Article(id=1199641487953719860, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1199641484963181075, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2023.07.005, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1663084800000, receivedDateStr=2022-09-14, revisedDate=1667923200000, revisedDateStr=2022-11-09, acceptedDate=null, acceptedDateStr=null, onlineDate=1763946418989, onlineDateStr=2025-11-24, pubDate=1689782400000, pubDateStr=2023-07-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1763946418989, onlineIssueDateStr=2025-11-24, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1763946418989, creator=13701087609, updateTime=1763946418989, updator=13701087609, issue=Issue{id=1199641484963181075, tenantId=1146029695717560320, journalId=1149653034449285133, year='2023', volume='56', issue='7', pageStart='1', pageEnd='113', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1763946418275, creator=13701087609, updateTime=1766563596176, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1210618724747440709, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1199641484963181075, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1210618724747440710, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1199641484963181075, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=25, endPage=31, ext={EN=ArticleExt(id=1199641488201183802, articleId=1199641487953719860, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Preparation and characterization of single component high thermal conductive structural adhesive, columnId=1190369066675179686, journalTitle=Insulating Materials, columnName=Material Research, runingTitle=null, highlight=null, articleAbstract=

A base gel was prepared with bisphenol A epoxy resin E124 as the main resin, polymercaptan as the curing agent, and imidazole as the accelerator. A single component high thermal conductive structural adhesive was prepared by adding different proportions and sizes of spherical alumina and irregular alumina into the base gel. The effects of different filling content and different particle sizes of alumina on the thermal conductivity, bonding strength, viscosity, and thixotropy of the single component high thermal conductive structural adhesive were studied. The results show that when the mass ratio of base gel to the three different particle sizes of alumina is m(base gel)∶m(40 μm Al2O3)∶m(2 μm Al2O3)∶m(0.5 μm Al2O3) =15∶59.5∶25.5∶6, m(base gel)∶m(40 μm Al2O3)∶m(5 μm Al2O3)∶m(0.5 μm Al2O3) =15∶59.5∶25.5∶8, m(base gel)∶m(40 μm Al2O3)∶m(10 μm Al2O3)∶m(0.5 μm Al2O3)=15∶68∶17∶8, three kinds of high thermal conductive structural adhesives cured at 90℃ for 15 min can be obtained, their thermal conductivity is 2.73, 3.05, 2.85 W/(m·K), their bonding strength is 5.49, 5.55 and 5.31 MPa, and their viscosity is 145 000, 127 467 and 118467 mPa·s, respectively. The volume resistivity of the three kinds of high thermal conductive structural adhesives is above 1014 Ω·m, and the adhesive survival rate after high temperature and humidity, cold and thermal shock is more than 70% and 90%, respectively. The performance of the high thermal conductive structural adhesive meets the basic performance requirements of screen printing and heat dissipation materials for chip packaging.

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以双酚A型环氧树脂E124为主体树脂、聚硫醇为固化剂,咪唑为促进剂制备基础胶液。在基础胶液种加入不同比例、不同尺寸的球形氧化铝和不规则氧化铝制备单组分高导热结构胶,探究了不同填充量、不同粒径氧化铝对单组分高导热结构胶热导率、粘接强度、黏度和触变性等性能的影响。结果表明:当基础胶液与3种不同粒径氧化铝质量之比m(基础胶液)∶m(40 μm Al2O3)∶ m(2 μm Al2O3)∶m(0.5 μm Al2O3)=15∶59.5∶25.5∶6;m(基础胶液)∶m(40 μm Al2O3)∶m(5 μm Al2O3)∶m(0.5 μm Al2O3)=15∶59.5∶25.5∶8;m(基础胶液)∶m(40 μm Al2O3)∶m(10 μm Al2O3)∶m(0.5 μm Al2O3)=15∶68∶17∶8时,可制得90℃×15 min固化的3种高导热结构胶,其热导率分别为2.73、3.05、2.85 W/(m·K),粘接强度分别为5.49、5.55、5.31 MPa,黏度分别为145 000、127 467、118 467 mPa·s。3种高导热结构胶的体积电阻率均在1014 Ω·m以上,经高温高湿和冷、热冲击后粘接残存率分别在70%和90%以上。该高导热结构胶的性能满足了丝网印刷工艺和芯片封装用散热材料的基本性能要求。

