Article(id=1235576336266351405, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1235576335565902637, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2021.06.002, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1608998400000, receivedDateStr=2020-12-27, revisedDate=1616342400000, revisedDateStr=2021-03-22, acceptedDate=null, acceptedDateStr=null, onlineDate=1772513954463, onlineDateStr=2026-03-03, pubDate=1624118400000, pubDateStr=2021-06-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1772513954463, onlineIssueDateStr=2026-03-03, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1772513954463, creator=13701087609, updateTime=1772513954463, updator=13701087609, issue=Issue{id=1235576335565902637, tenantId=1146029695717560320, journalId=1149653034449285133, year='2021', volume='54', issue='6', 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=1772513954297, creator=13701087609, updateTime=1773989561930, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1241765482630546068, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1235576335565902637, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1241765482634740373, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1235576335565902637, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=10, endPage=17, ext={EN=ArticleExt(id=1235576336631255855, articleId=1235576336266351405, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Development and Application of High Thermal Conductivity Main Insulation Materials for Large Generator——Influence of BN Filler on Properties of Epoxy Adhesive, columnId=1222482827711603484, journalTitle=Insulating Materials, columnName=Special Issue on Thermal Conductive Insulating, runingTitle=null, highlight=null, articleAbstract=

The most important component of high thermal conductivity main insulation material for large generators is high thermal conductive epoxy adhesive. As an important component of high thermal conductive epoxy adhesive, BN powder can improve the thermal conductivity of epoxy resin, but it would affect other properties. In this paper, the researches of high thermal conductivity main insulation materials were analyzed and summarized. It was found that BN powder can inhibit the generation and aggregation of space charge in BN/epoxy composites effectively, and reduce the threshold electric field of space charge in BN/epoxy composites. The addition of BN powder could reduce the electric strength of BN/epoxy composites, under the same BN mass fraction, the electric strength of micron BN/epoxy composites was lower, and the conductivity of the composites could be reduced more effectively by nano BN than by micro BN. The surface flashover voltage of the composite decreased after charging on its surface. Then the research direction of high thermal conductivity adhesives in the main insulation materials for large generators in China was proposed.

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大型发电机高导热主绝缘材料中最重要的成分是高导热环氧胶黏剂,BN粉体作为高导热环氧胶黏剂的重要组分,在提高环氧树脂导热性能的同时,对其他性能也会产生影响。本文对国内外关于高导热主绝缘材料的研究成果进行了分析总结,发现BN粉体能有效抑制BN/环氧复合材料内空间电荷的产生和聚集,并且降低BN/环氧复合材料的空间电荷的阈值电场;BN粉体的加入会降低环氧/BN复合材料的电气强度,相同BN质量分数下,微米BN/环氧复合材料的电气强度更低;相同BN质量分数下,纳米级BN比微米级BN能更有效地降低复合材料的电导率;对复合材料表面进行充电处理会降低材料表面闪络电压值。并提出了国内大型发电机主绝缘材料中的高导热胶黏剂的研究方向。

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付强(1968-),男(汉族),黑龙江双鸭山人,教授级高级工程师,主要从事绝缘材料、电介质及其制品的研究。
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邢向前(1973-),男(汉族),甘肃定西人,高级工程师,主要从事水力发电、新能源发电的研究。

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邢向前(1973-),男(汉族),甘肃定西人,高级工程师,主要从事水力发电、新能源发电的研究。

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邢向前(1973-),男(汉族),甘肃定西人,高级工程师,主要从事水力发电、新能源发电的研究。

