Article(id=1209928221139792130, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1209928218329616824, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2024.05.004, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1688659200000, receivedDateStr=2023-07-07, revisedDate=1694448000000, revisedDateStr=2023-09-12, acceptedDate=null, acceptedDateStr=null, onlineDate=1766398967299, onlineDateStr=2025-12-22, pubDate=1716134400000, pubDateStr=2024-05-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1766398967299, onlineIssueDateStr=2025-12-22, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1766398967299, creator=13701087609, updateTime=1766398967299, updator=13701087609, issue=Issue{id=1209928218329616824, tenantId=1146029695717560320, journalId=1149653034449285133, year='2024', volume='57', issue='5', pageStart='1', pageEnd='124', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1766398966629, creator=13701087609, updateTime=1766563901766, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1210620006501585415, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1209928218329616824, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1210620006501585416, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1209928218329616824, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=26, endPage=33, ext={EN=ArticleExt(id=1209928221399838983, articleId=1209928221139792130, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Preparation and insulating properties of spherical boron nitride/epoxy composites, columnId=1209928219172671930, journalTitle=Insulating Materials, columnName=Special Issue on High-performance Transformer Insulation, runingTitle=null, highlight=null, articleAbstract=

Aiming at the problems of large specific surface area of conventional flake boron nitride and sharp increase in resin viscosity when compounded with epoxy resin, we prepared spherical boron nitride and used it as a filler to compound with epoxy resin to prepare spherical boron nitride/epoxy composites. The preparation process and curing characteristics of spherical boron nitride/epoxy composites were studied, and the influences of the morphology and filling amount of flake/spherical boron nitride fillers on the mechanical and electrical properties of epoxy resin composites were compared. The results show that with the increase of reaction temperature, the curing degree change curve of epoxy resin shows “S” shape, and the curing process can be roughly divided into three stages of “slow-fast-slow”. In terms of mechanical properties, adding a small amount of boron nitride can improve the mechanical properties of the epoxy resin composites; when the filling amount is high, spherical boron nitride/epoxy composites have better mechanical properties than flake boron nitride/epoxy composites. In terms of electrical properties, the relative dielectric constant of the epoxy resin composites increases with the increase of boron nitride content, and the dielectric loss factor is lower than 0.02; compared with the flake boron nitride/epoxy composites, the spherical boron nitride/epoxy composites have less “filler-resin” interface, lower relative dielectric constant and dielectric loss factor; adding an appropriate amount of boron nitride can significantly improve the volume resistivity and electric strength of composites.

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针对常规片状氮化硼比表面积大,与环氧树脂复合时会急剧增大树脂黏度的问题,本研究制备了球形氮化硼,并将其作为填料与环氧树脂复合制备了球形氮化硼/环氧复合材料。研究了球形氮化硼/环氧复合材料的制备工艺和固化特性,对比研究了片状/球形氮化硼填料的形貌和填充量对环氧树脂复合材料力学性能和电学性能的影响规律。结果表明:随着反应温度升高,环氧树脂的固化度呈现“S”型曲线变化,整个固化过程可大致分为“慢-快-慢”3个阶段。力学性能方面,加入少量氮化硼可以提高环氧树脂复合材料的力学性能;高填充量时,球形氮化硼/环氧复合材料比片状氮化硼/环氧复合材料具有更优异的力学性能。电气性能方面,环氧树脂复合材料的相对介电常数随填料含量的增加而增大,介质损耗因数均低于0.02;与片状氮化硼/环氧复合材料相比,球形氮化硼/环氧复合材料的“填料-树脂”界面减少,具有更低的相对介电常数和介质损耗因数;添加适量的氮化硼能够显著提高复合材料的体积电阻率和电气强度。

