Refractory Metals Research Articles

Atomistic simulation of chemical short-range order on the irradiation resistance of HfNbTaTiZr high entropy alloy

High entropy alloys (HEAs) have been considered as one of the potential structural material candidates for fourth-generation nuclear reactors and fusion reactors due to their excellent irradiation resistance. Current studies have shown that the chemical short-range order (CSRO) usually exists in HEAs, which has a significant effect on the mechanical properties and irradiation resistance of HEAs. Refractory high entropy alloys (RHEAs), as a new class of HEAs have better mechanical properties at high temperatures than face-centered cubic (FCC) HEAs, and therefore have better prospects of application in the nuclear field. In this study, CSRO and its effect on the irradiation resistance of HfNbTaTiZr are analyzed via molecular dynamics (MD) and Monte Carlo (MC). The primary cascade simulations, multi-cascade simulations and surface bombardment simulations are carried out to simulate the generation and accumulation of irradiation damage. The results of the primary cascade simulations and surface bombardment simulations of CSRO models show that the presence of CSRO induces cascade splitting into subcascades. The presence of subcascades reduces the thermal peak enhancement effect and thus lowers the recombination rate of Frenkel pairs (FPs) in the damage zone when FPs concentrations are low. However, the creation of subcascades increases the size of the damage zone caused by the cascade. Thus, when the concentrations of FPs are high, the larger area of damage zone allows more of the already existing FPs to be included, thus promoting their recombination, i.e., impedes their accumulation when concentrations are high. These subcascades lower the recombination of FPs at low FPs concentrations but inhibit their accumulation at high FPs concentrations. The presence of CSRO is also beneficial in inhibiting the growth of point defect clusters, which further improves the resistance of HfNbTaTiZr to dislocation generation. Furthermore, the presence of CSRO facilitates the irradiation-induced phase transition. But it is found that HfNbTaTiZr shows suppression of HCP cluster growth. And the tendency to break down large HCP clusters into smaller ones is demonstrated in the CSRO model. From our calculations we also find that the irradiation-induced HCP atoms have a higher potential energy relative to the matrix. The potential energy difference between those energetic HCP atoms and the matrix can lead to generating a great number of insurmountable barriers pervading the matrix and largely suppressing the long-term mobility of FPs, thus limiting their aggregation and growth into clusters.

Effect of diffusion barriers on steam oxidation properties and interface evolutions of Cr coating for zirconium alloy at 1200 °C

Currently, Cr-based coatings are considered the most promising protective coatings for zirconium alloy claddings under the ATF design concept. However, the primary factor affecting the oxidation resistance of Cr coatings is the interdiffusion of Cr and Zr. In this study, Cr coatings with three refractory metal interlayers of Nb, Mo, and Ta were deposited on zirconium alloy surfaces using closed-field unbalanced magnetron sputtering. The study investigated the effects of different interlayers on the microstructure, oxidation properties, and interface evolution process of Cr coatings under steam conditions at 1200 ℃, and compared them with Cr coatings without intermediate layers. The results indicate that the refractory metal interlayer influences the orientation and growth rate of Cr coating grains. The formation of a Laves phase mixed layer in the interlayer during oxidation effectively hinders the diffusion of O and Cr to the zirconium alloy matrix, enhancing its oxidation resistance. Furthermore, the diffusion rate and vacancy concentration of Mo and Ta elements to the Zr layer exceed that of diffusion to the Cr layer. During the cooling process, a precipitate phase forms in the Zr-4 matrix, while the Nb coating forms an infinite solid solution in the β-Zr.

