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At least 37 records · Page 2

Mechanical and Tribological Performance of Additively Manufactured Nanocrystalline Aluminum via Cryomilling and Cold Spray

In this study, nanocrystalline (NC) aluminum (Al) and magnesium (Mg)-doped Al bulk components were fabricated using a hybrid manufacturing process that combines cryomilling and high-pressure cold spray (HPCS) additive deposition techniques. Yttria-stabilized zirconia (YSZ) was also added during the HPCS process to improve deposition efficiency and build-up thickness via peening. The evolution of morphology, crystallite size, and elemental composition of both cryomilled powders and cold-sprayed (CS’ed) components was systematically characterized using X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), and Transmission Electron Microscopy (TEM). Mechanical characterization was performed using Vickers microhardness and uniaxial tensile testing, while the tribological behavior was assessed using sliding wear tests under dry/lubricated conditions. XRD analysis revealed that increased cryomilling duration led to significant crystallite refinement, which directly correlated with enhanced hardness and strength. This mechanical strengthening was accompanied by an increase in coefficient of friction (COF) and lower wear rates. The results also showed that the Mg-doped Al exhibited superior hardness, tensile strength, and tribological performance compared to pure Al. The study further explores the underlying mechanisms responsible for these enhancements, highlighting the potential of solute-assisted grain boundary stabilization in tailoring high-performance NC Al alloys.

36 MATERIALS SCIENCE↗

Static and shock compression studies of eutectic high-entropy alloy AlCoCrFeNi 2.1 to ultrahigh pressures

The high-entropy alloy with composition AlCoCrFeNi 2.1 , additively manufactured with the laser powder-bed fusion technique, has a far-from-equilibrium BCC/FCC eutectic nanolamellar structure. We studied the high-pressure response of this alloy under both static compression and high-strain rate shock compression. The response to static compression using a diamond anvil cell was studied at pressures up to 302 GPa with synchrotron x-ray diffraction at the advanced photon source. The high-pressure FCC-only phase of the EHEA previously observed by Pope et al. [AIP Adv. 13, 035124 (2023)] is found to be stable up to the highest pressure achieved in this study with a volume compression of V/V 0 = 0.587 at ambient temperature. The shock experiments were performed by using GEKKO XII lasers at the Institute of Laser Engineering, Osaka University. The principal Hugoniot equation-of-state of the EHEA was measured up to a pressure of 515 GPa and a compression of V/V 0 = 0.613. Additionally, the thermal equation of state of the EHEA was measured up to 6.2 GPa and 1623 K using a large-volume Paris–Edinburgh cell to obtain the temperature dependence of bulk modulus and thermal expansion coefficients. The melting temperature for EHEA AlCoCrFeNi 2.1 at a pressure of 5.6 GPa was measured to be 1648 ± 25 K. These results can be used to refine stochastic (or special) quasi-random structure (SQS) models for high-pressure high-temperature behavior of high-entropy alloys.

36 MATERIALS SCIENCE↗

Piezochromic Behavior of 2,4,6-Triphenylpyrylium Tetrachloroferrate

In advanced photonics, there is a growing interest in piezochromic luminescent materials that exhibit multicolor switching, driven by their potential applications in optical recording, memory, and sensors. Here, the piezochromic behavior of 2,4,6-triphenylpyrylium tetrachloroferrate (Py-FeCl 4 ) under high pressures from 0 to 9 GPa is reported. The observed multicolor changing properties of Py-FeCl 4 (yellow–orange–red–maroon–black) are found to be fully reversible upon decompression to ambient conditions. The mechanism of Py-FeCl 4 piezochromism is investigated via Raman, infrared, and UV–vis spectroscopy combined with powder X-ray Diffraction. The absence of structural phase transitions as well as the abrupt shifts of bandgap values together with characteristic Raman and IR peaks within 0-9 GPa suggests that the Py-FeCl 4 multicoloring switching behavior is driven by an electron transfer between the inorganic FeCl 4 – anion and the organic pyrylium cation. The obtained results demonstrate that Py-FeCl 4 dye is a good candidate for developing high-pressure sensing technologies designed to function in extreme environments. Moreover, due to the inherent role of molecular-structure relationships in the pyrylium salt's photophysical properties, findings suggest the potential discovery of piezochromic behavior in other pyrylium compounds.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Multiframe X-ray diffraction on the OMEGA EP laser

