Effects of Sublattice Symmetry and Frustration on Ionic Transport in Garnet Solid Electrolytes
Not Available
Kozinsky, Boris↗
SEARCH · Engineering Papers
Results for “Structural phase transition”
Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
Dynamics and diffusion mechanism of low-density liquid silicon
A first-order phase transition from a high-density liquid to a low-density liquid has been proposed to explain the various thermodynamic anomies of water. It also has been proposed that such liquid–liquid phase transition would exist in supercooled silicon. Computer simulation studies show that, across the transition, the diffusivity drops roughly 2 orders of magnitude, and the structures exhibit considerable tetrahedral ordering. The resulting phase is a highly viscous, low-density liquid silicon. Investigations on the atomic diffusion of such a novel form of liquid silicon are of high interest. Here we report such diffusion results from molecular dynamics simulations using the classical Stillinger–Weber (SW) potential of silicon. We show that the atomic diffusion of the low-density liquid is highly correlated with local tetrahedral geometries. We also show that atoms diffuse through hopping processes within short ranges, which gradually accumulate to an overall random motion for long ranges as in normal liquids. There is a close relationship between dynamical heterogeneity and hopping process. We point out that the above diffusion mechanism is closely related to the strong directional bonding nature of the distorted tetrahedral network. Here, our work offers new insights into the complex behavior of the highly viscous low density liquid silicon, suggesting similar diffusion behaviors in other tetrahedral coordinated liquids that exhibit liquid–liquid phase transition such as carbon and germanium.
36 MATERIALS SCIENCE↗
Compression rate effects on the Bi-III stability field in dynamic diamond anvil cell XFEL studies of bismuth
This study aims to resolve conflicting observations of bismuth’s high-pressure phase transitions across static, intermediate, and shock compression regimes. We probed its high-pressure structural sequence using the dynamic diamond anvil cell with and time-resolved X-ray diffraction with microsecond resolution at an X-ray free-electron laser. At room temperature and pressures up to 20 gigapascals, bismuth evolves through the same structural sequence previously identified under static compression. However, the transformation behavior differs in important ways under dynamic loading. In particular, the transition from the incommensurate intermediate-pressure phase to the high symmetry high pressure phase begins at pressures about 2 to 4 gigapascals lower than in static experiments, and the onset of this transformation depends on the compression rate. As a result, the stability field of the intermediate-pressure phase is reduced under rapid compression. Our results suggest that at sufficiently fast loading rates the intermediate phase may be bypassed entirely, consistent with previous shock-compression observations.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
High-pressure structural parameters and equation of state of osmium to 207 GPa
We studied the most incompressible transition metal osmium (Os) under high pressure. There is significant interest in Os because of the structural anomalies attributed to topological transitions in the Fermi surface for valence electrons in the hexagonal close-packed phase. We report on measurements of structural parameters and equation of state on Os metal to a pressure of 207 GPa at ambient temperature using platinum as a pressure standard. We also obtained angle-dispersive X-ray diffraction data at a synchrotron source with closely spaced pressure intervals to observe any discontinuities or anomalies in the axial c/a ratio at high pressures. Rietveld refinements of X-ray diffraction data show a slowly varying axial ratio (c/a) with a broad minimum at 75 GPa. Our data do not provide any evidence of anomalous behavior in the c/a ratio in Os at 25 or 150 GPa as have been reported in previous studies. These experimental results are in agreement with theoretical calculations that do not predict any anomalous behavior in c/a ratio in Os under extreme conditions. We present an equation of state for Os to 207 GPa (V/V 0 = 0.761) at ambient temperature and compare our results with the previously published data.
