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The interplay between configurational entropy and the enthalpy of ordered structures governs phase stability in compositionally complex alloys. In the refractory alloy Re0.6(NbTiZrHf)0.4, this balance is particularly delicate: pressure stabilizes a disordered body-centred-cubic (bcc) solid solution over the ambient hexagonal Laves phase via a martensitic route. Using in situ laser heating with synchrotron X-ray diffraction in a diamond-anvil cell, we demonstrate that the metastable bcc phase can be controllably transformed into a large-scale 2×2×2 B2-type superstructure with primitive-cubic symmetry (Pm3 ̅m). This long-period ordered phase is crystallographically distinct from conventional B2 ordering in multicomponent alloys, establishing a pathway to achieve chemical ordering from pressure-stabilized solid solutions. More broadly, these findings demonstrate that combining compression with subsequent thermal activation can unlock recoverable three-dimensional superstructures, offering new opportunities to tailor strength, transport properties, and stability in compositionally complex alloys.more » « less
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At ambient conditions, the high-entropy alloy superconductor Re0.6(NbTiZrHf)0.4 exhibits exceptional mechanical properties among high-entropy alloys, with its hexagonal phase achieving nanoindentation hardness of 18.5 GPa. We report on a unique pressure-induced structural transformation from a hexagonal phase to a body-centered cubic (BCC) phase, revealed by synchrotron x-ray diffraction measurements up to 70 GPa. This first-order transition, accompanied by a 6.1% volume collapse, occurs at 44 GPa and results in a BCC structure with random site occupancy by the five constituent elements, which is remarkably retained upon decompression to ambient conditions. The transformation proceeds via a martensiticlike, diffusionless mechanism without elemental segregation, enabled by pressure-induced electronic redistribution and atomic-scale disorder. These findings demonstrate a rare case of metastable phase retention in a chemically complex alloy and offer new insights into structure-stability relationships under pressure.more » « less
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High-entropy alloys (HEAs) are a class of multi-element materials that exhibit unique structural and functional properties. This study reports on the synthesis and characterization of a superconducting HEA, (NbTa)0.55(HfTiZr)0.45 fabricated using the vacuum arc melting technique. Scanning electron microscopy and energy-dispersive x-ray spectroscopy were employed to analyze the material's morphology and composition. X-ray diffraction analysis revealed a single-phase body-centered cubic (BCC) structure with a measured nanoindentation hardness of 6.4 GPa and Young's modulus of 132 GPa. This HEA superconductor was investigated by x-ray diffraction at Beamline 13BM-C, Advanced Photon Source, and the BCC phase was stable to the highest pressure of 50 GPa. Superconductivity was characterized by four-probe resistivity measurements in a quantum design physical property measurement system, yielding a superconducting transition temperature (Tc) of 7.2 K at ambient pressure and reaching a maximum of 10.1 K at the highest applied pressure of 23.6 GPa. The combination of high structural stability enhanced superconducting performance under pressure and superior mechanical properties highlights (NbTa)0.55(HfTiZr)0.45 as a promising superconductor under extreme environments.more » « less
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A microwave plasma chemical vapor deposition system was used to synthesize cubic boron nitride (cBN) coatings on diamond seeded silicon substrates using direct current (DC) bias. Effects of the argon (Ar) flow rate and bias voltage on the growth of the cBN coatings were investigated. Hydrogen (H2), argon (Ar), a mixture of diborane in H2 (95% H2, 5% B2H6), and N2 were used in the feed gas. A DC bias system was used for external biasing of the sample, which facilitates the goal of achieving sp3 bonded cBN. Fourier Transform Infrared Spectroscopy (FTIR) and X-ray Photoelectron Spectroscopy (XPS) revealed the existence of sp3-bonded BN in the produced samples. With increasing Ar flow, the cBN content in the coating increases and reaches a maximum at the maximum Ar flow of 400 SCCM used in this study. High-resolution XPS scans for B1s and N1s indicate that the deposited coating contains more than 70% cBN. This study demonstrates that energetic argon ions generated in a microwave-induced plasma significantly increase cBN content in the coating.more » « less
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Microwave-induced plasma was used to anneal precursor powders containing five metal oxides with carbon and boron carbide as reducing agents, resulting in high entropy boride ceramics. Measurements of hardness, phase structure, and oxidation resistance were investigated. Plasma annealing for 45 min in the range of 1500–2000 °C led to the formation of predominantly single-phase (Hf, Zr, Ti, Ta, Mo)B2 or (Hf, Zr, Nb, Ta, Mo)B2 hexagonal structures characteristic of high entropy borides. Oxidation resistance for these borides was improved by as much as a factor of ten when compared to conventional commercial diborides. Vickers and nanoindentation hardness measurements show the indentation size effect and were found to be as much as 50% higher than that reported for the same high entropy boride configuration made by other methods, with average values reaching up to 38 GPa (for the highest Vickers load of 200 gf). Density functional theory calculations with a partial occupation method showed that (Hf, Zr, Ti, Ta, Mo)B2 has a higher hardness but a lower entropy forming ability compared to (Hf, Zr, Nb, Ta, Mo)B2, which agrees with the experiments. Overall, these results indicate the strong potential of using microwave-induced plasma as a novel approach for synthesizing high entropy borides.more » « less
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Boron nitride (BN) is primarily a synthetically produced advanced ceramic material. It is isoelectronic to carbon and, like carbon, can exist as several polymorphic modifications. Microwave plasma chemical vapor deposition (MPCVD) of metastable wurtzite boron nitride is reported for the first time and found to be facilitated by the application of direct current (DC) bias to the substrate. The applied negative DC bias was found to yield a higher content of sp3 bonded BN in both cubic and metastable wurtzite structural forms. This is confirmed by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). Nano-indentation measurements reveal an average coating hardness of 25 GPa with some measurements as high as 31 GPa, consistent with a substantial fraction of sp3 bonding mixed with the hexagonal sp2 bonded BN phase.more » « less
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null (Ed.)A novel approach is demonstrated for the synthesis of the high entropy transition metal boride (Ta, Mo, Hf, Zr, Ti)B2 using a single heating step enabled by microwave-induced plasma. The argon-rich plasma allows rapid boro-carbothermal reduction of a consolidated powder mixture containing the five metal oxides, blended with graphite and boron carbide (B4C) as reducing agents. For plasma exposure as low as 1800 °C for 1 h, a single-phase hexagonal AlB2-type structure forms, with an average particle size of 165 nm and with uniform distribution of the five metal cations in the microstructure. In contrast to primarily convection-based (e.g., vacuum furnace) methods that typically require a thermal reduction step followed by conversion to the single high-entropy phase at elevated temperature, the microwave approach enables rapid heating rates and reduced processing time in a single heating step. The high-entropy phase purity improves significantly with the increasing of the ball milling time of the oxide precursors from two to eight hours. However, further improvement in phase purity was not observed as a result of increasing the microwave processing temperature from 1800 to 2000 °C (for fixed ball milling time). The benefits of microwave plasma heating, in terms of allowing the combination of boro-carbothermal reduction and high entropy single-phase formation in a single heating step, are expected to accelerate progress in the field of high entropy ceramic materials.more » « less
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