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黄正勇(1988-),男(汉族),重庆人,副教授,博士,主要从事高电压试验技术、先进电工材料和内绝缘方面的研究。
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何润(1997-),男(汉族),重庆人,硕士生,主要从事先进电工材料的制备研究工作。

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何润(1997-),男(汉族),重庆人,硕士生,主要从事先进电工材料的制备研究工作。

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球形氮化硼/环氧复合材料的制备及绝缘性能研究
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何润 , 黄正勇 , 张樱凡 , 赵腾 , 李晨昕 , 李剑 , 胡清华
绝缘材料 | 高性能变压器绝缘专题 2024,57(5): 26-33
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绝缘材料 | 高性能变压器绝缘专题 2024, 57(5): 26-33
球形氮化硼/环氧复合材料的制备及绝缘性能研究
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何润, 黄正勇, 张樱凡, 赵腾, 李晨昕, 李剑, 胡清华
作者信息
  • 重庆大学 输配电装备及系统安全与新技术国家重点实验室,重庆 400044
  • 何润(1997-),男(汉族),重庆人,硕士生,主要从事先进电工材料的制备研究工作。

通讯作者:

黄正勇(1988-),男(汉族),重庆人,副教授,博士,主要从事高电压试验技术、先进电工材料和内绝缘方面的研究。
Preparation and insulating properties of spherical boron nitride/epoxy composites
Run HE, Zhengyong HUANG, Yingfan ZHANG, Teng ZHAO, Chenxin LI, Jian LI, Qinghua HU
Affiliations
  • State Key Laboratory of Power Transmission Equipment & System Security and New Technology, Chongqing University, Chongqing 400044, China
出版时间: 2024-05-20 doi: 10.16790/j.cnki.1009-9239.im.2024.05.004
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针对常规片状氮化硼比表面积大,与环氧树脂复合时会急剧增大树脂黏度的问题,本研究制备了球形氮化硼,并将其作为填料与环氧树脂复合制备了球形氮化硼/环氧复合材料。研究了球形氮化硼/环氧复合材料的制备工艺和固化特性,对比研究了片状/球形氮化硼填料的形貌和填充量对环氧树脂复合材料力学性能和电学性能的影响规律。结果表明:随着反应温度升高,环氧树脂的固化度呈现“S”型曲线变化,整个固化过程可大致分为“慢-快-慢”3个阶段。力学性能方面,加入少量氮化硼可以提高环氧树脂复合材料的力学性能;高填充量时,球形氮化硼/环氧复合材料比片状氮化硼/环氧复合材料具有更优异的力学性能。电气性能方面,环氧树脂复合材料的相对介电常数随填料含量的增加而增大,介质损耗因数均低于0.02;与片状氮化硼/环氧复合材料相比,球形氮化硼/环氧复合材料的“填料-树脂”界面减少,具有更低的相对介电常数和介质损耗因数;添加适量的氮化硼能够显著提高复合材料的体积电阻率和电气强度。

环氧树脂  /  球形氮化硼  /  绝缘性能  /  力学性能

Aiming at the problems of large specific surface area of conventional flake boron nitride and sharp increase in resin viscosity when compounded with epoxy resin, we prepared spherical boron nitride and used it as a filler to compound with epoxy resin to prepare spherical boron nitride/epoxy composites. The preparation process and curing characteristics of spherical boron nitride/epoxy composites were studied, and the influences of the morphology and filling amount of flake/spherical boron nitride fillers on the mechanical and electrical properties of epoxy resin composites were compared. The results show that with the increase of reaction temperature, the curing degree change curve of epoxy resin shows “S” shape, and the curing process can be roughly divided into three stages of “slow-fast-slow”. In terms of mechanical properties, adding a small amount of boron nitride can improve the mechanical properties of the epoxy resin composites; when the filling amount is high, spherical boron nitride/epoxy composites have better mechanical properties than flake boron nitride/epoxy composites. In terms of electrical properties, the relative dielectric constant of the epoxy resin composites increases with the increase of boron nitride content, and the dielectric loss factor is lower than 0.02; compared with the flake boron nitride/epoxy composites, the spherical boron nitride/epoxy composites have less “filler-resin” interface, lower relative dielectric constant and dielectric loss factor; adding an appropriate amount of boron nitride can significantly improve the volume resistivity and electric strength of composites.

