystal structures Form IV and Form V of paracetamol at high pressure and ambient temperature. The phase transformation from Form II to Form IV occurs at ~8.5 GPa and from Form IV to Form V occurs at ~11 GPa at ambient temperature. Our new data is combined with the previous ambient temperature high-pressure Raman and X- ray diffraction data to create the first HPHT phase diagram of paracetamol. Doe-NNSA Carnegie DOE Alliance Center (CDAC) under Grant Number DE-NA0002006.

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.

Liquid crystal waveguides: new devices enabled by >1000 waves of optical phase control

NASA Astrophysics Data System (ADS)

Davis, Scott R.; Farca, George; Rommel, Scott D.; Johnson, Seth; Anderson, Michael H.

2010-02-01

A new electro-optic waveguide platform, which provides unprecedented voltage control over optical phase delays (> 2mm), with very low loss (< 0.5 dB/cm) and rapid response time (sub millisecond), will be presented. This technology, developed by Vescent Photonics, is based upon a unique liquid-crystal waveguide geometry, which exploits the tremendous electro-optic response of liquid crystals while circumventing their historic limitations. The waveguide geometry provides nematic relaxation speeds in the 10's of microseconds and LC scattering losses that are reduced by orders of magnitude from bulk transmissive LC optics. The exceedingly large optical phase delays accessible with this technology enable the design and construction of a new class of previously unrealizable photonic devices. Examples include: 2-D analog non-mechanical beamsteerers, chip-scale widely tunable lasers, chip-scale Fourier transform spectrometer (< 5 nm resolution demonstrated), widely tunable micro-ring resonators, tunable lenses, ultra-low power (< 5 microWatts) optical switches, true optical time delay devices for phased array antennas, and many more. All of these devices may benefit from established manufacturing technologies and ultimately may be as inexpensive as a calculator display. Furthermore, this new integrated photonic architecture has applications in a wide array of commercial and defense markets including: remote sensing, micro-LADAR, OCT, FSO, laser illumination, phased array radar, etc. Performance attributes of several example devices and application data will be presented. In particular, we will present a non-mechanical beamsteerer that steers light in both the horizontal and vertical dimensions.

Phase change studies in Se85In15-xZnx chalcogenide thin films

NASA Astrophysics Data System (ADS)

Srivastava, Archana; Tiwari, S. N.; Alvi, M. A.; Khan, Shamshad A.

2018-03-01

This research work describes the phase change studies in Se85In15-xZnx thin films at various annealing temperatures. Glassy samples of Se85In15-xZnx were synthesized by the melt quenching method and thin films of thickness 400 nm were prepared by the vacuum evaporation technique on a glass/Si wafer substrate. The glass transition temperature (Tg) and the on-set crystallization temperature (Tc) of the prepared alloys were evaluated by non-isothermal differential scanning calorimetry studies. Thin films were annealed at three temperatures 330 K, 340 K, and 350 K (which are in between Tg and Tc of the synthesized samples) in a vacuum furnace for 2 h. High resolution X-ray diffraction studies demonstrate that the as-prepared films are amorphous in nature whereas the annealed films are of crystalline/polycrystalline in nature. Field emission scanning electron microscopy studies of thin films (as-deposited and crystallized) confirm the phase transformation in Se85In15-xZnx thin films. Optical band gaps were calculated from the Tauc's extrapolation procedure and were found to be enhanced with the Zn concentration and decrease with the increasing annealing temperature. Various optical parameters were evaluated for as-prepared and annealed Se85In15-xZnx thin films. The changes in optical parameters with annealing temperature were described on the basis of structural relaxation as well as changes in defect states and density of localized states during amorphous to crystalline phase transformation in Se85In15-xZnx thin films.

Bottom-up on-crystal in-chip formation of a conducting salt and a view of its restructuring: from organic insulator to conducting "switch" through microfluidic manipulation.

PubMed

Puigmartí-Luis, Josep; Paradinas, Markos; Bailo, Elena; Rodriguez-Trujillo, Romen; Pfattner, Raphael; Ocal, Carmen; Amabilino, David B