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6National Engineering Research Center-Hydropower Equipment, Harbin 150040, China
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5哈动国家水力发电设备工程技术研究中心有限公司, 黑龙江 哈尔滨 150040
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4State Key Laboratory of Hydropower Equipment, Harbin 150040, China
5Hadong National Engineering Research Center-Hydropower Equipment Company Limited, Harbin 150040, China
6National Engineering Research Center-Hydropower Equipment, Harbin 150040, China
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4水力发电设备国家重点 实验室,黑龙江 哈尔滨 150040
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tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1235576336266351405, language=EN, label=Tab.1, caption=Space charge density of epoxy/BN composites fabricated by different nanoscale dispersion techniques, figureFileSmall=null, figureFileBig=null, tableContent=
试样填料质量分数/%分散技术空间电荷密度/(C/m3)
纯环氧0.25
1#0.2Solvent0.14
2#0.2Speed-mixer0.11
3#0.2Nanomizer0.08
4#0.5Nanomizer0.03
5#0.6Speed-mixer0.08
6#1.0Speed-mixer0.41
7#1.0Solvent0.18
8#1.0Nanomizer0.07
9#5.0Solvent0.13
10#5.0Nanomizer0.06
), ArticleFig(id=1235576353580437815, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1235576336266351405, language=CN, label=表1, caption=

不同纳米分散技术制作的环氧/BN复合物的空间电荷密度

, figureFileSmall=null, figureFileBig=null, tableContent=
试样填料质量分数/%分散技术空间电荷密度/(C/m3)
纯环氧0.25
1#0.2Solvent0.14
2#0.2Speed-mixer0.11
3#0.2Nanomizer0.08
4#0.5Nanomizer0.03
5#0.6Speed-mixer0.08
6#1.0Speed-mixer0.41
7#1.0Solvent0.18
8#1.0Nanomizer0.07
9#5.0Solvent0.13
10#5.0Nanomizer0.06
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大型电机高导热主绝缘材料发展及应用状况——BN填料对环氧胶黏剂性能影响分析
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邢向前 1 , 刘世泽 2 , 冯雪萍 2 , 付强 3, 4, 5, 6, 7 , 管少博 3, 4, 5, 6, 7 , 冯超 3, 4, 5, 6, 7 , 黄程伟 3, 4, 5, 6, 7 , 王玉明 8
绝缘材料 | 导热绝缘专题 2021,54(6): 10-17
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绝缘材料 | 导热绝缘专题 2021, 54(6): 10-17
大型电机高导热主绝缘材料发展及应用状况——BN填料对环氧胶黏剂性能影响分析
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邢向前1, 刘世泽2, 冯雪萍2, 付强3, 4, 5, 6, 7, 管少博3, 4, 5, 6, 7, 冯超3, 4, 5, 6, 7, 黄程伟3, 4, 5, 6, 7, 王玉明8
作者信息
  • 1甘肃电力明珠集团公司,甘肃 兰州 730070
  • 2国网甘肃省电力公司刘家峡水电厂, 甘肃 永靖 731600
  • 3哈尔滨大电机研究所,黑龙江 哈尔滨 150040
  • 4水力发电设备国家重点 实验室,黑龙江 哈尔滨 150040
  • 5哈动国家水力发电设备工程技术研究中心有限公司, 黑龙江 哈尔滨 150040
  • 6国家水利发电设备工程技术研究中心,黑龙江 哈尔滨 150040
  • 7哈尔滨电机厂有限责任公司,黑龙江 哈尔滨 150040
  • 8中国水利水电第四工程局有限公司,甘肃 永靖 731600
  • 邢向前(1973-),男(汉族),甘肃定西人,高级工程师,主要从事水力发电、新能源发电的研究。

通讯作者:

