Article(id=1209927806394429932, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1209927804129514029, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2024.04.007, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1679328000000, receivedDateStr=2023-03-21, revisedDate=1687276800000, revisedDateStr=2023-06-21, acceptedDate=null, acceptedDateStr=null, onlineDate=1766398868415, onlineDateStr=2025-12-22, pubDate=1713542400000, pubDateStr=2024-04-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1766398868415, onlineIssueDateStr=2025-12-22, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1766398868415, creator=13701087609, updateTime=1766398868415, updator=13701087609, issue=Issue{id=1209927804129514029, tenantId=1146029695717560320, journalId=1149653034449285133, year='2024', volume='57', issue='4', pageStart='1', pageEnd='129', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1766398867876, creator=13701087609, updateTime=1766563872818, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1210619885072282300, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1209927804129514029, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1210619885072282301, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1209927804129514029, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=49, endPage=55, ext={EN=ArticleExt(id=1209927806625116654, articleId=1209927806394429932, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Synthesis and research of a silicon-based resin with low dielectric loss, columnId=1190369066675179686, journalTitle=Insulating Materials, columnName=Material Research, runingTitle=null, highlight=null, articleAbstract=
In order to improve the toughness and solubility of bismaleimide resin and improve its application in the field of high frequency and high speed copper clad laminate, a silicone modified bismaleimide resin (Si-D936) was designed and synthesized from silicone and D936 type bismaleimide in this paper. The characteristic structure of Si-D936 and silicon-D936 monomer were characterized by IR, NMR, and gel permeation chromatography. Additionally, the effects of different silicon contents on the solubility, heat resistance, mechanical properties, and dielectric properties at 10 GHz of the Si-D936 were explored. The results show that compared with the modified D936, the solubility of Si-D936 in butanone is obviously improved, and the highest solubility can reach 30% (at room temperature). However, with the increase of Si content, the molecular weight of Si-D936 increases, and the solubility decreases slightly. The Si-D936 modified resin has good thermal properties after curing, but the heat resistance and residual carbon rate decrease gradually with the increase of Si content. The silicone modification can improve the mechanical properties of D936 resin, in which the impact strength and tensile strength of Si-D936-1 (the molar ratio of D936 to HMM is 3:1) increase by 35% and 24.6%, respectively. However, with the further increase of Si content, the cross-linking degree of the modified resin is affected, and the impact strength, bending strength, and tensile strength of the modified resin decrease. After silicone modification, the dielectric properties of the modified resin are improved, and the dielectric loss is reduced from 0.009 4 to 0.007 2 (10 GHz).
