Article(id=1322941286042435949, tenantId=1146029695717560320, journalId=1322258626896822465, issueId=1322941226537857309, articleNumber=null, orderNo=null, doi=10.13700/j.bh.1001-5965.2025.0565, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1755014400000, receivedDateStr=2025-08-13, revisedDate=null, revisedDateStr=null, acceptedDate=1761235200000, acceptedDateStr=2025-10-24, onlineDate=1793343381653, onlineDateStr=2026-10-30, pubDate=1793376000000, pubDateStr=2026-10-31, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1793343381653, onlineIssueDateStr=2026-10-30, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1793343381653, creator=13701087609, updateTime=1793343381653, updator=13701087609, issue=Issue{id=1322941226537857309, tenantId=1146029695717560320, journalId=1322258626896822465, year='2026', volume='52', issue='10', pageStart='3237', pageEnd='3676', issueExtLink='null', onlineDate='null', pubDate='1793376000000', pubDateStr='2026-10-31', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=1, specialIssue=null, createTime=1793343367466, creator='13701087609', updateTime=1793344760378, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1322947068926505286, tenantId=1146029695717560320, journalId=1322258626896822465, issueId=1322941226537857309, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1322947068926505287, tenantId=1146029695717560320, journalId=1322258626896822465, issueId=1322941226537857309, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=3313, endPage=3328, ext={EN=ArticleExt(id=1322941286881296753, articleId=1322941286042435949, tenantId=1146029695717560320, journalId=1322258626896822465, language=EN, title=Progress in design and optimization of wide-temperature-range superelastic shape memory alloys, columnId=null, journalTitle=Journal of Beijing University of Aeronautics and Astronautics, columnName=null, runingTitle=null, highlight=null, articleAbstract=

Superelasticity is one of the most important functional characteristics of shape memory alloys, which essentially originates from stress-induced reversible thermoelastic martensitic transformation. The superelastic working temperature range is mainly influenced by the synergistic effect of alloy chemical composition and microstructure. The development status of several shape memory alloy systems with broad temperature range superelastic properties over the last ten years is methodically reviewed in this article, with an emphasis on contrasting the features and variations of various alloys in important performance parameters like recoverable strain, temperature dependence of critical stress, and superelastic temperature window. This article uses comparative analysis to support the design, preparation, and engineering application of novel wide-temperature-range superelastic shape memory alloys theoretically and practically, as well as to offer opportunities for the field's future development.

, authors=Mingfang QIAN1, 2, Zhao YIN1, Guisong WANG1, Xuexi ZHANG1, 3, *, Lin GENG1, 3, 4, authorsList=Mingfang QIAN, Zhao YIN, Guisong WANG, Xuexi ZHANG, Lin GENG, authorCompany=null, correspAuthors=Xuexi ZHANG, authorNote=null, correspAuthorsNote=
E-mail:
, copyrightStatement=Copyright © 2026 Journal of Beijing University of Aeronautics and Astronautics. 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, fund=null), CN=ArticleExt(id=1322941294812725654, articleId=1322941286042435949, tenantId=1146029695717560320, journalId=1322258626896822465, language=CN, title=宽温域超弹性形状记忆合金设计优化研究进展, columnId=null, journalTitle=北京航空航天大学学报, columnName=, runingTitle=null, highlight=null, articleAbstract=

超弹性是形状记忆合金最重要的功能特性之一,其本质来源于应力诱导的可逆热弹性马氏体相变。超弹性温度窗口主要受合金化学成分与微观组织结构的协同影响。为此,系统回顾了近10年来具有宽温域超弹性特性的多类形状记忆合金体系的发展现状,重点比较了不同合金在超弹性温度窗口、可恢复应变大小及临界应力对温度的依赖性等关键性能参数方面的差异与特点。通过对比分析,为新型宽温域超弹性形状记忆合金的设计、制备与工程应用提供了理论支持与实践参考,并对该领域未来的发展方向进行了展望。

, authors=钱明芳1, 2, 尹钊1, 王桂松1, 张学习1, 3, *, 耿林1, 3, 4, authorsList=钱明芳, 尹钊, 王桂松, 张学习, 耿林, authorCompany=null, correspAuthors=张学习, authorNote=null, correspAuthorsNote=
E-mail:
, copyrightStatement=版权所有 © 2026 北京航空航天大学学报(自然科学版)编辑部, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=wlwK30hqFiTiclnyI+wlPA==, magXml=EfZi6+Ha96vQnbrPhDjEBg==, pdfUrl=null, pdf=UtaUdwCXHB/p26PZ3b3eug==, pdfFileSize=9941338, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=UHOg9gaS5ghuxHVEDESQkg==, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=TLkoTPvpFkDBecoLejNupg==, mapNumber=null, fund=null)}, authors=[Author(id=1322941296263954857, tenantId=1146029695717560320, journalId=1322258626896822465, articleId=1322941286042435949, orderNo=0, firstName=null, middleName=null, lastName=null, nameCn=null, orcid=null, stid=null, country=null, authorPic=null, dead=0, email=null, emailSecond=null, emailThird=null, correspondingAuthor=0, authorType=1, ext={EN=AuthorExt(id=1322941296591110572, tenantId=1146029695717560320, journalId=1322258626896822465, articleId=1322941286042435949, authorId=1322941296263954857, language=EN, stringName=Mingfang QIAN, firstName=Mingfang, middleName=null, lastName=QIAN, prefix=null, suffix=null, authorComment=null, nameInitials=null, affiliation=null, department=null, xref=1, 2, address=1School of Materials Science and Engineering,Harbin Institute of Technology,Harbin 150001,China
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tenantId=1146029695717560320, journalId=1322258626896822465, articleId=1322941286042435949, language=CN, label=图10, caption=不同温度下合金的压缩应力-应变曲线, figureFileSmall=vtiPn8ZIZfNRN8evgUfvVA==, figureFileBig=4cfs4ttvgESIWmLLS7gFcA==, tableContent=null), ArticleFig(id=1322941308645540345, tenantId=1146029695717560320, journalId=1322258626896822465, articleId=1322941286042435949, language=EN, label=Table 1, caption=Performance parameters of wide temperature range superelastic Ni-Ti based SMA, figureFileSmall=null, figureFileBig=null, tableContent=
成分超弹性温区/K可逆应变/% $ \dfrac{\mathrm{d} \sigma_{\mathrm{c}}}{ \mathrm{d} T } \bigg/$(MPa·K−1)加载方式状态参考文献
 注:S表示固溶态,CD表示冷变形,NG表示纳米晶,CO表示复合材料。
Ni51.89Ti48.1140~2203.0~4.0−8.77/2.11压缩S/STG[32]
Ni51.8Ti48.240~1802.0~2.5−2.71/2.50压缩S/STG[33]
Ni51.63Ti48.3770~160~2.01.00压缩S/STG[32]
Ni51.54Ti48.4680~280~2.03.95压缩S/STG[32]
Ni50.8Ti49.2123~3233.5~4.0拉伸CD/STG[16]
Ni50.8Ti49.24.2~4752.5~5.0拉伸CD/STG[47]
Ni50.8Ti49.2119~3294.0~6.0拉伸CD/STG[51]
Ni50.8Ti49.2123~4234.8~8.6拉伸CD/STG[53]
Ni50.6Ti49.425~3001.75~2.2拉伸NG/STG[17]
Ni50Ti5093~4534.0~6.0拉伸CD/STG[52]
Ti49.2Ni44.8Co6123~223~4.03.17拉伸CD/NG[48]
Ti47.6Ni42.4Cu1070~200~1.5−3.25/1.96压缩S[34]
Ni49.4Ti48.1Sn2.5113~2983.6~5.0压缩S/STG[39]
Ni49.4Ti47.6Sn383~298~5.5压缩S/STG[39]
NiTiNb77~333~5.0−2.39/3.19拉伸CD/NG[49]
Ni50.2Ti49.8/
Ni46Ti47Nb3Fe4
77~4133.0~4.00.24/2.93拉伸CD/NG/CO[50]
), ArticleFig(id=1322941308758786555, tenantId=1146029695717560320, journalId=1322258626896822465, articleId=1322941286042435949, language=CN, label=表1, caption=

