The Phase Competition and Stability of High-Entropy Alloys

Phase competition and stability of several typical high-entropy alloys (HEAs) were studied, and the effects of alloying additions and processing conditions on phase formation in these alloys were discussed. Alloying with chemically incompatible elements having a large difference in either the atomic size or enthalpy of mixing with constituting components in HEAs, e.g., Cu and Al in the FeCoNiCr alloy system, inevitably induced phase separation and stimulated formation of duplex solid-solution phases and even intermetallic compounds. The solid-solution phase in the as-cast FeCoNiCrMn HEA is extremely stable due to the good chemical compatibility among constituent components, but in the FeCoNiCrAl and (FeCoNiCrAl)₉₉Si₁ HEAs with the incompatible elements Al and Si, pretreatment and annealing processes could induce phase transitions and the formation of new phases, indicating that the as-cast solid-solution phases were destabilized by quenched-in chemical segregation, resulting from additions of the dissimilar elements.     

Atomic size and chemical effects of alloying elements Cu,Mg and Si on the structure and dynamics of molten 8090-based AlLi alloy

The structural and dynamical properties of liquid Al₉₁Li₉ and Al₉₁Li₉M₃ (M = Cu, Mg, Si) alloys are investigated by means of ab initio molecular dynamic simulation. Pair distribution function analysis suggests that the atomic distances of Li–Li and Al–Li decrease after addition of alloying elements. The additive Cu and Si are manifested surrounded by Al and Li and hardly meet each other owing to the effects of atom size and their negative mixing enthalpy with Li. The topological environments of Al and Li in Al₉₁Li₉ are changed significantly by adding minor alloying elements. The diffusion of Al and Li is hindered by alloying elements, among which Cu and Si play more significant role. Furthermore, the metalloid additive Si illustrates different effects from the metallic additive Cu and Mg on the diffusivity of Al₉₁Li₉ liquid alloys.     

Alloy Design Strategies and Future Trends in High-Entropy Alloys

High-entropy alloys (HEAs) are newly emerging advanced materials. In contrast to conventional alloys, HEAs contain multiple principal elements, often five or more in equimolar or near-equimolar ratios. The basic principle behind HEAs is that solid-solution phases are relatively stabilized by their significantly high entropy of mixing compared to intermetallic compounds, especially at high temperatures. This makes them feasibly synthesized, processed, analyzed, and manipulated, and as well provides many opportunities for us. There are huge numbers of possible compositions and combinations of properties in the HEA field. Wise alloy design strategies for suitable compositions and processes to fit the requirements for either academic studies or industrial applications thus become especially important. In this article, four core effects were emphasized, several misconceptions on HEAs were clarified, and several routes for future HEA research and development were suggested.     

Classification of the role of microalloying elements in phase decomposition of Al based alloys

The fundamental role of microalloying elements in several aluminium alloys such as Al–Cu, Al–Li–Cu and Al–Cu–Mg has been investigated using a Monte Carlo computer simulation. All the utilized simulation parameters, e.g. pair interactions between same atoms species, between different atom species and between an atom and a vacancy, were derived from known thermodynamic or kinetic quantities. A small addition of Mg to Al–Cu alloys exhibits a strong tendency to form Mg/Cu/Vacancy complexes in the atom configurations, which is more remarkably revealed in Al–Li–Cu alloys. The combined addition of Ag or Si with Mg significantly increases the number of Mg/Cu/Vacancy complexes in Al–Cu–Mg alloys. From the comparison with experimentally reported results, these complexes are reasonably regarded as an effective heterogeneous nucleation site for GP zones, GPB zones and/or the Ω phase. The utilized simulation model, furthermore, permits the role of microalloying elements to be well classified in terms of the characteristic features of each element.     

