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At least 1,063 records · Page 59
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Ferroelectric to paraelectric phase transition mechanism in poled PVDF-TrFE copolymer films

Direct experimental insights into the structural and dynamical mechanisms for ferroelectric β to paraelectric α phase transition in a poled PVDF-TrFE copolymer is obtained from in situ x-ray diffraction and quasielastic neutron scattering measurements at high temperatures. It is observed that the β-to-α phase transition proceeds through two energetically distinct processes, which are identified here as the nucleation and growth of an intermediate γ phase with random skew linkages followed by a γ-to-α transition. The two energetically distinct microscopic processes can explain the stages of evolution for β-to-α phase transition observed from heat flow measurements.

36 MATERIALS SCIENCE↗
DOE OSTI2024

High Pressure–Temperature Study of MgF 2 , CaF 2 , and BaF 2 by Raman Spectroscopy: Phase Transitions and Vibrational Properties of AF 2 Difluorides

The phase transition of AF 2 difluorides strongly depends on pressure, temperature, and cationic radius. Here, we have investigated the phase transition of three difluorides, including MgF 2 , CaF 2 , and BaF 2 , at simultaneously high pressures and temperatures using Raman spectroscopy and X-ray diffraction in externally heated diamond anvil cells up to 55 GPa at 300–700 K. Rutile-type difluoride MgF 2 with a small cationic radius undergoes a transition to the CaCl 2 -type phase at 9.9(1) GPa and 300 K, to the HP-PdF 2 -type phase at 21.0(2) GPa, and to the cotunnite-type phase at 44.2(2) GPa. The phase transition pressure to the HP-PdF 2 and cotunnite structure at 300 K for our single crystal was found to be higher than that in previous studies using polycrystalline samples. Elevating the temperature increases the transition pressure from rutile- to the CaCl 2 -type phase but has a negative influence on the transition pressure when MgF 2 transforms from the HP-PdF 2 - to cotunnite-type phase. Meanwhile, the transition pressure from the CaCl 2 - to HP-PdF 2 -type phase for MgF 2 was identified to be independent of the temperature. Raman peaks suspected to belong to the α-PbO 2 -type phase were observed at 14.6–21.0(1) GPa and 400–700 K. At 300 K, difluorides CaF 2 and BaF 2 in the fluorite structure with larger cationic radii transform to the cotunnite-type phase at 9.6(3) and 3.0(3) GPa at 300 K, respectively, and BaF 2 further undergoes a transition to the Ni 2 In-type phase at 15.5(4) GPa. For both CaF 2 and BaF 2 , elevating the temperature leads to a lower transition pressure from fluorite- to the cotunnite-type phase but has little influence on the transition to the Ni 2 In structure. Raman data provide valuable insights for mode Grüneisen parameters. We note that the mode Grüneisen parameters for both difluorides and dioxides vary linearly with the cation radius. Further calculations for the mode Grüneisen parameters at high pressures for MgF 2 , CaF 2 , and BaF 2 yield a deeper understanding of the thermodynamic properties of the difluorides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Experimental verification of the high pressure crystal structures in NH{sub 3}BH{sub 3}

A detailed high-pressure study on NH{sub 3}BH{sub 3} has been carried out using in situ synchrotron X-ray diffraction (XRD) and Raman scattering with a diamond anvil cell up to 20 and 33 GPa, respectively. The Rietveld refinement based on the XRD pattern and analysis of Raman data indicate two first-order phase transitions from the ambient pressure I4 mm structure (α-NH{sub 3}BH{sub 3}) to a high pressure Cmc2{sub 1} phase (β-NH{sub 3}BH{sub 3}) at 2.14 GPa, and further into a monoclinic P2{sub 1} (Z = 2) phase (γ-NH{sub 3}BH{sub 3}) at 9.67 GPa. Fitting the measured volumetric compression data to the third order Birch-Murnaghan equation of state reveals a bulk modulus of B{sub 0} = 9.9 ± 0.5 and 17.0 ± 3.0 GPa (with fixed B{sub 0}{sup ′} = 4) for the β-NH{sub 3}BH{sub 3} below and above 5 GPa, respectively. Still, with the splitting of the NBH rock mode in Raman experiment, it is concluded that a second-order isostructural phase transition occurs at 5 GPa. By analyzing the dihydrogen bonding framework, the origin of the isostructural phase transition is attributed to the number of dihydrogen bondings per molecule in the Cmc2{sub 1} phase increasing from 12 to 14 at 5 GPa.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Imaging coherent phonons and precursor dynamics in LaFeAsO with 4D ultrafast electron microscopy