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为了改善双马来酰亚胺(BMI)树脂的韧性、溶解性,提高BMI树脂在高频高速覆铜板领域的应用性,本文采用有机硅与D936型BMI树脂合成了一种有机硅改性双马来酰亚胺树脂(Si-D936)。采用红外、核磁、凝胶渗透色谱对Si-D936的特征结构和硅基-D936单体进行了表征,同时探究了不同硅含量对Si-D936溶解性能、耐热性能、力学性能以及10 GHz下介电性能的影响。结果表明:与改性前的D936相比,Si-D936在丁酮中的溶解性能得到明显改善,质量溶解度最高能达到30%(室温),但随着Si含量的增加,Si-D936的分子量增大,溶解性能略有下降;Si-D936固化后具有良好的热学性能,但随着Si含量增加,耐热性能和残碳率逐渐下降;有机硅改性可改善D936树脂的力学性能,其中Si-D936-1(D936与HMM的物质的量之比为3∶1)固化物的冲击强度和拉伸强度较D936分别提升了35%和24.6%,随着Si含量的进一步增加,改性树脂的交联程度受到影响,树脂的冲击强度、弯曲强度、拉伸强度下降;有机硅改性D936树脂后,改性树脂的介电性能得到改善,介质损耗因数从0.009 4减小到0.007 2(10 GHz)。
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杨昊东(1997-),男(汉族),四川广安人,硕士生,主要从事有机硅改性双烯类单体的研究;
唐安斌(1968-),男(汉族),四川南充人,研究员,主要从事高性能阻燃、绝缘材料的研究。
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1Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, China
2University of Chinese Academy of Sciences, Beijing 100049, China, bio=null, bioImg=null, bioContent=null, aboutCorrespAuthor=null), CN=AuthorExt(id=1217486430666932777, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927806394429932, authorId=1217486430457217562, language=CN, stringName=杨昊东, firstName=昊东, middleName=null, lastName=杨, prefix=null, suffix=null, authorComment=null, nameInitials=null, affiliation=null, department=null, xref=
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1中国科学院成都有机化学研究所,四川 成都 610041
2中国科学院大学,北京 100049, bio={"content":"
杨昊东(1997-),男(汉族),四川广安人,硕士生,主要从事有机硅改性双烯类单体的研究;
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3四川东材科技集团股份有限公司 国家绝缘材料工程技术研究中心,四川 绵阳 621000, bio=null, bioImg=null, bioContent=null, aboutCorrespAuthor=null)}, companyList=[AuthorCompany(id=1217486430356554257, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927806394429932, xref=3, ext=[AuthorCompanyExt(id=1217486430364942867, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927806394429932, companyId=1217486430356554257, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=
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1Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, China
3National Insulating Material Engineering Research Center, Sichuan EM Technology Co., Ltd., Mianyang 621000, China, bio=null, bioImg=null, bioContent=null, aboutCorrespAuthor=null), CN=AuthorExt(id=1217486431212192336, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927806394429932, authorId=1217486431027642948, language=CN, stringName=唐安斌, firstName=安斌, middleName=null, lastName=唐, prefix=null, suffix=null, authorComment=null, nameInitials=null, affiliation=null, department=null, xref=
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1中国科学院成都有机化学研究所,四川 成都 610041
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唐安斌(1968-),男(汉族),四川南充人,研究员,主要从事高性能阻燃、绝缘材料的研究。
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唐安斌(1968-),男(汉族),四川南充人,研究员,主要从事高性能阻燃、绝缘材料的研究。
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3四川东材科技集团股份有限公司 国家绝缘材料工程技术研究中心,四川 绵阳 621000)])], figs=[ArticleFig(id=1217486433238041228, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927806394429932, language=EN, label=Fig.1, caption=
Synthetic route of silicone modified bismaleimide resin (Si-D936), figureFileSmall=C0ySXPik90r6qgFKAVHjBw==, figureFileBig=XBwqCHfuhveC7sQuqTSp6Q==, tableContent=null), ArticleFig(id=1217486433313538705, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927806394429932, language=CN, label=图1, caption=
有机硅改性双马来酰亚胺树脂(Si-D936)的合成路线, figureFileSmall=C0ySXPik90r6qgFKAVHjBw==, figureFileBig=XBwqCHfuhveC7sQuqTSp6Q==, tableContent=null), ArticleFig(id=1217486433435173534, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927806394429932, language=EN, label=Fig.2, caption=
