Article(id=1304921589200482739, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1304921526004904728, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2026.03.017, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1749312000000, receivedDateStr=2025-06-08, revisedDate=1752422400000, revisedDateStr=2025-07-14, acceptedDate=null, acceptedDateStr=null, onlineDate=1789047151136, onlineDateStr=2026-09-10, pubDate=1773936000000, pubDateStr=2026-03-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1789047151136, onlineIssueDateStr=2026-09-10, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1789047151136, creator=13701087609, updateTime=1789047151136, updator=13701087609, issue=Issue{id=1304921526004904728, tenantId=1146029695717560320, journalId=1149653034449285133, year='2026', volume='59', issue='3', pageStart='1', pageEnd='154', issueExtLink='null', onlineDate='null', pubDate='1773936000000', pubDateStr='2026-03-20', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1789047136068, creator='13701087609', updateTime=1789118116024, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1305219237560217894, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1304921526004904728, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1305219237560217895, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1304921526004904728, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=148, endPage=154, ext={EN=ArticleExt(id=1304921589406003636, articleId=1304921589200482739, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Preparation of liquid crystal modified epoxy resin and synergistic enhancement in its thermal-mechanical properties, columnId=1190369066675179686, journalTitle=Insulating Materials, columnName=Material Research, runingTitle=null, highlight=null, articleAbstract=

This research aims to synergistically enhance the thermal and mechanical properties of epoxy resin to cope with the risk of insulation failure under long-term electrical-thermal-mechanical multi-field coupling conditions. Biphenyl liquid crystal epoxy resin (BLCER) was introduced into the bisphenol A type epoxy resin (E-51) matrix, and liquid crystal-modified epoxy resin was obtained through melt blending followed by curing. The thermal and mechanical properties of the modified resin were tested, and the toughening and thermal conductivity modification mechanisms of BLCER on the resin matrix were analyzed. The results show that the addition of BLCER can enhance the thermal stability and thermal conductivity of the modified resin. When the mass fraction of BLCER reaches 20%, the thermal conductivity of the modified resin increases to 0.382 W/(m·K), which is 2.26 times higher than that of pure E-51. The mechanical properties of the material increase with the content of BLCER. When the mass fraction of BLCER reaches 20%, the tensile and flexural strengths of the modified resin reach 90 MPa and 120.9 MPa, respectively, and the impact strength reaches 40.1 kJ/m2, which are significantly higher than those of pure epoxy resin.

, authors=Zhiyong SHEN1, Lihua LI1, Mao LI1, Feng CHEN1, Wenjia LI1, Zhengyong HUANG2, *, Hanxiang WANG2, authorsList=Zhiyong SHEN, Lihua LI, Mao LI, Feng CHEN, Wenjia LI, Zhengyong HUANG, Hanxiang WANG, authorCompany=null, correspAuthors=Zhengyong HUANG, 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=1304921591058559429, articleId=1304921589200482739, tenantId=1146029695717560320, journalId=1149653034449285133, language=CN, title=液晶改性环氧树脂的制备及其热-力学性能协同提升研究, columnId=1190369066813591720, journalTitle=绝缘材料, columnName=材料研究, runingTitle=null, highlight=null, articleAbstract=

本文旨在协同提升环氧树脂的热-力学性能,以应对长期电-热-力多场耦合工况下的绝缘失效风险。向双酚A型环氧树脂(E-51)基体引入联苯型液晶环氧树脂(BLCER),通过熔融共混后固化得到液晶改性环氧树脂。测试改性树脂的热-力学性能,并分析BLCER对树脂基体的增韧和导热改性原理。结果表明:BLCER的添加能增强改性树脂的热稳定性和导热性能,当BLCER质量分数达到20%时,改性树脂的热导率提升至0.382 W/(m·K),为纯E-51的2.26倍;材料的力学性能随BLCER含量的增加而增强,当BLCER质量分数达到20%时,改性树脂的拉伸和弯曲强度分别达90 MPa和120.9 MPa,冲击强度达40.1 kJ/m2,均远高于纯环氧树脂。

