Article(id=1249065614225117601, tenantId=1146029695717560320, journalId=1249024468962553931, issueId=1249065613306569569, articleNumber=null, orderNo=null, doi=10.11868/j.issn.1005-5053.2025.000081, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1746633600000, receivedDateStr=2025-05-08, revisedDate=null, revisedDateStr=null, acceptedDate=1750608000000, acceptedDateStr=2025-06-23, onlineDate=1775730048947, onlineDateStr=2026-04-09, pubDate=1759248000000, pubDateStr=2025-10-01, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1775730048947, onlineIssueDateStr=2026-04-09, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1775730048947, creator=13041195026, updateTime=1775730048947, updator=13041195026, issue=Issue{id=1249065613306569569, tenantId=1146029695717560320, journalId=1249024468962553931, year='2025', volume='45', issue='5', pageStart='1', pageEnd='182', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=1, specialIssue=null, createTime=1775730048728, creator=13041195026, updateTime=1775730148042, updator=13041195026, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1249066029947757306, tenantId=1146029695717560320, journalId=1249024468962553931, issueId=1249065613306569569, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1249066029951951611, tenantId=1146029695717560320, journalId=1249024468962553931, issueId=1249065613306569569, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=61, endPage=77, ext={EN=ArticleExt(id=1249065614455804323, articleId=1249065614225117601, tenantId=1146029695717560320, journalId=1249024468962553931, language=EN, title=Research progress in high-temperature high-entropy alloys, columnId=1249065614292231012, journalTitle=Journal of Aeronautical Materials, columnName=Review, runingTitle=null, highlight=null, articleAbstract=

High-temperature high-entropy alloys(HEAs)show potential to surpass traditional Ni-based alloys through multi-principal element synergy and microstructural regulation. This review systematically examines three systems: high-entropy superalloys(HESAs), refractory HEAs(RHEAs) and refractory high-entropy superalloys(RSAs). HESAs emulate the γ/γ′ dual-phase structure of Ni-based alloys, achieving comparable strength at 800-1000 ℃. RHEAs utilize refractory elements to form high-melting-point solid solutions with superior performance above 1200 ℃. RSAs innovate with BCC/B2 nanobasket structures, outperforming Ni-based alloys across 25-1200 ℃. Current challenges include poor room-temperature ductility, oxidation resistance and phase stability, demanding breakthroughs in multi-scale microstructure control, dynamic phase transformation mechanisms and high-throughput design. Future directions prioritize multi-objective composition optimization, advanced processing, cross-scale characterization, and service-condition evaluation systems to guide extreme-environment applications like aeroengine components and nuclear reactors, etc.

, correspAuthors=Zhaolong MA, Xingwang CHENG, authorNote=null, correspAuthorsNote=null, copyrightStatement=Copyright ©2025 Journal of Aeronautical Materials. All rights reserved., copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, authorCompany=null, fund=null, authors=null, authorsList=Haiyang LI, Zhaolong MA, Xingwang CHENG), CN=ArticleExt(id=1249065617102410182, articleId=1249065614225117601, tenantId=1146029695717560320, journalId=1249024468962553931, language=CN, title=高温高熵合金研究进展, columnId=1249065614468391782, journalTitle=航空材料学报, columnName=综述, runingTitle=null, highlight=null, articleAbstract=

