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Optical pulse-induced ultrafast antiferrodistortive transition in SrTiO 3

The ultrafast dynamics of the antiferrodistortive phase transition in perovskite SrTiO 3 is monitored via time-domain Brillouin scattering. Using femtosecond optical pulses, we initiate a thermally driven tetragonal-to-cubic structural transformation and detect the crystal phase through changes in the frequency of Brillouin oscillations (BO) induced by propagating acoustic phonons. Coupling the measured BO frequency with a spatiotemporal heat diffusion model, we demonstrate that, for a sample kept in the tetragonal phase, deposition of sufficient thermal energy induces a rapid transformation of the heat-affected region to the cubic phase. The initial phase change is followed by a slower reverse cubic-to-tetragonal phase transformation occurring on a timescale of hundreds of picoseconds. Here, we attribute this ultrafast phase transformation in the perovskite to a structural resemblance between atomic displacements of the R-point soft optic mode of the cubic phase and the tetragonal phase, both characterized by anti-phase rotation of oxygen octahedra. The structural relaxation time exhibits a strong temperature dependence consistent with the prediction of the equation of motion describing collective oxygen octahedra rotation based on the energy landscape of the phenomenological Landau theory of phase transitions. Evidence of such a fast structural transition in perovskites can open up new avenues in information processing and energy storage sectors.

36 MATERIALS SCIENCE↗

Broadband Characterization and Circuit Model Development of Transmission-Scale Transformers

This report describes broadband measurements of transmission-scale transformers typical in the electric power grid. This work was performed as part of the EMP Resilient Grid LDRD project at Sandia National Laboratories to generate circuit models that can be used for high-altitude electromagnetic pulse (HEMP) coupling simulations and response predictions. The objective of the work was to obtain characterization data of substation yard equipment across a frequency range relevant to HEMP. Vector network analyzer measurements up to 100 MHz were performed on two power transformers at ABB-Hitachi and a single ITEC potential transformer. Custom cable breakouts were designed to interface with the transformer terminals and provide ground connections to the chassis at the base of the transformer bushings. The three-phase terminals of the power transformers were measured as a common mode impedance using a parallel resistive splitter, and the single-phase terminals of the potential transformer were measured directly. A vector fitting algorithm was used to empirically fit circuit models to the resulting two-port networks and input impedances of the measured objects. Simplified circuit representations of the input impedances were also generated to assess the degree of precision needed for high-altitude electromagnetic pulse response predictions, which were performed in Sandia's XYCE circuit simulator platform. HEMP coupling simulations using the transformer models showed significant reduction in the voltage peak and broadening in the pulse width seen at the power transformer compared to the traveling wave voltage. This indicated the importance of the load condition when defining the coupled insult in an electric power substation. Simplified circuit models showed a similar voltage at the transformer with a smoothed waveform. The presence of potential transformers in the simulation did not significantly change the simulated voltage at the power transformer. Single-port input impedance models were also developed to define load conditions when transfer characteristics were not necessary.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Grain size dependence of thermally induced oxidation in zirconium carbide

Here complementary analytical approaches were employed to probe the effect of grain size on thermally induced oxidation of zirconium carbide (ZrC) utilizing thermogravimetric analysis, differential scanning calorimetry, and Raman spectroscopy, as well as synchrotron-based and laboratory-based X-ray diffraction (XRD) experiments. The oxidation mechanism and phase behavior of nanocrystalline ZrC (grain size ~ 20 nm) were compared with that of the more documented microcrystalline ZrC (grain size ~ 1 µm). Synchrotron XRD at the Advanced Photon Source with a hydrothermal diamond anvil cell (HDAC) used as a sample chamber revealed that the onset of oxidation is at ~ 380 °C for microcrystalline ZrC which is in agreement with previous work. In contrast, the critical oxidation temperature was ~ 330 °C for nanocrystalline ZrC. Additional high-temperature synchrotron XRD experiments at the National Synchrotron Light Source II using a lamp furnace in combination with Raman analysis showed that tetragonal ZrO 2 forms as an initial oxidation product and transforms at higher temperatures to the monoclinic phase. Thermogravimetric analysis (TGA) coupled with differential scanning calorimetry (DSC) confirmed the X-ray results of a lower critical oxidation temperature for the nanocrystalline sample. The phase transformations in the oxide phase with associated critical temperatures were also evident in the thermodynamic data as exothermic heat events.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Resolving complex intralayer transition motifs in high-Ni-content layered cathode materials for lithium-ion batteries