, authors=慎志勇1, 李利华1, 李茂1, 陈锋1, 李汶珈1, 黄正勇2, *, 汪瀚湘2, authorsList=慎志勇, 李利华, 李茂, 陈锋, 李汶珈, 黄正勇, 汪瀚湘, authorCompany=null, correspAuthors=黄正勇, authorNote=

慎志勇(1975-),男(汉族),湖北当阳人,正高级工程师,主要从事水电站电力设备绝缘材料、漏磁治理和局部放电的研究

, correspAuthorsNote=
黄正勇(1988-),男(汉族),重庆人,研究员,主要从事高电压试验技术、先进电工材料和内绝缘的研究。
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慎志勇(1975-),男(汉族),湖北当阳人,正高级工程师,主要从事水电站电力设备绝缘材料、漏磁治理和局部放电的研究

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慎志勇(1975-),男(汉族),湖北当阳人,正高级工程师,主要从事水电站电力设备绝缘材料、漏磁治理和局部放电的研究

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Polymer,2004(45):3505-3510., articleTitle=Viscoelastic effect on the phase separation in thermoplastics modified cyanate ester resin, refAbstract=null), Reference(id=1304921597450678821, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304921589200482739, doi=null, pmid=null, pmcid=null, year=1987, volume=27, issue=6, pageStart=410, pageEnd=423, url=null, language=null, rfNumber=20, rfOrder=28, authorNames=GABOR K, journalName=Polymer Engineering and Science, refType=null, unstructuredReference=GABOR K. In situ composites: blends of isotropic polymers and thermotropic liquid crystalline polymers[J]. 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(a) 纯E-51 (b) 试样5

, figureFileSmall=R9poOvAmJMj6tC8vpmM8jw==, figureFileBig=qZOfBKaEi9fcVJDAdKoE6A==, tableContent=null), ArticleFig(id=1304921594502083071, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304921589200482739, language=EN, label=Fig.5, caption=TGA curves of modified resins at different BLCER contents, figureFileSmall=YVOG3vgz+ubFKp/pifLzBg==, figureFileBig=8w4ZXhdsdY6iY/jDyrz1Qw==, tableContent=null), ArticleFig(id=1304921594577580544, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304921589200482739, language=CN, label=图5, caption=不同BLCER含量下改性树脂的热失重曲线, figureFileSmall=YVOG3vgz+ubFKp/pifLzBg==, figureFileBig=8w4ZXhdsdY6iY/jDyrz1Qw==, tableContent=null), ArticleFig(id=1304921594653078017, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304921589200482739, language=EN, label=Fig.6, caption=Glass transition temperature of modified resins at different BLCER contents, figureFileSmall=epnVKODQXPQnWOx6vjs7qg==, figureFileBig=4b58K7HAbaUBQ3kS11OD/Q==, tableContent=null), ArticleFig(id=1304921594741158402, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304921589200482739, language=CN, label=图6, caption=不同BLCER含量下改性树脂的玻璃化转变温度, figureFileSmall=epnVKODQXPQnWOx6vjs7qg==, figureFileBig=4b58K7HAbaUBQ3kS11OD/Q==, tableContent=null), ArticleFig(id=1304921594808267267, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304921589200482739, language=EN, label=Fig.7, caption=Thermal conductivity of modified resins at different BLCER contents and the POM images, figureFileSmall=LOyJSnO96dBM12q3cgmGeA==, figureFileBig=5vfV+bIuphH22s8j56Zdpg==, tableContent=null), ArticleFig(id=1304921594883764740, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304921589200482739, language=CN, label=图7, caption=不同BLCER含量下改性树脂的热导率及其POM图, figureFileSmall=LOyJSnO96dBM12q3cgmGeA==, figureFileBig=5vfV+bIuphH22s8j56Zdpg==, tableContent=null), ArticleFig(id=1304921594955067909, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304921589200482739, language=EN, label=Fig.8, caption=Schematic diagram of heat transfer in modified resin, figureFileSmall=+J3LXBSRZysZRw4UuQCtFg==, figureFileBig=uE86ab0TU46kC6mqHysMUg==, tableContent=null), ArticleFig(id=1304921595030565382, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304921589200482739, language=CN, label=图8, caption=改性树脂热量传递示意图, figureFileSmall=+J3LXBSRZysZRw4UuQCtFg==, figureFileBig=uE86ab0TU46kC6mqHysMUg==, tableContent=null), ArticleFig(id=1304921595106062855, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304921589200482739, language=EN, label=Table 1, caption=

