Article(id=1321490203722764459, tenantId=1146029695717560320, journalId=1220038251117760515, issueId=1321490128967675980, articleNumber=null, orderNo=null, doi=10.11868/j.issn.1001-4381.2023.000830, pmid=null, cstr=32421.14.j.issn.1001-4381.2023.000830, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1702224000000, receivedDateStr=2023-12-11, revisedDate=null, revisedDateStr=null, acceptedDate=1710432000000, acceptedDateStr=2024-03-15, onlineDate=1792997416668, onlineDateStr=2026-10-26, pubDate=1768838400000, pubDateStr=2026-01-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1792997416668, onlineIssueDateStr=2026-10-26, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1792997416668, creator=13701087609, updateTime=1792997416668, updator=13701087609, issue=Issue{id=1321490128967675980, tenantId=1146029695717560320, journalId=1220038251117760515, year='2026', volume='54', issue='1', pageStart='1', pageEnd='259', issueExtLink='null', onlineDate='null', pubDate='1768838400000', pubDateStr='2026-01-20', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1792997398845, creator='13701087609', updateTime=1792997398845, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext=null, issueFiles=null, downloadFileDto=null}, startPage=168, endPage=177, ext={EN=ArticleExt(id=1321490205475983535, articleId=1321490203722764459, tenantId=1146029695717560320, journalId=1220038251117760515, language=EN, title=Microstructure and mechanical properties of 304 stainless steel joints brazed by using BNi82CrSiB-xCu filler metals, columnId=1220689384450478826, journalTitle=Journal of Materials Engineering, columnName=RESEARCH ARTICLE, runingTitle=null, highlight=null, articleAbstract=

To overcome the drawback of the brittle borides formed in the stainless steel joint brazed using Ni-based filler metals and further improve the mechanical properties of the joint, a small amount of Cu powders are added into the BNi-2 filler metal to suppress the formation of brittle borides in the joints. The 304 stainless steels are brazed using the BNi-2 and BNi-2 with Cu as filler metals, respectively. The influences of holding time, brazing temperature, and Cu content on the microstructure and mechanical properties of the brazed joints are investigated. The results indicate that for the BNi-2 filler metal, increasing the brazing temperature and time are favorable for reducing the boride content formed in the joint center. In addition, increasing the brazing temperature and time can accelerate the intergranular diffusion of borides, thereby leading to a degradation of joint shear strength. For the BNi-2 filler metal with Cu, when the Cu content is 1%(mass fraction,the same below), the borides in the joint center are inhibited remarkably, forming a full Ni-based solid solution in the joint center. The joint shear strength obtained is (713.9±16.4) MPa, which is 19% higher than that of the joint without Cu additive. The joint failure occurs at the base metal/filler metal interface, recognized as a ductile fracture. However, when the Cu content increases to 5%, the borides reprecipitate in the joint center, resulting in the reduction of shear strength. In this case, the joint failure evolves to a composite mode with the co-existence of ductile and brittle fracture.

, authors=Jiejie GUO1, Huaxin LI1, 2, 3, Liangyi CAI1, Shuai ZHU4, Chuanyang LYU1, 2, 3, Yanming HE1, 2, 3, Jianguo YANG1, 2, 3, authorsList=Jiejie GUO, Huaxin LI, Liangyi CAI, Shuai ZHU, Chuanyang LYU, Yanming HE, Jianguo YANG, authorCompany=null, correspAuthors=Huaxin LI, 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=1321490214653120724, articleId=1321490203722764459, tenantId=1146029695717560320, journalId=1220038251117760515, language=CN, title=采用BNi82CrSiB-xCu钎料钎焊304不锈钢接头的微观组织与力学性能, columnId=1220689384622445292, journalTitle=材料工程, columnName=研究论文, runingTitle=null, highlight=null, articleAbstract=

为克服常规镍基钎料钎焊不锈钢接头易形成脆性硼化物的缺点,进一步提升接头的力学性能,本工作提出了在BNi-2镍基钎料中引入少量Cu的方法,以抑制接头中脆性硼化物的形成。分别采用BNi-2钎料和Cu改性的BNi-2钎料对304不锈钢进行真空钎焊,研究了保温时间、钎焊温度与BNi-2钎料中Cu含量对钎缝组织及力学性能的影响。结果表明,对于BNi-2钎料,随着保温时间的延长和钎焊温度的升高,钎缝中心的硼化物含量减少,但母材中的沿晶扩散硼化物增加,扩散距离也随之延长。添加质量分数1%Cu的BNi-2钎料接头,成功抑制了钎缝中心硼化物的生成,接头剪切强度为(713.9±16.4) MPa,相比BNi-2钎料接头提高了19%,接头断裂在母材/钎缝界面,断裂方式为韧性断裂。添加质量分数5%Cu的BNi-2钎料接头,钎缝中心重新析出硼化物,接头剪切强度下降,同时呈现韧性断裂与脆性断裂结合的断裂方式。