高温高熵合金凭借其独特的多主元协同效应和微观组织调控潜力,有望突破传统镍基合金的性能极限。本文系统综述高熵高温合金(HESAs)、难熔高熵合金(RHEAs)和难熔高熵高温合金(RSAs)三大体系的研究进展与发展趋势。HESAs借鉴镍基合金的γ+γ′双相结构,在800~1000 ℃区间达到与商用镍基合金相当的高温强度;RHEAs基于难熔元素体系构建高熔点固溶体,在1200 ℃以上具有显著的性能优势;RSAs则创新性发展出BCC+B2纳米网篮结构,在25~1200 ℃全温域强度显著超越镍基合金。当前高温高熵合金研究面临室温塑性差、抗氧化性能不足、长时相稳定性欠缺等共性挑战,需重点突破多尺度组织调控、动态相变机制、高通量设计方法等关键技术。未来发展趋势将聚焦于多目标成分优化模型构建、先进制备工艺开发、跨尺度性能表征技术融合,以及服役环境下的综合性能评估体系建立,为航空发动机热端部件、核反应堆结构等极端环境应用提供指导。

, correspAuthors=马兆龙, 程兴旺, authorNote=null, correspAuthorsNote=
马兆龙(1987—),男,博士,教授,研究方向为高熵合金,联系地址:北京市海淀区中关村南大街5号(100081),E-mail:
程兴旺(1976—),男,博士,教授,研究方向为高熵合金,联系地址:北京市海淀区中关村南大街5号(100081),E-mail:
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Comparison of three types of high-entropy high-temperature alloys

, figureFileSmall=null, figureFileBig=null, tableContent=
AlloyRepresentative constituteStrengthening
mechanism
Phase structureMechanical propertyChallenge
HESAsAl,Co,Cr,Fe,NiPrecipitation strengtheningγ+ γ′Tensile ductility at 25 ℃:>25%; yield strength at 800 ℃:>600 MPaPhase stability
RHEAsTi,V,Cr,Zr,Nb,Mo,Hf,Ta,W,Al,Sisolid solution strengtheningBCC,Laves,Silicide,etc.Tensile ductility at 25 ℃:1%-50%; yield strength at 1000 ℃:100-1000 MPaOxidation,phase stability
RSAsAl,Mo,Nb,Ta,Ti,Zr,VPrecipitation strengtheningBCC+B2Compressive ductility at 25 ℃:5%-60%; yield strength at 1000 ℃:400-1000 MPaDuctile deformation capacity,phase stability
), ArticleFig(id=1249065623083487993, tenantId=1146029695717560320, journalId=1249024468962553931, articleId=1249065614225117601, language=CN, label=表1, caption=

三类高熵高温合金的对比

, figureFileSmall=null, figureFileBig=null, tableContent=
AlloyRepresentative constituteStrengthening
mechanism
Phase structureMechanical propertyChallenge
HESAsAl,Co,Cr,Fe,NiPrecipitation strengtheningγ+ γ′Tensile ductility at 25 ℃:>25%; yield strength at 800 ℃:>600 MPaPhase stability
RHEAsTi,V,Cr,Zr,Nb,Mo,Hf,Ta,W,Al,Sisolid solution strengtheningBCC,Laves,Silicide,etc.Tensile ductility at 25 ℃:1%-50%; yield strength at 1000 ℃:100-1000 MPaOxidation,phase stability
RSAsAl,Mo,Nb,Ta,Ti,Zr,VPrecipitation strengtheningBCC+B2Compressive ductility at 25 ℃:5%-60%; yield strength at 1000 ℃:400-1000 MPaDuctile deformation capacity,phase stability
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高温高熵合金研究进展
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李海洋 1 , 马兆龙 1, 2, 3, 4, * , 程兴旺 1, 2, 3, 4, *
航空材料学报 | 综述 2025,45(5): 61-77
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航空材料学报 | 综述 2025, 45(5): 61-77
高温高熵合金研究进展
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李海洋1, 马兆龙1, 2, 3, 4, * , 程兴旺1, 2, 3, 4, *
作者信息
  • 1北京理工大学 材料科学与工程学院,北京 100081
  • 2冲击环境材料技术国家级重点实验室,北京 100081
  • 3北京理工大学 唐山研究院,河北 唐山 063000
  • 4北京理工大学(珠海) 材料智能研发实验室,广东 珠海 519088

通讯作者:

马兆龙(1987—),男,博士,教授,研究方向为高熵合金,联系地址:北京市海淀区中关村南大街5号(100081),E-mail:
程兴旺(1976—),男,博士,教授,研究方向为高熵合金,联系地址:北京市海淀区中关村南大街5号(100081),E-mail:
Research progress in high-temperature high-entropy alloys
Haiyang LI1, Zhaolong MA1, 2, 3, 4, * , Xingwang CHENG1, 2, 3, 4, *
Affiliations