High-Ni-content layered materials are promising cathodes for next-generation lithium-ion batteries. However, investigating the atomic configurations of the delithiation-induced complex phase boundaries and their transitions remains challenging. Here, in this study, by using deep-learning-aided super-resolution electron microscopy, we resolve the intralayer transition motifs at complex phase boundaries in high-Ni cathodes. We reveal that an O3 → O1 transformation driven by delithiation leads to the formation of two types of O1–O3 interface, the continuous- and abrupt-transition interfaces. The interfacial misfit is accommodated by a continuous shear-transition zone and an abrupt structural unit, respectively. Atomic-scale simulations show that uneven in-plane Li+ distribution contributes to the formation of both types of interface, and the abrupt transition is energetically more favourable in a delithiated state where O1 is dominant, or when there is an uneven in-plane Li + distribution in a delithiated O3 lattice. Moreover, a twin-like motif that introduces structural units analogous to the abrupt-type O1–O3 interface is also uncovered. The structural transition motifs resolved in this study provide further understanding of shear-induced phase transformations and phase boundaries in high-Ni layered cathodes.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

In Situ Scattering Studies of Crystallization Kinetics in a Phase-Separated Zr–Cu–Fe–Al Bulk Metallic Glass

In this work, thermal stability and the crystallization kinetics of a phase-separated Zr-Cu-Fe-Al bulk metallic glass were investigated using in situ high-energy synchrotron X-ray and neutron diffraction, as well as small-angle synchrotron X-ray scattering. It was revealed that this glass with excellent glass-forming ability possesses a two-step crystallization behavior. The crystalline products and their evolution sequence are more complicated than a homogeneous Zr-Cu-Al glass with average glass-forming ability. The experimental results indicate that a finely distributed nanometer-sized cubic Zr 2 Cu phase forms first and then transforms to a tetragonal Zr 2 Cu phase, while the matrix transforms to an orthorhombic Zr3Fe phase. The strength of the Zr-Cu-Fe-Al composite containing cubic Zr 2 Cu phase and glass matrix increases, and the plasticity also improves compared to the as-cast Zr-Cu-Fe-Al bulk metallic glass. Our results suggest that the formation of multiple and complex crystalline products would be the characteristics of the Zr-Cu-Fe-Al glass with better glass-forming ability. Our study may shed light on the synthesis of bulk-sized glass-nanocrystals composites of high strength and good plasticity.

36 MATERIALS SCIENCE↗

Atomistic evidence of nucleation mechanism for the direct graphite-to-diamond transformation

The direct graphite-to-diamond transformation mechanism has been a subject of intense study and remains debated concerning the initial stages of the conversion, the intermediate phases, and their transformation pathways. Here, we successfully recover samples at the early conversion stage by tuning high-pressure/high-temperature conditions and reveal direct evidence supporting the nucleation-growth mechanism. Atomistic observations show that intermediate orthorhombic graphite phase mediates the growth of diamond nuclei. Furthermore, we observe that quenchable orthorhombic and rhombohedra graphite are stabilized in buckled graphite at lower temperatures. These intermediate phases are further converted into hexagonal and cubic diamond at higher temperatures following energetically favorable pathways in the order: graphite → orthorhombic graphite → hexagonal diamond, graphite → orthorhombic graphite → cubic diamond, graphite → rhombohedra graphite → cubic diamond. Furthermore, these results significantly improve our understanding of the transformation mechanism, enabling the synthesis of different high-quality forms of diamond from graphite.