In this work, we used 4D ultrafast electron microscopy (UEM) to directly image femtosecond photoinduced structural dynamics in single-crystal LaFeAsO at initial temperatures of 300 and 100 K, above and below the known structural and magnetic phase-transition temperatures, respectively. With nanometer-picosecond resolution, we resolved an initial (precursor) sigmoidlike response arising from photothermal expansion and lattice reorientation that precedes the onset of propagating coherent acoustic phonons (CAPs). In the specific regions probed, the precursor response at 100 K is shorter than at 300 K ($t$ 0.5;100 K = 11.3ps vs $t$ 0.5;300 K = 17.8ps), and the CAP oscillation frequency is lowered with cooling (ƒ CAP;100 K = 12 GHz vs ƒ CAP;300 K = 21 GHz), correlated to known lattice softening due to the structural phase change. The transient CAP behaviors at 300 K are dispersive, displaying an exponentially decaying phase velocity over the first nanosecond. Further, the CAP symmetry at 300 K matches a first-order antisymmetric shear mode (A 1 ), while at 100 K it is best matched by a mostly nondispersive zero-order symmetric mode (S 0 ). These findings illustrate the sensitivity of UEM imaging to spatially heterogeneous dynamics in the Fe-pnictide materials and more broadly in other quantum materials.

36 MATERIALS SCIENCE↗
DOE OSTI2022

In situ study on medium-range order evolution during the polyamorphous phase transition in a Pd-Ni-P nanostructured glass

Engineering multiscale structural hierarchies in glassy alloys enable a broad spectrum of potential applications. Metallic glasses were born in hierarchical structures from atomic-to-nanometer scales. However, the frozen-in structures in traditional metallic glasses prepared by rapid quenching techniques are challenging to tailor. Here, we show that a Pd 40 Ni 40 P 20 bulk nanostructured glass of polyamorphous interfacial structures was prepared by inert-gas condensation with a laser evaporation source, and its multiscale structures could be engineered. In-situ scattering experiment results reveal polyamorphous phase transitions occurred in the interfacial regions, which are accompanied by the evolution of medium-range order and the nanoscale heterogeneous structures during the condensation process of glassy nanoparticles under high pressure and the following heating process. Moreover, changes in the cluster connectivity resulting from repacking of the local ordering induced by pressure and temperature could be observed. The thermophysical and mechanical properties, including boson peaks, hardness, and elasticity modulus, could be changed as a function of heat-treatment parameters. In conclusion, our findings would shed light on the synthesis of bulk nanostructured glassy alloys with tailorable thermodynamic and dynamical behavior as well as mechanical properties based on the understanding of metastability for polyamorphous interfacial phases.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Prediction of new high pressure structural sequence in thorium carbide: A first principles study

In the present work, we report the detailed electronic band structure calculations on thorium monocarbide. The comparison of enthalpies, derived for various phases using evolutionary structure search method in conjunction with first principles total energy calculations at several hydrostatic compressions, yielded a high pressure structural sequence of NaCl type (B1) → Pnma → Cmcm → CsCl type (B2) at hydrostatic pressures of ∼19 GPa, 36 GPa, and 200 GPa, respectively. However, the two high pressure experimental studies by Gerward et al. [J. Appl. Crystallogr. 19, 308 (1986); J. Less-Common Met. 161, L11 (1990)] one up to 36 GPa and other up to 50 GPa, on substoichiometric thorium carbide samples with carbon deficiency of ∼20%, do not report any structural transition. The discrepancy between theory and experiment could be due to the non-stoichiometry of thorium carbide samples used in the experiment. Further, in order to substantiate the results of our static lattice calculations, we have determined the phonon dispersion relations for these structures from lattice dynamic calculations. The theoretically calculated phonon spectrum reveal that the B1 phase fails dynamically at ∼33.8 GPa whereas the Pnma phase appears as dynamically stable structure around the B1 to Pnma transition pressure. Similarly, the Cmcm structure also displays dynamic stability in the regime of its structural stability. The B2 phase becomes dynamically stable much below the Cmcm to B2 transition pressure. Additionally, we have derived various thermophysical properties such as zero pressure equilibrium volume, bulk modulus, its pressure derivative, Debye temperature, thermal expansion coefficient and Gruneisen parameter at 300 K and compared these with available experimental data. Further, the behavior of zero pressure bulk modulus, heat capacity and Helmholtz free energy has been examined as a function temperature and compared with the experimental data of Danan [J. Nucl. Mater. 57, 280 (1975)].