  • 1School of Materials Science and Engineering,Beijing Institute of Technology,Beijing 100081,China
  • 2National Key Laboratory of Science and Technology on Materials Under Shock and Impact,Beijing 100081,China
  • 3Tangshan Research Institute,Beijing Institute of Technology,Tangshan 063000,Hebei,China
  • 4Materials Intelligent Innovation Laboratory,Beijing Institute of Technology,ZHUHAI,Zhuhai 519088,Guangdong,China
出版时间: 2025-10-01 doi: 10.11868/j.issn.1005-5053.2025.000081
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高温高熵合金凭借其独特的多主元协同效应和微观组织调控潜力,有望突破传统镍基合金的性能极限。本文系统综述高熵高温合金(HESAs)、难熔高熵合金(RHEAs)和难熔高熵高温合金(RSAs)三大体系的研究进展与发展趋势。HESAs借鉴镍基合金的γ+γ′双相结构,在800~1000 ℃区间达到与商用镍基合金相当的高温强度;RHEAs基于难熔元素体系构建高熔点固溶体,在1200 ℃以上具有显著的性能优势;RSAs则创新性发展出BCC+B2纳米网篮结构,在25~1200 ℃全温域强度显著超越镍基合金。当前高温高熵合金研究面临室温塑性差、抗氧化性能不足、长时相稳定性欠缺等共性挑战,需重点突破多尺度组织调控、动态相变机制、高通量设计方法等关键技术。未来发展趋势将聚焦于多目标成分优化模型构建、先进制备工艺开发、跨尺度性能表征技术融合,以及服役环境下的综合性能评估体系建立,为航空发动机热端部件、核反应堆结构等极端环境应用提供指导。

高温高熵合金  /  高熵高温合金  /  难熔高熵合金  /  难熔高熵超合金  /  成分设计  /  微观组织  /  力学性能

High-temperature high-entropy alloys(HEAs)show potential to surpass traditional Ni-based alloys through multi-principal element synergy and microstructural regulation. This review systematically examines three systems: high-entropy superalloys(HESAs), refractory HEAs(RHEAs) and refractory high-entropy superalloys(RSAs). HESAs emulate the γ/γ′ dual-phase structure of Ni-based alloys, achieving comparable strength at 800-1000 ℃. RHEAs utilize refractory elements to form high-melting-point solid solutions with superior performance above 1200 ℃. RSAs innovate with BCC/B2 nanobasket structures, outperforming Ni-based alloys across 25-1200 ℃. Current challenges include poor room-temperature ductility, oxidation resistance and phase stability, demanding breakthroughs in multi-scale microstructure control, dynamic phase transformation mechanisms and high-throughput design. Future directions prioritize multi-objective composition optimization, advanced processing, cross-scale characterization, and service-condition evaluation systems to guide extreme-environment applications like aeroengine components and nuclear reactors, etc.

high-temperature high entropy alloy  /  high entropy superalloy  /  refractory high entropy alloy  /  refractory high entropy superalloy  /  composition design  /  microstructure  /  mechanical property
李海洋, 马兆龙, 程兴旺. 高温高熵合金研究进展. 航空材料学报, 2025 , 45 (5) : 61 -77 . DOI: 10.11868/j.issn.1005-5053.2025.000081
Haiyang LI, Zhaolong MA, Xingwang CHENG. Research progress in high-temperature high-entropy alloys[J]. Journal of Aeronautical Materials, 2025 , 45 (5) : 61 -77 . DOI: 10.11868/j.issn.1005-5053.2025.000081
随着航空航天、能源动力等领域对动力系统性能要求的持续提升,涡轮发动机的推重比和热效率已成为衡量国家高端装备制造水平的关键指标。其热端部件(如涡轮叶片)需在极端高温环境下长期服役,同时承受复杂机械应力和氧化腐蚀的共同作用[1]。在近数十年间,通过持续的合金成分优化与先进制备工艺研发,镍基合金的耐高温性能显著提升,其平均工作温度可达1050 ℃水平,达到其熔点约90%的临界值,并且由于较高的密度,难以满足新一代发动机对耐温能力和轻量化的双重要求[2]
高熵合金的出现为开发下一代耐高温材料以及突破镍基高温合金的性能瓶颈开辟了新的技术方向。高熵合金(HEAs)的概念最早在2004年由叶均蔚教授提出,其通过五种及以上主元元素的近等原子比设计,形成由高混合熵驱动的固溶体结构,突破了传统单一主元合金的限制[3]。HEAs的核心特性主要体现在四个方面:高熵效应增强热力学稳定性,抑制脆性金属间化合物的形成[4];晶格畸变效应源于多元原子尺寸的差异,产生强烈的固溶强化作用[5-6];迟滞扩散效应降低高温原子迁移速率,抑制晶粒粗化和相变[7-8];鸡尾酒效应通过多元素的协同作用,实现性能“1+1>2”的突破[4]。这些效应赋予HEAs高强度、高硬度、耐高温和耐腐蚀等优异性能,使其在高温应用领域展现出巨大潜力[9-11]