, authors=郭杰杰1, 李华鑫1, 2, 3, 蔡良益1, 朱帅4, 闾川阳1, 2, 3, 贺艳明1, 2, 3, 杨建国1, 2, 3, authorsList=郭杰杰, 李华鑫, 蔡良益, 朱帅, 闾川阳, 贺艳明, 杨建国, authorCompany=null, correspAuthors=李华鑫, authorNote=null, correspAuthorsNote=
李华鑫(1990—),男,副研究员,博士,主要研究方向:核材料制备与连接,联系地址:浙江省杭州市西湖区留和路288号浙江工业大学屏峰校区机械工程学院(310023),E-mail:
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processes and Cu contents, figureFileSmall=eR2yNYTb0sYqZJjcKj+nRw==, figureFileBig=xKDNd1D+/l3kpcNozXtceA==, tableContent=null), ArticleFig(id=1321927475861504469, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321490203722764459, language=CN, label=图9, caption=不同钎焊工艺及Cu含量的BNi-2钎料接头剪切强度, figureFileSmall=eR2yNYTb0sYqZJjcKj+nRw==, figureFileBig=xKDNd1D+/l3kpcNozXtceA==, tableContent=null), ArticleFig(id=1321927477518254550, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321490203722764459, language=EN, label=Fig.10, caption=Representative fracture morphologies of BNi-2 filler metals joints

(a)-(c)different brazing processes;(d)-(f)different Cu contents;(g)high magnification image of region Ⅰ in Fig.(d);(h)high magnification image of region Ⅱin Fig.(f);(i)high magnification image of region Ⅲ in Fig.(f)

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(a)~(c)不同钎焊工艺;(d)~(f)不同Cu含量;(g)图(d)中Ⅰ区高倍断口形貌;(h)图(f)中Ⅱ区高倍断口形貌;(i)图(f)中Ⅲ区高倍断口形貌

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Chemical compositions of BNi-2 filler metal (mass fraction/%)

, figureFileSmall=null, figureFileBig=null, tableContent=
CrBSiFeNi
7.03.04.53.0Bal.
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BNi-2钎料化学成分表(质量分数/%)

, figureFileSmall=null, figureFileBig=null, tableContent=
CrBSiFeNi
7.03.04.53.0Bal.
), ArticleFig(id=1321927478151594460, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321490203722764459, language=EN, label=Table 2, caption=

Composition and properties of testing brazing filler metal

, figureFileSmall=null, figureFileBig=null, tableContent=
Mass fraction of Cu/%BNi-2Ti/℃Tf/℃
0Bal.971.51017.6
1Bal.971.41014.8
3Bal.968.71013.9
5Bal.964.11013.7
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实验钎料成分与性能

, figureFileSmall=null, figureFileBig=null, tableContent=
Mass fraction of Cu/%BNi-2Ti/℃Tf/℃
0Bal.971.51017.6
1Bal.971.41014.8
3Bal.968.71013.9
5Bal.964.11013.7
), ArticleFig(id=1321927478281617886, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321490203722764459, language=EN, label=Table 3, caption=

Chemical compositions of points marked in Fig.4(atom fraction/%)

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PointFeCrNiMnSiCBPossible phase
A1.5137.584.81—0.847.2548.01CrB
B12.706.4962.58—4.9613.28—Ni(Fe,Cr)
C55.5838.574.661.19———σ-FeCr
D31.1920.271.36—0.2510.3236.61(Fe,Cr)B
E68.0720.009.661.101.17——SS304
), ArticleFig(id=1321927478579413471, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321490203722764459, language=CN, label=表3, caption=

图4中标记点的化学成分(原子分数/%)

