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At least 1,711 records · Page 95
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Asymmetry of the Ferroelectric Phase Transition in BaTiO 3

Symmetry changes during phase transformations fundamentally determine the behavior of thermodynamic systems, governing phenomena as diverse as water evaporation, fermion condensation, and epidemic spreading. Phase transitions are conventionally divided into two classes, and this classification is typically assumed to remain invariant upon reversing the transition. Here, an asymmetric phase transformation is uncovered in the ferroelectric–paraelectric transition of single-crystal BaTiO 3 , a model system for first-order transitions. Under slow temperature variation (≤0.1 °C min −1 ), thermodynamic, dielectric, and domain-structure measurements reveal that the ferroelectric-to-paraelectric transition exhibits latent heat, phase coexistence, and a discontinuous order parameter, while these signatures are absent upon cooling. Complementary phase-field simulations demonstrate similar behavior, attributing it to distinct elastic strain energy accumulation and release during heating and cooling. These findings reveal a first-order character upon heating but a second-order-like behavior upon cooling, challenging the conventional paradigm of symmetric phase-transition classification and suggesting new possibilities for ferroelectric-based energy storage.

Hershkovitz, Asaf [Technion-Israel Institute of Te↗
DOE OSTI2017

Probing Induced Structural Changes in Biomimetic Bacterial Cell Membrane Interactions with Divalent Cations

Biological membranes, formed primarily by the self-assembly of complex mixtures of phospholipids, provide a structured scaffold for compartmentalization and structural processes in living cells. The specific physical properties of phospholipid species present in a given membrane play a key role in mediating these processes. Phosphatidylethanolamine (PE), a zwitterionic lipid present in bacterial, yeast, and mammalian cell membranes, is exceptional. In addition to undergoing the standard lipid polymorphic transition between the gel and liquid-crystalline phase, it can also assume an unusual polymorphic state, the inverse hexagonal phase (HII). Divalent cations are among the factors that drive the formation of the HII phase, wherein the lipid molecules form stacked tubular structures by burying the hydrophilic head groups and exposing the hydrophobic tails to the bulk solvent. Most biological membranes contain a lipid species capable of forming the HII state suggesting that such lipid polymorphic structural states play an important role in structural biological processes such as membrane fusion. In this study, the interactions between Mg2+ and biomimetic bacterial cell membranes composed of PE and phosphatidylglycerol (PG) were probed using differential scanning calorimetry (DSC), small-angle x-ray scattering (SAXS), and fluorescence spectroscopy. The lipid phase transitions were examined at varying ratios of PE to PG and upon exposure to physiologically relevant concentrations of Mg2+. An understanding of these basic interactions enhances our understanding of membrane dynamics and how membrane-mediated structural changes may occur in vivo.

biomembranes↗
DOE OSTI2019

Unveiling a Novel, Cation-Rich Compound in a High-Pressure Pb–Te Binary System

Because of the common oxidation states of group IV elements (+2 or +4) and group VI elements (–2), 1:1 and 1:2 are two typical stoichiometries found in the IV–VI compounds. Particularly, in the Pb–Te binary system, the 1:1 stoichiometric PbTe is believed to be the only stable compound. Herein, using evolutionary algorithms, density functional theory, a laser-heated diamond anvil cell, and synchrotron X-ray diffraction experiments, we discovered a novel Pb–Te compound with an unexpected stoichiometry of 3:2 above 20 GPa. This tetragonal Pb 3 Te 2 is the one of the very few cation-rich compounds that has ever been discovered in the entire IV–VI binary system. Further analyses based on electron density distribution, electron localization function, and Bader charge have shown that this newly discovered compound has a mixed character of chemical bonding with a decreased ionicity. By further calculating the electron–phonon interaction, Pb 3 Te 2 is predicted to exhibit a superconducting transition at low temperatures. Lastly, the discovery of Pb 3 Te 2 paves the way for further explorations of other novel cation-rich IV–VI group compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Metastable Li 1+δ Mn 2 O 4 (0 ≤ δ ≤ 1) Spinel Phases Revealed by in Operando Neutron Diffraction and First-Principles Calculations

Here, we examine the reaction mechanisms driven by the lithiation of Li 1+δ Mn 2 O 4 (0 ≤ δ ≤ 1) spinels via in operando neutron powder diffraction (NPD). New reaction mechanisms are proposed involving solid-solution regions within both cubic and tetragonal spinel phases in addition to a continuous phase transition between them. In operando NPD is an ideal tool to follow the light elements such as lithium and oxygen in cathode materials which are often the key to fully understand their structural evolutions. Here, we report a novel methodology to prepare an extremely thick electrode with ~378 mg·cm –2 loading density suitable for the in operando NPD studies. Enabled by such thick electrode, we find that the metal oxygen M–O (M = Li and Mn) bond lengths in both end members LiMn 2 O 4 and Li 2 Mn 2 O 4 experience pronounced changes larger than dictated by the change in lattice parameters because of the locally formed Jahn–Teller distorted Mn 3+ . First-principles density functional theory calculations confirm these metastable intermediates and further propose atomistic reaction pathways for the phase transition by coupling a global structure search algorithm. In conclusion, these findings redefine the conventional understandings on two-phase reactions of this spinel material.