宽温域超弹性Ni-Ti基SMA性能参数

, figureFileSmall=null, figureFileBig=null, tableContent=
成分超弹性温区/K可逆应变/% $ \dfrac{\mathrm{d} \sigma_{\mathrm{c}}}{ \mathrm{d} T } \bigg/$(MPa·K−1)加载方式状态参考文献
 注:S表示固溶态,CD表示冷变形,NG表示纳米晶,CO表示复合材料。
Ni51.89Ti48.1140~2203.0~4.0−8.77/2.11压缩S/STG[32]
Ni51.8Ti48.240~1802.0~2.5−2.71/2.50压缩S/STG[33]
Ni51.63Ti48.3770~160~2.01.00压缩S/STG[32]
Ni51.54Ti48.4680~280~2.03.95压缩S/STG[32]
Ni50.8Ti49.2123~3233.5~4.0拉伸CD/STG[16]
Ni50.8Ti49.24.2~4752.5~5.0拉伸CD/STG[47]
Ni50.8Ti49.2119~3294.0~6.0拉伸CD/STG[51]
Ni50.8Ti49.2123~4234.8~8.6拉伸CD/STG[53]
Ni50.6Ti49.425~3001.75~2.2拉伸NG/STG[17]
Ni50Ti5093~4534.0~6.0拉伸CD/STG[52]
Ti49.2Ni44.8Co6123~223~4.03.17拉伸CD/NG[48]
Ti47.6Ni42.4Cu1070~200~1.5−3.25/1.96压缩S[34]
Ni49.4Ti48.1Sn2.5113~2983.6~5.0压缩S/STG[39]
Ni49.4Ti47.6Sn383~298~5.5压缩S/STG[39]
NiTiNb77~333~5.0−2.39/3.19拉伸CD/NG[49]
Ni50.2Ti49.8/
Ni46Ti47Nb3Fe4
77~4133.0~4.00.24/2.93拉伸CD/NG/CO[50]
), ArticleFig(id=1322941308855255549, tenantId=1146029695717560320, journalId=1322258626896822465, articleId=1322941286042435949, language=EN, label=Table 2, caption=Performance parameters of wide temperature range superelastic Fe-based SMA, figureFileSmall=null, figureFileBig=null, tableContent=
成分超弹性温区/K可逆应变/% $\dfrac{\mathrm{d} \sigma_{\mathrm{c}}}{ \mathrm{d} T }\bigg/ $(MPa·K−1)加载方式状态参考文献
 注:PG表示多晶,SG表示单晶。
Fe43.5Mn34Al15Ni7.5223~423~5.50.530拉伸PG[60]
Fe42Mn34Al15Ni7.5Ti1.5123~293~1.50.340压缩SG[61]
Fe43.5Mn34Al15Ni7.510~300~1.30.510压缩SG[19]
Fe42Mn34Al13.5Cr3Ni7.510~4731.1~2.30.085压缩SG[19]
Fe41Mn34Al12.5Cr5Ni7.510~3001.2~1.4−0.370压缩SG[19]
Fe38Mn36Al11Cr7.5Ni7.510~293~1.2−0.860压缩SG[19]
Fe43.5Mn34Al15Ni7.5193~4331.7~2.00.540拉伸 [1 0 0]SG[64]
Fe43.5Mn34Al15Ni7.5193~4331.5~2.00.410压缩 [1 0 0]SG[64]
Fe43.5Mn34Al15Ni7.5193~4331.8~2.00.580压缩 [1 2 3]SG[66]
Fe68.8Pd31.2240~3500.6~3.7压缩 [0 0 1]SG[69]
), ArticleFig(id=1322941309161439746, tenantId=1146029695717560320, journalId=1322258626896822465, articleId=1322941286042435949, language=CN, label=表2, caption=

宽温域超弹性Fe基SMA性能参数

, figureFileSmall=null, figureFileBig=null, tableContent=
成分超弹性温区/K可逆应变/% $\dfrac{\mathrm{d} \sigma_{\mathrm{c}}}{ \mathrm{d} T }\bigg/ $(MPa·K−1)加载方式状态参考文献
 注:PG表示多晶,SG表示单晶。
Fe43.5Mn34Al15Ni7.5223~423~5.50.530拉伸PG[60]
Fe42Mn34Al15Ni7.5Ti1.5123~293~1.50.340压缩SG[61]
Fe43.5Mn34Al15Ni7.510~300~1.30.510压缩SG[19]
Fe42Mn34Al13.5Cr3Ni7.510~4731.1~2.30.085压缩SG[19]
Fe41Mn34Al12.5Cr5Ni7.510~3001.2~1.4−0.370压缩SG[19]
Fe38Mn36Al11Cr7.5Ni7.510~293~1.2−0.860压缩SG[19]
Fe43.5Mn34Al15Ni7.5193~4331.7~2.00.540拉伸 [1 0 0]SG[64]
Fe43.5Mn34Al15Ni7.5193~4331.5~2.00.410压缩 [1 0 0]SG[64]
Fe43.5Mn34Al15Ni7.5193~4331.8~2.00.580压缩 [1 2 3]SG[66]
Fe68.8Pd31.2240~3500.6~3.7压缩 [0 0 1]SG[69]
), ArticleFig(id=1322941309501178371, tenantId=1146029695717560320, journalId=1322258626896822465, articleId=1322941286042435949, language=EN, label=Table 3, caption=Performance parameters of wide temperature range superelastic Cu-based SMAs, figureFileSmall=null, figureFileBig=null, tableContent=
成分超弹性温区/K可逆应变/% $\dfrac{\mathrm{d} \sigma_{\mathrm{c}}}{ \mathrm{d} T }\bigg/ $(MPa·K−1)加载方式状态参考文献
 注:BG表示竹节晶织构,CG表示粗晶,SG表示单晶。
Cu70.6Al17.5Mn11.9215~393~10.01.86拉伸CG[8]
Cu68.8Al17.9Mn13.377~3536.0~10.02.00拉伸CG[8]
Cu68Al17Mn1577~2230.8~1.32.23拉伸BG[72]
Cu68Al17Mn154.2~160~2.02.05拉伸SG[10]
Cu71.1Al17.2Mn11.7223~313~8.02.92拉伸BG[9]
), ArticleFig(id=1322941309610230277, tenantId=1146029695717560320, journalId=1322258626896822465, articleId=1322941286042435949, language=CN, label=表3, caption=

