难熔高熵合金在反应堆结构材料领域的机遇与挑战

传统反应堆结构材料性能已趋于极限,亟需开发新型材料。难熔高熵合金是以多种难熔元素作为主元的新型金属材料,具有独特的力学、物理和化学性质,尤其在高温力学、抗辐照等方面表现出优异的性能。难熔高熵合金在第4代核裂变反应堆包壳材料、核聚变堆面向第一壁材料等关键领域具有广阔的应用前景。本文结合具有代表性的文献,围绕难熔高熵合金的力学性能、抗辐照性能、抗氧化性能阐述了其强化机制与抗辐照机理,梳理了难熔高熵合金的发展脉络,在此基础上展望了难熔高熵合金在反应堆结构材料领域的应用前景。     

难熔高熵合金综述（英文）

综述了近年来难熔高熵合金(RHEAs)在合金设计、显微组织和力学性能方面的研究进展,并重点讨论了内在的强化机制和变形行为。难熔高熵合金主要由近等摩尔比的难熔元素组成,具有优异的力学性能,尤其是高温力学性能。然而,大多数难熔高熵合金的室温塑性有限。为了解决这一问题,研究人员已开展了大量相关研究工作,其中某些难熔高熵合金材料具有很大的高温实际应用潜力。难熔高熵合金除了具有优异的力学性能外,在其他性能方面也有优势,如生物相容性和耐磨性。最后,还讨论了难熔高熵合金目前存在的问题和对未来发展的建议。     

FCC结构高熵合金的析出强化研究进展

高熵合金是近年来涌现出的一种新型合金,突破了以一种或者两种元素为主、少量添加元素为辅的传统合金设计理念。作为高熵合金体系一个重要分支—FCC结构的高熵合金,具有高损伤容限、良好的抗辐照能力、高耐磨、耐腐蚀性能等一系列优异的性能,可以作为理想的工程结构材料。然而,FCC结构高熵合金强度-塑性不匹配严重制约了其工程应用。研究表明,析出强化可以有效提高FCC结构高熵合金的强度,产生优异的强度-塑性匹配性能,各国学者相继开发出大量的高性能析出强化高熵合金体系。本文主要介绍了FCC结构高熵合金的析出强化研究,包括非共格析出相和共格析出相,着重介绍了研究现状以及强韧化的影响机制,并对未来高熵合金析出强化研究进行了展望。     

轻质高熵合金的研究进展

目前以一种或两种金属元素为主元的传统轻质合金在工业应用上有诸多局限性,如铝合金室温强度低、镁合金室温塑性和耐腐蚀性差且不易加工等。2004年叶均蔚首次正式提出高熵合金概念。高熵合金概念的提出为轻质合金的发展提供了新方向。区别于传统轻质合金,轻质高熵合金具有多种主元元素且混合熵较高,往往倾向于生成简单固溶体相。且轻质高熵合金表现出四大显著效应,即热力学上的高熵效应、动力学上的缓慢扩散效应、结构上的晶格畸变效应及性能上的"鸡尾酒"效应。独特的晶体结构和特性,使得轻质高熵合金具有传统轻质合金无法比拟的优点,如高强度、高硬度、优良的高温抗氧化性和耐腐蚀性能等。综述了轻质高熵合金的研究现状,阐述了轻质高熵合金的组元设计、制备方法、微观结构及合金性能,分析了轻质高熵合金现存的问题,并对轻质高熵合金未来的发展趋势进行了展望。     

Effect of Constituent Elements on the Corrosion Resistance of Single-Phase CoCrFeNi High-Entropy Alloys in NaCl SolutionEI北大核心CSCD

