Refractory High-entropy Alloys Research Articles

Microstructural and Mechanical Investigations in the Solution Annealing Heat Treatment of AlMo0.5NbTa0.5TiZr Refractory High-Entropy Alloy

Microstructural and Mechanical Investigations in the Solution Annealing Heat Treatment of AlMo0.5NbTa0.5TiZr Refractory High-Entropy Alloy

Microstructural study on in-situ high-entropy (NbMoTaWV)C reinforced nanocrystalline NbMoTaWVC refractory high entropy alloys prepared by mechanically alloying

Microstructural study on in-situ high-entropy (NbMoTaWV)C reinforced nanocrystalline NbMoTaWVC refractory high entropy alloys prepared by mechanically alloying

Diffusion coefficients and atomic mobilities in the BCC phase of the Al–Nb–V system

Diffusion coefficients in the BCC phase of the Al–Nb–V ternary system are studied for the first time, including an assessment of the atomic mobilities. Ternary interdiffusion coefficients are obtained from the intersecting diffusion paths of several sets of diffusion couples that are annealed at both 1100 °C and 1200 °C. Existing experimental data from the pertinent binary systems are also employed for the assessments of atomic mobilities using the 1-parameter Z-Z-Z binary diffusion coefficient model developed by Zhong et al [1]. Interdiffusion coefficients in the BCC region of the Al–V system are also extracted through a forward-simulation analysis and incorporated into the mobility modeling. A complete description of diffusion in the BCC phase of the Al–Nb–V system is presented following the Binary and Cross-Binary Parameters Only (BCBPO) model developed by Zhong and Zhao [2]. Our data will be valuable input to diffusion-related simulation of refractory high entropy alloys containing aluminum.

Elemental Influence on Oxidation Behaviour of Cantor‐Based and Refractory High Entropy Alloys: A Critical Review

This article reviews the oxidation behaviour of the two most significant high entropy alloy systems (HEAs) namely Cantor‐based and refractory HEAs. HEAs have been extensively researched and show potential applications in various industries, including marine engine manufacturing, chemical industry, furnaces, ducting, heat exchangers, jet engines, steam turbines, nuclear reactors and electronic devices, among others. Effect of the presence of elements such as aluminium, manganese, chromium, silicon, tantalum, vanadium etc. is studied for catalysing the oxidation of HEAs. Aluminium, chromium, and silicon are reportedly found to considerably impact the oxidation kinetics and enhance the oxidation resistance. However, silicon can positively or adversely affect the oxidation resistance depending on its concentration and alloy composition. Other elements like manganese tend to adversely impact the oxidation resistance of FeCoNi‐based HEAs. Refractory elements are typically found to be not suitable for oxidation studies due to the formation of non‐protective oxide layers. However, refractory HEAs offer interesting trends both in terms of enhancing or reducing oxidation resistance depending on the alloying elements. Similarly, findings related to other elements are also presented and elaborated.

Revealing the mechanical behavior of Ti48-xZrxHf26Nb26 high-entropy alloy through zirconium content variations

Refractory high-entropy alloys (RHEAs) composed of Ti, Zr, Hf, and Nb have emerged as promising materials for high-temperature aerospace applications due to their exceptional balance of strength and toughness, coupled with a reduced density and softening resistance. This study delves into the influence of alloy composition on the mechanical properties, a pivotal aspect in the design of RHEAs. We investigate a series of Ti48-xZrxHf26Nb26 (x = 14, 18, 22, 26, 30, 34) alloys, prepared through suction casting and homogenization treatments. The phases, microstructure, and fracture morphology of these alloys are analyzed using X-ray diffraction (XRD), scanning electron microscopy (SEM), and electron backscattered diffraction (EBSD), subsequent tensile tests provide insights into the strength and elongation characteristics of alloys. The homogenized alloys consistently exhibit one BCC phase with equiaxed grains, whereas the fracture mode shifts from intergranular to transgranular, and return to intergranular as the Zr content increases. Experimental results reveal an asymmetry mechanical behavior, alloys with higher Ti content display superior toughness (elongation 17.83 % for Ti = 34 at%) compared to those with higher Zr content (elongation 16.05 % for Zr = 34 at%). Among them, the Ti22Zr26Hf26Nb26 alloy achieves the peak tensile strength of 695.25 MPa, indicating an inverse relationship between strength and toughness. Solid-solution strengthening and chemical short-range orderings emerge as the predominant contributors to the overall strength of the TiZrHfNb alloys. To gain a deeper understanding of the mechanical behavior at the atomic scale, we performed first-principles calculations to investigate the elastic properties and charge density of Ti48-xZrxHf26Nb26 alloys in the BCC structure. These calculations shed light on the underlying mechanisms governing the strength and toughness behavior. The present work offers valuable insights into the design of mechanical properties of TiZrHfNb RHEAs, serving as a paradigm for future materials development in this field.