宽温域超弹性Cu基SMA性能参数

, figureFileSmall=null, figureFileBig=null, tableContent=
成分超弹性温区/K可逆应变/% $\dfrac{\mathrm{d} \sigma_{\mathrm{c}}}{ \mathrm{d} T }\bigg/ $(MPa·K−1)加载方式状态参考文献
 注:BG表示竹节晶织构,CG表示粗晶,SG表示单晶。
Cu70.6Al17.5Mn11.9215~393~10.01.86拉伸CG[8]
Cu68.8Al17.9Mn13.377~3536.0~10.02.00拉伸CG[8]
Cu68Al17Mn1577~2230.8~1.32.23拉伸BG[72]
Cu68Al17Mn154.2~160~2.02.05拉伸SG[10]
Cu71.1Al17.2Mn11.7223~313~8.02.92拉伸BG[9]
), ArticleFig(id=1322941309689922056, tenantId=1146029695717560320, journalId=1322258626896822465, articleId=1322941286042435949, language=EN, label=Table 4, caption=Performance parameters of other wide temperature range superelastic SMA, figureFileSmall=null, figureFileBig=null, tableContent=
成分超弹性温区/K可逆应变/% $\dfrac{\mathrm{d} \sigma_{\mathrm{c}}}{ \mathrm{d} T }\bigg/ $(MPa·K−1)加载方式状态参考文献
 注:SG表示单晶。
Ni45Co5Mn36In144.2~200~2.0−0.83压缩SG[74]
Co51Cr27Ga11Si11198~298~3.5−3.18压缩SG[75]
Co55.7Cr23.3Al10.5Si10.5198~423~2.5−1.12/1.09压缩 [0 0 1]SG[76]
Ni35Co20Fe18Ga27123~423~11.0拉伸SG[77]
Mg78.7Sc21.3123~298~1.0拉伸STG[14]
Ti75.25Al20Cr4.754.2~400~5.7−2.13/2.49拉伸SG[78]
), ArticleFig(id=1322941309924803081, tenantId=1146029695717560320, journalId=1322258626896822465, articleId=1322941286042435949, language=CN, label=表4, caption=

其他宽温域超弹性SMA性能参数

, figureFileSmall=null, figureFileBig=null, tableContent=
成分超弹性温区/K可逆应变/% $\dfrac{\mathrm{d} \sigma_{\mathrm{c}}}{ \mathrm{d} T }\bigg/ $(MPa·K−1)加载方式状态参考文献
 注:SG表示单晶。
Ni45Co5Mn36In144.2~200~2.0−0.83压缩SG[74]
Co51Cr27Ga11Si11198~298~3.5−3.18压缩SG[75]
Co55.7Cr23.3Al10.5Si10.5198~423~2.5−1.12/1.09压缩 [0 0 1]SG[76]
Ni35Co20Fe18Ga27123~423~11.0拉伸SG[77]
Mg78.7Sc21.3123~298~1.0拉伸STG[14]
Ti75.25Al20Cr4.754.2~400~5.7−2.13/2.49拉伸SG[78]
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宽温域超弹性形状记忆合金设计优化研究进展
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钱明芳 1, 2 , 尹钊 1 , 王桂松 1 , 张学习 1, 3, * , 耿林 1, 3, 4
北京航空航天大学学报 | 2026,52(10): 3313-3328
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北京航空航天大学学报 | 2026 , 52 (10) : 3313 -3328
宽温域超弹性形状记忆合金设计优化研究进展
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钱明芳1, 2, 尹钊1, 王桂松1, 张学习1, 3, * , 耿林1, 3, 4
作者信息
  • 1哈尔滨工业大学 材料科学与工程学院,哈尔滨 150001
  • 2哈尔滨工业大学 材料结构精密焊接与连接全国重点实验室,哈尔滨 150001
  • 3哈尔滨工业大学 金属精密热加工国家级重点实验室,哈尔滨 150001
  • 4哈尔滨工业大学 苏州研究院,苏州 215104
通讯作者:
Progress in design and optimization of wide-temperature-range superelastic shape memory alloys
Mingfang QIAN1, 2, Zhao YIN1, Guisong WANG1, Xuexi ZHANG1, 3, * , Lin GENG1, 3, 4
Affiliations
  • 1School of Materials Science and Engineering,Harbin Institute of Technology,Harbin 150001,China
  • 2State Key Laboratory of Precision Welding and Joining of Materials and Structures,Harbin Institute of Technology,Harbin 150001,China
  • 3State Key Laboratory of Metal Precision Hot Processing,Harbin Institute of Technology,Harbin 150001,China
  • 4Suzhou Research Institute,Harbin Institute of Technology,Suzhou 215104,China
  • Corresponding Author:
出版时间: 2026-10-31 doi: 10.13700/j.bh.1001-5965.2025.0565
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超弹性是形状记忆合金最重要的功能特性之一,其本质来源于应力诱导的可逆热弹性马氏体相变。超弹性温度窗口主要受合金化学成分与微观组织结构的协同影响。为此,系统回顾了近10年来具有宽温域超弹性特性的多类形状记忆合金体系的发展现状,重点比较了不同合金在超弹性温度窗口、可恢复应变大小及临界应力对温度的依赖性等关键性能参数方面的差异与特点。通过对比分析,为新型宽温域超弹性形状记忆合金的设计、制备与工程应用提供了理论支持与实践参考,并对该领域未来的发展方向进行了展望。

形状记忆合金  /  超弹性  /  宽温域  /  马氏体相变  /  组织调控

Superelasticity is one of the most important functional characteristics of shape memory alloys, which essentially originates from stress-induced reversible thermoelastic martensitic transformation. The superelastic working temperature range is mainly influenced by the synergistic effect of alloy chemical composition and microstructure. The development status of several shape memory alloy systems with broad temperature range superelastic properties over the last ten years is methodically reviewed in this article, with an emphasis on contrasting the features and variations of various alloys in important performance parameters like recoverable strain, temperature dependence of critical stress, and superelastic temperature window. This article uses comparative analysis to support the design, preparation, and engineering application of novel wide-temperature-range superelastic shape memory alloys theoretically and practically, as well as to offer opportunities for the field's future development.