epoxy resin  /  spherical boron nitride  /  insulating properties  /  mechanical properties
何润, 黄正勇, 张樱凡, 赵腾, 李晨昕, 李剑, 胡清华. 球形氮化硼/环氧复合材料的制备及绝缘性能研究. 绝缘材料, 2024 , 57 (5) : 26 -33 . DOI: 10.16790/j.cnki.1009-9239.im.2024.05.004
Run HE, Zhengyong HUANG, Yingfan ZHANG, Teng ZHAO, Chenxin LI, Jian LI, Qinghua HU. Preparation and insulating properties of spherical boron nitride/epoxy composites[J]. Insulating Materials, 2024 , 57 (5) : 26 -33 . DOI: 10.16790/j.cnki.1009-9239.im.2024.05.004
随着电力设备逐步向高电压、大容量和小型化方向发展[1-3],具有高绝缘特性的聚合物基复合材料引起了人们的广泛关注。环氧树脂因交联固化后具有良好的机械强度、绝缘性能、耐老化和耐酸碱腐蚀等特性而被广泛应用于电子封装和电力设备领域[4-5]。电压等级的提高会加速环氧树脂绝缘材料的老化、分解,导致环氧树脂绝缘材料的力学性能和电气性能发生劣化[6-8]。而材料力学性能和电气性能的劣化将会严重影响输电过程的可靠性、高效性和安全性,在严重时甚至可能会引发火灾或造成设备的损坏,使整个电力系统的稳定运行以及可靠供电无法得到保障[9-10]。如何使环氧树脂绝缘材料在高电压、大容量、高温等恶劣环境中保持良好的力学性能以及电气性能是目前亟待解决的问题。
根据国内外研究报道[11-12],目前提升环氧树脂绝缘材料性能的主要途径是添加填料到环氧树脂基体中,经过固化得到相应的环氧树脂复合材料。六方氮化硼(h-BN)是一种具有高导热、低密度、高电气强度的二维片状材料,以氮化硼为填料制备的氮化硼/环氧复合材料具有低介电常数、高体积电阻率和高电气强度等特性。FENG T等[13]采用离子液体对羟基化氮化硼纳米片(BNO)进行改性,并将其添加到环氧树脂中,发现引入质量分数为2%的BNO纳米片可以提高环氧树脂的热稳定性。Y ANDRIANI等[14]通过加入极低浓度的非共价修饰的氮化硼纳米片(BNNSs),提升了双酚A环氧树脂的热性能和力学性能。HE S等[15]在环氧树脂中添加胺官能化氮化硼纳米片制备的环氧树脂复合材料表现出更好的电荷耗散性能、较低的介电常数和更高的电气强度。然而片状氮化硼由于比表面积大,表面难以被环氧树脂充分润湿,仅在填充量较低时具有较好的改性效果,随着填充量的增加,树脂黏度呈指数型上升,浇注成型难度增大,多种因素叠加造成复合材料内部存在微气泡、界面孔隙等缺陷[16]
针对上述片状氮化硼的问题,本研究制备球形氮化硼填料,并将其填充到环氧树脂基体中制备球形氮化硼/环氧复合材料。研究球形氮化硼/环氧树脂的制备过程和固化特性,对比分析片状/球形氮化硼填料的形貌和填充量对环氧复合材料力学性能和电气性能的影响规律,希望可以为高性能环氧复合材料的制备提供参考。
双酚A二缩水甘油醚环氧树脂(CYD-128)、脂环族环氧树脂(2021P),岳阳巴陵石化公司;六方氮化硼片(h-BN)、促进剂N,N-二甲基苄胺、固化剂甲基六氢邻苯二甲酸酐,上海阿拉丁试剂公司。
选用双酚A型环氧树脂(CYD-128)作为基体,脂环族环氧树脂(2021P)作为活性稀释剂,甲基六氢邻苯二甲酸酐作为固化剂,将三者按比例混合均匀作为复合树脂基体。以六方氮化硼片为原料通过喷雾干燥法[14]制得不同粒径的球形氮化硼。将球形氮化硼/片状氮化硼按照一定比例分别与复合树脂基体混合于烧杯中,然后用转速为1 400 r/min的真空脱泡机搅拌8 min混合均匀。