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李会录(1966-),男(汉族),陕西渭南人,副教授,主要从事环氧树脂和光敏树脂合成的研究。
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陈嘉亮(1996-),男(汉族),甘肃天水人,硕士生,主要从事环氧树脂的研究。

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陈嘉亮(1996-),男(汉族),甘肃天水人,硕士生,主要从事环氧树脂的研究。

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陈嘉亮(1996-),男(汉族),甘肃天水人,硕士生,主要从事环氧树脂的研究。

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Orlando, USA:IEEE,2014., articleTitle=Predicting thermo-mechanical degradation of first-level thermal interface materials (TIMs) in flip-chip electronic packages, refAbstract=null)], funds=[Fund(id=1217475253832438698, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199641487953719860, awardId=51903207, language=CN, fundingSource=国家自然科学基金资助项目(51903207), fundOrder=null, country=null)], companyList=[AuthorCompany(id=1217475246995722929, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199641487953719860, xref=null, ext=[AuthorCompanyExt(id=1217475247004111539, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199641487953719860, companyId=1217475246995722929, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=College of Material Science and Engineering, Xi′an University of Science and Technology, Xi′an 710054, China), AuthorCompanyExt(id=1217475247008305844, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199641487953719860, companyId=1217475246995722929, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=西安科技大学 材料科学与工程学院,陕西 西安 710054)])], figs=[ArticleFig(id=1217475251110335311, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199641487953719860, language=EN, label=Fig.1, caption=Thermal conductivity of thermal conductive structural adhesive with different contents of 0.5 μm irregular alumina, figureFileSmall=0LcL0I6+/BuYvPNwnTf6FQ==, figureFileBig=5yIAqB1lZIpmSUW0qNyu3A==, tableContent=null), ArticleFig(id=1217475251215192918, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199641487953719860, language=CN, label=图1, caption=添加不同含量的0.5 μm不规则氧化铝的导热结构的导热性能, figureFileSmall=0LcL0I6+/BuYvPNwnTf6FQ==, figureFileBig=5yIAqB1lZIpmSUW0qNyu3A==, tableContent=null), ArticleFig(id=1217475251315856219, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199641487953719860, language=EN, label=Fig.2, caption=Bonding strength of different particle size filler compound glue, figureFileSmall=p4NPHDzYpf4yfLHZb0zF/A==, figureFileBig=30RrWLgZRvgYYIir1XjjcA==, tableContent=null), ArticleFig(id=1217475251408130915, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199641487953719860, language=CN, label=图2, caption=不同粒径填料复配胶液的粘接强度, figureFileSmall=p4NPHDzYpf4yfLHZb0zF/A==, figureFileBig=30RrWLgZRvgYYIir1XjjcA==, tableContent=null), ArticleFig(id=1217475251500405609, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199641487953719860, language=EN, label=Fig.3, caption=The viscosity of adhesive filled with different mass fractions of 0.5 μm irregular alumina, figureFileSmall=ZHbV2ly7cWT62jFlBdYMEA==, figureFileBig=l0S9beGF8bVmzvbuj8sNTg==, tableContent=null), ArticleFig(id=1217475251575903087, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199641487953719860, language=CN, label=图3, caption=添加不同质量分数的0.5 μm不规则氧化铝胶液的黏度, figureFileSmall=ZHbV2ly7cWT62jFlBdYMEA==, figureFileBig=l0S9beGF8bVmzvbuj8sNTg==, tableContent=null), ArticleFig(id=1217475251655594866, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199641487953719860, language=EN, label=Fig.4, caption=Surface morphology of thermal conductivie structural adhesives filled with different alumina, figureFileSmall=OlaDM/RsE6AdAppYBMhCsw==, figureFileBig=7LmuVA4tkALsZ/pd9eDanQ==, tableContent=null), ArticleFig(id=1217475251752063864, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199641487953719860, language=CN, label=图4, caption=不同氧化铝导热结构胶的微观表面形貌, figureFileSmall=OlaDM/RsE6AdAppYBMhCsw==, figureFileBig=7LmuVA4tkALsZ/pd9eDanQ==, tableContent=null), ArticleFig(id=1217475251865310079, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199641487953719860, language=EN, label=Fig.5, caption=Volume resistivity of compound adhesive filled with three particle size of thermal conductive fillers, figureFileSmall=M3HPEAXSP+GcWzS53s4UnA==, figureFileBig=/VOaM2/lJghbeO8jxN0IRg==, tableContent=null), ArticleFig(id=1217475253131989895, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199641487953719860, language=CN, label=图5, caption=3种粒径导热填料复配胶液的体积电阻率, figureFileSmall=M3HPEAXSP+GcWzS53s4UnA==, figureFileBig=/VOaM2/lJghbeO8jxN0IRg==, tableContent=null), ArticleFig(id=1217475253220070284, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199641487953719860, language=EN, label=Tab.1, caption=Different formula of high thermal conductive structural adhesive, figureFileSmall=null, figureFileBig=null, tableContent=
项目ABCD
基础胶液/份15151515
40 μm氧化铝/份059.559.568
10 μm氧化铝/份00017
5 μm氧化铝/份0000
2 μm氧化铝/份025.525.50
0.5 μm氧化铝/份0688
), ArticleFig(id=1217475253396231058, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199641487953719860, language=CN, label=表1, caption=