付强(1968-),男(汉族),黑龙江双鸭山人,教授级高级工程师,主要从事绝缘材料、电介质及其制品的研究。
Development and Application of High Thermal Conductivity Main Insulation Materials for Large Generator——Influence of BN Filler on Properties of Epoxy Adhesive
Xiangqian XING1, Shize LIU2, Xueping FENG2, Qiang FU3, 4, 5, 6, 7, Shaobo GUAN3, 4, 5, 6, 7, Chao FENG3, 4, 5, 6, 7, Chengwei HUANG3, 4, 5, 6, 7, Yuming WANG8
Affiliations
  • 1Gansu Electric Power Pearl Group Corporation, Lanzhou 730070, China
  • 2Liujiaxia Hydro Power Station, State Grid Gansu Electric Power Company, Yongjing 731600, China
  • 3Harbin Institute of Large Electric Machinery, Harbin 150040, China
  • 4State Key Laboratory of Hydropower Equipment, Harbin 150040, China
  • 5Hadong National Engineering Research Center-Hydropower Equipment Company Limited, Harbin 150040, China
  • 6National Engineering Research Center-Hydropower Equipment, Harbin 150040, China
  • 7Harbin Electric Machinery Company Limited, Harbin 150040, China
  • 8Sinohydro Engineering Bureau 4 Co., Ltd., Yongjing 731600, China
出版时间: 2021-06-20 doi: 10.16790/j.cnki.1009-9239.im.2021.06.002
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大型发电机高导热主绝缘材料中最重要的成分是高导热环氧胶黏剂,BN粉体作为高导热环氧胶黏剂的重要组分,在提高环氧树脂导热性能的同时,对其他性能也会产生影响。本文对国内外关于高导热主绝缘材料的研究成果进行了分析总结,发现BN粉体能有效抑制BN/环氧复合材料内空间电荷的产生和聚集,并且降低BN/环氧复合材料的空间电荷的阈值电场;BN粉体的加入会降低环氧/BN复合材料的电气强度,相同BN质量分数下,微米BN/环氧复合材料的电气强度更低;相同BN质量分数下,纳米级BN比微米级BN能更有效地降低复合材料的电导率;对复合材料表面进行充电处理会降低材料表面闪络电压值。并提出了国内大型发电机主绝缘材料中的高导热胶黏剂的研究方向。

高导热胶黏剂  /  BN填料  /  空间电荷  /  电气强度  /  体积电阻率  /  表面闪络电压

The most important component of high thermal conductivity main insulation material for large generators is high thermal conductive epoxy adhesive. As an important component of high thermal conductive epoxy adhesive, BN powder can improve the thermal conductivity of epoxy resin, but it would affect other properties. In this paper, the researches of high thermal conductivity main insulation materials were analyzed and summarized. It was found that BN powder can inhibit the generation and aggregation of space charge in BN/epoxy composites effectively, and reduce the threshold electric field of space charge in BN/epoxy composites. The addition of BN powder could reduce the electric strength of BN/epoxy composites, under the same BN mass fraction, the electric strength of micron BN/epoxy composites was lower, and the conductivity of the composites could be reduced more effectively by nano BN than by micro BN. The surface flashover voltage of the composite decreased after charging on its surface. Then the research direction of high thermal conductivity adhesives in the main insulation materials for large generators in China was proposed.

