Impact of W alloying on microstructure, mechanical property and corrosion resistance of face-centered cubic high entropy alloys: A review

Face-centered cubic (f.c.c.) high entropy alloys (HEAs) are attracting more and more attention owing to their excellent strength and ductility synergy, irradiation resistance, etc. However, the yield strength of f.c.c. HEAs is generally low, significantly limiting their practical applications. Recently, the alloying of W has been evidenced to be able to remarkably improve the mechanical properties of f.c.c. HEAs and is becoming a hot topic in the community of HEAs. To date, when W is introduced, multiple strengthening mechanisms, including solid-solution strengthening, precipitation strengthening (μphase,σphase, and b.c.c. phase), and grain-refinement strengthening, have been discovered to be activated or enhanced. Apart from mechanical properties, the addition of W improves corrosion resistance as W helps to form a dense WO_(3) film on the alloy surface. Until now, despite the extensive studies in the literature, there is no available review paper focusing on the W doping of the f.c.c. HEAs. In that context, the effects of W doping on f.c.c. HEAs were reviewed in this work from three aspects, i.e., microstructure,mechanical property, and corrosion resistance. We expect this work can advance the application of the W alloying strategy in the f.c.c. HEAs.

电场对Al-Mn-Mg合金的微结构和织构形成的影响

利用透射电子显微镜观察(TEM)和X射线衍射技术(ODFs分析),研究了电场对Al-Mn-Mg合金的回复和再结晶组织演变、再结晶织构的形成和发展的影响。结果表明,电场对再结晶的影响其强度有一个门槛值(3～4 kV/cm),低于此值电场对该合金的再结晶没有明显的影响。强度为4 kV/cm的电场对再结晶形核的影响较大,可抑制Al-Mn-Mg合金的回复和再结晶,促进再结晶立方织构的形成。其主要原因是电场降低了各取向的形变储能,推迟了再结晶进程,抑制储存能小的取向晶核的形成和长大,促进储存能大的S取向晶粒向立方织构择优生长。

Texture Evolutions in Fe-6.5%Si Produced by Rapid Solidification and Chemical Vapor Deposition

Fe-Si ribbons and thin sheets with 6.5%Si content were prepared by means of the single roller rapid solidification and chemical vapor deposition (CVD), respectively. The initial textures of rapidly solidified Fe-6.5%Si ribbons were characteristic of the {100} fiber-type, which became weakened during primary recrystallization in various atmospheres. At the stage of secondary recrystallization, the {100} texture formed in Ar and the {110} texture in hydrogen, while there occurred a texture transformation from the {100} type to the {110} type in vacuum with the increase of annealing temperature. For Fe-6.5%Si sheets prepared by Si deposition in cold-rolled Fe-3%Si matrix sheets, their textures were dominated by the η-fiber (<001>//RD) with the maximum density at the {120}<001> orientations. After homogenization annealing, the η-fiber could evolve into the {130}<001> type or become more concentrated on the {120}<001> orientations, depending on the cold rolling modes of Fe-3%Si matrix sheets.

Manipulation of magnetocaloric and elastocaloric effects in Ni-Mn-In alloys by lattice volume and magnetic variation:Effect of Co and Fe co-doping