Sample formula

, figureFileSmall=null, figureFileBig=null, tableContent=
试样质量分数/%
E-51BLCERDDS
1100060
298260
395560
4901060
5802060
), ArticleFig(id=1304921595219309064, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304921589200482739, language=CN, label=表1, caption=

试样配方

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试样质量分数/%
E-51BLCERDDS
1100060
298260
395560
4901060
5802060
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慎志勇 1 , 李利华 1 , 李茂 1 , 陈锋 1 , 李汶珈 1 , 黄正勇 2, * , 汪瀚湘 2
绝缘材料 | 材料研究 2026,59(3): 148-154
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绝缘材料 |材料研究 2026 , 59 (3) : 148 -154
液晶改性环氧树脂的制备及其热-力学性能协同提升研究
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慎志勇(1975-),男(汉族),湖北当阳人,正高级工程师,主要从事水电站电力设备绝缘材料、漏磁治理和局部放电的研究

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慎志勇1, 李利华1, 李茂1, 陈锋1, 李汶珈1, 黄正勇2, *, 汪瀚湘2
作者信息
  • 1中国长江电力股份有限公司白鹤滩水力发电厂,四川 凉山 615000
  • 2重庆大学 电气工程学院,重庆 400044
通讯作者:
黄正勇(1988-),男(汉族),重庆人,研究员,主要从事高电压试验技术、先进电工材料和内绝缘的研究。
作者简介:

慎志勇(1975-),男(汉族),湖北当阳人,正高级工程师,主要从事水电站电力设备绝缘材料、漏磁治理和局部放电的研究

Preparation of liquid crystal modified epoxy resin and synergistic enhancement in its thermal-mechanical properties
Zhiyong SHEN1, Lihua LI1, Mao LI1, Feng CHEN1, Wenjia LI1, Zhengyong HUANG2, *, Hanxiang WANG2
Affiliations
  • 1Baihetan Hydropower Plant, China Yangtze Power Co., Ltd., Liangshan 615000, China
  • 2School of Electrical Engineering, Chongqing University, Chongqing 400044, China
出版时间: 2026-03-20 doi: 10.16790/j.cnki.1009-9239.im.2026.03.017
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本文旨在协同提升环氧树脂的热-力学性能,以应对长期电-热-力多场耦合工况下的绝缘失效风险。向双酚A型环氧树脂(E-51)基体引入联苯型液晶环氧树脂(BLCER),通过熔融共混后固化得到液晶改性环氧树脂。测试改性树脂的热-力学性能,并分析BLCER对树脂基体的增韧和导热改性原理。结果表明:BLCER的添加能增强改性树脂的热稳定性和导热性能,当BLCER质量分数达到20%时,改性树脂的热导率提升至0.382 W/(m·K),为纯E-51的2.26倍;材料的力学性能随BLCER含量的增加而增强,当BLCER质量分数达到20%时,改性树脂的拉伸和弯曲强度分别达90 MPa和120.9 MPa,冲击强度达40.1 kJ/m2,均远高于纯环氧树脂。