high thermal conductive adhesive  /  BN filler  /  space charge  /  electric strength  /  volume resistivity  /  surface flashover voltage
邢向前, 刘世泽, 冯雪萍, 付强, 管少博, 冯超, 黄程伟, 王玉明. 大型电机高导热主绝缘材料发展及应用状况——BN填料对环氧胶黏剂性能影响分析. 绝缘材料, 2021 , 54 (6) : 10 -17 . DOI: 10.16790/j.cnki.1009-9239.im.2021.06.002
Xiangqian XING, Shize LIU, Xueping FENG, Qiang FU, Shaobo GUAN, Chao FENG, Chengwei HUANG, Yuming WANG. Development and Application of High Thermal Conductivity Main Insulation Materials for Large Generator——Influence of BN Filler on Properties of Epoxy Adhesive[J]. Insulating Materials, 2021 , 54 (6) : 10 -17 . DOI: 10.16790/j.cnki.1009-9239.im.2021.06.002
大型发电机定子线棒使用的主绝缘材料主要由云母纸、玻璃丝布、胶黏剂构成,其中胶黏剂主要是环氧树脂类材料。主绝缘材料的导热性能主要取决于胶黏剂,为了提高主绝缘材料的导热性能,首先需要提高胶黏剂的导热性能,目前国内外开发的高导热主绝缘材料主要是在胶黏剂中添加导热填料。六方BN因导热性能优异、电气强度高,并且形状为类似云母材料的片状,成为大型发电机高导热绝缘常用的填料。然而,六方BN在提高胶黏剂导热性能的同时,对其他性能也会产生影响。本文首先从空间电荷密度、空间电荷逾渗电场等方面分析BN添加量对环氧/BN复合材料空间电荷特性的影响规律;其次分析BN添加量、不同分散方法等对环氧/BN复合材料电气强度和体积电阻率的影响规律;最后讨论添加BN粉体对复合材料表面闪络电压的影响。
一般而言,宏观固体介质可以看成由许多相同结构的单元所组成,这些结构单元一般是电中性的。如果在固体介质中的电荷不能相互中和,那么这些在固体介质内一个或多个结构单元内不能互相中和的正、负电荷就被定义为在相应位置上的空间电荷。空间电荷的产生、聚集、迁移和消散等变化会影响电介质内部局部区域的电场分布。目前,在国际研究领域已经普遍认为,这种由空间电荷的相关作用而引起电介质内部局部区域的电场畸变,最终会对绝缘材料的老化、电导、击穿等特性产生不利影响。
在高导热胶黏剂中引入填料后,绝缘材料内部会存在一些缺陷(陷阱),这些缺陷在电场作用下会产生空间电荷,空间电荷对材料内部的电场分布有一定的影响,从而对绝缘材料的老化、电导、击穿等性能产生影响[1]。如果环氧/BN复合材料中空间电荷密度足够大,局部泊松电场强度会明显增大,导致材料老化加速,最终发生击穿事故。因此有必要研究环氧/BN复合材料中的空间电荷变化规律。
龚瑾等[2]在环氧树脂中添加尺寸为1 μm的BN,然后将不同BN添加量的复合材料分别在20 kV/mm和40 kV/mm电场加压30 min,测得空间电荷密度如图1所示。从图1可以看出,微米级BN质量分数为5%的BN/环氧树脂复合材料内的平均空间电荷密度最小,微米级BN质量分数为30%的BN/环氧树脂复合材料内的平均空间电荷密度最大,但在40 kV/mm电场下仍小于纯环氧树脂,表明掺杂BN颗粒可以减小环氧树脂复合材料在直流高压电场下的平均空间电荷密度。虽然引入BN颗粒,在BN/环氧树脂复合材料中会产生一些缺陷,但是由于BN颗粒与环氧树脂结合形成相互作用区,胶黏剂中少量空间电荷无法在BN和环氧树脂的界面移动,有效抑制了复合材料内空间电荷的产生和聚集。