The effects of Co and Fe co-doping Ni-Mn-In alloy on the phase stability,lattice parameters,mag-netic properties,and electronic structures are systematically investigated by using the first-principles calculations.Results indicate that Fe atoms replace the excess Mn2 atoms by direct and indirect coex-istence(Fe→Mn 2 and Fe→In→Mn2);Co substitutes the Ni atoms by direct substitution(Co→Ni)for the Ni-Mn-In alloy.The austenites all exhibit the ferromagnetic(FM)state for the studied composi-tions.The NM martensites are in the ferrimagnetic(FIM-1)state for the Ni_(2)Mn_(1.5)In_(0.5),Ni_(2)Mn_(1.25)In_(0.5)Fe 0.25,Ni_(1.75)Mn_(1.5)In_(0.5)Co_(0.25),and Ni_(1.75)Mn_(1.25)In_(0.5)Co_(0.25)Fe 0.25 alloys,while the other compositions are in the FM state.The phase stability of austenite and martensite decreases with increasing Co and Fe co-doping.A magnetic-structural coupling transition occurs at x<0.25 and y<0.25.The Ni_(1.91)Mn_(1.5)In_(0.5)Co_(0.08)and Ni_(1.91)Mn_(1.42)In_(0.5)Co_(0.08)Fe_(0.08)alloys exhibit an A→6M→NM transformation,accompanied by a magnetic transition.When Co and Fe are co-doped,the hybridization strength between Co and Fe is greater than that between Co/Fe and Mn.The enhancement of magnetocaloric and elastocaloric effects is favored by larger magnetization difference(△M)and lattice volume change(△V/V_(0)).Based on the calculated phase stability,magneto-structure coupling,△V/V 0 and c/a ratio,one can predict that the Ni_(2)-x Mn_(1.5)-y In_(0.5)Co x Fe y alloy with Co content 0≤x≤0.25 and Fe content 0≤y≤0.05 is predicted to have good magneto-controlled functional behavior.

A first-principle assisted framework for designing high elastocaloric Ni-Mn-based magnetic shape memory alloy

A large adiabatic temperature change(△T_(ad))is a prerequisite for the application of elastocaloric refriger-ation.Theoretically,a large volume change ratio(△V/V_(0))during martensitic transformation is favorable to enhance△T_(ad).However,the design or prediction of△V/V_(0)in experiments is a complex task because the structure of martensite changes simultaneously when the lattice parameter of austenite is tuned by mod-ifying chemical composition.So far,the solid strategy to tailor△V/V_(0)is still urgently desirable.In this work,a first-principles-based method was proposed to estimate△V/V_(0)for Ni-Mn-based alloys.With this method,the substitution of Ga for In is found to be an effective method to increase the value of△V/V_(0)for Ni-Mn-In alloys.Combined with the strategies of reducing the negative contribution of magnetic en-tropy change(via the substitution of Cu for Mn)and introducing strong crystallographic texture(through directional solidification),an outstanding elastocaloric prototype alloy of Ni_(50)(Mn_(28.5)Cu_(4.5))(In_(14)Ga_(3))was fabricated experimentally.At room temperature,a huge△T_(ad)of-19 K and a large specific adiabatic temperature change of 67.8 K/GPa are obtained.The proposed first-principle-assisted framework opens up the possibility of efficiently tailoring△V/V_(0)to promote the design of advanced elastocaloric refrigerants.

Phase Stability,Magnetic Properties,and Martensitic Transformation of Ni_(2−x)Mn_(1+x+y)Sn_(1−y) Heusler Alloy with Excess Mn by First‑Principles Calculations

The phase stability,magnetic properties,martensitic transformation,and electronic properties of the Ni_(2−x)Mn_(1+x+y)Sn_(1−y) system with excess Mn have been systematically investigated by the first-principles calculations.Results indicate that the excess Mn atoms will directly occupy the sublattices of Ni(MnNi)or Sn(MnSn).The formation energy(Ef)of the austenite has a relationship with the Mn content:Ef=135.27(1+x+y)−293.01,that is,the phase stability of the austenite decreases gradually with the increase in Mn content.According to the results of the formation energy of austenite,there is an antiparallel arrangement of the magnetic moment between the excess and normal Mn atoms in the Ni_(2−x)Mn_(1+x+y)Sn_(1−y)(x=0 or y=0)system,while the magnetic moment direction of the normal Mn atoms arranges antiparallel to that of MnNi atoms and parallel to that of MnSn atoms in the Ni_(2−x)Mn_(1+x+y)Sn_(1−y)(x,y≠0)system.The martensitic transformation occurs in some Ni_(2−x)Mn_(1+x+y)Sn_(1−y)(x,y≠0)alloys with large magnetic moments of ferrimagnetic austenite.Besides,the valence electrons tend to distribute around the Ni or MnNi atoms and mainly bond with the normal Mn atoms.The results of this work can lay a theoretical foundation for further development of the Ni_(2−x)Mn_(1+x+y)Sn_(1−y) system as the potential ferromagnetic shape memory alloys.