不同高导热结构胶胶液配方

, figureFileSmall=null, figureFileBig=null, tableContent=
项目ABCD
基础胶液/份15151515
40 μm氧化铝/份059.559.568
10 μm氧化铝/份00017
5 μm氧化铝/份0000
2 μm氧化铝/份025.525.50
0.5 μm氧化铝/份0688
), ArticleFig(id=1217475253526254490, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199641487953719860, language=EN, label=Tab.2, caption=Adhesive strength of different high thermal conductive structural adhesives, figureFileSmall=null, figureFileBig=null, tableContent=
样品常温粘接强度/MPa高温高湿粘接强度/MPa高温高湿残留率/%冷、热冲击粘接强度/MPa冷、热冲击残留率/%
A8.703.4539.668.2194.37
B5.764.2673.965.2991.84
C5.984.5375.755.5893.31
D5.514.1274.775.0792.01
), ArticleFig(id=1217475253610140575, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199641487953719860, language=CN, label=表2, caption=

不同高导热结构胶的粘接强度

, figureFileSmall=null, figureFileBig=null, tableContent=
样品常温粘接强度/MPa高温高湿粘接强度/MPa高温高湿残留率/%冷、热冲击粘接强度/MPa冷、热冲击残留率/%
A8.703.4539.668.2194.37
B5.764.2673.965.2991.84
C5.984.5375.755.5893.31
D5.514.1274.775.0792.01
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单组份高导热结构胶的制备及性能表征
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陈嘉亮 , 王刚 , 夏婷 , 苏建峰 , 李会录
绝缘材料 | 材料研究 2023,56(7): 25-31
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绝缘材料 | 材料研究 2023, 56(7): 25-31
单组份高导热结构胶的制备及性能表征
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陈嘉亮, 王刚, 夏婷, 苏建峰, 李会录
作者信息
  • 西安科技大学 材料科学与工程学院,陕西 西安 710054
  • 陈嘉亮(1996-),男(汉族),甘肃天水人,硕士生,主要从事环氧树脂的研究。

通讯作者:

李会录(1966-),男(汉族),陕西渭南人,副教授,主要从事环氧树脂和光敏树脂合成的研究。
Preparation and characterization of single component high thermal conductive structural adhesive
Jialiang CHEN, Gang WANG, Ting XIA, Jianfeng SU, Huilu LI
Affiliations
  • College of Material Science and Engineering, Xi′an University of Science and Technology, Xi′an 710054, China
出版时间: 2023-07-20 doi: 10.16790/j.cnki.1009-9239.im.2023.07.005
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以双酚A型环氧树脂E124为主体树脂、聚硫醇为固化剂,咪唑为促进剂制备基础胶液。在基础胶液种加入不同比例、不同尺寸的球形氧化铝和不规则氧化铝制备单组分高导热结构胶,探究了不同填充量、不同粒径氧化铝对单组分高导热结构胶热导率、粘接强度、黏度和触变性等性能的影响。结果表明:当基础胶液与3种不同粒径氧化铝质量之比m(基础胶液)∶m(40 μm Al2O3)∶ m(2 μm Al2O3)∶m(0.5 μm Al2O3)=15∶59.5∶25.5∶6;m(基础胶液)∶m(40 μm Al2O3)∶m(5 μm Al2O3)∶m(0.5 μm Al2O3)=15∶59.5∶25.5∶8;m(基础胶液)∶m(40 μm Al2O3)∶m(10 μm Al2O3)∶m(0.5 μm Al2O3)=15∶68∶17∶8时,可制得90℃×15 min固化的3种高导热结构胶,其热导率分别为2.73、3.05、2.85 W/(m·K),粘接强度分别为5.49、5.55、5.31 MPa,黏度分别为145 000、127 467、118 467 mPa·s。3种高导热结构胶的体积电阻率均在1014 Ω·m以上,经高温高湿和冷、热冲击后粘接残存率分别在70%和90%以上。该高导热结构胶的性能满足了丝网印刷工艺和芯片封装用散热材料的基本性能要求。