, figureFileSmall=null, figureFileBig=null, tableContent=
PointFeCrNiMnSiCBPossible phase
A1.5137.584.81—0.847.2548.01CrB
B12.706.4962.58—4.9613.28—Ni(Fe,Cr)
C55.5838.574.661.19———σ-FeCr
D31.1920.271.36—0.2510.3236.61(Fe,Cr)B
E68.0720.009.661.101.17——SS304
), ArticleFig(id=1321927478659105248, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321490203722764459, language=EN, label=Table 4, caption=

Proportion of borides in filler zone under different brazing processes

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Brazing processBoride proportion in filler zone/%
1050 ℃/10 min13.3
1075 ℃/10 min9.92
1100 ℃/10 min7.78
1050 ℃/10 min13.3
1050 ℃/20 min10.5
1050 ℃/30 min9.08
), ArticleFig(id=1321927478726214113, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321490203722764459, language=CN, label=表4, caption=

不同钎焊工艺下钎缝区硼化物占比

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Brazing processBoride proportion in filler zone/%
1050 ℃/10 min13.3
1075 ℃/10 min9.92
1100 ℃/10 min7.78
1050 ℃/10 min13.3
1050 ℃/20 min10.5
1050 ℃/30 min9.08
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采用BNi82CrSiB-xCu钎料钎焊304不锈钢接头的微观组织与力学性能
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郭杰杰 1 , 李华鑫 1, 2, 3 , 蔡良益 1 , 朱帅 4 , 闾川阳 1, 2, 3 , 贺艳明 1, 2, 3 , 杨建国 1, 2, 3
材料工程 | 研究论文 2026,54(1): 168-177
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材料工程 |研究论文 2026 , 54 (1) : 168 -177
采用BNi82CrSiB-xCu钎料钎焊304不锈钢接头的微观组织与力学性能
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郭杰杰1, 李华鑫1, 2, 3 , 蔡良益1, 朱帅4, 闾川阳1, 2, 3, 贺艳明1, 2, 3, 杨建国1, 2, 3
作者信息
  • 1.浙江工业大学 化工机械设计研究所,杭州 310023
  • 2.浙江工业大学 过程装备及其再制造 教育部工程研究中心,杭州 310023
  • 3.浙江工业大学 机械工程学院,杭州 310023
  • 4.上海航天设备制造总厂有限公司,上海 200245
通讯作者:
李华鑫(1990—),男,副研究员,博士,主要研究方向:核材料制备与连接,联系地址:浙江省杭州市西湖区留和路288号浙江工业大学屏峰校区机械工程学院(310023),E-mail:
Microstructure and mechanical properties of 304 stainless steel joints brazed by using BNi82CrSiB-xCu filler metals
Jiejie GUO1, Huaxin LI1, 2, 3 , Liangyi CAI1, Shuai ZHU4, Chuanyang LYU1, 2, 3, Yanming HE1, 2, 3, Jianguo YANG1, 2, 3
Affiliations
  • 1.Institute of Process Equipment and Control Engineering,Zhejiang University of Technology,Hangzhou 310023,China
  • 2.Engineering Research Center of Process Equipment and Remanufacturing,Ministry of Education,Zhejiang University of Technology,Hangzhou 310023,China
  • 3.College of Mechanical Engineering,Zhejiang University of Technology,Hangzhou 310023,China
  • 4.Shanghai Aerospace Equipment Manufacturing Co. ,Ltd. ,Shanghai 200245,China
出版时间: 2026-01-20 doi: 10.11868/j.issn.1001-4381.2023.000830
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为克服常规镍基钎料钎焊不锈钢接头易形成脆性硼化物的缺点,进一步提升接头的力学性能,本工作提出了在BNi-2镍基钎料中引入少量Cu的方法,以抑制接头中脆性硼化物的形成。分别采用BNi-2钎料和Cu改性的BNi-2钎料对304不锈钢进行真空钎焊,研究了保温时间、钎焊温度与BNi-2钎料中Cu含量对钎缝组织及力学性能的影响。结果表明,对于BNi-2钎料,随着保温时间的延长和钎焊温度的升高,钎缝中心的硼化物含量减少,但母材中的沿晶扩散硼化物增加,扩散距离也随之延长。添加质量分数1%Cu的BNi-2钎料接头,成功抑制了钎缝中心硼化物的生成,接头剪切强度为(713.9±16.4) MPa,相比BNi-2钎料接头提高了19%,接头断裂在母材/钎缝界面,断裂方式为韧性断裂。添加质量分数5%Cu的BNi-2钎料接头,钎缝中心重新析出硼化物,接头剪切强度下降,同时呈现韧性断裂与脆性断裂结合的断裂方式。