On the nature of a peculiar initial yield behavior in metastable β titanium alloy Ti-5Al-5Mo-5V-3Cr-0.5Fe with different initial microstructures

The compressive yielding phenomenon of titanium alloys is not as focused and sufficiently ascertain as the tensile yielding phenomenon.In the present work,the peculiar compressive yielding behavior and the different dynamic responses of three different initial microstructures(singleβ,clavateβand lamellarβ)were investigated in an attractive metastableβtitanium alloy Ti-5553 using electron microscopes/crystallographic calculation/crystal plastic finite element simulation.Results reveal that the distinct compressive yielding behavior,steep peaks of sudden drop in the initial stage(very small true strain 0.03)of stress loading have appeared in the compression stress-strain curves except for the lamellarβinitial microstructure.Dislocation slip is the essential mechanism of the initial yielding behavior.Interlaced multiple-slip bands formed in the singleβinitial microstructure during the warm deformation process.A small quantity of single slip bands was observed in the deformed clavateβinitial microstructure.The abundant varied nano/ultrafineβsprecipitates were nucleated dynamically and dispersedly in all the three deformed initial microstructures.The multiple-slip bands formation and substantial nanoscaleβsresult in the highest peak of flow stress for singleβinitial microstructure.The compressive slip bands are formed early in the elastic–plastic deformation stage.As the increasing strain,the sample showed a significant compressive bulge,or eventually forming a strong adiabatic shear band or crack.These results are expected to provide a reference for the study of deformation behavior and mechanical properties of metastableβtitanium alloys.

具有亚微米晶精细组织Mg-Zn合金薄片的制备（英文）

具有超细晶结构的金属材料具有优异的力学性能,然而,通过简单的工艺方法制备超细晶结构的块体或者片体金属材料仍然是个难题.镁合金室温变形的各向异性,使制备超细晶结构的镁合金片体材料更是难上加难.目前,某些精密的电子电器领域、大功率镁阳极电池领域以及航空航天领域亟需的镁合金片材大多依靠进口.针对这种现状,本文提供了一个简便的工艺解决方案.首先选取Mg-Zn合金,进行热轧制以及退火.然后,在室温环境下进行快速轧制,通过此工艺成功地制备了具有超细晶组织结构的完好镁合金薄片.本文还对Mg–Zn合金在快速冷轧过程中涉及的材料学问题进行了研究,认为在冷轧过程中多晶面位错滑移的启动是材料获得完好室温冷轧性的关键所在.

Excellent mechanical properties and large magnetocaloric effect of spark plasma sintered Ni-Mn-In-Co alloy

The Ni43.75Mn37.5In12.5Co6.25 alloy was obtained by using the spark plasma sintering(SPS)technique.The martensitic transformation,magnetic and mechanical properties of the SPS alloy were investigated.Key findings demonstrate that the martensitic transformation temperature of this alloy is about 10 K lower than that of the as-cast one.Both SPS and as-cast alloys show a 7 layered modulated martensite(7M)at room temperature.The compressive fracture strength and strain of the SPS alloy increase by 176.92%and 33.33%compared with the as-cast alloy,achieving 1440 MPa and 14%,respectively.The maximum magnetic entropy change Smis 17.1 J kg^(-1)K^(-1)for the SPS alloy at the magnetic field of 5 T.

