Article(id=1321927919388181287, tenantId=1146029695717560320, journalId=1220038251117760515, issueId=1321926982078681131, articleNumber=null, orderNo=null, doi=10.11868/j.issn.1001-4381.2024.000179, pmid=null, cstr=32421.14.j.issn.1001-4381.2024.000179, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1710172800000, receivedDateStr=2024-03-12, revisedDate=null, revisedDateStr=null, acceptedDate=1713715200000, acceptedDateStr=2024-04-22, onlineDate=1793101776215, onlineDateStr=2026-10-27, pubDate=1771516800000, pubDateStr=2026-02-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1793101776215, onlineIssueDateStr=2026-10-27, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1793101776215, creator=13701087609, updateTime=1793101776215, updator=13701087609, issue=Issue{id=1321926982078681131, tenantId=1146029695717560320, journalId=1220038251117760515, year='2026', volume='54', issue='2', pageStart='1', pageEnd='311', issueExtLink='null', onlineDate='null', pubDate='1771516800000', pubDateStr='2026-02-20', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1793101552742, creator='13701087609', updateTime=1793101552742, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext=null, issueFiles=null, downloadFileDto=null}, startPage=268, endPage=276, ext={EN=ArticleExt(id=1321927919627256616, articleId=1321927919388181287, tenantId=1146029695717560320, journalId=1220038251117760515, language=EN, title=Precipitation strengthening mechanisms in Cu/Ni alloyed steel, columnId=1220689384450478826, journalTitle=Journal of Materials Engineering, columnName=RESEARCH ARTICLE, runingTitle=null, highlight=null, articleAbstract=

The microstructural evolution and yield strength changes of medium-Mn steels with Cu, Ni, and Cu/Ni composite additions after aging at 500 ℃ are systematically compared using electron backscatter diffraction (EBSD), transmission electron microscopy (TEM) with energy-dispersive spectroscopy (EDS), and mechanical property tests. The precipitation strengthening mechanism is further revealed. The results show that aging at 500 ℃ increases the yield strength by approximately 125, 540 MPa, and 575 MPa for the Cu, Ni, and Cu/Ni alloyed steels, respectively, due to precipitation strengthening. The strengthening effect in the Ni and Cu/Ni alloyed steels is much greater than that in the Cu alloyed one, mainly because the number of precipitated nanoparticles in the former two steels is much greater than that in the Cu alloyed steel. Although Cu addition promotes the precipitation of NiAl phases, leading to larger size and higher number of Cu-NiAl composite precipitates in the Cu/Ni alloyed steel compared with the single NiAl precipitates in the Ni alloyed steel, the precipitation strengthening effect of the Cu-NiAl composite precipitates is not significantly higher than that of the single NiAl precipitates. This is because the latter, with its single precipitate sizes below the critical size, strengthen through the dislocation shearing mechanism, whereas the former, with its composite precipitates exceeding the critical size, strengthen via the dislocation Orowan mechanism, resulting in weakened precipitation strengthening. Consequently, the aging precipitation strengthening effect of Cu/Ni steel is not higher than that of the Ni steel.

, authors=Weiqiang LAI, Fanglin DING, Bin HU, Haiwen LUO, authorsList=Weiqiang LAI, Fanglin DING, Bin HU, Haiwen LUO, authorCompany=null, correspAuthors=Bin HU, Haiwen LUO, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, 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=1321927923221775162, articleId=1321927919388181287, tenantId=1146029695717560320, journalId=1220038251117760515, language=CN, title=Cu/Ni合金化钢析出强化机制研究, columnId=1220689384622445292, journalTitle=材料工程, columnName=研究论文, runingTitle=null, highlight=null, articleAbstract=

通过电子背散射衍射(EBSD)、透射电子显微镜(TEM)及其能谱(EDS)分析和力学性能测试,系统对比Cu、Ni及Cu/Ni复合添加中锰钢在500 ℃时效后的显微组织演变与屈服强度变化,并深入揭示其析出强化机理。结果表明:含Cu钢、含Ni钢和含Cu/Ni钢经500 ℃时效处理因析出强化使屈服强度分别增加了125、540 MPa和575 MPa左右,含Ni和含Cu/Ni钢的析出强化显著高于含Cu钢,主要是因为前两者中析出的纳米颗粒数量远大于Cu钢。虽然加入Cu可促进NiAl相析出,使得Cu/Ni钢中的Cu-NiAl复合析出相尺寸和数量均大于Ni钢中的单一NiAl相,但Cu-NiAl复合析出相析出强化效果并没有显著高于单一NiAl相。这是因为后者单一析出的尺寸小于临界尺寸,通过位错剪切机制实现强化,而前者复合析出相尺寸超过临界尺寸,从而通过位错绕过机制强化,导致析出强化效果减弱,因此Cu/Ni钢的时效析出强化效果并未高于Ni钢。