龚瑾[3]还在20 kV/mm电场下检测了活化处理和未活化处理BN纳米颗粒(粒径为50 nm)添加量对环氧复合材料空间电荷密度的影响。结果发现无论纳米BN表面是否进行活化处理,复合材料的空间电荷密度均随着纳米BN添加量的增加呈现增大趋势。纳米BN表面进行活化处理后所得复合材料的空间电荷密度小于未进行表面活化处理纳米BN对应的复合材料。
D SAHA等[4]利用粒径为70 nm的BN为导热填料,研究不同BN添加量的BN/环氧复合材料在不同直流电场下的空间电荷状态,结果如图2所示。
图2可知,纯环氧树脂的空间电荷阈值电场值约为14 kV/mm,添加0.2%体积分数BN的复合物空间电荷阈值电场增大到15 kV/mm,电荷注入现象得到抑制。这是由于BN颗粒的添加减少了复合材料在极化期间空间电荷的聚集数量[5]。空间电荷聚集数量的减少有多种原因:由于电极-绝缘体附近区域的空间电荷注入深度低,导致出现同性电荷,将限制注入电荷的进一步发展;纳米颗粒与聚合物基体之间的相互作用可能产生表面能态,改变了能带结构,相互作用程度越大,聚合物分子的固定程度越大,这对纳米复合材料中的空间电荷行为十分有利,因此纳米颗粒使复合物内部能带结构变化是确定阈值电场值的一个重要的因素。然而如果填料添加量过大,填料颗粒之间的相互作用增大,这将减小填料颗粒和聚合物分子链之间相互作用,而且纳米界面数量也会增多,进而导致更多陷阱出现,对纳米复合材料中的空间电荷行为产生不利影响[5]
图3为复合材料中BN添加量与其空间电荷阈值电场的关系。由图3可知,当BN的体积分数为0~0.5%时,随着填料含量的增加,复合材料空间电荷阈值电场开始增大,表明电荷注入现象得到很好的限制。当BN的体积分数为0.5%~1.0%时,虽然电荷注入阈值电场降低,但是对电荷注入的抑制效果仍然很明显。而当BN的体积分数为1.0%~5.0%时,空间电荷注入阈值电场一直在降低,表明填料越多,可能出现均匀分布的陷阱数量越多,减弱了对空间电荷的抑制效果[6]
在制备BN/环氧复合材料时,所用BN纳米分散技术对复合材料中空间电荷行为也有很重要的影响。D SAHA等[7]分别使用Nanomizer技术、Solvent技术、Speed mixer技术等3种纳米分散技术制备了环氧/BN复合材料,并利用电声脉冲法(pulsed electroacoustic method,PEA)在30 kV/mm直流电场下测试不同试样中的空间电荷状态,研究不同的纳米分散技术对环氧/BN复合材料空间电荷状态的影响,结果如表1所示。
表1可知,在相同添加量下,采用Nanomixer技术制得的复合材料试样中空间电荷密度最小。当BN的体积分数为0.2%~5.0%时,采用Nanomixer技术制得的复合材料试样中空间电荷密度几乎没有变化,即填料浓度对其空间电荷聚集行为几乎没有影响,这对提高BN含量进而提高复合材料的导热性能十分有利。而应用Solvent技术和Speedmixer技术制得的复合材料试样中空间电荷抑制行为均受填料浓度影响。有效的纳米颗粒分散技术能在纳米复合物中产生较多的均匀分布的陷阱,阻止电荷持续注入,导致较好的空间电荷抑制行为,这与文献[5-6]介绍的结果有矛盾,因为所使用的分散方法不同。因此,良好的纳米分散技术(如Nanomizer技术)对聚合物纳米复合材料的性能非常重要。
电气强度是表征大型发电机定子线棒用高导热绝缘材料绝缘性能的一个重要参数,因此有必要了解添加BN导热填料后BN/环氧复合材料的电气强度变化情况。
龚瑾等[2]在环氧树脂中分别添加尺寸为1 μm和50 nm的BN,并测试了复合材料的电气强度,结果如图4所示。从图4可以看出,纳米BN的质量分数为1%~3%时,BN/环氧复合材料的电气强度高于纯环氧,而当纳米BN的质量分数达到5%时,复合材料的电气强度低于纯环氧。添加微米BN的环氧复合材料,其电气强度均低于纯环氧,且随着微米BN含量的增加,复合材料的电气强度逐渐降低,当微米BN的质量分数为10%时,复合材料的电气强度相比纯环氧降低了12.33%。