36 MATERIALS SCIENCE↗
Chemical Compensation Challenges in Processing Antiferroelectric PbZrO 3 Thin Films
The electric field-induced antipolar-to-polar phase transition in antiferroelectric materials is accompanied by large changes in the structural and functional response, making them attractive for many applications ranging from pulsed energy capacitors to high-strain-high (blocking-)force actuators, solid-state heating and cooling systems, and optoelectronic devices. PbZrO 3 , as an end member of the PZT, (x)PbZr 1–x Ti x O 3 , solid solution, has been the subject of many studies. However, processing of perovskite PbZrO 3 is extremely challenging due to phase instabilities induced by Pb loss at the temperatures necessary for perovskite crystallization. Here, we discuss the challenges associated with Pb loss, as well as its compensation through bulk Pb overstoichiometry and interfacial PbO additions, in chemical solution processed, highly oriented PbZrO 3 thin films. For both 042 o - and 001 o -oriented (o-orthorhombic distortion) PbZrO 3 thin films, the crystallization interfaces are the most important contributors to Pb loss and off-stoichiometric outcomes, and no single approach was sufficient to address these challenges. Pb-rich and Pb-deficient nonperovskite phases including ZrO x were only observable through microscopic characterization, and X-ray diffraction alone could not rule out the presence of such secondary phases. “Ideal” macroscopic antiferroelectric polarization-electric field double hysteresis curves were observed despite (at times) the large presence of secondary phases. However, reduced saturation polarization and increased phase transition electric fields were observed concomitantly with the presence of secondary phase(s) and tentatively assigned to the voltage drop across the ZrO x nanocrystals. Based on these results, it is imperative that the presence of secondary phases always be addressed (beyond X-ray diffraction spectra) in order to correctly evaluate the properties of antiferroelectric films.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Magnetic phase diagram and multiferroicity of Ba 3 MnNb 2 O 9 : A spin - 5 2 triangular lattice antiferromagnet with weak easy-axis anisotropy
Here we have performed magnetic, electric, thermal and neutron powder diffraction (NPD) experiments as well as density functional theory (DFT) calculations on Ba 3 MnNb 2 O 9 . All results suggest that Ba 3 MnNb 2 O 9 is a spin-5/2 triangular lattice antiferromagnet (TLAF) with weak easy-axis anisotropy. At zero field, we observed a narrow two-step transition at T N1 = 3.4 K and T N2 = 3.0 K. The neutron diffraction measurement and the DFT calculation indicate a 120 spin structure in ab plane with out-of-plane canting at low temperatures. With increasing magnetic field, the 120 spin structure evolves into up-up-down (uud) and oblique phases showing successive magnetic phase transitions, which fits well to the theoretical prediction for the 2D Heisenberg TLAF with classical spins. Ultimately, multiferroicity is observed when the spins are not collinear but suppressed in the uud and oblique phases.
72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
Ce stabilized Ni–SrO as a catalytic phase transition sorbent for integrated CO 2 capture and CH 4 reforming
Integration of carbon dioxide capture from flue gas with dry reforming of CH 4 represents an attractive approach for CO 2 utilization. The selection of a suitable bifunctional material serving as a catalyst/sorbent is the key. This paper reports Ni decorated and CeO x -stabilized SrO (SrCe 0.5 Ni 0.5 ) as a multi-functional, phase transition catalytic sorbent material. The effect of CeO x on the morphology, structure, decarbonation reactivity, and cycling stability of the catalytic sorbent was determined with TEM-EDX, XRD, in situ XRD, CH 4 -TPR and TGA. Here, cyclic process tests were conducted in a packed bed reactor. The results indicate that large Ni clusters were present on the surface of the SrNi sorbent, and the addition of CeO 2 promoted even distribution of Ni on the surface. Moreover, the Ce–Sr interaction promoted a complex carbonation/decarbonation phase-transition, i.e. SrCO 3 + CeO 2 ↔ Sr 2 CeO 4 + CO 2 as opposed to the conventional, simple carbonation/decarbonation cycles (e.g. SrCO 3 ↔ SrO + CO 2 ). This double replacement crystalline phase transition mechanism not only adjusts the carbonation/calcination thermodynamics to facilitate SrCO 3 decomposition at relatively low temperatures but also inhibits sorbent sintering. As a result, excellent activity and stability were observed with up to 91% CH 4 conversion, >72% CO 2 capture efficiency and ~100% residual O 2 capture efficiency from flue gas by utilizing the CeO 2 ↔ Ce 2 O 3 redox transition. This renders an intensified process with zero coke deposition. Moreover, the SLDRM with SrCe 0.5 Ni 0.5 has the flexibility to produce concentrated CO via CO 2 -splitting while co-producing a syngas with tunable H 2 /CO ratios.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Formation of Carbon–Carbon Interlinkage Bonds under High Pressure
The formation of carbon–carbon interlinkage bonds (CCIBs) via the chemical binding of interlayer carbon atoms of many sp 2 -bonded carbon precursors is an essential step for synthesizing various diamond and diamond-like materials. Although the existence of CCIBs may be reasonably assumed under high-pressure conditions, direct experimental evidence has been scarce. Micro-Raman spectroscopy is here employed to track in situ the evolution of C–C bonds in a pressure range from ambient to 54 GPa. A pressure-induced two-stage (polynomial and linear) shift of the G peak and new generation of the CCIB peak at about 1550 cm –1 are observed in multiple types of layer-structured carbon precursors, including glassy carbon, natural graphite, and carbon nanotubes. In conclusion, the experimental discovery of CCIBs holds significance in comprehending phase transitions of sp 2 -bonded carbon materials and has implications for the advancement of novel carbon structures.