, authors=赖伟强, 丁方林, 胡斌, 罗海文, authorsList=赖伟强, 丁方林, 胡斌, 罗海文, authorCompany=null, correspAuthors=胡斌, 罗海文, authorNote=null, correspAuthorsNote=
罗海文(1972—),男,教授,博士,主要从事先进钢铁材料的设计与制备方向的研究工作,联系地址:北京市海淀区学院路30号北京科技大学冶金与生态工程学院(100083),E-mail:
胡斌(1988—),男,副教授,博士,主要从事先进钢铁材料的组织性能调控方面的研究工作,联系地址:北京市海淀区学院路30号北京科技大学冶金与生态工程学院(100083),E-mail:
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Reference(id=1321927954981045166, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321927919388181287, doi=null, pmid=null, pmcid=null, year=2016, volume=null, issue=null, pageStart=null, pageEnd=null, url=null, language=null, rfNumber=[38], rfOrder=48, authorNames=WANG X J, journalName=null, refType=null, unstructuredReference=WANG X J.Mechanism research of nanoscale composite precipitates in Fe-Cu-Ni-Al-Mn steel[D].Shanghai:Shanghai University,2016., articleTitle=null, refAbstract=null), Reference(id=1321927955098485679, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321927919388181287, doi=null, pmid=null, pmcid=null, year=2010, volume=527, issue=15, pageStart=3546, pageEnd=3551, url=null, language=null, rfNumber=[39], rfOrder=49, authorNames=HOLZER I, KOZESCHNIK E, journalName=Materials Science and Engineering:A, refType=null, unstructuredReference=HOLZER I, KOZESCHNIK E.Computer simulation of the yield strength evolution in Cu-precipitation strengthened ferritic steel[J].Materials Science and Engineering:A,2010,527(15):3546-3551., articleTitle=Computer simulation of the yield strength evolution in Cu-precipitation strengthened ferritic steel, refAbstract=null), Reference(id=1321927955169788848, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321927919388181287, doi=null, pmid=null, pmcid=null, year=2017, volume=23, issue=2, pageStart=350, pageEnd=359, url=null, language=null, rfNumber=[40], rfOrder=50, authorNames=SHEN Q, CHEN H, LIU W Q, journalName=Microscopy and Microanalysis, refType=null, unstructuredReference=SHEN Q, CHEN H, LIU W Q.Effect of Cu on nanoscale precipitation evolution and mechanical properties of a Fe-NiAl alloy[J].Microscopy and Microanalysis,2017,23(2):350-359., articleTitle=Effect of Cu on nanoscale precipitation evolution and mechanical properties of a Fe-NiAl alloy, refAbstract=null)], funds=[Fund(id=1321927937033618298, tenantId=1146029695717560320, 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journalId=1220038251117760515, articleId=1321927919388181287, language=EN, label=Table 1, caption=

Chemical compositions of experimental steels(mass fraction/%)

, figureFileSmall=null, figureFileBig=null, tableContent=
SteelCMnAlCuNiVMoFe
Cu steel0.303.001.102.000.330.52Bal.
Ni steel0.303.002.055.090.370.55Bal.
CuNi steel0.283.001.981.614.940.310.54Bal.
), ArticleFig(id=1321927932931588978, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321927919388181287, language=CN, label=表1, caption=

实验钢的化学成分(质量分数/%)

, figureFileSmall=null, figureFileBig=null, tableContent=
SteelCMnAlCuNiVMoFe
Cu steel0.303.001.102.000.330.52Bal.
Ni steel0.303.002.055.090.370.55Bal.
CuNi steel0.283.001.981.614.940.310.54Bal.
), ArticleFig(id=1321927933246161780, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321927919388181287, language=EN, label=Table 2, caption=

Comparison of tensile properties of three experimental steels before and after aging treatment

, figureFileSmall=null, figureFileBig=null, tableContent=
SteelProcessYield strength/MPaUltimate tensile strength/MPaTotal elongation/%
Cu steelHR1390±12.81980±9.711.87±0.41
500-2 h1515±11.31645±7.63.96±0.28
Ni steelHR1350±15.42150±6.512.09±0.35
500-2 h1890±9.52075±8.44.50±0.32
CuNi steelHR1310±13.62085±10.112.12±0.38
500-2 h1885±10.22065±9.92.30±0.20
), ArticleFig(id=1321927933363602293, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321927919388181287, language=CN, label=表2, caption=