早期的高熵合金(如FeCrMnNiCo)因高温强度不足且相稳定性较差,难以满足航空航天、能源及核工业的高温使役需求。图1为高熵合金的分类,表1为三类高熵合金的对比。经过近十年的发展,通过热力学建模、微观结构工程以及成分优化,目前开发出三种有望用于高温环境的高熵合金,即高熵高温合金(HESAs)、难熔高熵合金(RHEAs)和难熔高熵高温合金(RSAs)。HESAs是基于Al-Co-Cr-Fe-Ni-Ti体系设计的一类高熵合金,其借鉴镍基高温合金的γ+ γ′结构,依靠γ′相(L12型有序相)强化机制,在高熵效应和晶格畸变的协同作用下,展现出卓越的高温性能。RHEAs由Ti、V、Nb、Ta、W等难熔元素组成,凭借高熔点的特性,在高于镍基合金熔点的超高温环境下仍能保持优异的强度,拓宽了应用范围。RSAs是RHEAs中的特殊类别,拥有BCC+ B2纳米双相网篮状组织,兼具低密度和高强度的优势,与镍基合金的γ+ γ′结构模式相似,具有显著的发展潜力。然而,高温HEAs在高温强度、室温塑性、抗氧化性和密度等方面仍面临挑战,亟需深入研究以推动其工程化应用。
为此,本文系统综述高温HEAs的研究进展,聚焦HESAs、RHEAs和RSAs的成分设计理念、微观组织特征及力学性能表现,剖析其核心难题与最新突破,并展望未来发展趋势,以期为高温合金的发展提供参考。
传统单相面心立方(FCC)结构的HEAs,如CoCrFeMnNi,在室温和低温环境下展现出优异的强度与韧性,适用于宇航、超导和生物医学等领域[12-13]。然而,这类合金面临着一个突出问题,即高温下强度严重衰减,这种高温强度不足的特性极大地限制其应用范围。为了深入探究这一情况,Wu等[14]对 CoCrFeNi、CoCrMnNi、CoCrNi、CoNi和Ni等合金进行不同温度下的力学性能测试。结果均显示,这些合金的高温强度会随着温度的升高而快速降低。Otto等[15]发现 CoCrFeMnNi 合金在600 ℃时,其屈服强度仅有76 MPa。在高温条件下,热激活作用会显著降低位错运动的阻力,这就使得固溶强化和晶界强化等传统的强化手段难以发挥作用,从而导致材料的高温强度下降。借鉴传统镍基合金引入 L12型γ′相(Ni3Al)强化合金的设计理念,学者们在HEAs中引入高体积分数的γ′相,并开发出Al-Co-Cr-Fe-Ni-Ti系高熵高温合金[16]
HESAs 的主要相结构为γ + γ′,这一相结构是其具备优异性能的基础。Daoud等[17]采用感应熔炼的方法制备Al10Co25Cr8Fe15Ni36Ti6合金。该合金经过1220 ℃/20 h+900 ℃/50 h热处理后,γ′相和B2(NiAl)相的体积分数分别约为46%和5%。 经测试,该合金在700 ℃和800 ℃下的屈服强度分别达到486 MPa和581 MPa,在所有测试温度下的力学性能均优于Inconel 617和Alloy 800H等商业合金。这表明HESAs具有一定高温应用的潜力。然而,较低的γ′相含量使得该合金在高温下的力学性能弱于一些更先进的铸造高温合金,例如Mar-M247。由此可见,提高HESAs中的γ′相含量对于提升其力学性能具有重要意义。
在成分设计时还需要考虑多重因素:(1)在HESAs的成分设计过程中应避免η(Ni3Ti)、σ相和β相等有害相的形成。这些有害相的存在可能会导致合金的脆性增加、强度降低,严重影响合金的性能和使用寿命[18-20]。因此,HESAs中的Cr和 Fe的最大含量应受到限制,因为过量的Cr和Fe元素会导致富Cr的体心立方(BCC)相和σ相的形成,这些相不利于合金性能[21]。(2)需要对Al/Ti含量进行调控。Joseph等[22]通过相图计算并结合实验验证,对Al-Co-Cr-Fe-Ni-Ti体系中无有害金属间化合物的γ + γ′平衡相结构进行成分设计。研究表明,在Al-Co-Cr-Fe-Ni-Ti体系中,γ′相的强度和含量会随着Al和Ti含量的增加而上升。但是,为了保证细小的γ′相能在γ基体中均匀析出,Al和Ti的原子分数之和需要控制在18%以内。这是因为如果Al和Ti含量过高,可能会导致γ′相尺寸过大、分布不均,从而影响合金的性能。(3)Al/Ti比例对 HESAs 的微观组织和力学性能都有着重要影响。Chen等[23]发现,Ti元素是γ′相的主要形成剂,而Al元素是γ′相的稳定剂。如果Al/Ti元素比例过高,会分别导致B2和η相的形成,这些脆性相的出现会危害合金力学性能。通过热力学计算可知,当Al/Ti元素比处于0.8~3之间时,有利于γ + γ′组织形成,如Ni51Co18Fe5Cr10Al12Ti4的γ′体积分数为62%,在660~1188 ℃之间保持着γ + γ′双相结构[21]。He等[24]运用原子探针层析(APT)技术对 Ni2CoCrFeTixAlyx+y=0.3,x/y=0.5,1,1.5)三种合金的元素分配行为进行研究。较高的Ti/Al比会使γ′相的体积分数和反向畴界能(APB)增加,显著提高合金的屈服强度。在800 ℃时,Ni2CoCrFeTi0.2Al0.1展现出最高的屈服强度(约685 MPa),而 Ni2CoCrFeTi0.1Al0.2的屈服强度最低(约500 MPa)。 综上所述,高熵高温合金的成分设计需综合调控γ′相含量、抑制η相和σ相等有害金属间化合物的析出,并通过优化Al/Ti原子比的方法获得性能优异的HESAs。
通过对HESAs微观组织的深入分析可知,γ + γ′双相组织结构是其具备优异高温性能的关键因素。图2对比了CoCrFeMnNi[15]、HESAs[17,21-22,25-26] 和典型镍基高温合金[27-28]在不同温度下的力学性能,为深入了解HESAs的性能提供了直观依据。从图2(a)可清晰看出,γ′相的引入显著提升HESAs在各测试温度下的屈服强度,使其远高于CoCrFeMnNi。这种提升可归因于高含量γ′相为合金提供强有力的析出强化作用。一些特定成分的HESAs,如Ni51Co18Fe5Cr10Al12Ti4、Ni51Co18Fe5Cr10Al8Ti8、Ni51Co18Fe5Cr10Al10.7Ti5.3、Ni45(FeCoNi)40(AlTi)15、Ni29.9Co30Fe13Cr15Al6Ti6B0.1等,在800~1000 ℃的高温区间内表现出卓越的性能,其屈服强度超过Inconel 718等传统变形镍基高温合金。以Inconel 718为例,该合金中γ′'相的溶解温度约为700~750 ℃,当温度超出此范围时,γ′'相会逐渐溶解,致使晶内强化效果显著降低。而HESAs中的γ′相具有较高的固溶温度,这使得HESAs在800 ℃以上的高温环境中,相较于Inconel 718等变形高温合金具有显著优势。这种优势使得HESAs 在高温工作环境中,能够保持更稳定的力学性能,减少因温度变化导致的性能波动。当前研究表明,L12相强化的HESAs在室温环境下大多具有优异的塑性变形能力(δ>0.25)[26,29-30]。例如Yang等[30]通过在(FeCoNi)86Al7Ti7高熵合金中引入高密度的韧性多组元L12型纳米颗粒,使得合金在室温下的强塑性同时提高,表现出1.5 GPa的超高抗拉强度和高达50%的室温拉伸塑性。首先, Fe和Co元素的添加降低L12有序化能量,提高其固有塑性;同时,Ti的掺杂降低了Al含量,减少L12相环境脆化,并通过提高反相边界能量和促进位错交滑移,增强加工硬化。其次,低晶格错配率使L12相在纳米尺度上稳定且均匀分布,减少应力集中和微裂纹萌生。此外,低价电子浓度值避免了L12相从韧性相到脆性相的转变。多组元L12型纳米颗粒的这些特性综合提升了合金的强度和塑性,克服传统合金设计中的强度-塑性权衡问题。