2015-06-01

The chemical modification of an immobilized single crystal in a fluid cell is reported, whereby a material with switching functions is generated in situ by generating a chemical reagent in the flow. Crystals of the insulating organic crystal of TCNQ (tetracyanoquinodimethane) were grown in a microfluidic channel and were trapped using a pneumatic valve, a nascent technique for materials manipulation. They were subsequently reduced using solution-deposited silver to provide a conducting material in situ by a heterogeneous reaction. Removal of the new material from the chip proved it to be the silver salt of reduced TCNQ. Uniquely, conducting atomic force microscope (CAFM) studies show three regions in the solid. The localized original neutral organic material crystal is shown to be an insulator but to produce areas with Ohmic conducting characteristics after reduction. This inhomogeneous doping provides an opportunity for probing electrical materials properties side by side. Measurements with the CAFM witness this conducting material where the TCNQ is fully transformed to the silver salt. Additionally, an intermediate phase is observed that exhibits bipolar resistive switching typical of programmable resistive memories. Raman microscopy proves the conversion of the material in specific regions and clearly defines the intermediate phase region that could be responsible for the switching effect in related materials. This kind of "on crystal chemistry" exploiting immobilization and masking by a pneumatic clamp in a microfluidic channel shows how material can be selectively converted to give different functionalities in the same material piece, even though it is not a single crystal to single crystal conversion, and beckons exploitation for the preparation of systems relevant for molecular electronics as well as other areas where chemical manipulation of single crystals could be beneficial.

Membrane protein structure determination by SAD, SIR, or SIRAS phasing in serial femtosecond crystallography using an iododetergent

PubMed Central

Nakane, Takanori; Hanashima, Shinya; Suzuki, Mamoru; Saiki, Haruka; Hayashi, Taichi; Kakinouchi, Keisuke; Sugiyama, Shigeru; Kawatake, Satoshi; Matsuoka, Shigeru; Matsumori, Nobuaki; Nango, Eriko; Kobayashi, Jun; Shimamura, Tatsuro; Kimura, Kanako; Mori, Chihiro; Kunishima, Naoki; Sugahara, Michihiro; Takakyu, Yoko; Inoue, Shigeyuki; Masuda, Tetsuya; Hosaka, Toshiaki; Tono, Kensuke; Joti, Yasumasa; Kameshima, Takashi; Hatsui, Takaki; Inoue, Tsuyoshi; Nureki, Osamu; Iwata, So; Murata, Michio; Mizohata, Eiichi

2016-01-01

The 3D structure determination of biological macromolecules by X-ray crystallography suffers from a phase problem: to perform Fourier transformation to calculate real space density maps, both intensities and phases of structure factors are necessary; however, measured diffraction patterns give only intensities. Although serial femtosecond crystallography (SFX) using X-ray free electron lasers (XFELs) has been steadily developed since 2009, experimental phasing still remains challenging. Here, using 7.0-keV (1.771 Å) X-ray pulses from the SPring-8 Angstrom Compact Free Electron Laser (SACLA), iodine single-wavelength anomalous diffraction (SAD), single isomorphous replacement (SIR), and single isomorphous replacement with anomalous scattering (SIRAS) phasing were performed in an SFX regime for a model membrane protein bacteriorhodopsin (bR). The crystals grown in bicelles were derivatized with an iodine-labeled detergent heavy-atom additive 13a (HAD13a), which contains the magic triangle, I3C head group with three iodine atoms. The alkyl tail was essential for binding of the detergent to the surface of bR. Strong anomalous and isomorphous difference signals from HAD13a enabled successful phasing using reflections up to 2.1-Å resolution from only 3,000 and 4,000 indexed images from native and derivative crystals, respectively. When more images were merged, structure solution was possible with data truncated at 3.3-Å resolution, which is the lowest resolution among the reported cases of SFX phasing. Moreover, preliminary SFX experiment showed that HAD13a successfully derivatized the G protein-coupled A2a adenosine receptor crystallized in lipidic cubic phases. These results pave the way for de novo structure determination of membrane proteins, which often diffract poorly, even with the brightest XFEL beams. PMID:27799539

Membrane protein structure determination by SAD, SIR, or SIRAS phasing in serial femtosecond crystallography using an iododetergent.

PubMed

Nakane, Takanori; Hanashima, Shinya; Suzuki, Mamoru; Saiki, Haruka; Hayashi, Taichi; Kakinouchi, Keisuke; Sugiyama, Shigeru; Kawatake, Satoshi; Matsuoka, Shigeru; Matsumori, Nobuaki; Nango, Eriko; Kobayashi, Jun; Shimamura, Tatsuro; Kimura, Kanako; Mori, Chihiro; Kunishima, Naoki; Sugahara, Michihiro; Takakyu, Yoko; Inoue, Shigeyuki; Masuda, Tetsuya; Hosaka, Toshiaki; Tono, Kensuke; Joti, Yasumasa; Kameshima, Takashi; Hatsui, Takaki; Yabashi, Makina; Inoue, Tsuyoshi; Nureki, Osamu; Iwata, So; Murata, Michio; Mizohata, Eiichi

