A critical review on solid-state welding of high entropy alloys-processing,microstructural characteristics and mechanical properties of joints

The high entropy alloys(HEAs)are the newly developed high-performance materials that have gained significant importance in defence,nuclear and aerospace sector due to their superior mechanical properties,heat resistance,high temperature strength and corrosion resistance.These alloys are manufactured by the equal mixing or larger proportions of five or more alloying elements.HEAs exhibit superior mechanical performance compared to traditional engineering alloys because of the extensive alloying composition and higher entropy of mixing.Solid state welding(SSW)techniques such as friction stir welding(FSW),rotary friction welding(RFW),diffusion bonding(DB)and explosive welding(EW)have been efficiently deployed for improving the microstructural integrity and mechanical properties of welded HEA joints.The HEA interlayers revealed greater potential in supressing the formation of deleterious intermetallic phases and maximizing the mechanical properties of HEAs joints.The similar and dissimilar joining of HEAs has been manifested to be viable for HEA systems which further expands their industrial applications.Thus,the main objective of this review paper is to present a critical review of current state of research,challenges and opportunities and main directions in SSW of HEAs mainly CoCrFeNiMn and Al_xCoCrFeNi alloys.The state of the art of problems,progress and future outlook in SSW of HEAs are critically reviewed by considering the formation of phases,microstructural evolution and mechanical properties of HEAs joints.

Characterization of local chemical ordering and deformation behavior in high entropy alloys by transmission electron microscopy

Short-range ordering(SRO)is one of the most important structural features of high entropy alloys(HEAs).However,the chemical and structural analyses of SROs are very difficult due to their small size,complexed compositions,and varied locations.Transmission electron microscopy(TEM)as well as its aberration correction techniques are powerful for characterizing SROs in these compositionally complex alloys.In this short communication,we summarized recent progresses regarding characterization of SROs using TEM in the field of HEAs.By using advanced TEM techniques,not only the existence of SROs was confirmed,but also the effect of SROs on the deformation mechanism was clarified.Moreover,the perspective related to application of TEM techniques in HEAs are also discussed.

Spark plasma sintering of tungsten-based WTaVCr refractory high entropy alloys for nuclear fusion applications

W-based WTaVCr refractory high entropy alloys (RHEA) may be novel and promising candidate materials for plasma facing components in the first wall and diverter in fusion reactors. This alloy has been developed by a powder metallurgy process combining mechanical alloying and spark plasma sintering (SPS). The SPSed samples contained two phases, in which the matrix is RHEA with a body-centered cubic structure, while the oxide phase was most likely Ta2VO6through a combined analysis of X-ray diffraction (XRD),energy-dispersive spectroscopy (EDS), and selected area electron diffraction (SAED). The higher oxygen affinity of Ta and V may explain the preferential formation of their oxide phases based on thermodynamic calculations. Electron backscatter diffraction (EBSD) revealed an average grain size of 6.2μm. WTaVCr RHEA showed a peak compressive strength of 2997 MPa at room temperature and much higher micro-and nano-hardness than W and other W-based RHEAs in the literature. Their high Rockwell hardness can be retained to at least 1000°C.

Microstructure and Properties of AlCoCrFeNiTi High-Entropy Alloy Coatings Prepared by Laser Cladding

21-4N(5Cr21Mn9Ni4N)is extensively employed in the production of engine valves,operating under severe conditions.Apart from withstanding high-temperature gas corrosion,it must also endure the impact of cylinder explosion pressure.The predominant failure mode of 21-4N valves is abrasive wear.Surface coatings serve as an effective approach to prevent such failures.In this investigation,Laser cladding technology was utilized to fabricate AlCoCrFeNiTi high entropy alloy coatings onto the surfaces of 21-4N valves.According to the findings,the cladding zone has a normal dendritic microstructure,a good substrate-to-cladding layer interaction,and no obvious flaws.In terms of hardness,the cladding demonstrates an average hardness of 620 HV.The hardness has increased by 140%compared to the substrate.The average hardness of the cladding remains at approximately 520 HV even at elevated temperatures.Regarding frictional wear performance,between 400℃and 800℃,the cladding layer exhibits an average friction coefficient of 0.4,with the primary wear mechanisms being abrasive wear,adhesive wear,and a minor degree of plastic deformation.