shape memory alloy  /  superelasticity  /  wide temperature range  /  martensitic transformation  /  microstructure regulation
钱明芳, 尹钊, 王桂松, 张学习, 耿林. 宽温域超弹性形状记忆合金设计优化研究进展. 北京航空航天大学学报, 2026 , 52 (10) : 3313 -3328 . DOI: 10.13700/j.bh.1001-5965.2025.0565
Mingfang QIAN, Zhao YIN, Guisong WANG, Xuexi ZHANG, Lin GENG. Progress in design and optimization of wide-temperature-range superelastic shape memory alloys[J]. Journal of Beijing University of Aeronautics and Astronautics, 2026 , 52 (10) : 3313 -3328 . DOI: 10.13700/j.bh.1001-5965.2025.0565
形状记忆合金(shape memory alloy,SMA)因其独特的形状记忆效应和超弹性特性,在航空航天、汽车、医疗器械等领域受到广泛关注[1-3]。SMA的超弹性是指材料在外力作用下发生可逆的大应变(通常4%~8%,甚至更高),卸载后几乎完全恢复原始形状,而无需加热恢复的一种力学行为,其源于应力诱导马氏体相变(stress-induced martensitic transformation, SIMT)。施加外载时,母相转变为马氏体,产生显著的非线性变形;卸除外载后,马氏体因热力学不稳定性自发逆转变为奥氏体,从而实现形变恢复[4]。需要说明的是,本文所讨论的“超弹性(superelasticity)”是材料学和SMA研究领域普遍采用的术语,特指由应力诱导的可逆马氏体相变所导致的可恢复应变行为[4-5],而非力学学科中多用于橡胶、高分子、软组织等高弹性体的“超弹性(hyperelasticity)”概念,高弹性体的超弹性主要来源于分子链的拉伸与收缩,通常可用超弹性本构模型来描述[6-7]。
根据应力-应变曲线的特征,SMA的超弹性可分为宽滞后型与窄滞后型2类。宽滞后超弹性通常伴随着一级马氏体相变[8-10],具有明显的应力滞后,可在循环加卸载过程中形成应力-应变环,从而实现机械能耗散,可应用于被动阻尼和缓冲器件[11-13]。相比之下,窄滞后或近线性超弹性通常与应力诱导弱马氏体相变或连续马氏体相变有关[14-17],其应力响应更平滑、滞后更小,适用于对灵敏度、精度、循环稳定性和能量效率要求较高的精密工程场景[16]。
考虑到SMA广泛的应用领域,其实际应用往往涉及多变或极端的温度环境。例如,民用汽车中发动机舱的温度可达233~398 K,驾驶舱区域通常处于233~358 K之间[18]。而在深空探测等极端场景下,SMA器件需面对更严峻的环境挑战,如火星地表温度波动范围为120~290 K,月球昼夜温差甚至高达100~400 K[19-20]。因此,为实现SMA在复杂工况下的功能响应,亟须开发具有宽温域超弹性的合金体系。调控材料的成分、相变特征、进行组织结构设计,已成为构建适应多温区环境功能器件的关键手段。
尽管近年来已有诸多宽温域超弹性SMA的研究工作,但目前仍缺乏系统综述不同合金体系在超弹性温度窗口调控方面的最新进展的文献。过去10年间,宽温域超弹性SMA的研究取得了长足发展,本文旨在系统总结上述研究成果,特别是围绕合金设计理念、组织调控手段、制备工艺路径等方面进行归纳与分析,为未来高性能宽温域超弹性SMA的研究提供理论指导与设计思路。需要说明的是,本文以超弹性温度窗口大于100 K作为宽温域超弹性SMA的评判标准,据此标准筛选了目前研究较为系统、代表性强的合金体系,包括Ni-Ti基、Cu基、Fe基、Ni基、Co-Cr-Al-Si、Mg-Sc及Ti-Al-Cr等SMA,并对其超弹性温度窗口、微观组织结构演化机制与适用工况进行比较分析,力求系统呈现该领域研究进展。
马氏体相变是一种典型的一级相变,具有明显的温度和应力滞后,这种特性限制了超弹性在宽温域内的稳定表现。因此,为实现宽温域超弹性功能,有必要采取策略性设计以有效拓宽SMA的超弹性温度窗口。
通常而言,SMA的超弹性温度窗口由2个界限决定,如图1所示。下限温度由逆马氏体相变结束温度Af控制,当环境温度低于Af时,材料超弹性行为迅速减弱甚至消失,转而表现为形状记忆效应。上限温度则由材料屈服强度σs决定,由Clausius-Clapeyron关系[4]可知,SIMT的临界应力σc随温度升高而增加,而σs则趋于下降。当二者相等时,即标志着达到超弹性的温度上限。超过此温度,塑性变形(如位错滑移)优先于SIMT发生,材料超弹性迅速衰减[8]。因此,为在更高温度下获得超弹性,必须使材料具备高的屈服强度。综上,降低Af的同时提高σs,是实现宽温域超弹性的通用策略之一,适用于大多数SMA。
另外,近年来发展出以组织调控获得应变玻璃(strain glass, STG)转变的超弹性合金,为拓宽超弹性温度窗口提供了另一种有效路径。STG起源于合金中缺陷(点缺陷、位错、纳米析出相等)引入的随机应力场,其抑制了合金的一级马氏体相变,使得马氏体相变不能形成长程有序相,而是被“冻结”在局域纳米尺度上。STG具有以下典型特征:①宏观晶体结构不随温度的变化而变化,体现在变温X射线衍射(X-ray diffraction,XRD)衍射峰保持不变和DSC相变峰消失;②纳米尺度有序,体现在透射电子显微镜(transmission electron microscope,TEM)下观察到纳米畴的存在;③零场冷却/场冷却(zero-field cooling/field cooling,ZFC/FC)实验中冷却时遍历性的连续损失;④符合Vogel-Fulcher关系的储能模量频散[22-25]。STG合金表现出窄滞后、宽温域的独特超弹性特性[22-25]。其核心设计理念是在奥氏体基体中引入纳米尺度的马氏体胚(纳米畴),这些稳定存在的微结构单元在宽温度范围内可作为马氏体形核核心,在加载与卸载过程中发生可逆性长大与收缩。这种机制不仅显著降低了σc对温度的敏感性,还有效拓宽了超弹性响应的工作温区。此外,晶粒细化同样有助于降低σc的温度敏感性[26-27],并提高屈服强度,从而进一步拓宽超弹性温度窗口。
综上所述,拓宽SMA的超弹性温度窗口可通过3条路径协同实现:①降低马氏体相变温度;②提升合金屈服强度;③降低σc对温度的敏感性。上述策略的结合有利于开发出性能优异的宽温域超弹性材料。
Ni-Ti基SMA是目前研究最为广泛的SMA体系之一。为拓宽其超弹性温度窗口,研究者主要采用以下策略:①引入适量点缺陷以降低相变温度,并通过固溶强化提升屈服强度;②通过高密度点缺陷或位错诱导材料转变为STG合金,以降低σc的温度敏感性;③利用共格纳米析出相和位错双重机制强化基体,提高σs;④构建复合结构以协同提高超弹性响应性能。通常,这些手段会组合应用以提高Ni-Ti基合金在更宽温域内的超弹性表现。