真空钎焊  /  镍基钎料  /  钎焊机理  /  显微组织  /  力学性能

To overcome the drawback of the brittle borides formed in the stainless steel joint brazed using Ni-based filler metals and further improve the mechanical properties of the joint, a small amount of Cu powders are added into the BNi-2 filler metal to suppress the formation of brittle borides in the joints. The 304 stainless steels are brazed using the BNi-2 and BNi-2 with Cu as filler metals, respectively. The influences of holding time, brazing temperature, and Cu content on the microstructure and mechanical properties of the brazed joints are investigated. The results indicate that for the BNi-2 filler metal, increasing the brazing temperature and time are favorable for reducing the boride content formed in the joint center. In addition, increasing the brazing temperature and time can accelerate the intergranular diffusion of borides, thereby leading to a degradation of joint shear strength. For the BNi-2 filler metal with Cu, when the Cu content is 1%(mass fraction,the same below), the borides in the joint center are inhibited remarkably, forming a full Ni-based solid solution in the joint center. The joint shear strength obtained is (713.9±16.4) MPa, which is 19% higher than that of the joint without Cu additive. The joint failure occurs at the base metal/filler metal interface, recognized as a ductile fracture. However, when the Cu content increases to 5%, the borides reprecipitate in the joint center, resulting in the reduction of shear strength. In this case, the joint failure evolves to a composite mode with the co-existence of ductile and brittle fracture.

