A review of refractory high-entropy alloys

This work reviews recent progress in the alloy design,microstructure,and mechanical properties of refractory high-entropy alloys(RHEAs).What’s more,the underlying strengthening mechanisms and deformation behavior are discussed.Composed mainly of near-equimolar refractory elements,RHEAs have superior mechanical properties,especially at high temperatures.However,many of them have limited room-temperature ductility.Much work has been done to solve this trade-off,and some of the RHEAs have the potential to be used for high-temperature applications in the future.In addition to their mechanical properties,RHEAs have other attractive properties,such as biocompatibility and wear resistance,which are discussed.Finally,current problems and future suggestions for RHEAs are discussed.

Phase,microstructure and compressive properties of refractory high-entropy alloys CrHfNbTaTi and CrHfMoTaTi

New refractory high-entropy alloys,CrHfNbTaTi and CrHfMoTaTi,derived from the well-known HfNbTaTiZr alloy through principal element substitution were prepared using vacuum arc melting.The phase components,microstructures,and compressive properties of the alloys in the as-cast state were investigated.Results showed that both alloys were composed of BCC and cubic Laves phases.In terms of mechanical properties,the yield strength increased remarkably from 926 MPa for HfNbTaTiZr to 1258 MPa for CrHfNbTaTi,whereas a promising plastic strain of around 15.0%was retained in CrHfNbTaTi.The morphology and composition of the network-shaped interdendritic regions were closely related to the improved mechanical properties due to elemental substitution.Dendrites were surrounded by an incompact interdendritic shell after Mo incorporation,which deteriorated yield strength and accelerated brittleness.

Effect of Ti content on microstructure and properties of TixZrVNb refractory high-entropy alloys

This study aimed to investigate the microstructure and mechanical properties of TixZrVNb(x=1,1.5,2)refractory high-entropy alloys at room and elevated temperatures.The TiZrVNb alloy consisted of the body-centered cubic(bcc)matrix with a small amount of V2Zr phase.The Ti1.5ZrVNb and Ti2ZrVNb alloys exhibited a single-phase bcc structure.At room temperature,the tensile ductility of the as-cast alloys increased from 3.5%to 12.3%with the increase in the Ti content.The TixZrVNb alloys exhibited high yield strength at 600°C,and the ultimate yield strength was more than 900 MPa.Softening occurred at 800°C,but the ultimate yield strength could still exceed 200 MPa.Moreover,the TixZrVNb alloys displayed low densities but high specific yield strengths(SYSs).The lowest density of TixZrVNb alloys was only 6.12 g/cm^3,but the SYS could reach about 180 MPa·cm^3·g^−1,which is better than those of most reported high-entropy alloys(HEAs).

Laser metal deposition of refractory high-entropy alloys for high-throughput synthesis and structure-property characterization

Progress in materials development is often paced by the time required to produce and evaluate a large number of alloys with different chemical compositions.This applies especially to refractory high-entropy alloys(RHEAs),which are difficult to synthesize and process by conventional methods.To evaluate a possible way to accelerate the process,high-throughput laser metal deposition was used in this work to prepare a quinary RHEA,TiZrNbHfTa,as well as its quaternary and ternary subsystems by in-situ alloying of elemental powders.Compositionally graded variants of the quinary RHEA were also analyzed.Our results show that the influence of various parameters such as powder shape and purity,alloy composition,and especially the solidification range,on the processability,microstructure,porosity,and mechanical properties can be investigated rapidly.The strength of these alloys was mainly affected by the oxygen and nitrogen contents of the starting powders,while substitutional solid solution strengthening played a minor role.

