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At least 1,297 records · Page 72

Temperature- and Rate-Dependent Pathways in Formation of Metastable Silicon Phases under Rapid Decompression

High-pressure metallic beta-Sn silicon (Si-II), depending on temperature, decompression rate, stress, etc., may transform to diverse metastable forms with promising semiconducting properties under decompression. However, the underlying mechanisms governing the different transformation paths are not well understood. Here, two distinctive pathways, viz., a thermally activated crystal-crystal transition and a mechanically driven amorphization, were characterized under rapid decompression of Si-II at various temperatures using in situ time-resolved x-ray diffraction. Under slow decompression, Si-II transforms to a crystalline bc8/r8 phase in the pressure range of 4.3-9.2 GPa through a thermally activated process where the overdepressurization and the onset transition strain are strongly dependent on decompression rate and temperature. In comparison, Si-II collapses structurally to an amorphous form at around 4.3 GPa when the volume expansion approaches a critical strain via rapid decompression beyond a threshold rate. The occurrence of the critical strain indicates a limit of the structural metastability of Si-II, which separates the thermally activated and mechanically driven transition processes. The results show the coupled effect of decompression rate, activation barrier, and thermal energy on the adopted transformation paths, providing atomistic insight into the competition between equilibrium and nonequilibrium pathways and the resulting metastable phases.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Synchrotron X‐Ray‐Driven Nitrogen Reduction on an AgCu Thin Film

Abstract Nitrogen (N 2 ) is an essential element for life, but kinetically stable N 2 in the atmosphere needs to be reduced to biologically available forms as a nutrient for organisms. Abiotic nitrogen fixation is critical to the origin of life on the early Earth, which is due to lightning or mineral‐based reduction. Here, synchrotron X‐ray‐induced silver nitrate formation on a silver copper (AgCu) thin‐film is reported. Time‐resolved X‐ray diffraction measurements show that under intense X‐ray exposure, initially formed silver oxides (AgOx) are quickly converted to silver nitrate (AgNO 3 ). Interestingly, AgNO 3 is first formed in its high‐temperature phase with a space group of R3cH , which gradually transforms to the room temperature phase with a space group of Pbca under continuous X‐ray irradiation. The result not only provides a new clue about the abiotic nitrogen reduction prior to life but also demonstrates a novel strategy of materials synthesis using synchrotron X‐rays.

Hui, Jian↗

Impact of the optical parametric amplification phase on laser pulse compression

Optical parametric chirped-pulse amplification (OPCPA) is an effective way to generate ultrashort pulses that has been used extensively for a variety of applications requiring high peak intensities. Precise control and measurement of a system’s spectral and spatial phases are required for Fourier transform–limited pulse compression and diffraction-limited focusing. Phase accumulated during optical parametric amplification (OPA) can degrade the compressibility and focusability of the pulse, reducing peak intensity. We used analytic and numerical analysis of OPA to study the influence of crystal parameters, wavefront of the pump and signal, and their relative optical alignment on the accumulated phase. Here, we show that the accumulated signal phase is largely independent of amplifier saturation and, with significant local wavefront gradients in the signal or pump beam, the quality of the compressed pulses can be degraded. We use first-order expressions for the pump- and signal-angle sensitivity to evaluate an OPCPA system consisting of a highly deuterated potassium dihydrogen phosphate (DKDP) amplifier designed to support bandwidth for 15 fs pulses centered at 920 nm.

47 OTHER INSTRUMENTATION↗

Low temperature hydrogen plasma permeation in palladium and its alloys for fuel recycling in fusion systems