三种实验钢时效处理前后的拉伸性能对比

, figureFileSmall=null, figureFileBig=null, tableContent=
SteelProcessYield strength/MPaUltimate tensile strength/MPaTotal elongation/%
Cu steelHR1390±12.81980±9.711.87±0.41
500-2 h1515±11.31645±7.63.96±0.28
Ni steelHR1350±15.42150±6.512.09±0.35
500-2 h1890±9.52075±8.44.50±0.32
CuNi steelHR1310±13.62085±10.112.12±0.38
500-2 h1885±10.22065±9.92.30±0.20
), ArticleFig(id=1321927933715923830, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321927919388181287, language=EN, label=Table 3, caption=

Diameter,number density and volume fraction of precipitated particles in three alloyed steels after aging

, figureFileSmall=null, figureFileBig=null, tableContent=
SteelParticleDiameter/nmNumber density/m-3Volume fraction/%
Cu steelCu-rich7.0±1.92.34×10220.42
Ni steelNiAl4.0±1.31.44×10231.06
CuNi steelCu-NiAl5.8±2.22.10×10231.93
), ArticleFig(id=1321927934064051063, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321927919388181287, language=CN, label=表3, caption=

三种钢时效样品中析出颗粒的尺寸、数量密度和体积分数

, figureFileSmall=null, figureFileBig=null, tableContent=
SteelParticleDiameter/nmNumber density/m-3Volume fraction/%
Cu steelCu-rich7.0±1.92.34×10220.42
Ni steelNiAl4.0±1.31.44×10231.06
CuNi steelCu-NiAl5.8±2.22.10×10231.93
), ArticleFig(id=1321927935779521400, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321927919388181287, language=EN, label=Table 4, caption=

Calculated strengthening increments and measured increments for Cu steel, Ni steel, and CuNi steel by different strengthening mechanisms

, figureFileSmall=null, figureFileBig=null, tableContent=
SteelParticleSize/nmσshear/MPaσOrowan/MPaΔσd/MPaMeasured Δσ/MPaσp=Δσ+Δσd/MPa
Cu steelCu-rich7.0±1.918921057125182
Ni steelNiAl4.0±1.357661551540591
CuNi steelCu-NiAl5.8±2.279858652575627
), ArticleFig(id=1321927936177980281, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321927919388181287, language=CN, label=表4, caption=

Cu钢、Ni钢和CuNi钢采用不同强化机制计算的强化增量与实测增量

, figureFileSmall=null, figureFileBig=null, tableContent=
SteelParticleSize/nmσshear/MPaσOrowan/MPaΔσd/MPaMeasured Δσ/MPaσp=Δσ+Δσd/MPa
Cu steelCu-rich7.0±1.918921057125182
Ni steelNiAl4.0±1.357661551540591
CuNi steelCu-NiAl5.8±2.279858652575627
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Cu/Ni合金化钢析出强化机制研究
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赖伟强 , 丁方林 , 胡斌 , 罗海文
材料工程 | 研究论文 2026,54(2): 268-276
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材料工程 |研究论文 2026 , 54 (2) : 268 -276
Cu/Ni合金化钢析出强化机制研究
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赖伟强, 丁方林, 胡斌 , 罗海文
作者信息
  • 北京科技大学 冶金与生态工程学院,北京 100083
通讯作者:
罗海文(1972—),男,教授,博士,主要从事先进钢铁材料的设计与制备方向的研究工作,联系地址:北京市海淀区学院路30号北京科技大学冶金与生态工程学院(100083),E-mail:
胡斌(1988—),男,副教授,博士,主要从事先进钢铁材料的组织性能调控方面的研究工作,联系地址:北京市海淀区学院路30号北京科技大学冶金与生态工程学院(100083),E-mail:
Precipitation strengthening mechanisms in Cu/Ni alloyed steel
Weiqiang LAI, Fanglin DING, Bin HU , Haiwen LUO
Affiliations
  • School of Metallurgical and Ecological Engineering,University of Science and Technology Beijing,Beijing 100083,China
出版时间: 2026-02-20 doi: 10.11868/j.issn.1001-4381.2024.000179
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通过电子背散射衍射(EBSD)、透射电子显微镜(TEM)及其能谱(EDS)分析和力学性能测试,系统对比Cu、Ni及Cu/Ni复合添加中锰钢在500 ℃时效后的显微组织演变与屈服强度变化,并深入揭示其析出强化机理。结果表明:含Cu钢、含Ni钢和含Cu/Ni钢经500 ℃时效处理因析出强化使屈服强度分别增加了125、540 MPa和575 MPa左右,含Ni和含Cu/Ni钢的析出强化显著高于含Cu钢,主要是因为前两者中析出的纳米颗粒数量远大于Cu钢。虽然加入Cu可促进NiAl相析出,使得Cu/Ni钢中的Cu-NiAl复合析出相尺寸和数量均大于Ni钢中的单一NiAl相,但Cu-NiAl复合析出相析出强化效果并没有显著高于单一NiAl相。这是因为后者单一析出的尺寸小于临界尺寸,通过位错剪切机制实现强化,而前者复合析出相尺寸超过临界尺寸,从而通过位错绕过机制强化,导致析出强化效果减弱,因此Cu/Ni钢的时效析出强化效果并未高于Ni钢。