环氧树脂  /  联苯型液晶  /  热性能  /  力学性能

This research aims to synergistically enhance the thermal and mechanical properties of epoxy resin to cope with the risk of insulation failure under long-term electrical-thermal-mechanical multi-field coupling conditions. Biphenyl liquid crystal epoxy resin (BLCER) was introduced into the bisphenol A type epoxy resin (E-51) matrix, and liquid crystal-modified epoxy resin was obtained through melt blending followed by curing. The thermal and mechanical properties of the modified resin were tested, and the toughening and thermal conductivity modification mechanisms of BLCER on the resin matrix were analyzed. The results show that the addition of BLCER can enhance the thermal stability and thermal conductivity of the modified resin. When the mass fraction of BLCER reaches 20%, the thermal conductivity of the modified resin increases to 0.382 W/(m·K), which is 2.26 times higher than that of pure E-51. The mechanical properties of the material increase with the content of BLCER. When the mass fraction of BLCER reaches 20%, the tensile and flexural strengths of the modified resin reach 90 MPa and 120.9 MPa, respectively, and the impact strength reaches 40.1 kJ/m2, which are significantly higher than those of pure epoxy resin.

epoxy resin  /  biphenyl liquid crystal  /  thermal properties  /  mechanical properties
慎志勇, 李利华, 李茂, 陈锋, 李汶珈, 黄正勇, 汪瀚湘. 液晶改性环氧树脂的制备及其热-力学性能协同提升研究. 绝缘材料, 2026 , 59 (3) : 148 -154 . DOI: 10.16790/j.cnki.1009-9239.im.2026.03.017
Zhiyong SHEN, Lihua LI, Mao LI, Feng CHEN, Wenjia LI, Zhengyong HUANG, Hanxiang WANG. Preparation of liquid crystal modified epoxy resin and synergistic enhancement in its thermal-mechanical properties[J]. Insulating Materials, 2026 , 59 (3) : 148 -154 . DOI: 10.16790/j.cnki.1009-9239.im.2026.03.017