Superpermeation of hydrogen isotopes through metal foils is a critical component for efficient fuel recycling in fusion power systems. In that context hydrogen permeation through foils of palladium and its alloys with silver and copper was studied at low temperature (60 - 200°C) under plasma exposure. These alloys differ significantly in both bulk and surface properties, and comparisons can provide mechanistic insights. Here, permeation was observed only during plasma operation, confirming the negligible contribution of molecular hydrogen to the observed flux. As-received foils required surface treatment to achieve top performance. For Pd and Pd75Ag25 an oxidation treatment increased permeation an order of magnitude, but proved unstable as this desirable surface was reduced under hydrogen plasma exposure. In contrast, an Ar plasma cleaning step provided both high and stable flux. As-received FCC phase Pd60Cu40 foils required annealing to transform it into the high permeability BCC phase that delivered top performance. All foils displayed similar temperature dependence with flux declining with temperature, suggesting that the primary rate-limiting step is absorption of superthermal hydrogen. Among these foils the hydrogen flux through PdCu was 3 - 5X greater than that of Pd or PdAg, which were similar. The superiority of BCC PdCu is attributed to its superior hydrogen desorption kinetics. Using PdCu 100% permeation of supplied hydrogen was achieved, and the flux saturated with increasing plasma power at values >10 –2 mol H•m –2 •s– 1 , and under these conditions permeation rates are equivalent with or without the membrane present. The fluxes achieved are the highest reported to date at these conditions, and the results highlight the important roles of both surface and bulk properties.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Thermal Stability of LiNi x Mn y Co z O 2 Cathode Materials

Here, the thermal evolution of LiNi x Mn y Co z O 2 (NMC) lithium-ion battery electrode materials is examined at various states of charge (SOC) or lithium concentrations for a variety of Ni:Mn:Co ratios or electrode compositions. Synchrotron X-ray diffraction (XRD) combined with Rietveld analysis shows the onset decomposition temperatures of phases, decomposition products, lattice parameters, and phase fractions as a function of composition and SOC. SOC impacts the lattice parameters of the NMC phase, where a collapse of the c-axis in the NMC phases is noted due to lithium extraction. Among the compositions examined, the low-Ni NMC111 uncycled sample (NMC111 0% SOC) exhibited the highest thermal stability, with a decomposition temperature approximately 250 °C higher than that of NMC532 0% and NMC811 0%. When the SOC exceeds 50% (i.e., more than 0.4 mol of Li ions extracted), the influence of Ni content on the decomposition temperature becomes negligible, with decomposition occurring around 250−300 °C for all compositions. Ni content also affects the decomposition pathways: NMC111 tends to first form a TM 3 O 4 -type phase, where TM represents transition metals, before transforming into a TMO-type phase, whereas most of the NMC811 samples directly decompose into the TMO phase. The presence of metallic phases was confirmed by both XRD and thermogravimetric-differential scanning calorimetry (TGA-DSC) analysis, as a result of heating under inert conditions. The TGA-DSC results suggest that metallic phase formation is favored at lower SOC in samples with a higher Ni content. This work provides comprehensive insight into the thermal degradation pathways of NMC materials as a function of composition, SOC, and temperature.

Peng, Jian [Univ. of New South Wales, Sydney, NSW ↗

Phase change instability in the mantle

Earth upper mantle phase change instability, discussing temperature gradient, transformation influence on fluid, olivine-spinel phase flow patterns and tectonics

Oxburgh, E. R.↗

From atomistic models to machine learning: Predictive design of nanocarbons under extreme conditions

The formation of technologically valuable nanocarbon structures under extreme conditions, such as those produced during high-explosive detonations, remains poorly understood but holds significant potential for the development of controlled synthesis pathways. While detonation shockwaves provide the high-pressure, high-temperature environment required for nanodiamond formation, subsequent cooling and decompression dictate whether the diamond phase is preserved or transformed into other nanocarbon structures. Here, in this study, we employ GPU-accelerated reactive molecular dynamics (ReaxFF) simulations to investigate the graphitization and structural remodeling of detonation nanodiamond under nonlinear quench and pressure-release trajectories. We further investigate how the initial nanodiamond morphology; cuboctahedral, octahedral, or hexagonal prism influences the resulting transformation products. Evolution of nanostructure, allotrope (via simulated x-ray diffraction), carbon hybridization, and ring statistics are tracked during a two-stage quench from 5000 K to 60 GPa. Rapid cooling combined with slow decompression optimizes cubic diamond retention, whereas slow cooling with rapid pressure release promotes surface-to-core graphitization, producing concentric sp 2 -hybridized layers and hollowed inner shells. Octahedral nanodiamonds evolve into carbon nano-onions, initially forming bucky diamonds that progressively transform into fully sp 2 -hybridized structures, while hexagonal prisms preferentially form parallel-stacked graphite layers resembling carbon dots. Transient hexagonal diamond (lonsdaleite) emerges as an interfacial phase, suggesting potential reversibility in the shock-induced graphite-to-diamond transformation pathway transformation route. To extend predictive capabilities, we trained machine learning (ML) regressors on over 10 5 node-hours of molecular dynamics (MD) trajectories. A multilayer perceptron (MLP) model reliably predicts the number of graphitized layers from temperature–pressure trajectories with a coefficient of determination (R 2 ) exceeding 0.90. This high predictive fidelity enables efficient, high-throughput mapping of the synthesis parameter space for optimized graphitization outcomes. Collectively, morphological control combined with optimized quench–decompression conditions promote the selective synthesis of nanocarbon allotropes. This work establishes a data-driven framework for the rational, a priori design of carbon nanomaterials for applications in energy storage, sensing, and biomedicine.