中锰钢  /  时效  /  析出相  /  复合析出  /  剪切机制  /  Orowan机制

The microstructural evolution and yield strength changes of medium-Mn steels with Cu, Ni, and Cu/Ni composite additions after aging at 500 ℃ are systematically compared using electron backscatter diffraction (EBSD), transmission electron microscopy (TEM) with energy-dispersive spectroscopy (EDS), and mechanical property tests. The precipitation strengthening mechanism is further revealed. The results show that aging at 500 ℃ increases the yield strength by approximately 125, 540 MPa, and 575 MPa for the Cu, Ni, and Cu/Ni alloyed steels, respectively, due to precipitation strengthening. The strengthening effect in the Ni and Cu/Ni alloyed steels is much greater than that in the Cu alloyed one, mainly because the number of precipitated nanoparticles in the former two steels is much greater than that in the Cu alloyed steel. Although Cu addition promotes the precipitation of NiAl phases, leading to larger size and higher number of Cu-NiAl composite precipitates in the Cu/Ni alloyed steel compared with the single NiAl precipitates in the Ni alloyed steel, the precipitation strengthening effect of the Cu-NiAl composite precipitates is not significantly higher than that of the single NiAl precipitates. This is because the latter, with its single precipitate sizes below the critical size, strengthen through the dislocation shearing mechanism, whereas the former, with its composite precipitates exceeding the critical size, strengthen via the dislocation Orowan mechanism, resulting in weakened precipitation strengthening. Consequently, the aging precipitation strengthening effect of Cu/Ni steel is not higher than that of the Ni steel.