Microstructure characteristics and mechanical properties of NbMoTiVWSix refractory high-entropy alloys

Refractory high-entropy alloys are considered as potential structural materials for elevated temperature applications.To obtain refractory high-entropy alloys with high strength,different amounts of Si were added into the NbMoTiVW refractory high-entropy alloys.The effects of Si on the phase constitution,microstructure characteristics and mechanical properties of NbMoTiVWSi_(x) alloys were investigated.Results show that when the addition of Si is 0,0.025 and 0.05(molar ratio),the alloys are consisted of primary BCC and secondary BCC in the intergranular area.When the addition of Si is increased to 0.075 and 0.1,eutectic structure including silicide phase and secondary BCC phase is formed.The primary BCC phase shows dendritic morphology,and is refined by adding Si.The volume fraction of intergranular area is increased from 12.22%to 18.13%when the addition of Si increases from 0 to 0.1.The ultimate compressive strength of the NbMoTiVW alloy is improved from 2,242 MPa to 2,532 MPa.Its yield strength is also improved by the addition of Si,and the yield strength of NbMoTiVWSi_(0.1) reaches maximum of 2,298 MPa.However,the fracture strain of the alloy is decreased from 15.31%to 12.02%.The fracture mechanism of the alloys is changed from mixed fracture of ductile and quasi-cleavage to cleavage fracture with increasing of Si.The strengthening of alloys is attributed to the refinement of primary BCC phase,volume fraction increment of secondary BCC phase,and formation of eutectic structure by addition of Si.

Light-weight refractory high-entropy alloys: A comprehensive review

In recent years,high-entropy alloys(HEAs)have become a research hotspot in materials community,and great progress has been made in exploring various high-performance HEAs.As a special class,the light-weight refractory high-entropy alloys(RHEAs)own both excellent high-temperature comprehensive properties and low density and have accordingly attracted more and more attention.In this paper,we presented a comprehensive review of the recent progress and status in light-weight RHEAs.Based on an exhausting search of the literature reports,one strategy in terms of phase numbers after preparation was first proposed to classify the light-weight RHEAs into three categories.Then,the status on the fundamental thermodynamic and thermophysical data/databases,computational approaches for alloy designing,and preparation/fabrication techniques of light-weight RHEAs was introduced one after another.After that,the progress on mechanical properties and oxidation/corrosion/wear behaviors of light-weight RHEAs at room and high temperatures was summarized.Finally,the conclusions of this review were drawn.By pointing out the shortcomings of the current research,the follow-up development directions in the field of light-weight RHEAs were also given.

Microstructure and mechanical properties of WMoTaNbTi refractory high-entropy alloys fabricated by selective electron beam melting

WMoTaNbTi RHEAs formed by SEBM with negative defocus distance were investigated.Four scanning speeds were applied,an electron beam with scanning speed at 2.5 m/s completely fused the premixed WMoTaNb alloyed powder and pure Ti powder.Significant vaporization of Nb and Ti elements happened during the formation of WMoTaNbTi RHEAs,however,the single BCC phase remains stable.Weakened solid-solute strengthening caused by elemental vaporization,dropping percentage of Nb and Ti solutes in the matrix as well as improved ductilizing effects with decreasing scanning speeds leads to falling microhardness and better local ductility.Microhardness of scanning speed at 4.0 m/s,3.5 m/s,3.0 m/s and 2.5 m/s is 578±17 HV,576±12 HV,573±10 HV and 511±2 HV,respectively.The as-deposited WMoTaNbTi RHEA formed at a scanning speed of 2.5 m/s displays ultimate strength of 1312 MPa.

Dynamic compression behavior of TiZrNbV refractory high-entropy alloys upon ultrahigh strain rate loading