Optimizing Al content to eliminate the brittle phase in lightweight TiZrNbTa0.1Alx refractory high-entropy alloys

Body-centered cubic (BCC) lightweight refractory high-entropy alloys (LWRHEAs) with Al contents have attracted much attention due to their low density and excellent mechanical properties. However, these typical lightweight alloys often suffer from poor room temperature plasticity. In this study, we prepared TiZrNbTa0.1Alx LWRHEAs by using a high-vacuum arc-melting technique and investigated the influence of Al content on the phase structures and mechanical properties. It was found that the TiZrNbTa0.1Al1 alloy showed a BCC solid solution matrix with some micrometer-sized Al3Zr5 precipitates and exhibited a density of 6.110 ± 0.003 g/cm3. The TiZrNbTa0.1Al1 alloy had a low mixed enthalpy of −20.831 kJ/mol, a compressive yield strength of 1037 ± 178 MPa, and a fracture plasticity of ∼6%. As a result of reducing the Al content, the TiZrNbTa0.1Al0.2 alloy showed a simple BCC phase structure without any precipitates and maintained a low density of 6.743 ± 0.008 g/cm3. The TiZrNbTa0.1Al0.2 alloy had a relatively high mixed enthalpy of −4.5577 kJ/mol, a high yield strength of 1022 ± 51 MPa, and a plasticity of >70%. The TEM analysis results demonstrated that the excellent mechanical properties of this LWRHEA were mainly attributed to the reducing Al content, which could elevate the mixed enthalpy of the alloy to eliminate the brittle Al3Zr5 phase and induce the formation of dense network dislocations at the grain boundaries.

Wet oxidation of TiZrHfNbTaV high-entropy alloys: Role of grain-boundary and interdendritic diffusion

Refractory high-entropy alloys (RHEAs) are sensitive to thermal oxidation, significantly restricting their service performance and potential applications. However, the wet oxidation behavior of RHEAs has remained poorly understood despite the potential risk of catastrophic oxidation caused by water vapor. In this study, the oxidation mechanism of an equiatomic TiZrHfNbTaV high-entropy alloy (HEA) has been investigated in a wet atmosphere at elevated temperatures. Synchronous oxidation of all elements occurs at temperatures below 800 °C. At temperatures above 800 °C, preferential oxidation of Nb, Ti, and Zr, and internal oxidation of V occur on HEAs, which are thermodynamically less preferred as compared with oxidations of more reactive Hf and Ta. Experimental and theoretical analyses show that the oxide grain boundaries and substrate interdendritic regions of HEAs act as diffusion pathways for V and oxidizing species during preferential and internal oxidation processes. This work provides a fundamental understanding of the oxidation of multicomponent alloys in wet environments, which is helpful in the development of effective oxidation resistance strategies and innovative surface engineering techniques.

Ultra strong FCC structured Ni8Cr4Co4Fe6W2 high entropy alloys with high strength and ductility by laser powder bed fusion

The high entropy alloys (HEAs) are widely used in high temperature service environment (such as aviation engine blades) with bright application potential in additive manufacturing. Laser powder bed fusion (LPBF) is technology currently offers the best reproducibility and dimensional accuracy for part production. The unique atomic lattice structure of HEA makes its plastic deformation mechanism different from that of traditional dilution alloy, resulting in the strengthening effect of face-centered cubic high-entropy alloy different from that of traditional metal alloy materials. In this paper, Ni8Cr4Co4Fe6W2 was designed by means of composition control. Its spherical powders with uniform composition were successfully prepared by high temperature remelting spheroidization (PHTR) method, compared with gas atomization (GA) method. The strain rate sensitivity m values of GA-Selective Laser Melting and PHTR-Selective Laser Melting samples were 0.030 and 0.027, respectively. The hardness of Ni8Cr4Co4Fe6W2 high-entropy alloy showed a trend of continuous increase with the decrease of grain size, while the elastic modulus didn’t change much (PHTR-SLM is 193 Gpa and GA-SLM is 189 Gpa). The simulated value of the contact stress decreased by 23 % compared with the theoretical value. The contact radius increased with the increase of plastic deformation in addition to the reduction of contact pressure. The printing sample value of the elongation, yield strength (YS) and Ultimate Tensile Strength (UTS) on PHTR-SLM has increased by 39.6 %, 33.7 % and 25.9 %, respectively in additive manufacturing, compared to GA-SLM. The ability to produce refractory HEAs through PHTR method will make it possible to manufacture complex geometry shapes at a reasonable cost.