medium Mn steel  /  aging  /  precipitate  /  composite precipitate  /  shearing mechanism  /  Orowan mechanism
赖伟强, 丁方林, 胡斌, 罗海文. Cu/Ni合金化钢析出强化机制研究. 材料工程, 2026 , 54 (2) : 268 -276 . DOI: 10.11868/j.issn.1001-4381.2024.000179
Weiqiang LAI, Fanglin DING, Bin HU, Haiwen LUO. Precipitation strengthening mechanisms in Cu/Ni alloyed steel[J]. Journal of Materials Engineering, 2026 , 54 (2) : 268 -276 . DOI: 10.11868/j.issn.1001-4381.2024.000179
析出强化是指材料通过在基体中析出弥散细小的纳米颗粒,从而提高强度的强化方式。根据纳米析出相的物理特性、分布特征及其与位错滑移之间的交互作用,分为两种不同的强化机制:一种是位错直接切过纳米析出相的剪切机制;另一种为位错绕过纳米析出相并留下环绕纳米相位错环的Orowan绕过机制[1-2]。析出强化作为提高强度最有效的方法之一,已广泛应用于钢铁材料[3-6],如Hu等[7]研究发现,富Cu相的析出使钢的屈服强度提高了267 MPa;Ping等[8]通过时效析出纳米NiAl相使得钢的强度提升到1400 MPa以上。
随着汽车、航空等行业的持续发展,对材料强度的要求不断提升,促使越来越多的研究人员关注通过多种析出相协同作用来进一步提升钢材强度的可行途径[9-10]。与单一析出相强化相比,不同析出相析出时,由于析出相成分和晶体结构存在差异,其强化作用可能具有某种叠加作用,从而可超过单一纳米相的析出强化。如有学者研究发现富Cu纳米相和NiAl纳米相在钢中共同析出时,其叠加强化作用非常明显[11-13]。Kapoor等[14]利用NiAl相和富Cu相的复合析出,使钢的屈服强度提高到1600 MPa;梁恩溥等[15]研究发现,富Cu相和NiAl相复合析出时钢的强度相比于单一NiAl相的钢提高了150 MPa;Shen等[16]在对Fe-Ni-Cu合金的研究中也发现富Cu相和NiAl相复合析出的强化效果大于单一Cu相的析出,但析出相与位错的相互作用不仅受到析出相种类和数量的影响,还与析出相的尺寸以及强化机制密切相关。由于不同类型、尺寸的析出相与位错的交互作用相对复杂,其复合析出相的强化作用是否必然优于单一析出相,目前尚未有明确结论。基于此,本工作研究了经时效处理后析出不同类型析出相的钢材显微组织和力学性能,对比了单一析出与复合析出等不同类型的析出强化增量,并结合不同强化机制下计算得到的强化增量进行对比分析,从而明确不同类型析出相的强化机制。
实验所采用的Cu、Ni、CuNi三种合金化的中锰钢化学成分如表1所示。三种钢均在50 kg真空感应炉中进行熔炼,铸锭热锻为60 mm厚锻坯,之后将锻坯加热至1150 ℃均匀化2 h,经八道次热轧成3.5 mm厚的热轧板,控制每道次的压下量小于33%且终轧温度在850 ℃左右。轧后油淬至室温(记为热轧样品,工艺记为HR)。已有大量研究表明Cu或NiAl等时效析出温度在450~600 ℃范围内[11,13],因此将三种钢的热轧板在峰值时效温度500 ℃时效2 h,然后空冷至室温(记为时效样品,工艺记为500-2 h)。
沿轧制方向加工出标距为25 mm的板状拉伸试样,在室温下以10-3 s-1应变速率进行单向拉伸实验用以检测实验钢的拉伸性能。通过ULVAC-PHI710扫描俄歇纳米探针配合EDAX OIM6.0探头及D8 DISCOVER A25型X射线衍射(XRD)仪、JEM-2200FS透射电子显微镜(TEM)和能谱仪(EDS)等对样品组织进行表征。其中XRD和EBSD样品经过标准磨抛后,在20%(体积分数,下同)高氯酸酒精溶液中、20 V电压下进行电解抛光以去除残余应力;TEM样品经机械抛光成50 µm厚的薄片,然后在5%高氯酸和95%乙醇溶液中、约-20 ℃温度下进行双射流穿孔。将XRD测得的(200)γ、(200)α、(220)γ、(211)α、(311)γ衍射峰的综合积分强度按照式(1)计算得到各样品中的残余奥氏体(retained austenite,RA)体积分数:
VA=11+GIα/Iγ
式中:VA为样品的残余奥氏体体积分数;Iα和Iγ分别为奥氏体和铁素体所对应晶面的衍射峰积分强度;G为与奥氏体和铁素体晶面强度比值相关的因子。析出相尺寸是在TEM观察中随机选取10个区域进行STEM-EDS检测,对检测结果中析出相的尺寸和数量进行统计,将统计的平均尺寸和体积分数代入N=3πR2/4f求出数量密度。