Graphite-diamond phase transformation↗

An implementation of the phase-field model based on coupled thermomechanical finite element solvers for large-strain twinning, explicit dynamic fracture and the classical Stefan problem

The implementation of a phase-field model in finite elements usually requires significant expertise and involves the development of a user element with additional degrees of freedom. An alternative implementation of the phase-field model within a thermo-mechanical finite element simulation package was presented in (Cho et al 2012 Int. J. Solids Struct. 49 1973–1992), where the phase-field variable is treated as the temperature degree of freedom. However, this approach has only been used for small strain phase-field modelling of martensitic transformations and quasistatic phase-field modelling of fracture. Here, we present a phase-field finite element implementation via the temperature degree of freedom for several additional cases from the literature: (i) the large-strain phase-field description of deformation twinning presented in (Clayton and Knap 2011 Physica D 240 841–858), (ii) phase-field description of brittle fracture with inertial effects based on the theory from (Molnár and Gravouil 2017, Finite Elem. Anal. Des. 130 27–38) and (Miehe et al 2010 Int. J. Numer. Methods Eng. 83 1273–1311) and (iii) the classical Stefan problem of solidification presented in (Mackenzie and Robertson 2002 J. Comput. Phys. 181 526–544). The last problem involves the temperature and phase-field variables as unknowns.

36 MATERIALS SCIENCE↗

Evidence of distinct nonpolar/polar ordering at long/short ranges in relaxor ferroelectrics

Distinct atomic nonpolar/polar ordering is determined at long, intermediate, and short ranges using synchrotron x-ray diffraction, Raman scattering, and pair distribution function data in K 0.5 Na 0.5 NbO 3 -doped BaTiO 3 -based relaxor ferroelectrics, viz., (1 - x) Ba 0.9 Sr 0.1 TiO 3 -x KNN 50. Two different polar phases with distinct symmetries are identified at short/intermediate ranges for x = 0.10, where a monoclinic phase at short ranges gradually transforms into a rhombohedral phase at intermediate ranges. Here, in contrast, a nonpolar phase with average cubic symmetry is found to be stable at long ranges for a wide temperature range (100 ≤ T ≤ 500 K). The polar behavior of short/intermediate-range ordering is quantified in terms of the amplitude of ferroelectric phonon mode $Γ^-_4$ (q = 0, 0, 0) (which corresponds to the zone center of the cubic Brillouin zone). The amplitude of the $Γ^-_4$ phonon mode increases with decreasing temperature, suggesting the enhancement of ferroelectric polarization at short/intermediate ranges on lowering temperatures. Enhanced ferroelectric polarization at low temperature is also visible and evident by ferroelectrostriction and is quantified by the increase in magnitude of spontaneous volume ferroelectrostriction. Consequently, Zero thermal expansion is observed at low temperatures.

36 MATERIALS SCIENCE↗

Unraveling peculiar magnetism and band topology in Mn 3 Sb

Magnetic, pseudogap, topological, magnetostructural, and elastic behaviors of Mn 3 Sb have been unraveled. The ferrimagnetism (FIM) is described by localized and delocalized electron magnetism resulting in different magnetic moments on Mn atoms, confirming the neutron diffraction data. The identified magnetostructural properties are due to the non-equivalent Mn atoms in its lowest symmetry structure. The electronic structure is also unique due to variable valance states of Mn atoms. The magnetic moment (4.10 μB) of non-equivalent Mn1 atom is antiparallely aligned with the magnetic moments (2.34 μB) of Mn 2 and Mn 3 atoms. The estimated Curie temperature, TC, is higher than the room temperature, which may have above the room temperature applications in spintronic devices. The band structure and density of states (DOS) show the characteristics of band topology (opening of a gap in Dirac-like band features) and pseudo-gap, respectively, around the Fermi level. While expanding the unit cell, the tetragonal FIM ground state transforms to the cubic primitive FIM phase, however, the contraction transforms it to the L1 2 ferromagnetic (FM) phase. The estimated elastic constants, bulk to shear modulus ratio, and elastic anisotropy factor indicate that Mn3Sb exhibits mechanically stable, ductile, and anisotropic behaviors, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solid-state transformations during laser directed energy deposition of Ti-6Al-4V powder hydride-dehydrided from scrap metals

During laser directed energy deposition (DED-LB), thermal cycling and powder chemical composition produce distinct thermal histories, which vary mechanical properties. Using real-time X-ray diffraction, this study investigates solid-state transformations during DED-LB to understand process-structure-property relationships for angular Ti-6Al-4V powder hydride–dehydrided from scrap metals. Results showed that regions near the molten pool experienced high cooling rates, leading to martensitic transformation from the β phase and increased hardness. Regions farther from the molten pool underwent tempering without solid-state transformation and decreased hardness. These findings support alternative feedstocks for metal additive manufacturing for a circular economy and resilient supply chains.