In this study,the dynamic compressive response behavior of a body-centered cubic(BCC)single-phase TiZrNbV refractory high-entropy alloy(RHEA)was investigated under impact at speeds of 313-1584 m s^(-1)using two-stage,gas-gun-driven,high-speed plate-impact experiments;recovery sample analysis;and theoretical calculations.The strain rate and pressure were approximately 10^(7) s^(−1) and 5.07-29.37 GPa,respectively.The results showed that the TiZrNbV RHEA had a Hugoniot elastic limit of 4.12-5.86 GPa and a spall strength of 1.84-2.03 GPa.The initial yield strength of the alloy showed a strong strain-rate dependence and could be described by the modified Zerilli-Armstrong model,while the phonon-damping effect was the main reason for its high strain-rate sensitivity.Microstructural analysis showed that the dynamic deformation of the TiZrNbV RHEA was controlled by the dislocation slip,dislocation proliferation,intersection of the deformation bands,and grain refinement.The analysis also showed that the intergranular,transgranular,and mixed-type cracks dominated the spall failure of the material.The dynamic Hall-Petch effect and pinning from the lattice distortion led to high dynamic yield strength.The critical strain rate for the phonon drag effect was positively related to the relative atomic mass and local strain field of the metals.Within the experimental loading range,the RHEA showed good structural stability,and simultaneously,the theoretical calculation method for the equation of state based on a cold-energy mixture could accurately predict its shock-response behavior.The valence-electron concentration(VEC)had a direct effect on the shock-compression properties of the HEAs;higher VEC implied more difficulty in compressing the HEAs.The findings of this study provide insights into understanding the mechanical response characteristics of RHEAs under extreme conditions such as high-speed impact and ultrahigh strain-rate loading.

Development and Property Tuning of Refractory High-Entropy Alloys:A Review

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 fi eld 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 eff ect 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 fi eld. 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.

Relationship between the unique microstructures and behaviors of high-entropy alloys

High-entropy alloys(HEAs),which were introduced as a pioneering concept in 2004,have captured the keen interest of nu-merous researchers.Entropy,in this context,can be perceived as representing disorder and randomness.By contrast,elemental composi-tions within alloy systems occupy specific structural sites in space,a concept referred to as structure.In accordance with Shannon entropy,structure is analogous to information.Generally,the arrangement of atoms within a material,termed its structure,plays a pivotal role in dictating its properties.In addition to expanding the array of options for alloy composites,HEAs afford ample opportunities for diverse structural designs.The profound influence of distinct structural features on the exceptional behaviors of alloys is underscored by numer-ous examples.These features include remarkably high fracture strength with excellent ductility,antiballistic capability,exceptional radi-ation resistance,and corrosion resistance.In this paper,we delve into various unique material structures and properties while elucidating the intricate relationship between structure and performance.

Refractory high-entropy alloys:A focused review of preparation methods and properties

In recent years,high-entropy alloys(HEAs)have become prominent metallic materials due to their unique design strategies and excellent mechanical properties.The HEAs-inherent high-entropy,lattice-distortion,sluggish-diffusion,and cocktail effects make HEAs maintain high strength,oxidation resistance,corrosion resistance,wear resistance,and other excellent comprehensive properties,showing stronger competitiveness relative to traditional alloys.Refractory high-entropy alloys(RHEAs)are considered as a new kind of high-temperature materials with great application prospects due to their excellent mechanical properties and have the potential to replace nickel-based superalloy as the next generation of high-temperature materials.We reviewed the research status and preparation methods of RHEAs in recent years,including the metallurgical smelting,powder metallurgy,magnetron sputtering,and additive manufacturing technologies.The microstructure and phase-transformation process of RHEAs were analyzed.The mechan-ical properties and main strengthening and toughening mechanisms of RHEAs,such as solid-solution strengthening,precipitation strengthening,and the transformation-induced plasticity(TRIP),were discussed,and the deformation mechanism of RHEAs was revealed.The properties of RHEAs,including high strength,oxidation resistance,corrosion and wear resistance were reviewed.RHEAs will meet the huge market demand in the engineering materials field,but there are still many challenges,such as the tradeoff between high strength and high ductility,structural design,and performance optimization of RHEAs with brittle BCC structures.We believe that this combination of knowledge may shape the future of RHEAs and break through the mutually exclusive conundrum of high strength and high toughness for RHEAs.

