Article(id=1199655356906439284, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1199644777219191267, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2023.12.016, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1690646400000, receivedDateStr=2023-07-30, revisedDate=1693756800000, revisedDateStr=2023-09-04, acceptedDate=null, acceptedDateStr=null, onlineDate=1763949725605, onlineDateStr=2025-11-24, pubDate=1703001600000, pubDateStr=2023-12-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1763949725605, onlineIssueDateStr=2025-11-24, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1763949725605, creator=13701087609, updateTime=1763949725605, updator=13701087609, issue=Issue{id=1199644777219191267, tenantId=1146029695717560320, journalId=1149653034449285133, year='2023', volume='56', issue='12', pageStart='1', pageEnd='135', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1763947203211, creator=13701087609, updateTime=1766563728010, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1210619277716099586, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1199644777219191267, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1210619277716099587, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1199644777219191267, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=122, endPage=127, ext={EN=ArticleExt(id=1199655357170680438, articleId=1199655356906439284, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Effect of curing temperature on insulating properties of epoxy impregnated paper, columnId=1199644778280350182, journalTitle=Insulating Materials, columnName=Advanced Electrical Materials for Large Capacity Offshore Wind Power Transmission, runingTitle=null, highlight=null, articleAbstract=

Epoxy impregnated paper is one of the main insulation materials of valve-side bushing, and its performance is affected by curing process. In order to explore the effect of curing temperature on the electrical properties of epoxy impregnated paper, we prepared epoxy impregnated papers at 120℃, 130℃, 140℃ and 145℃ of post-curing temperature, respectively, and their glass transition temperature, dielectric properties, and DC breakdown strength were tested. The results show that with the increase of post-curing temperature, the glass transition temperature increases, the DC breakdown strength increases at first and then decreases, and the dielectric loss factor decreases at first and then increases. The analysis shows that the addition of hydroxyl-rich wrinkle paper will increase the curing rate in interface area of epoxy impregnated paper, leading to the frequency of interface relaxation peak decrease at first and increase, which affects the insulation properties of epoxy impregnated paper.

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环氧浸渍纸材料是阀侧套管的主绝缘材料之一,其运行性能受固化工艺的影响。为探究固化温度对环氧浸渍纸材料电气性能的影响规律,在后固化温度分别为120、130、140、145℃下制备了环氧浸渍纸材料,并对其玻璃化转变温度、介电特性、直流击穿强度等性能进行测试。结果表明:随着后固化温度的升高,环氧浸渍纸材料的玻璃化转变温度提升,直流击穿强度先增大后减小,而介质损耗因数呈现先减小后增大的趋势。分析认为富含羟基皱纹纸的加入会增大环氧浸渍纸材料内部界面区域的固化速率,导致界面弛豫峰的频率呈先下降后升高的趋势,从而影响材料整体的绝缘性能。

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周远翔(1966-),男(汉族),福建莆田人,教授,博士,主要从事高电压技术与绝缘材料的研究。
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滕陈源(1992-),男(汉族),浙江温州人,讲师,博士,主要从事先进绝缘材料的研究。

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滕陈源(1992-),男(汉族),浙江温州人,讲师,博士,主要从事先进绝缘材料的研究。

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滕陈源(1992-),男(汉族),浙江温州人,讲师,博士,主要从事先进绝缘材料的研究。

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试样固化工艺玻璃化转变温度/℃
T120100℃/2 h+120℃/2 h+120℃/4 h126.7
T130100℃/2 h+120℃/2 h+130℃/4 h130.2
T140100℃/2 h+120℃/2 h+140℃/4 h137.1
T145100℃/2 h+120℃/2 h+145℃/4 h141.0
), ArticleFig(id=1211311079062369211, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199655356906439284, language=CN, label=表1, caption=

固化温度与玻璃化转变温度

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试样固化工艺玻璃化转变温度/℃
T120100℃/2 h+120℃/2 h+120℃/4 h126.7
T130100℃/2 h+120℃/2 h+130℃/4 h130.2
T140100℃/2 h+120℃/2 h+140℃/4 h137.1
T145100℃/2 h+120℃/2 h+145℃/4 h141.0
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温度/℃试样形状参数直流击穿强度/(kV/mm)
90T12023.9115.4
T13031.1116.5
T14029.1118.4
T14538.6115.8
100T12041.6104.7
T13038.6106.4
T14030.5111.3
T14535.2108.2
110T12039.696.9
T13035.297.9
T14063.4101.3
T14545.496.6
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不同测试温度下环氧浸渍纸的直流击穿强度