vacuum brazing  /  Ni-based brazing filler  /  brazing mechanism  /  microstructure  /  mechanical property
郭杰杰, 李华鑫, 蔡良益, 朱帅, 闾川阳, 贺艳明, 杨建国. 采用BNi82CrSiB-xCu钎料钎焊304不锈钢接头的微观组织与力学性能. 材料工程, 2026 , 54 (1) : 168 -177 . DOI: 10.11868/j.issn.1001-4381.2023.000830
Jiejie GUO, Huaxin LI, Liangyi CAI, Shuai ZHU, Chuanyang LYU, Yanming HE, Jianguo YANG. Microstructure and mechanical properties of 304 stainless steel joints brazed by using BNi82CrSiB-xCu filler metals[J]. Journal of Materials Engineering, 2026 , 54 (1) : 168 -177 . DOI: 10.11868/j.issn.1001-4381.2023.000830
304不锈钢因其制造工艺成熟、价格较低,具有良好的耐蚀性和机械强度,在医疗化工、食品加工、生物技术、核能工业等领域有着广泛的应用[1-2]。在不锈钢构件修复与复杂不锈钢部件成形制造中,焊接技术是一种不可或缺的手段。目前不锈钢主要焊接方法有熔焊、压焊、钎焊等[3]。相较于其他焊接方式,钎焊技术具有焊接变形小、结构适应性强、焊接效率高等优点,是不锈钢焊接的优选方法[4]。
工业中常用的不锈钢钎料有铜基钎料、银基钎料、镍基钎料[5]。铜基钎料熔点较高,接头耐蚀性较差;银基钎料接头性能良好但成本较高;镍基钎料成本较低,接头耐高温、耐腐蚀,在极端环境中具有突出的应用优势[6-9]。但镍基钎料中含有的B、P等降熔元素会导致钎缝处形成脆性相,从而影响接头的力学性能。为解决镍基钎料中降熔元素易形成脆性相的问题,国内外通常采用添加一定量其他元素的方法,来抑制脆性相的形成,从而提升接头性能[10-13]。
Hdz-García等[10]使用添加W颗粒的BNi-9钎料钎焊304不锈钢,W颗粒显著细化了钎缝中的硼化物,使接头硬度大幅降低,但未能完全消除硼化物。Chen等[11]在镍基钎料中添加大量的Fe元素制得(Ni,Fe)基箔片,用来钎焊304不锈钢,Fe元素的加入抑制了钎缝中硼化物的生成,接头形成了Fe基固溶体,但Fe元素的降熔效果较差,(Ni,Fe)基箔片熔点过高。Qin等[12]在BNi-7钎料粉末中添加了一定的Cu粉末,熔炼成块并制成箔片,用来钎焊316L不锈钢,结果发现,Cu的添加使得钎料熔点下降,同时细化并降低了钎缝中心脆性相的含量,从而提高了接头强度,但未能完全消除脆性相。此外,还有其他研究表明[13-14],Cu元素的加入可以提高镍基钎料和不锈钢的抗腐蚀性。综上所述,与其他元素相比,在镍基钎料中添加Cu元素具有明显的优势。然而,传统的合金熔炼添加元素的方法操作复杂、成本较高,不利于工业应用。为了实现快速工业应用的可行性,本工作采用更加快速便捷的球磨方式在镍基钎料中添加Cu,以探究该方法是否能完全消除脆性相,进一步提高接头性能。
本工作采用了添加Cu的BNi82CrSiB (BNi-2)粉末钎料真空钎焊304不锈钢,分析了钎焊温度、钎焊时间以及钎料中Cu含量对接头微观组织和力学性能的影响,并探究界面组织形成机理。
实验所用钎料由BNi-2粉末和Cu粉末球磨混合而成,其中Cu的质量分数分别为1%、3%和5%。实验用母材为304不锈钢,使用电火花线切割机将母材加工为4 mm×4 mm×4 mm 和4 mm×10 mm×10 mm两种规格的试样。使用220号、600号、1000号金相砂纸依次对试样进行打磨,将打磨后的试样放入丙酮中超声清洗,随后按图1(a)所示将母材和钎料进行装配。剪切实验示意图见图1(b)。真空钎焊工艺曲线如图2所示。
使用MTS CMT4204型万能试验机对钎焊接头进行剪切实验,十字头移动速度为0.5 mm·min-1,每组实验参数下至少取4个剪切试样进行测试。使用STA 499 F3型同步热分析仪(TG-DSC)测定钎料的熔化区间,采用ZEISS Sigma Gemini 500型扫描电子显微镜(SEM)观察接头的微观组织和断口形貌,利用Bruker Nano X flash Detector 5010型能谱仪(EDS)对接头进行化学成分分析,采用D/Max 2500V型X射线衍射仪(XRD)对接头进行物相分析。