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2018

Analysis of the structural, electronic, elastic and thermodynamic properties of CuAl2X4 (X = O, S) spinel structure

Highlights: • Fundamental properties of CuAl{sub 2}X{sub 4} (X = O, S) aluminate spinels have been investigated. • The pressure dependence of the elastic constants C{sub ij} can be successfully fit by a straight line. • CuAl{sub 2}X{sub 4} (X = O, S) compounds are mechanically stable at ambient conditions. • Temperature and pressure dependences of some macroscopic parameters are achieved. - Abstract: The structural, electronic, elastic and thermodynamic properties of oxo- and thio-spinels have been predicted based on the ultrasoft pseudo-potential scheme as implemented in the CASTEP code. The exchange-correlation potential was treated within the generalized gradient approximation (GGA-PBE). The calculated structural parameters such as lattice constants and internal parameters are in good agreement with the available experimental data. The ground state electronic band structure revealed that CuAl{sub 2}X{sub 4} (XO, S) spinels are direct band gap semiconductors with a transition along Γ-Γ symmetry points. The calculated values of elastic constants satisfy the Born criteria at ambient conditions and confirm that the spinel structures of CuAl{sub 2}O{sub 4} and CuAl{sub 2}S{sub 4} are mechanically stable. The thiospinel structure may have a phase transition under pressure, due to the negative value of C{sub 44}. The influence of temperature and pressure on macroscopic characteristics of CuAl{sub 2}O{sub 4} and CuAl{sub 2}S{sub 4} compounds was estimated using the quasi-harmonic Debye model.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2019

Compressional behavior and spin state of δ-(Al,Fe)OOH at high pressures

Hydrogen transport from the surface to the deep interior and distribution in the mantle are important in the evolution and dynamics of the Earth. An aluminum oxy-hydroxide, δ-AlOOH, might influence hydrogen transport in the deep mantle because of its high stability extending to lower mantle conditions. The compressional behavior and spin states of δ-(Al,Fe 3+ )OOH phases were investigated with synchrotron X-ray diffraction and Mössbauer spectroscopy under high pressure and room temperature. Pressure-volume (P-V) profiles of the δ-(Al 0.908(9) 57 Fe 0.045(1) )OOH 1.14(3) [Fe/(Al+Fe) = 0.047(10), δ-Fe5] and the δ-(Al 0.832(5) 57 Fe 0.117(1) )OOH 1.15(3) [Fe/(Al+Fe) = 0.123(2), δ-Fe12] show that these hydrous phases undergo two distinct structural transitions involving changes in hydrogen bonding environments and a high- to low-spin crossover in Fe 3+ . A change of axial compressibility accompanied by a transition from an ordered ( P 2 1 nm ) to disordered hydrogen bond ( Pnnm ) occurs near 10 GPa for both δ-Fe5 and δ-Fe12 samples. Through this transition, the crystallographic a and b axes become stiffer, whereas the c axis does not show such a change, as observed in pure δ-AlOOH. A volume collapse due to a transition from high- to low-spin states in the Fe 3+ ions is complete below 32–40 GPa in δ-Fe5 and δ-Fe12, which i ~10 GPa lower than that reported for pure ε-FeOOH. Evaluation of the Mössbauer spectra of δ-(Al 0.824(10) 57 Fe 0.126(4) )OOH 1.15(4) [Fe/(Al+Fe) = 0.133(3), δ-Fe13] also indicate a spin transition between 32–45 GPa. Phases in the δ-(Al,Fe)OOH solid solution with similar iron concentrations as those studied here could cause an anomalously high ρ/ν Φ ratio (bulk sound velocity, defined as √K/ρ at depths corresponding to the spin crossover region (~900 to ~1000 km depth), whereas outside the spin crossover region a low ρ/ν Φ anomaly would be expected. Here, these results suggest that the δ-(Al,Fe)OOH solid solution may play an important role in understanding the heterogeneous structure of the deep Earth.