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温度/℃试样形状参数直流击穿强度/(kV/mm)
90T12023.9115.4
T13031.1116.5
T14029.1118.4
T14538.6115.8
100T12041.6104.7
T13038.6106.4
T14030.5111.3
T14535.2108.2
110T12039.696.9
T13035.297.9
T14063.4101.3
T14545.496.6
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固化温度对环氧浸渍纸材料绝缘性能的影响研究
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滕陈源 1 , 丁逸超 1 , 周远翔 2 , 赵磊 3 , 李烁 1 , 丁画 4
绝缘材料 | 面向大容量海上风电送出的先进电工材料 2023,56(12): 122-127
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绝缘材料 | 面向大容量海上风电送出的先进电工材料 2023, 56(12): 122-127
固化温度对环氧浸渍纸材料绝缘性能的影响研究
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滕陈源1, 丁逸超1, 周远翔2, 赵磊3, 李烁1, 丁画4
作者信息
  • 1浙江工业大学 信息工程学院,浙江 杭州 310023
  • 2清华大学 电机系 新型电力系统运行与 控制全国重点实验室,北京 100084
  • 3国网新乡供电公司, 河南 新乡 453002
  • 4国网综合能源服务集团有限公司,北京 100032
  • 滕陈源(1992-),男(汉族),浙江温州人,讲师,博士,主要从事先进绝缘材料的研究。

通讯作者:

周远翔(1966-),男(汉族),福建莆田人,教授,博士,主要从事高电压技术与绝缘材料的研究。
Effect of curing temperature on insulating properties of epoxy impregnated paper
Chenyuan TENG1, Yichao DING1, Yuanxiang ZHOU2, Lei ZHAO3, Shuo LI1, Hua DING4
Affiliations
  • 1College of Information Engineering, Zhejiang University of Technology, Hangzhou 310034, China
  • 2State Key Laboratory of Control and Simulation of Power Systems and Generation Equipment,Department of Electrical Engineering, Tsinghua University, Beijing 100084, China
  • 3State Grid Xinxiang Electric Power Company, Xinxiang 453002, China
  • 4State Grid Integrated Energy Service Company, Beijing 100032, China
出版时间: 2023-12-20 doi: 10.16790/j.cnki.1009-9239.im.2023.12.016
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环氧浸渍纸材料是阀侧套管的主绝缘材料之一,其运行性能受固化工艺的影响。为探究固化温度对环氧浸渍纸材料电气性能的影响规律,在后固化温度分别为120、130、140、145℃下制备了环氧浸渍纸材料,并对其玻璃化转变温度、介电特性、直流击穿强度等性能进行测试。结果表明:随着后固化温度的升高,环氧浸渍纸材料的玻璃化转变温度提升,直流击穿强度先增大后减小,而介质损耗因数呈现先减小后增大的趋势。分析认为富含羟基皱纹纸的加入会增大环氧浸渍纸材料内部界面区域的固化速率,导致界面弛豫峰的频率呈先下降后升高的趋势,从而影响材料整体的绝缘性能。

环氧浸渍纸  /  固化温度  /  介电响应  /  直流击穿强度

Epoxy impregnated paper is one of the main insulation materials of valve-side bushing, and its performance is affected by curing process. In order to explore the effect of curing temperature on the electrical properties of epoxy impregnated paper, we prepared epoxy impregnated papers at 120℃, 130℃, 140℃ and 145℃ of post-curing temperature, respectively, and their glass transition temperature, dielectric properties, and DC breakdown strength were tested. The results show that with the increase of post-curing temperature, the glass transition temperature increases, the DC breakdown strength increases at first and then decreases, and the dielectric loss factor decreases at first and then increases. The analysis shows that the addition of hydroxyl-rich wrinkle paper will increase the curing rate in interface area of epoxy impregnated paper, leading to the frequency of interface relaxation peak decrease at first and increase, which affects the insulation properties of epoxy impregnated paper.