表1为BNi-2钎料的化学成分。表2为实验钎料的成分和热物性能。实验钎料的 DSC曲线如图3所示。由图可知,随着Cu元素含量从0%(质量分数,下同)增加到5%,实验钎料的固相线温度Ti从971.5 ℃降至964.1 ℃,液相线温度Tf从1017.6 ℃降至1013.7 ℃。相较于通过合金熔炼在镍基钎料中添加Cu的方法[12],通过球磨在镍基钎料中添加Cu的方法对固、液相线温度的影响并不显著。这是因为通过球磨添加的Cu与钎料粉末之间仅实现了单纯的机械混合,并未形成新的化合物或固溶体,因此无法显著降低钎料的熔点。
图4为使用BNi-2钎料,在钎焊温度1050 ℃、保温时间10 min工艺下,304不锈钢钎焊接头的典型微观组织,图中标记点的EDS能谱分析结果如表3所示。采用BNi-2钎料的钎焊接头实现了紧密连接,无明显孔洞、裂纹等缺陷(图4)。304不锈钢接头可以分为母材(base metal,BM)、扩散区(diffusing zone,DZ)和钎缝区(filler zone,FZ)3个区域。FZ区为钎料熔化区,主要由长条状的灰白色组织和不规则的黑色相组成;DZ区为钎料与母材的扩散反应区,其内生成了大量细小密集的灰色相。同时DZ区及靠近DZ区的BM区中还存在大量链状的灰黑色相。
由表3可知,FZ区中A点的黑色相主要由B和Cr两种元素组成,二者的原子比接近1∶1,根据前人研究可知该相为CrB[15];B点的灰白色组织是由Ni、Fe、Cr等元素固溶而成的Ni基固溶体[16]。DZ区中的灰色相C主要由Fe、Cr组成,形成σ-FeCr相[17]。BM区中D点的灰黑色相主要由Fe、Cr、B 3种元素构成,推测其为含Fe、Cr的硼化物(Fe,Cr)B。
钎焊接头的反应相形成机制如下:母材晶界处疏松的结构以及位错、空位等缺陷的存在,使得钎焊过程中B元素沿母材晶界处的扩散程度远高于晶内扩散[18],并在母材晶界处生成了(Fe,Cr)B。随着B元素向母材的不断扩散,固液界面逐步向钎料中心移动,发生等温凝固过程,并随之生成Ni基固溶体相[19]。由于钎焊温度和保温时间的限制,钎料中心的B元素未能通过扩散降低至Ni的极限固溶度之下[20],降温过程中B元素析出,形成黑色的CrB。
图5为使用BNi-2钎料、保温时间10 min条件下,不同钎焊温度(1050、1075、1100 ℃)试样的接头微观形貌。图6为使用BNi-2钎料、钎焊温度1050 ℃条件下,不同保温时间(10、20、30 min)试样的接头微观形貌。由图可知,随着钎焊温度的升高和保温时间的延长,钎料中B元素向母材晶界处的扩散程度愈发剧烈,同时FZ区中的黑色硼化物相含量逐渐减少。不同钎焊工艺下接头FZ区中硼化物占比如表4所示。由表4可知,相较于延长保温时间(10 min),升高钎焊温度(25 ℃)对B元素向母材扩散的促进效果更明显。
图7为钎焊温度1050 ℃,保温时间10 min工艺下,采用不同Cu含量(1%、3%、5%)的BNi-2钎料得到的不锈钢接头微观形貌图,以及1%Cu含量的BNi-2钎料接头EDS元素分布图。由图可知,当BNi-2钎料中Cu添加量为1%和3%时,钎缝中心脆性硼化物的形成被抑制,同时在母材/钎缝界面处形成了明显的母材晶界凹槽。EDS元素分布图显示,FZ区富集了大量的Ni元素,形成了完全的Ni基固溶体组织;母材晶界处富集大量的Cr元素,进一步验证了此处形成了大量的铬硼化物;在母材/钎缝界面,晶界凹槽处Fe、Ni元素重叠加剧,表明Fe、Ni元素在该区域的相互扩散更为剧烈。当BNi-2钎料中Cu添加量为5%时,接头FZ区宽度明显增加,母材晶界凹槽沿平行于钎缝方向扩展,同时FZ区充斥着大量细小密集的硼化物,与图5(a)中FZ区硼化物分布的微观形貌明显不同,说明两者的形成机制有所差异。
Cu作为不锈钢的降熔元素[21],钎焊过程中Cu元素向母材的扩散会加速母材的溶解。钎料中的Cu元素优先沿母材晶界扩散,导致母材晶界处先一步发生溶解,形成晶界凹槽。由于晶界凹槽处液/固界面的卷曲和晶界处较高的扩散系数,进一步促进了钎料母材元素间的相互扩散[22],随着Cu元素含量的增加,晶界凹槽逐渐扩张,元素的相互扩散程度越高。另一方面,Cu与Ni无限固溶,Cu元素主要固溶于FZ区Ni基固溶体中。由于Cu的原子半径大于Ni,Cu的溶入使得Ni基固溶体的晶格常数增加,晶体间隙增大[23],有利于B元素对Ni基固溶体的间隙溶入。因此,BNi-2钎料中少量Cu元素(1%、3%)的添加,促进了钎料中B元素对母材的扩散以及对Ni基固溶体的溶解,从而消除了钎缝中脆性的硼化物相。