36 MATERIALS SCIENCE↗
DOE OSTI2016

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

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

36 MATERIALS SCIENCE↗
DOE OSTI2025

Dual roles of stepped surfaces: Catalytic initiators and stabilizers of oxygen-induced reconstructions

Understanding surface restructuring under reactive conditions is crucial for designing next-generation catalysts with enhanced activity and selectivity. Here, we employ in situ transmission electron microscopy to directly observe the dynamic behavior of Cu(100) and Cu(410) surfaces under both oxidizing and vacuum annealing conditions, revealing a complex interplay among surface crystallography, local oxygen coverage, Cu atom mobility, and step-edge reactivity. The stepped Cu(410) surface acts as an active site for O 2 dissociation, triggering the oscillatory transformation of the c(2 × 2)–O phase into the more stable (2$\sqrt2$ ×$\sqrt2$)R45°–O missing-row (MR) structure on the adjacent flat Cu(100) terrace. Under subsequent vacuum annealing, this same Cu(410) facet exhibits remarkable structural resilience, preserving the MR reconstruction and chemisorbed oxygen. In contrast, the Cu(100) surface undergoes reversible transitions from the MR structure back to the c(2 × 2)–O phase. These results highlight the critical role of surface morphology in directing both the formation and stability of oxygen-induced reconstructions, demonstrating that stepped surfaces serve dual roles as both catalytic initiators and structural stabilizers. Furthermore, this work offers atomic-level insights into the environment-responsive behavior of copper surfaces, establishing a mechanistic basis for designing Cu-based catalysts through facet-specific control of surface reactivity.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Cation Disordered Anti-Perovskite Cathode Materials with Enhanced Lithium Diffusion and Suppressed Phase Transition

Recently, a new family of anti-perovskite Li 2 TMSO was discovered as promising cathode materials for Li-ion batteries (LIBs) with superiorities in high specific capacity, low cost, and environmental friendliness. However, the applications of these anti-perovskite materials meet severe challenges in the cyclability and rate performance. In this work, a cation-disordered anti-perovskite type solid solution Li 2 Fe 1– x Mn x SO (LFMSO, x = 0, 0.2, 0.5) with excellent electrochemical performance is reported. On the basis of comprehensive structural characterizations, the role of the cation disordering in LFMSO is clarified. In comparison with Li 2 FeSO (LFSO), the reduced Li-ion diffusion barrier and the increased Li-rich octahedral configurations in LFMSO with higher configurational entropy imply the facilitated long-range Li-ion diffusion and the suppressed phase transition, which favor the high-rate capability and cycling stability. In addition, the large lattice distortion and Coulombic interaction between the anions and cations lead to the breathing of the unit cell during charge/discharge. The variation of the unit cell volume decreases to 2.5% upon Li-ion delithiation. A superstructure is observed in LFMSO for the first time. These findings help to pave the way for the research and development of novel cathode materials for the next generation LIBs.

25 ENERGY STORAGE↗
DOE OSTI2022

Information transfer with a twist

Holographic duals for CFTs compactified on a Riemann surface Σ with a twist are cast in the language of wedge holography. Σ starts as part of the field theory geometry in the UV and becomes part of the internal space in the IR. This allows to associate entanglement entropies with splits of the internal space in the IR geometry. Decomposing the internal space in the IR and geometrizing the corresponding subsystems separately leads to two interacting gravitational systems, similar to the intermediate holographic description in braneworld models. For Σ = T 2 the setups are used to model information transfer from a black hole to a gravitating bath. This leads to Page curves with a phase structure which precisely mirrors that in braneworld models. The transition from geometric to non-geometric entropies is also discussed for Σ = S 2 as a model for more general internal spaces in AdS/CFT.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2018