High entropy alloys (HEAs) origin from a new alloy design concept with multi-principal elements, which have attracted significant interests in the past decade. The high configurational entropy in HEAs results in simple solid solutions with fcc and bcc structures. Especially, the single solid solution CoCrFeNi alloy exhibits excellent properties in many aspects, such as mechanical properties, thermal stability, radiation resistance and corrosion resistance. The excellent corrosion resistance of CoCrFeNi alloy is ascribed to the single-phase structure and uniform element distribution coupled with much higher Cr content than stainless steel. The single-phase structure and uniform element distribution can prevent the occurrence of localized corrosion, and higher Cr content can protect the alloy surface better with the form of oxidation film. Moreover, the corrosion resistance of CoCrFeNi-based HEAs, such as CoCrFeNiAlx, CoCrFeNiCux, CoCrFeNiTix, have also been extensively investigated. In most CoCrFeNi-based HEAs, the elements of Co, Cr, Fe and Ni are with equal-atomic ratio. However, the equal-atomic ratio is not necessary to obtain satisfactory properties and to ensure the single fcc structure in Co-Cr-Fe-Ni system. Accordingly, it is essential to further consider the effect of alloying elements on the corrosion resistance in Co-Cr-Fe-Ni HEA. In this work, the effect of Co, Fe and Ni elements on the corrosion resistance of single fcc Co-Cr-Fe-Ni system with concentrated constitution but different atomic ratios in 3.5% NaCl solution are investigated by using LSCM and EIS. The potentiodynamic polarization results indicate that the increase of Fe and the decrease of Ni will decrease the passivation current density of the alloys when the Co and Cr contents are equal. With the increase of Co and the decrease of Ni, the alloys show smaller passivation current density and better corrosion resistance when the Fe and Cr contents are equal. With the decrease of Co and the increase of Fe and Ni, the alloys show higher corrosion potential and smaller corrosion tendency when the Cr content is constant. These results will be helpful for the design of corrosion resistant HEAs in NaCl aqueous solution.     

轻质高熵合金的研究进展与展望

高熵合金是一种具有优异物理化学性能的新型合金,其中含有轻质元素的轻质高熵合金具有较高的比强度和比硬度及耐蚀性能等突出特点,其潜在的工程应用价值引起了人们的关注。因此,本文详细阐述了轻质高熵合金的研究现状,归纳了轻质高熵合金的组元设计规则与方法,分析了轻质高熵合金的微观相结构,总结了高熵合金的各种性能,探讨了轻质高熵合金目前存在的问题,并提出了轻质高熵合金的发展趋势。     

High-Temperature Oxidation Behavior of Refractory High-Entropy Alloys: Effect of Alloy Composition

The high-temperature oxidation behavior of a new family of refractory high-entropy alloys (HEAs) with compositions of W–Mo–Cr–Ti–Al, Nb–Mo–Cr–Ti–Al and Ta–Mo–Cr–Ti–Al was studied at 1000 and 1100 °C. Based on these equimolar starting compositions, the main incentive of this study was to select the most promising alloy system whose properties may then be successively improved. Despite the high amount of refractory elements, Ta–Mo–Cr–Ti–Al showed good oxidation resistance at 1000 and 1100 °C. Moderate values of mass gain and complex oxidation kinetics were observed for the W- and Nb-containing HEAs. These alloys formed inhomogeneous oxide scales possessing regions with thick and porous layers as well as areas revealing quite thin oxide scales due to the formation of discontinuous Cr- and Al-rich scales. The most promising behavior was shown by the alloy Ta–Mo–Cr–Ti–Al which followed the parabolic rate law for oxide growth due to the formation of a thin and compact Al-rich layer.     

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.     

高熵合金制备及热处理工艺研究进展

与传统合金相比,高熵合金表现出了高强韧、良好的软磁性、高温稳定性、耐腐蚀性等突出特点,在许多的领域应用潜力巨大。本文主要介绍真空熔炼、粉末冶金、激光熔覆和磁控溅射等制备高熵合金方法的研究进展及优缺点,分析了不同热处理工艺对组织结构和力学性能的影响,并对高熵合金制备和模拟计算等方面提出了展望。     

