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Phase separation into an A2+B2 two-phase microstructure in refractory compositionally complex alloys (RCCA) has been speculated as being spinodal in nature with continuous chemical distribution during the separation. However, these reactions might instead occur as precipitation by nucleation and growth. In order to unequivocally elucidate the distinct nature of phase separation sequence in RCCA from the system Ta-Mo-Ti-Cr-Al, atom probe tomography and electron microscopy techniques were utilized on samples that were annealed over multiple orders of magnitude in time. The composition 82(TaMoTi)-8Cr-10Al (at.%) was chosen, as it exhibits a two-phase microstructure, with a desired A2 matrix and embedded B2 phase. Quenching the samples from 1200°C resulted in a microstructure consisting of ordered clusters (2 nm) of distinct chemical composition. Subsequent annealing at 800°C to 1000°C leads to an increase in the volume fraction of the precipitating phase, which saturates after 10 h. Further annealing leads to the ripening of the microstructure; however, the absolute size of the precipitates stays <100 nm even after 1000 h. For the investigated conditions, the interface between matrix and precipitate can be considered sharp within the resolution of the applied techniques and no significant change in the transition of chemical composition across the interface is observed. Therefore, the phase separation mechanism is confirmed to be phase nucleation and growth in contrast to the possible spinodal decomposition, as hypothesized for other RCCA systems. The impact of precipitation and coarsening on the hardness of the alloy is discussed.

In this work, the RM(Nb)IC alloy Nb–30Ti–10Si–5Cr–5Sn–3Fe–2Al–2Hf (NV2) was studied in the as-cast and heat-treated conditions; its isothermal oxidation at 700, 800 and 900 °C and its room temperature hardness and specific strength were compared with other Sn-containing RM(Nb)ICs—in particular, the alloy Nb–24Ti–18Si–5Cr–5Fe–5Sn (NV5)—and with RCCAs and RHEAs. The addition of Fe (a) stabilised Nbss; A15–Nb3X (X = Al, Si and Sn) and Nb3Si; metastable Nb3Si-m’ and Nb5Si3 silicides; (b) supported the formation of eutectic Nbss + Nb5Si3; (c) suppressed pest oxidation at all three temperatures and (d) stabilised a Cr- and Fe-rich phase instead of a C14–Nb(Cr,Fe)2 Laves phase. Complex concentrated (or compositionally complex) and/or high entropy phases co-existed with “conventional” phases in all conditions and after oxidation at 800 °C. In NV2, the macrosegregation of Si decreased but liquation occurred at T >1200 °C. A solid solution free of Si and rich in Cr and Ti was stable after the heat treatments. The relationships between solutes in the various phases, between solutes and alloy parameters and between alloy hardness or specific strength and the alloy parameters were established (parameters δ, Δχ and VEC). The oxidation of NV2 at 700 °C was better than the other Sn-containing RM(Nb)ICs with/without Fe addition, even better than RM(Nb)IC alloys with lower vol.% Nbss. At 800 °C, the mass change of NV2 was slightly higher than that of NV5, and at 900 °C, both alloys showed scale spallation. At 800 °C, both alloys formed a more or less continuous layer of A15–Nb3X below the oxide scale, but in NV5, this compound was Sn-rich and severely oxidised. At 800 °C, in the diffusion zone (DZ) and the bulk of NV2, Nbss was more severely contaminated with oxygen than Nb5Si3, and the contamination of A15–Nb3X was in-between these phases. The contamination of all three phases was more severe in the DZ. The contamination of all three phases in the bulk of NV5 was more severe compared with NV2. The specific strength of NV2 was comparable with that of RCCAs and RHEAs, and its oxidation at all three temperatures was significantly better than RHEAs and RCCAs.