58 GEOSCIENCES↗
DOE OSTI2015

Structural, electronic and vibrational properties of few-layer 2H-and 1T-TaSe 2

Two-dimensional metallic transition metal dichalcogenides (TMDs) are of interest for studying phenomena such as charge-density wave (CDW) and superconductivity. Few-layer tantalum diselenides (TaSe 2 ) are typical metallic TMDs exhibiting rich CDW phase transitions. However, a description of the structural, electronic and vibrational properties for different crystal phases and stacking configurations, essential for interpretation of experiments, is lacking. We present first principles calculations of structural phase energetics, band dispersion near the Fermi level, phonon properties and vibrational modes at the Brillouin zone center for different layer numbers, crystal phases and stacking geometries. Evolution of the Fermi surfaces as well as the phonon dispersions as a function of layer number reveals dramatic dimensionality effects in this CDW material. Lastly, our results indicate strong electronic interlayer coupling, detail energetically possible stacking geometries, and provide a basis for interpretation of Raman spectra.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Kohn Anomaly and Phase Stability in Group VB Transition Metals

In the periodic table, only a few pure metals exhibit lattice or magnetic instabilities associated with Fermi surface nesting, the classical examples being α-U and Cr. Whereas α-U displays a strong Kohn anomaly in the phonon spectrum that ultimately leads to the formation of charge density waves (CDWs), Cr is known for its nesting-induced spin density waves (SDWs). Recently, it has become clear that a pronounced Kohn anomaly and the corresponding softening in the elastic constants is also the key factor that controls structural transformations and mechanical properties in compressed group VB metals—materials with relatively high superconducting critical temperatures. This article reviews the current understanding of the structural and mechanical behavior of these metals under pressure with an introduction to the concept of the Kohn anomaly and how it is related to the important concept of Peierls instability. We review both experimental and theoretical results showing different manifestations of the Kohn anomaly in the transverse acoustic phonon mode TA (ξ00) in V, Nb, and Ta. Specifically, in V the anomaly triggers a structural transition to a rhombohedral phase, whereas in Nb and Ta it leads to an anomalous reduction in yield strength.

36 MATERIALS SCIENCE↗
NASA NTRS1983

Calculation of high-pressure phase transitions in solid N2 and the pressure dependence of intramolecular mode frequencies

A calculation that minimizes the energy of solid N2 with respect to a rhombohedral distortion of the Pm 3n structure shows that a low-temperature phase transition occurs into the R 3c calcite structure at P = 19.2 kbar with a volume change of 0.125 cu cm/mole. This transition agrees with recent Raman scattering measurements. Another transition from R 3c into R3(bar)m is predicted at P = 67.5 kbar, with a volume change of 0.1 cu cm/mole. The pressure dependence of the intramolecular mode frequencies for the R 3c structure are in reasonably good agreement with the two main branches observed experimentally.

Chandrasekharan, V.↗
DOE OSTI2022

Local structure elucidation of tungsten-substituted vanadium dioxide (V$$_{1-x}$$W$$_x$$O$$_2$$)

Abstract Initially, vanadium dioxide seems to be an ideal first-order phase transition case study due to its deceptively simple structure and composition, but upon closer inspection there are nuances to the driving mechanism of the metal-insulator transition (MIT) that are still unexplained. In this study, a local structure analysis across a bulk powder tungsten-substitution series is utilized to tease out the nuances of this first-order phase transition. A comparison of the average structure to the local structure using synchrotron x-ray diffraction and total scattering pair-distribution function methods, respectively, is discussed as well as comparison to bright field transmission electron microscopy imaging through a similar temperature-series as the local structure characterization. Extended x-ray absorption fine structure fitting of thin film data across the substitution-series is also presented and compared to bulk. Machine learning technique, non-negative matrix factorization, is applied to analyze the total scattering data. The bulk MIT is probed through magnetic susceptibility as well as differential scanning calorimetry. The findings indicate the local transition temperature ( $$T_c$$ T c ) is less than the average $$T_c$$ T c supporting the Peierls-Mott MIT mechanism, and demonstrate that in bulk powder and thin-films, increasing tungsten-substitution instigates local V-oxidation through the phase pathway VO $$_2\, \rightarrow$$ 2 → V $$_6$$ 6 O $$_{13} \, \rightarrow$$ 13 → V $$_2$$ 2 O $$_5$$ 5 .