将搅拌均匀的环氧树脂混合物倒入聚四氟乙烯(PTFE)模具中,将模具放入恒温烤箱中进行热固化处理,阶梯式热固化程序为95℃/30 min+125℃/60 min+145℃/30 min,其中氮化硼质量分数每增加5%,每个阶梯温度保持时间相应增加5 min。热固化完成后,将模具从烘箱中取出并冷却至室温,将样品从模具中取出,得到氮化硼/环氧复合材料。
采用NDJ-79A型旋转黏度计,根据ISO 3219:1993对不同脂环族环氧树脂含量下的环氧树脂基体进行黏度测试;采用TA DSC 2500型差示扫描量热仪根据ASTM D3418-2015进行不同酸酐用量下的固化反应热测试;采用Apreo 2S型扫描电子显微镜观察球形氮化硼的微观形貌。
拉伸强度测试:按照GB/T 2567—2008相关要求制样,然后将样品在AGX-V-10kN型万能材料试验机上进行拉伸强度测试。每组样品分别测试5次,取5次测试结果的平均值作为该组样品的拉伸强度。
冲击强度测试:按照GB/T 2567—2008相关要求制样,采用EPT7000E型摆锤式冲击试验仪对样品进行冲击强度测试,试验条件为无缺口冲击。每组样品分别测试5次,取5次测试结果的平均值作为该组样品的冲击强度。
介电性能测试:采用Novocontrol Concept 80型宽频介电谱仪对氮化硼/环氧复合材料的介电性能进行测试,频率范围为10-1~106 Hz。
体积电阻率测试:采用固体绝缘材料体积电阻率常用的测试方法“三电极法”对复合材料的体积电阻率进行测试。
工频击穿特性测试:按照GB/T 1408.1—2016中固体绝缘材料的工频电气强度测试方法对氮化硼/环氧复合材料进行电气强度测试。测试过程中以0.5 kV/s的速率匀速升压,直至样品击穿,记录击穿时的电压值,对每组样品分别测试10次。
图1为不同稀释剂含量下环氧树脂基体的黏温曲线。从图1可以看出,双酚A型环氧树脂、脂环族环氧树脂在25℃下黏度分别约为9 000 mPa·s和200 mPa·s,脂环族环氧树脂的加入可以极大地降低环氧树脂的黏度,随着脂环族环氧树脂添加量的增加,复合树脂体系的黏度逐渐降低,当脂环族环氧树脂的含量超过67份时,降黏效果减弱。由于脂环族环氧树脂的分子链短,交联密度过高,固化产物脆、韧性差,为保证环氧树脂整体具有良好的柔韧性,选择脂环族环氧树脂的含量为67份,双酚A型环氧树脂为33份。
酸酐与环氧基发生交联反应是形成网状结构固化物的重要一环,当固化反应放热量最大时,即表示环氧基与酸酐已完全发生交联反应。图2为不同酸酐用量下复合树脂体系的固化反应热测试结果。从图2可以看出,以双酚A型环氧树脂、脂环族树脂共100份为标准,当固化剂添加量为95份时,固化反应的放热量达到最大值,说明此时固化效果最佳。综上所述,确定了复合树脂体系的配方组成为:CYD-128树脂、CELLOXIDE 2021P树脂、甲基六氢邻苯二甲酸酐的质量比为33∶67∶95。
采用低浓度(质量分数为10%)和高浓度(质量分数为20%)的氮化硼分散液制备的球形氮化硼颗粒的SEM图如图3所示。从图3可以看出,采用低浓度氮化硼分散液制备的球形氮化硼颗粒结构较为疏松且直径较小,表面粗糙度大;提升氮化硼分散液浓度后,由于固含量增大,雾化后的液滴体积较大,可以形成大直径颗粒,同时水分含量减少,雾化液滴表面水分可迅速蒸发,形成近似球形的片状氮化硼聚集颗粒。表明本研究通过调节氮化硼分散液的浓度成功制备了不同直径的球形氮化硼颗粒。
图4(a)是升温速率为10℃/min时,不同球形氮化硼填充量下氮化硼/环氧复合材料放热量随温度的变化曲线。从图4(a)可以看出,随着氮化硼填充量的增加,复合材料的固化起始温度、峰值温度逐渐升高,原因在于球形氮化硼的存在使得环氧树脂基团之间不能充分碰撞运动,需要更多的热量才能完成交联固化反应。