Impact of B alloying on ductility and phase transition in the Ni–Mn-based magnetic shape memory alloys:Insights from first-principles calculation

Brittleness is a bottleneck hindering the applications of fruitful functional properties of Ni–Mn-based multiferroic alloys.Recently,experimental studies on B alloying shed new light on this issue.However,the knowledge related to B alloying is limited until now.More importantly,the mechanism of the improved ductility,which is intrinsically related to the chemical bond that is difficult to reveal by routine experiments,is still unclear.In this context,by first-principles calculations,the impact and the correlated mechanism of B alloying were systemically studied by investigating four alloying systems,i.e.,(Ni_(2-x)B_(x))MnGa,Ni_(2)(Mn_(1-x)B_(x))Ga,Ni_(2)Mn(Ga_(1-x)B_(x))and(Ni_(2)MnGa)_(1-x)B_(x).Results show that B prefers the direct occupation manner when it replaces Ni,Mn and Ga.For interstitial doping,B tends to locate at octahedral rather than tetrahedral interstice.Calculations show that the replacement of B for Ga can effectively improve(reduce)the inherent ductility(inherent strength)due to the weaker covalent strength of Ni(Mn)–B compared with Ni(Mn)–Ga.In contrast,B staying at octahedral interstice will lead to the formation of new chemical bonds between Ni(Mn)and B,bringing about a significantly improved strength and a greatly reduced ductility.Upon the substitutions for Ni and Mn,they affect both the inherent ductility and strength insignificantly.For phase transition,the replacement of B for Ga tends to destabilize the austenite,which can be understood in the picture of the band Jahn–Teller effect.Besides,the substitution for Ga would not lead to an obvious reduction of magnetization.

Probing martensitic transformation,kinetics,elastic and magnetic properties of Ni2-xMn1.5In0.5Cox alloys

The martensitic transformation,kinetics,elastic and magnetic properties of the Ni2-xMn1.5In0.5Cox(x=0-0.33)ferromagnetic shape memory alloys were investigated experimentally and theoretically by first-principles calculations.First-principles calculations show that Co directly occupies the site of Ni sublattice,and Co atoms prefer to distribute evenly in the structure.The optimized lattice constants are consistent with the experimental results.The martensitic transformation paths are as follows:PA↔FA↔6MFIM↔NMFIM when 0≤x<0.25;PA↔FA↔6MFM↔NMFIM with 0.25≤x<0.3 and PA↔FA↔NMFM with 0.3≤x≤0.33 for Ni2-xMn1.5In0.5Cox(x=0-0.33)alloys.The fundamental reasons for the decrease of TM with increasing Co content are explained from the aspects of first-principles calculations and martensitic transformation kinetics.The component interval of the magnetostructural coupling is determined as 0≤x≤0.25 by first-principles calculations.Furthermore,the origin of the demagnetization effect during martensitic transformation is attributed to the shortening of the nearest neighboring distances for Ni-Ni(Co)and Mn-Mn.Combining the theoretical calculations with experimental results,it is verified that the TM of the Co6 alloy is near room temperature and its magnetization differenceM is 94.6 emu/g.Therefore,magnetic materials with high performance can be obtained,which may be useful for new magnetic applications.

Observation of magnetic domain evolution in constrained epitaxial Ni–Mn–Ga thin films on MgO(0 0 1) substrate

Epitaxial Ni–Mn–Ga thin films have promising application potential in micro-electro-mechanical sensing and actuation systems. To date, large abrupt magnetization changes have been observed in some epitaxial Ni–Mn–Ga thin films, but their origin-either from magnetically induced martensite variant reorientation(MIR) or magnetic domain evolution-has been discussed controversially. In the present work, we investigated the evolutions of the magnetic domain and microstructure of a typical epitaxial Ni–Mn–Ga thin film through wide-field magneto-optical Kerr-microscopy. It is demonstrated that the abrupt magnetization changes in the hysteresis loops should be attributed to the magnetic domain evolution instead of the MIR.

