Designing Rules of Laser-Clad High-Entropy Alloy Coatings with Simple Solid Solution Phases

The criteria of process parameters(μ≤4),atomic size difference(ε≤5.8,δ≤11 and α≤2),thermodynamic(-14.5 ≤△H_(mix)≤6.5 and Ω≥ 1.8) in the prediction of the phase stability for laser-clad high-entropy alloy coatings are studied in detail.Besides,the criteria of valence electron concentration(VEC) applied to distinguish the stability of different solid solution phases are as follows:VEC7.65 for simple BCC,VEC≥7.65 for simple face-centered cubic(FCC),7.14 VEC 7.78 for dual-phase BCC and FCC.Among them, μ and ε proposed firstly separate the phase stability of laserclad high-entropy alloy coatings quite precisely.The other modified criteria(δ,α,△H_(mix),Ω,VEC) are proved to be different from those of the high-entropy alloys synthesized by the traditional casting and smelting processes.     

激光熔覆AlxNbMn2FeMoTi0.5高熵合金涂层的组织与性能

使用激光熔覆技术在Q235钢基体上制备Al_xNbMn₂FeMoTi_0.5高熵合金涂层,期望借此提高干切削技术适用刀具表层的硬度和耐磨性。经过初步筛选之后,主要研究了Al_xNbMn₂FeMoTi_0.5(x=1、1.5、2)高熵合金涂层体系,并采用XRD和3D激光扫描成像等手段分析了不同Al含量的Al_xNbMn₂FeMoTi_0.5合金涂层的晶相结构、显微组织和具体元素分布。结果显示,对于Al_xNbMn₂FeMoTi_0.5高熵合金涂层,随着Al含量的增加,涂层的相结构由单一的BCC相逐渐转变为双相BCC结构,晶粒逐渐细化。当x=2时,Al_xNbMn₂FeMoTi_0.5高熵合金涂层硬度最高,平均为1089.6 HV0.3,大约为基材的5倍,且其具有最优的耐磨损性能。x=1.5时,Al_xNbMn₂FeMoTi_0.5高熵合金涂层的自腐蚀电位最高,自腐蚀电流密度最小,耐腐蚀性最好。     

基于第一性原理的CrCuFeNiTi高熵合金涂层的相及稳定性分析

采用等离子弧在45钢基体上熔覆了CrCuFeNiTi高熵合金涂层,经X射线衍射分析涂层中的物相有BCC、FCC和Fe₂Ti相,并对BCC、FCC和Fe₂Ti相进行了成分测试,采用CASTEP中的虚拟晶体近似方法建立了BCC、FCC和Fe₂Ti相的晶体结构模型,基于第一性原理计算了涂层中BCC、FCC和Fe₂Ti相的晶格常数,并与涂层中BCC、FCC和Fe₂Ti相的X射线测试结果进行了比较,另外计算了BCC和FCC相的弹性常数C_ij、体积模量B、剪切模量G、杨氏模量E和泊松比ν。结果表明,涂层中BCC和FCC相以及Fe₂Ti的晶格常数计算值与试验值的误差为0.43%~3.05%,BCC、FCC和Fe₂Ti相的生成热均为负值且BCC和FCC相的弹性常数C₁₁、C₁₂和C₄₄满足立方结构高熵合金的力学稳定性限制条件,可知BCC、FCC和Fe₂Ti相是稳定的。另外由C₁₂-C₄₄>0,G/B<0.57,ν>0.26可知BCC和FCC相以金属键结合且呈现韧性的特征。     