A method of measuring multiple temporally resolved powder x-ray diffraction measurements during a single dynamic compression laser experiment has been demonstrated on the OMEGA EP laser. Up to four time-gated snapshots of the x-ray diffraction pattern are collected on an ultrafast x-ray framing camera with a 2θ scattering angle coverage of 48°–65° and 400-ps temporal resolution with the potential for 10°–160° and 200-ps resolution. X-ray diffraction snapshots capture the transformation to a high-pressure β phase in ramp-compressed Zr, constraining the atomic structure and pressure–density equation-of-state in a single shot. Here, this platform will be used to constrain transition pressures, understand the role of kinetics, and verify the existence of hysteresis and metastability on phase transformations at the lattice level under single-shot dynamic compression.

47 OTHER INSTRUMENTATION↗

Hydrogenation of calcite and change in chemical bonding at high pressure: Diamond formation above 100GPa

Synchrotron X-ray diffraction (XRD) and Raman spectroscopy in laser heated diamond anvil cells and first principles molecular dynamics (FPMD) calculations have been used to investigate the reactivity of calcite and molecular hydrogen (H 2 ) at high pressures up to 120 GPa. We find that hydrogen reacts with calcite starting below 0.5 GPa at room temperature forming chemical bonds with carbon and oxygen. This results in the unit cell volume expansion; the hydrogenation level is much higher for powdered samples. Single-crystal XRD measurements at 8–24 GPa reveal the presence of previously reported III, IIIb, and VI calcite phases; some crystallites show up to 4% expansion, which is consistent with the incorporation of ≤ 1 hydrogen atom per formula unit. At 40–102 GPa XRD patterns of hydrogenated calcite demonstrate broadened features consistent with the calcite VI structure with incorporated hydrogen atoms. Above 80 GPa, the C–O stretching mode of calcite splits suggesting a change in the coordination of C–O bonds. Laser heating at 110 GPa results in the formation of C–C bonds manifested in the crystallization of diamond recorded by in situ XRD at 300 K and 110 GPa and by Raman spectroscopy on recovered samples commenced with C 13 calcite. We explored several theoretical models, which show that incorporation of atomic hydrogen results in local distortions of CO 3 groups, formation of corner-shared C–O polyhedra, and chemical bonding of H to C and O, which leads to the lattice expansion and vibrational features consistent with the experiments. In conclusion, the experimental and theoretical results support recent reports on tetrahedral C coordination in high-pressure carbonate glasses and suggest a possible source of the origin of ultradeep diamonds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhancing Properties with Distortion: A Comparative Study of Two Iron Phosphide Fe 2 P Polymorphs

Iron phosphide (Fe 2 P) crystallizes in its own hexagonal crystal structure type (h-Fe 2 P). As found in meteorites, orthorhombic polymorph (o-Fe 2 P) was originally reported as a high-temperature and high-pressure phase. Recently, o-Fe 2 P was described as being stable at ambient pressure, yet no synthetic methods were developed for single-crystal growth or single-phase bulk powder synthesis. Here, we report a successful method for growing o-Fe 2 P single crystals and synthesizing phase-pure polycrystalline samples using tin-flux. In situ powder X-ray diffraction studies showed that the phase transition from o-Fe 2 P to h-Fe 2 P occurs at about 873 K, and below that temperature, the formation of the o-Fe 2 P phase is favored thermodynamically rather than kinetically. Systematic comparison of transport, magnetic, and electrocatalytic properties of both h-Fe 2 P and o-Fe 2 P phases showed a substantial impact of the crystal structure on properties. The orthorhombic structural distortion resulted in considerable changes in magnetic properties, with the o-Fe 2 P phase exhibiting a 60% lower Fe magnetic moment and a substantially higher ferromagnetic Curie temperature than h-Fe 2 P. Further, electrochemical measurements toward the hydrogen evolution reaction in acidic media showed that the o-Fe 2 P phase requires an 80 mV lower overpotential than the h-Fe 2 P phase to generate a current density of -10 mA/cm 2 , and their electronic structures suggest that the higher density of states at the Fermi energy is the origin of superior catalytic activity in o-Fe 2 P.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pressure-Stabilized MnSb2 with Complex Incommensurate Magnetic Order