Infrared spectra of D936 and the silicon-based D936 monomer, figureFileSmall=+v1TrfolHJOsFlIQ904yKA==, figureFileBig=IarkW0krcLi1yQjunkqlcQ==, tableContent=null), ArticleFig(id=1217486433523253924, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927806394429932, language=CN, label=图2, caption=
D936与硅基-D936单体的红外光谱图, figureFileSmall=+v1TrfolHJOsFlIQ904yKA==, figureFileBig=IarkW0krcLi1yQjunkqlcQ==, tableContent=null), ArticleFig(id=1217486433619722921, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927806394429932, language=EN, label=Fig.3, caption=
The GPC spectra of D936 and the silicon-based D936 monomer, figureFileSmall=AH/whnEwML31yI/bGUEq5g==, figureFileBig=d0CC7IYJXhGEHofvyE5kwQ==, tableContent=null), ArticleFig(id=1217486433753940653, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927806394429932, language=CN, label=图3, caption=
D936与硅基-D936单体凝胶渗透色谱, figureFileSmall=AH/whnEwML31yI/bGUEq5g==, figureFileBig=d0CC7IYJXhGEHofvyE5kwQ==, tableContent=null), ArticleFig(id=1217486433846215347, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927806394429932, language=EN, label=Fig.4, caption=
1H-NMR spectrum of D936, figureFileSmall=Y1f5zaQrcUWolMIwCF2qxw==, figureFileBig=QEgHtzqZp0oDP3h4OIDhQg==, tableContent=null), ArticleFig(id=1217486433951072956, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927806394429932, language=CN, label=图4, caption=
D936核磁共振氢谱, figureFileSmall=Y1f5zaQrcUWolMIwCF2qxw==, figureFileBig=QEgHtzqZp0oDP3h4OIDhQg==, tableContent=null), ArticleFig(id=1217486434068513473, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927806394429932, language=EN, label=Fig.5, caption=
1H-NMR spectrum of the silicon-based D936 monomer, figureFileSmall=fnHlzm8CP4tJJhrH9i4/ww==, figureFileBig=4LoLjWLojMUrZ6zaLYHGfg==, tableContent=null), ArticleFig(id=1217486434185953993, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927806394429932, language=CN, label=图5, caption=
硅基-D936单体核磁共振氢谱, figureFileSmall=fnHlzm8CP4tJJhrH9i4/ww==, figureFileBig=4LoLjWLojMUrZ6zaLYHGfg==, tableContent=null), ArticleFig(id=1217486434257257168, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927806394429932, language=EN, label=Fig.6, caption=
DSC curves of D936 at different heating rates, figureFileSmall=sMXUfVm9sUmxWw+4JYX6EQ==, figureFileBig=MQ82JBR9BiLjoyBK7jaokQ==, tableContent=null), ArticleFig(id=1217486434362114777, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927806394429932, language=CN, label=图6, caption=
D936在不同升温速率下的DSC曲线, figureFileSmall=sMXUfVm9sUmxWw+4JYX6EQ==, figureFileBig=MQ82JBR9BiLjoyBK7jaokQ==, tableContent=null), ArticleFig(id=1217486434534081249, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927806394429932, language=EN, label=Fig.7, caption=
DSC curves of Si-D936-2 at different heating rates, figureFileSmall=FYvKK0mn0SQGLimybU3Rvg==, figureFileBig=Eqz7WQJvh9P+QxSZQcVEzA==, tableContent=null), ArticleFig(id=1217486434622161639, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927806394429932, language=CN, label=图7, caption=
Si-D936-2在不同升温速率下的DSC曲线, figureFileSmall=FYvKK0mn0SQGLimybU3Rvg==, figureFileBig=Eqz7WQJvh9P+QxSZQcVEzA==, tableContent=null), ArticleFig(id=1217486434710242029, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927806394429932, language=EN, label=Fig.8, caption=
TGA curves of D936 and Si-D936 cured resin, figureFileSmall=xjo327hXpnzJwK44IFhCww==, figureFileBig=SV4qcK2Kbp+rJSIMmFQt+A==, tableContent=null), ArticleFig(id=1217486434810905335, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927806394429932, language=CN, label=图8, caption=