实验钢的拉伸应力-应变曲线如图1所示,其强度和伸长率特征值列于表2。三种钢的热轧样品均表现出相近的屈服强度与伸长率,其中屈服强度介于1310~1390 MPa之间,伸长率约为10%(图1(a)),表现为典型的马氏体钢力学行为[17],具有高屈服强度、高加工硬化能力。经时效处理后,三种钢的屈服强度均得到提升,但抗拉强度降低,其中Cu钢经时效处理后,屈服强度提高了125 MPa左右,抗拉强度下降了335 MPa左右;而Ni钢和CuNi钢经时效处理后,屈服强度均提高了560 MPa左右,强化增量相近;Cu钢的屈服增量远小于Ni钢和CuNi钢(图1(b))。
图2与图3分别为实验钢显微组织的EBSD和XRD表征结果。从图2的EBSD表征结果可以看出,三种钢热轧样品和时效样品的显微组织主要由马氏体和少量残余奥氏体组成。根据图3的XRD谱图计算结果,三种钢热轧样品在时效处理后其残余奥氏体体积分数的变化很小,均不超过1.5%。另外,对残余奥氏体的晶粒尺寸进行统计,发现三种钢时效处理前后的残余奥氏体晶粒尺寸也均在100 nm左右,即时效处理对残余奥氏体尺寸和体积分数均影响较小。
图4、图5与图6分别为Cu钢、Ni钢和CuNi钢时效样品的显微组织及其对应的STEM-EDS分析结果。通过图4可以发现,Cu钢时效后在位错附近弥散析出纳米颗粒,尺寸在7.0 nm左右,EDS分析为富Cu相。而Ni钢时效后可发现NiAl纳米粒子的弥散析出,尺寸在4.0 nm左右(图5)。CuNi钢时效后可发现基体中有Cu和NiAl的弥散析出,且它们的析出位置高度重合,应为Cu-NiAl的复合析出相,尺寸约5.8 nm(图6),较Ni钢中单一NiAl相尺寸更大。此外,在三种钢的EDS分析中并未发现V的析出相,说明时效时没有含V碳化物析出,这是因为VC析出温度在600~650 ℃左右[18],而时效温度远低于此温度。进一步对析出相的数量密度进行统计,如表3所示,可以看出Ni钢和CuNi钢经时效处理后其纳米粒子的数量密度明显大于Cu钢。
对比三种钢时效前后的残余奥氏体体积分数的变化,可以发现时效处理对残余奥氏体含量的变化影响很小,且根据EBSD显微组织中的统计结果,时效前后残余奥氏体晶粒尺寸变化也不明显。这是因为时效温度过低,并未达到奥氏体的逆转变温度,使得奥氏体晶粒不能有效长大,导致时效前后残余奥氏体的体积分数及尺寸基本不变。
透射电镜的观察表明,三种钢时效后分别析出了富Cu相、NiAl相、Cu-NiAl复合相。Cu钢中析出的富Cu相的数量密度和体积分数远小于Ni钢、CuNi钢析出的纳米颗粒,一方面是由于Ni钢中加入的Ni含量较高,在500 ℃时效析出的相平衡体积分数NiAl相(2.0%)大于富Cu相(1.7%);另一方面是因为Mn元素容易在NiAl相中偏聚,占据了NiAl相中Al元素的位置[19-20],减少其弹性应变能,从而促进NiAl相的析出,显著增加了NiAl相的密度[21-22]。而CuNi钢中时效析出的Cu-NiAl相的尺寸大于Ni钢中的NiAl相,这主要归因于富Cu相和NiAl相复合析出的相互作用,并且Cu元素的加入促进了NiAl相的析出和长大,具体可从以下两方面进行阐述。首先Cu与Mn在NiAl相中的作用相似[21-22],在析出过程中,由于Cu原子的原子半径小于Al原子,Cu取代NiAl相中Al元素可使NiAl相与α-Fe基体之间的晶格失配应变显著降低[22],从而降低NiAl相形核的临界能。另外,由于NiAl相与基体共格难以粗化,但CuNi钢中富Cu相和NiAl相复合析出时,一方面富Cu相能够作为NiAl相形核核心促进析出,另一方面Cu取代NiAl相中Al时造成晶格畸变形成缺陷,这会加速Ni、Al元素的扩散,从而促进NiAl相的长大和粗化[23]。因此,CuNi钢中纳米析出相的尺寸和数量密度均大于Ni钢。Schnitzer等[24-25]在研究Cu元素对Fe-Cr-Ni-Al-Ti马氏体时效钢析出相演变过程的影响中,也发现了同样的现象,证实Cu元素的添加加速了NiAl相的析出。
根据图1和表2可以发现,热轧样品中,相较于Ni钢(1350 MPa)和CuNi钢(1310 MPa),Cu钢具有更高的屈服强度(1390 MPa),这主要是由于Cu钢中不含Ni元素,其较高的马氏体相变开始温度(Ms点)有助于降低组织内的残余应力,从而提升了材料的屈服强度[26]。经时效处理后,Ni钢和CuNi钢的屈服强度与屈服强度增量均显著高于Cu钢,但Ni钢和CuNi钢的屈服强度与强化增量相近,CuNi钢并未表现出预期中更高的强化增量。此外,时效处理后三种钢的抗拉强度均出现下降,这是马氏体钢回火后的典型特征,主要归因于时效处理释放了因马氏体相变导致的内应力和位错回复,显著降低了材料中的位错密度[17],导致加工硬化率下降。