Chemical and mechanistic modelling of green solvent extraction of metallic species with 4-acylpyrazolones

Solvent extraction chemistry of metals needs the use of suitable organic ligands like 4-acylpyrazolones to coordinate the studied cation, to make it soluble in an organic phase and then allow its phase transfer from the aqueous phase. The competitive solvent extraction test of almost 25 metal ions by one powerful ligand, i.e. 3-methyl-1-phenyl-4-(4-trifluoromethylbenzoyl)-pyrazol-5-one diluted in one ionic liquid ([C1Cnim+][Tf2N−]) has been conducted to get a snapshot of its efficacy. Effect of diluents on the liquid–liquid extraction of 4f-ions with a series of chelating ligands of 4-acylpyrazolones family (∼5) is presented comparing ionic liquids and typical organic diluents: 14 in number. In addition, the solvent extraction of 12 refractory metals with a series of chelating extractants is investigated in five diluents: four 4-acylpyrazolones with different radicals. The solvent extraction stoichiometry of MoO42− and Zr4+ is studied in detail using molecular and ionic diluent for comparative purposes through slope analysis method. Ethylene glycol is used to develop a non-aqueous process for Gd3+ switchable extraction, i.e. boost of two immiscible organic phases. Furthermore, EPR, NMR, IR and DTA-TG-MS spectroscopies have been used to study the extracted d- and f-species in the obtained organic extracts in ionic liquid solutions.

Enhanced thermomechanical fatigue resistance in W10Re alloys: Microstructural and surface engineering approaches

Thermomechanical fatigue of refractory metals is commonly observed in high-temperature environments like first walls and divertors for proposed fusion reactors or X-ray anodes for medical imaging. Typically, alloying with rhenium or optimized microstructures are employed to counteract or delay the detrimental effects of fatigue in tungsten. Additionally, a novel concept is the utilization of surface structures to compensate cyclic thermal stresses. This work aimed to investigate the combination of these approaches, by comparing two W10Re alloys with vastly different microstructures, as well as engineered surface conditions of varying scales. Samples were subjected to thermocyclic fatigue under pulsed electron beam exposure, mimicking the surface temperatures typically encountered in a rotating X-ray anode. Analysis of several in-situ data streams, post-mortem investigations by metallography, and finite element methods revealed the interplay between microstructure and surface modifications. The columnar microstructure exhibited higher resistance to severe surface damage compared to the globular one, linked to the deflection of cracks along grain boundaries and subsequent melting. Coarse structuring was found to partly relieve the surface stresses during thermal cycling, preventing most of the damage accumulation. A full damage relief and performance equivalence between columnar and globular microstructure was achieved by engineering fine-structured surfaces, which led to a ten-fold increase in fatigue resistance over the non-structured condition.

A 220 GHz GaN‐based monolithic integrated frequency doubler delivering over 0.25 W output power

AbstractA 220 GHz GaN‐based monolithic integrated frequency doubler with high continuous‐wave output power has been developed. The doubler achieves improved heat dissipation by establishing the terahertz (THz) monolithic integrated circuit topology with GaN Schottky barrier diodes integrated on a high thermal conductivity SiC substrate. It features six anodes to enhance the power‐handling capabilities. A refractory Schottky metal stack is adopted for better thermal stability. The doubler realizes satisfactory performance by introducing the suspended microstrip and an all‐in‐one output structure. For verification, a prototype of the proposed frequency doubler was fabricated and tested. Measured results show that the proposed doubler produces a continuous‐wave output power of 255 mW at 220 GHz with an efficiency of 14.6%, exhibiting excellent potential for powerful THz sources.

STUDIES THE CRUCIAL ROLE OF SELECTION OF EXTRACTANT TO EXTRACT NIOBIUM FROM SULFURYL FLUORIDE SOLUTION AND OPTIMIZATION OF EXTRACTION CONDITIONS

The increasing demand for rare refractory metals such as niobium in high-tech industries requires the development of efficient and sustainable methods to extract them from secondary sources, including industrial by-products. This study studied niobium extraction from a fluoride-sulfuric acid solution obtained by leaching a niobium-containing intermediate product. A comprehensive assessment of various organic extractants, including methyl isobutyl ketone, tributyl phosphate, trioctylamine, and Cyanex 923, was performed, focusing on the recoverability of niobium from this solution. Experimental results show that Cyanex 923 is significantly superior to other extractants in efficacy. The extraction of niobium at different concentrations of this extractant in toluene and the ratios of organic and aqueous phases were studied. It is established that an increase in the contact time of the phases does not contribute to additional niobium recovery. Studies show that applying concentrated Cyanex 923 in toluene ensures complete recovery of niobium into the organic phase. The three-stage counter-current extraction shows a slightly higher niobium recovery efficiency than the single-stage process.