(FeCoNiCr)100-xMnx高熵合金在NaCl和NaOH溶液中的抗腐蚀性能

研究了放电等离子烧结(FeCoNiCr)_100-xMn_x(x=4,8,12,20)高熵合金的组织结构及在NaCl和NaOH溶液中的耐腐蚀性能。结果表明,(FeCoNiCr)_100-xMn_x合金主要由FCC单相组织和少量BCC相组成。(FeCoNiCr)₈₈Mn₁₂合金在3.5wt%NaCl 溶液中具有最好的耐腐蚀性能。Mn的添加使合金在1 mol NaOH 溶液中耐腐蚀性增强。退火对合金在1 mol NaOH 溶液中抗腐蚀性能影响不大。(FeCoNiCr)_100-xMn_x合金在3.5wt%NaCl溶液和1 mol NaOH溶液中的抗腐蚀性能均优于304S不锈钢。     

Effects of Ti and Cu on the Microstructure Evolution of AlCoCrFeNi High-Entropy Alloy During Heat Treatment

The microstructure evolution of AlCoCrFeNiTi_(0.5) alloy and AlCoCrFeNiCu alloy during heat treatment was systematically studied,to reveal the influence rules of chemical activity of adding element on the microstructure evolution of AlCoCrFeNi system.Owing to the negative mixing enthalpy with the constituent elements,Ti element was mainly dissolved in the Al-Nirich phases,and aggravated the lattice distortion of B2 phase.The structure variation of BCC phase by adding Ti inhibited the formation of FCC phase and enhanced the precipitation of σ phase during heat treatment.Owing to the positive mixing enthalpy with constituent elements,Cu element tended to be repelled to the ID region and formed metastable Cu-rich FCC1 phase which would transform into Cu-Al-Ni-rich FCC2 phase with increasing temperature.The addition of Cu inhibited the precipitation of σ phase during heat treatment.Adding Ti maintained the stable dendritic morphology,while adding Cu reduced the thermal stability of microstructure.Two dramatic morphology changes occurred at 1000~℃ and 1100~℃ in the AlCoCrFeNiCu alloy.The lattice distortion of phase in AlCoCrFeNiTi_(0.5) alloy was aggravated with increasing temperature up to 800~℃,then relaxed together with the dissolution of σ phase when temperature was above 900~℃.The variation in lattice distortion dominated the hardness of AlCoCrFeNiTi_(0.5) alloy.With increasing heating temperature,the increasing volume fraction of region with FCC structure due to the transformation between FCC phases,and the pronounced coarsening in microstructure due to the reduced thermal stability,resulted in the mainly decreasing trend in the hardness of AlCoCrFeNiCu alloy.     

Addition Al and/or Ti Induced Modifi cations of Microstructures,Mechanical Properties,and Corrosion Properties in CoCrFeNi High-Entropy Alloy Coatings

The purpose of this work is to study the influences of Al and/or Ti addition on the microstructures, mechanical properties and corrosion properties of CoCrFeNi-(Al, Ti) high entropy alloy(HEA) coatings. Three coatings, AlCoCrFeNi(Ⅰ), CoCrFeNiTi_(0.5)(Ⅱ) and AlCoCrFeNiTi_(0.5)(Ⅲ), were fabricated by laser cladding successfully. The AlCoCrFeNi(Ⅰ) coating exhibited a simple body-centered cubic(BCC) solid-solution structure, whereas the CoCrFeNiTi_(0.5)(Ⅱ) alloy exhibited a face-centered cubic(FCC) solid-solution and a small amount of Laves phase. The BCC phases in AlCoCrFeNiTi _(0.5)(Ⅲ) coating were characterized as Fe–Cr rich disordered BCC phases(A2) and Al-Ni–Ti-rich ordered BCC phases(L2_1) separately. The AlCoCrFeNiTi_(0.5)(Ⅲ) coating with dual-phase BCC structure showed the optimal performance of both mechanical and corrosion properties, which was superior to BCC-based AlCoCrFeNi(Ⅰ) and FCC-based CoCrFeNiTi_(0.5)(Ⅱ) coatings. Nanoindentation tests and quantitative investigations on the strengthening mechanisms of AlCoCrFeNiTi_(0.5)(Ⅲ) coating were conducted, suggesting that the precipitation strengthening is the dominant strengthening mechanism. In short, the addition of moderate amount of Al and Ti in CoCrFeNi HEA shows potential for the development of a high strength and corrosion-resistant coating.     