Progress in weldability research of high entropy alloys

High entropy alloys usually show good weldability.The weldability problems of high entropy alloys are segregation,cracks,and hardening or softening of weld,etc.When an Al_(x)CoCrFeNi alloy is welded,Al and Ni will segregate to the interdendritic region in the weld,but the degree of segregation is less than that of the base metal.When an Al_(x)CoCrCu_(x)FeNi alloy or a CoCrCu_(x)FeNi alloy is welded,Cu tends to segregate to the interdendritic region in the weld.Increasing the cooling rate of the welding process,such as with laser welding,is conducive to reducing the segregation in the weld.The segregation in the weld and the heat affected zone,especially the segregation of Cu,will lead to the generation of hot cracks.Hot cracking is the main form of cracking in high entropy alloys joints.Welding will lead to changes in the hardness of the weld.The main factors affecting the hardness change are the grain sizes and the precipitations.With laser welding,if the base metal is cold rolled,the hardness of the weld will decrease.If the base metal is hot rolled and annealed or cast,the hardness of the weld will increase.With TIG welding,the hardness of the weld is usually lower than that of the base metal,unless the grain of the base metal is particularly coarse before welding.With friction stir welding,recrystallization and grain refinement occur in the stir zone,and the hardness of the stir zone will be significantly improved no matter the original base metal is cold rolled or cast.

Influences of Milling Time and NbC on Microstructure of AlCoCrFeNi_(2.1)High Entropy Alloy by Mechanical Alloying

AlCoCrFeNi_(2.1)eutectic high entropy alloy(EHEA)and AlCoCrFeNi_(2.1)-x NbC(x=2.5wt%,5.0wt%,7.5wt%,and 10wt%)high entropy alloy(HEAs)were prepared by mechanical alloying(MA).The effects of milling time and NbC content on the alloying behavior and grain size of the AlCoCrFeNi_(2.1)EHEA were investigated.The experimental results show that the AlCoCrFeNi_(2.1)EHEA primarily consists of order BCC(B2)and face-centered-cubic(FCC)phases,while the AlCoCrFeNi_(2.1)-x NbC(x=2.5wt%,5.0wt%,7.5wt%,and 10wt%)HEAs are composed of B2,FCC,and NbC phases.With the increase of milling time,the powder goes through three stages,irregularity,cold welding fracture and spheroidization.The particle size of AlCoCrFeNi_(2.1)EHEA powder shows a trend of first increasing and then decreasing.Therein,the particle size presents a normal distribution during 0-50 h alloying.With the addition of NbC,the AlCoCrFeNi_(2.1)-x NbC HEAs powders are significantly refined.And the degree of grain refinement gradually increases with the increase of NbC content.

FeCoNiCrMo high entropy alloy nanosheets catalyzed magnesium hydride for solid-state hydrogen storage

The catalytic effect of FeCoNiCrMo high entropy alloy nanosheets on the hydrogen storage performance of magnesium hydride(MgH_(2))was investigated for the first time in this paper.Experimental results demonstrated that 9wt%FeCoNiCrMo doped MgH_(2)started to dehydrogenate at 200℃and discharged up to 5.89wt%hydrogen within 60 min at 325℃.The fully dehydrogenated composite could absorb3.23wt%hydrogen in 50 min at a temperature as low as 100℃.The calculated de/hydrogenation activation energy values decreased by44.21%/55.22%compared with MgH_(2),respectively.Moreover,the composite’s hydrogen capacity dropped only 0.28wt%after 20 cycles,demonstrating remarkable cycling stability.The microstructure analysis verified that the five elements,Fe,Co,Ni,Cr,and Mo,remained stable in the form of high entropy alloy during the cycling process,and synergistically serving as a catalytic union to boost the de/hydrogenation reactions of MgH_(2).Besides,the FeCoNiCrMo nanosheets had close contact with MgH_(2),providing numerous non-homogeneous activation sites and diffusion channels for the rapid transfer of hydrogen,thus obtaining a superior catalytic effect.

On the Superconductivity in High-Entropy Alloy (NbTa)1-X(HfZrTi)X

The superconductivity in (NbTa)1-X(HfZrTi)X high-entropy alloy is analyzed using the theory of strong-coupled superconductor. It is concluded that (NbTa)1-X(HfZrTi)X is a strong coupled superconductor. The variation in the superconducting transition temperature from 7.9 K to 4.6 K as x increases from 0.2 to 0.84 arises because of the decrease in electronic band width due to localization and broadening of the band. It is suggested that the decrease in electronic band width is due to crystalline randomness which gives rise to the mobility edge.