轻质高熵合金的研究进展

高熵合金是由多种元素以等摩尔或近等摩尔的比例混合形成的一种新型合金,较大的密度极大地限制了其应用。为了降低高熵合金的密度,出现了由Al、Li、Mg、Ti等轻质合金元素组成的轻质高熵合金,其在交通运输、航空航天领域潜在的应用前景引起了广泛关注。本文阐述了轻质高熵合金的研究现状,分析了轻质高熵合金的组元设计方法、相组成以及制备工艺,进而归纳总结了目前不同种类的轻质高熵合金的性能,包括高强度、高硬度、高温抗氧化性、耐蚀性能等。最后总结了轻质高熵合金目前存在的一些问题以及对轻质高熵合金未来的研究方向进行了展望。     

Strong and Ductile Non-equiatomic High-Entropy Alloys: Design,Processing, Microstructure,and Mechanical Properties

We present a brief overview on recent developments in the field of strong and ductile non-equiatomic high-entropy alloys (HEAs). The materials reviewed are mainly based on massive transition-metal solute solutions and exhibit a broad spectrum of microstructures and mechanical properties. Three relevant aspects of such non-equiatomic HEAs with excellent strength–ductility combination are addressed in detail, namely phase stability-guided design, controlled and inexpensive bulk metallurgical processing routes for appropriate microstructure and compositional homogeneity, and the resultant microstructure–property relations. In addition to the multiple principal substitutional elements used in these alloys, minor interstitial alloying elements are also considered. We show that various groups of strong and ductile HEAs can be obtained by shifting the alloy design strategy from single-phase equiatomic to dual- or multiphase non-equiatomic compositional configurations with carefully designed phase instability. This design direction provides ample possibilities for joint activation of a number of strengthening and toughening mechanisms. Some potential research efforts which can be conducted in the future are also proposed.     

The high-entropy alloys with high hardness and soft magnetic property prepared by mechanical alloying and high-pressure sintering

The equiatomic multiprincipal CoCrFeCuNi and CoCrFeMnNi high-entropy alloys (HEAs) were consolidated via high pressure sintering (HPS) from the powders prepared by the mechanical alloying method (MA). The structures of the MA'ed CoCrFeCuNi and CoCrFeMnNi powders consisted of a face-centered-cubic (FCC) phase and a minority body-centered cubic (BCC) phase. After being consolidated by HPS at 5 GPa, the structure of both HEAs transformed to a single FCC phase. The grain sizes of the HPS'ed CoCrFeCuNi and CoCrFeMnNi HEAs were about 100 nm. The alloys keep the FCC structure until the pressure reaches 31 GPa. The hardness of the HPS'ed CoCrFeCuNi and CoCrFeMnNi HEAs were 494 Hv and 587 Hv, respectively, much higher than their counterparts prepared by casting. Both alloys show typical paramagnetism, however, possessing different saturated magnetization. The mechanisms responsible for the observed influence of Cu and Mn on mechanical behavior and magnetic property of the HEAs are discussed in detail.     

Aluminum Alloying Effects on Lattice Types, Microstructures, and Mechanical Behavior of High-Entropy Alloys Systems

The crystal lattice type is one of the dominant factors for controlling the mechanical behavior of high-entropy alloys (HEAs). For example, the yield strength at room temperature varies from 300 MPa for the face-centered-cubic (fcc) structured alloys, such as the CoCrCuFeNiTi _x system, to about 3,000 MPa for the body-centered-cubic (bcc) structured alloys, such as the AlCoCrFeNiTi _x system. The values of Vickers hardness range from 100 to 900, depending on lattice types and microstructures. As in conventional alloys with one or two principal elements, the addition of minor alloying elements to HEAs can further alter their mechanical properties, such as strength, plasticity, hardness, etc. Excessive alloying may even result in the change of lattice types of HEAs. In this report, we first review alloying effects on lattice types and properties of HEAs in five Al-containing HEA systems: Al _x CoCrCuFeNi, Al _x CoCrFeNi, Al _x CrFe_1.5MnNi_0.5, Al _x CoCrFeNiTi, and Al _x CrCuFeNi₂. It is found that Al acts as a strong bcc stabilizer, and its addition enhances the strength of the alloy at the cost of reduced ductility. The origins of such effects are then qualitatively discussed from the viewpoints of lattice-strain energies and electronic bonds. Quantification of the interaction between Al and 3d transition metals in fcc, bcc, and intermetallic compounds is illustrated in the thermodynamic modeling using the CALculation of PHAse Diagram method.     