Additive manufacturing (AM)↗

A constitutive model for glass–ceramic materials

Glass–ceramics have received recent attention for use in glass–ceramic to metal hermetic seals. Due to their heterogeneous microstructure, these materials exhibit a number of advantageous responses over conventional glass based seals. Key amongst them is the possibility of a controllable thermal strain response and apparent coefficient of thermal expansion which may be used to minimize thermally induced residual stresses for aforementioned seals. Furthermore, these behaviors result from an inorganic glass matrix and variety of crystalline ceramic phases including silica polymorph(s) that may undergo reversible solid-to-solid transformations with associated inelastic strain. Correspondingly, these materials exhibit complex thermomechanical responses associated with multiple inelastic mechanisms (viscoelasticity and phase transformation). While modeling these behaviors is essential for developing and analyzing the corresponding applications, no such model exists. Therefore, in this work a three-dimensional continuum constitutive model for glass–ceramic materials combining these various inelastic mechanisms is developed via an internal state variable approach. A corresponding fully implicit three dimensional numerical formulation is also proposed and implemented. The model is used to simulate existing experiments and validate the proposed formalism. As an example, the simple seal problem of a glass–ceramic seal inside a concentric metal shell is explored. Finally, the impact of the cooling rates, viscoelastic shift factors, and inelastic strain on final residual stress state are all investigated and the differing contributions highlighted.

36 MATERIALS SCIENCE↗

Evolution of intermetallic phases in an Al–Si–Ti alloy during solution treatment

A cast Al–Si–Ti alloy was solution treated at 540 °C for different periods between 0 and 72 h to understand the evolution of intermetallic phases. Only an (Al,Si) 3 Ti intermetallic phase with a low Si content was found in the as-cast alloy. The (Al,Si) 3 Ti particles were converted partly into a lamellar structure, a eutectoid phase, consisting of a Si-rich phase and an Al phase during solution treatment. The amount of the lamellar structure increased with the solution treatment time, but the composition of either constitute was kept almost unchanged regardless of the solution treatment times. The lamellar Si-rich phase is (Al,Si) 2 Ti (τ 2 ) with a TiSi 2 (C49-type) structure based on thermodynamic calculations and high-resolution TEM analyses. FCC Al phase is the product residing between the τ 2 lamellae after the completion of transformation from (Al,Si) 3 Ti to τ 2 phase. A near-rational orientation relationship (OR) between the Al and τ 2 phases is determined as Al [110]//τ 2 [100], Al ()//τ 2 [060]. The phase transformation from (Al,Si) 3 Ti to τ 2 being a result of the diffusion of Ti and Si within the original (Al,Si) 3 Ti particulates as well as the Si diffusion from the Al matrix during solution treatment is proposed. The formation of the lamellar structure in the microstructure is attributed mainly to the limited diffusivity of Ti element.

36 MATERIALS SCIENCE↗

Topological Spin Textures in an Insulating van der Waals Ferromagnet

Generation and control of topological spin textures constitutes one of the most exciting challenges of modern spintronics given their potential applications in information storage technologies. Of particular interest are magnetic insulators, which due to low damping, absence of Joule heating and reduced dissipation can provide energy-efficient spin-textures platform. Here, it is demonstrated that the interplay between sample thickness, external magnetic fields, and optical excitations can generate a prolific paramount of spin textures, and their coexistence in insulating CrBr 3 van der Waals (vdW) ferromagnets. Using high-resolution magnetic force microscopy and large-scale micromagnetic simulation methods, the existence of a large region in T-B phase diagram is demonstrated where different stripe domains, skyrmion crystals, and magnetic domains exist and can be intrinsically selected or transformed to each-other via a phase-switch mechanism. Lorentz transmission electron microscopy unveils the mixed chirality of the magnetic textures that are of Bloch-type at given conditions but can be further manipulated into Néel-type or hybrid-type via thickness-engineering. The topological phase transformation between the different magnetic objects can be further inspected by standard photoluminescence optical probes resolved by circular polarization indicative of an existence of exciton-skyrmion coupling mechanism. The findings identify vdW magnetic insulators as a promising framework of materials for the manipulation and generation of highly ordered skyrmion lattices relevant for device integration at the atomic level.