Simultaneously enhancing strength–ductility synergy in refractory high entropy alloys by a heterogeneous structure design

Improvement in the strength of metallic materials is often achieved at the expense of material ductility; this long-standing conflict is referred to as the strength–ductility trade-off. In this study, the composition design of high-entropy alloys was combined with the design of multiscale microstructures, and heterogeneous refractory high-entropy alloys (RHEA) with multi-sized grains were fabricated via a simple rolling-annealing treatment process, which significantly alleviates the strength–ductility trade-off. The RHEA annealed at 970 ℃ was composed of fully-recrystallized grains of size 25 μm surrounded by nanosized grains. Owing to the heterogeneity in the structure, dislocations preferentially accumulated at soft recrystallization grain boundaries, thus inducing dislocation interactions such as cross-slip and jog, strengthening the soft region grains, and resulting in Heterogeneous deformation-induced (HDI) strengthening. This mechanism resulted in a significant increase in the work hardening rate during tensile deformation and ensured a high tensile strength of 905 MPa, while improving its uniform elongation to 10.6%. Thus, the proposed heterogeneous design accomplished by simple thermal treatments presents a novel strategy to develop a new generation of high-strength and high-ductility high-entropy alloys.

Tensile creep behavior of the Nb45Ta25Ti15Hf15 refractory high entropy alloy

The tensile creep behavior of a vacuum arc-melted Nb45Ta25Ti15Hf15 refractory high entropy alloy was investigated over a constant true stress range of 50–300 MPa at a temperature of 1173 K. Creep tests were carried out in both high vacuum (5 × 10−6 torr) and ultrahigh purity Ar gas to examine the environmental effect. The samples tested in vacuum exhibited power law behavior with a stress exponent of 4.1 and exceptional tensile creep ductility, whereas those tested in Ar suffered significant embrittlement due to HfO2 formation at grain boundaries, which was exacerbated at low applied stresses where extended exposure to residual O2 gas resulted in more extensive brittle intergranular fracture. Phase decomposition occurred after long-term thermal exposure, where a second Hf-rich body-centered cubic phase formed predominantly at grain boundaries but did not cause embrittlement. Compared to the equiatomic TaNbHfZrTi (Senkov alloy) and face-centered cubic multiple-principal element alloys, Nb45Ta25Ti15Hf15 has superior creep resistance, especially at high applied stresses, while maintaining excellent creep ductility. Transmission electron microscopy revealed that creep deformation in Nb45Ta25Ti15Hf15 at 1173 K is controlled by cross-kink collisions from screw dislocations that results in dipole drag at lower strain rates and jog drag at higher strain rates.

Body-centered cubic phase stability in cobalt-free refractory high-entropy alloys

Cobalt-free refractory high-entropy alloys (RHEAs) are strong contenders for structural materials in nuclear reactors because they do not exhibit cobalt activity under irradiation. The mechanical properties and thermal stability of RHEAs are primarily attributed to the solid solution phase, which is essentially the body-centered cubic (BCC) phase. The BCC phase formation rules thus became the basic criterion in the compositional design of RHEAs. In this paper, the BCC phase formation rules in cobalt-free RHEAs were determined via the calculation of six semiempirical parameters, namely, the entropy of mixing, enthalpy of mixing, atomic size difference, Ω-parameter, d-orbital energy level and valance electron concentration. The mixing enthalpy and atomic size differences are more effective than other semiempirical parameters for predicting BCC phase stability in cobalt-free RHEAs. The presence of aluminum is found to cause a notable alteration in the range of phase stability in cobalt-free RHEAs.

Irradiation-Hardening Model of TiZrHfNbMo0.1 Refractory High-Entropy Alloys.