Superior mechanical properties and strengthening mechanisms of lightweight AlxCrNbVMo refractory high-entropy alloys(x=0,0.5,1.0)fabricated by the powder metallurgy process

Light and strong AlxCrNbVMo(x=0,0.5,and 1.0)refractory high-entropy alloys(RHEAs)were designed and fabricated via a the powder metallurgical process.The microstructure of the AlxCrNbVMo alloys consisted of a single BCC crystalline structure with a sub-micron grain size of 2-3μm,and small amounts(<4 vol.%)of fine oxide dispersoids.This homogeneous microstructure,without chemical segregation or micropores was achieved via high-energy ball milling and spark-plasma sintering.The alloys exhibited superior mechanical properties at 25 and 1000℃compared to those of other RHEAs.Here,CrNbVMo alloy showed a yield strength of 2743 MPa at room temperature.Surprisingly,the yield strength of the CrNbVMo alloy at 1000℃was 1513 MPa.The specific yield strength of the CrNbVMo alloy was increased by 27%and 87%at 25 and 1000℃,respectively,compared to the AlMo_(0.5) NbTa_(0.5)TiZr RHEA,which exhibited so far the highest specific yield strength among the cast RHEAs.The addition of Al to CrNbVMo alloy was advantageous in reducing its reduce density to below 8.0 g/cm^(3),while the elastic modulus decreased due to the much lower elastic modulus of Al compared to that of the CrNbVMo alloy.Quantitative analysis of the strengthening contributions,showed that the solid solution strengthening,arising from a large misfit effect due to the size and modulus,and the high shear modulus of matrix,was revealed to predominant strengthening mechanism,accounting for over 50%of the yield strength of the AlxCrNbVMo RHEAs.

Microstructure and mechanical properties of C_(x)Hf_(0.25)NbTaW_(0.5) refractory high-entropy alloys at room and high temperatures

The microstructure and mechanical properties of as-cast and isothermally annealed C_(x)Hf_(0.25)NbTaW_(0.5)(x=0,0.05,0.15,0.25)refractory high-entropy alloys(RHEAs)were studied.Both the as-cast and annealed RHEAs consisted of disordered body-centered cubic solid solution phase and metal carbide(MC)phase with a face-centered cubic crystal structure(Fm-3 m space group).The primary carbides were enriched with Hf and C elements and tended to form lamellar eutectic-like microstructure in the interdendrites.The lamellar eutectic-like structure in the interdendrites would be formed from the decomposition of sub-carbide M_(2)C under the influence of Hf element.After isothermal annealing,slatted carbides were precipitated on the matrix,and the distribution became more uniform with high C content.The formation of carbides strongly influenced the mechanical properties both at room and high temperatures.The yield strength values of C_(x)Hf_(0.25)NbTaW_(0.5) RHEA at 1473 and 1673 K were 792 and 749 MPa,respectively.The result had exceeded the high temperature mechanical properties of currently known RHEAs.Moreover,this RHEA exhibited high-temperature performance stability and excellent plasticity,exceeding 30 and 50%at room and elevated temperatures(above 1273 K),respectively.During thermal deformation,carbon-containing RHEAs obtained more severe work hardening than that of ACHO RHEAs,and required greater dynamic recrystallization to achieve the dynamic equilibrium.

Effect of hafnium and molybdenum addition on inclusion characteristics in Co-based dual-phase high-entropy alloys

Specific grades of high-entropy alloys(HEAs)can provide opportunities for optimizing properties toward high-temperature applications.In this work,the Co-based HEA with a chemical composition of Co_(47.5)Cr_(30)Fe_(7.5)Mn_(7.5)Ni_(7.5)(at%)was chosen.The refractory metallic elements hafnium(Hf)and molybdenum(Mo)were added in small amounts(1.5at%)because of their well-known positive effects on high-temperature properties.Inclusion characteristics were comprehensively explored by using a two-dimensional cross-sectional method and extracted by using a three-dimensional electrolytic extraction method.The results revealed that the addition of Hf can reduce Al_(2)O_(3)inclusions and lead to the formation of more stable Hf-rich inclusions as the main phase.Mo addition cannot influence the inclusion type but could influence the inclusion characteristics by affecting the physical parameters of the HEA melt.The calculated coagulation coefficient and collision rate of Al_(2)O_(3)inclusions were higher than those of HfO_(2)inclusions,but the inclusion amount played a larger role in the agglomeration behavior of HfO_(2)and Al_(2)O_(3)inclusions.The impurity level and active elements in HEAs were the crucial factors affecting inclusion formation.