An investigation of Ti addition to optimize the tribological properties of TiCrNbTaW refractory high-entropy alloy

Many refractory high-entropy alloys (RHEAs) with high melting points suffer from severe wear-fracture failures due to compositional segregation, which is a key factor limiting their widespread application as structural parts. In this work, two novel TixCrNbTaW (x = 1 and 1.5) RHEAs were prepared using composition modulation and liquid phase assisted sintering strategies. The results showed that the further addition of Ti enhanced the strength, toughness and microstructural homogeneity of the RHEAs, which effectively suppressed the wear-fracture behavior. In addition, the dense oxidized amorphous layer formed in-situ has higher hardness than the matrix, which can provide additional load-bearing capacity. The synergistic effect of the above factors promotes the wear rate of Ti1.5 alloy to be as low as 2.9 × 10−5 mm3/(N·m). The present work provides some insights into the design of high anti-wear RHEAs.

The hierarchical energy landscape of edge dislocation glide in refractory high-entropy alloys

Refractory high-entropy alloys (RHEAs) are considered as potential candidates for high-temperature applications, with the glide resistance of edge dislocations being a crucial factor in determining the high-temperature strength. However, the solid-solution strengthening mechanism of edge dislocations in RHEAs is not fully understood. The existing Labusch-type models mainly focus on the long-range interaction of solute atoms with the dislocation stress field, while there is little attention paid to the short-range interaction in the dislocation core region. Here, we conduct carefully designed atomic simulations to decouple the long-range and short-range interactions in a typical RHEA, NbMoTaW. Furthermore, the total change in solute-dislocation interaction energy is decomposed, and a hierarchical energy landscape is revealed, demonstrating that the short-range interaction at the core region gains more importance in the solid-solution strengthening of edge dislocations in NbMoTaW. Then, we determine the Larkin length, which signifies the transition from size-dependent to size-independent dislocation behavior. The activation barrier extracted from the simulation with the dislocation length above the Larkin length is incorporated into the crystal plasticity model, and the high-temperature yield strength is well predicted by the strengthening from edge dislocations. Our work provides deep insight into the solid-solution strengthening mechanism in random solution solids, elucidating the importance of the local atomic configuration around the dislocation core.

Electrochemical corrosion behavior of Nbx(MoTaW)(1−x) (x = 0.25, 0.4, 0.55, and 0.7) refractory multicomponent alloys

The current study investigates the effect of increasing Nb concentration in Nbx(MoTaW)(1−x) refractory multicomponent alloys (RMCAs) on corrosion behavior in 3.5 wt% NaCl. The as-processed alloys showed a single-phase BCC crystal structure. With increasing Nb content, the open circuit potential values increase towards the positive direction, which indicates the formation of a stable oxide layer. In addition, polarization curves of RMCAs showed the passive layer formation, while pitting was not observed upto 2 V. The corrosion rate decreased as the Nb content increased, which may be attributed to the presence of coarse grains in high Nb-content RMCAs. Finally, the corrosion resistance of Nb0.7(MoTaW)0.3 is high compared to other alloys. Following the corrosion test, the presence of pits was not observed, indicating uniform corrosion, which is also corroborated by polarization data. X-ray photoelectron spectroscopy detected the presence of Nb2O5, Ta2O5, WO3 and MoO3 in the oxide layer, showing the active participation of all alloying elements in the corrosion process.

Research progress in modification of MoSi2 coatings on surface of refractory metals and their alloys: a review

Research progress in modification of MoSi2 coatings on surface of refractory metals and their alloys: a review