Processing effects on the magnetic and mechanical properties of FeCoNiAl_(0.2)Si_(0.2) high entropy alloy

High entropy alloys with the composition of FeCoNiA10.2Si0.2 were prepared by arc melting and induction melting, denoted by A1 and A2, respectively. The samples prepared by these two techniques have a face-centered cubic （FCC） phase structure and a typical dendrite morphology. The tensile yield strength and maximum strength of A2 samples are about 280 and 632 MPa, respectively. Moreover~ the elongation can reach 41.7%. These two alloys prepared by the different methods possess the similar magnetic properties. The saturation magnetization and coercivity can reach 1.151 T and 1400 A/m for A1 samples and 1.015 T and 1431 A/m for A2 samples, respectively. Phases in A2 samples do not change, which are heat treated at different temperatures, then quenched in water. Only the sample, which is heat treated at 600~C for 3 h and then furnace cooled, has a new phase precipitated. Besides, the coercivity decreases obviously at this temperature. Cold rolling and the subsequent heat treatment cannot improve the magnetic properties effectively. However, cold rolling plays an important role in improving the strength.

Azo dye degradation behavior of AlFeMnTiM(M = Cr, Co, Ni) high-entropy alloys

Because of the potential carcinogenic effects and difficult degradation of azo dyes, their degradation has been a longstanding problem. The degradation of azo dye Direct Blue 6(DB6) using ball-milled(BM) high-entropy alloy(HEA) powders was characterized in this work. Newly designed AlFeMnTiM(M = Cr, Co, Ni) HEAs synthesized by mechanical alloying(MA) showed excellent performance in the degradation of azo dye DB6. The degradation efficiency of AlFeMnTiCr is approximately 19 times greater than that of the widely used commercial Fe–Si–B amorphous alloy ribbons and more than 100 times greater than that of the widely used commercial zero-valent iron(ZVI) powders. The galvanic-cell effect and the unique crystal structure are responsible for the good degradation performance of the BM HEAs. This study indicates that BM HEAs are attractive, valuable, and promising environmental catalysts for wastewater contaminated by azo dyes.

Effects of Annealing on Microstructure, Mechanical and Electrical Properties of AlCrCuFeMnTi High Entropy Alloy

The multi-component A1CrCuFeMnTi high entropy alloy was prepared using a vacuum arc melting process. Serial annealing processes were subsequently performed at 590 ℃, 750 ℃, 955 ℃ and 1 100 ℃ respectively with a holding time of 4 h at each temperature. The effects of annealing on microstructure, mechanical and electrical properties of as-cast alloy were investigated by using differential thermal analysis （DTA）, X-ray diffraction （XRD）, scanning electron microscopy （SEM） and transmission electron microscopy （TEM）. The experimental results show that two C14 hexagonal structures remain unchanged after annealing the as-cast A1CrCuFeMnTi alloy specimens being heated to 1 100℃. Both annealed and as-cast microstructures show typical cast-dendrite morphology and similar elemental segregation. The hardness of alloys declines as the annealing temperature increases while the strength of as-cast alloy improves obviously by the annealing treatment. The electrical conductivities of annealed and as-cast alloys are influenced by the distribution of interdendrite re^ions which is rich in Cu element.

Electrochemical Synthesis and Magnetic Studies of Ni-Fe-Co-Mn-Bi-Tm High Entropy Alloy Film

Amorphous Ni-Fe-Co-Mn-Bi-Tm high entropy alloy films were firstly prepared by potentiostatic electro- deposition. The results indicate that the six elements can be co-deposited in an organic system of DMF （N,N-dimethylformamide）-CH3CN. The surface of the film is composed of compact and uniform particles with triangular cone shape and a particle size of 100-200 nm. A simple face-centered-cubic structure is identified by XRD patterns after the films were annealed under Ar atmosphere. The annealed alloy film shows soft magnetic properties and the magnetization decreases with Fe content decreasing.