36 MATERIALS SCIENCE↗

Design and Optimization of High-frequency Transformer for Isolated Single-Stage Three-Phase AC/DC Converter using Bidirectional Switches

This paper presents the design and optimization of the high-frequency transformer for an isolated single-stage threephase AC/DC converter enabled by the 4H-SiC BiDirectional Field Effect Transistor (BiDFET). Non-dominated Sorting Genetic Algorithm II (NSGA-II) is used to perform a multiobjective optimization to minimize loss, weight, and volume. A 20 kW, 50 kHz hardware prototype based on the selected optimal point is characterized by a power amplifier. The finite element analysis simulation results are also presented to validate the core magnetic flux density and winding electric field strength. The experimental prototype was tested at 800 Vdc/480 Vrms at 10 kW rated power.

BiDFET, High-frequency transformer, Multiobjective↗

Unraveling the transformation pathway of the 𝛽 to 𝛾 phase transition in Ga 2 ⁢O 3 from atomistic simulations

Defect spinel 𝛾−Ga 2 ⁢O 3 is the least stable polymorph of Ga 2 ⁢O 3 , so its frequent appearance as a structural defect within or on the surface of monoclinic 𝛽−Ga 2 ⁢O 3 remains a mystery. Through first-principles calculations, we explore potential pathways for the phase transition from 𝛽−Ga 2⁢ O 3 to 𝛾−Ga 2 ⁢O 3 , and examine two key driving forces: tensile strain and Ga deficiency. When configurational entropy contributions to phase energies are included, the 𝛾 phase becomes energetically competitive with the 𝛽 phase, with the free energy difference between these phases diminishing even further under Ga-deficient conditions. Notably, a stability crossover occurs at room temperature at high vacancy concentrations ([V$^{3−}_{Ga}$]>3%) . A simple model 𝛽 → 𝛾 transformation pathway is identified, comprising two primary reactions, that enables the formation of the 𝛾 phase via simultaneous migration of Ga atoms from tetrahedral lattice sites to octahedral interstitial positions. The transformation barriers are prohibitively large in pristine Ga 2 ⁢O 3 , but can be substantially reduced by: (1) the presence of Ga vacancies, (2) elongational strains along the crystallographic 𝑎-axis, and (3) when volumetric relaxations are possible during transformation. These results elucidate prior experimental observations, where 𝛾−Ga 2⁢ O 3 is seen on damaged surfaces or in highly 𝑛-type 𝛽−Ga 2⁢ O 3 environments, which support Ga deficiency and mechanical strain. The insights into the driving forces and mechanisms of 𝛾−Ga 2⁢ O 3 formation enhance understanding of how localized strain and nonequilibrium defect concentrations may facilitate its formation from the 𝛽 phase.

Defects↗

Microstructure evolution in U-10Zr alloy irradiated by swift Xe ions at 700 °C

The post-irradiation examination (PIE) results of U-10Zr binary metallic fuel that was irradiated by 84 MeV Xe ions at 700 °C are reported here. The U-10Zr specimen was synthesized by homogenizing elemental U and Zr powders through arc-melting. The as-fabricated U-10Zr was dominated by the sub-micron acicular α+ δ phase. After being irradiated by 84 MeV Xe ions at 700 °C up to 2.19 ×10 17 ions/cm 2 fluence, the U-10Zr was speculated to evolve into micro-scale γ 1 + γ 2 phases as predicted by the U-Zr phase diagram. During post-irradiation cooling, the U-rich γ 1 phase was mainly transformed to the αphase, while the Zr-rich γ 2 phase was partially retained along with formation of hexagonal structure phase (δ or ω). Xe bubbles formed in the γ 1 and γ 2 phases have salient different morphologies, implying faster Xe diffusion in the γ 1 phase than the γ 2 phase. The quantitative bubble morphology data collected in this study can provide valuable references for the development and validation of fuel performance models for this fuel.