Anode materials↗
Quantification of High-Temperature Transition Al2O3 and Their Phase Transformations
High temperature exposure of ?-Al2O3 can lead to a series of polymorphic transformations, including the formation of ?-Al2O3 and ?-Al2O3. Quantification of the microstructure in the ?/?-Al2O3 formation range represents a formidable challenge as both phases accommodate a high degree of structural disorder. In this work, we explore the use of XRD recursive stacking formalism for quantification of high temperature transition aluminas. We formulate the recursive stacking methodology for modelling of disorder in ?-Al2O3 and twinning in ?-Al2O3 and show that explicitly accounting for the disorder is necessary to reliably model the XRD patterns of high temperature transition alumina. In the second part, we use the recursive stacking approach to study phase transformation during high temperature (1050 ºC) treatment. We show that the two different intergrowth modes of ?-Al2O3 have different transformation characteristics, and that a significant portion of ?-Al2O3 is stabilized with ?-Al2O3 even after prolonged high-temperature exposures. In discussions, we outline the limitation of the current XRD approach and discuss a possible multimodal XRD and NMR approach which can improve analysis of complex transition aluminas. This work was performed in the Wiley Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by DOEs Office of Biological and Environmental Research and located at PNNL. The work was supported by the U.S. Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences.
Kovarik, Libor↗
Bose–Einstein condensation versus Dicke–Hepp–Lieb transition in an optical cavity
We provide an exact solution for the interplay between Bose–Einstein condensation and the Dicke–Hepp–Lieb self-organization transition of an ideal Bose gas trapped inside a single-mode optical cavity and subject to a transverse laser drive. Based on an effective action approach, we determine the full phase diagram at arbitrary temperature, which features a bi-critical point where the transitions cross. We calculate the dynamically generated band structure of the atoms and the associated suppression of the critical temperature for Bose–Einstein condensation in the phase with a spontaneous periodic density modulation. Moreover, we determine the evolution of the polariton spectrum due to the coupling of the cavity photons and the atomic field near the self-organization transition, which is quite different above or below the Bose–Einstein condensation temperature. At low temperatures, the critical value of the Dicke–Hepp–Lieb transition decreases with temperature and thus thermal fluctuations can enhance the tendency to a periodic arrangement of the atoms. -- Highlights: •Atoms inside a driven cavity can undergo two transitions: self-organization and BEC. •The phase diagram has four phases which coexist at a bi-critical point. •Atom–cavity coupling creates a dynamical lattice for the atoms. •Finite temperature can enhance the tendency towards self-organization. •We calculate the detailed spectrum of the polaritonic excitations.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
Tunable Nanostructures from Inverse Surfactants
Hierarchical materials in the natural world are often made through the self-assembly of amphiphilic molecules. Achieving similar structural complexity in synthetic materials requires understanding how various molecular parameters affect assembly behavior. In recent years, inverse surfactants─molecules with hydrophobic head groups and hydrophilic macromolecular tails─have been shown to self-assemble into supramolecular assemblies in aqueous solutions that show promise for a number of applications, including drug delivery. Here, we build an understanding of the morphological phase diagram of inverse surfactants using insights from scattering experiments, computer simulations, and statistical mechanics. The scattering and simulation results reveal that changing the headgroup size is an important molecular knob in controlling morphological transitions. The molecular size ratio of the hydrophobic group to the hydrophilic group emerges as a crucial dimensionless quantity in our theory and plays a determining role in setting the micelle structure and the transition from mesoscale to macroscale aggregates. Our minimal theory is able to qualitatively explain the key features of the morphological phase diagram, including the prevalence of fiber-like structures in comparison to spherical and planar micelles. Together, these findings provide a more complete picture of the molecular dependencies of assemblies of inverse surfactants, which we hope may aid in the de novo design of supramolecular structures.