Ni-Ti二元合金的相变温度对Ni含量极敏感。在富Ni合金中,Ni的摩尔分数每增加0.01,马氏体相变开始温度Ms将下降约100 K[28-29]。然而,由于富Ni合金在673~773 K时效处理过程中会析出Ni4Ti3相,使基体Ni含量下降,从而导致相变温度再次升高。因此,为获得具有低相变温度的稳定组织,通常采用1173~1273 K高温固溶处理与水淬工艺。这种通过引入点缺陷的方法降低了Ni-Ti合金的相变温度,同时也通过固溶强化效应提高了合金的屈服强度。
当研究者向Ni-Ti合金中添加足量Ni元素后(Ni的摩尔分数大于0.51),发现了一种新的应变状态,即STG[30]。STG的特征是不发生热致马氏体相变及B2基体中存在可长大的马氏体纳米畴。随后,Wang等[31]证明,尽管STG本身不会发生自发的长程有序马氏体相变,但在额外外场(如应力场)的作用下,仍能够克服局部动态势垒,从而诱发长程有序的马氏体相变。
Niitsu等[32-33]对不同成分高掺杂量富镍Ni-Ti固溶态多晶合金进行了深入研究,通过过量掺杂Ni元素使合金处于STG状态,从而获得宽温域超弹性。图2为4种不同成分STG合金在不同温度下的压缩应力-应变曲线,4种合金均具有宽温域超弹性特性。图中:数字表示温度值,单位为K。但是,如图2(a)所示,当温度升高至接近室温时,合金的残余应变随着温度升高而增加,说明固溶态Ni-Ti合金在高温下的强度不够,温度升高,位错滑移加剧,不利于获得较高温度下的超弹性。
第三元素的添加同样可以降低SMA的相变温度,如Cu[34-35]、Fe[36-37]、Nb[38]、Sn[39-40]、V[41-42]、Co[43-44]、Cr[43]、Mn[43]和Hf[45-46]等。2016年,Kimura等[34]研究了Ti50−xNi40+xCu10合金(x = 0~3.0)的马氏体相变行为与超弹性,发现样品中存在B2→B19、B19→B19'、B2→I和I→B19多种相变过程,并且在不发生热致相变的Ti47.6Ni42.4Cu10合金中检测到宽温域超弹性特性,温度窗口为70~200 K,但当温度低于100 K时,超弹性应变无法完全恢复。最近,Yin等[39]报道了具有宽温域超弹性特性的Ni49.4Ti50.6−xSnx(x=2.5,3)三元合金,当Sn掺杂含量摩尔分数>0.025时,合金处于STG状态,其中,Ni49.4Ti47.6Sn3合金在83~298 K具有约5.5%的压缩超弹性特性,不过,虽然通过固溶强化效果提高了合金屈服强度,但高温下合金的超弹性性能仍然不佳。
上述报道中的材料均为固溶态Ni-Ti基SMA,且在低于室温的环境下展现出良好的宽温域超弹性特性,但在高温条件下的超弹性表现仍存在明显不足。这主要归因于:固溶态Ni-Ti基合金的屈服强度较低,当温度升高,容易发生位错滑移,从而破坏SIMT机制,导致超弹性性能迅速衰减。因此,为进一步拓宽Ni-Ti基SMA的超弹性温度窗口,亟须通过适当的热-机械处理手段对合金的组织结构进行优化调控,提升合金的高温屈服强度与结构稳定性,从而实现更宽温域内的稳定超弹性响应。
冷变形是在Ni-Ti合金中引入位错等缺陷的一种有效方法,Ni-Ti基SMA中常见的冷变形方法有冷轧、冷拉拔、等通道挤压、高压扭转等。在冷变形过后,一般会进行473~723 K的短时退火,退火的目的除了使部分位错回复、恢复超弹性性能外,还有细化晶粒、引入纳米析出相或纳米马氏体畴,提高合金可恢复应变、提高疲劳性能的作用。
Liang等[15-16]研究了不同冷轧变形量Ni50.8Ti49.2合金的相变行为与应力应变响应,当冷轧变形量超过27%时,Ni50.8Ti49.2合金处于STG状态,基体中存在B19'马氏体纳米畴,在加卸载过程中,纳米畴的连续长大与收缩导致了合金具有近线性超弹性的特征,并且在123~323 K范围内获得了约4%的可恢复应变(见图3(a)),指出可以通过“缺陷工程”在SMA中诱导STG态从而获得优异超弹性。除了室温冷轧变形外,Zhao等[47]研究了液氮温度冷轧Ni50.8Ti49.2合金,对比室温冷轧NiTi合金,合金在马氏体状态下更容易产生位错等缺陷,这使得在液氮温度冷轧13%变形量即可获得STG合金,并在4.2~475 K具有宽温域超弹性特性。Ahadi等[17]报道了严重塑性变形Ni50.6Ti49.4合金的宽温域超弹性特性,合金组织由约5 nm的奥氏体晶粒、高密度位错及B19'马氏体纳米畴组成,降温过程中合金发生STG转变,最终获得了25~300 K范围的近线性超弹性,可恢复应变为1.5%~2%,如图3(b)所示。
2023年,Dang等[48]报道了具有大可恢复应变(6%)的宽温域超弹性Ti49.2Ni44.8Co6合金,并展现出较高的绝热温变(10.7 K)和循环稳定性,如图3(c)所示。合金通过45%冷轧变形结合673 K/1 h退火处理,最终得到纳米晶、残余位错、纳米Ni4Ti3析出相共存的组织结构。纳米晶的晶界、Co原子掺杂和残余位错引起的局部晶格畸变应力场稳定奥氏体母相,降低了相变温度。此外,纳米结构和纳米析出强化了基体,加载过程中有效抑制了位错滑移和形变孪生,使材料在加载与卸载过程中表现出较大的稳定功能响应。
除了冷轧外,还有研究者通过冷拔丝获得具有宽温域超弹性的Ni-Ti基SMA。马之远[49]通过冷拔工艺(变形率56%)制备了非晶Ni-Ti-Nb微丝,随后通过低温退火使非晶合金晶化形成纳米晶,与商用NiTi合金相比,晶粒尺寸为20 nm的NiTiNb微丝具有超高的σc,所有温度下的σc均超过1.4 GPa,并且微丝在77~333 K的温度范围内具有超弹性。这种特性主要源于纳米尺度成分非均匀对相变热力学、动力学及屈服强度3方面的影响。Hu等[50]设计了一种纳米晶NiTi/NiTiNbFe层状复合材料,在宽温度范围内利用晶格应变匹配和纳米晶强化机制,通过组合2种本身不具有宽温域超弹性的组分,实现了宽温域超弹性特性(77~413 K),这种复合机制为制备宽温域超弹性合金提供了另一种可行方法。
一般来说,673~723 K退火是冷变形NiTi合金获得优异超弹性的典型手段。然而,近年来还有研究者探究了更低温度(如473~573 K)退火对合金超弹性特性的影响,并取得了显著的成果。Liang等[51]对40%冷轧变形Ni50.8Ti49.2合金在473 K退火2 h后发现合金在降温过程中发生了两步STG转变,即B2→R相STG→B19'相STG,相较更高温度退火合金(发生一级马氏体相变),这种两步STG转变合金在室温具有更好的可恢复应变与循环稳定性,并在119~329 K具有宽温域超弹性,这种特性源自473 K退火合金中R相纳米畴和B19'纳米畴的同时存在。Qian等[52]对45%冷轧变形Ni50Ti50合金在573 K短时退火2~10 min后获得了一种交叉STG合金,这种合金具有宽的工作温度窗口(93~453 K)及大的可恢复应变(4%~6%),这种特性源于交叉STG合金独特的纳米组织演变路径,冷却过程中,这种合金内部发生STG的结晶过程,即STG缓慢转变为马氏体,随着温度的降低,在B2母相基体内逐步出现尺寸在数纳米至数十纳米范围的B19'马氏体结构,这一过程贯穿于较宽的温度范围,促进了大可恢复应变与宽工作温度范围的实现。