D936和Si-D936固化物的TGA曲线, figureFileSmall=xjo327hXpnzJwK44IFhCww==, figureFileBig=SV4qcK2Kbp+rJSIMmFQt+A==, tableContent=null), ArticleFig(id=1217486434878014204, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927806394429932, language=EN, label=Fig.9, caption=
Dielectric properties of D936 and Si-D936 cured resin, figureFileSmall=AjLiwk+2f/F/ugUZs9QSQQ==, figureFileBig=4hpeMLuICZJGgDgQheLc3Q==, tableContent=null), ArticleFig(id=1217486434961900291, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927806394429932, language=CN, label=图9, caption=
D936与Si-D936固化物的介电性能, figureFileSmall=AjLiwk+2f/F/ugUZs9QSQQ==, figureFileBig=4hpeMLuICZJGgDgQheLc3Q==, tableContent=null), ArticleFig(id=1217486435075146508, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927806394429932, language=EN, label=Tab.1, caption=
The GPC data of D936 and the silicon-based D936 monomer, figureFileSmall=null, figureFileBig=null, tableContent=
| 样品 | Mn | 馏出时间/min |
|---|
| D936 | 439 | 24.4 |
| Si-D936 | 1 011 | 22.5 |
), ArticleFig(id=1217486435163226896, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927806394429932, language=CN, label=表1, caption=
D936与硅基-D936单体凝胶渗透色谱数据
, figureFileSmall=null, figureFileBig=null, tableContent=
| 样品 | Mn | 馏出时间/min |
|---|
| D936 | 439 | 24.4 |
| Si-D936 | 1 011 | 22.5 |
), ArticleFig(id=1217486435268084504, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927806394429932, language=EN, label=Tab.2, caption=
Solubility of D936 and Si-D936 in solvent, figureFileSmall=null, figureFileBig=null, tableContent=
| 溶剂 | D936 | Si-D936-1 | Si-D936-2 | Si-D936-3 |
|---|
| 甲苯 | 6.0 | 6.0 | <1.0 | <1.0 |
| 丁酮 | 25.0 | 30.0 | 28.5 | 26.0 |
| DMF | 44.5 | 55.0 | 50.0 | 45.0 |
| THF | 34.0 | 37.0 | 35.0 | 35.0 |
), ArticleFig(id=1217486435377136410, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927806394429932, language=CN, label=表2, caption=
D936与Si-D936在溶剂中的溶解度
, figureFileSmall=null, figureFileBig=null, tableContent=
| 溶剂 | D936 | Si-D936-1 | Si-D936-2 | Si-D936-3 |
|---|
| 甲苯 | 6.0 | 6.0 | <1.0 | <1.0 |
| 丁酮 | 25.0 | 30.0 | 28.5 | 26.0 |
| DMF | 44.5 | 55.0 | 50.0 | 45.0 |
| THF | 34.0 | 37.0 | 35.0 | 35.0 |
), ArticleFig(id=1217486435481994016, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927806394429932, language=EN, label=Tab.3, caption=
DSC data of D936 at different heating rates, figureFileSmall=null, figureFileBig=null, tableContent=
| β/(℃/min) | Ti/℃ | Tp/℃ | Tf/℃ | lnβ | ln(β/Tp2) | 1 000/Tp |
|---|
| 10 | 257.9 | 302.2 | 335.6 | 2.302 6 | -9.119 6 | 3.309 1 |
| 15 | 264.5 | 308.4 | 339.4 | 2.708 1 | -8.754 7 | 3.242 5 |
| 20 | 267.6 | 316.4 | 346.4 | 2.995 7 | -8.518 3 | 3.160 6 |
), ArticleFig(id=1217486435586851623, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927806394429932, language=CN, label=表3, caption=
D936在不同升温速率下的DSC数据
, figureFileSmall=null, figureFileBig=null, tableContent=
| β/(℃/min) | Ti/℃ | Tp/℃ | Tf/℃ | lnβ | ln(β/Tp2) | 1 000/Tp |
|---|
| 10 | 257.9 | 302.2 | 335.6 | 2.302 6 | -9.119 6 | 3.309 1 |
| 15 | 264.5 | 308.4 | 339.4 | 2.708 1 | -8.754 7 | 3.242 5 |
| 20 | 267.6 | 316.4 | 346.4 | 2.995 7 | -8.518 3 | 3.160 6 |
), ArticleFig(id=1217486435666543405, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927806394429932, language=EN, label=Tab.4, caption=
DSC data of Si-D936-2 at different heating rates, figureFileSmall=null, figureFileBig=null, tableContent=
| β/(℃/min) | Ti/℃ | Tp/℃ | Tf/℃ | lnβ | ln(β/Tp2) | 1 000/Tp |
|---|
| 10 | 215.9 | 238.8 | 298.7 | 2.302 6 | -8.648 7 | 4.187 6 |
| 15 | 232.3 | 243.8 | 309.7 | 2.708 1 | -8.284 6 | 4.101 7 |
| 20 | 235.9 | 249.5 | 312.2 | 2.995 7 | -8.043 2 | 4.008 0 |