环氧树脂因其卓越的加工性能、可靠的绝缘特性,已成为电力装备绝缘和电子封装领域的关键材料[1-3]。随着电气设备向小型化和大容量方向发展,设备内部更容易积聚热量,加速设备绝缘老化,导致绝缘件电气及力学性能的下降,对电力系统的稳定性与可靠性构成潜在风险[4-5]。因此,提升环氧树脂的导热能力对保障电力系统安全可靠运行至关重要。目前,常用的方法是将具有高导热性能的无机填料与聚合物共混复合,该方法利用填料在基体中构建连续导热通路,从而有效提升材料的热传导能力。然而,为了让聚合物获得较高的热导率,往往需要加入高填充量的填料,导致复合材料中聚合物基体含量大幅下降,体系黏度变大,材料加工困难,并且填料过多时会团聚,从而增大复合材料的刚性和脆性,对环氧树脂复合材料的力学和绝缘性能产生直接影响[6-8]。为此,环氧树脂断裂韧性不足等问题也是电力领域需要关注的。目前学术界已开展了广泛而深入的研究工作[9],如采用橡胶弹性体对环氧树脂进行改性、利用热塑性树脂实现增韧以及运用互穿网络(IPN)技术来增韧。然而上述增韧手段在改善韧性的同时,也不可避免地引发了复合材料耐热性以及弹性模量的下降问题,这些提升复合材料韧性的常用方法往往需要牺牲其部分耐热性[10-11]
液晶环氧树脂(LCER)因其独特的微观有序结构,近年来引发了科研者的广泛研究[12],作为一种热固性材料,它在宏观层面呈现出与常规环氧树脂相似的各向同性;而在微观尺度上,其结构则由高度有序的介晶单元构成,形成各向异性的液晶相。相较于普通环氧树脂,LCER内部包含刚棒状介晶结构单元,这些单元能够在固化过程中自发取向排列,以此提高分子的排列有序性,进而增加聚合物的结晶度,从而促进声子传输。此外,高度有序的结构不仅可以引导裂纹偏转和桥接,还可以通过屈服和塑性变形吸收和分散能量[13]。因此液晶环氧树脂能显著增强材料的导热性能和力学性能。ZHANG F Y等[14]通过调控液晶环氧(LCE)与E-51环氧树脂的比例,实现LCER类玻璃高分子从软弹性体到强韧体的连续调节。当LCE摩尔分数达到75%时,材料获得导热-力学性能协同优化,面内热导率较纯E-51提高108%,拉伸强度与韧性较纯E-51分别增长2.88倍与2.45倍。QI Y等[15]通过共混生物基热致液晶单体(THMT-EP)与石油基环氧树脂(TGDDM),以4,4′-二氨基二苯砜(DDS)为固化剂,在优化固化工艺下可使固化后的共混体系交联网络中的液晶域固定,性能表征表明共混体系的冲击强度高达31.1 kJ/m2,弯曲模量与弯曲强度分别提高5.1%和48.5%,并通过阻燃认证。FAN Q Q等[16]结合了液晶有序和网络交联的特点,合成了生物基液晶环氧树脂(THBR-EP),在维持传统环氧树脂热稳定性与刚度的前提下,其断裂韧性显著提升,弯曲强度提升16.4%,冲击强度达48.8 kJ/m2,同时玻璃化转变温度与5%热失重温度同步提高。以上研究表明,针对环氧树脂基绝缘材料导热性能差、力学韧性低等问题,通过在环氧树脂基体中引入液晶环氧树脂,有望使复合材料打破热、力学性能的传统耦合限制,实现多目标性能的协同提升。
本文采用联苯型液晶改性环氧树脂,探究改性树脂的热、力学性能,并对液晶改性环氧树脂的增韧原理与导热原理进行深入分析和探究。
联苯型液晶环氧树脂(biphenyl liquid crystal epoxy resin,BLCER),工业纯,甘肃泰升化工科技有限公司;4,4′-二氨基二苯基砜(DDS),分析纯,上海阿拉丁生化科技股份有限公司;双酚A型环氧树脂(E-51),工业纯,山东德源环氧科技有限公司。
采用高温熔融浇注工艺制备联苯型液晶改性环氧树脂(BLCER/E-51/DDS),试样配方如表1所示。按配方称取BLCER、E-51和固化剂DDS。先将BLCER粉末加热至180℃熔化,另在烧杯中加入E-51并加热至70℃降黏,随后把熔融BLCER倒入烧杯,升温至100℃搅拌,按计量比缓慢加入DDS,充分搅拌至均匀。将混合体系经20 min真空除气处理后注入预加热模具,采用阶梯升温固化:160℃/120 min+180℃/120 min。待固化完成后自然冷却至室温脱模,获得系列BLCER含量梯度变化的复合材料试样。