2024年,Xu等[53]报道了一种具有超高强度(1.8 GPa)、超低模量(10.5 GPa)及宽温域(123~423 K)超弹性的双种子STG(dual seed STG,DS-STG)Ni50.8Ti49.2合金,如图4所示,通过三步法制备获得这种合金,先将合金拉伸至50%伸长率,随后在573 K短时退火10 min,获得双交叉STG(dual crossover STG,DC-STG),最终将退火的合金再次拉伸12%的变形获得DS-STG,这种DS-STG合金内部具有R相和B19'相2类纳米晶种子结构,该独特的DS-STG状态使合金具有类似聚合物的超低模量特性、宽温域超弹性、超过百万次的室温超弹性循环稳定性(5×106)。
综上所述,Ni-Ti基SMA可通过多种结构调控手段实现宽温域超弹性,主要包括点缺陷掺杂、位错引入、析出相强化及纳米晶组织设计等,其本质是通过对合金微观组织的精准调控,构建出有利于应力诱导相变和形变可逆性的多级结构,从而实现热力学稳定性与力学响应性能的协同提升。此外,基于异质结构的复合强化策略,通过不同功能相的协同效应,实现材料性能的“功能叠加”,也是当前实现宽温域超弹性的一种发展方向。
表1对近年来已报道的Ni-Ti基宽温域超弹性合金的关键参数进行了系统归纳。需要指出的是,对于窄滞后型超弹性合金,由于其应力-应变曲线呈现近线性特征,难以明确界定σc,在dσc/dT斜率统计中不予包含。对于具有凹型σc-T的Ni-Ti基合金,分别给出了其在低温段与高温段的斜率数值,下文涉及其他合金体系的统计方式也遵循相同标准。
SMA的超弹性行为源于其热弹性马氏体相变机制。在冷却过程中,马氏体相逐步扩展长大,而在加热过程中,则可逆地收缩回奥氏体相。这一相变的可逆性是实现可恢复形变的基础。然而,与Ni-Ti基合金不同,大多数Fe基SMA表现出非热弹性的马氏体相变特征,其相变过程通常伴随不可逆的微观结构,导致缺乏可逆应变行为,难以展现典型的超弹性性能。因此,构建热弹性马氏体相变机制是Fe基SMA实现宽温域超弹性的先决条件[54-58]。
研究表明,通过在Fe基合金母相中引入共格析出相,可在局部区域建立稳定的应力场,促使合金发生可逆的热弹性马氏体相变。这一机制为Fe基合金实现超弹性提供了理论基础,并为其宽温域超弹性设计提供了思路。
1) 共格析出相对超弹性的影响。对于三元Fe-Mn-Al合金,其本征马氏体相变属于非热弹性/半热弹性类型[59]。当掺杂Ni元素后,多晶Fe-Mn-Al-Ni合金中会形成共格析出相,促使合金发生热弹性马氏体相变,从而展现出超弹性特性[60]。Omori等[60]在Fe43.5Mn34Al15Ni7.5多晶合金中成功实现了超弹性,向Fe-Mn-Al合金中添加Ni后,在A2无序基体中形成了纳米级B2有序析出相,在冷却和加热过程中分别观察到马氏体片的生长与收缩,证实了热弹性马氏体相变的发生。如图5所示,与商用Ni-Ti合金相比(插图),多晶Fe43.5Mn34Al15Ni7.5合金表现出更优异的宽温域超弹性行为,其可恢复应变超过5%。该合金还呈现出一个独特特性:在宽温度范围内,σc具有低的温度依赖性,即合金在77~513 K温度区间内,临界拉伸应力随温度变化的斜率仅为0.53 MPa/K,表明其在深空探测等极端环境应用中具有巨大潜力。
此后,共格析出相的尺寸、体积分数及成分对超弹性的影响得到了广泛研究。Tseng等[55]指出析出相对材料超弹性具有显著调控作用,在Fe43.5Mn34Al15Ni7.5合金中,时效温度与时间会改变B2纳米析出相的尺寸、体积分数及化学成分,进而影响相变温度、超弹性应变、σc及滞后效应,研究发现,473 K保温3 h的最优时效处理可形成6~10 nm的第二相析出颗粒,使材料在室温下获得约7.2%的超弹性应变。需要注意,虽然纳米级共格析出相有利于Fe-Mn-Al-Ni-X合金的超弹性性能,但并非所有析出相都具有积极作用。例如,在晶界处析出的γ相就会对Fe-Mn-Al-Ni-X合金的超弹性产生不利影响[61]。
在Vollmer等[61]的研究中,通过用Ti替代Al元素,成功降低了Fe-Mn-Al-Ni单晶合金对淬火工艺的敏感性,并提升了其超弹性性能,研究结果表明,Ti元素的添加能显著抑制γ相的形成,该相在其前期研究中被发现会形成锯齿状晶界形貌,会对可逆相变过程产生不利影响[62],最终,经523 K时效3 h后,Fe42Mn34Al15Ni7.5Ti1.5合金在123~293 K温域内展现出658~719 MPa的高σc,且应力滞后约达400 MPa,表明其具有优异的阻尼性能,值得注意的是,该合金的σc和应力滞后大小值达到前文所述473 K时效3 h的Fe43.5Mn34Al15Ni7.5合金[55]的2倍和3倍。
2020年,Xia等[19]报道了一种Fe-Mn-Al-Cr-Ni五元超弹性合金,其在10~400 K的宽温域范围内表现出近乎零或负的σc温度依赖性,研究者认为这一现象源于极小的熵变ΔS及ΔS的改变,与四元合金类似[63],该五元合金中析出的β-NiAl相对热弹性马氏体相变起关键作用。当Cr含量(摩尔分数)从0.000增至0.075时,σc的温度依赖性由正转负。并且添加摩尔分数为0.03的Cr的合金,其σc-T曲线平均斜率仅为0.085 MPa/K(见图6,图中数字表示温度值,单位为K),较传统Fe-Mn-Al-Ni合金(0.514 MPa/K)和商用Ti-Ni合金(5.87 MPa/K)降低了1~2个数量级,这为深空探测用材料提供了新的选择方案。
2) 加载方向与加载方式对超弹性的影响。Tseng等[55,64]研究了Fe43.5Mn34Al15Ni7.5单晶沿[1 0 0]方向的拉伸与压缩超弹性,发现在193~433 K的宽温域内,合金在拉伸(0.51 MPa/K)和压缩(0.41 MPa/K)状态下均表现出较低的σc温度依赖性(见图7(a)、图7(d))。值得注意的是,压缩测试中的样品展现出比拉伸测试更优的形状恢复性能。这种差异主要源于2个因素:①拉伸样品在奥氏体基体中具有发卡状位错(见图7(b)),并且在奥氏体-马氏体界面上存在高密度平行位错(见图7(c));而压缩样品的界面相对平整,奥氏体基体中未见发卡状位错(见图7(e))。这些位错对马氏体相产生钉扎效应,导致拉伸样品的可恢复性降低。②拉伸样品仅激活一个马氏体变体(见图7(c)),而压缩样品可激活2个变体(见图7(f))。更多活性马氏体变体的存在有助于更好地协调相变应变,因此,压缩样品表现出更优异的形状恢复性能。