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。     

FeCrNiCo(Cu/Mn)高熵合金组织及腐蚀性能

采用电弧熔炼方法制备了FeCrNiCoCu及FeCrNiCoMn两种高熵合金,借助第一性原理模拟计算及腐蚀电化学测试技术,研究Cu、Mn元素对制备高熵合金在3.5%NaCl、5%NaOH和0.5 mol/L H2SO4溶液中的电化学腐蚀行为的影响规律。结果表明:FeCrNiCoCu及FeCrNiCoMn高熵合金均为单一的FCC结构,其中FeCrNiCoMn态密度达到最大值时对应的能量较低,结构更趋于稳定,耐蚀倾向性好。FeCrNiCoMn高熵合金在三种溶液中的耐蚀性均高于FeCrNiCoCu的,这是由于Cu元素的存在会引起元素偏聚,降低了合金的耐蚀性。而Mn元素以金属间化合物的形式存在,降低了合金中耐蚀性差的元素含量,提高了合金的耐蚀性。     

Computational Thermodynamics Aided High-Entropy Alloy Design

Thermodynamic calculation is used to shed light on the design and development of high-entropy alloys (HEAs) in this article. A thermodynamic database for the Al-Co-Cr-Fe-Ni was developed, and phase diagrams of this system were calculated. The calculated results, such as primary solidified phases, which are fractions of stable phases at a given alloy composition, explain the published experimental observations fairly well for both as-cast and homogenized alloys. These calculations also confirm the effect of each element on the face-centered cubic (fcc)/body-centered cubic (bcc) structure transition as published in the literature. The role of thermodynamic calculation in aiding effective design of HEAs is clearly demonstrated by this work.     

Empirical design of single phase high-entropy alloys with high hardness

We collect the available basic properties of nearly 100 high-entropy alloys (HEAs) with a single face centered cubic (fcc) or body centered cubic (bcc) phase. HEAs crystallizing in the fcc structure are mainly composed of the late 3d elements (LTM-HEAs), whereas HEAs consisting of the early (refractory) transition elements and the LTM-HEAs containing an increased level of bcc stabilizer form the bcc structure. Guided by the solid solution theory, we investigate the structure and hardness of HEAs as a function of the valence electron concentration (VEC) and the atomic size difference (δ). The fcc structure is found for VEC between 7.80 and 9.50, whereas the structure is bcc for VEC between 4.33 and 7.55. High strength is obtained for an average valence electron number VEC ∼ 6.80 and for an average atomic size difference δ ≈ 6%. Based on these empirical correlations, one can design the high-entropy alloys with desired hardness.     

合金组元与含量对激光熔覆高熵合金涂层的影响研究综述∗

高熵合金被视为是近年来合金化理论的一次创新,打破了传统合金以一种或两种金属元素为主元的设计理念,将合金设计体系扩展到以五种及以上元素为主元的领域,由于能够组成高熵合金的元素种类繁多且含量可调,所以具有巨大的开发潜力。 激光熔覆技术作为一种先进的新型材料表面改性技术与装备维修技术,与高熵合金结合,可为该合金材料的应用开辟出新的空间。 通过对现有研究梳理,归纳总结激光熔覆高熵合金涂层的耐腐蚀性能、硬度与摩擦磨损性能以及抗高温氧化性能的性能强化机理;概括分析常见高熵合金的组成元素及其含量变化,对激光熔覆技术制备合金涂层组织结构和性能的影响,为高熵合金涂层组元的选取提供借鉴参考。 最后指出激光熔覆高熵合金涂层在当前研究中的不足与仍需深入研究的问题,展望了高熵合金的应用前景与未来的研究方向。 系统梳理 Al、Ti、Nb、Mo、Ni、Si、B、C 等合金化元素对激光熔覆技术制备高熵合金涂层组织结构和性能的影响规律和作用效果,为激光熔覆高熵合金涂层的合金分成设计提供理论指导。     

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.     

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.     