对不同升温速率β下的热流曲线进行积分,可得图4(b)中不同升温速率β下固化度(α)随反应温度的变化规律。从图4(b)可以看出,随着反应温度升高,复合材料的固化度呈“S”型变化,整个固化过程可大致分为“慢-快-慢”3个阶段:①α≤0.2,此阶段仅有少量的环氧基参与反应,环氧树脂固化速度慢;②0.2<α≤0.8,在这个阶段内,环氧树脂快速交联固化,固化度几乎随时间线性增加,大量的热被释放,多数基团在这个阶段内完成反应;③α>0.8,随着网状结构的形成,剩余自由基团被束缚,运动困难,反应逐渐变慢。
图4(c)为复合材料固化反应放热与球形氮化硼填料含量的关系图。从图4(c)可以看出,随着球形氮化硼填充量的增加,复合材料的固化反应放热量快速下降,这是由于球形氮化硼不参与反应,填料含量升高导致反应物减少。
图5为不同填充量下球形/片状氮化硼分别制备的氮化硼/环氧复合材料的表面形貌。从图5可以看出,纯环氧树脂材料为略带淡黄色的透明状固体,随着氮化硼填充量的增加,复合材料样品逐渐变为不透明的白色固体。在图5(a)中,当片状氮化硼质量分数达到20%时,由于复合树脂体系黏度过大,流动性差,复合材料样品表面存在很多缺陷,同时由于片状氮化硼的比表面积大,已不能被树脂充分润湿,固化后复合材料为粉末状固体。而填充球形氮化硼的体系中,即使填料的质量分数达到30%,仍可浇注成表面光滑的复合材料,可见将片状氮化硼进行球形化处理后可以提高氮化硼在环氧树脂中的填充量。由于片状氮化硼的质量分数超过20%后复合材料已无法成型,失去了研究意义,本研究中片状氮化硼的质量分数最大为20%,球型氮化硼的质量分数最大为30%。
不同氮化硼含量下环氧复合材料的拉伸强度变化曲线如图6所示。从图6可以看出,随着氮化硼含量的增加,复合材料的拉伸强度先增大后减小,在填料质量分数为5%时,拉伸强度达到峰值;在填料质量分数为10%时,片状氮化硼/环氧复合材料的拉伸强度仍略高于球型氮化硼/环氧复合材料,这是因为片状填料自身的结构具有均匀应力的效果;当片状氮化硼质量分数大于10%时,复合材料的拉伸强度急剧下降,这是因为填料含量较大时,复合材料的黏度会急剧增大,导致复合材料内部出现很多微气泡,在外力作用时微气泡处容易出现裂纹,而裂纹逐渐延伸会导致断裂。而当球形氮化硼的质量分数大于10%时,复合材料的拉伸强度呈现缓慢下降的趋势,原因可能在于球形氮化硼独特的球形结构,其在填充时能够较好地均匀应力,吸收裂纹的破坏能,阻碍裂纹进一步发展。
不同氮化硼含量下环氧复合材料的冲击强度变化曲线如图7所示。从图7可以看出,随着氮化硼含量的增加,复合材料的冲击强度同样呈现先增大后减小的趋势。对于球形氮化硼/环氧复合材料,在球形氮化硼质量分数为10%时,其冲击强度达到峰值(9.98 kJ/m2),原因在于少量的氮化硼填料可以均匀动态负荷,吸收冲击能量。对于片状氮化硼/环氧复合材料,在填料质量分数高于10%时,其耐冲击性能急剧下降,造成这种现象的原因是高填充量的片状氮化硼与环氧树脂混合时会产生大量的微气泡、界面空隙,导致复合材料的力学性能劣化。
图8是冲击强度测试后复合材料断面的SEM图。从图8可以看出,纯环氧树脂材料的断面裂纹排列整齐,而球形氮化硼质量分数为30%的环氧复合材料断面没有明显的裂纹,说明球形氮化硼可以分散外界施加的作用力。但是在高填料含量下,填料与填料之间接触的概率更大,且填料与填料之间的界面结合力较差,因此在很大程度上会影响复合材料的力学性能,导致其冲击强度降低。
图9为不同氮化硼含量下环氧复合材料的相对介电常数。从图9可以看出,随着片状/球形氮化硼含量的增加,环氧复合材料的相对介电常数增大。
环氧树脂及其复合材料的相对介电常数主要取决于各组分的位移极化、树脂中极性基团的转向极化和无机填料-树脂基体界面处的界面极化。环氧树脂属于极性分子,即使经交联固化后,仍含有少量的羟基等极性基团,在外电场作用下,极性基团会发生转向极化,但由于固化后的环氧树脂链节较长,同时形成的三维网状结构连接紧密,极性基团转向困难,导致环氧树脂的相对介电常数较低。当在环氧树脂中加入无机填料时,复合材料的相对介电常数会明显升高,这是由于无机填料的介电常数通常高于环氧树脂,并且无机填料的添加会产生大量的无机-有机界面。在界面处,由于两种材料的介电常数存在差异,将会加深复合材料的界面极化程度,因此复合材料的相对介电常数随之增大[15]