Superior corrosion resistance-dependent laser energy density in(CoCrFeNi)95Nb5 high entropy alloy coating fabricated by laser cladding

(CoCrFeNi)95Nb5 high entropy alloy(HEA)coatings were successfully fabricated on a substrate of Q235 steel by laser cladding technology.These(CoCrFeNi)95Nb5 HEA coatings possess excellent properties,particularly corrosion resistance,which is clearly superior to that of some typical bulk HEA and common engineering alloys.In order to obtain appropriate laser cladding preparation process parameters,the effects of laser energy density on the microstructure,microhardness,and corrosion resistance of(CoCrFeNi)95Nb5 HEA coating were closely studied.Results showed that as the laser energy density increases,precipitation of the Laves phase in(CoCrFeNi)95Nb5 HEA coating gradually decreases,and diffusion of the Fe element in the substrate intensifies,affecting the integrity of the(CoCrFeNi)95Nb5 HEA.This decreases the microhardness of(CoCrFeNi)95Nb5 HEA coatings.Moreover,the relative content of Cr2O3,Cr(OH)3,and Nb2O5 in the surface passive film of the coating decreases with increasing energy density,causing corrosion resistance to decrease.This study demonstrates the controllability of a high-performance HEA coating using laser cladding technology,which has significance for the laser cladding preparation of other CoCrFeNi-system HEA coatings.

Research Progress of Refractory High Entropy Alloys:A Review

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.

Progress in Light-weight High Entropy Alloys

High entropy alloys(HEAs)possess good mechanical properties and a wide range of industrial applications.In this paper,phase formation prediction theory,microstructure,properties and preparation methods of light-weight HEAs(LWHEAs)were reviewed.The problems and challenges faced by LWHEAs development were analyzed.The results showed that many aspects are still weak and require investigation for future advanced alloys,such as clarification of the role of entropy in phase formation and properties of HEAs,improved definition and different generations division of HEAs,close-packed hexagonal(HCP)phase structure prediction and corresponding alloy design and fabrication.Finally,some suggestions were presented in this paper including in-depth research on formation mechanism of multi-component alloy phase and strengthening of large-scale HEA preparation methods via technology compounding and 3D printing technology.Also,there is a need for more research on the in-situ preparation of HEA coatings and films,as well as developing LWHEAs with superior strength and elevated temperature resistance or ultra-low temperature resistance to meet the requirements of future engineering applications.

Microstructural evolution and mechanical properties of FeCoCrNiCu high entropy alloys:a microstructure-based constitutive model and a molecular dynamics simulation study

High entropy alloys(HEAs)attract remarkable attention due to the excellent mechanical performance.However,the origins of their high strength and toughness compared with those of the traditional alloys are still hardly revealed.Here,using a microstructure-based constitutive model and molecular dynamics(MD)simulation,we investigate the unique mechanical behavior and microstructure evolution of FeCoCrNiCu HEAs during the indentation.Due to the interaction between the dislocation and solution,the high dislocation density in FeCoCrNiCu leads to strong work hardening.Plentiful slip systems are stimulated,leading to the good plasticity of FeCoCrNiCu.The plastic deformation of FeCoCrNiCu is basically affected by the motion of dislocation loops.The prismatic dislocation loops inside FeCoCrNiCu are formed by the dislocations with the Burgers vectors of a/6[112]and a/6[112],which interact with each other,and then emit along the<111>slip direction.In addition,the mechanical properties of FeCoCrNiCu HEA can be predicted by constructing the microstructure-based constitutive model,which is identified according to the evolution of the dislocation density and the stress-strain curve.Strong dislocation strengthening and remarkable lattice distortion strengthening occur in the deformation process of FeCoCrNiCu,and improve the strength.Therefore,the origins of high strength and high toughness in FeCoCrNiCu HEAs come from lattice distortion strengthening and the more activable slip systems compared with Cu.These results accelerate the discovery of HEAs with excellent mechanical properties,and provide a valuable reference for the industrial application of HEAs.