Marcasite-type compounds have been proposed as promising hosts of exotic magnetic quantum states, yet experimental realizations in stoichiometric, disorder-free systems remain limited. Here, we report the high-pressure stabilization and magnetic characterization of MnSb2, a marcasite-type compound that is thermodynamically metastable under ambient pressure. Single crystals were synthesized using a cubic multianvil press at 3.3 GPa and 490 °C for 24 h, and powder and single-crystal X-ray diffraction confirm the orthorhombic Pnnm structure. These crystals are stable at ambient pressure for a long time up to between 450 and 500 K. Heat-capacity measurements reveal phase transitions at approximately T0 ∼ 118 K and T1 ∼ 220 K. Neutron diffraction uncovers an unconventional magnetic state below T1 ∼ 220 K. Magnetic powder neutron diffraction refinements reveal possible multiple magnetic configurations that provide comparably acceptable fits to the experimental data. While most solutions are consistent with a spin-density-wave (SDW) description, helical models systematically yield inferior agreement factors. Across a broad range of models, the Mn ordered moment reaches a maximum value of approximately 2 μB and remains predominantly collinear, with minimal canting along the c-axis. At 200 K, the magnetic propagation vector is q = (0, 0.3975, 0.3783); upon cooling, the b component increases toward 0.5, reflecting a temperature-dependent evolution of the modulation. The need for modification of the magnetic model between high and low temperatures further highlights the complex and strongly temperature-dependent nature of the magnetic order in this system. These results establish MnSb2 as a pressure-stabilized marcasite magnet with a tunable, complex magnetic state and a compelling stoichiometric platform for exploring unconventional magnetic behavior, including potential altermagnetism.

Xu, Mingyu [Michigan State University , , , ,; Iow↗

Phase stability of a eutectic high entropy alloy under extremes of pressures and temperatures

Additively manufactured high-entropy alloys are of interest because of their unique combination of high yield strength and large ductility achieved with far-from-equilibrium crystalline phases and micro/nanostructure morphology. We report on the phase transformation and thermal equation of state of the eutectic high-entropy alloy (EHEA) Al 18 Co 20 Cr 10 Fe 10 Ni 40 W 2 , produced by laser powder-bed fusion (L-PBF). The EHEA was studied in a large-volume Paris–Edinburgh cell using energy-dispersive x-ray diffraction to a pressure of 5.5 GPa and a temperature of 1723 K. Static compression studies in diamond anvil cells using angle-dispersive x-ray diffraction extended the high-pressure structural data to 317 GPa at ambient temperature. The initial dual-phase nanolamellar face-centered cubic (FCC) and body-centered cubic (BCC) structure of Al 18 Co 20 Cr 10 Fe 10 Ni 40 W 2 transforms into a single FCC phase under high pressure, with the BCC-to-FCC phase transformation completing at 9 ± 2 GPa. The FCC phase remained stable up to the highest pressure of 317 GPa. The measured thermal equation of state for the FCC phase of Al 18 Co 20 Cr 10 Fe 10 Ni 40 W 2 is presented up to 5.5 GPa and 1473 K. We observed melting of the EHEA at 1698 ± 25 K at a pressure of 5.5 GPa, and the recrystallized sample shows an increased fraction of the CsCl-type (B2) phase at ambient conditions following release from the high-pressure high-temperature state. The BCC-to-FCC phase transition completion pressure is correlated with the nanolamellae thickness of the BCC layer in this diffusion-less transformation at ambient temperature.