值得注意的是,Ni51Co18Fe5Cr10Al8Ti8和Ni45(FeCoNi)40(AlTi)15的高温屈服强度略高于 Mar-M-247(图2(a))。Mar-M-247作为典型的定向凝固高温合金,具有高体积分数的γ′相(约 62%),并且添加了W、Mo、Ta等高熔点元素,为合金基体提供强的固溶强化[31]。HESAs 在对比中展现出优异的高温强度,一方面,因其γ′相合金化程度高,晶格畸变效应增大;另一方面,HESAs中高Ti含量使γ′相的反向畴界能(APB)高于传统高温合金[32],以 Ni40.7Al7.8Co20.6Cr12.2Fe11.5Ti7.2和Mar-M-247为例,它们的APB能量分别为0.25、0.19 J/m2。更高的APB能量意味着位错需要更高的能量才能完成切割过程,从而增强了γ′相对位错的钉扎作用,进一步提升合金的高温强度[33]
尽管HESAs在高温性能方面表现出色,但与第二代单晶镍基高温合金CMSX-4相比,仍存在一定差距。从图2(a)可知,CMSX-4 在高温(≥600 ℃)下的屈服强度显著高于HESAs。但CMSX-4也存在明显的不足,它包含大量W、Hf、Ta和Re等高密度和价格昂贵的元素,这不仅提高了合金的密度,也大幅增加了生产成本。如图2(b)所示,新型高熵高温合金Ni45(FeCoNi)40(AlTi)15在高温比屈服强度指标上已接近商用单晶镍基高温合金CMSX-4水平,同时展现出显著的成本优势。该合金体系中Fe、Ti等廉价金属元素的占比显著高于传统镍基合金,经测算其原料成本较CMSX-4降低约50%,这为工程化应用提供了重要的经济性支撑。值得注意的是,尽管高熵高温合金在成本控制方面具有突破性进展,但在800 ℃以上高温区域,其强度性能与单晶镍基合金仍存在较大差距。这种特性组合使高熵高温合金在当前阶段更适合应用于温度相对较低(700~800 ℃)且成本敏感的关键部件,例如航空发动机低压涡轮叶片或工业燃气轮机热端部件,这为其在特定领域的商业化替代开辟了差异化发展路径。
综上所述,HESAs凭借独特的γ + γ′双相组织结构,在高温性能方面展现出与传统镍基高温合金竞争的潜力。传统镍基合金主要依赖有序γ′相沉淀强化,而HESAs除沉淀强化外,还具有高熵效应产生的晶格畸变强化等多种机制。目前HESAs在高温长期组织稳定性方面的研究尚不充分。性能方面,尽管HESAs在高温强度上仍与单晶镍基合金存在差距,但其成本优势明显。未来需加强组织稳定性研究,同时随着科研投入增加和技术突破,HESAs的综合性能有望进一步提升。
自HEAs提出之后,材料科学领域的研究方向发生了新的转变,探索复杂相空间中的广阔中心区域成为材料研究新方向,吸引了大量科研人员的开展研究。与此同时,工业界对新型高温合金的需求也愈发迫切。在这一背景下,2010年,Senkov等[34] 科研人员提出难熔高熵合金(RHEAs)的概念。这一创新理念的提出,为高温合金的发展开辟了新的道路。其中,典型的RHEAs有WNbMoTaV和HfNbTaTiZr这两类。WNbMoTaV合金具有高熔点和高强度的特点,在1600 ℃的高温环境下,其屈服强度仍能达到477 MPa[35];HfNbTaTiZr合金则具有轻质高强的特点,室温压缩断裂应变大于30%,在1000 ℃下仍保持约295 MPa的屈服强度[36]。这种卓越的高温性能,使得RHEAs迅速成为高温应用领域的关注焦点。随着研究的不断深入,RHEAs的元素拓宽至Ⅳ族(Ti、Zr和Hf)、Ⅴ族(V、Nb和Ta)和Ⅵ族(Cr、Mo和W)中的九种难熔元素,此外,为进一步优化合金性能,有时会也会向合金中添加Al、Si、C等元素[37]。合金成分的不断演进和优化,使RHEAs在高温应用领域具有巨大的潜力。
在难熔高熵合金(RHEAs)体系中,多数呈现单相体心立方(BCC)固溶体结构,部分合金因添加Al、Si等元素而呈现多相结构。在RHEAs中BCC相占主导地位是合理的,一方面,Ⅴ族和Ⅵ族的难熔金属元素均为BCC晶体结构,且在高温下具有良好的互溶性;另一方面,Ⅳ族元素(Ti、Zr、Hf)在高温下也呈BCC结构,虽然经同素异构转变后室温下为密排六方(HCP)结构。Senkov等[38]通过电弧熔炼制备的HfNbTaTiZr为单一的BCC结构。Feuerbacher等[39]制备的ZrNbTiVHf经历1500 ℃/6 h的均匀化处理后为BCC单相结构。
Al元素密度低且抗氧化能力优异,因此在难熔高熵合金(RHEAs)成分设计中是重要元素。由于Al与难熔元素之间具有较高的负混合焓,在RHEAs中引入Al元素时,常伴随B2相的形成[40-42]。值得注意的是,过量Al元素的添加使得合金基体发生有序化,表现为单一B2相结构[43]。少量添加Al元素则会在基体中引入纳米B2相,纳米B2沉淀相与位错的相互作用可有效提高合金的强度和塑性[44-45]。有一类特殊的BCC+B2双相RHEAs也称为难熔高熵超合金。
Laves相也是RHEAs中常见相之一,其形成通常与合金中Cr、Nb和Zr等元素,或者与Al、V和Zr三个元素组合相关[46-51]。Yurchenko等[49]制备一系列AlNbTiVZrxx = 0, 0.1, 0.25, 0.5, 1, 1.5)RHEAs,当Zr原子分数达到0.5后,合金中有ZrAlV类型的C14结构Laves相形成。Laves相在Cr-Zr、Cr-Ta、Cr-Ti和Cr-Mo-Zr等二元或三元体系中在固相线以下是稳定相,其形成可以归因于不同难熔元素之间原子尺寸之间的差异。Laves相的存在可以有效提高合金的室温和高温强度,但会显著降低合金的塑性[52-53]。此外Cr元素作为Laves相的重要形成元素,富Cr的Laves相存在也会提高合金的抗氧化能力[54-55]
除了B2和Laves相两类最常见的第二相,在RHEAs中还有硅化物和碳化物等析出相[56-63]。Xu等[58] 制备了(VNbTiTa)100−xSixx=0,2.5,5,10)RHEAs,Si元素的添加可以降低合金密度,提高合金的抗氧化能力,同时可以引入具有高熔点和高强度的硅化物提高合金的高温力学性能,达到提高合金综合性能的研究目标。(VNbTiTa)100−xSixx=2.5,5,10)在枝晶间区域形成了BCC+M5Si3共晶组织,当Si元素原子分数增加至10%时,有块状的M3Si形成。硅化物的存在显著提高了合金的室温和高温强度。通过对(VNbTiTa)100−xSix 进行高温压缩性能测试样品进行分析,发现合金在1200 ℃压缩后BCC基体上有纳米M5Si3型硅化物形成,这归因于基体中过饱和的硅元素在热压缩过程中发生了脱溶析出。受到这一启发, Xu等[64]通过简单的热轧工艺使最初脆性的VNbTiTaSi0.1具有良好的塑性变形能力。图3为TiVNbTaSi0.1合金组织和力学性能,如图3所示,热变形细化了VNbTiTaSi0.1的微观结构,并诱导了高密度的纳米硅化物(图3(b)),帮助合金获得约1250 MPa的屈服强度和约8%的断后伸长率(图3(g)、(h)中HR85)。Wang等[63]制备了AlNbTiV2Sixx=0,0.1,0.2,0.3,0.4,0.5)RHEAs,Si元素引入后形成M5Si3型硅化物,降低合金密度的同时,显著提高了合金的强度。在1073 K下AlNbTiV2Si0.5具有1154 MPa,当温度升高至1273 K时,硅化物的强化效果减弱。Wei等[59]通过电弧熔炼制备了Re0.5MoNbW(TaC)0.5,铸态组织由BCC相和MC类型的碳化物组成,BCC相和碳化物形成的共晶组织分布于枝晶BCC初生相的晶界上。
综上所述, RHEAs体系的相结构复杂多样,不同相的形成与合金元素的种类和含量密切相关,且相结构对合金性能具有至关重要的影响。深入研究这些相的形成机制和性能特点,对于开发高性能RHEAs具有重要意义。