对于5%Cu含量BNi-2钎料接头,FZ区宽度明显增加,并重新析出大量硼化物,这与Cu元素的含量密不可分。Atabaki等[22]采用Cu作为中间层扩散连接304不锈钢,结果发现Cu元素在不锈钢晶界处扩散明显,并形成Fe-Cu固溶体溶入中间层中;陈汝淑等[24]采用Cu箔对碳钢和304不锈钢进行扩散连接,研究发现仅在Cu/304不锈钢界面,铜液侵蚀不锈钢晶界,随着扩散时间的延长和扩散温度的升高,界面处的奥氏体晶粒逐渐与母材分离、脱落并溶于铜液中,同时中间层厚度也随之增加。类似地,钎料中过量Cu元素的添加使得钎料对母材的溶解程度进一步增强,更多的母材基体元素进入钎缝中,导致FZ区宽度增加。同时,晶界凹槽处卷曲的液/固界面沿平行于钎缝的方向扩展。一方面,由于晶体结构和化学亲和力等因素的影响,B元素在Fe中的固溶度低于在Ni中的固溶度[25-26]。并且Fe与Ni无限固溶,而Cr在Ni中的溶解度极为有限。对于5%Cu含量的钎料接头,母材中的Fe、Cr大量溶解扩散到钎料中,导致钎料对B的溶解度降低,对Cr的溶解度达到极限,从而析出CrB相。另一方面,由于B元素较小的原子体积,相较于Cu元素,B元素更早向母材扩散,并在母材中生成CrB相。随着Cu元素的扩散,母材向钎缝大量溶解,母材中的CrB相又重新溶于钎料。因此,5%Cu含量的钎料接头FZ区中重新析出大量细小密集的硼化物。
图8为BNi-2钎料和含Cu的BNi-2钎料钎焊不锈钢的接头组织演变示意图。对于BNi-2钎料接头,B元素在母材中的扩散优先沿着晶界进行,并在晶界处生成了(Fe,Cr)B相。由于钎焊温度和保温时间的限制,钎缝中心未充分扩散至固溶度之下的B元素与Cr元素生成CrB相。随着钎焊温度升高和保温时间的延长,B元素的扩散更加充分,钎缝中心CrB相含量逐渐降低,沿晶扩散的程度也变得更加剧烈。对于含Cu的BNi-2钎料接头,Cu元素优先进行沿晶扩散,并且Cu元素溶入不锈钢会降低不锈钢熔点,进而加速母材在晶界处的溶解,形成晶界凹槽。晶界凹槽的形成一方面增加了母材和钎料的接触面积,另一方面在晶界处形成了扩散通道,促进了母材与钎料之间的元素扩散。随着钎料中Cu含量的增加,母材晶界处的晶界凹槽逐渐长大并沿平行于钎缝的方向向两侧扩展,同时母材溶解的程度进一步加剧,钎缝中心重新析出大量的硼化物相。
图9为不同钎焊工艺及Cu含量对BNi-2钎料接头抗剪强度的影响。由图可知,对于BNi-2钎料不锈钢接头,在相同的保温时间(10 min)下,随着钎焊温度从1050 ℃提高到1100 ℃,接头强度从(599.8±45.1) MPa降低至(455.2±56.2) MPa。在相同的钎焊温度(1050 ℃)下,随着保温时间从10 min延长到30 min,接头强度从(599.8±45.1) MPa下降至(508.6±63.4) MPa。这种变化趋势归因于随钎焊温度的升高和保温时间的延长,B元素的沿晶扩散更剧烈,沿晶扩散处的结合强度也随之降低,并逐渐成为接头的首要失效位置,如图10接头断口形貌所示。对于不同Cu含量BNi-2钎料接头,在相同的钎焊工艺1050 ℃/10 min下,随着钎料中Cu元素含量从1%增加至5%,接头强度从(713.9±16.4) MPa降低至(423.5±49.0) MPa。钎料中Cu添加量为1%时,接头强度最高,相较于相同钎焊工艺但未添加Cu的BNi-2钎料接头,接头强度提高了19%,这是由于Cu的添加在保证沿晶扩散处强度的前提下,消除了钎缝中心的硼化物。然而,随着钎料中Cu添加量的增加,母材的溶解程度愈加剧烈,晶界凹槽逐渐扩张,B元素的沿晶扩散程度加剧,导致接头母材晶界处的结合强度降低。同时5%Cu含量的钎料接头FZ区重新析出了大量硼化物相,也在一定程度上降低了接头强度。
图10为不同钎焊工艺及Cu含量的BNi-2钎料接头断口形貌。由图可知,不锈钢接头断口形貌可以分为3个区域,分别为沿母材/钎缝界面处断裂的韧性断裂区Ⅰ区、沿FZ区中心硼化物处断裂的脆性断裂区Ⅱ区、沿母材沿晶扩散处断裂的脆性断裂区Ⅲ区。
对于BNi-2钎料接头,在1050 ℃/10 min工艺下,接头首先于结合较薄弱的母材/钎缝界面处产生裂纹,由于钎缝中心脆性的CrB相与周围钎料的界面处存在较大的应力集中,裂纹随后扩展至钎缝中心的CrB处发生脆性断裂。随着保温时间的延长,B元素对母材的沿晶扩散程度增加,沿晶扩散处的结合强度随之降低。在1050 ℃/30 min工艺下,接头母材沿晶扩散处的结合强度低于母材/钎缝界面处的结合强度,导致接头首先在母材沿晶扩散处开始失效,随后裂纹扩展到母材/钎缝界面,最终在钎缝中心的CrB相处脆性断裂,接头强度降低。根据前文内容,相较于保温时间延长(10 min),连接温度升高(25 ℃)对B元素扩散的促进作用更为明显。在1100 ℃/10 min工艺下,B元素的进一步扩散使得母材沿晶扩散处的结合强度进一步降低,同时由于钎缝中心CrB 相的减少,CrB相处的应力集中减小,导致接头首先在母材沿晶扩散处失效,随后裂纹扩展至母材/钎缝界面处,而在未达到钎缝中心的脆性断裂极限之前就已经完全失效,因此接头强度进一步降低。