Detonation nanodiamond remodeling↗

Bi aliovalent substitution in Li 7 La 3 Zr 2 O 12 garnets: Structural and ionic conductivity effects

We report on the synthesis of cubic-phase garnet-type solid-state electrolytes based on Bi-doped Li 7 La 3 Zr 2 O 12 (LLZO). Bi aliovalent substitution of Zr in LLZO utilizing the Pechini processing method is employed to synthesize Li 7-x La 3 Zr 2-x Bi x O 12 compounds. A strong dependence of the ionic conductivity on Bi content is observed, and under our synthesis and sintering conditions, a >100-fold increase over the un-doped sample is observed for x=0.75. Cubic-phase Li 6 La 3 Zr 1 BiO 12 compounds are generated upon annealing in air in the temperature range 650 °C-900 °C. In contrast, in the absence of Bi, the cubic garnet phase of Li 7 La 3 Zr 2 O 12 is not formed below 700 °C and a transformation to the tetragonal phase is observed at similar to 900 °C for this un-doped compound. The role of Bi in lowering the formation temperature of the garnet cubic phase and in the ionic conductivity improvements is investigated in this work. We ascribe the effect of Bi-doping on ionic conductivity increments to changes in Li + -site occupancy and lattice parameters and the reduction in the formation temperature for the cubic-phase formation to rate enhancements of the solid-state reaction. To identify the site occupancy of Bi in the garnet structure, we employ synchrotron extended x-ray absorption fine structure spectroscopy. Our results indicate that Bi additions occupy the Zr-type sites exclusively, to within the accuracy of the measurements.

36 MATERIALS SCIENCE↗

Deciphering Extreme Mineral Records; Microstructural Phase Heritage of Shocked Materials

High-pressure minerals such as coesite, stishovite, and reidite are often used as indicators of shock metamorphism. However, high-pressure and high-temperature phases are metastable at ambient conditions and, therefore, often revert to a more energetically favorable phase. During solid-state transformations, the crystallographic orientations of the stable polymorph are controlled by the transformation pathway from the parent. Microstructural orientation analysis using electron backscatter diffraction (EBSD) of the stable phase can reveal systematic intercrystalline orientation relationships (OR) diagnostic of solid-state transformations from these high-pressure or high-temperature polymorph phases (Cayron et al., 2006). Knowledge of polymorph stability fields for a given system can thus be used to infer minimum shock P and/or T conditions that rocks have experienced, which are otherwise unavailable using traditional thermobarometers such as element partition coefficients. Using orientation relationships to infer the former presence of mineral phases has been termed microstructural “phase heritage”, and has successfully been used to probe for evidence of extreme pressures and temperatures resulting from hypervelocity impacts. The reconstruction of polymorphs of ZrSiO4 (zircon, reidite) and ZrO2 (baddeleyite) have further elucidated the behavior of these phases under hypervelocity impact conditions (Timms et al., 2017a; White et al., 2018), and OR analysis of shocked monazite has identified a previously unrecognized tetragonal high-P polymorph (Erickson et al., 2019). Zircon will convert to the low tetragonal polymorph reidite at shock stresses above ~21 GPa. However, upon decompression at temperatures above 1200 °C reidite will revert to zircon (Kusaba et al., 1985). Recrystallized zircon neoblasts encased in impact melt often show systematic misorientation relationships of 90° about <110> indicative of reversion from the reidite (Fig. 1), and preserving cryptic evidence of the high-P history that is often erased by the post shock thermal spike (Cavosie et al., 2016). Microstructural OR analysis of a dissociated zircon corona composed of baddeleyite (monoclinic-ZrO2) has identified the former presence of cubic zirconia within impact melt glass from the Mistastin Lake impact structure, Labrador, CA. Based on stability fields in the ZrO2-SiO2 binary phase diagram, cubic zirconia records thermal conditions in excess of 2370 °C at ambient P, indicating that the Mistastin impact melt is the hottest rock identified on Earth’s surface (Timms et al., 2017b). Shock-deformed monazite (monoclinic La,Ce,ThPO4) containing lamellae comprised of interlocking laths has been identified from the Haughton Dome impact structure, Nunavut, Canada and Nördlinger-Ries Crater, southern Germany. The lath-structured lamellae are composed of four systematic orientation variants, which OR analyses indicate originate from a tetragonal parent whereby the [010]monoclinic aligns with either [100] or [010]tetragonal (Erickson et al., 2019). These results highlight utility of microstructural phase heritage analyses for the identification of unstable high-P or high-T polymorphs that uniquely record the extremely transient shock conditions produced by hypervelocity impacts.