Design of High-Entropy Alloy: A Perspective from Nonideal Mixing

Since the advent in 2004, high-entropy alloys (HEAs) have been attracting a great deal of research interest worldwide. Being deemed as a major paradigmatic shift, the design of HEAs without base elements poses challenges to the existing thermodynamic models and theories that were long established for traditional alloys, one of which is related to the thermodynamic mechanisms for the formation of random solid solution in a concentrated multicomponent alloy. In this article, we discuss the design of HEAs from the perspective of correlated mixing (nonideal mixing of atoms with interatomic correlations). In a quantitative manner, we can show that the formation of a random solid solution in HEAs depends not only on the number of constituent elements but also on the alloy’s melting/processing temperature and on various interatomic correlations. Through the correlated mixing rule, we further demonstrate a strategy to screen out equiatomic alloys with the thermodynamic characteristics close to those of random solid solutions from an expanded library of 20 candidate elements.     

Microstructure and Properties of Aluminum-Containing Refractory High-Entropy Alloys

A new metallurgical strategy, high-entropy alloying (HEA), was used to explore new composition and phase spaces in the development of new refractory alloys with reduced densities and improved properties. Combining Mo, Ta, and Hf with “low-density” refractory elements (Nb, V, and Zr) and with Ti and Al produced six new refractory HEAs with densities ranging from 6.9 g/cm³ to 9.1 g/cm³. Three alloys have single-phase disordered body-centered cubic (bcc) crystal structures and three other alloys contain two bcc nanophases with very close lattice parameters. The alloys have high hardness, in the range from H _v = 4.0 GPa to 5.8 GPa, and compression yield strength, σ _0.2 = 1280 MPa to 2035 MPa, depending on the composition. Some of these refractory HEAs show considerably improved high temperature strengths relative to advanced Ni-based superalloys. Compressive ductility of all the alloys is limited at room temperature, but it improves significantly at 800°C and 1000°C.     

Microstructure and deformation resistance of quinary Pb-(Al,Mg, Sn,Li) alloys

The structure and deformation resistance of some quinary Pb-(Al, Mg, Sn, Li) alloys were investigated. The respective alloys were originally cast and analyzed spectrographically prior to testing. Specimens were metallographically prepared and appropriate microstructures were evaluated. Deformation was by extrusion through a series of circular dies.It was found that a strong trend or correlation existed between the alloy structure and the deformation behavior, both of which depended directly on alloying concentration. The implications on the mechanical and corrosion behavior were highlighted. These findings were supported with optical and electron microscopy.     

High-Entropy Alloys with a Hexagonal Close-Packed Structure Designed by Equi-Atomic Alloy Strategy and Binary Phase Diagrams

High-entropy alloys (HEAs) with an atomic arrangement of a hexagonal close-packed (hcp) structure were found in YGdTbDyLu and GdTbDyTmLu alloys as a nearly single hcp phase. The equi-atomic alloy design for HEAs assisted by binary phase diagrams started with selecting constituent elements with the hcp structure at room temperature by permitting allotropic transformation at a high temperature. The binary phase diagrams comprising the elements thus selected were carefully examined for the characteristics of miscibility in both liquid and solid phases as well as in both solids due to allotropic transformation. The miscibility in interest was considerably narrow enough to prevent segregation from taking place during casting around the equi-atomic composition. The alloy design eventually gave candidates of quinary equi-atomic alloys comprising heavy lanthanides principally. The XRD analysis revealed that YGdTbDyLu and GdTbDyTmLu alloys thus designed are formed into the hcp structure in a nearly single phase. It was found that these YGdTbDyLu and GdTbDyTmLu HEAs with an hcp structure have delta parameter (δ) values of 1.4 and 1.6, respectively, and mixing enthalpy (ΔH _mix) = 0 kJ/mol for both alloys. These alloys were consistently plotted in zone S for disordered HEAs in a δ-ΔH _mix diagram reported by Zhang et al. (Adv Eng Mater 10:534, 2008). The value of valence electron concentration of the alloys was evaluated to be 3 as the first report for HEAs with an hcp structure. The finding of HEAs with the hcp structure is significant in that HEAs have been extended to covering all three simple metallic crystalline structures ultimately followed by the body- and face-centered cubic (bcc and fcc) phases and to all four simple solid solutions that contain the glassy phase from high-entropy bulk metallic glasses.     