Revealing essence of magnetostructural coupling of Ni-Co-Mn-Ti alloys by first-principles calculations and experimental verification

In this work,the effects of Co doping on the magnetostructural coupling transformation of Ni_(50-x)Co_(x)Mn_(50-y)Ti_(y)(x=0-15,y=12.5-15)Heusler alloys were systematically investigated through the first-princi-ples calculations and experimental verification.The cal-culation result indicates that the doped Co atoms prefer to occupy the Ni sublattice.The Co atoms tend to flock together in terms of the lowest energy principle.Since the formation energy of the austenite is higher than that of the martensite,the alloys will undergo martensitic transfor-mation for the Ni_(50-x)Co_(x)Mn_(37.5)Ti_(12.5)alloys(x=0-12.5).The magnetostructural coupling point of Ni_(50-x)Co_(x)Mn_(37.5)Ti_(12.5)alloys is predicted in the vicinity of x=11-12.Based on the computational composition Ni_(37.5)Co_(12.5)Mn_(37.5)Ti_(12.5),the Ni_(36)Co_(14)Mn_(36)Ti_(14)alloy with magnetostructural coupling near room temperature was experimentally developed by simultaneously increasing the Ti and Co contents.The largest magnetization change(ΔM)and magnetic entropy changes(ΔS_(m))obtained under magnetic field of 5 T for the martensitic transformation in the Ni_(36)Co_(14)Mn_(36)Ti_(14) alloy are about 87.6 A·m^(2)·kg^(-1)and 21 J·kg^(-1)·K^(-1),respectively.The fracture strength and strain for non-textured polycrystalline Ni_(36)Co_(14)Mn_(36)Ti_(14)alloy reach 953 MPa and 12.3%,respectively.The results show that the alloy not only possesses a large magne-tocaloric effect but also has excellent mechanical proper-ties.In addition,the 6 M modulated martensite is evidenced in the Ni-Co-Mn-Ti alloys via transmission electron microscopy technique.

Machine-learning-assisted discovery of empirical rule for inherent brittleness of full Heusler alloys

Brittleness is a critical issue hindering the potential application of the X_2YZ-type full Heusler alloys in several fields of state-of-the-art technologies.To realize optimization of brittleness or design a ductile Heuser alloy,it is greatly urgent to identify the key materials factors deciding brittleness and establish an empirical rule to effectively evaluate ductility.For this purpose,by using a machine learning and human analysis cooperation approach,the brittleness of the X_2YZ-type Heusler alloys was systematically studied.Results showed that the ductility is majorly decided by 6 key materials factors in the studied alloys.Using these 6 factors,a machine learning model to predict the Pugh's ratio k was constructed.Further analyses showed that the crystal structure of the X component could be the most critical factor deciding the ductility.The X component has the face-centered cubic(FCC)structure for most of the alloys with superior ductility.To effectively estimate ductility and guide materials design,an empirical formula of k=mEWF_(m+n)G_(m)+k_(0)was established based on the known information of electron work function(EWF)and shear modulus(G)of the X,Y,and Z elements where the subscript m represents the weight-average value.The coefficients of m(negative)and n(positive)were confirmed to have opposite signs,which can be explained based on the relations between the ductility and the deformation/fracture resistance.This work is expected to deepen the understanding in ductility and promote the design of advanced ductile Heusler alloys.

Revealing the role of site occupation in phase stability,magnetic and electronic properties of Ni-Mn-In alloys by ab initio approach

The effects of site occupation on the phase stability,martensitic transformation,and the magnetic and electronic properties of a full series of Ni-Mn-In alloys are theoretically studied by using the ab initio calculations.Results indicate that the excess atoms of the rich component directly take the sublattices of the deficient components of the Ni2Mn_(1+x)In_(1-x),Ni2-xMn_(1+x)In,and Ni_(2+x)Mn_(1-x)In alloys.Nevertheless,the mixed and indirect site occupations may coexist in the Ni_(2+x)Mn In_(1-x)system.The relevant magnetic configurations of the austenite for the four alloy systems have also been determined.The results show that,except for the austenite in the Ni2-xMn_(1+x)In alloys,which tend to be ferrimagnetic,the other alloys all present ferromagnetic austenite.Thus,the site occupation and associated magnetic states are the crucial influencing factors of the phase stability,martensitic transformation,and the total magnetic moment.The electronic structure of the austenite phase also shows that the covalent bonding plays an important role in the phase stability.The key finding of this work is both Ni2Mn_(1+x)In_(1-x)and Ni_(2+x)Mn In_(1-x)alloys serve as the potential shape memory alloys.