Effects of V Addition on Microstructural Evolution and Mechanical Properties of AlCrFe2Ni2 High-Entropy Alloys

The effects of vanadium addition on the microstructural evolution and mechanical properties of AlCrFe₂Ni₂ high-entropy alloy (HEA) were investigated. The results showed that the AlCrFe₂Ni₂V_0.2 HEA was composed of FCC phase, disordered BCC phase, and ordered BCC (B2) phase. With the increase in vanadium content, the formation of FCC phase was inhibited, and a transition from FCC phase to BCC phase occurred. The FCC phase disappeared completely when the value of x exceeds 0.4 in AlCrFe₂Ni₂V_x HEAs. Besides, the amplitude-modulated microstructure morphology transformed from a B2 phase matrix with dispersed BCC nano-phase into an alternating interconnected B2 and BCC phases. Vanadium element has the function of stabilizing BCC phase and B2 phase in AlCrFe₂Ni₂V_x alloys. The hardness of AlCrFe₂Ni₂V_x alloys increased from HV 332.4 to HV 590.7, while the yield strength increased from 765 to 1744.6 MPa with increasing vanadium content, which was mainly due to the decreasing content of FCC phase and the solid solution strengthening of vanadium element. At the same time, the compression ratio of the alloys decreased with the disappearance of the FCC phase. Among the alloys, the AlCrFe₂Ni₂V_0.2 alloy possessed the most excellent comprehensive mechanical properties with yield strength, fracture strength, and compressive ratio 1231.1, 2861.9 MPa, and 44.5%, respectively.     

第一性原理计算Mo含量及压力对CrZrNbTiMox难熔高熵合金性能的影响

利用基于密度泛函理论的第一性原理方法研究Mo含量和压力对CrZrNbTiMo_x难熔高熵合金相结构、弹性常数和弹性模量的影响。计算了CrZrNbTiMo_x难熔高熵合金的混合焓(ΔH_mix)、混合熵(ΔS_mix)、原子半径差(δ)、价电子浓度(VEC)以及参数Ω。结果表明,CrZrNbTiMo_x难熔高熵合金主要以单一的BCC无序固溶体结构为主。随着Mo含量的增加,合金的晶格畸变不断减小,但力学性能稳定且始终以金属键结合。Mo的添加对合金的抗体积变形能力提升较大、对抗切应变能力及刚度影响较小,合金表现为韧性材料。在0～25 GPa压力作用下,CrZrNbTiMo_0.6合金表现出优异的相稳定性和力学稳定性,体弹性模量(B)增幅较小,剪切弹性模量(G)、杨氏模量(E)变化较小;泊松比μ及G/B计算结果表明合金为韧性材料。     

Microstructure and Mechanical Behavior of CrFeNi2V0.sWx (x=0, 0.25)High-Entropy Alloys

CrFeNi₂V_0.5W_x (x = 0, 0.25) alloys based on these parameters of mixing enthalpy (ΔH_mix), mixing entropy (ΔS_mix), atomic radius difference (δ), valance electron concentration, and electronegativity difference(Δχ) were designed and prepared. The microstructure and room-temperature mechanical behavior of both alloys were investigated. Compressive test results showed that the CrFeNi₂V_0.5W_0.25 alloy had higher yield strength than that of the W-free CrFeNi₂V_0.5 alloy, although they all exhibited quite larger compressive plasticity (ε > 70%). Compression fracture surface of CrFeNi₂V_0.5W_0.25 alloy revealed a ductile fracture in the face-centered cubic (FCC) phase and a brittle-like fracture in the σ phase. Moreover, tensile test results indicated that the CrFeNi₂V_0.5W_0.25 alloy exhibited excellent mechanical property with an ultimate tensile strength of 640 MPa and a high tensile elongation of 15.7%. The tensile deformation mode of the FCC phase in the CrFeNi₂V_0.5W_0.25 alloy is dominated by planar glide, relating to dislocation configurations, high-density dislocations, and dislocation wall. Therefore, dislocation slip plays a significant role in tensile deformation of CrFeNi₂V_0.5W_0.25 high-entropy alloy. The higher strength of CrFeNi₂V_0.5W_0.25 alloy is predominantly due to the solid solution strengthening of W element and σ phase precipitation strengthening. Combination of the higher tensile strength and plasticity suggests that the CrFeNi₂V_0.5W_0.25 alloy can be a promising aerospace material.     