2016-11-15

The 3D structure determination of biological macromolecules by X-ray crystallography suffers from a phase problem: to perform Fourier transformation to calculate real space density maps, both intensities and phases of structure factors are necessary; however, measured diffraction patterns give only intensities. Although serial femtosecond crystallography (SFX) using X-ray free electron lasers (XFELs) has been steadily developed since 2009, experimental phasing still remains challenging. Here, using 7.0-keV (1.771 Å) X-ray pulses from the SPring-8 Angstrom Compact Free Electron Laser (SACLA), iodine single-wavelength anomalous diffraction (SAD), single isomorphous replacement (SIR), and single isomorphous replacement with anomalous scattering (SIRAS) phasing were performed in an SFX regime for a model membrane protein bacteriorhodopsin (bR). The crystals grown in bicelles were derivatized with an iodine-labeled detergent heavy-atom additive 13a (HAD13a), which contains the magic triangle, I3C head group with three iodine atoms. The alkyl tail was essential for binding of the detergent to the surface of bR. Strong anomalous and isomorphous difference signals from HAD13a enabled successful phasing using reflections up to 2.1-Å resolution from only 3,000 and 4,000 indexed images from native and derivative crystals, respectively. When more images were merged, structure solution was possible with data truncated at 3.3-Å resolution, which is the lowest resolution among the reported cases of SFX phasing. Moreover, preliminary SFX experiment showed that HAD13a successfully derivatized the G protein-coupled A2a adenosine receptor crystallized in lipidic cubic phases. These results pave the way for de novo structure determination of membrane proteins, which often diffract poorly, even with the brightest XFEL beams.

Residual glass and crystalline phases in a barium disilicate glass–ceramic

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

Araujo, Marcel C.C.; Botta, Walter J.; Kaufmann, Michael J.

2015-12-15

Investigations about the presence of residual glass are scarce, despite its fundamental role in the crystallization kinetics and luminescent properties of barium disilicate glass–ceramics (BaO·2SiO{sub 2}–BS{sub 2}) with a quasi-stoichiometric composition. Non-isothermal (DTA/DSC) experiments have demonstrated that BS{sub 2} presents a polymorphic transformation, where the h-BS{sub 2} (monoclinic structure) phase is completely transformed in l-BS{sub 2} (orthorhombic structure) at temperatures higher than 1020 °C (10 °C/min). In this study, BS{sub 2} monolithic samples were heat-treated at 1000 °C (BS2-10) and 1100 °C (BS2-11) in a DSC furnace at a heating rate of 10 °C/min. In addition, the crystalline and amorphousmore » phases were characterized and quantified by Transmission Electron Microscopy (TEM) and X-ray Diffraction (XRD) experiments, respectively. Although the complete polymorphic transformation from h-BS2 to l-BS2 was achieved at 1100 °C, our results demonstrated that BS2-11 contains a minor, albeit not negligible, amount of residual glass. - Highlights: • The crystalline and amorphous phases in a barium disilicate glass were characterized and quantified by XRD and TEM. • The BS2-10 sample was constituted by two main crystalline phases, which consists of 2 polymorphic forms: h-BS2 and l-BS2. • The orthorhombic BS2 phase (l-BS2) was predominant at 1100 °C. • The complete polymorphic transformation from h-BS2 to l-BS2 was achieved at 1100 °C. • Nevertheless, our XRD and TEM results demonstrated that BS2-11 contains a minor amount of residual glass.« less

Change in generally accepted regularity of phase transformations of quartzite

NASA Astrophysics Data System (ADS)

Kukartsev, V. A.; Kukartsev, V. V.; Chzhan, E. A.; Tynchenko, V. S.; Stupina, A. A.

2018-05-01

The subject of this research is phasic transformations of quartzites that are under temperature treatment to remove moisture. This technology is used in enterprises operating melting furnaces. The studies have shown that using a temperature regime consisting in heating to 800° C and holding for 2 hours, after cooling, quartzite changes its color and appears a shift in the angle of the interplanar distances of the crystal lattice by 6.6% in it. The use of a temperature treatment regime consisting in heating to 200° C and holding for 4 hours does not reveal such changes. With subsequent exposure to these samples of the temperature regime corresponding to the sintering process of the liner, the following is established. In a sample pretreated with a temperature of 800° C, at a temperature of 1550° C, a tridymite phase appears. In the sample of a 200° C pretreated with temperature, a phase of cristobalite appears without tridymite.