马万里等[8]将尺寸为2 μm和10 nm的BN分别添加到环氧中,并测试复合材料的交流电气强度,结果发现在BN质量分数较低时(低于1%),微米BN和纳米BN的添加都提高了复合材料的电气强度。当填料质量分数大于5%时,复合材料的电气强度逐渐减低。微米BN与纳米BN填充的复合材料电气强度随填料含量表现出一致的趋势。
WANG S J等[9]在环氧树脂中添加尺寸为1 μm的BN,发现当填料质量分数为10%时,复合材料的电气强度比纯环氧的高;当BN的质量分数大于20%时,随着BN添加量的增加,复合材料的电气强度逐步降低,且低于纯环氧的电气强度。
付强等[10]将微米BN添加到环氧树脂中,并对所得复合材料进行电气性能测试。结果发现当微米BN质量分数小于40%时,复合材料的电气强度大幅下降,当微米BN质量分数达到50%时,复合材料的电气强度开始提高,并且随着填料含量的增加,电气强度逐步提升,最后几乎达到与纯环氧材料一样的水平。龚瑾等[2]将尺寸为10 μm的BN与环氧树脂复合制得BN/环氧复合材料,发现其电气强度随着填料含量增加有同样的变化趋势,在BN质量分数为40%时,复合材料的电气强度最低,而在BN质量分数为50%时开始略微上升。与上述研究结果不同,WANG Z等[11]采用尺寸为5.5 μm的BN为填料,与环氧复合制备了BN/环氧复合材料,发现当BN质量分数为40%时,复合材料的电气强度降幅很小。但是当BN质量分数为超过40%时,复合材料的电气强度快速下降。
QIANG D等[12]将粒径为0.15 μm的BN添加到环氧中,并对所得复合材料进行电气性能测试。结果发现当填料质量分数为0~5%时,随着填料含量的增加,复合材料的电气强度逐渐降低。
有部分学者的研究结果表明,微米级BN也能提高BN/环氧复合材料的电气强度,L DESMARS等[13]对BN/环氧复合材料进行交流耐压测试,结果表明添加质量分数为30%的微米(6~20 μm)BN填料,BN/环氧复合材料的电气强度比纯环氧提高了10.81%~29.72%,在文献[14-15]中也有相关报道。
BN对环氧复合材料电气强度的影响有以下几种解释:①环氧基体与BN颗粒之间的介电常数不同,会在复合材料内导致电场畸变,降低复合材料的电气强度。②BN颗粒会改变复合材料的空间电荷行为,减少材料内部的空间电荷积累,从而降低电极与试样截面之间交流电场畸变的概率,提高复合材料的电气强度。③BN粉体添加到环氧中会引入一些气隙[11],导致复合材料的电气强度降低。如果采取共混或杂化混合等适宜方法减少气隙含量,能够将复合物的电气强度恢复到一定程度。对填料表面进行活化处理也可适当减少气隙。④相同BN质量分数下,微米BN/环氧的电气强度比纳米BN/环氧更低,这是由于微米BN的比表面积小,且化学活性差,难以像纳米BN一样与环氧形成紧密的结构,微米BN与环氧间的松散结构会引入更多的缺陷,这些缺陷会使初始电子更容易运动,并随着电子的碰撞产生更多的二次电子,使电气强度降低。
I A TSEKMES等[16]分别利用Speed mixer技术、Solvent技术将尺寸为70 nm的BN混合到环氧树脂中,并测试了不同BN添加量复合材料的电气强度,结果如图5所示。从图5可以看出,纳米BN的体积分数为0.2%时,BN/环氧复合材料的电气强度略优于纯环氧树脂,当填料体积分数增加到0.6%时,复合材料的电气强度较大,比纯环氧材料增大了18.5%左右。而当BN体积分数增加到5.0%时,两种分散方法制得的复合材料电气强度均比纯环氧降低了约14.5%。两种分散方法制得的复合材料表现出相同的变化趋势,表明复合材料的电气强度主要与填料浓度有关,与分散方法关系不大。同样也说明在相同添加量条件下,不同分散工艺制得的复合材料具有相似的击穿性能。