Cr含量对CrxMoNbTiZr系高熵合金组织与性能的影响

采用真空电弧熔炼的方法制备了Cr_xMoNbTiZr系高熵合金(x=0, 0.5, 1, 1.5)。利用X射线衍射仪(XRD)、扫描电镜(SEM)、能谱仪(EDS)、显微硬度计以及电化学工作站研究了Cr含量对该高熵合金结构、组织、硬度和耐蚀性能的影响。结果表明,Cr的添加使合金由单相BCC结构转变为富Zr相与富Mo-Nb相的双相BCC结构,随着Cr含量增加,在富Zr相中还有富Cr的Laves相析出;Cr_1.5MoNbTiZr合金具有最高硬度765.53 HV,这是由于第二相析出强化、固溶强化与高熵合金晶格畸变的共同作用;Cr的加入增加了Cr_xMoNbTiZr系高熵合金在质量分数为3.5%NaCl溶液中发生腐蚀倾向,但降低了该系高熵合金的腐蚀速率,同时发现Cr的添加存在一个临界值来保证合金的抗点蚀能力,超过这个临界值合金就会更容易发生点蚀现象。     

CrFeCoNiB0.05Tix高熵合金的显微组织和力学性能

采用机械合金化和放电等离子烧结工艺制备了CrFeCoNiB_0.05Ti_x(x=0.2、0.4、0.6、0.8、1.0)高熵合金材料,通过X射线衍射分析、扫描电镜观察和能谱分析以及维氏硬度测试和压缩强度测试等,研究了Ti含量对高熵合金微观组织和力学性能的影响。结果表明,CrFeCoNiB_0.05Ti_x(x=0.2、0.4、0.6、0.8、1.0)高熵合金由FCC、BCC和α相组成。当x=1.0时,合金由BCC结构转向HCP结构并析出新相Laves相,其具有最高硬度416.54 HV0.2。当x=0.8时,合金达到最大抗压强度586.3 MPa。     

Novel (CoFe_2NiV_(0.5)Mo_(0.2))_(100-x)Nb_x Eutectic High-Entropy Alloys with Excellent Combination of Mechanical and Corrosion Properties

The emergence of eutectic high-entropy alloys(EHEAs) offers new insights into the design of next generation structural alloys,which is due to their stable dual-phase microstructure and outstanding mechanical properties from room to elevated temperatures.In this work,a series of(CoFe_2 NiV_(0.5)Mo_(0.2))_(100-x)Nb_x(0≤x ≤12) EHEAs were designed and prepared via vacuum arc-melting.Typical eutectic microstructure composing lamellar face-centered cubic solid solution phase and C14 Laves phase appears in the as-cast EHEA when x=9.The microstructure turns to hypoeutectic or hypereutectic when x is below or beyond that critical value accordingly.The volume fraction of the hard Laves phase is proportional to the Nb addition,leading to the strength increment yet at the expense of ductility at room temperature.In particular,the EHEA having4 at% Nb shows a compressive strength of 2.1 GPa with an elongation to fracture of 45%,while EHEAs containing 9 and10 at% Nb exhibit ultrahigh yield strengths of over 1.4 GPa.The effect of Nb addition on the corrosion resistance of this Crfree EHEA system was also studied.The EHEA containing 9 at% Nb has the best anti-corrosion performance in the 3.5 wt%NaCl solution at 298±1 K,indicating a good combination of mechanical and corrosion properties.     