In order to find more excellent structural materials resistant to radiation damage, high-entropy alloys (HEAs) have been developed due to their characteristics of limited point defect diffusion such as lattice distortion and slow diffusion. Specially, refractory high-entropy alloys (RHEAs) that can adapt to a high-temperature environment are badly needed. In this study, TiZrHfNbMo0.1 RHEAs are selected for irradiation and nanoindentation experiments. We combined the mechanistic model for the depth-dependent hardness of ion-irradiated metals and the introduction of the scale factor f to modify the irradiation-hardening model in order to better describe the nanoindentation indentation process in the irradiated layer. Finally, it can be found that, with the increase in irradiation dose, a more serious lattice distortion caused by a higher defect density limits the expansion of the plastic zone.

Design of refractory high entropy alloys for extreme environment by using CALPHAD

Design of refractory high entropy alloys for extreme environment by using CALPHAD

Microstructural evolution and mechanical behavior of novel TiZrTaxNbMo refractory high-entropy alloys

The refractory high-entropy alloy (RHEA) with a body-centered-cubic (BCC) solid-solution structure has excellent high-temperature softening resistance, which has attracted wide interest in the field of high-temperature alloys. However, its limited room-temperature plasticity has greatly hindered its engineering application. To obtain an excellent strength-plasticity matching relationship, in this reported study, the Ta content in the high-entropy alloy (HEA) was adjusted to rectify this shortcoming. A series of TiZrTaxNbMo (x = 1.0, 0.9, 0.8, 0.7, and 0.6 at. percent, at%) RHEAs were prepared using the vacuum arc-melting technique, and the microstructure and mechanical properties of these RHEA alloys were systematically investigated. The experimental results show that the TiZrTaxNbMo RHEAs are composed of main BCC1 and minor BCC2 phases, which exhibit a dendritic structure. By reducing the Ta content, the elemental segregation caused by the non-equilibrium solidification is reduced. In terms of mechanical properties, with the decrease of Ta content, the hardness and room-temperature yield strength of the alloy decreases slightly, but the room-temperature plasticity increases significantly. The Ta0.7 alloy has the highest plasticity (34.8 %), which is about twice that of the equimolar Ta 1.0 alloy, while the yield strength remained at 1297 MPa. The excellent mechanical properties of the alloys can be attributed to solid-solution strengthening and the formation of moderate amounts of interdendritic regions. The interaction between slip bands and dislocations formed during compression of the Ta0.7 alloy decreased its work hardening. Moreover, the theoretical model of solid-solution strengthening elucidates that the calculated values of the alloy’s yield strength are consistent with that obtained experimentally.

Effects of Nitrogen Doping on Microstructures and Irradiation Resistance of Ti–Zr–Nb–V–Mo Refractory High-Entropy Alloy

Effects of Nitrogen Doping on Microstructures and Irradiation Resistance of Ti–Zr–Nb–V–Mo Refractory High-Entropy Alloy

Characterization of structural and mechanical properties of HfNbTaTiZr refractory high entropy alloy after gas nitriding

This study was initiated to improve surface hardness and wear resistance of a HfNbTaTiZr refractory high entropy alloy (RHEA) by gas nitriding at a medium temperature (600 °C) for 3 h. Structural characterizations conducted by X-ray diffractometer (XRD), X-ray photoelectron spectroscopy (XPS) and energy dispersive spectroscopy (EDS) equipped scanning electron microscope (SEM) revealed that nitriding led to formation of a 1.5 μm thick surface layer containing precipitates of oxides and nitrides of the alloying elements. Detection of oxides within the surface layer was attributed to the presence residual oxygen in the nitriding atmosphere. Nevertheless, the employed gas nitriding provided remarkably higher scratch resistance compared to the untreated state, as the results of increment in the surface hardness and development of larger compressive residual stress.

Competition between phase ordering and phase segregation in the TixNbMoTaW and TixVNbMoTaW refractory high-entropy alloys

Refractory high-entropy alloys are under consideration for applications where materials are subjected to high temperatures and levels of radiation, such as in the fusion power sector. However, at present, their scope is limited because they are highly brittle at room temperature. One suggested route to mitigate this issue is by alloying with Ti. In this theoretical study, using a computationally efficient linear-response theory based on density functional theory calculations of the electronic structure of the disordered alloys, we study the nature of atomic short-range order in these multi-component materials, as well as assessing their overall phase stability. Our analysis enables direct inference of phase transitions in addition to the extraction of an atomistic, pairwise model of the internal energy of an alloy suitable for study via, e.g., Monte Carlo simulations. Once Ti is added into either the NbMoTaW or VNbMoTaW system, we find that there is competition between chemical phase ordering and segregation. These results shed light on observed chemical inhomogeneity in experimental samples, as well as providing fundamental insight into the physics of these complex systems.