Fe Vacancy Order and Domain Distribution in A{sub x}Fe{sub 2−y}Se{sub 2}

The Fe vacancy and its ordering pattern is a unique property of the A{sub x}Fe{sub 2−y}Se{sub 2} (A = K, Rb, Cs) superconductors. Below the structural transition temperature T{sub S} ∼ 550 K, the system phase separates into the I4/mmm phase with no Fe vacancy and the I4/m phase with the √5×√5×1 vacancy order. In this work, an Ising-like Hamiltonian defined on the Fe-sublattice is constructed and employed in a Metropolis Monte Carlo simulation to study the Fe vacancy order and the domain distribution under different thermal treatments. A third phase with randomly distributed Fe vacancies and space group I4/mmm is observed in the simulation. The response of the volume fraction of this simulated phase under thermal treatment shows a direct connection to the change of the superconducting shielding fraction under annealing and quenching processes, indicating a close relation between the vacancy disordered I4/mmm phase and the superconducting phase.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

Role of reduced precursor and solvolytic reagent molar ratio on preparation and properties of ionogel

In the present study, ionogels have been synthesized by immobilizing IL (1-ethyl-3-methylimidazolium tetrafluoroborate) in silica gel matrices using non-aqueous route. In this process, tetraethyl orho-silane (TEOS) as a precursor to silicon dioxide and formic acid as a solvolytic gelating reagent in reduced molar ratio 1:4 were used. We find that reduced molar concentration of formic acid results the formation of ionogels having less number of closed pores (totally isolated from their neighbours), larger density and stable monolithic form. TEM and SEM measurements are used to visualize the morphology of sample and closed pores present in the sample. N{sub 2}-sorption measurement is used to measure the pore parameters of the silica matrices which shows the mesoporous structure. DSC and TGA results show the change in phase transition temperature and thermal stability of IL upon confinement in silica matrices. Moreover, ionic conductivity of bulk and confined IL is measured using impedance spectroscopy and it has been found that it increases with increasing the temperature as well as concentration of IL in ionogels. Apart from these characterization techniques, ionogels have been characterized using FTIR and fluorescence spectroscopy which exhibit the change in vibrational frequencies and fluorescence behaviour of confined IL. - Highlights: • Synthesis of stable ionogel using non-hydrolytic route with reduced precursor and solvolytic reagent molar ratio. • Ionogels are free from entrapped residual reaction product. • The ionogels synthesized with higher amount of ionic liquids show bulk liquid like electrical behaviour.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Zinc-Doped High-Nickel, Low-Cobalt Layered Oxide Cathodes for High-Energy-Density Lithium-Ion Batteries

High-Ni layered oxides with Ni contents greater than 90% are promising cathode candidates for high-energy-density Li-ion batteries. However, drastic electrode-electrolyte reactions and mechanical degradation issues limit their cycle life and practical viability. We demonstrate here that LiNi 0.94 Co 0.04 Zn 0.02 O 1.99 (NCZ), obtained by incorporating 2 mol% Zn 2+ into an ultrahigh-Ni baseline cathode material LiNi 0.94 Co 0.06 O 2 (NC), delivers superior cell performance. NCZ retains 74% of the initial capacity after 500 cycles in full cell assembled with graphite anode, outperforming NC (62% retention). NCZ also possesses a higher average discharge voltage relative to NC with an outstanding average voltage retention of over 99% after 130 cycles in half cells. Bulk structural investigations unveil that Zn doping promotes a smoother phase transition, suppresses anisotropic lattice distortion, and maintains the mechanical integrity of cathode particles. Furthermore, NCZ shows an enhanced interphase stability after long-term cycling, in contrast to the seriously degraded surface chemistry in NC. Finally, this work provides a practically viable approach for designing higher-energy-density high-Ni layered oxide cathodes for lithium-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2023

Leveraging the Polymer Glass Transition to Access Thermally Switchable Shear Jamming Suspensions

Suspensions of polymeric nano-and microparticles are fascinating stress-responsive material systems that, depending on their composition, can display a diverse range of flow properties under shear, such as drastic thinning, thickening, and even jamming (reversible solidification driven by shear). However, investigations to date have almost exclusively focused on nonresponsive particles, which do not allow in situ tuning of the flow properties. Polymeric materials possess rich phase transitions that can be directly tuned by their chemical structures, which has enabled researchers to engineer versatile adaptive materials that can respond to targeted external stimuli. Reported herein are suspensions of (readily prepared) micrometer-sized polymeric particles with accessible glass transition temperatures (T g ) designed to thermally control their non-Newtonian rheology. The underlying mechanical stiffness and interparticle friction between particles change dramatically near T g . Capitalizing on these properties, it is shown that, in contrast to conventional systems, a dramatic and nonmonotonic change in shear thickening occurs as the suspensions transition through the particles' T g . This straightforward strategy enables the in situ turning on (or off) of the system's ability to shear jam by varying the temperature relative to T g and lays the groundwork for other types of stimuli-responsive jamming systems through polymer chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Effects of Calcination Condition on Porous Reduced Titanium Oxides and Oxynitrides via Preceramic Polymer Route