图4(a)、(b)分别对比了RHEAs[27,46,52-53,58,65-72]、Inconel 718和Mar-M-247在不同温度下的屈服强度和比屈服强度。从图中可以清晰地看到,RHEAs 在800 ℃及以上的温度区间拥有显著的强度优势。对于高熔点和强度的WNbMoTa系列RHEAs,在1200~1600 ℃这一超出镍基合金应用范围的高温区间内,依然保持着卓越的强度。WNbMoTa和WNbMoTaV合金在1600 ℃时的屈服强度分别达到405 MPa和477 MPa[35]。Sun等[73]设计了NbxMoxTa50−xW50−xx = 5, 25, 45)系列RHEAs,通过成分设计调整枝晶偏析,Nb45Mo45Ta5W5达到较大室温压缩塑性(约6.1%)的同时在1600 ℃下具有约440 MPa的高屈服强度。这类RHEAs合金中含有大量Mo、Ta 和 W等高熔点元素,这充分表明此类元素对显著提升RHEAs高温力学性能的作用。为了保持RHEA高温下的力学性能,同时降低合金密度,Wang等[68] 还设计了 VxNbMoTa(x=0.25, 0.5, 0.75, 1.0)系列 RHEAs。随着 V 元素含量的增加,合金在凝固过程中会引发更强的溶质效应,进而提高晶粒生长限制因子,实现晶粒尺寸的细化,同时增大合金的晶格畸变程度。这些微观结构的优化显著提升了合金在室温和高温下的强度。具体而言,VNbMoTa合金在1000 ℃时的屈服强度和比屈服强度分别达到811 MPa和76 MPa·g−1·cm3,这一性能显著优于Mar-M-247和Inconel 718等传统高温合金。
还有一类以TiZrHfNb等为主元素的轻质RHEAs,具有优异高温强度的同时,密度显著低于WNbMoTa系列RHEAs。Senkov等 [35]制备的HfNbTaTiZr合金密度约为9.94 g/cm3,在800、1000 ℃下具有535、295MPa的屈服强度。Wang等[66]通过在HfNbTaTiZr合金中引入Mo/W元素,显著增强固溶强化效应。HfNbTaTiZrMoW合金在1000 ℃和1200 ℃时的屈服强度约为736 MPa和703 MPa,相比HfNbTaTiZr合金在相同温度下的屈服强度,HfNbTaTiZrMoW合金高温强度有了极大的提高。Senkov等[74]通过使用Al元素部分替代Hf元素,设计出Al0.4Hf0.6NbTaTiZr合金。Al元素与难熔元素之间具有较高的负混合焓,这有助于促进 B2 型短程有序结构的形成,从而提高合金的强度。Al0.4Hf0.6NbTaTiZr合金的室温强度显著提升至1841 MPa,在800 ℃和1000 ℃下的屈服强度约为796 MPa和298 MPa,超越了许多传统变形镍基高温合金。综上所述,RHEAs在高温应用领域表现突出,特别是在1200~1600 ℃这一温度区间,相较于传统高温合金,展现出显著优势。
此外,高抗蠕变能力是高温应用的关键要求。蠕变是指材料在恒定应力或恒定载荷作用下,随时间推移而发生的塑性变形行为。近年来,RHEAs在高温下的蠕变行为受到了广泛关注[75-78]。Sahragard-Monfared等[76] 对Nb45Ta25Ti15Hf15 RHEAs在900 ℃和50~300 MPa恒定真应力范围的拉伸蠕变行为进行深入研究。结果表明,Nb45Ta25Ti15Hf15在真空环境下的蠕变具有典型的幂律行为,应力指数为4.1,其蠕变行为主要由螺位错的交叉扭折碰撞控制(图4(c))。在低应变率(低于10−6 s−1)条件下,蠕变受空位/间隙偶极子的拖拽控制;而在较高应变率(≈10−5 s−1)下,蠕变则受割阶拖拽控制。如图4(d)所示,与氧化物弥散增强的CoCrNi合金相比,Nb45Ta25Ti15Hf15具有更好的抗蠕变能力。尽管其蠕变性能弱于CMSX-4,但优于CMSX-4不含γ′相的FCC基体。RHEAs在高温下展现出的优异力学性能,使其成为未来高温应用的潜在候选材料。
然而,RHEAs也存在诸多问题,如密度高、室温塑性差和抗氧化能力弱等问题。过去十几年间,针对RHEAs的问题,学者们提出了诸多有效的策略和范例[64,79-88]。Lei等[84] 制备了掺杂原子分数2%O的(TiZrHfNb)98O2 RHEAs,合金中的O以有序氧复合体的形式存在。与HEAs中常见的短程有序不同,有序氧复合体对位错运动有强烈的钉扎作用,促进了位错的交滑移,导致位错大量快速增加,使得(TiZrHfNb)98O2的变形模式从TiZrHfNb的平面滑移转变为波浪滑移,合金的强度和塑性均显著提升(屈服强度约1110 MPa,断后伸长率约28%)。Wei等[79]利用难熔元素之间的自然混合特性,设计了一种Ti38V15Nb23Hf24 RHEAs,该合金在铸态下具有>20%的拉伸断后伸长率,在1000 ℃下具有良好的相稳定性。Ti38V15Nb23Hf24的BCC基体上分布着大量纳米沉淀相β',β'相为体心四方结构,其与位错之间的相互作用有效提升了合金的塑性变形能力,这种成分筛选方法可有效指导新型RHEAs的设计。Wang等[81]提出一种调节Al-V-Nb-Ti-Zr系RHEAs平面滑移带的策略,Ti50Zr18Nb15V12Al5实现了约25%的均匀伸长率和近50%的断裂伸长率,同时屈服强度约为980 MPa。经过300 ℃/7天的长时间时效,基体上有大量B2类型的局部化学有序(LCO)形成,大量LCO分散了平面滑移带,而且变形中LCO的破坏会产生严重晶格畸变,促进了第二代滑移带的形成,丰富滑移带之间的相互作用为合金提供了稳定的加工硬化。Liu等[85]设计了Nb40Ti40Ta10Cr10和Nb45Ti30Ta15Al10两个低密度(分别约为7.7 g/cm3和8.0 g/cm3)RHEAs,二者具有良好的室温强塑性匹配(抗拉屈服≈800 MPa,断后伸长率>20%),而且在800 ℃下具有优异的抗氧化能力(20 h平均氧化速率<7.2 mg/cm2)。
综上所述,RHEAs高温下的强化机制主要为固溶强化,也可引入第二相获得析出强化。凭借着高熔点和高晶格畸变,在镍基合金使用温度以上的温度范围内(1200~1600 ℃),有着极为广阔的应用前景。然而,与镍基合金相比,RHEAs 的组织稳定性仍然较差,提升 RHEAs 的组织稳定性需要进一步精细的成分设计。在未来的发展进程中,应当致力于推动更多有关 RHEAs 综合性能的深入研究,助力 RHEAs 尽快实现实际应用。
在RHEAs提出四年后,Senkov等[74]在RHEAs中发现了类似传统镍基合金的微观结构。AlMo0.5NbTa0.5TiZr、 Al0.3NbTaTi1.4Zr1.3和Al0.5NbTa0.8Ti1.5V0.2Zr这三种合金最先被报道,三者均表现为BCC+B2纳米共格双相结构,后续具有类似微观结构的 RHEAs 被陆续发现[89-90]。因其组织结构类似于镍基高温合金中的γ+γ′结构,这类RHEAs被赋予新的名称—难熔高熵高温合金(RSAs)[91]。RSAs不仅具备密度低的优势,还展现出了优异的高温性能,在航空航天、能源动力等对材料高温性能要求极高的领域,RSAs具有相当的应用潜力。
RSAs微观组织最主要的特征就是BCC+B2相所构成的网篮状组织,其中大量弥散的BCC无序相被B2有序相构成的连续通道包围(图5(a)[92]),两相之间具有共格取向关系。Jensen等[92]通过真空电弧熔炼制备了AlMo0.5NbTa0.5TiZr,合金经过1400 ℃/24 h的均匀化以10 ℃/min的冷却速率炉冷后晶粒内部出现典型的网篮状组织,晶界处存在Al4Zr5六方相。无序的BCC相以块状沉淀物的形式存在,有序的B2相则以沉淀物之间的连续薄通道及通道交叉处的较厚结构形式存在。BCC相两个正交方向上的尺寸分别为10~55 nm和25~55 nm,B2相通道的宽度约为7 nm,两相之间的取向关系为〈100〉BCC // 〈100〉B2,{100}BCC // {100}B2,如图5(a)~(d)所示[92]