马万里等[8]研究了微米BN、纳米BN填充的环氧复合材料电导率随温度的变化,结果如图6所示。从图6可以看出,在测试温度范围内,微米BN、纳米BN的掺杂有效抑制了复合材料电导率随温度升高而增大的趋势,在温度高于80℃时,这种抑制作用更明显。这是因为分散在环氧树脂基体中的微米BN、纳米BN填料可以优先占据环氧树脂中的非晶区,减小了自由体积,阻碍了载流子的迁移,所以复合材料的电导率显著降低[17]。当填料质量分数为5%时,纳米BN/环氧(EPN)比微米BN/环氧(EPM)的电导率更小。这是由于与纳米BN相比,单个微米BN的粒径更大,微米BN与环氧树脂之间形成的结构较松散,更易产生缺陷,而这些缺陷有助于载流子的迁移,使微米BN/环氧的电导率更大。
如果纳米BN在剥离过程中表面存在一些杂质和吸附水,这些杂质的引入会使BN/环氧树脂复合材料的体积电阻略微下降。虞锦洪[18]测得纯环氧材料、纳米BN/环氧复合材料的体积电阻率分别为2.2×1016 Ω·cm、1.2×1016 Ω·cm,这是由于纳米BN表面存在杂质或吸附水,导致纳米BN/环氧树脂复合材料的体积电阻比纯环氧树脂的稍小。
付强等[10]在环氧树脂中添加微米BN,并对BN/环氧复合材料进行体积电阻率检测,发现在温度为20~40℃下,当BN的质量分数为70%时,复合材料的体积电阻率最大,其余BN添加量下复合材料的体积电阻率差别不大。当测试温度为60~80℃时,复合材料的绝缘电阻随着BN含量的增加而逐渐增大。不同BN添加量的复合材料体积电阻率均大于1011 Ω·cm,添加BN材料没有降低胶黏剂的电阻值[19],因此,BN/环氧胶黏剂复合材料可以作为大型发电机定子线棒主绝缘的胶黏剂材料。
L DESMARS等[13]测试不同场强下环氧树脂、微米BN/环氧复合材料的电导率,发现两种材料的电导率随着场强表现出相同的变化趋势,低电场下具有较低的电导率,高电场下具有较高的电导率。但是微米BN/环氧复合材料的电导率明显比纯环氧的小。
WANG S J等[9]比较了填充10 μm和1 μm BN对环氧复合材料电阻率的影响,结果如图7所示。从图7可以看出,添加质量分数为10%的1 μm BN后,BN/环氧复合材料的体积电阻率比纯环氧的高,随着1 μm BN添加量的进一步增加,复合材料的体积电阻率逐渐降低。相比纯环氧树脂,添加10 μm BN的环氧复合材料体积电阻率均有所降低。尽管如此,当填料质量分数达到50%时,两种环氧复合材料的体积电阻率仍然大于1016 Ω·cm,表明BN/环氧复合材料仍具有较好的绝缘性能。
KAN Y等[20]在环氧中添加质量分数为5%~20%的纳米BN,并对试样进行闪络电压试验,结果如图8所示。从图8可以看出,环氧复合材料的闪络电压随着填料含量的增加而增大。在纳米BN质量分数为20%~30%时,复合材料的闪络电压在12.15 kV附近波动,闪络电压不再明显增大。
CHEN Y等[21]研究结果表明,影响材料表面闪络性能的主要因素是陷阱类型和陷阱密度。填料的添加量不同会导致复合材料中的陷阱能级不同,根据能级水平可将陷阱分为深陷阱和浅陷阱。陷阱深度对闪络特性有明显影响,陷阱深度越大越能抑制闪络发展过程中的二次电子倍增,从而提高闪络电压。因为BN添加量增加进一步提高了陷阱深度增大的概率,所以随着BN填料含量的增加,复合材料的闪络电压一直增加。在环氧树脂中添加纳米BN后,材料中将出现陷阱,当填料含量较低时,材料中的深陷阱数量较少,此时浅陷阱占主导地位。随着填料含量的增加,陷阱数量也增加,同时深陷阱逐渐占主导地位。电荷被深陷阱捕获后很难移动到材料表面,外部电荷也很难注入到材料表面,陷阱中的电荷沿着内部渠道衰减,从而抑制了表面闪络的发展。