Timmons Erickson↗

Nanocrystalline strain glass TiNiPt and its superelastic behavior

TiNi-based shape-memory alloys are known to exhibit a strain glass state under certain conditions, generally in the presence of high-density defects such as excess solute atoms or alloying elements, dislocations, and nanoprecipitates. In this paper, we report a strain glass transition in a nanocrystalline Ti 50 Ni 35 Pt 15 alloy. The nanocrystalline strain glass state is achieved by a combined effect of high-density grain boundaries and high concentration doping of Pt atoms in the B2 matrix. The nanocrystalline Ti 50 Ni 35 Pt 15 strain glass alloy showed a large near-complete progressive superelasticity with a recovery strain of about 6% and a low apparent Young's modulus of about 30 GPa in a wide temperature range of over 200 °C. In situ synchrotron x-ray diffraction measurement showed that the strain glass B2 [B2(SG)] phase experienced B2(SG)→R→B19 transformation upon loading and B19→B2(SG) upon unloading. The findings of this study provide insight for the development of nanocrystalline strain glass shape-memory alloys.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Intercalation And High-Pressure Effects On Structural Phase Transitions In Layered As x P 1-x Alloys

This project was aimed at understanding the role of composition, intercalation, and high pressure on the structural evolution of black phosphorous (BP) and layered arsenic phosphorous alloys, As y P 1-y . Under normal conditions, BP is the most stable phase of phosphorous, known as the α-phase, characterized by an orthorhombic honeycomb puckered crystal structure with the Cmca space group. On the other hand, the most stable phase of arsenic is its β-phase, known as gray arsenic (g-As), which has a rhombohedral buckled layered crystal structure with the R3m space group. In a wide range of compositions (y < 0.83), the arsenic phosphorous alloys form the α-phase, known as black arsenic phosphorous (b-As y P 1-y ) with a similar structure to BP. The project was aimed at the synthesis of BP and b-As y P 1-y with different compositions and at studying the structural evolution of these materials during intercalation with alkali metal (especially Li), and under high-pressure conditions. The main goals were to gain a better understanding of these processes and structural changes taking place under these conditions. In particular, the project was aimed at addressing whether such conditions could induce a structural transition between the α- and β-phases. For this, a series of systematic in-situ studies were conducted, including electrochemical lithium intercalation in an in-situ electrochemical cell, and high-pressure experiments in a diamond anvil cell (DAC). Overall, both types of experiments have shown that above a certain composition-dependent threshold level of intercalation or high pressure, the system undergoes phase segregation rather than phase transition. Specifically, the segregation of the excess arsenic was observed, and a single-phase system of b-As y P 1-y transformed into a two-phase system consisting of b-As y P 1-y and g-As, through the following process: 1∗(b-As y P 1-y ) → 1∗(b As y-δ P 1-y ) + δ∗(g-As). Also, the study showed that intercalation and high-pressure are two competing rather than synergistic processes causing at least a partial cancelation of these two factors