36 MATERIALS SCIENCE↗

High-pressure high-temperature synthesis and characterization of B 10 C

The boron-rich boron carbide materials have been traditionally synthesized by adding boron powder to B 4 C material and subjecting it to hot pressing sintering for materials composition containing 8.8–20 at. % carbon in boron (composition range of B 10.4 C to B 4 C). Our study explores a synthesis route for B 10 C starting from high-purity boron and carbon and direct conversion under high pressure and high temperature (HPHT) conditions of 2000 °C and 6–8 GPa. Synthesis was verified via x-ray diffraction analysis, showing the conversion of the high-purity boron and carbon powder mixture into a hexagonal B 10 C structure (R-3m space group) with lattice parameters of a = b = 5.6115 Å and c = 12.197 Å. The concentration of boron was measured through x-ray photoelectron spectroscopy, confirming the B 10 C ratio. The measured nanoindentation mean hardness of B 10 C was 40 GPa. Raman spectroscopy of the HPHT synthesized sample shows characteristic vibrational breathing modes of boron icosahedron and an additional intense band at a vibrational frequency of 380 cm –1 . This Raman band, which appears notably weaker in earlier studies and B 4 C samples, is assigned to the linear chain of B–B–B and attributed to the maximal incorporation of boron within the hexagonal structure.

36 MATERIALS SCIENCE↗

Shock compression of crystalline TeO 2 to the high-pressure fluid regime: Insights from ab initio molecular dynamics simulations

The shock response of fully-dense and porous crystalline tellurium dioxide (TeO 2 ⁠) to the high-pressure and high-temperature fluid regime was investigated within the framework of density functional theory with Mermin’s generalization to finite temperatures. The principal and porous shock Hugoniot curves were predicted from canonical ab initio molecular dynamics (AIMD) simulations, with the phase space sampled along isotherms up to 80 000 K, for densities ranging from ρ = 3 to 17 g/cm 3 . The polymorphs investigated are α-TeO 2 paratellurite (⁠P4 1 2 1 2), TeO 2 cotunnite (⁠Pnma⁠), and TeO 2 post-cotunnite (⁠P2 1 /m⁠). Based on the discontinuity found in the calculated U s – u p slope of TeO 2 post-cotunnite at a shock velocity of U s ≃ 8.35km/s and a particle velocity of u p ≃ 3.64 km/s, the shock melting temperature and pressure are predicted to be ≃ 6500 K and ≃ 170 GPa. Results from the AIMD simulations are in line with the static compression data of TeO 2 paratellurite and cotunnite, and with the recent shock Hugoniot data for single-crystal α- TeO 2 for pressures up to 85 GPa, obtained using the inclined-mirror method and the velocity interferometer system for any reflector combined with powder gun and two-stage light-gas gun.

74 ATOMIC AND MOLECULAR PHYSICS↗

Effect of Ni substitution on the fragile magnetic system La 5 Co 2 Ge 3

La 5⁢ Co 2 ⁢Ge 3 is an itinerant ferromagnet with a Curie temperature T C of ~3.8K and a remarkably small saturated moment of 0.1µ B /Co. Here we present the growth and characterization of single crystals of the La 5 ⁢(Co 1–x⁢ Ni x ) 2 Ge 3 series for 0.00 ≤ x ≤ 0.186. Here we measured powder x-ray diffraction, composition as well as anisotropic temperature-dependent resistivity, temperature and field-dependent magnetization along with heat capacity on these single crystals. We also measured muon-spin rotation/relaxation (μ⁢SR) for some Ni substitutions (x = 0.027,0.036,0.074) to study the evolution of internal field with Ni substitution. Using the measured data we infer a low temperature, transition temperature-composition phase diagram for La 5 ⁢(Co 1–x ⁢Ni x ) 2 Ge 3 . We find that T C is suppressed for low dopings, x ≤ 0.014; whereas for 0.036 ≤ x ≤ 0.186, the samples are antiferromagnetic with a Néel temperature T N that goes through a weak and shallow maximum (T N ~ 3.4K for x~0.07) and then gradually decreases to 2.4 K by x = 0.186. For intermediate Ni substitutions, 0.016 ≤ x ≤ 0.027, two transition temperatures are inferred with T N >T C . Whereas the T–x phase diagram for La 5 ⁢(Co 1–x ⁢Ni x ) 2 Ge 3 and the T–p phase diagram determined for the parent La 5 ⁢Co 2 ⁢Ge 3 under hydrostatic pressure are grossly similar, changing from a low-doping or low-pressure ferromagnetic (FM) ground state to a high-doped or high-pressure antiferromagnetic (AFM) state, perturbation by Ni substitution enabled us to identify an intermediate doping regime where both FM and AFM transitions occur.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