The effects of interstitial oxygen on mechanical properties of TiZrNb medium-entropy alloy over a wide temperature range

Interstitial oxygen plays an important role in the microstructure and mechanical properties of recently developed refractory high-entropy or complex concentrated alloys. However, the mechanical properties of the oxygen-doped complex concentrated refractory alloy over a wide temperature range remain unclear. In this work, the effect of interstitial oxygen on the mechanical behavior of TiZrNb medium-entropy alloys (MEAs) has been investigated. At room temperature (RT), the interstitial oxygen improves the yield strength and tensile ductility owing to interstitial solid-solution strengthening and strain-hardening enhancement. However, simultaneous improvement of the RT strength-ductility by adding interstitial oxygen comes at the expense of increasing the ductile-brittle transition temperature (DBTT). Furthermore, the high-temperature yield strength of TiZrNb alloy can be improved up to 800 °C with the addition of 2 at% oxygen. The results above provide valuable insight into the mechanical properties of TiZrNb MEA, which would contribute to optimizing the high-performance refractory complex concentrated alloys in various applications.

Unraveling microstructure and mechanical response of an additively manufactured refractory TiVHfNbMo high-entropy alloy

Refractory high-entropy alloys (RHEAs) have attracted considerable interest due to their elevated melting points and exceptional softening resistance. Nevertheless, the ambient-temperature brittleness and inadequate high-temperature oxidation resistance commonly restrict the processability of RHEAs. Direct energy deposition (DED) additive manufacturing technology is ideal for fabricating refractory alloys due to design flexibility and oxygen-free environment. In this work, a novel Ti41V27Hf13Nb13Mo6 RHEA was successfully manufactured by DED, and a comprehensive investigation was conducted to explore the microstructure evolution and mechanical response during tension. The as-deposited RHEAs exhibit a grain-size graded microstructure with a body-centred-cubic (BCC) matrix and precipitates. Increasing laser energy density suppressed the grain boundary precipitation, effectively enhancing the ambient-temperature tensile ductility to ∼11.3%. The optimized specimens achieved an unprecedented yield strength of ∼1.2 GPa among the DEDed RHEAs, which can be attributed to a significant solid solution strengthening from the volume misfit of 5.03%. We revealed that dislocation interactions maintained the working hardening capacity. Moreover, in-situ characterization indicated that slip transfer, grain rotation, and kinking accommodated the plastic deformation. Crack nucleation was caused by slip inhibition at grain boundaries and dislocation pile-ups at intragranular precipitates. The kink band formation relieved stress concentration induced by intragranular precipitates and promoted a ductile fracture. These exceptional outcomes provide opportunities for additive manufacturing RHEAs and greatly advance understanding of their strengthening and deformation mechanisms.

Radiation-enhanced precipitation and the impact on He bubble formation in V-Ti-based refractory alloys containing interstitial impurities

V-Ti-based refractory high entropy alloys (RHEAs), e.g., VTiTa and VTiTaNb, have been found with outstanding mechanical properties and irradiation resistance, granting them application potential in nuclear engineering. Nonetheless, similar to conventional V-Ti-based alloys such as V-4Ti-4Cr, these alloys are sensitive to C/N/O interstitial impurities. Under irradiation, such impurities may promote the formation of precipitates which may affect the defect evolution, especially at the appearance of helium. Previous studies have observed different helium behavior in the above alloys, including the heterogeneous distribution of helium bubbles in VTiTa, but the origin was not clear. In this work, detailed microstructural characterization is performed to analyze the irradiation induced precipitates and their impact on helium bubble formation in these alloys. Under helium ion irradiation at 700 °C, the TiN precipitates with NaCl structure are formed in all the three alloys. Nonetheless, the interfaces between precipitates and matrix in VTiTa and VTiTaNb are semi-coherent while those in V-4Ti-4Cr are coherent, due to the various lattice parameters of the alloys. Moreover, severe lattice distortion is found also inside the precipitates in the two RHEAs. Consequently, significant heterogeneous nucleation of He bubbles are observed in these two RHEAs but not in V-4Ti-4Cr. Among the three alloys, the growth of precipitates is the fastest in VTiTa, causing the formation of bubble clusters. Furthermore, the growth direction/shape of precipitates affect the shape of bubbles, leading to the {001} cuboids shape in V-4Ti-4Cr and the truncated {110} dodecahedra shape in V-Ti-Ta and V-Ti-Ta-Nb.