36 MATERIALS SCIENCE↗

Gradient flow based phase-field modeling using separable neural networks

Allen–Cahn equation is a reaction–diffusion equation and is widely used for modeling phase separation. Machine learning methods for solving the Allen–Cahn equation in its strong form suffer from inaccuracies in collocation techniques, errors in computing higher-order spatial derivatives, and the large system size required by the space–time approach. To overcome these challenges, we propose solving the gradient flow of the Ginzburg–Landau free energy functional, which is equivalent to the Allen–Cahn equation, thereby avoiding the second-order spatial derivatives associated with the Allen–Cahn equation. A minimizing movement scheme is employed to solve the gradient flow problem, eliminating the complexities of a space–time approach. We utilize a separable neural network that efficiently represents the phase field through low-rank tensor decomposition. As we use the minimizing movement scheme to numerically solve the gradient flow problem, we thus, refer to the proposed method as the Separable Deep Minimizing Movement (SDMM) method. The evaluation of the functional in the minimizing movement scheme using the Gauss quadrature technique bypasses the inaccuracies associated with collocation techniques traditionally used to solve partial differential equations. A hyperbolic tangent transformation is introduced on the phase field prior to the evaluation of the functional to ensure that it remains strictly bounded within the values of the two phases. For this transformation, theoretical guarantee for energy stability of the minimizing movement scheme is established. Our results suggest that this transformation helps to improve the accuracy and efficiency significantly. The proposed method resolves the challenges faced by state-of-the-art machine learning techniques, outperforming them in both accuracy and efficiency. It is also the first machine learning method to achieve an order of magnitude speed improvement over the finite element method. In addition to its formulation and computational implementation, several case studies illustrate the applicability of the proposed method.

42 ENGINEERING↗

Effect of Zn Addition on Phase Evolution in AlCrFeCoNiZn High–Entropy Alloy

The addition of Zn to AlCrFeCoNi high-entropy alloy (HEA) poses intriguing questions as to how it would affect phase evolution. Herein, the phase evolution in AlCrFeCoNiZn is studied using a combination of experimental techniques (X-ray diffraction, scanning electron microscopy, energy-dispersive spectroscopy, and differential scanning calorimetry) and computational (density-functional theory [DFT], calculation of phase diagrams, and machine-learning) methods. Mechanically alloyed and spark-plasma-sintered AlCrFeCoNiZn assumes a metastable single-phase, body-centered-cubic (BCC) structure that undergoes diffusion-controlled phase separation upon subsequent heat treatment to form separate (Al, Cr)-rich, (Fe, Co)-rich, and (Zn, Ni)-rich phases. The formation of (Al, Cr)-rich phase, not reported previously in AlCrFeCoNi-based HEAs, is attributed to strong clustering tendency of Cr–Zn and Cr–Ni pairs, combined with the strong ordering of Zn–Ni pair, driving out Cr that in turn combines with Al to form a (Al, Cr)-rich phase. In the DFT results, the formation of thermodynamically stable L1 2 phase is shown wherein Cr–Fe–Zn [Al–Ni-Co] preferably occupy1a (000) [3c (0 ½ ½)] positions. Furthermore, the sluggish diffusional transformation to L1 2 phase from BCC precursors is attributed to the small stacking-fault energy of AlCrFeCoNiZn. The equilibrated HEA exhibits a high microhardness of 8.24 GPa with an elastic modulus of 184 GPa.