Chondroitin sulfate template-mediated biomimetic synthesis of nano-flake hydroxyapatite

NASA Astrophysics Data System (ADS)

He, Dan; Xiao, Xiufeng; Liu, Fang; Liu, Rongfang

2008-11-01

By Ca(NO 3) 2·4H 2O and (NH 4) 3PO 4·3H 2O as reagents and chondroitin sulfate (ChS) as a template, nano-flake hydroxyapatite (HA) is synthesized using a biomimetic method according to the biomineralization theory. HA crystals obtained are characterized in crystalline phase, microstructure, chemical composition and morphology by X-ray diffraction (XRD), Fourier transform infrared spectroscope (FTIR), transmission electron microscopy (TEM) and elemental analysis respectively. UV-vis spectrum is adopted to investigate interactions between functional groups ChS and HA. The results show that HA crystal nucleation and growth take place in chemical interactions between HA crystals and ChS as a template. And elemental analysis indicates that obtained HA contains a small amount of ChS. Furthermore, ChS concentration significantly affects the morphology of HA crystals. Staple-fiber-like HA crystals can be obtained at a low concentration in ChS, and flake-like HA crystals synthesized at a high concentration (≥0.5 wt.%) of ChS as a template.

Pressures of Partial Crystallization of Magmas Along Transforms: Implications for Crustal Accretion

NASA Astrophysics Data System (ADS)

Scott, J. L.; Zerda, C.; Brown, D.; Ciaramitaro, S. C.; Barton, M.

2016-12-01

Plate spreading at mid-ocean ridges is responsible for the creation of most of the crust on earth. The ridge system is very complex and many questions remain unresolved. Among these is the nature of magma plumbing systems beneath transform faults. Pervious workers have suggested that increased conductive cooling along transforms promotes higher pressures of partial crystallization, and that this explains the higher partial pressures of crystallization inferred for magmas erupted along slow spreading ridges compared to magmas erupted along faster spreading ridges. To test this hypothesis, we undertook a detailed analysis of pressures of partial crystallization for magmas erupted at 3 transforms along the fast to intermediate spreading East Pacific Rise(Blanco, Clipperton, and Siqueiros) and 3 transforms along the slow spreading Mid Atlantic Ridge(Famous Transform B, Kane, and 15°20'N). Pressures of partial crystallization were calculated from the compositions of glasses (quenched liquids) lying along the P (and T) dependent olivine, plagioclase, and augite cotectic using the method described by Kelley and Barton (2008). Published analyses of mid-ocean ridge basalt glasses sampled from these transforms and surrounding ridge segments were used as input data. Samples with anomalous chemical compositions and samples that yielded pressures associated with unrealistically large uncertainties were filtered out of the database. The pressures of partial crystallization for the remaining 916 samples ranged from 0 to 520 MPa with the great majority ( 95%) of sample returning pressures of less than 300 MPa. Pressures of < 300 MPa are within error of the pressure range associated with partial crystallization within oceanic crust with a thickness of 7 km. Higher (sub-crustal) pressures (>300 MPa) are associated with a small number of samples from the Pacific segments. Except for the Blanco, pressures of partial crystallization do not increase as transforms are approached. These observations contrast with those of previous workers, who reported anomalously high pressures (up to 1000 MPa) for a large number of samples erupted near both Atlantic and Pacific Transforms. We conclude that higher rates of cooling along transform does not have a major effect on the onset of partial crystallization along the mid-ocean ridges

Dual-Emission SG7@MOF Sensor via SC-SC Transformation: Enhancing the Formation of Excimer Emission and the Range and Sensitivity of Detection.

PubMed

Fu, Hong-Ru; Wu, Xiao-Xia; Ma, Lu-Fang; Wang, Fei; Zhang, Jian

2018-05-30

In this study, a water stable metal-organic framework FIR-53 is applied as a single-crystal container for anion exchange. The exceptional chemical stability and low crystallographic symmetry of FIR-53 makes it possible to determine anionic guests. Through ion exchange and single-crystal to single-crystal (SC-SC) transformation, 8-hydroxypyrene-1,3,6-trisulfonate (SG7, solvent green 7, ion form as SG7 3- ) is introduced into the pores of FIR-53 to obtain SG7@FIR-53. Because of the spatial confinement and partition effect, SG7@FIR-53 shows the bright exciter emission of SG7 ions. Interestingly, the composite SG7@FIR-53 exhibits a sensitive fluorescence quenching response against Cr 2 O 7 2- and MnO 4 - in aqueous solution. Especially, the detection limit toward MnO 4 - is as low as 0.12 ppb, which is the smallest value to date. Moreover, the prepared SG7@FIR-53 film also displays a broad response to nitro explosives in vapor/aqueous phase. Compared with the results of FIR-53, the range and sensitivity were greatly improved.