从理论上讲,填料的含量不能太高,否则复合物的主体材料将从环氧树脂变为填料,填料临界添加质量分数在40%左右。DU B X等[22]将质量分数分别为5%、10%、20%、30%、40%的100 nm BN与环氧树脂复合制备环氧复合材料,并对其进行表面闪络试验,结果如图9所示。从图9可以看出,掺杂BN环氧复合试样的闪络电压低于纯环氧试样,这是由于填料引入聚合物内部时引入了界面缺陷,在复合材料内部产生电荷集聚中心,从而降低复合材料表面的闪络电压值,而且BN添加量越多,缺陷影响越显著,所以复合材料的闪络电压随着BN添加量的增加而逐渐减小。当BN添加量达到一定程度时,由于颗粒之间的界面会重叠,缺陷的影响减弱。
图9还可以看出,在试样表面进行正极性和负极性充电后,降低了材料的表面闪络电压。然而,当充电极性和测试电源极性相反时,电荷累积对闪络电压的敏感度低。原因是异性电荷相互抵消,因此闪络电压相对较大。
环氧树脂中添加BN纳米颗粒对复合材料表面闪络电压有影响,其中电荷累积是其闪络电压降低的主要原因。当纳米颗粒添加到聚合物中时,会在材料中引入陷阱,产生电荷累积中心,随着表面充电,在试样表面出现电荷累积现象,使得材料的闪络电压降低。对试样进行充电后,存储在陷阱中的电荷随着时间延长会逐渐消散,陷阱深度会影响电荷消散的速度,在深陷阱中电荷很难逸出,对于BN添加量较多的复合材料试样,在陷阱中累积的电荷较多,消耗速度非常慢,所以闪络电压相对较低。
BN粉体由于具有良好的电气性能和导热性能,在高导热胶黏剂领域有着广阔的应用前景,尤其是六方晶体结构的BN具有与云母类似的片状结构,适合应用在大电机定子高导热绝缘材料中。但是目前对BN掺杂环氧复合材料内部的复合机制及对材料性能的影响仍不明确,今后还需从以下几方面进一步开展研究工作:①研究不同粒径BN粉体对环氧/BN复合材料空间电荷密度阈值电场的影响规律;②在BN粉体分散技术方面开展进一步研究工作,期望利用良好的分散技术研究BN粉体添加量与环氧/BN复合材料的空间电荷密度的关系;③进一步分析纳米BN与微米BN共同掺杂对环氧/BN复合材料电气性能的影响。
  • 黑龙江省自然科学基金重点项目(ZD2018011)
  • 水力发电设备国家重点实验室基金资助项目(820-03-1705)
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doi: 10.16790/j.cnki.1009-9239.im.2021.06.002
  • 接收时间:2020-12-27
  • 首发时间:2026-03-03
  • 出版时间:2021-06-20
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  • 收稿日期:2020-12-27
  • 修回日期:2021-03-22
基金
黑龙江省自然科学基金重点项目(ZD2018011)
水力发电设备国家重点实验室基金资助项目(820-03-1705)
作者信息
    1甘肃电力明珠集团公司,甘肃 兰州 730070
    2国网甘肃省电力公司刘家峡水电厂, 甘肃 永靖 731600
    3哈尔滨大电机研究所,黑龙江 哈尔滨 150040
    4水力发电设备国家重点 实验室,黑龙江 哈尔滨 150040
    5哈动国家水力发电设备工程技术研究中心有限公司, 黑龙江 哈尔滨 150040
    6国家水利发电设备工程技术研究中心,黑龙江 哈尔滨 150040
    7哈尔滨电机厂有限责任公司,黑龙江 哈尔滨 150040
    8中国水利水电第四工程局有限公司,甘肃 永靖 731600

通讯作者:

付强(1968-),男(汉族),黑龙江双鸭山人,教授级高级工程师,主要从事绝缘材料、电介质及其制品的研究。
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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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