采用偏光显微镜(POM,Leica Dmrx型)在常温下观察材料中液晶环氧树脂的形态与分布。
采用差示扫描量热仪(DSC,404F3型,德国耐驰公司)测试样品比热容Cp,温度范围为0~220℃,升温速率为10℃/min,N2气氛。
采用激光热导仪(LFA457型,德国耐驰公司)测试样品的热扩散系数α,采用排水法测试样品密度ρ,通过式(1)计算样品的热导率γ
γ=αρCp
采用热失重分析仪(TGA-1型,梅特勒公司) 测试样品的热稳定性,氮气气氛,气体流速为50 mL/min,温度范围为30~800℃,加热速率为10℃/min。
采用摆锤冲击试验仪(ZBC2302-4型,美斯特工业系统(中国)有限公司)根据GB/T 2567—2021测试样品的冲击强度,样品尺寸为80 mm×10 mm×4 mm。
采用电子万能试验机(AG-X10KN型,日本岛津公司)根据GB/T 2567—2021进行拉伸强度测试,拉伸速率为2 mm/min。
采用电子万能试验机依据GB/T 2567—2021测试样品的弯曲强度,通过三点弯曲加载模式进行,加载速率控制为2 mm/min。
采用扫描电子显微镜(SEM,S型,日本Hitachi公司)观察经过冲击测试后的样品断面微观形貌,加速电压为25 kV。
图1为不同BLCER含量下改性树脂中BLCER的形态与分布POM图。从图1可以看出,与纯E-51相比,在本文固化条件下,BLCER通过固化剂与环氧树脂反应生成高度有序且深度交联的网络结构。随着BLCER含量的增加,偏光显微镜视野呈现显著增亮现象,此光学响应源于改性体系中液晶环氧所诱导的双折射效应。同时观测到液晶微畴尺寸随BLCER含量增加而持续扩展。与之对比,未改性环氧树脂固化后形成各向同性的无序状态。在改性环氧树脂中,取向排列的液晶有序微区与各向同性的环氧树脂基体构成复合结构。当BLCER质量分数为5%时,环氧基体作为连续相包覆少量BLCER分散相,仅能形成微量介晶区域,导致液晶相不明显。随着BLCER含量增加,反应过程中相分离程度加剧,介晶结构单元持续聚集并促使刚棒状介晶域增大。此外,体系内各向异性介晶域在环氧交联固化过程中被固定,最终形成稳定的两相拓扑结构,表明液晶环氧与普通环氧树脂构成部分相容体系。
图2展示了不同BLCER含量下改性树脂的冲击强度。从图2可以看出,当BLCER质量分数从0逐渐增加到20%时,改性树脂的冲击强度显著提高,峰值达40.1 kJ/m2,是纯环氧树脂体系(23.1 kJ/m2)的1.74倍。这可能是由于BLCER与E-51树脂之间具有相容性,在固化过程中形成了交联网络结构。改性树脂中BLCER的液晶微纤不仅在E-51环氧网络中实现了分子级的交织与相互贯穿,而且随着BLCER含量的增加,这些液晶微纤逐渐发生聚集并持续生长,这种微观结构的演化对固化体系的冲击强度产生了显著的提升效果,使材料在受到外力冲击时能够更好地分散应力,从而增强了材料的韧性。
不同BLCER含量下改性树脂的拉伸与弯曲性能测试结果如图3所示。从图3可以看出,改性树脂的拉伸与弯曲强度随BLCER含量的增加而提高,当BLCER质量分数达到20%时,拉伸和弯曲强度分别达90 MPa和120.9 MPa,均远高于纯环氧树脂。该现象可能是由于BLCER/E-51/DDS共混体系在固化交联阶段受到剪切作用时,液晶相会形成高度取向的微纤结构。这些微纤在E-51树脂基体中稳定分散并最终固定,继而与环氧树脂基体发生协同固化,共同构建三维网络结构,从而实现了原位增强的效果[17]。在固化反应进程中,液晶环氧树脂中的羟基(-OH)能与固化剂产生分子间的氢键作用,并交联约束液晶基元而形成层状有序结构,进而诱导产生具有高堆砌密度的近晶相液晶网络。这种拓扑结构赋予固化体系更高弹性模量,实现了材料弯曲性能的优化提升。