纳米双相组织的形成机制以及合金成分对微观组织的影响引发广泛研究[74,89,93-98]。Senkov等 [89]在AlMo0.5NbTa0.5TiZr的基础上设计了AlMo0.5NbTa0.5TiZr0.5、AlNbTa0.5TiZr0.5、Al0.5Mo0.5NbTa0.5TiZr和Al0.25NbTaTiZr。降低Zr元素含量可消除AlMo0.5NbTa0.5TiZr0.5中的BCC相,将Mo元素替换为Nb元素后,AlNbTa0.5TiZr0.5中的Al4Zr5六方相进一步消失。AlMo0.5NbTa0.5TiZr0.5在1000 ℃下的屈服强度约为935 MPa,AlNbTa0.5TiZr0.5在1000 ℃的屈服强度仅为535 MPa。降低Al元素的含量会形成由有序B2相基体和共格球形BCC相组成的Al0.5Mo0.5NbTa0.5TiZr。进一步减少Al元素,用Ta元素替代Mo元素,Al0.25NbTaTiZr保留了纳米双相组织,但BCC相的形态由球形转变为块状沉淀。Al0.5Mo0.5NbTa0.5TiZr和Al0.25NbTaTiZr在1000 ℃下的屈服强度分别为579 MPa和366 MPa。对可用的二元相图进行分析,由于合金体系中Nb/Ta和Zr元素之间存在混溶间隙,单一BCC相在高温冷却过程中会分解为两种BCC相。如果Zr元素含量降低,合金的成分就会偏离混溶间隙,相分离也就不会发生。由于Al与Zr之间具有较高的负混合焓,富Al和Zr元素的BCC相在冷却过程中有序化,从而形成B2相。Mo元素的添加可增强RSAs中的B2相,从而使合金在1000 ℃下具有更高强度。Whitfield等[95]制备了Ti45Ta15Zr40、Ti45Ta25Zr30、Ti45Ta35Zr20和Ti45Ta45Zr10,四种合金经过均匀化后于不同温度下进行长时间保温,在1000 ℃时四种合金均为单相BCC结构。在更低的温度下,存在两相区,Ti45Ta15Zr40、Ti45Ta25Zr30和Ti45Ta35Zr20显示出网篮状组织,与AlMo0.5NbTa0.5TiZr中的组织类似,这表明网篮状组织的形成与Ta、Zr元素之间的混溶间隙密切相关。
对于高温合金而言,高温环境下微观结构的稳定性是一项基本特征,RSAs在高温下的组织稳定性得到了深入研究[90,99-102]。Whitfield等[102]对AlMo0.5NbTa0.5TiZr RSAs在800 ℃和1200 ℃之间进行了1000 h的保温,结果表明BCC+B2双相组织并不稳定,在所有温度下晶粒内部形成大量Al-Zr金属间化合物,这种金属间化合物对合金的力学性能不利。1200 ℃下AlMo0.5NbTa0.5TiZr的相平衡状态为BCC相+Al-Zr金属间化合物,这说明B2相高温下不稳定,其形成是由于富Al/Zr的BCC相在冷却过程发生有序化。Soni等[99]对均匀化后的Al0.5NbTa0.8Ti1.5V0.2Zr RSAs在600~1200 ℃温度范围的相稳定性进行研究。在800 ℃和1000 ℃下均观察到Al-Zr金属间化合物的形成。未来需要对RSAs的成分设计进行深入的研究,以避免 Al-Zr 金属间化合物的形成。
图5(e)、(f)可以看出,AlMo0.5NbTa0.5TiZr在25~1200 ℃温度范围内的屈服强度和比屈服强度均高于三种镍基高温合金。AlMo0.5NbTa0.5TiZr合金的高强度源于其精细的纳米双相组织,高体积分数的相界面提供了较高的界面强化,在1200 ℃下仍具有约250 MPa的屈服强度。尽管RSAs在高温下具有显著的性能优势,但其室温压缩率普遍低于10%,因此RSAs很可能不具备拉伸变形能力[74,89,93]。RSAs的室温变形能力较差可能归因于有序的B2相为基体,若能实现“组织倒置”,即以BCC相为基体、B2相为纳米颗粒,则预计可提升RSAs的室温塑性。Soni等[103] 将均匀化后的Al0.5NbTa0.8Ti1.5V0.2Zr置于600 ℃下保温120 h后,其微观组织发生演变,BCC相转变为基体,B2相转变为沉淀相。实现组织倒置后的Al0.5NbTa0.8Ti1.5V0.2Zr不仅在室温和600 ℃下分别具有1345 MPa和1423 MPa的屈服强度,其室温压缩塑性也显著提高(>20%)。组织倒置主要是由弹性应变能和系统界面能降低驱动的。退火过程中成分的变化导致B2相的弹性模量增加,两相之间弹性模量的不均匀性使系统的弹性应变能增加,进而降低了微观组织的稳定性。此外,B2相纳米通道的断裂促使相邻BCC颗粒聚结并长大,有助于减少两相界面积并降低系统界面能[104]
RSAs的室温塑性较低,阻碍了其工业化应用的实现。因此,深入了解RSAs缺乏延展性的原因显得尤为重要。 Kumar等[105] 研究了Al0.5Nb1.25Ta1.25TiZr在室温至1200 ℃下的微观结构和性能。通过将均匀化后的合金分别在600 ℃(HT600)和800 ℃(HT800)下进行长时保温,形成两种双相微观结构。其中,HT600的基体为B2相,而HT800的基体为 BCC 相。HT800在室温下比HT600具有更高的压缩塑性,这归因于HT800以较软的BCC相为基体。然而,对HT800和HT600在不同温度下进行拉伸测试时发现,合金在弹性阶段即发生断裂,表现为典型的晶间断裂。通过对HT600在1000 ℃拉伸试样的分析可知,连续的Al-Zr金属间化合物在晶界处形成,沿晶界的无沉淀区发生剪切局部化。同时,Al-Zr金属间化合物为晶界裂纹的扩展提供了一条便捷路径(图6(a)[105])。最近Viswanathan等[106]制备了AlMo0.5NbTa0.5TiZr纳米双相组织,其中B2相为基体,晶界处存在Al4Zr5金属间化合物。对合金进行纳米压痕测试,研究发现B2相本身并不是固有的脆性,在纳米压痕变形过程中,B2相中会产生大量的位错,这些位错的布氏矢量为1/2〈111〉,并在{011}晶面上进行滑移(图6(b)~(e))。这些滑移系统的激活使B2相存在五个以上的剪切系统,预计B2相具有一定的塑性,B2相和BCC之间的滑移传递也被观察到。Al4Zr5金属间化合物硬且脆,在测试过程中会发生开裂,在压痕下方几乎没有位错产生和运动的迹象。因此,合金晶界处的Al4Zr5相为脆性相,导致AlMo0.5NbTa0.5TiZr缺乏塑性变形能力。若是消除晶界处Al-Zr金属间化合物,并且晶粒内的BCC相足够粗大,即使RSAs的基体为B2相,也可能具备室温塑性。
综上所述,RSAs与传统镍基高温合金类似,都具有双相组织,其强化机制主要依赖BCC+B2纳米双相结构。与镍基合金相比,RSAs在高温环境下相稳定性较差,其B2相会逐渐转变为HCP相。由于以硬而脆的B2相作为基体,RSAs的室温塑性表现不佳。未来,加强RSAs的成分设计与组织调控研究,对于优化其性能、提高其应用潜力具有重要意义。
HESAs、RHEAs和RSAs这三类高温HEAs因其卓越的高温性能,有望成为新一代高温合金,在航空航天、核工业等关键领域展现出巨大的应用潜力。然而,目前高温HEAs的研究仍局限于实验室,距离工业化应用还有诸多挑战。基于当前研究现状,对未来高温HEAs的发展趋势提出以下建议:
(1)对于HESAs,尽管其在高温强度、密度和抗氧化能力方面表现出色,但仍需在以下方面深入研究以加速其实际应用:
成分设计方面,需在降低密度和成本的同时确保高温性能的稳定性。通过添加Fe、Al、Ti、Cr等元素可有效减轻密度,但需要借助热力学建模(如CALPHAD)预测相稳定性,避免生成σ相或Laves相等有害脆性相。未来可引入Hf、Nb、W等难熔元素以增强高温强度,并添加Si、B等微量元素以优化晶界强度和抗氧化性能。为加速成分优化,建议结合高通量计算与机器学习技术,构建成分-组织-性能数据库,利用大数据分析筛选出兼具低密度、高强度和优异抗氧化性的合金配比。此外,探索新型多组元体系并优化析出相分布,以进一步提升合金的综合性能。
制备技术方面,需要突破实验室规模的限制,开发适用于工业生产的加工方法。目前,HESAs多采用真空电弧熔炼或粉末冶金等传统工艺,但这些方法难以制造复杂构件。未来可借助3D打印技术(如选区激光熔化或电子束熔融)制备复杂形状部件,并通过优化激光功率、扫描速率等参数精确调控微观结构,从而减少气孔和裂纹的产生。定向凝固技术可用于制备单晶或柱状晶HESAs,以显著提升其高温蠕变性能,增强工程适用性。同时,还需关注HESAs的焊接性能和机械加工性能,以满足工业应用的需求。
性能评价方面,需要加强对高温蠕变、疲劳和抗氧化性能的测试。当前研究多集中于短时高温力学性能,而对长期服役条件下的蠕变和疲劳行为了解不足。建议采用原位表征技术(如高温同步辐射X射线或中子散射)实时监测相演变和变形机制,揭示高熵效应对蠕变抗力的影响。此外,结合多尺度实验与模拟,构建性能预测模型,也有助于为该类材料的工程化应用提供相关理论支撑。
针对工业应用,HESAs的高温力学性能与单晶镍基高温合金相比仍有一定差距,且其组织稳定性和蠕变性能亟待评估。突破当前设计框架,深入探索合金高熵化对性能提升的潜在机制,仍是未来研究的重点方向。
(2)对于RHEAs,虽然其在高温强度方面表现出色,尤其在1200~1600 ℃的高温区间具有显著强度优势,但在抗氧化能力和组织稳定性等方面仍存在诸多挑战,仍需在以下方面深入研究以加速其实际应用:
在成分设计方面,需要平衡室温塑性、高温强度和抗氧化性能之间的关系。具有单相BCC结构的RHEAs的高温强度与其熔点呈正相关,然而,高熔点元素(例如W、Mo)的添加往往导致密度增加以及室温脆性问题。未来的研究方向应聚焦于开发多相RHEAs,通过设计具有韧性的BCC基体,并引入析出强化相(如B2或L12相)来优化性能。建议运用高通量计算方法,筛选出兼具低密度、优异抗氧化能力和相稳定性的成分体系。同时,借助热力学和动力学模拟来预测析出相的形核与生长行为,从而优化相比例和分布,以提升合金综合性能。
在制备技术方面,需要解决因合金熔点较高带来的制备加工难题。目前,RHEAs主要通过电弧熔炼或粉末冶金等传统方法制备。但由于合金熔点较高,液态金属流动性差,导致铸锭组织中常出现大量缩孔和缩松等缺陷。此外,含有较多W、Mo等元素的RHEAs室温塑性较差,难以采用常规机加工手段进行加工。3D打印技术作为未来制备这类难加工合金的潜在手段,可以利用其原位冶金优势实现材料成型一体化。深入研究3D打印技术,通过优化打印参数来调控析出相的尺寸和分布,有望提升合金的高温性能。
在性能评价方面,目前对于高温变形机理和抗氧化机制的研究相对有限。建议通过原位高温拉伸/压缩实验,并结合电子背散射衍射(EBSD)和透射电镜(TEM)等技术,揭示位错滑移、孪生和相变等机制。同时,需系统地测试RHEAs在氧化性环境下的长期稳定性,并深入研究Cr、Al、Si等元素在抗氧化膜形成过程中的作用机制。此外,可借助机器学习方法预测蠕变寿命和疲劳性能,并建立性能数据库以指导合金优化。RHEAs的性能研究应以核反应堆高温部件、航空发动机涡轮盘、叶片等应用场景为目标,着重研究与应用相关的高温蠕变/疲劳、室温塑性、抗氧化性等综合性能,为其极端环境应用提供基础数据支撑。
在工业应用方面,RHEAs相比镍基合金而言,其优势在于更高的熔点,这使得RHEAs能够在高温下维持高强度。然而,目前RHEAs存在室温与高温性能难以兼顾、抗氧化性能不佳等问题,且高熔点特性也使得一些传统制备手段(例如感应熔炼和气雾化制粉等)难以适用。如何充分利用RHEAs的高熔点优势,同时有效解决上述问题,将是RHEAs未来实现工业应用的关键所在。
(3)对于RSAs,尽管其在密度和高温强度方面表现出显著优势,但这类合金的室温塑性和组织稳定性较差,仍需要在以下方面深入研究以加速其实际应用:
在成分设计方面,需要重点关注B2相的形成与稳定性机制。在Al-Mo-Nb-Ta-Ti-Zr体系中,BCC+B2结构的形成与Ta/Nb-Zr的混溶间隙密切相关,然而,Al与难熔元素的二元体系通常无法形成B2相。未来研究可探索稳定二元B2相(例如Al-Ru、Al-Pd、Nb-Ru等),并利用热力学建模预测多组元体系中B2相的析出路径(如脱溶析出或调幅分解)。同时,应筛选具有本征塑性的B2相,优化BCC+B2双相结构的成分配比,此外,可探索具有调幅分解特征的体系(如Ti-Mo、Ti-W),以调控纳米级析出相的尺寸和分布,以优化合金综合力学性能。
在制备技术方面,需要实现纳米级微观结构的精确调控。目前,RSAs的制备多采用电弧熔炼或机械合金化,但析出相的均匀性难以控制。未来可深入研究3D打印技术在RSAs制备中的应用潜力,通过优化工艺参数来调控BCC/B2相的界面特性。此外,热处理和变形加工(如热轧或挤压)也有助于调控析出相的形貌和分布,从而提升合金的强度与塑性。
在性能评价方面,需要深入研究B2相的稳定性和双相界面的力学行为。建议采用原位TEM和同步辐射技术实时观察B2相在高温下的析出与演变过程,揭示其形核与生长机制;系统研究BCC/B2双相界面处的弹塑性约束,探索界面滑移和位错交互对抗裂扩展的影响。此外,还需要对合金的抗氧化性能进行研究,揭示Al、Cr等元素在提高合金抗氧化性能方面的作用机制。机器学习方法可用于预测力学性能和相稳定性,加速优异合金的筛选进程。
在工业应用方面,RSAs在组织稳定性和制备加工方面的问题限制了其工业应用。未来需要进一步研究RSAs的组织调控方法,以提高合金B2相的热稳定性,改善合金的变形加工能力,相关问题的解决对于推动RSAs的工业应用具有重要意义。
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2025年第45卷第5期
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doi: 10.11868/j.issn.1005-5053.2025.000081
  • 接收时间:2025-05-08
  • 首发时间:2026-04-09
  • 出版时间:2025-10-01
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  • 收稿日期:2025-05-08
  • 录用日期:2025-06-23
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    1北京理工大学 材料科学与工程学院,北京 100081
    2冲击环境材料技术国家级重点实验室,北京 100081
    3北京理工大学 唐山研究院,河北 唐山 063000
    4北京理工大学(珠海) 材料智能研发实验室,广东 珠海 519088

通讯作者:

马兆龙(1987—),男,博士,教授,研究方向为高熵合金,联系地址:北京市海淀区中关村南大街5号(100081),E-mail:
程兴旺(1976—),男,博士,教授,研究方向为高熵合金,联系地址:北京市海淀区中关村南大街5号(100081),E-mail:
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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