Many bcc refractory alloys show excellent high-temperature mechanical properties, while their fabricability can be limited by brittleness near room temperature. For the purpose of predicting ductile alloys, a number of ductility metrics based on atomic structures and crystal properties, ranging from mechanistic to empirical, have been proposed. In this work, we propose an “average bond stiffness” as a new ductility metric that is also convenient to obtain from first-principles calculations, in addition to using the average magnitude of static displacements of atoms. The usefulness of average bond stiffness is validated by comparing first-principles calculation results to experimental data on the “rhenium effect” in Mo/W-base and V/Nb/Ta-base binary alloys. The average bond stiffness also correlates well with the room-temperature ductility of refractory high-entropy alloys, with a better performance than some ductility metrics previously reported. While in reality the ductility of an alloy can be influenced by many factors, from processing and microstructure, the average magnitude of static displacements and the average bond stiffness are atomistic-level features useful for design of alloy composition towards a desired level of ductility.

W–Cu refractory alloys are widely used in aerospace, aviation, electronics, power, and other fields. However, because of its large melting point difference between alloy elements, the conventional powder metallurgy method required a long time of high temperature sintering is very likely to cause low density and abnormal grain size growth. Therefore, 90W-10Cu refractory alloys were successfully prepared by hot oscillatory pressing (HOP) under different sintering time in this work. Then the influence of sintering time on the microstructure, grain size, density, Vickers hardness, room-tensile property, and electrical conductivity of the W–Cu refractory alloy was systematically invested. The results showed that during the short sintering time (30–90 min), the density, Vickers hardness, tensile strength, and electrical conductivity of the W–Cu refractory alloy increased significantly to 98.7%, 163.29 HV 30 , 507.3 MPa, and 14.2% International Annealed Copper Standard with the sintering time increasing, respectively, while its grain size showed no obvious change. When the sintering time further increased to 120 min, the density was basically consistent with the sintering time of 90 min. Nevertheless, the prolonged high temperature sintering resulted in the grain growth of the samples, which caused the deterioration of the Vickers hardness, room-tensile strength, and conductivity properties of the W–Cu refractory alloy. At the same sintering time, the density, Vickers hardness, and electrical conductivity of the HOP sintered W–Cu refractory alloy were significantly higher than those of the HP sintered sample. It was indicated that high density, fine-grain, and excellent properties W–Cu refractory alloys could be prepared by hot oscillatory pressing under appropriate sintering time.

To develop strong refractory high-entropy alloys for use at elevated temperatures as well as to overcome grain-boundary brittleness, an equimolar HfMoNbTaTiZr alloy was prepared, and a minor amount of boron (0.1 at.%) was added into the alloy. The microstructures of the alloys were characterized, and their macro-to-microscale mechanical properties were measured. The microstructural observations indicated that the matrices of both the alloys were composed of a body-centered cubic solid-solution structure, and the added boron induced the precipitation of hexagonal close-packed borides (most likely the (Hf, Zr)B2) at the grain boundaries. The modulus and hardness of differently oriented grains were about equivalent, suggesting a diminished anisotropy, and many small slips occurred on multiple {110} planes. While the hardness of the matrix was not increased, the intergranular precipitation of the borides markedly raised the hardness of the grain boundaries. Owing to the enhanced grain boundary cohesion, the work hardenability and ductility were effectively improved with the addition of boron.

In the past decade, multi-principal element high-entropy alloys (referred to as high-entropy alloys, HEAs) are an emerging alloy material, which has been developed rapidly and has become a research hotspot in the field of metal materials. It breaks the alloy design concept of one or two principal elements in traditional alloys. It is composed of five or more principal elements, and the atomic percentage (at.%) of each element is greater than 5% but not more than 35%. The high-entropy effect caused by the increase of alloy principal elements makes the crystals easy form body-centered cubic or face-centered cubic structures, and may be accompanied by intergranular compounds and nanocrystals, to achieve solid solution strengthening, precipitation strengthening, and dispersion strengthening. The optimized design of alloy composition can make HEAs exhibit much better than traditional alloys such as high-strength steel, stainless steel, copper-nickel alloy, and nickel-based superalloy in terms of high strength, high hardness, high-temperature oxidation resistance, and corrosion resistance. At present, refractory high-entropy alloys (RHEAs) containing high-melting refractory metal elements have excellent room temperature and high-temperature properties, and their potential high-temperature application value has attracted widespread attention in the high-temperature field. This article reviews the research status and preparation methods of RHEAs and analyzes the microstructure in each system and then summarizes the various properties of RHEAs, including high strength, wear resistance, high-temperature oxidation resistance, corrosion resistance, etc., and the common property tuning methods of RHEAs are explained, and the existing main strengthening and toughening mechanisms of RHEAs are revealed. This knowledge will help the on-demand design of RHEAs, which is a crucial trend in future development. Finally, the development and application prospects of RHEAs are prospected to guide future research.