基于前期对[1 0 0]晶向Fe43.5Mn34Al15Ni7.5单晶的研究[64],研究者发现能够协调相变应变的活性马氏体变体数量显著受晶体取向或加载方向的影响。为深入探究晶体取向对该单晶合金超弹性的作用机制,随后Tseng研究团队又分别通过拉伸[65]和压缩[66]试验系统研究了单晶超弹性行为的取向依赖性,研究发现,在拉伸测试中,[1 0 0]晶向的可恢复超弹性应变明显小于[1 2 3]晶向。这主要归因于2个微观结构特征:①奥氏体基体中形成高密度位错;②奥氏体-马氏体界面处产生发卡状位错,这些位错对马氏体相产生钉扎效应。与[1 2 3]取向样品相比,[1 0 0]取向样品中马氏体变体的激活能力较弱,导致其超弹性响应较差。在压缩条件下,[1 0 0]与[1 1 1]晶向的σc存在显著差异,这源于理论相变应变及其在Clausius-Clapeyron关系中作用的差异。其中,[1 0 0]方向表现出最大的相变应变,而[1 1 1]方向的应变最小。对于[1 2 3]取向,理论预测应变与实验测得的相变应变相符,表明该取向存在孪晶马氏体形貌。尽管Fe43.5Mn34Al15Ni7.5单晶展现出显著的超弹性应变,但其可恢复性能较差,表现为较大的不可逆应变,这对循环性能产生不利影响。图8(a)~图8(c)分别展示了[0 0 1]、[1 1 1]和[1 2 3]取向固溶处理单晶的应力-应变曲线,图8(d)则显示了[1 2 3]取向时效处理单晶的曲线。可以得出以下结论:①不同晶向的σc及σc-T曲线斜率存在显著差异,其中,[1 1 1]取向的σc和σc-T曲线斜率最大;②经473 K时效3 h后,σc升高,其对温度的依赖性降低(见图8(e)、图8(f))[66]。
在Fe-Pd合金体系中,研究人员目前仅发现2种合金具有热弹性马氏体相变特性:有序结构的Fe75Pd25合金和Fe70Pd30合金[67]。研究表明,Fe68.8Pd31.2单晶在应力作用下能实现6.5%的大幅可逆应变,并伴随窄滞后特性,这主要归因于单马氏体变体晶格参数的应力调控连续变化[68]。
Xiao等[69]报道了一种Fe68.8Pd31.2单晶合金,该材料在宽温域范围内展现出卓越的超弹性性能,当沿[0 0 1]晶向施加压缩应力时,样品在240~350 K温区内表现出具有窄应力滞后的超弹性行为,研究者将其归因于母相[0 0 1]方向弹性模量的温度依赖性。另一项研究也报道了类似现象[70]。
综上所述,Fe-Mn-Al-Ni-X 合金体系是当前 Fe基SMA中研究最为深入、应用前景最广的一类。该体系主要通过在无序基体中引入有序共格析出相,实现热弹性马氏体相变,从而赋予材料可逆应变能力。此外,加载方式(如拉伸或压缩)与晶粒取向对合金的超弹性行为也具有显著影响,是实现性能最优化的重要调控手段。虽然近年来也有其他类型Fe基宽温域超弹性SMA被报道(如Fe-Pd合金),但目前仅有少数材料在实验上被证实具备宽温域超弹性行为。因此,现阶段Fe基宽温域超弹性合金的研究仍集中在Fe-Mn-Al-Ni-X合金体系。表2总结了已报道的Fe基宽温域超弹性SMA的相关信息。
Cu基SMA是另一类被广泛研究的超弹性材料。相较于Ni-Ti基和Fe基SMA,Cu基合金具有原材料成本低等优势。通过调控合金成分,尤其是Cu、Al及其他合金元素的比例,可有效降低其马氏体相变温度,从而拓宽超弹性温度窗口的下限,实现更宽温域范围内的稳定超弹性响应。目前,报道的宽温域超弹性Cu基SMA主要为Cu-Al-Mn[8-10,71-72]合金。
Wang等[8]对不同成分的柱状晶Cu-Al-Mn合金进行了系统研究,其中,Cu70.6Al17.5Mn11.9合金在215~393 K温区内表现出约10%的可逆超弹性应变(见图9(a)),Cu68.6Al18.1Mn13.3合金展现出更优异的宽温域超弹性,其超弹性温度窗口从77 K延伸至353 K,特别是在103~313 K的温区内实现了10%的完全可逆应变(见图9(b)),基于Ms与合金成分的实验数据建立了Ms与Al、Mn含量的线性关系式:Ms = 1890−4210CAl−7800CMn。其中,CAl和CMn分别为Al和Mn摩尔分数数值。需要指出的是,由于制备加工条件对合金相变温度具有显著影响,不同研究者得出的线性关系式可能存在差异。
Niitsu等[72]报道了一种具有竹节状粗晶组织的Cu68Al17Mn15合金,该合金在77~273 K内不发生热致马氏体相变,但表现出宽温域超弹性特性,值得注意的是,即使在77 K的低温测试条件下,该合金仍能实现约8.5%的可恢复应变,研究还发现,随着温度降低,σc呈现下降趋势,且变化梯度在低温区域逐渐减小,研究者将其归因于低温下ΔS的减小。2018年,该团队进一步报道了通过循环热处理制备的Cu68Al17Mn15单晶[10]在4.2~160 K具有宽温域超弹性,所有温度下应力-应变曲线均表现出极小且一致的应力滞后(30 MPa),并且在4.2 K的极低温条件下仍能保持超过7%的超弹性应变,但超弹性应变未能达到理论应变值9.1%[73],这种差异可能源于Mn含量变化和温度共同导致的晶格参数改变[10]。
此外,Yuan等[9]研究了通过Taylor拔丝法制备的竹节晶Cu71.1Al17.2Mn11.7微丝(直径约150 μm)的宽温域超弹性特性,结果表明,在223 ~313 K温区内可实现8%的固定应变超弹性,曲线中出现的多重应力台阶现象,源于不同取向晶粒诱发马氏体相变所需σc的差异,这种独特的微丝结构使得应力滞后(σhys)保持恒定值(~40 MPa),且不受温度变化和外加应力的影响。
综上所述,在Cu基SMA中,Cu-Al-Mn合金因其宽温域超弹性特性成为研究较为广泛的体系,其马氏体相变温度主要取决于合金成分。值得注意的是,微观组织结构对Cu基SMA的超弹性行为具有显著影响:具有单晶、柱状晶或竹节状结构的Cu-Al-Mn合金均展现出优异的宽温域超弹性性能。虽然Cu-Al-Mn合金中已报道大量宽温域超弹性案例,但其他Cu基合金体系的相关研究仍较为有限。表3总结了已报道的Cu基宽温域超弹性SMA的相关信息。
Niitsu等[74]报道了Ni45Co5Mn36In14单晶在200 K以下低温区间具有完美超弹性特性(见图10(a)),发现在4.2 K和7 K的应力-应变曲线中存在锯齿状波动,这可归因于动能存储与绝热局部热释放效应,最重要的是,研究者发现应力诱导相变与磁场诱导相变的滞回温度变化趋势具有一致性,证明应力和磁场对马氏体相变的影响具有等价性。同年,Xu等[75]报道的铁磁Heusler合金Co51Cr27Ga11Si11呈现出σc的反常温度依赖性(见图10(b)),认为这种异常现象主要源于母相的铁磁转变。后续研究中,Odaira等[76]用Al替代Ga,制备出具有[0 0 1]主取向的Co55.7Cr23.3Al10.5Si10.5伪单晶,其超弹性温度窗口扩展至198~423 K(见图10(c))。特别值得注意的是,该合金σc随温度呈抛物线型变化,这是由于母相磁效应导致ΔS从负值演变为正值所致。
2020年,Chen等[77]报道了一种具有可变钴含量的无滞后超弹性Ni55−xCoxFe18Ga27合金,该独特性能被命名为“超临界弹性”(supercritical elasticity, SCE),其中,Co20成分的纤维样品不仅实现了高达10%的应变,还展现出无滞回超弹性及极低的温度依赖性,研究者认为,SCE可能源于连续相变过程,该现象与有序-无序晶体结构的原子级纠缠态密切相关。