Hot hydrogen testing of Mo30W matrix surrogate cermets

High temperature hydrogen exposure is one of the most challenging material issues for nuclear thermal propulsion (NTP) fuel development. Under legacy NTP programs, ceramic-metallic (cermet) fuel forms with a refractory metal matrix and dispersed uranium dioxide (UO2) fuel particles were developed and showed promising performance following hot hydrogen testing. However, since the conclusion of those programs, established fabrication techniques, material feedstocks, and the ability to use highly enriched have been reduced or lost all together. In this study, a cermet consisting of a solid solution alloy of molybdenum with 30 wt percent tungsten (Mo30W) was fabricated using spark plasma sintering. Fabrication process parameters were selected to optimize the cermet microstructure using lessons learned from historic NTP programs. Yttria stabilized zirconia particles (50 to 70 % volumetric loading) were used as a fuel particle surrogate. To evaluate whether as-fabricated microstructures exhibited similar resilience as legacy cermet fuels to a hot hydrogen environment, samples were exposed to hot flowing hydrogen from 1920 to 2500 °C (∼2290 to 2770 K). The cermets performed well with minimal mass loss, minor to no cracking, and good retention of internal surrogate particles. Based on these findings, recommendations for future studies with Mo30W-UO2 cermets as an NTP fuel form are provided.

Rotational deformation twins in a HfNbTaTiZr refractory high entropy alloy

Results of the analysis of deformation twins formed in a HfNbTaTiZr refractory high entropy alloy during compression deformation at 20 °C – 600 °C are reported. All studied twins were formed by rotation of the matrix crystal lattice around a 〈110〉 pole and have the common reciprocal twinning plane K2 = {001} and reciprocal twinning direction η2 = <11¯0>. At the same time, the twinning plane K1 and direction η1 depend on the degree of rotation of K2 and η2 around the common 〈110〉 pole. The following rotational twinning modes have been identified in HfNbTaTiZr: {11¯4}<22¯1¯> (38.94° rotation), {11¯5}<55¯2¯> (31.58°), {11¯6}<33¯1¯> (26.54°), {11¯7}<77¯2¯> (22.84°), and {11¯8}<44¯1¯> (20.04°). A rotational mechanism of twinning, with the rotation axis 〈011〉 or 〈001〉, is proposed as an alternative to the commonly accepted shear mechanism.

Surface morphology evolution, microstructural response and mechanical property variation of Au-ion irradiated CrNbZrMoV, TiCrZrMoV, TiNbCrMoV, TiNbZrCrV and TiNbZrMoCr high-entropy alloy coatings

In this work, the CrNbZrMoV, TiCrZrMoV, TiNbCrMoV, TiNbZrCrV and TiNbZrMoCr refractory high-entropy alloy (RHEA) coatings (1.67∼2.77 μm of thickness) were prepared by magnetron sputtering. Then, 6 MeV Au-ion irradiations with 2.5 × 1015 to 1.0 × 1016 ions/cm2 fluences were performed on these coatings at 473 K, and the surface morphology, microstructure and mechanical property were investigated. The peak damage of the CrNbZrMoV, TiCrZrMoV, TiNbCrMoV, TiNbZrCrV and TiNbZrMoCr coatings under 1.0 × 1016 ions/cm2 fluence are 48, 48, 44, 48 and 48 dpa, respectively. The peak Au concentration of the CrNbZrMoV, TiCrZrMoV, TiNbCrMoV, TiNbZrCrV and TiNbZrMoCr coatings under 1.0 × 1016 ions/cm2 fluence are 4.27 × 103, 4.12 × 103, 4.13 × 103, 4.16 × 103 and 4.37 × 103 appm, respectively. The surface morphology of the CrNbZrMoV, TiCrZrMoV, TiNbZrCrV and TiNbZrMoCr coatings were smoothed obviously. For BCC TiNbCrMoV coating, irradiation caused the growth of the nanocrystalline. For amorphous coatings, the crystallization occurred in the CrNbZrMoV, TiCrZrMoV and TiNbZrMoCr coatings after 2.5 × 1015 fluence irradiation (≥12 dpa), while the TiNbZrCrV coating remain mainly amorphous structure after all irradiation. It was found that irradiation induced continuous crystallization occurred not only at the surface but also in the peak damage zone of the coating, and then grew inside the irradiated region. Apparent irradiation hardening was observed in all the coatings except the TiNbZrCrV coating. The structural stability of these coatings under the current irradiation condition was discussed. Preliminary study shows that the great irradiation tolerance of amorphous TiNbZrCrV coating may be related to the lowest electronegativity difference (Δχ = 0.121) and large atomic size difference (δ = 9.042 %) that stabilize the structure and inhibit atomic diffusion, respectively. These findings provide the guidance for the development of high irradiation tolerance materials for future nuclear energy applications with great structural stability.