First-Principles Investigation on Phase Stability,Elastic and Magnetic Properties of Boron Doping in Ni-Mn-Ti Alloy

The all-d-metal Ni-Mn-Ti Heusler alloy has giant elastocaloric eff ect and excellent mechanical properties,which is diff erent from the conventional Ni-Mn-based Heusler alloys.In this work,the preferred site occupation,phase stability,martensitic transformation,magnetic properties,and electronic structure of the B-doped Ni_(2)Mn_(1.5)Ti_(0.5)alloys are systematically investigated by the fi rst-principles calculations.The results show that B atoms preferentially occupy the octahedral interstitial.The doped B atoms tend to exist in the(Ni_(2)Mn_(1.5)Ti_(0.5))_(1-x)B_(x)(x=0.03,0.06,0.09)alloy in the form of aggregation distribution,and the martensitic transformation temperature decreases with the increase in the B content.For octahedral interstitial doping,the toughness and plasticity of the(Ni_(2)Mn_(1.5)Ti_(0.5))_(1-x)B_(x) alloys decrease,but the strength and rigidity are greatly enhanced.This is because a small part of the d-d hybridization in ternary Ni-Mn-Ti alloy is replaced by the p-d hybridization in Ni-Mn-Ti-B alloy.

Composition-Dependent of 6 M Martensite Structure and Magnetism in Cu-Alloyed Ni-Mn-In-Co by First-Principles Calculations

The composition dependence of the crystal structure and magnetism of the 6 M martensite for the Cu-doped Ni_(43.75)Mn_(37.5)In_(12.5)Co_(6.25) alloy at different site occupations(Cu substitution for Ni, Mn, In, and Co, respectively) is investigated in detail with the first-principles calculations. Results show that the austenite(A) phase exhibits a ferromagnetic(FM) state in all occupation manners, the 6 M martensite possesses an FM state except for the case of Cu substitution at the normal Mn(Mn1) site, and the non-modulated(NM) martensite displays a ferrimagnetic(FIM) state apart from the Cu substitution at the Ni, Mn1, or In sites. The Cu atom destabilizes the A, 6 M, and NM phases regardless of the occupation manner. The one-step martensitic transformation from the A to NM phase occurs in the case of Cu substituting for Mn1, excess Mn(Mn2), or Co;for Cu substituting Ni, a martensitic transformation including 6 M martensite happens, i.e., A → 6 M → NM;however, the martensitic transformation disappears when Cu replaces In site. From the equilibrium lattice constants, it can be speculated that the substitution of Cu for Ni can effectively reduce the thermal hysteresis( ΔT_(Hys)). The magnetic properties are found to be greatly reduced by the substitution of the non-magnetic element Cu for the ferromagnetic Mn atom, whereas the effect is fewer in the remaining cases. It is predicted that the alloy has more favorable properties when Cu replaces Ni. The present results can lay a theoretical foundation for further development of multielement magnetic shape memory alloys.

Investigation of martensitic transformation behavior in Ni-Mn-In Heusler alloy from a first-principles study

Composition dependence of martensitic transformations as well as the magnetic properties for the Ni_2 Mn_(1+x)In_(1-x)(0.25≤x≤0.58)alloys were investigated by using the first-principles calculations.Key results demonstrate that the stability of parent austenite(A)decreases gradually with increasing Mn content whilst it is opposite for the martensitic phase.This causes the total energy difference between the austenite and martensite phases increscent with increasing Mn contents.When x=0.33,the martensite transformation during cooling is PA→FA→NM.When x≥0.42,an intermartensitic transformation occurs from modulated 6 M martensite to non-modulated(NM)martensite with the martensite transformation sequence of PA→FA→6 M→NM.The martensitic transformation from austenite to martensite accompanies the transition from ferromagnetic to ferrimagnetic state.This is a typical magneto-structural coupling transformation.The analysis of the density of states demonstrates that the Ni 3 d state plays an important role in the phase stability.