Soft-Magnetic High-Entropy AlCoFeMnNi Alloys with Dual-Phase Microstructures Induced by Annealing

The simultaneous enhancement of magnetic and mechanical properties is desirable but challenging for soft-magnetic materials.A fabrication strategy to meet this requirement is therefore in high demand.Herein,bulk equiatomic dual-phase AlCoFeMnNi high-entropy alloys were fabricated via a magnetic levitation induction melting and casting process followed by annealing at 700-1000℃,and their microstructures as well as mechanical and magnetic properties were investigated.The as-cast alloy possessed a single metastable B2-ordered solid solution that decomposed upon annealing into a dual-phase structure comprising an Al-and Ni-rich body-centered cubic(BCC) matrix and Fe-and Mn-rich face-centered cubic(FCC)precipitates both in the grain interior and along the grain boundaries.The magnetic and mechanical properties were closely related to the relative volume fraction of FCC in the alloy.The FCC volume fraction could be increased by increasing the annealing temperature,thereby offering tunable properties.The optimal annealing temperature for balanced magnetic and mechanical properties was found to be 800℃.The alloy annealed at this temperature had an average BCC grain size of 12±3μm and FCC volume fraction of 41±4%.Correspondingly,the s aturation magnetization and coercivity reached 82.57 Am~2/kg and 433 A/m,respectively.The compressive yield strength and fracture strength were 1022 and 2539 MPa,respectively,and the plasticity was 33%.Owing to its adjustable microstructure and properties,the AlCoFeMnNi alloy has potential for use as a multi-functional soft-magnetic material.     

Effect of Nb Content on Microstructure and Mechanical Properties of Mo0.25V0.25Ti1.5Zr0.5Nbx High-Entropy Alloys

High-entropy alloys (HEAs) have significant application prospects as promising candidate materials for nuclear industry due to their excellent mechanical properties, corrosion resistance and irradiation resistance. In this work, the Mo_0.25V_0.25Ti_1.5Zr_0.5Nb_x(x=0, 0.25, 0.5, 0.75 and 1.0) HEAs were designed and fabricated. The alloys were prepared by vacuum arc melting, and all the ingots were annealed at 1200°C for 24 h. The microstructures, ...     

Tix(AlNbZr)100-x系多主元合金力学性能的第一性原理研究

通过对合金的固溶体参数以及相比例图进行计算,研究了Ti_x(AlNbZr)_100-x系多主元合金的固溶体相形成规律,运用基于密度泛函理论的第一性原理方法研究了Ti含量变化对Ti_x(AlNbZr)_100-x系多主元合金结构稳定性以及力学性能的影响。结果表明,Ti_x(AlNbZr)_100-x系多主元合金可以形成稳定的固溶体相,且合金主要由BCC相和Al₃Zr₅相组成,随Ti含量增加,合金的液相线降低,Al₃Zr₅相的相形成温度减小,直到Ti含量为60%~70%时,Al₃Zr₅相消失,合金由单一BCC相组成;Ti含量增加可以提高合金的结构稳定性,当Ti含量为25%~70%时,合金具有良好的力学稳定性,合金的体积模量、剪切模量以及杨氏模量随着Ti含量的增加呈上升趋势。Ti_x(AlNbZr)_100-x系多主元合金的基态能量和形成热随着Ti含量的增加而降低,表明增加Ti含量可以增加该合金系的热力学稳定性,使合金更易形成固溶体相。     

Al含量对热轧FeMnCoCr系高熵合金组织和性能的影响

研究了Al含量对(Fe₅₀Mn₃₀Co₁₀Cr₁₀)_100-xAl_x高熵合金微观组织、变形机制和拉伸性能的影响。采用真空电弧熔炼炉制备合金铸锭,对合金进行压下率为80%的热轧火淬,利用SEM和EBSD对合金的组织结构进行了分析。结果表明,随着Al含量(原子分数,下同)由0%增加到6%,热轧淬火后合金组织由FCC+HCP双相转变成FCC单相,Al含量为8%时产生了BCC相;随着Al含量由0%增加到6%,在拉伸过程中TRIP效应受到抑制,TWIP效应明显增加,合金的屈服强度变化不大,抗拉强度稍有降低,断后伸长率显著增加,当Al含量为6%时断后伸长率达到最高,为79%。     