36 MATERIALS SCIENCE↗

Polymorphism of gold under laser-based ramp compression to 690 GPa

The high-pressure behavior and polymorphism of gold has attracted strong recent interest from theory as well as from both static and dynamic experiments. In this study, gold was dynamically ramp-compressed to 690 GPa via laser ablation using the Omega Laser Facility (U. Rochester) in order to investigate the stability regions of this noble metal's polymorphs. Here, stresses were determined from measurements of surface or interface velocities by laser interferometry. In situ X-ray diffraction was carried out to constrain the structure and density. The ambient face-centered-cubic (fcc) phase was observed at 162 GPa, followed by a mixed phase region consisting of the fcc and body-centeredcubic (bcc). The presence of only the bcc phase was observed between 377 and 690 GPa. Our results are consistent with recent shock compression experiments and demonstrate that gold transforms to the bcc phase under conditions of both ramp and shock loading.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Ultrafast olivine-ringwoodite transformation during shock compression

Meteorites from interplanetary space often include high-pressure polymorphs of their constituent minerals, which provide records of past hypervelocity collisions. These collisions were expected to occur between kilometre-sized asteroids, generating transient high-pressure states lasting for several seconds to facilitate mineral transformations across the relevant phase boundaries. However, their mechanisms in such a short timescale were never experimentally evaluated and remained speculative. Here, we show a nanosecond transformation mechanism yielding ringwoodite, which is the most typical high-pressure mineral in meteorites. An olivine crystal was shock-compressed by a focused high-power laser pulse, and the transformation was time-resolved by femtosecond diffractometry using an X-ray free electron laser. Our results show the formation of ringwoodite through a faster, diffusionless process, suggesting that ringwoodite can form from collisions between much smaller bodies, such as metre to submetre-sized asteroids, at common relative velocities. Even nominally unshocked meteorites could therefore contain signatures of high-pressure states from past collisions.

42 ENGINEERING↗

Optical Tweezers Array and Nimble Tweezers Probe Generated by Spatial- Light Modulator

An optical tweezers is being developed at the NASA Glenn Research Center as a visiblelight interface between ubiquitous laser technologies and the interrogation, visualization, manufacture, control, and energization of nanostructures such as silicon carbide (SiC) nanotubes. The tweezers uses one or more focused laser beams to hold micrometer-sized particles called tools (sometimes called tips in atomic-force-microscope terminology). A strongly focused laser beam has an associated light-pressure gradient that is strong enough to pull small particles to the focus, in spite of the oppositely directed scattering force; "optical tweezers" is the common term for this effect. The objective is to use the tools to create carefully shaped secondary traps to hold and assemble nanostructures that may contain from tens to hundreds of atoms. The interaction between a tool and the nanostructures is to be monitored optically as is done with scanning probe microscopes. One of the initial efforts has been to create, shape, and control multiple tweezers beams. To this end, a programmable spatial-light modulator (SLM) has been used to modify the phase of a laser beam at up to 480 by 480 points. One program creates multiple, independently controllable tweezer beams whose shapes can be tailored by making the SLM an adaptive mirror in an interferometer (ref. 1). The beams leave the SLM at different angles, and an optical Fourier transform maps these beams to different positions in the focal plane of a microscope objective. The following figure shows two arrays of multiple beams created in this manner. The patterns displayed above the beam array control the intensity-to-phase transformation required in programming the SLM. Three of the seven beams displayed can be used as independently controllable beams.

Decker, Arthur J.↗

Melt-Processed Halide Perovskite Thin Films from a Two-Dimensional Ruddlesden–Popper Phase Precursor

While halide perovskite thin films have enormous potential for photovoltaics and other optoelectronics, the use of environmentally hazardous solvents during their deposition and processing poses a barrier to their commercialization. In this work, we demonstrated the deposition of melt-processable precursors and subsequent transformation into halide perovskite thin films without using environmentally hazardous solvents. We melted the wide-bandgap layered perovskites [(C 6 H 5 CH(CH 3 )CH 2 NH 3 ) 2 PbI 4 :β-Me-PEA 2 PbI 4 ] at ~210 °C and blade coated them into films. The β-Me-PEA 2 PbI 4 films were subsequently transformed to perovskite-phase methylammonium or formamidinium lead iodide films using a cation-exchange process in an alcohol-based solvent. Lastly, we demonstrate the potential and limitations of a completely solvent-free approach that uses solid-state transformation of a β-Me-PEA 2 PbI 4 film. As a result, this work represents a substantial step toward eliminating environmentally hazardous solvents and enables inexpensive industrial-scale liquid-phase deposition processes that do not require expensive systems for handling and disposing of environmentally hazardous solvents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