Superior high-temperature strength of a carbide-reinforced high-entropy alloy with ultrafine eutectoid structure

Refractory alloys with high-temperature softening resistance are crucial for extreme high-temperature components in aerospace and weapon equipment. Traditional alloys and single-phase refractory high-entropy alloys suffer from unstable microstructures and loss of strength at high temperatures. Here we report a strategy to obtain a superior strong high-entropy alloy by introducing carbides to form micro-nano scale eutectic and eutectoid structures. These metal-carbide interfaces remain stable under high-temperature deformation and exhibit strong dislocation blocking effects. The ultrafine eutectoid structure provides a primary strengthening effect due to its numerous enhanced phase interfaces. The resulting alloy achieves a high temperature yield strength of 1.17 GPa at 1473 K and 0.92 GPa at 1673 K. This work provides valuable insights for optimizing the high-temperature performance and microstructure design of high-temperature composites to further extend their potential applications in high-temperature areas.

CALPHAD-aided design for superior mechanical behavior in Ti40Zr20Hf40-xCrx eutectic refractory high-entropy alloys

TiZrHf-based refractory high entropy alloys (RHEAs) are becoming the focus in advanced metal materials owing to the excellent mechanical properties under the condition of medium and high temperatures. Nevertheless, the strength of TiZrHf-based RHEAs at medium temperatures has hindered the further application. This work proposed a novel approach to improve the mechanical properties of TiZrHf-based RHEAs. An innovative series of Ti40Zr20Hf40-xCrx (x = 19, 24 and 29, denoted by HfCr19, HfCr24 and HfCr29, respectively) eutectic refractory high entropy alloys (ERHEAs) were designed and prepared. The designed Ti40Zr20Hf40-xCrx alloys can form lamellar eutectic structure including BCC/HCP phase and Laves precipitating phase in solidification with the decrease of Hf/Cr ratio. The microstructure of HfCr19 and HfCr24 alloys was composed of BCC, HCP and Laves phase, while the HfCr29 alloy consisted of BCC and Laves phase. The formation of HCP phase in the Ti40Zr20Hf40-xCrx alloy were attributed to the lattice of Ti0.5Zr0.5 phase reconstruction during the rapid cooling, which promoted the formation of isomers in the alloy. Hence, the part of BCC phase was transformed into HCP phase in the HfCr19 and HfCr24 alloys, and the lamellar eutectic structure consisted of BCC/HCP phase and Laves phase. In addition, compared with the near-eutectic HfCr19 and HfCr29 alloys, the HfCr24 alloy with a complete lamellar eutectic structure has higher compressive strength at room temperature, which can reach 1648.7 MPa. In addition, the compressive strength (1261.7 MPa) can still be achieved at 600 °C. This work successfully prepared a high-strength TiZrHf-based ERHEA, and the compression mechanical properties at room temperature and middle-high temperature were studied and analyzed.

Effect of annealing temperature on the microstructure and mechanical properties of Al0.2CrNbTiV lightweight refractory high-entropy alloy

The DSC analysis and heat treatment of the newly proposed Al0.2CrNbTiV lightweight refractory high-entropy alloy prepared by vacuum arc melting was investigated, and the evolutions of the microstructure and mechanical properties of the alloy after homogenization annealing at 650 °C, 850 °C and 1050 °C for 12 h were analyzed. The results show that the Al0.2CrNbTiV high-entropy alloy could maintain stable BCC solid solution structure from room temperature to 800 °C. The alloy annealed at 650 °C exhibited simple BCC structure with coarse equiaxed grains; after annealing at 850 °C, fine acicular and irregular block-like C14 Laves phases were uniformly precipitated in the grain and grain boundaries, meanwhile, the C14 Laves phase get coarser with the annealing temperature increased to 1050 °C. With the increase of annealing temperature, the microhardness of the Al0.2CrNbTiV alloy increased first and then decreased, reaching the maximum value of 692 HV after annealing at 850 °C. Due to the high dislocation density and the formation of kink bands, the alloy annealed at 650 °C showed a good combination of plastic and strength, with the work hardening ability strengthened simultaneously, the compressive yield strength could be up to 1454 MPa, with strain >50 %. Due to the precipitation of the hard and brittle C14 Laves phase, the load-bearing capacity of the alloy was reduced after annealing at 850 °C and 1050 °C. However, the wear resistance of the alloy also improved with the presence of the hard phase. The friction coefficient of Al0.2CrNbTiV alloy annealed at 650 °C is 0.67, with the abrasive wear acting as the main wear mechanism, and the alloy after annealing at 850 °C shew the best wear resistance, with the friction coefficient of 0.63, and delamination wear mechanism.