Owing to superior comprehensive performance than conventional superalloys at high temperature, refractory high entropy alloy (RHEA) is becoming a promising candidate for the next generation high-temperature material. Herein, contemporary aspects of corresponding development of RHEAs are reviewed to discuss various factors affecting the organization structure and service performance. It mainly covers alloying system and strengthening mechanism, the preparation method, plastic deformation and the related mechanism, as well as microstructure control by heat treatment. Firstly, the alloy systems and strengthening mechanism are introduced. This is followed by different preparation methods and the comparison of strengths and shortcomings based on different RHEAs. Then, hot deformation behavior and plastic deformation under different loadings are analyzed. Based on this, the influence of heat treatment on microstructures prior to and after the deformation is further summarized. Finally, some important research areas to be carried out in future are pointed out. This review will give a deep understanding of the effects of different factors on the service performance and provide scientific guide in designing RHEAs with improved performance.

During the past decade, refractory high-entropy alloys (RHEA) have attracted great attention of scientists, engineers and scholars due to their excellent mechanical and functional properties. The W-containing RHEAs are favored by researchers because of their great application potential in aerospace, marine and nuclear equipment and other high-temperature, corrosive and irradiated fields. In this review, more than 150 W-containing RHEAs are summarized and compared. The preparation techniques, microstructure and mechanical properties of the W-containing RHEAs are systematically outlined. In addition, the functional properties of W-containing RHEAs, such as oxidation, corrosion, irradiation and wear resistance have been elaborated and analyzed. Finally, the key issues faced by the development of W-containing RHEAs in terms of design and fabrication techniques, strengthening and deformation mechanisms, and potential functional applications are proposed and discussed. Future directions for the investigation and application of W-containing RHEAs are also suggested. The present work provides useful guidance for the development, processing and application of W-containing RHEAs and the RHEA components.

Refractory high entropy alloys have broad application prospects due to their excellent comprehensive properties in high temperature environments, and they have been widely implemented in many complex working conditions. According to the latest research reports, the preparation technology of bulk and coating refractory high entropy alloys are summarized, and the advantages and disadvantages of each preparation technology are analyzed. In addition, the properties of refractory high entropy alloys, such as mechanical properties, wear resistance, corrosion resistance, oxidation resistance, and radiation resistance are reviewed. The existing scientific problems of refractory high entropy alloys, at present, are put forward, which provide reference for the development and application of refractory high entropy alloys in the future, especially for plasma-facing materials in nuclear fusion reactors.

Over 150 refractory high-entropy alloys (RHEAs) have been proposed in the last decade. Early alloys such as MoNbTaW and MoNbTaVW still show an unparalleled yield strength of approximately 400 MPa at 1600°C. However, RHEAs with even elevated high-temperature strength are necessary in aerospace vehicles and nuclear reactors to cope with advanced technology in the future. Here, solid-solution strengthening calculation and melting point prediction are combined to design single-phase RHEA for attaining ultrahigh strength at 1600°C. The results show that Hf 0.5 MoNbTaW and HfMoNbTaW alloys after fully homogeneous treatment at 2100°C for 2 h reveal a homogenous body-centered cubic phase. HfMoNbTaW alloy exhibits a yield strength of 571 MPa at 1600°C, much higher than that of MoNbTaVW (477 MPa). It is found that a plateau of strength occurs from 800°C to 1200°C, which is important for raising the strength level of RHEAs at high temperatures. This strengthening mechanism is explained with the change of deformation mode from screw to edge dislocations, which contributes an edge-dislocation-induced strength. A similar alloy design strategy could be applied to develop more RHEAs with an ultrahigh strength level.