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Si-D936-2在不同升温速率下的 DSC数据
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| β/(℃/min) | Ti/℃ | Tp/℃ | Tf/℃ | lnβ | ln(β/Tp2) | 1 000/Tp |
|---|
| 10 | 215.9 | 238.8 | 298.7 | 2.302 6 | -8.648 7 | 4.187 6 |
| 15 | 232.3 | 243.8 | 309.7 | 2.708 1 | -8.284 6 | 4.101 7 |
| 20 | 235.9 | 249.5 | 312.2 | 2.995 7 | -8.043 2 | 4.008 0 |
), ArticleFig(id=1217486435964339004, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927806394429932, language=EN, label=Tab.5, caption=
TGA data of D936 and Si-D936 cured resin, figureFileSmall=null, figureFileBig=null, tableContent=
| 样品 | Td5%/℃ | 残碳率(700℃)/% |
|---|
| D936 | 532.5 | 37.62 |
| Si-D936-1 | 482.5 | 25.29 |
| Si-D936-2 | 449.2 | 21.83 |
| Si-D936-3 | 399.6 | 15.91 |
), ArticleFig(id=1217486436052419392, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927806394429932, language=CN, label=表5, caption=
D936与Si-D936固化物的TGA数据
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| 样品 | Td5%/℃ | 残碳率(700℃)/% |
|---|
| D936 | 532.5 | 37.62 |
| Si-D936-1 | 482.5 | 25.29 |
| Si-D936-2 | 449.2 | 21.83 |
| Si-D936-3 | 399.6 | 15.91 |
), ArticleFig(id=1217486436161471305, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927806394429932, language=EN, label=Tab.6, caption=
The mechanical properties data of D936 and Si-D936 cured resin, figureFileSmall=null, figureFileBig=null, tableContent=
| 样品 | 冲击强度/(kJ/m2) | 弯曲强度/MPa | 拉伸强度/MPa |
|---|
| D936 | 2.0 | 35.2 | 17.5 |
| Si-D936-1 | 2.7 | 38.3 | 21.8 |
| Si-D936-2 | 2.3 | 36.5 | 18.2 |
| Si-D936-3 | 1.8 | 34.3 | 16.4 |
), ArticleFig(id=1217486436253746000, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927806394429932, language=CN, label=表6, caption=
D936与Si-D936固化物的力学性能数据
, figureFileSmall=null, figureFileBig=null, tableContent=
| 样品 | 冲击强度/(kJ/m2) | 弯曲强度/MPa | 拉伸强度/MPa |
|---|
| D936 | 2.0 | 35.2 | 17.5 |
| Si-D936-1 | 2.7 | 38.3 | 21.8 |
| Si-D936-2 | 2.3 | 36.5 | 18.2 |
| Si-D936-3 | 1.8 | 34.3 | 16.4 |
), ArticleFig(id=1217486436320854869, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927806394429932, language=EN, label=Tab.7, caption=
Water absorption data of D936 and Si-D936 cured resin, figureFileSmall=null, figureFileBig=null, tableContent=
| 样品 | 饱和吸水率/% | 标准差σ/% |
|---|
| D936 | 3.35 | 0.02 |
| Si-D936-1 | 3.10 | 0.08 |
| Si-D936-2 | 2.93 | 0.02 |
| Si-D936-3 | 2.85 | 0.04 |
), ArticleFig(id=1217486437541397338, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927806394429932, language=CN, label=表7, caption=
D936与Si-D936固化物的饱和吸水率数据
, figureFileSmall=null, figureFileBig=null, tableContent=
| 样品 | 饱和吸水率/% | 标准差σ/% |
|---|
| D936 | 3.35 | 0.02 |
| Si-D936-1 | 3.10 | 0.08 |
| Si-D936-2 | 2.93 | 0.02 |
| Si-D936-3 | 2.85 | 0.04 |
), ArticleFig(id=1217486437637866337, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927806394429932, language=EN, label=Tab.8, caption=
Dielectric properties data of D936 and Si-D936 cured resin, figureFileSmall=null, figureFileBig=null, tableContent=
| 样品 | | |
|---|
| D936 | 2.832 | 0.009 4 |
| Si-D936-1 | 2.823 | 0.008 7 |
| Si-D936-2 | 2.831 | 0.007 8 |
| Si-D936-3 | 2.825 | 0.007 2 |
), ArticleFig(id=1217486437734335331, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927806394429932, language=CN, label=表8, caption=
D936与Si-D936固化物的介电性能数据
, figureFileSmall=null, figureFileBig=null, tableContent=
| 样品 | | |
|---|
| D936 | 2.832 | 0.009 4 |
| Si-D936-1 | 2.823 | 0.008 7 |
| Si-D936-2 | 2.831 | 0.007 8 |
| Si-D936-3 | 2.825 | 0.007 2 |
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