Alloy Design and Properties Optimization of High-Entropy Alloys

This article reviews the recent work on the high-entropy alloys (HEAs) in our group and others. HEAs usually contain five or more elements, and thus, the phase diagram of HEAs is often not available to be used to design the alloys. We have proposed that the parameters of ?? and ?? can be used to predict the phase formation of HEAs, namely ??????1.1 and ??????6.6%, which are required to form solid-solution phases. To test this criterion, alloys of TiZrNbMoV _x and CoCrFeNiAlNb _x were prepared. Their microstructures mainly consist of simple body-centered cubic solid solutions at low Nb contents. TiZrNbMoV _x alloys possess excellent mechanical properties. Bridgman solidification was also used to control the microstructure of the CoCrFeNiAl alloy, and its plasticity was improved to be about 30%. To our surprise, the CoCrFeNiAl HEAs exhibit no apparent ductile-to-brittle transition even when the temperatures are lowered from 298?K to 77?K.     

Al-Li-Mg合金电场下自由能的TF方程计算

基于Thomas-Fermi（TF）模型，确定电场作用下的内势场边界条件，建立了电场作用下单原子、化合物，固溶体、实际工业合金的自由能计算方法，系统地定量计算研究了电场作用下自由能的变化趋势。结果表明：单原子自由能变化趋势在电场作用下是关于非零电场对称的，并且不同元素的自由能对电场的敏感性不同，Al，Mg，Li3元素在正电场一侧的敏感性依次为Al，Li，Mg：在负电场一侧的敏感性依次为Al，Mg，Li。电场作用下Al3Li化合物和固溶体Al．2．14％Li（原子分数，下同）的自由能在460K和800K表现出不同电场对称性和电场敏感性。在两种温度下，Al—2．14％Li固溶体自由能的电场敏感性要高于化合物Al3Li。而且在800K高电场下固溶体Al-2．14％Li的自由能明显高于化合物Al3Li的自由能，在460K相同的电场下，化合物的自由能低于固溶体的自由能。1420合金自由能的变化趋势是关于零电场对称的，时效电场下1420合金的拉伸性能也是关于零电场对称的。     

锶、钕对Mg-9Al-1Si-0.3Zn合金微观组织和力学性能的影响

当镁合金中添加含量较高的Si时,会形成大量粗大汉字状的Mg2Si,严重影响合金的力学性能。通过Sr和Nd及其复合添加细化Mg-9Al-1Si-0.3Zn合金中粗大的Mg2Si,研究添加元素对合金微观组织和室温力学性能的影响,分析了Sr和Nd对Mg2Si的细化机制。结果表明,随着Sr的加入,汉字状Mg2Si的形貌得到改善,形成了均匀的多边形块状;当Sr添加到0.16%(质量分数,下同)时,Mg2Si得到了完全的细化。当同时添加Nd和Sr元素时,合金中出现新的以Mg,Al,Nd和Si形成的物相;随着Nd的增加,这种新的物相增多,这种化合物提供了Mg2Si相细化的异质核心。在Sr和Nd的复合作用下,汉字状Mg2Si被细化,合金的力学性能得到改善。     