Microstructural evaluation and nanohardness of an AlCoCuCrFeNiTi high-entropy alloy

An AlCoCuCrFeNiTi high-entropy alloy(HEA) was prepared by mechanical alloying and sintering to study the effect of Ti addition to the widely studied AlCoCuCrFeNi system. The structural and microstructural characteristics were investigated by X-ray diffraction(XRD), scanning electron microscopy(SEM), and transmission electron microscopy(TEM). The formation of four micrometric phases was detected: a Cu-rich phase with a face-centered cubic(fcc) structure, a body-centered cubic(bcc) solid solution with Cu-rich plate-like precipitates(fcc), an ordered bcc phase, and a tetragonal structure. The XRD patterns corroborate the presence of a mixture of bcc-, fcc-, and tetragonal-structured phases. The Vickers hardness of the alloy under study was more than twice that of the AlCoCuCrFeNi alloy. Nanoindentation tests were performed to evaluate the mechanical response of the individual phases to elucidate the relationship between chemical composition, crystal structure, and mechanical performance of the multiphase microstructure of the AlCoCuCrFeNiTi HEA.

Thermodynamic analysis of the simple microstructure of AlCrFeNiCu high-entropy alloy with multi-principal elements

AlCrFeNiCu high-entropy alloy （THA） was synthesized by the arc melting and casting method. The alloy exhibits simple FCC and BCC solid solution phases rather than intermetallic compounds. The reason is that the Gibbs free energy of mixing of the equimolar A1CrFeNiCu alloy is smaller than that of inter-metallic compounds by calculation according to the Miedema model .

Magnetic entropy change involving martensitic transition in NiMn-based Heusler alloys

Our recent progress on magnetic entropy change（S） involving martensitic transition in both conventional and metamagnetic NiMn-based Heusler alloys is reviewed.For the conventional alloys,where both martensite and austenite exhibit ferromagnetic（FM） behavior but show different magnetic anisotropies,a positive S as large as 4.1 J·kg^-1·K^-1 under a field change of 0-0.9 T was first observed at martensitic transition temperature T M～197 K.Through adjusting the Ni：Mn：Ga ratio to affect valence electron concentration e/a,T M was successfully tuned to room temperature,and a large negative S was observed in a single crystal.The △S attained 18.0 J·kg^-1·K^-1 under a field change of 0-5 T.We also focused on the metamagnetic alloys that show mechanisms different from the conventional ones.It was found that post-annealing in suitable conditions or introducing interstitial H atoms can shift the T M across a wide temperature range while retaining the strong metamagnetic behavior,and hence,retaining large magnetocaloric effect（MCE） and magnetoresistance（MR）.The melt-spun technique can disorder atoms and make the ribbons display a B2 structure,but the metamagnetic behavior,as well as the MCE,becomes weak due to the enhanced saturated magnetization of martensites.We also studied the effect of Fe/Co co-doping in Ni 45（Co1-xFex）5 Mn36.6In13.4 metamagnetic alloys.Introduction of Fe atoms can assist the conversion of the Mn-Mn coupling from antiferromagnetic to ferromagnetic,thus maintaining the strong metamagnetic behavior and large MCE and MR.Furthermore,a small thermal hysteresis but significant magnetic hysteresis was observed around TM in Ni51Mn49-xInx metamagnetic systems,which must be related to different nucleation mechanisms of structural transition under different external perturbations.

Microstructures and Mechanical Properties of AlCrFeNiMo0.5Tix High Entropy Alloys

Effects of Ti addition on the microstructures and mechanical properties of AICrFeNiMo0.5 Tix （x = 0, 0.25, 0.4, 0.5, 0.6, 0.75） high entropy alloys （HEAs） are investigated. All these HEAs of various Ti contents possess dual BCC structures, indicating that Ti addition does not induce the formation of any new phase in these alloys. As Ti addition x varies from 0 to 0.75, the Vickers hardness （HV） of the alloy system increases from 623.7HV to 766.2HV, whereas the compressive yield stress firstly increases and then decreases with increasing x above 0.5. Meanwhile, the compressive ductility of the alloy system decreases with Ti addition. The AlCrFeNiMo0.5 Ti0.6 and AlCrFeNiMo0.5Ti0.75 HEAs become brittle and fracture with very limited plasticity. In the AlCrFeNiMo0.5Tix HEAs, the AlCrFeNiMoo.5 HEA possesses the highest compressive fracture strength of 4027 MPa and the largest compressive plastic strain of 27.9%, while the AlCrFeNiMo0.5 Ti0.5 HEA has the highest compressive yield strength of 2229 MPa and a compressive plastic strain of 10.1%. The combination of high strength and large plasticity of the AICrFeNiMoo.sTix （x = 0, 0.25, 0.4, 0.5） HEAs demonstrates that this alloy system is very promising for engineering applications.