高熵金属材料在氢环境中的脆性行为研究进展

氢脆广泛发生于各种金属及合金材料中,氢脆存在隐蔽性和时间滞后性,一旦发生往往带来灾难性事故,制约了金属材料在极端工况环境下的应用。研究发现,一些高熵合金(HEA)或多主元合金在力学性能、耐蚀性、抗氢脆性能等方面表现出超越传统合金材料(如钢、镍基合金、铝合金等)的性能特点,有望成为极端恶劣工况环境下装备用材料。在此基础上,对氢脆的机理和抗氢脆多主元合金领域的研究进展进行了综述。首先介绍了氢脆的概念,并梳理了几种金属氢脆机理,包括氢压理论、氢致局部塑性变形、氢增强解离、氢增强应变诱导空位、纳米空位聚合、氢促进位错发射等。随后,结合慢应变速率拉伸实验结果,梳理了影响多主元合金(尤其是高熵合金)抗氢脆性能的因素,包括氢含量、合金元素、微观结构、制备工艺、热处理工艺和实验条件等。最后,结合影响多主元合金抗氢脆性能的因素,提出通过优化制备工艺、改善热处理工艺和调整元素含量来提高CoCrFeMnNi高熵合金的抗氢脆性能,以及采用机器学习辅助开发新的抗氢脆多主元合金的观点,可为抗氢脆材料的研发提供参考。     

镍基单晶高温合金的研发进展EI北大核心CSCD

单晶高温合金是先进航空发动机、燃气轮机的核心热端材料,单晶叶片要求高、制造工艺复杂、容错空间小,在高温、复杂应力、氧化和热腐蚀等苛刻环境下工作。本文概述了近几年镍基单晶高温合金在合金研制、组织性能演化和表征、近服役环境下力学行为评价以及叶片制造工艺等方面的研发进展,并简单介绍了难熔高熵合金等“下一代”新型高温结构材料的研发情况。     

高熵合金涂层的研究进展

高熵合金涂层在工程实际应用中较传统合金具有良好的前景,对近年来高熵合金涂层的研究进展进行了概述。首先对制备高熵合金涂层的表面熔覆技术进行详细的介绍,其中包括激光熔覆技术、等离子熔覆技术、氩弧熔覆技术,分析了各表面熔覆技术的优缺点;然后总结了高熵合金涂层的组织及性能特征,涂层中相的组成包括:固溶体相、金属间化合物、纳米析出相、非晶相;性能上,高熵合金涂层由于各种效应的作用,具有高强度及硬度、优异的耐磨性、良好的耐腐蚀性及高温抗氧化性等一系列优异的性能;而后进一步分析了表面熔覆技术工艺参数对高熵合金涂层质量的影响规律、合金元素对高熵合金涂层性能的影响及热处理对高熵合金涂层相组织演变的影响;最后对高熵合金涂层的应用前景及其未来的研究方向进行展望。     

激光熔覆制备高熵合金涂层的研究进展

激光熔覆技术具有高的冷却速度、低的稀释率、涂层与基体冶金结合等优点,采用激光熔覆技术制备耐磨性和耐腐蚀好的高熵合金涂层是近几年高熵合金领域的研究热点之一。首先概括了激光熔覆技术制备的高熵合金体系及组织结构特征,大多高熵合金涂层以固溶相为主,少数合金涂层形成了非晶相,与熔炼制备高熵合金块体材料相比,涂层组织具有均匀、细小致密等特点。然后介绍了涂层的性能特征,涂层具有较高的硬度、良好的耐磨性,同时指明高耐磨性涂层不仅具有高的硬度,同时还需要具有一定的塑韧性。涂层合金中大多包含有Al、Cr、Si和Co等形成稳定氧化膜的元素,呈现优异的抗腐蚀性能。随后重点概述了合金元素（Al、Mo、V、Ti、B、Ni、Nb和Cu等）、熔覆工艺参数（激光功率、扫描速度和预制层粉末厚度）和热处理工艺对涂层组织结构和性能的影响规律。其中,熔覆工艺参数对涂层组织结构和性能的影响研究相对较少,将是未来研究的重点内容之一。最后对激光熔覆技术制备高熵合金涂层存在的问题和未来的研究方向做了展望。