36 MATERIALS SCIENCE↗

Disordered interfaces of alkaline aluminate salt hydrates provide glimpses of Al 3+ coordination changes

Hypothesis: The precipitation and dissolution of aluminum-bearing mineral phases in aqueous systems often proceed via changes in both aluminum coordination number and connectivity, complicating molecular-scale interpretation of the transformation mechanism. Here, the thermally induced transformation of crystalline sodium aluminum salt hydrate, a phase comprised of monomeric octahedrally coordinated aluminate which is of relevance to industrial aluminum processing, has been studied. Because intermediate aluminum coordination states during melting have not previously been detected, it is hypothesized that the transition to lower coordinated aluminum ions occurs within a highly disordered quasi-two-dimensional phase at the solid-solution interface. Experiments and simulations: In this work, in situ X-ray diffraction (XRD), Raman and 27 Al nuclear magnetic resonance (NMR) spectroscopy were used to monitor the melting transition of nonasodium aluminate hydrate (NSA, Na 9 [Al(OH) 6 ] 2 ·3(OH)·6H 2 O). A mechanistic interpretation was developed based on complementary classical molecular dynamics (CMD) simulations including enhanced sampling. A reactive forcefield was developed to bridge speciation in the solution and in the solid phase. Findings: In contrast to classical dissolution, aluminum coordination change proceeds through a dynamically stabilized ensemble of intermediate states in a disordered layer at the solid-solution interface. In both melting and dissolution of NSA, octahedral, monomeric aluminum transition through an intermediate of pentahedral coordination. The intermediate dehydroxylates to form tetrahedral aluminate (Al(OH)$_4^–$) in the liquid phase. This coordination change is concomitant with a breaking of the ionic aluminate-sodium ion linkages. The solution phase Al(OH)$_4^–$ ions subsequently polymerize into polynuclear aluminate ions. However, there are some differences between bulk melting and interfacial dissolution, with the onset of the surface-controlled process occurring at a lower temperature (~30 °C) and the coordination change taking place more gradually as a function of temperature. This work to determine the local structure and dynamics of aluminum in the disordered layer provides a new basis to understand mechanisms controlling aluminum phase transformations in highly alkaline solutions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

“Breathing” organic cation to stabilize multiple structures in low-dimensional Ge-, Sn-, and Pb-based hybrid iodide perovskites

Low-dimensional hybrid inorganic–organic perovskites are excellent candidates for stable optoelectronic devices. The dimensionality of these perovskites depends largely on the organic and inorganic compositions, as well as the synthetic conditions. We report five new hybrid iodides, (ETU) 4 Ge 5 I 18 , (ETU)GeI 4 , (ETU)SnI 4 , (ETU)PbI 4 , and (ETU) 3 Pb 2 I 10 using only one type of organic cation, namely, S-(2-aminoethyl)isothiouronium (ETU). (ETU)GeI 4 and (ETU)SnI 4 belong to the (110)-oriented structure-type with “3 × 3” sawtooth corrugated layers and crystallize in a structure with the orthorhombic space group Pbca. (ETU) 4 Ge 5 I 18 crystallizes in a structure with the triclinic space group P$\bar{1}$with combining macron], featuring a 2D layered structure with combinations of corner, edge, and face-sharing [GeI 6 ] octahedra. For the Pb-based series, (ETU)PbI 4 has the conventional (100) – oriented 2D type whereas (ETU) 3 Pb 2 I 10 has a unique 0D structure. Remarkably, the unstable 2D orange-phase (ETU)PbI 4 transforms to a stable 0D yellow phase (ETU) 3 Pb 2 I 10 , accompanied by the reduction of the C–S–C angle of the organic cation ETU. The optical band gaps are largely regulated by the diverse types of structure and are in the range of 1.8 eV to 2.8 eV. (ETU)SnI 4 is the only material showing notable photoluminescence at room-temperature. Our work showcases the flexibility of the organic cation in determining the structural dimensionality and provides a new strategy in generating new hybrid materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