Local chemical inhomogeneities in TiZrNb-based refractory high-entropy alloys

Multi-principal element solid solutions are prone to develop local chemical inhomogeneities,i.e.,chemi-cal order/clustering and/or compositional undulation.However,these structural details from short-range(first couple of nearest-neighbor atomic shells)to nanometer length scale are very challenging to re-solve in both experimental characterization and computer simulations.For instance,Monte Carlo model-ing based on density-functional-theory calculations is severely limited by the sample size and the sim-ulation steps practical in the simulations.Adopting the cluster expansion approach,here we systemati-cally reveal the local chemical inhomogeneity,including chemical order and compositional fluctuation,in three representative equiatomic TiZrNb-based body-centered cubic refractory high-entropy alloys(HEAs):TiZrNb,TiZrHfNb and TiZrHfNbTa.Ti-Zr pairs are found to exhibit the highest degree of chemical pref-erence among all atomic pairs.Such chemical short-range order(CSRO)induces an accompanying com-positional undulation,both extending to characteristic dimensions of the order of one nanometer.The chemical inhomogeneity trend uncovered for this series of TiZrNb-based HEAs is expected to impact their mechanical properties;e.g.,incorporating the CSRO effects in a current model significantly improves its agreement with experimental measured yield strength.

Utlra-fast hydrolysis performance of MgH_(2) catalyzed by Ti-Zr-Fe-Mn-Cr-V high-entropy alloys

Hydrogen energy is one of the ideal energy alternatives and the upstream of the hydrogen industry chain is hydrogen production,which can be achieved via the reaction of inorganic materials with water,known as hydrolysis.Among inorganic materials,the high hydrogen capacity for hydrolysis of MgH_(2)(15.2 wt%)makes it a promising material for hydrogen production via hydrolysis.However,the dense Mg(OH)_(2) passivation layer will block the reaction between MgH_(2) and the solution,resulting in low hydrogen yield and sluggish hydrolysis kinetics.In this work,the hydrogenyield and hydrogen generation rate of MgH_(2) are considerably enhanced by adding Ti-Zr-Fe-Mn-Cr-V high-entropy alloys(HEAs) for the first time.In particular.the MgH_(2)-3 wt% TiZrFe_(1.5)MnCrV_(0.5)(labelled as MgH_(2)-3 wt% Fe_(1.5)) composite releases 1526.70 mL/g H_(2) within 5 min at 40℃,and the final hydrolysis conversion rate reaches 95.62% within 10 min.The mean hydrogen generation rate of the MgH_(2)-3 wt% Fe_(1.5) composite is 289.16 mL/g/min,which is 2.38 times faster than that of pure MgH_(2).Meanwhile,the activation energy of the MgH_(2)-3 wt% Fe_(1.5) composite is calculated to be 12.53 kJ/mol. The density functional theory(DFT) calculation reveals that the addition of HEAs weakens the Mg-H bonds and accelerates the electron transfer between MgH_(2) and HEAs,Combined with the cocktail effect of HEAs as well as the formation of more interfaces and micro protocells,the hydrolysis performance of MgH_(2) is considerably improved.This work provides an appealing prospect for real-time hydrogen supply and offers a new effective strategy for improving the hydrolysis performance of MgH_(2).

Comprehensive insights into recent innovations:Magnesium-inclusive high-entropy alloys

This review focuses on thermodynamic and physical parameters,synthesis methods,and reported phases of Magnesium(Mg)containing high-entropy alloys(HEAs).Statistical data of publications concerning Mg-containing HEAs were collected and analyzed.Data on the chemical elements included in Mg-containing HEAs,their theoretical end experimental densities,thermodynamic parameters,physical parameters,fabricated techniques and reported phases were also collected and discussed.On the basis of this information,a new classification for HEAs was proposed.It is also shown that the existing thermodynamic parameters cannot accurately predict the formation of a single phase solid solution for Mg-containing HEAs.The physical parameters of Mg-containing HEAs are within a wide range,and most of the synthesized Mg-containing HEAs have a complex multiphase structure.