High-pressure synthesis and neutron scattering study of tantalum hydride TaH 1.23(5) and a tantalum polymorph with A15-type structure

A unique type of tantalum hydride was synthesized by exposing tantalum dihydride to the high hydrogen pressure of 9 GPa and a temperature of using toroid-type high-pressure chambers. The samples of this hydride were cooled down to 100 K, recovered to ambient pressure, and studied in a metastable state by hot extraction, powder x-ray and neutron diffraction, and inelastic neutron scattering. X-ray diffraction demonstrated that this hydride had an A15-type crystal structure of metal lattice (space group , Ta atoms at the 2a and 6c Wyckoff positions) and a lattice parameter of a = 5.150(5) Å at T = 85 K. The hydrogen content determined by hot extraction was H/Ta - 1.23(5). Hydrogen desorption during heating the sample in vacuum proceeded in two steps—first, Δ⁢H⁡/Ta=0.2 was desorbed at around -70 °⁢C, and then the rest of the hydrogen was desorbed between 100 ⁢°C and 390 ⁢°⁢C. The A⁢15-type metal lattice was preserved upon hydrogen removal, leaving a unique polymorph of tantalum. Neutron diffraction of A⁢15-TaH 1.23⁢(5) demonstrated that hydrogen atoms occupy the 24⁢k and 16⁢i Wyckoff sites in the crystal structure, and annealing at 250 K resulted in a decrease of the 24⁢k and an increase of the 16⁢i site occupancies. Inelastic neutron scattering revealed four vibrational modes in the fundamental band of A⁢15-TaH 1.23⁢(5) at 72, 135, 145, and 166 meV, the first three and the last one of which were tentatively assigned to the vibrations of H atoms at the 24⁢k and 16⁢i sites, respectively. No superconductivity was found in A⁢15-TaH 1.1 and hydrogen-free A15-Ta at temperatures down to 1.5 K.

36 MATERIALS SCIENCE↗

Elastic properties of the W 0.75 R e 0.25 alloy at high pressure up to 183 GPa

The high pressure equation of state for the W 0.75 R e 0.25 alloy is experimentally determined up to 183 GPa with synchrotron angle-dispersive powder x-ray diffraction in the diamond-anvil cell and to ∼925 GPa with density-functional theory. W-Re alloys are used in many industrial high-temperature applications and as a confining gasket material in high-pressure diamond-anvil cell research. The inclusion of 25 wt. % Re achieves the highest performance in terms of strength and ductility while also maintaining the body-centered-cubic (bcc) crystal structure, yet to date there has been no investigation into its elastic behavior at high pressure. We present the experimentally and theoretically determined volumetric and elastic pressure response and systematically compare these results to other W-Re alloys, finding that the bulk modulus of W-Re alloys varies nonlinearly with Re content and W 0.75 Re 0.25 becomes less incompressible than W at 85 GPa. Published by the American Physical Society 2025

Alloys↗

Crystal plasticity finite element simulation of lattice rotation and x-ray diffraction during laser shock compression of tantalum

Here we present a crystal plasticity model tailored for high-pressure, high-strain-rate conditions that uses a multiscale treatment of dislocation-based slip kinetics. We use this model to analyze the pronounced plasticity-induced lattice rotations observed in shock-compressed polycrystalline tantalum via in situ x-ray diffraction. By making direct comparisons between experimentally measured and simulated texture evolution, we can explain how the details of the underlying slip kinetics control the degree of lattice rotation that ensues. Specifically, we show that only the highly nonlinear kinetics caused by dislocation nucleation can explain the magnitude of the rotation observed under shock compression. We demonstrate a good fit between our crystal plasticity model and x-ray diffraction data and exploit the data to quantify the dislocation nucleation rates that are otherwise poorly constrained by experiment in the dynamic compression regime.