The preceramic polymer route from titanium-based inorganic-organic hybrid networks provides electro conductive N-doped reduced titanium oxides (TinO2n–1) and titanium oxynitrides (TiOxNy) with a monolithic shape as well as well-defined porous structure. This methodology demonstrates advantageously lower temperature of crystal phase transition compared to the reduction of TiO2 by carbon or H2. In this study, effects of calcination condition on various features of the products have been explored by adopting three different atmospheric conditions and varying the calcination temperature. The detailed crystallographic and elemental analyses disclose the distinguished difference in phase transition behavior with respect to calcination atmosphere. Correlation between the crystallization and nitridation behaviors, porous properties and electric conductivities in the final products has been discussed.

Hasegawa, George↗
DOE OSTI2018

Phase Coexistence and Kinetic Arrest in the Magnetostructural Transition of the Ordered Alloy FeRh

In materials where two or more ordering degrees of freedom are closely matched in their free energies, coupling between them, or multiferroic behavior can occur. These phenomena can produce a very rich phase behavior, as well as emergent phases that offer useful properties and opportunities to reveal novel phenomena in phase transitions. The ordered alloy FeRh undergoes an antiferromagnetic to ferromagnetic phase transition at ~375 K, which illustrates the interplay between structural and magnetic order mediated by a delicate energy balance between two configurations. We have examined this transition using a combination of high-resolution x-ray structural and magnetic imaging and comprehensive x-ray magnetic circular dichroism spectroscopy. We find that the transition proceeds via a defect-driven domain nucleation and growth mechanism, with significant return point memory in both the structural and magnetic domain configurations. In conclusion, the domains show evidence of inhibited growth after nucleation, resulting in a quasi- 2nd order temperature behavior.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Sustainable layered cathode with suppressed phase transition for long-life sodium-ion batteries

Sodium-ion batteries are among the most promising alternatives to lithium-based technologies for grid and other energy storage applications due to their cost benefits and sustainable resource supply. For the cathode—the component that largely determines the energy density of a sodium-ion battery cell—one major category of materials is P2-type layered oxides. Unfortunately, at high state-of-charge, such materials tend to undergo a phase transition with a very large volume change and consequent structural degradation during long-term cycling. Here we address this issue by introducing vacancies into the transition metal layer of P2-Na$_{0.7}$Fe$_{0.1}$Mn$_{0.75\square}$$_{0.15}$O2 (‘$_{\square}$’ represents a vacancy). The transition metal vacancy serves to suppress migration of neighbouring Na ions and therefore maintain structural and thermal stability in Na-depleted states. Moreover, the specific Na-O-$_{\square}$ configuration triggers a reversible anionic redox reaction and boosts the energy density. As a result, the cathode design here enables pouch cells with energy densities of 170 Wh kg -1 and 120 Wh kg -1 that can operate for over 600 and 1,000 cycles, respectively. In conclusion, our work not only suggests a feasible strategy for cathode design but also confirms the possibility of developing a battery chemistry that features a reduced need for critical raw materials.

25 ENERGY STORAGE↗
DOE OSTI2016

Widely tunable alloy composition and crystal structure in catalyst-free InGaAs nanowire arrays grown by selective area molecular beam epitaxy

We delineate the optimized growth parameter space for high-uniformity catalyst-free InGaAs nanowire (NW) arrays on Si over nearly the entire alloy compositional range using selective area molecular beam epitaxy. Under the required high group-V fluxes and V/III ratios, the respective growth windows shift to higher growth temperatures as the Ga-content x(Ga) is tuned from In-rich to Ga-rich InGaAs NWs. Using correlated x-ray diffraction, transmission electron microscopy, and micro-photoluminescence spectroscopy, we identify structural defects to govern luminescence linewidths in In-rich (x(Ga) < 0.4) and Ga-rich (x(Ga) > 0.6) NWs, whereas limitations at intermediate Ga-content (0.4 < x(Ga) < 0.6) are mainly due to compositional inhomogeneities. Most remarkably, the catalyst-free InGaAs NWs exhibit a characteristic transition in crystal structure from wurtzite to zincblende (ZB) dominated phase near x(Ga) ∼ 0.4 that is further reflected in a cross-over from blue-shifted to red-shifted photoluminescence emission relative to the band edge emission of the bulk ZB InGaAs phase.

36 MATERIALS SCIENCE↗