在1050 ℃/10 min工艺下,不同Cu含量的BNi-2钎料不锈钢接头表现出不同的断裂特征。相较于同工艺的BNi-2钎料接头,1%Cu含量的钎料接头由于钎缝中硼化物的消除,其仅沿母材/钎缝界面发生韧性断裂,强度最高,承载能力最强。随着钎料中Cu含量的增加,B元素向母材晶界的扩散程度加剧,导致母材沿晶扩散处的结合强度进一步降低。因此,3%Cu含量的钎料接头在母材沿晶扩散处首先失效,随后裂纹扩展至母材/钎缝界面直至断裂,接头强度降低。对于5%Cu含量的钎料接头,由于此时FZ区重新析出大量的CrB,导致钎缝中心重新出现较大的应力集中,裂纹仍首先在最薄弱的母材沿晶扩散处生成,随后扩展至母材/钎缝界面,最终断裂于钎料中心的CrB处。
图11为1050 ℃/10 min钎焊工艺下,BNi-2钎料接头断口的XRD图谱。结果显示,接头断口处主要是由Ni基固溶体组成,其次还含CrB、Cr2B等硼化物,这进一步证明了接头的断裂是从母材/钎缝界面处产生,随后扩展至FZ区脆性硼化物相处。
(1)采用BNi-2钎料实现了304不锈钢的良好钎焊,接头钎缝中心与钎缝两侧晶界处生成了脆性的硼化物,在一定范围内改良钎焊工艺无法消除钎缝中心的硼化物。在BNi-2钎料中加入适量的Cu元素 (1%、3%),消除了钎缝中心脆性的硼化物,但随着Cu含量的进一步增加, 钎缝中心重新析出大量细小的硼化物。
(2)随钎焊温度的升高和保温时间的延长,304不锈钢/BNi-2/304不锈钢接头的剪切强度逐渐降低。在1050 ℃/10 min工艺下,剪切强度最高,为(599.8±45.1) MPa,此时接头表现为韧性断裂与脆性断裂相结合的断裂方式。在1050 ℃/10 min工艺下,随着BNi-2钎料中Cu含量的增加,钎焊接头的剪切强度逐渐降低。1%Cu含量钎料接头剪切强度最高,为(713.9±16.4) MPa,比未添加Cu的接头提高了19%,此时接头的断裂方式为韧性断裂。
(3)BNi-2钎料中适量Cu元素(1%、3%)的加入促使母材晶界处形成凹槽,加速了B元素向母材的扩散。同时,Cu元素的加入导致钎缝中Ni基固溶体的晶格常数增加、晶体间隙增大,有利于B元素的间隙溶入,从而消除了钎缝中心的硼化物。但过量Cu元素(5%)的添加促使母材过度溶解,使得母材中已经生成的硼化物重新溶入钎料,同时Fe、Cr等元素对钎料的大量溶入,也促进了B、Cr等元素的析出,导致钎缝中重新析出细小密集的硼化物。
  • 国家自然科学基金(52005445)
  • 浙江省自然科学基金(LQ21E050018)
  • 中国博士后科学基金(2022M712820)
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2026年第54卷第1期
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doi: 10.11868/j.issn.1001-4381.2023.000830
  • 接收时间:2023-12-11
  • 首发时间:2026-10-26
  • 出版时间:2026-01-20
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  • 收稿日期:2023-12-11
  • 录用日期:2024-03-15
基金
国家自然科学基金(52005445)
浙江省自然科学基金(LQ21E050018)
中国博士后科学基金(2022M712820)
作者信息
    1.浙江工业大学 化工机械设计研究所,杭州 310023
    2.浙江工业大学 过程装备及其再制造 教育部工程研究中心,杭州 310023
    3.浙江工业大学 机械工程学院,杭州 310023
    4.上海航天设备制造总厂有限公司,上海 200245

通讯作者:

李华鑫(1990—),男,副研究员,博士,主要研究方向:核材料制备与连接,联系地址:浙江省杭州市西湖区留和路288号浙江工业大学屏峰校区机械工程学院(310023),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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