Evolution of helium bubbles in FeCoNiCr-based high-entropy alloys containing γ′ nanoprecipitates

A series of high-entropy alloys(HEAs) containing nanoprecipitates of varying sizes is successfully prepared by a non-consuming vacuum arc melting method.In order to study the irradiation evolution of helium bubbles in the FeCoNiCrbased HE As with γ' precipitates,these samples are irradiated by 100-keV helium ions with a fluence of 5 × 10^(20) ions/m^(2) at 293 K and 673 K,respectively.And the samples irradiated at room temperature are annealed at different temperatures to examine the diffusion behavior of helium bubbles.Transmission electron microscope(TEM) is employed to characterize the structural morphology of precipitated nanoparticles and the evolution of helium bubbles.Experimental results reveal that nanosized,spherical,dispersed,coherent,and ordered L1_(2)-type Ni_(3)Ti γ' precipitations are introduced into FeCoNiCr(Ni_(3)Ti)_(0.1) HEAs by means of ageing treatments at temperatures between 1073 K and 1123 K.Under the ageing treatment conditions adopted in this work,γ' nanoparticles are precipitated in FeCoNiCr(Ni_(3)Ti)_(0.1) HE As,with average diameters of 15.80 nm,37.09 nm,and 62.50 nm,respectively.The average sizes of helium bubbles observed in samples after 673-K irradiation are 1.46 nm,1.65 nm,and 1.58 nm,respectively.The improvement in the irradiation resistance of FeCoNiCr(Ni_(3)Ti)_(0.1) HEAs is evidenced by the diminution in bubbles size.Furthermore,the FeCoNiCr(Ni_(3)Ti)_(0.1) HEAs containing γ' precipitates of 15.8 nm exhibits the minimum size and density of helium bubbles,which can be ascribed to the considerable helium trapping effects of heterogeneous coherent phase boundaries.Subsequently,annealing experiments conducted after 293-K irradiation indicate that HEAs containing precipitated phases exhibits smaller apparent activation energy(E_(a)) for helium bubbles,resulting in larger helium bubble size.This study provides guidance for improving the irradiation resistance of L1_(2)-strengthened high-entropy alloy.

High-entropy alloys in thermoelectric application:A selective review

Since the superior mechanical,chemical and physical properties of high-entropy alloys(HEAs)were discovered,they have gradually become new emerging candidates for renewable energy applications.This review presents the novel applications of HEAs in thermoelectric energy conversion.Firstly,the basic concepts and structural properties of HEAs are introduced.Then,we discuss a number of promising thermoelectric materials based on HEAs.Finally,the conclusion and outlook are presented.This article presents an advanced understanding of the thermoelectric properties of HEAs,which provides new opportunities for promoting their applications in renewable energy.

Mechanical and tribological performance of AlCr_(0.5)NbTa_(x)Ti_(4-x)(x=0,0.5,1)refractory high-entropy alloys

The tribological behavior of AlCr_(0.5)NbTa_(x)Ti_(4-x)(x=0,0.5,and 1)refractory high-entropy alloys was systematically investigated from room temperature to 800℃.The relationship between the alloy composition,microstructure,mechanical properties,and tribological performance was analyzed.The results show that all three alloys have a body-centered cubic(bcc)single-phase structure.The Ta addition enhances solid solution strengthening and increases the melting point that would resist high-temperature thermal softening.As a result,high-temperature strength is enhanced considerably,the coefficients of friction(COF)and wear rates of the alloys are reduced considerably at elevated temperatures,demonstrating excellent friction-reducing and anti-wear properties,e.g.,the COF and wear rate of AlCr_(0.5) NbTaTi_(3) alloy at 800℃ are 0.34 and 4.40×10^(-7) mm^(3) N^(-1) m^(-1),respectively.The excellent wear resistance at high temperatures can be attributed to the formation of an oxide-tribo layer(Ta_(2)O_(5) and TiO_(2))with ultrafine-grained layers and good high-temperature mechanical properties.