36 MATERIALS SCIENCE↗

Diffraction Measurement of Reaction Products in Shock Compressed TATB on the NIF

The shock-induced reaction of high explosives to gaseous and solid reaction products is a rapid, complex process. Understanding solid reaction product structure and formation kinetics is essential in determining the high-pressure equation of state of these multicomponent systems. We use the National Ignition Facility (NIF) to shock compress ~500-µm thick pressed powder high-explosive TATB samples to 70-135 GPa and collect in situ structural data on detonation byproducts using the TARDIS X-ray diffraction diagnostic. Velocimetry is used to record the transmitted compression wave profile, which is well described by Cheetah hydrocode simulations coupled with a reactive flow model, providing strong evidence of reaction in the TATB sample. While an unambiguous determination of the product phases was not possible owing to the low signal-to-noise quality of the diffraction signal, X-ray diffraction data of the product phases formed within the first 50 ns of the reaction is most consistent with a mixture of amorphous products and crystalline hexagonal diamond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis and Thermal Oxidation Resistance of Boron-Rich Boron–Carbide Material

A boron-rich boron–carbide material (B4+δC) was synthesized by spark plasma sintering of a ball-milled mixture of high-purity boron powder and graphitic carbon at a pressure of 7 MPa and a temperature of 1930 °C. This high-pressure, high-temperature synthesized material was recovered and characterized by X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, Vickers hardness measurements, and thermal oxidation studies. The X-ray diffraction studies revealed a single-phase rhombohedral structure (space group R-3m) with lattice parameters in hexagonal representation as a = 5.609 ± 0.007 Å and c = 12.082 ± 0.02 Å. The experimental lattice parameters result in a value of δ = 0.55, or the composition of the synthesized compound as B4.55C. The high-resolution scans of boron binding energy reveal the existence of a B-C bond at 188.5 eV. Raman spectroscopy reveals the existence of a 386 cm−1 vibrational mode representative of C-B-B linear chain formation due to excess boron in the lattice. The measured Vickers microhardness at a load of 200 gf shows a high hardness value of 33.8 ± 2.3 GPa. Thermal gravimetric studies on B4.55C were conducted at a temperature of 1300 °C in a compressed dry air environment, and its behavior is compared to other high-temperature ceramic materials such as high-entropy transition metal boride. The high neutron absorption cross section, high melting point, high mechanical strength, and thermal oxidation resistance make this material ideal for applications in extreme environments.

36 MATERIALS SCIENCE↗

High-pressure study of the new Y-Ba-Cu-O superconducting compound system

Hydrostatic effects on the superconducting transition temperature of the Y-Ba-Cu-O compound system, resistively, up to 19 kbar are investigated. It is found that pressure has little effect on the superconducting state of Y-Ba-Cu-O, in marked contrast to the behavior of the K2NiF4-phase La-Ba-Cu-O and La-Sr-Cu-O systems. It is suggested that this effect may be due to chemical pressure associated with the smaller Y atoms already present in Y-Ba-Cu-O. X-ray powder-diffraction studies show that the high-temperature superconductivity in Y-Ba-Cu-O can only be attributed to one or more phases with structures different from the cubic perovskite or tetragonal layered ones.

Hor, P. H.↗

Bench-scale synthesis of nanoscale materials

A novel flow-through hydrothermal method used to synthesize nanoscale powders is introduced by Pacific Northwest Laboratory. The process, Rapid Thermal Decomposition of precursors in Solution (RTDS), uniquely combines high-pressure and high-temperature conditions to rapidly form nanoscale particles. The RTDS process was initially demonstrated on a laboratory scale and was subsequently scaled up to accommodate production rates attractive to industry. The process is able to produce a wide variety of metal oxides and oxyhydroxides. The powders are characterized by scanning and transmission electron microscopic methods, surface-area measurements, and x-ray diffraction. Typical crystallite sizes are less than 20 nanometers, with BET surface areas ranging from 100 to 400 sq m/g. A description of the RTDS process is presented along with powder characterization results. In addition, data on the sintering of nanoscale ZrO2 produced by RTDS are included.

Buehler, M. F.↗