环氧树脂  /  黏度  /  热导率  /  粘结强度  /  氧化铝  /  填料

A base gel was prepared with bisphenol A epoxy resin E124 as the main resin, polymercaptan as the curing agent, and imidazole as the accelerator. A single component high thermal conductive structural adhesive was prepared by adding different proportions and sizes of spherical alumina and irregular alumina into the base gel. The effects of different filling content and different particle sizes of alumina on the thermal conductivity, bonding strength, viscosity, and thixotropy of the single component high thermal conductive structural adhesive were studied. The results show that when the mass ratio of base gel to the three different particle sizes of alumina is m(base gel)∶m(40 μm Al2O3)∶m(2 μm Al2O3)∶m(0.5 μm Al2O3) =15∶59.5∶25.5∶6, m(base gel)∶m(40 μm Al2O3)∶m(5 μm Al2O3)∶m(0.5 μm Al2O3) =15∶59.5∶25.5∶8, m(base gel)∶m(40 μm Al2O3)∶m(10 μm Al2O3)∶m(0.5 μm Al2O3)=15∶68∶17∶8, three kinds of high thermal conductive structural adhesives cured at 90℃ for 15 min can be obtained, their thermal conductivity is 2.73, 3.05, 2.85 W/(m·K), their bonding strength is 5.49, 5.55 and 5.31 MPa, and their viscosity is 145 000, 127 467 and 118467 mPa·s, respectively. The volume resistivity of the three kinds of high thermal conductive structural adhesives is above 1014 Ω·m, and the adhesive survival rate after high temperature and humidity, cold and thermal shock is more than 70% and 90%, respectively. The performance of the high thermal conductive structural adhesive meets the basic performance requirements of screen printing and heat dissipation materials for chip packaging.