Synthesis of complex concentrated silicide coatings via reactive melt-infiltration: Exploring interfacial phenomena between Si-B melt and MoNbTaW high-entropy alloy

High-entropy silicide (HES) coatings are a promising solution to the problem of poor oxidation resistance of metallic refractory alloys. However, their practical development is still in the early stages. For the first time, this study evaluates the feasibility of synthesizing complex concentrated silicide coatings using a reactive melt infiltration approach. For this purpose, a sessile drop experiment was carried out in which a binary eutectic silicon‑boron alloy (Si8B at.%) was subjected to contact heating with the MoNbTaW refractory high entropy alloy (RHEA) substrate at temperatures up to 1450 °C. After the high-temperature test, the solidified couple was characterized by X-ray diffraction, scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy, electron backscatter diffraction systems, and microhardness techniques. The coating had an average thickness of 75 μm and was composed of different layers, including a primary MSi2 layer, a transition MSi2 + M5Si3 silicide layer, and M5Si3 silicides (M = metal). Additionally, borosilicides and boride particles were dispersed throughout the layers. However, future research should prioritize refining process parameters to eliminate porosity and improve the integrity of the coating layer.

Effect of Al and Nb on microstructure and mechanical properties of novel Al-Mo-Nb-Ti-V-Zr lightweight refractory high-entropy alloys

Refractory high-entropy alloys (RHEAs) are a new family of metallic alloys which have been intensively studied in the last decade. Indeed, RHEAs likely have the potential of overcoming the high-temperature performances of conventional Ni-based superalloys. Nevertheless, up to date, their high density and poor room temperature ductility still compromise their industrial uptake. In this study, novel RHEAs compositions are investigated to provide insights on the development of strong and ductile lightweight RHEAs. Specifically, AlxMoNbyTiVZr alloys (with x = 0, 0.25, 0.5, 0.75, 1 and y = 1, 2) have been produced and characterized. These alloys have been designed to probe the possibility of reducing the density of RHEAs by increasing the Al content. At the same time, the content of Nb was also increased in the attempt to counterbalance the embrittlement effect related to Al addition.

Impact Mill

An impact mill has been developed to produce powders from shavings of refractory metals using impact grinding method for reuse in electrometallurgy in devices with screw feed, for example, in 3D printers. The proposed device provides high uniformity of grinding with a minimum content of dust fraction and impurity content at low technical and economic costs. The result is achieved by using a Laval nozzle, which operates in the supersonic jet formation mode. In the area of the first Mach disk there are rod fenders arranged in a cascade, and the impact plate is located in the turbulence zone and is equipped with winglets with holes for separating crushed metal.

Exceptional hardness in multiprincipal element alloys via hierarchical oxygen heterogeneities

Refractory multiprincipal element alloys (RMPEAs) are potential successors to incumbent high-temperature structural alloys, although efforts to improve oxidation resistance with large additions of passivating elements have led to embrittlement. RMPEAs containing group IV and V elements have a balance of properties including moderate ductility, low density, and the necessary formability. We find that oxidation of group IV-V RMPEAs induces hierarchical heterogeneities, ranging from nanoscale interstitial complexes to tertiary phases. This microstructural hierarchy considerably enhances hardness without indentation cracking, with values ranging between 12.1 and 22.6 GPa from the oxide-adjacent metal to the surface oxides, a 3.7 to 6.8× increase over the interstitial-free alloy. Our fundamental understanding of the oxygen influence on phase formation informs future alloy design to enhance oxidation resistance and obtain exceptional hardness while preserving plasticity.