树脂的断面形貌可以在一定程度上反映树脂的力学性能。由于BLCER质量分数为20%的复合材料(试样5)冲击、拉伸、弯曲强度均为最大,将其断面与纯E-51树脂断面进行对比,如图4所示。
图4(a)可以看出,纯树脂断面SEM形貌呈现典型的脆性断裂特征,断裂表面平整光滑,无明显条纹结构,且断裂路径局限于单一平面,缺乏多级断裂层次。从图4(b)可以看出,试样5断面存在大量微裂纹网络,裂纹扩展呈现多向交织分布,并拉出许多纤维状结构,表明相比于纯环氧树脂,其韧性大幅增强。大量交错的结构表明BLCER在树脂中取向形成有序的介晶域,构成宏观两相体系。两相界面间的有效应力传递促使材料呈现韧性断裂特征。
在设法提高材料力学性能的同时,也要保证改性树脂较好的耐热性能。图5为不同含量BLCER下改性树脂的热失重曲线。从图5可以看出,4条曲线大致重合,说明改性树脂与纯E-51在热分解机理上具有相似性。与纯环氧体系相比,添加20%BLCER的改性树脂5%热失重温度(T5%)提升了7.92℃,表明BLCER的引入提高了共混固化产物的热分解温度,热稳定性能显著改善。当引入BLCER时,其有序的液晶微畴充当刚性结构单元,分散并固定于E-51固化交联网络之中,当其含量超过一定阈值时,液晶分子容易在固化交联网络中形成有序的晶区,引发分子协同作用,促使三维交联网络密度提升,最终增强了体系的热力学稳定性。此外,BLCER的引入在固化进程中使分子间产生额外的氢键作用,使固化体系的失重起始温度得到提升,进而增强了体系的热稳定性。
通过对不同BLCER含量的改性树脂进行DSC测试,得到固化物的玻璃化转变温度(Tg)如图6所示。从图6可以看出,固化产物的Tg随BLCER含量增加而持续升高。Tg的高低取决于分子链运动的难易程度,而BLCER的加入阻碍了分子链迁移。微观机制在于:BLCER与E-51分子构型存在显著差异,前者为双苯环共平面结构形成的高刚性介晶单元,这些取向排列的介晶域促使分子堆砌密度提升,在基体内形成有序分散的刚性棒状微区。相较于纯E-51交联网络,共混体系呈现更致密的三维拓扑结构,自由体积显著压缩,导致链段运动需克服更高的能量势垒,最终表现为Tg的升高。
图7为不同BLCER含量下改性树脂的热导率及其POM图。从图7可以看出,随着BLCER含量的增加,改性树脂的热导率呈现递增趋势,当BLCER质量分数达到20%时,其热导率为0.382 W/(m·K),较纯E-51树脂(0.169 W/(m·K))提升126%;同时从图7中POM图能进一步看出BLCER含量、结构取向、导热性能三者间的关系:相较于纯E-51固化体系,BLCER改性树脂固化体系中形成了均匀分散的刚性棒状液晶微畴结构,这些介晶结构在基体交联网络中维持取向状态,且随BLCER含量的增加,取向程度显著增强,因此体系热导率随之增大。
国内外已有大量研究表明,将高度有序的液晶结构引入各向同性热固性树脂中可增强树脂基体的热传导性能。这是因为引入有序结构至聚合物中有利于声子传输[18]——高度有序排列的结构能够增加声子的平均自由程,为声子传输提供有利通道,减少声子散射,提高声子的传输效率,从而增强热量传递效率;与之相反,普通环氧固化体系因无序相中存在大量结构缺陷,导致热传输过程中热阻增加,声子散射严重,呈现低热导率。基于此,在热固性环氧体系中引入高度有序结构可以促进声子的传输,最终实现改性树脂导热能力的有效提升。QING S T等[19]成功合成了耐热性优异的液晶环氧热固性材料,研究证实,固化体系中液晶环氧(LCE)的关键性能参数受芳香介晶结构单元与柔性间隔基长度的协同调控,当体系内刚棒状有序区域的几何尺寸显著增大时,所得材料表现出更佳的热稳定性,使其成为构建耐高温液晶网络(LC网络)的优选材料。
结合图1不同BLCER含量下改性树脂的POM观测结果,与未改性的纯E-51固化体系相比,BLCER改性树脂固化体系内形成了有序排列的棒状液晶介晶微区。该介晶结构能够在树脂基体中维持自身的取向特性,当BLCER含量达到较高水平时,其介晶单元在E-51树脂基体中相互连接构成导热传导路径,热量能够通过单个介晶结构传递至相邻介晶单元,从而有效降低声子散射,提升体系传热速率。同时,BLCER的加入使树脂固化体系结构更加致密有序,减少非晶区交联网络孔隙引发的声子散射。热量传递原理图如图8所示。