退火对AlCuFeNiTiCrx高熵合金硬度的影响

采用铜模吸铸法制备AlCuFeNiTiCr_x(x=0.5, 1.0, 1.5, 2.0)高熵合金,并在1000℃下进行3 h退火处理。通过X射线衍射仪(XRD)、光学显微镜、维氏硬度计,分别测试了铸态和退火态AlCuFeNiTiCr_x(x=0.5, 1.0, 1.5, 2.0)高熵合金的微观结构演变及维氏硬度值。发现铸态和退火态试样仅由简单的体心立方(BCC)和面心立方(FCC)固溶体相组成,而退火态试样中的FCC相与铸态试样中的FCC相相比有所增加。根据金相显微照片,两种状态下的高熵合金仅存在枝晶和晶间相,且退火后的显微组织变得更加均匀。两种状态下高熵合金的硬度均随Cr含量的增加而增加,且退火态试样的硬度值远大于铸态试样。     

H13钢表面激光熔覆AlCoCrFeNiWx高熵合金涂层及其性能

以热作模具钢H13作为基体,通过激光熔覆制备AlCoCrFeNiW_x(x=0, 0.5)高熵合金涂层,并研究W元素的添加对其组织结构以及热稳定性和耐磨性的影响。激光熔覆AlCoCrFeNiW_x高熵合金涂层相组织结构随W元素的添加会发生变化,W的添加会促进BCC相的形成,并且在晶界处形成富含W的第二相,其生长方向会沿着冷却方向形成细长状的枝晶,这些第二相会起到耐磨和强化涂层的作用。经800 ℃长时间保温后测试AlCoCrFeNiW_x高熵合金涂层的热稳定性。结果表明,AlCoCrFeNiW_x高熵合金涂层均能够保持较高的硬度和耐磨性,14 h保温后的硬度仍大于400 HV0.2,加入W元素后的涂层抗回火软化能力更强,800 ℃保温14 h后的耐摩擦磨损性能是基体的两倍以上。     

WC颗粒对激光熔覆FeCoCrNiCu高熵合金涂层组织与硬度的影响

采用CO2横流激光器制备添加WC颗粒的FeCoCrNiCu高熵合金涂层,研究WC含量对涂层的组织结构及硬度的影响.结果表明:不同WC含量的高熵合金涂层均由简单的面心立方结构(FCC)和体心立方结构(BCC)两相组成.随着WC含量的提高,涂层中FCC相含量不断减少,BCC相含量不断增加.WC颗粒在激光熔覆过程中发生溶解并完全溶入FCC相和BCC相中,并未引起复杂碳化物相的生成.不同WC含量的涂层均为树枝晶组织.激光熔覆过程中的快速凝固条件有利于抑制枝晶和枝晶间的成分偏聚.WC含量的提高使枝晶细化,硬度提高.     

Effect of Mo Addition on Corrosion Behavior of High-Entropy Alloys CoCrFeNiMo_x in Aqueous Environments

The corrosion behavior of CoCrFeNiMo_x alloys was investigated in aqueous environments, NaCl and H_2SO_4 solutions,respectively, to simulate typical neutral and acidic conditions. The cyclic polarization curves in NaCl and the potentiodynamic curves in H_2SO_4 clearly reveal the beneficial effects of Mo and the detrimental effect of σ-phase on the corrosion resistance. The X-ray photoelectron spectroscopy results of CoCrFeNiMo_x alloys in H_2SO_4 solution indicate that Cr and Mo predominate the corroded surface of the alloys, where Mo primarily exists in the form of MoO_3.