Christakopoulos, Panagiotis [ORNL] (ORCID:00090004↗
Nonequilibrium Lattice Dynamics in Photoexcited 2D Perovskites
Abstract Interplay between structural and photophysical properties of metal halide perovskites is critical to their utility in optoelectronics, but there is limited understanding of lattice response upon photoexcitation. Here, 2D perovskites butylammonium lead iodide, (BA) 2 PbI 4 , and phenethylammonium lead iodide, (PEA) 2 PbI 4 , are investigated using ultrafast transient X‐ray diffraction as a function of optical excitation fluence to discern structural dynamics. Both powder X‐ray diffraction and time‐resolved photoluminescence linewidths narrow over 1 ns following optical excitation for the fluence range studied, concurrent with slight redshifting of the optical bandgaps. These observations are attributed to transient relaxation and ordering of distorted lead iodide octahedra stimulated mainly by electron–hole pair creation. The c axis expands up to 0.37% over hundreds of picoseconds; reflections sampling the a and b axes undergo one tenth of this expansion with the same timescale. Post‐photoexcitation appearance of the (110) reflection in (BA) 2 PbI 4 would suggest a transient phase transition, however, through new single‐crystal XRD, reflections are found that violate glide plane conditions in the reported Pbca structure. The static structure space group is reassigned as P 2 1 2 1 2 1 . With this, a nonequilibrium phase transition is ruled out. These findings offer increased understanding of remarkable lattice response in 2D perovskites upon excitation.
36 MATERIALS SCIENCE↗
An in-situ study of magnetic domain structures in undercooled Fe-29.5 at. %Pd magnetostrictive alloys by Lorentz microscopy and electron holography
Understanding of correlation between magnetic domain structure and functional properties is of importance for the magnetic field driven phase transition (e.g., martensitic transformation) or microstructure variation (e.g., twin boundary motion) materials. In this work, we report a Fe-29.5 at. %Pd shape memory alloy treated by undercooling processing upon a degree of 320 K below the liquid temperature. The effect of high undercooling on the solidified microstructure and martensitic transformation temperatures was investigated. By in-situ Lorentz transmission electron microscopy and electron holography, magnetic domain structure and the field-induced domain wall motion behavior in as-cast and undercooled samples have been schematically studied. The irregular domain structure can be observed in these alloys. On the application of a field up to 300 Oe, the domain walls for both samples are able to move along the direction of the external magnetic field, but structural transition and rearrangement of variants are not observed in the undercooled alloy. The large magnetostriction of Fe-29.5 at. %Pd undercooled alloy originates from the irregular domain walls motion instead of the rearrangement of martensitic twin variants.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
Orbital Domain Dynamics in Magnetite below the Verwey Transition
Here, the metal-insulator phase transition in magnetite, known as the Verwey transition, is characterized by a charge-orbital ordering and a lattice transformation from a cubic to monoclinic structure. We use x-ray photon correlation spectroscopy to investigate the dynamics of this charge-orbitally ordered insulating phase undergoing the insulator-to-metal transition. By tuning to the Fe L 3 edge at the (001/2) superlattice peak, we probe the evolution of the Fe t 2g orbitally ordered domains present in the low temperature insulating phase and forbidden in the high temperature metallic phase. We observe two distinct regimes below the Verwey transition. In the first regime, magnetite follows an Arrhenius behavior and the characteristic timescale for orbital fluctuations decreases as the temperature increases. In the second regime, magnetite phase separates into metallic and insulating domains, and the kinetics of the phase transition is dictated by metallic-insulating interfacial boundary conditions.