图9还可以看出,当填料含量相同时,球形氮化硼/环氧复合材料的介电常数比片状氮化硼/环氧复合材料略低,这是由片状氮化硼与球形氮化硼本身的结构特点决定的,片状氮化硼的比表面积比球形氮化硼大,与环氧树脂结合后会存在更多的无机-有机界面,界面极化程度更大,因此片状氮化硼/环氧复合材料的介电常数更高。
介质损耗因数(tanδ)反映了复合材料在交变电场中能量损耗的大小,是衡量复合材料电气绝缘性能的重要参量之一。氮化硼/环氧树脂复合材料在电场作用下产生的能量损耗由两部分组成:一是电导引起的损耗,这是由复合材料内部的载流子在电场作用下定向迁移形成的传导电流将电场能量转化成热能产生的损耗;二是由松弛极化[18]引起的损耗,复合材料中极性基团的转向极化和界面极化都需要一定的时间建立,在高频电场的作用下,偶极子转向慢于电场的周期性变化,出现松弛现象,引起能量消耗,并且随着电场频率的升高,松弛损耗逐渐占据主导地位。
不同氮化硼含量下环氧复合材料介质损耗因数随频率的变化曲线如图10所示。从10可以看出,氮化硼/环氧复合材料的介质损耗因数均低于0.02,满足电气绝缘对材料介质损耗因数的要求。对于不同形貌与填充量下的氮化硼/环氧复合材料,其介质损耗因数均随电场频率升高呈现出先减小后增大的趋势,这是由于在低频区,复合材料内各种极化均来得及建立,介质损耗主要由电导损耗和界面极化贡献,随着频率的升高,复合材料内部载流子在电场作用下的定向迁移率将会降低,导致传导电流减小,电导损耗下降,进而使得复合材料的介质损耗下降;随着频率的进一步升高,介质损耗主要由复合材料内环氧树脂极性基团的转向极化贡献,氮化硼的加入使得环氧树脂的相对含量减少,聚合物分子偶极运动引起的介质损耗被显著抑制,因此复合材料的介质损耗因数低于纯环氧树脂材料。另外由于片状氮化硼/环氧复合材料的界面极化程度大,其介质损耗也略大于球形氮化硼/环氧复合材料。
图11为氮化硼/环氧复合材料的体积电阻率测试结果。从图11可以看出,纯环氧树脂材料的体积电阻率为1015 Ω·cm级,氮化硼的加入提高了环氧复合材料的体积电阻率,原因在于氮化硼颗粒对环氧树脂中载流子的迁移具有限制作用,降低了复合材料中载流子的迁移率[17-18];但是当填料质量分数高于10%时,由于氮化硼通过表面的氧原子或氮原子与环氧树脂的羟基形成氢键,过多的氢键将会降低环氧树脂的固化程度,在基体中留下过多未参与反应的极性官能团,导致复合材料的体积电阻率有所降低[19]
此外,片状氮化硼/环氧复合材料在低填料含量下体积电阻率略高于球形氮化硼/环氧树脂复合材料,这是因为在填料含量较低时,片状氮化硼在环氧树脂中分散更为均匀,有着更多的填料-树脂界面,对载流子的限制作用更强。对于填料质量分数为20%的片状氮化硼/环氧复合材料,由于黏度急剧增大,其内部形成很多的微气泡,在较高的电场作用(1 kV/mm)下微气泡会发生局部放电现象,导致泄漏电流急剧增大,超出了微电流测量仪的测量范围,因此无法获得其体积电阻率。
图12为不同球形氮化硼含量下环氧复合材料的电气强度试验数据以及威布尔分布概率函数拟合结果。选取失效概率P为63.2%时片状/球形氮化硼填充的环氧复合材料电气强度绘制于图13中。从图13可以看出,在填料含量较低时,片状氮化硼/环氧复合材料的电气强度略高于球形氮化硼/环氧复合材料,这是因为低含量片状氮化硼与环氧树脂基体结合更加紧密,限制了载流子的迁移。但在高填充量下,片状氮化硼/环氧复合材料表现出更低的电气强度,这是因为填料含量较高时,环氧树脂体系黏度增大,导致复合材料内部的缺陷增多,填料质量分数为20%的片状氮化硼/环氧复合材料内部含有很多的微气泡,导致其起始放电电压很低且分散性较大,已不具备作为绝缘电介质的应用价值。相比之下,球形氮化硼/环氧复合材料在填料质量分数为30%时,仍然具有良好的抗击穿性能。