Effect of minor Sc and Zr on microstructures and mechanical properties of Al-Zn-Mg based alloys

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熔盐电解制备四元Mg-Zn-Li-Ca合金(英文)

在LiCl-KCl-MgCl2-ZnCl2-CaCl2熔盐体系中,以钼为惰性电极,在温度为943K时,直接电解制备Mg-Zn-Li-Ca四元合金。循环伏安研究表明,在LiCl-KCl熔盐体系中,添加MgCl2、ZnCl2和CaCl2后,Li的析出电位明显正移。计时电位研究表明,当阴极电流密度等于或者更负于-1.55A/cm2时,Mg、Li/Zn和Ca能够实现四元沉积。X射线衍射研究表明,恒电流电解可以制备出由不同相组成的Mg-Zn-Li-Ca合金。采用金相显微镜和电子扫描显微镜对合金样品进行表征。能谱分析结果表明,Mg元素和Ca元素在合金中分布均匀,而Zn元素主要分布在基体的边缘。     

Revealing the Microstates of Body-Centered-Cubic (BCC) Equiatomic High Entropy Alloys

Attributing to the attractive mechanical properties, e.g., high yield strength and fracture toughness, the atomic and electronic basis for high entropy alloys (HEAs) are under extensive studies. In the present work, the local atomic arrangement of body-centered-cubic (BCC) equiatomic HEAs are revealed by the CN14 cluster-plus-glue-atom model and the 32 atoms special quasirandom structures. Moreover, the cluster-plus-glue-atom model is utilized to generate ordered and disordered configurations. The bonding lengths among the same and different alloying elements are comprehensively compared in term of their partial pair correlation function (PCF). According to the specific (well-defined) position of each partial PCF of the BCC structure, the order–disorder/random configurational transitions are revealed by the absence of partial PCF peaks. Here, the WMoTM₁TM₂ (TM = Ta, Nb, and V) BCC equiatomic refractory HEAs are selected as a case study. Through mixing various groups of alloying elements, the atomic-size differences not only result in the lattice mismatch/distortion but also yield the formation of weak spots. Their bonding-charge density captures the electron redistributions caused by the coupling effect of the lattice distortion and valance electron differences among various elements, which also presents the physical nature of the loosely-bonded weak spots and the tightly-bonded clusters. It is worth mentioning that both the PCF and the negative enthalpy of mixing can be utilized to characterize the clusters or the short range ordering in the HEAs. The microstates revealed by the cluster-plus-glue-atom model are in line with the novel small set of the ordered structures method reported in the literature.     

Microstructure,Mechanical Properties,and Corrosion Behavior of MoNbFeCrV,MoNbFeCrTi, and MoNbFeVTi High-Entropy Alloys

The development of high-entropy alloys(HEAs) has stimulated an ever-increasing interest from both academia and industries.In this work, three novel MoNbFeCrV, MoNbFeCrTi, and MoNbFeVTi HEAs containing low thermal neutron absorption cross section elements were prepared by vacuum arc melting. The microstructure, mechanical properties, and corrosion behaviors were investigated. A dominant body-centered cubic(BCC) phase was present in all these three HEAs. In addition,an ordered Laves phase was found to be another major phase in both MoNbFeCrV and MoNbFeCrTi alloys, whereas an ordered BCC(B2) phase was observed in the MoNbFeVTi alloy. The phase formation in these three alloys was discussed. It is found that the formation of the secondary phase in these alloys is mainly ascribed to the large atomic size difference and electronegativity difference. All the three HEAs show high hardness, high yield strength but limited plasticity. Moreover, the MoNbFeCrV, MoNbFeCrTi and MoNbFeVTi alloys exhibit excellent corrosion resistance in both deaerated 1 mol/L NaCl and 0.5 mol/L H _2 SO _4 solutions at room temperature. However, further composition adjustment and/or thermomechanical processing is required to enhance the mechanical properties of the three alloys.