36 MATERIALS SCIENCE↗
Structural Amorphization-Induced Topological Order
Electronic properties of crystals are inherently pertained to crystalline symmetry, so that amorphization that lowers and breaks symmetry is detrimental. One important crystalline property is electron band topology which is known to be weakened and destroyed by structural disorder. Here, we report a counterintuitive theoretical discovery that atomic structural disorder by amorphization can in fact induce electronic order of topology in an otherwise topologically trivial crystal. The resulting nontrivial topology is characterized by a nonzero spin Bott index, associated with robust topological edge states and quantized conductance. Further, the underlying topological phase transition (TPT) from a trivial crystal to a topological amorphous is analyzed by mapping out a phase diagram in the degree of structural disorder using an effective medium theory. The atomic disorder is revealed to induce topological order by renormalizing the spectral gap toward nontriviality near the phase boundary. As a concrete example, we further show such TPT in amorphous stanane by first-principles calculations. Our findings point to possible observation of an electronic ordering transition accompanied by a structural disorder transition.
36 MATERIALS SCIENCE↗
Green-emitting cubic GaN/In 0.16 Ga 0.84 N/GaN quantum well with 32% internal quantum efficiency at room temperature
Structural and optical properties of a green-emitting cubic (i.e., zinc blende) GaN/In 0.16 Ga 0.84 N/GaN single quantum well structure are reported. The active layer is grown on a phase-pure (i.e., 100%) cubic GaN enabled on a 1 × 1 cm 2 U-grooved silicon (100) through aspect ratio phase trapping. Energy dispersive x-ray spectroscopy combined with room temperature cathodoluminescence reveals 522 nm green light emission at room temperature with only 16.0% ± 1.6% of indium content, which is ~30% less than the amount of indium needed in a traditional green-emitting hexagonal (i.e., wurtzite) well. Temperature-dependent behavior of the green emission, such as activation energy, s-shaped peak energy shift, and linewidth, is reported. Cathodoluminescence at 8 and 300 K reveals an internal quantum efficiency of 32.0% ± 0.6%, which is higher than any reported value for cubic wells. Altogether, phase-pure cubic active layers on phase transition cubic GaN are shown to be promising for green and longer wavelength emitters.
42 ENGINEERING↗
The Effect of Structural Inhomogeneities and Gas-Forming Impurities on the Functional Properties of High Purity Rare-Earth Metals
Rare-earth metals (REM) gadolinium and dysprosium, and also the Gd–H and Dy–H systems in which magnetic order–order and order–disorder phase transitions are accompanied by significant magnetocaloric effect, have been studied. The materials have been prepared in various structural states. It is stated that there is a substantial difference of their functional properties in the dependence on the features of the structural state and also on the existence of a gas-forming impurity. It has been proved experimentally and theoretically that the Curie temperatures of Gd samples with grain sizes of ~200 nm increases as a result of hydrogenation, while the magnetic phase transition temperatures of Dy are almost unchanged Inhomogeneities.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Investigation of electrical behavior and dielectric properties in polycristalline Pr0.8Sr0.2MnO3 manganite perovskite
Highlights: • Transport properties of Pr{sub 0.8}Sr{sub 0.2}MnO{sub 3} are investigated in a large range of temperature (80–500 K) and frequency (40–10{sup 7} Hz). • DC measurements show two conduction mechanisms at low and high temperature. • The complex impedance shows that our structure obeys at Cole-Cole model. • Dielectric results reveal a dielectric transition which is well fitted by Curie-Weiss law. • AC conductivity is described by Jonscher power law. The NSPT and Drude models are used to describe the conduction mechanism. - Abstract: The electrical and dielectric properties of Pr{sub 0.8}Sr{sub 0.2}MnO{sub 3} perovskite prepared by the solid-state method were investigated. The complex impedance results showed the contribution of grain and grain boundaries in the conduction mechanism. The dielectric data have confirmed the presence of interfacial polarization in the structure. Moreover, a dielectric transition fitted by Curie-Weiss law was observed. Besides, the observed relaxation diffuse phase transition is attributed to a strong heterogeneity introduced by the substitution of Pr by Sr ions. DC electrical measurements indicate that the structure exhibits a semiconductor behavior and the conductivity is governed by hopping process. The AC conductivity measurements show a clear semiconductor-metallic transition at high temperatures. The AC conductivity data can be divided into two parts, the first of which is a semiconductor one, described by the NSPT model, at low temperatures and the second is a metallic regime, fitted by the classical Drude model, at high temperatures.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