经时效处理后,三种钢中残余奥氏体的体积分数和尺寸变化甚微,不会对其屈服强度的增加产生显著影响[27-28],但三种钢中分别有大量富Cu相、NiAl相、Cu-NiAl复合相析出,因此,其屈服增量(Δσ)主要来源于析出强化σp和时效处理时位错回复导致的屈服强度降低Δσd,即
Δσ=σp-Δσd
而Δσd可根据以下公式计算[29-30]:
ρ=β2/4.35×b2
σd=MαGbρ
Δσd=σdHR-σd
式中:ρ为位错密度;β为XRD谱图的半峰全宽(full width at half maximum,FWHM);M为Taylor因子,M=3;α为比例系数;G是基体的剪切模量,约为80 GPa[31];b为Burgers矢量,b=0.25 nm;σdHR和σd分别为热轧样品和时效样品的位错强化增量。通过计算得到,时效处理后Cu钢、Ni钢和CuNi钢因位错回复所导致的屈服强度下降值分别为57、51 MPa和52 MPa,即三种钢因位错回复所导致的软化幅度相差很小,因此析出强化对三种钢屈服强度的变化起主导作用。
NiAl相和Cu-NiAl复合相的时效析出强化效果远大于富Cu相,而CuNi钢中的Cu-NiAl复合析出相强化效果并未显著高于Ni钢中的NiAl相。根据析出相的物理特性、分布特征及其与滑移位错的交互作用,析出强化分为切过机制和绕过机制两种不同的强化机制[1-2]。钢中的强化增量与第二相尺寸变化如图7所示,随着析出颗粒的长大,当颗粒尺寸超过临界尺寸dC后,强化机制会由切过机制转变为Orowan绕过机制,此时析出相提供的强化增量将会减小;而只有位于临界尺寸dC时,析出强化才达到最大值。对于剪切机制的强化增量σshear,屈服强度的提高主要源于有序强化σorder、共格强化σcoh和模量强化σmod [32],分别按照以下公式进行计算:
σshear=σcoh+σorder+σmod
σcoh=4.1MGε3/2f1/2Rb1/2
σorder=Mγapd3/2b4rsfπT1/2
σmod=MGbλ1-EpEm23/4
式中:ε为约束晶格参数失配,ε=2/3Δa/a,Δa/a为纳米相与基体之间的晶格参数失配,约为0.002[33];f为NiAl相的体积分数;γapd为纳米相的反相边界平均能[34],γapd=0.5 J·m-2;rs为滑动平面内的平均粒子半径[35],rs=2/31/2R;T为位错的线张力,T=Gb2/2 [35];λ为位错滑移面的平均粒子间距[35],λ=0.866⋅rN-1/2;Ep和Em分别为析出相和基体的位错线能量,Ep/Em的比值取决于析出相的半径R [36],取0.983。
当析出相通过Orowan机制强化时,其强化增量可由式(10)计算[37]:
σOrowan=0.84M1.2Gb2πλlnL2b
式中:L表示外截止距离,L=22/31/2R。
当富Cu相与NiAl相的尺寸较小时,两者分别呈BCC结构[38]与B2有序结构。而B2有序NiAl相的晶格常数与BCC基体接近[15],因此二者均能与基体形成共格界面[38],并通过剪切机制实现强化;其中富Cu相以共格强化和模量强化为主要机制[39],而NiAl相以有序强化和模量强化为主[32],相似尺寸及分布的富Cu相和NiAl相析出强化的贡献并不一致。随着析出相的长大,其难以与基体保持共格关系,当尺寸超过某个临界值时,位错不再切过而是绕过析出相,并留下位错环,强化机制随之转变为绕过机制。相关研究[10,27]发现含Cu/Ni钢中析出的富Cu相和NiAl相极易以B2结构团簇方式复合析出,且复合析出的Cu-NiAl相根据添加化学元素成分的不同通常有两种结构,一种为NiAl相与富Cu相紧密接触的邻近结构,另一种是以富Cu相为核心、NiAl相为外壳的核壳结构。而无论复合团簇以何种结构析出,在计算时均应将其视为一个整体单元与位错发生相互作用。根据表3统计的析出相尺寸和数量密度以及上述公式进行计算,结果如表4所示。可以看出,当分别采用不同强化机制公式计算平均尺寸为4.0 nm的NiAl相析出强化增量时,切过机制的析出强化增量小于绕过机制;而平均尺寸为5.8 nm的Cu-NiAl相对应的切过机制和绕过机制计算的强化增量分别为798 MPa和586 MPa,绕过机制强化小于切过机制。对于Cu钢和Ni钢而言,富Cu相和NiAl相按剪切机制计算出的强化增量分别为189 MPa和576 MPa,而绕过机制强化增量的计算值分别为210 MPa和615 MPa;通过实测屈服强度增量推算出Cu钢和Ni钢的析出强化增量分别为182 MPa和591 MPa,这与剪切机制计算值较吻合,由此可见,两种钢中富Cu相和NiAl相更倾向于按剪切机制进行强化;而CuNi钢推算出的时效析出强化增量为627 MPa,这明显与Cu-NiAl相的复合析出通过绕过强化机制的计算值586 MPa更接近。