原位复合[20]概念可用于阐释BLCER在热固性树脂体系中构建高度有序结构以提升材料力学性能的内在原理。在原位复合体系中,增强相的形成并非依赖于碳纤维、玻璃纤维等纤维状颗粒的外加引入,而是在材料形成过程中生成。环氧复合材料里的刚性棒状液晶分子会定向有序排列,具有较大长径比的微纤状介晶域得以形成,该介晶域固定于环氧树脂基体与固化剂发生交联反应生成的三维交联网络体系中,从而使复合材料呈现出多相结构。借助偏光显微镜可观察到(图1),呈现透光性的介晶区域内介晶单元呈现定向有序排布状态,而周边黑暗域(不透光)则对应普通环氧树脂形成的固化交联网络结构。尽管复合材料在宏观尺度上仍表现出各向同性的无序特征,但其内部结构的均匀性已被破坏。
当复合材料受到外部冲击载荷作用时,液晶环氧树脂固化形成的微纤状介晶结构与环氧树脂基体在强度及刚度参数上存在性能差异,这种差异会在两相界面区域引发应力集中现象,进而导致材料断裂区域产生银纹缺陷。此时,均匀分布于环氧树脂基体交联网络中的微纤状介晶结构可视为连接断裂区域银纹的结构,从而实现不同银纹之间的有效连接。当银纹缺陷扩展至介晶区域界面时,其扩展路径会发生偏转或分支,进而使扩展进程得到有效遏制,避免进一步发展为裂纹,在提升材料韧性方面发挥了重要作用。
本文通过将联苯型液晶环氧树脂引入双酚A型环氧树脂基体,在环氧树脂基体中形成由取向介晶基元相互接触构成的导热通路,从而提高基体的热导率;并通过介晶基元的引入改善环氧树脂固化网络脆性大、易开裂等问题,达到热-力学性能协同提升的效果。对改性环氧树脂的力学性能、热稳定性以及导热性能等进行测试分析,结论如下:
(1)偏光显微镜测试结果显示,BLCER/E-51/DDS共混固化体系属于部分相容体系,且固化产物中有刚性棒状介晶单元生成,这些介晶结构在基体交联网络中维持取向状态且介晶基元的大小与分散密度随BLCER含量的增加而增大。
(2)液晶环氧树脂的加入能提高改性树脂的热稳定性与导热性能,当BLCER质量分数增加到20% 时,改性树脂的T5%较纯E-51提高7.92℃,热导率提升至0.382 W/(m·K),较纯E-51提高126%。
(3)当BLCER质量分数不超过20%时,BLCER的加入对BLCER/E-51/DDS共混固化体系有明显的增韧效果,且随BLCER含量的增加增韧效果越明显;当BLCER质量分数为20%,改性树脂的拉伸和弯曲强度分别达90 MPa和120.9 MPa,冲击强度达40.1 kJ/m2

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doi: 10.16790/j.cnki.1009-9239.im.2026.03.017
  • 接收时间:2025-06-08
  • 首发时间:2026-09-10
  • 出版时间:2026-03-20
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  • 收稿日期:2025-06-08
  • 修回日期:2025-07-14
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    1中国长江电力股份有限公司白鹤滩水力发电厂,四川 凉山 615000
    2重庆大学 电气工程学院,重庆 400044

通讯作者:

黄正勇(1988-),男(汉族),重庆人,研究员,主要从事高电压试验技术、先进电工材料和内绝缘的研究。
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

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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