epoxy resin  /  viscosity  /  thermal conductivity  /  bonding strength  /  alumina  /  filler
陈嘉亮, 王刚, 夏婷, 苏建峰, 李会录. 单组份高导热结构胶的制备及性能表征. 绝缘材料, 2023 , 56 (7) : 25 -31 . DOI: 10.16790/j.cnki.1009-9239.im.2023.07.005
Jialiang CHEN, Gang WANG, Ting XIA, Jianfeng SU, Huilu LI. Preparation and characterization of single component high thermal conductive structural adhesive[J]. Insulating Materials, 2023 , 56 (7) : 25 -31 . DOI: 10.16790/j.cnki.1009-9239.im.2023.07.005
电子和通信等技术的蓬勃发展促进各类电子产品层见叠出,推动着人类生产和生活方式加速转变。先进电子器件及产品高密度和多功能化集成发展使以芯片为代表的电子元器件的集成度和功耗不断增加,导致电子产品的散热快速增大[1]。十度升温法则[1]反映电子元器件的工作温度每增加10℃,其散热性能就会降低25%~50%。如果这些电子元器件的热量不能及时有效消散,将对电子产品的可靠性和使用寿命造成严重的影响,因此各类新型导热、散热材料一直是电子产业的重点研究方向之一[2]。国内外已经分别研制出热导率为2.8 W/(m·K)和2.9 W/(m·K)的高分子导热胶,占据着国内的主要市场。YUAN H等[3]通过聚多巴胺包覆铜纳米线制备环氧复合材料,提高了材料的热导率,当铜纳米线质量分数为3.1%时,热导率达到2.87 W/(m·K)。但现有导热胶仍存在黏度过大(大于200 000 mPa·s),不能满足丝网印刷工艺及固化效率低等问题,因此亟需研制黏度更低、固化效率更高的高性能高分子导热胶产品以满足高效率作业[4]
在单组份高导热结构胶中,基础胶液仅占很小部分,且其热导率(约为0.2 W/(m·K))远低于各种导热填料,因而导热结构胶的高导热主要体现在导热填料的选择与使用[5-6]。理论上导热填料添加量越多,越容易产生更多的导热触点,形成更加完善的导热通路和网络,导热结构胶的导热性能越好。但是由于树脂润湿能力有限,加之导热填料的粒径和形貌有差异,导致导热填料不能无限量添加。此外大量添加导热填料会牺牲导热结构胶的力学性能和加工性能,因此导热结构胶要在保证高导热性能的同时满足力学性能和加工性能的要求,由此应对导热结构胶的填料进行深入研究[7]
本文以氧化铝(Al2O3)为填料复合基础胶液制备高导热结构胶,选择不同粒径的不规则氧化铝和球形氧化铝复配作为导热填料加入基础胶液的最佳配方中,通过测试及分析探究填料对高导热结构胶的影响。
环氧树脂(E124),工业级,广东宏昌电子材料有限公司;聚硫醇,工业级,广州格凌贸易有限公司;咪唑,试剂级,日本三井公司;咪唑促进剂(PN-H),试剂级,日本味之素公司;炭黑,工业级,上海科德威化有限公司;稳定剂,自制;粒径分别为2、5、10 μm的球形氧化铝,工业级,上海百图高新材料有限公司。
根据产品性能要求,选择合适的树脂、固化剂等,确定基础胶液的固化工艺。通过实验设计,对配方中环氧树脂、聚硫醇固化剂、咪唑促进剂等其他助剂分别进行计算并均匀混合制备高导热结构胶的基础胶液。加料过程中需注意环氧树脂为高结晶的树脂,使用前需加热使其变为流动液体后再添加其他组分,然后分别再加入聚硫醇和PN-H,并使用高速分散机使其分散均匀。
将基础胶液与不同氧化铝导热填料混合均匀制备单组份高导热结构胶。调节不同尺寸、形状的Al2O3添加量,以实验室制备的导热填料大小粒径复配最合理的配比(m(40 μm Al2O3)∶m(10 μm Al2O3)=8∶2;m(40 μm Al2O3)∶m(5 μm Al2O3)=7∶3;m(40 μm Al2O3)∶m(2 μm Al2O3)=7∶3)为基础粉体搭配[8],向其中添加0.5 μm不规则氧化铝制备高导热结构胶,测试导热结构胶的热导率、热阻等综合性能的变化,并对高导热结构胶固化前后的综合性能进行检测。
使用DV2T型数显旋转黏度计测试不同恒温胶液的黏度。胶液在25℃下恒温处理,每组胶液取3个不同位置进行多次测试,取平均值作为胶液黏度。
按照ASTM D5470-2012的测试方法,使用DRL-IIL型热导率测试仪,通过稳态热流法对不同导热胶样品进行热导率测试。