因此,综合图7所示的强化增量与第二相尺寸及强化机制间的关系,并结合三种实验钢屈服强度增量的实测结果,说明位错与平均尺寸为7.0 nm的Cu粒子相互作用以剪切机制为主导,这与文献中报道的富Cu相粒子临界尺寸约为8 nm[38]的结论相吻合;位错与4.0 nm的NiAl粒子的主要作用机制同样为剪切,而对于尺寸为5.8 nm的Cu-NiAl复合析出粒子,位错则主要以绕过机制通过,说明NiAl相强化由切过向绕过机制转变的临界尺寸在4.0~5.8 nm之间,这与文献中报道的NiAl相临界尺寸约为5 nm[21,32-33]的结果相吻合,Cu与NiAl的复合并未对该临界尺寸产生显著影响。需要指出,析出相的实际尺寸呈一定分布,上述分析并非指所有粒子均以单一机制与位错相互作用。当平均尺寸小于临界尺寸时,大部分粒子以切过机制为主;反之,则以绕过机制为主。然而,当平均尺寸接近临界尺寸时,切过与绕过两种机制在实际材料中往往并存,由此导致计算的强化增量与实测值之间出现偏差。
Shen等[40]在相关研究中发现富Cu相和NiAl相复合析出的强化效果大于单一NiAl相,主要归因于复合析出的数量密度大于单一析出相,但并未考虑到纳米颗粒尺寸的变化可导致强化作用机制的转变。本研究中尺寸较小的NiAl相通过剪切机制强化,而CuNi钢中的Cu-NiAl相尽管数量密度较高,但其尺寸大于临界尺寸,位错无法切过析出相而只能通过绕过机制强化;这导致后者的强化效果并没有高于前者,两者的屈服强度增幅相近,即复合析出并未表现出比单一析出更高的析出强化效果。
(1)含Cu、含Ni和含Cu/Ni钢经500 ℃时效处理析出纳米相后,其屈服强度分别增加了125、540 MPa和575 MPa左右,这是由于在三种钢中时效时分别析出了平均尺寸为7.0 nm的富Cu相、4.0 nm的NiAl相和5.8 nm的Cu-NiAl相纳米粒子。含Ni钢与含CuNi钢的屈服强度增量显著高于含Cu钢,这是由于二者中时效析出的纳米相与含Cu钢中的富Cu相在晶体结构上存在差异,且其数量远大于后者,从而产生了更为显著的析出强化效果。
(2)CuNi钢时效析出的Cu-NiAl相的尺寸、数量密度均大于Ni钢时效析出的NiAl相,这主要是因为在CuNi钢中,Cu元素能够促进NiAl的形核和长大,形成Cu-NiAl复合析出相。
(3)NiAl相强化机制由切过机制向绕过机制转变的临界尺寸在4.0~5.8 nm之间,而时效后Ni钢中的NiAl相平均尺寸约为4.0 nm,其强化机制为切过机制,CuNi钢中的Cu-NiAl相平均尺寸为5.8 nm,大于临界尺寸,其强化机制转变为绕过机制,这导致强化效果相对减弱,因此,尽管CuNi钢中纳米粒子的尺寸与数量均大于Ni钢,但两者的析出强化效果相近,即复合析出相较于单一析出并未表现出更加显著的析出强化效果。
  • 国家自然科学基金项目(52233018)
  • 国家自然科学基金项目(51831002)
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doi: 10.11868/j.issn.1001-4381.2024.000179
  • 接收时间:2024-03-12
  • 首发时间:2026-10-27
  • 出版时间:2026-02-20
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  • 收稿日期:2024-03-12
  • 录用日期:2024-04-22
基金
国家自然科学基金项目(52233018)
国家自然科学基金项目(51831002)
作者信息
    北京科技大学 冶金与生态工程学院,北京 100083

通讯作者:

罗海文(1972—),男,教授,博士,主要从事先进钢铁材料的设计与制备方向的研究工作,联系地址:北京市海淀区学院路30号北京科技大学冶金与生态工程学院(100083),E-mail:
胡斌(1988—),男,副教授,博士,主要从事先进钢铁材料的组织性能调控方面的研究工作,联系地址:北京市海淀区学院路30号北京科技大学冶金与生态工程学院(100083),E-mail:
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2种不同金属材料的力学参数
科
Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)
属
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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