STG转变现象并非Ni-Ti基SMA所独有。2022年,Liu等[14]在Mg-Sc合金中首次发现了STG转变现象,当Sc含量(摩尔分数)为0.195时,合金表现出典型的马氏体相变行为,然而当Sc含量(摩尔分数)增至0.213时,合金在冷却过程中发生STG转变,Mg78.7Sc21.3 STG展现出独特的宽温域超弹性特性,在123~298 K温区内呈现近线性的超弹性行为,且疲劳寿命超过百万次循环,特别值得注意的是,Mg78.7Sc21.3 STG表现出Elinvar效应,其弹性模量在宽温域内保持温度不敏感性,研究者认为,该现象源于STG转变过程中适度的模量软化与持续弹性硬化相互抵消的作用机制。
最近,Song等[78]提出了一种Ti75.25Al20Cr4.75合金,其兼具超宽温域超弹性(4.2~400 K)、低密度(4.36×103 kg/m3)和高比强度(185×103 (Pa·m3)/kg)的特点,为航天、极端低温与医疗器械提供了强有力的材料候选,在低温区域(<200 K),合金σc随温度降低而升高,呈现反常趋势,这种行为归因于B2母相剪切模量随温度降低而增强,即晶格剪切稳定性增强,从而推迟马氏体形核,研究者通过原位中子衍射解释了超弹性源于应力诱导有序体心立方B2相到有序正交B19相的马氏体转变,类似于Ni-Ti-Cu合金中观察到的马氏体转变[79]。表4总结了其他成分宽温域超弹性SMA的相关信息。
随着深空探测和极端环境工程的不断推进,传统结构材料已难以满足在超低温或温度波动环境下的高可靠性与高适应性需求。宽温域超弹性SMA因其可逆应变能力、良好的力学性能和适应性调控潜力,正成为面向未来航空航天、汽车工程等领域的新一代功能结构材料。
在航天探索领域,深空探测任务(如火星和月球探测)对材料提出了严苛挑战。例如,火星表面温度变化范围为120~290 K,而月球昼夜温差甚至可达100~400 K。如此极端且频繁波动的热环境,对材料的热稳定性与循环响应提出极高要求。具备宽温域超弹性的SMA可用于火星车轮胎柔性骨架,以适应多变地形并提供减震缓冲功能;也可集成于航天器内部的振动控制系统、热调控结构(如智能散热翅片、微致动器)或自修复组件中。在民用汽车方面,宽温域超弹性SMA不容易受四季环境温度变化而出现性能恶化,可用于智能车身结构与碰撞吸能元件。
从材料体系角度来看,Ni-Ti基SMA是目前研究最成熟、应用最广的SMA。该类合金具有良好的热-力性能耦合响应和较高的恢复应变,且加工工艺成熟、适于大规模工业生产。近年来,通过“缺陷工程”“多元合金化”“热-机械处理”等方法,其超弹性温度窗口进一步拓宽,可满足一定范围内的复杂应用需求。然而,其高密度(约6.5 g/cm3)在一定程度上限制了其在对质量极为敏感的空间航天器件中的应用潜力。
相比之下,Fe基与Cu基SMA在低成本、制备简单等方面具有优势,部分Fe-Mn-Al-Cr-Ni单晶合金已实现高达463 K的超弹性温度窗口。然而,这类材料往往依赖于单晶或少晶结构,生产工艺复杂、成材率低,加之对微结构控制要求极高,限制了其在大尺寸或复杂构件中的推广应用。近年来兴起的轻质SMA,如Mg-Sc和Ti-Al-Cr合金,则因其低密度而备受关注。轻质化特性使其在航空航天、无人机、微型驱动器等领域具备减重优势。然而,Mg-Sc合金目前的可逆应变较低(约1%),力学性能尚难满足工程实际负载需求;而Ti-Al-Cr类合金大多需单晶态下才能实现宽温超弹性,依赖复杂晶体生长过程,效率低、成本高,同样制约了其应用拓展。
综上,不同SMA体系在性能、工艺与应用适配性方面各有优劣。面向实际应用场景,必须综合考虑目标温度窗口、形变恢复能力、材料密度、可加工性、循环寿命及成本等因素,针对性选择最优合金体系。未来,跨体系复合设计(如NiTi基与轻质元素掺杂)、增材制造工艺结合微结构调控技术,将可能在实现高性能宽温域SMA材料的同时解决其产业化瓶颈。
基于上述讨论,本文展望了开发具有宽温域超弹性SMA的潜在途径:
1) 轻量化的材料设计与性能优化。为实现宽温域超弹性SMA的实用化应用,轻量化与高性能需同步推进。未来可借助材料基因组工程与机器学习方法,在合金成分设计上进行智能筛选与性能预测,探索基于轻元素(如Ti、Mg)构建的新型SMA。同时,可通过多元掺杂策略调控相变温度、抑制位错滑移、强化相界匹配,从而拓宽超弹性温度窗口。此外,“高熵合金”理念的引入也可能赋予合金更优异的力学一致性与结构稳定性,在保持较低密度的前提下实现高强度-高超弹性的协同。
2) 结构调控机制创新与多尺度架构设计。微观结构调控是实现宽温域超弹性的核心手段。未来研究可重点围绕“晶界工程”“缺陷工程”与“纳米结构调控”等多尺度设计策略展开。通过构建多级层次结构(如纳米孪晶、纳米析出强化、纳米级成分波动、梯度结构等)同时提高材料的可恢复应变与超弹性温度窗口。此外,异相界面调控技术如半共格匹配、多重应变相互作用等,也可能在提高应变恢复性与疲劳寿命方面发挥关键作用。
3) 制备工艺的创新与升级。增材制造为复杂构件与微结构的精准控制提供了可能。未来可进一步探索复合梯度结构构建、制备策略优化、多尺度热处理等工艺,以兼顾构形复杂性与微观性能统一性。

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2026年第52卷第10期
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doi: 10.13700/j.bh.1001-5965.2025.0565
  • 接收时间:2025-08-13
  • 首发时间:2026-10-30
  • 出版时间:2026-10-31
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  • 收稿日期:2025-08-13
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    1哈尔滨工业大学 材料科学与工程学院,哈尔滨 150001
    2哈尔滨工业大学 材料结构精密焊接与连接全国重点实验室,哈尔滨 150001
    3哈尔滨工业大学 金属精密热加工国家级重点实验室,哈尔滨 150001
    4哈尔滨工业大学 苏州研究院,苏州 215104

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2种不同金属材料的力学参数
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占总种数比例
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属
Genus
种数
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species
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Percentage of total
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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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