根据GB/T 7124—2008的要求使用GNT200计算机程控万能试验机进行粘接强度测试,每种胶液制备粘接片5个,取平均值作为胶液粘接强度。
使用DRL-IIL型热导率测试仪通过稳态热流法测试不同导热胶样品的接触热阻,取3组样品的平均值作为该导热结构胶的接触热阻。
使用VEGA Ⅱ XMU扫描电子显微镜进行测试,对固化后经打磨的导热片进行表面喷金处理,然后观察导热结构胶中氧化铝与基础胶液的混合分散程度。
将制备好的粘接片放置24 h后放入KSD-TH-80L恒温恒湿循环试验箱中,温度、湿度分别设置为85℃、85%,放置500 h后取出测试粘接强度并计算其残留率。
将已配制均匀的胶液倒入特制的硅胶模具中,制备体积电阻率测试样片,直径(φ)为50 mm,厚度(h)为0.5~2 mm。根据GB/T 1410—2006的要求,取3次测试结果的平均值作为样片的体积电阻率。体积电阻率的计算公式如式(1)所示。
Pv=RVA/h
式(1)中:Pv为体积电阻率,单位为Ω·m;R为选取的倍率;V为试样的电压,单位为V;A为测量电极的有效面积,单位为m2h为试样的平均厚度,一般将样片随机5个不同位置厚度的平均值视为样片平均厚度,单位为mm。
填充型导热结构胶导热通路所构成的导热网络越完善,其导热性能越好,不同粒径的球形氧化铝合理搭配,可以实现导热粒子的大量堆积,形成大量的导热通路和网络,且对导热结构胶的导热性能、粘接性能和自流平性能都有一定保证,但规则的球形氧化铝之间依然存在少量“自由体积”,导热通路仍可被进一步完善[9]
单组份高导热结构胶的基础胶液决定了导热填料的填充量和固化工艺,影响着导热结构胶的使用工艺和固化效率,通过实验选用环氧树脂E124和聚硫醇的低温快速固化体系,并确定了基础胶液体系聚硫醇和PN-H的最佳添加量和最佳固化工艺:
(1)环氧树脂E124与聚硫醇自身反应较为缓慢,一定量的PN-H可以加快体系固化速率,通过实验得到基础胶液的最佳配方为:m(双酚A环氧树脂E124)∶m(低黏度聚硫醇)∶m(PN-H)=100∶79∶3,此时可得到25℃下黏度仅为720 mPa·s的低黏度基础胶液,有利于球形氧化铝导热填料的高填充。
(2)凝胶化时间测试表明该基础胶液不宜在120℃以上温度反应。基础胶液经90℃/15 min后可实现中温快速完全固化,能够满足工业化的快速连续生产,但是固化时应在保持固化效率的前提下尽量避免升温速率过高。
以合理搭配不同粒径的导热填料为基础粉体(m(40 μm Al2O3)∶m(10 μm Al2O3)=8∶2;m(40 μm Al2O3)∶m(5 μm Al2O3)=7∶3;m(40 μm Al2O3)∶m(2 μm Al2O3)=7∶3),加入不同含量的0.5 μm不规则氧化铝制备高导热结构胶,由于高导热结构胶中已有85%的导热填料存在,0.5 μm不规则氧化铝的质量分数分别占2%、4%、6%、8%、10%。图1为添加不同含量0.5 μm不规则氧化铝的导热结构胶的导热性能测试结果。从图1可以看出,起初Al2O3添加量较少,此时胶液为连续的“海相”,Al2O3粒子间没有相互作用,以“岛相”在胶液中孤立存在,导热结构胶的热传导大多依靠热导率极低的基础胶液,仅有少量的热在Al2O3和基础胶液之间进行传导,因此导热结构胶的热导率较小;继续增大氧化铝的添加量,Al2O3之间不再孤单存在,相互形成联通的“岛相”,开始形成导热通路,此时导热结构胶的热传导主要依靠导热填料来实现,其热导率不断增大。这是因为0.5 μm的不规则氧化铝可以填充体系剩余的少量“自由体积”,使导热结构胶氧化铝的有效质量分数增加,同时可以提供更多的导热触点,使体系原有的导热网络更加密集和完善,所以导热结构胶的热导率随之增大。随着0.5 μm不规则氧化铝填充到3种氧化铝复配的导热结构胶中,填料的质量分数进一步增大,其热导率和平均热阻变化趋势相同,二者均相应增大。0.5 μm不规则氧化铝的加入,体系的氧化铝数量相应增加,填料之间的接触面积增加,由于0.5 μm不规则氧化铝的比表面积(4.24 m2/g)远大于体系其他填料的比表面积(2、5、10、40 μm球形氧化铝的比表面积分别为1.27、0.36、0.17、0.12 m2/g),使导热结构胶的界面影响因子增大,因此平均热阻也相应增大,这对导热结构胶的热传导能力是不利的[10]。热导率和平均热阻均增大这一相互矛盾的结果之所以最终使导热结构胶的导热能力增强,是由于0.5 μm不规则氧化铝颗粒的加入对系统热导率的增强效果更为显著,因此导热结构胶的综合导热能力是增强的。此外,从图1(a)可知,40 μm和10 μm氧化铝复配的胶液中不规则氧化铝的最大质量分数在8%左右,若继续添加不规则氧化铝,胶液无法完全包裹所有填料,制备的导热结构胶无任何使用价值。从图1(b)图1(c)可知,40 μm和5 μm、40 μm和2 μm氧化铝复配的胶液中不规则氧化铝的添加量相对更高,在不规则氧化铝质量分数为10%时,才出现类似的添加极限现象。因此40 μm和2 μm、40 μm和5 μm以及40 μm和10 μm氧化铝复配的导热结构胶中添加0.5 μm不规则氧化铝的最佳质量分数分别为6%、8%和8%,此时的热导率分别为2.73、3.05、2.85 W/(m·K)。从3种填料的导热性能和接触热阻曲线中可以看出,40 μm和5 μm氧化铝复配再添加0.5 μm不规则氧化铝的导热结构胶导热性能最好。