Wilson, Catrina E. (ORCID:0000000173397318)↗
DOE OSTI2015

Synthesis of 0.1% & 0.2% neodymium doped barium zirconium titanate (BaZr{sub 0.2}Ti{sub 0.8}O{sub 3}) and study of their dielectric behaviour

Efforts have been made to ease process of producing widely used multilayered ceramics of Barium Zirconium Titanium Oxides and study their dielectric behaviour and structural properties. For this purpose, adequate proportions of Barium Carbonate, Zirconium Oxide and Titanium Oxide were taken and hand milled for 2 hours. Neodymium composition of the order of 0.1% and 0.2% was used for doping to weight percentage of BaZr0.2Ti0.8O3. The samples were authenticated using raw data obtained from Bruker AXS D8 advance Copper KL alpha source XRD equipment. Further, the samples were studied for their phase transition, composition, single phase perovskite structure using XRD technique. The technique has also been applied to know formation of stable homogeneous solid solution from XRD parameters. The other physical parameters like the morphology, micro structural information, crystal arrangements and topography have also been observed through SEM. The SEM has revealed information related to grain size development and composition of sample with fine agglomerates. For complete study of the compounds the atomic and weight composition has also been examined by Electron Dispersive Spectroscopy patterns. The comparison has been made with other works on ceramics at various frequencies and has yielded very interesting results.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Temperature scaling in the quantum-Hall-effect regime in a HgTe quantum well with an inverted energy spectrum

The longitudinal and Hall magnetoresistances of HgTe/HgCdTe heterostructures with an inverted energy spectrum (the HgTe quantum well width is d = 20.3 nm) are measured in the quantum-Hall-effect regime at T = 2–50 K in magnetic fields up to B = 9 T. Analysis of the temperature dependences of conductivity in the transition region between the first and second plateaus of the quantum Hall effect shows the feasibility of the scaling regime for a plateau–plateau quantum phase transition in 2D-structures on the basis of mercury telluride.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Directional effects of antiferromagnetic ordering on the electronic structure in NdSb

The recent discovery of unconventional surface-state pairs, which give rise to Fermi arcs and spin textures, in antiferromagnetically ordered NdBi raised the interest in rare-earth monopnictides. Several scenarios of antiferromagnetic (AFM) order have been suggested to explain the origin of these states with some of them being consistent with the presence of nontrivial topologies. Here, in this paper, we use angle-resolved photoemission spectroscopy (ARPES) and density-functional-theory (DFT) calculations to investigate the electronic structure of NdSb. We found the presence of distinct domains that have different electronic structures at the surface. These domains correspond to different orientations of magnetic moments in the AFM state with respect to the surface. We demonstrated remarkable agreement between DFT calculations and ARPES that capture all essential changes in the band structure caused by the transition to a magnetically ordered state.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Structural evolution in the crystallization of rapid cooling silver melt

The structural evolution in a rapid cooling process of silver melt has been investigated at different scales by adopting several analysis methods. The results testify Ostwald’s rule of stages and Frank conjecture upon icosahedron with many specific details. In particular, the cluster-scale analysis by a recent developed method called LSCA (the Largest Standard Cluster Analysis) clarified the complex structural evolution occurred in crystallization: different kinds of local clusters (such as ico-like (ico is the abbreviation of icosahedron), ico-bcc like (bcc, body-centred cubic), bcc, bcc-like structures) in turn have their maximal numbers as temperature decreases. And in a rather wide temperature range the icosahedral short-range order (ISRO) demonstrates a saturated stage (where the amount of ico-like structures keeps stable) that breeds metastable bcc clusters. As the precursor of crystallization, after reaching the maximal number bcc clusters finally decrease, resulting in the final solid being a mixture mainly composed of fcc/hcp (face-centred cubic and hexagonal-closed packed) clusters and to a less degree, bcc clusters. This detailed geometric picture for crystallization of liquid metal is believed to be useful to improve the fundamental understanding of liquid–solid phase transition. - Highlights: • A comprehensive structural analysis is conducted focusing on crystallization. • The involved atoms in our analysis are more than 90% for all samples concerned. • A series of distinct intermediate states are found in crystallization of silver melt. • A novelty icosahedron-saturated state breeds the metastable bcc state.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