氮化硼对环氧复合材料电气强度的影响可以从以下两个方面进行解释:一方面是填料与环氧树脂在两者界面处紧密结合,具有很强的相互作用,限制了载流子的迁移,提高了环氧复合材料的电气强度[17,20];另一方面是在固体电介质短时击穿过程中,击穿以电树枝的方式发展。如图14所示,当电树枝遇到无机填料时,由于分散在树脂基体中的氮化硼自身的电气强度高,其只能“绕过”或“沿着”氮化硼的表面继续发展,相当于击穿路径变长,因此电树枝的发展受阻和击穿路径的变长是环氧复合材料电气强度提高的重要因素[21]
(1)固化特性方面,随着反应温度升高,环氧树脂的固化度呈“S”型变化,整个固化过程可大致分为“慢-快-慢”3个阶段,随着氮化硼含量的增加,环氧复合材料的固化起始温度、峰值温度逐渐增大,同时固化反应热快速下降。
(2)力学性能方面,加入少量的氮化硼可以提升环氧复合材料的拉伸强度和冲击强度。在高填料含量下,球形氮化硼较片状氮化硼可以更好地改善黏度带来的缺陷问题,能够较好地保持环氧复合材料优异的力学性能。同时从微观角度发现纯环氧树脂材料的断面裂纹排列整齐而球形氮化硼/环氧复合材料的断面未出现明显的裂纹,说明球形氮化硼可以在一定程度上均匀应力,分散外界施加的作用力。
(3)电学性能方面,氮化硼填料的加入会提高复合材料的界面极化程度,使得复合材料的相对介电常数随填料含量的增加而增大,介质损耗因数均随电场频率升高呈先减小后增大的趋势且均低于0.02。由于氮化硼球化后环氧复合材料中“填料-树脂”界面减少,与片状氮化硼/环氧复合材料相比,球形氮化硼/环氧复合材料具有更低的相对介电常数和介质损耗因数。在填料添加量较低时,氮化硼的加入可以提高复合材料的体积电阻率和电气强度,且片状氮化硼/环氧复合材料的体积电阻率和电气强度略高于球形氮化硼/环氧复合材料。
  • 国家自然科学基金资助项目(51707016)
  • 芜湖市科技局项目(2022hg15)
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2024年第57卷第5期
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doi: 10.16790/j.cnki.1009-9239.im.2024.05.004
  • 接收时间:2023-07-07
  • 首发时间:2025-12-22
  • 出版时间:2024-05-20
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  • 收稿日期:2023-07-07
  • 修回日期:2023-09-12
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国家自然科学基金资助项目(51707016)
芜湖市科技局项目(2022hg15)
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    重庆大学 输配电装备及系统安全与新技术国家重点实验室,重庆 400044

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黄正勇(1988-),男(汉族),重庆人,副教授,博士,主要从事高电压试验技术、先进电工材料和内绝缘方面的研究。
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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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