图2为不同粒径的填料复配不同质量分数的0.5 μm不规则氧化铝胶液的粘接强度测试结果。从图2可以看出,随着不规则氧化铝的添加,导热结构胶的粘接强度均不断降低,且在接近或到达最大填充量时粘接强度出现明显的下降,此时粘接强度均小于5.2 MPa,无法满足芯片封装对导热结构胶的粘接要求。0.5 μm不规则氧化铝的加入使体系填料的填充量进一步增大,基础胶液含量相对减少,体系的交联密度进一步降低,导致粘接强度下降。在达到最大填充量后,小粒径填料无法完全填充到导热胶液中,小粒径球形氧化铝之间易团聚,在胶液中形成缺陷,引起部分胶液交联程度不足。此外不规则氧化铝的增稠效果使导热结构胶的黏度骤然增大,这些都会导致材料的粘接强度出现大幅降低。2、5、10 μm球形氧化铝复配6%、8%、8%的0.5 μm不规则氧化铝时胶液的粘接强度分别为5.49、5.55、5.31 MPa,可满足芯片封装领域对高导热结构胶的粘接要求。
图3为添加不同质量分数的0.5 μm不规则氧化铝胶液的黏度测试结果,使用旋转黏度计7号转子在不同速率下对不同胶液进行黏度测试。从图3可以看出,随着0.5 μm不规则氧化铝的添加,体系黏度不断增大,尽管小粒径氧化铝的添加量并不大,但由于其巨大的比表面积使体系的黏度增大明显。在剪切速率不同时,胶液的黏度有一定差异,说明胶液具有一定的触变性。可以根据产品实际的应用场合和工艺要求选择合适的导热结构胶,保证芯片封装的导热及散热性能。当40 μm和2 μm、40 μm和5 μm以及40 μm和10 μm球形氧化铝再复配6%、8%、8%的0.5 μm不规则氧化铝时,胶液在25℃、转速为20 r/s时的黏度分别为145 000、127 467和118 467 mPa·s。
图4(a)(b)(c)分别是质量分数为20%的2 μm氧化铝、质量分数为70%的10 μm氧化铝、质量分数为80%的5 μm氧化铝单一粒径导热结构胶的SEM图。从图中可以看出,单一粒径导热结构胶中氧化铝添加量的增加使导热结构胶内球形氧化铝的数量增多,彼此间距逐渐缩短,形成导热通路和网络的概率增加,导热性能相应增强;在未达到极限填充量之前,不同粒径氧化铝粒子均能均匀分散在低黏度的基础胶液中,无明显的填料团聚现象。图4(d)(e)为大小粒径球形氧化铝之比为9∶1和7∶3时两种球形氧化铝导热结构胶的SEM图,图4(f)为40、2、0.5 μm氧化铝最佳配比时导热结构胶的SEM图。从图中可以看出,多种粒径混合的导热结构胶中一定量的小粒径氧化铝可以均匀填充在大粒径之间,氧化铝的导热触接点增加,导热通路和网络更加密集和完善,导热结构胶的导热性能随之提高。2种粒径球形氧化铝和不规则氧化铝混合时氧化铝和基础胶液之间的相界面已经十分模糊,较高的界面结合强度使体系没有明显的气孔、“填料团聚”等界面缺陷,使导热结构胶的热导率和粘接强度等性能得到保证[11]
材料的绝缘性能通常可以通过单位尺寸的电阻率或电导率来反映[12]。体积电阻率为材料每单位体积对电流的阻抗,可以体现材料的导电能力,通常体积电阻率数值越大,材料的绝缘性能越好[13]。高导热结构胶的电绝缘性可以有效避免芯片和底部电路短路等带来的质量和安全问题,因此对不同高导热结构胶在500 V下的体积电阻率进行测量和计算,结果如图5所示。从图5可以看出,在相同球形填料填充时,随着0.5 μm不规则氧化铝含量的增加,导热结构胶的体积电阻率一直降低;在加入相同量的0.5 μm不规则氧化铝时,不同导热结构胶的体积电阻率也有所差别。当0.5 μm不规则氧化铝质量分数为2%时,其中40 μm和10 μm氧化铝体系的体积电阻率最大,为19.64×1014 Ω·m,40 μm和 2 μm氧化铝体系的体积电阻率次之,为13.96×1014 Ω·m,40 μm和5 μm氧化铝体系的体积电阻率最小,为11.16×1014 Ω·m。虽然环氧树脂本身的电绝缘性能优异,但在超过85%氧化铝的填充下,体系的绝缘性能主要取决于大量的填料(氧化铝)[14]。通过测试可知粒径分别为40、10、5、2、0.5 μm氧化铝的电导率分别为4.65、4.05、5.65、5.40、22.03 μS/cm,电导率越高,绝缘性能越差。因此在0.5 μm不规则氧化铝不断加入后,体系的导电介质增多,体积电阻率不断下降;在相同量的0.5 μm不规则氧化铝填充时,40、10、5、2 μm氧化铝不同的电导率也使体系的电阻率有所差别。2、5、10 μm与40 μm氧化铝搭配的高导热结构胶在0.5 μm不规则氧化铝质量分数分别为6%、8%、8%时的体积电阻率分别为6.541×1014、3.523×1014、7.541×1014 Ω·m。
高导热结构胶作为高分子聚合物,随着时间或环境的变化其各项性能会有所改变,但是它作为芯片封装材料,被广泛应用在各种电子设备和不同环境中,必须具备良好的耐候性能和稳定性能。经研究发现高导热结构胶粘接强度的变化是影响其耐候性能和稳定性能的主要因素[15]。按照m(E124)∶m(聚硫醇固化剂)∶m(PN-H)=100∶79∶3配制基础胶液,用表1的配方制备不同高导热结构胶胶液和粘接样片,并分别在温度为85℃、相对湿度为85%的高温高湿环境下处理500 h和在低温为-40℃、高温为90℃下进行高、低温冲击并停留30 min,共进行15个循环,之后对粘接样片进行粘接强度测试,结果如表2所示。
表2可以看出,在常温下固化完全后不添加氧化铝的基础胶液A粘接强度最高,添加大量不同粒径、形状氧化铝的B、C、D样品粘接强度相对较低,但仍在5 MPa以上。在温度为85℃和相对湿度为85%的条件下经500 h处理后,体系的粘接强度均有所损失,其中无任何填料的基础胶液A粘接强度损失最大,仅为常温下粘接强度的39.66%,而添加大量不同填料的B、C、D样品粘接强度残留率在70%以上。在高、低温冲击循环15次后,不加填料的基础胶液A和添加大量不同粒径填料的B、C、D样品均保持90%以上的粘接强度。由此表明,大量氧化铝填料的加入会使基础胶液的粘接强度下降,但耐高温高湿性能提高,且耐高、低温性能得以保持。因此制备的3种高导热结构胶具有优异的耐湿热老化和耐高、低温性能,其良好的耐候性能和使用寿命可以有效保证芯片的正常运行,提高电子产品的稳定性和使用寿命。
(1)本文制备的3种高导热结构胶热导率分别为2.73、3.05、2.85 W/(m·K),粘接强度分别为5.49、5.55、5.31 MPa,黏度分别为145 000、127 467、118 467 mPa·s,经高温高湿处理后粘接强度残留率由39.66 %提高到75.75 %,经冷、热冲击后粘接强度残留率保持在90%以上,具有优异的耐候性能和热稳定性能,满足丝网印刷工艺和芯片封装散热材料的使用要求。
(2)导热结构胶的导热性主要取决于氧化铝形成的导热通路和网络的密集程度。不同粒径球形氧化铝搭配时,小粒径氧化铝可填充在大粒径氧化铝的“自由体积”之间,提供更多的导热触点,形成更加密集和完善的导热通路;0.5 μm不规则氧化铝可进一步填充填料间的“自由体积”,得到更高热导率、更大粘接强度和更低黏度的导热结构胶,但高导热结构胶的体积电阻率会减小,综合性能最佳的氧化铝导热结构胶体积电阻率分别为6.541×1014、3.523×1014、7.541×1014 Ω·m,可满足芯片封装的绝缘要求。
  • 国家自然科学基金资助项目(51903207)
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2023年第56卷第7期
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doi: 10.16790/j.cnki.1009-9239.im.2023.07.005
  • 接收时间:2022-09-14
  • 首发时间:2025-11-24
  • 出版时间:2023-07-20
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  • 收稿日期:2022-09-14
  • 修回日期:2022-11-09
基金
国家自然科学基金资助项目(51903207)
作者信息
    西安科技大学 材料科学与工程学院,陕西 西安 710054

通讯作者:

李会录(1966-),男(汉族),陕西渭南人,副教授,主要从事环氧树脂和光敏树脂合成的研究。
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2种不同金属材料的力学参数

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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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