epoxy impregnated paper  /  curing temperature  /  dielectric response  /  DC breakdown strength
滕陈源, 丁逸超, 周远翔, 赵磊, 李烁, 丁画. 固化温度对环氧浸渍纸材料绝缘性能的影响研究. 绝缘材料, 2023 , 56 (12) : 122 -127 . DOI: 10.16790/j.cnki.1009-9239.im.2023.12.016
Chenyuan TENG, Yichao DING, Yuanxiang ZHOU, Lei ZHAO, Shuo LI, Hua DING. Effect of curing temperature on insulating properties of epoxy impregnated paper[J]. Insulating Materials, 2023 , 56 (12) : 122 -127 . DOI: 10.16790/j.cnki.1009-9239.im.2023.12.016
为实现我国“碳达峰、碳中和”目标,需要进一步加速发展以风电、光伏为主的可再生能源。其中,海上风电凭借着资源丰富、开发效率高等优势,已成为目前可再生能源发展的重点领域之一[1-2]。直流输电可以灵活调控有功、无功功率,能够提升电网接入新能源的同时实现电能的远距离、大容量输送。因此,直流输电技术的发展对于新能源的消纳和优化配置具有重要作用[3]。阀侧套管作为直流输电工程中换流变压器的关键组部件之一,运行时同时承受轴向和径向的电场,内部存在着很高的电、热和机械应力,因此提高套管的绝缘性能可以使变压器运行更稳定。环氧浸渍纸材料是阀侧套管的主绝缘材料之一,它是由环氧树脂与绕包在载流导管周围的皱纹纸和铝箔经真空浸渍、高温固化形成[4]。研究表明,环氧树脂材料的固化工艺会影响其理化性能和介电性能[5]。因此研究环氧浸渍纸材料的固化工艺,对胶浸纸绝缘套管介电性能的提升具有重要意义。
在环氧材料的固化过程中需要进行加热以促进固化反应的进行,从而满足固化温度和时间等要求[5-7]。文献[8]制备了不同固化温度的环氧/碳纤维复合材料,发现固化温度会对环氧的交联程度产生影响,过高的固化温度会让阻尼性能下降;文献[9]通过制备不同固化剂配比的环氧复合材料,发现固化剂配比与固化温度应相互匹配,固化温度过低会降低固化效率;文献[10]将分子动力学与实验研究相结合,发现随着固化温度的提高,材料的玻璃化转变温度更高,其介电性能也会受到影响。
上述研究表明固化温度会对环氧树脂材料的性能产生影响。环氧浸渍纸是由环氧树脂与皱纹纸组成的有机复合绝缘材料。皱纹纸主要由富含羟基的纤维素构成。研究表明,羟基的含量会影响环氧树脂的固化反应过程[11-12],环氧树脂的固化温度选取方法不一定适用于环氧浸渍纸,因此,固化温度对环氧浸渍纸材料性能变化规律的影响仍需进一步揭示。然而目前很少有研究对环氧浸渍纸材料的固化温度进行讨论。
本文通过制备不同固化温度的环氧浸渍纸材料,并基于玻璃化转变温度测试(DSC)、介电特性测试与直流击穿测试的结果讨论固化温度对材料理化性能和电学性能的影响规律,期望能为环氧浸渍纸材料的固化工艺提供一定的理论依据。
环氧树脂为双酚A型液体环氧树脂(E51),环氧当量为186~190 g/eq,南通星辰合成材料有限公司;固化剂为甲基六氢邻苯二甲酸酐(MHHPA),纯度为98.6%,濮阳惠成电子材料有限公司;促进剂为二甲基苄胺(BDMA),纯度为99%,阿拉丁试剂(上海)有限公司;套管用皱纹纸,魏德曼有限公司。
将皱纹纸置于真空干燥箱中,在110℃下真空预处理8 h。将双酚A环氧树脂、固化剂以及促进剂按100∶85∶2的质量比快速机械搅拌混合。随后,将混合后的环氧树脂置于50℃的真空干燥箱中抽真空30 min,待无气泡后,将环氧树脂液体倒入已固定好皱纹纸的模具中,并进行真空浸渍处理,其中真空度均为0.1 MPa。最后,采用三段式固化,根据固化动力学得出最佳的固化参数为:100℃预固化2 h、120℃固化2 h、145℃后固化4 h。为进一步分析固化温度对环氧浸渍纸材料电学性能的影响,将后固化温度分别设置为120、130、140、145℃,并将相应试样编号为T120、T130、T140、T145。试样厚度均为1 mm。
玻璃化转变温度可有效表征试样的热特性。利用DSC250型差示扫描量热仪(美国TA公司)对环氧浸渍纸的玻璃化转变温度进行测试。在氮气氛围中,以20℃/min的升、降温速率开展测试,测试温度范围为40~250℃,取第二轮升温测试曲线作为结果。每组重复测试2次。在测试温度上升的过程中,当热流速率在短时内发生大幅转变时即为样品的玻璃化转变温度。
直流击穿强度测试依据GB/T 1408—2016《绝缘材料电气强度试验方法》开展。测试前,将试样和电极置于测量烘箱中预热2 h。上电极为球电极,直径为20 mm,下电极为平板电极,电压上升速率为1 kV/s,测试温度分别为90、100、110℃。测试时,为防止沿面闪络,需将试样和电极浸没在变压器油中。每组测试20次,并作威布尔分布图[13-14]
利用Concept 80型宽频介电谱仪(德国NOVOCONTROL公司)测试材料的介电性能。测试温度为40~180℃,电压频率为10-1~107 Hz。为了使电极与样品充分接触,消除气隙给测试结果带来的误差,需要对环氧浸渍纸材料上、下表面进行镀金处理。
玻璃化转变温度是聚合物材料从玻璃态转变为高弹态的临界温度,该温度与环氧树脂材料的固化特性密切相关。在玻璃化转变温度附近,环氧树脂材料内部分子链段的运动加剧,其绝缘性能会大幅下降[15-16]图1为环氧浸渍纸材料的DSC升温速率曲线,表1给出了不同试样的玻璃化转变温度具体数值。
图1可知,T120试样的玻璃化转变温度最低,仅为126.7℃。随着后固化温度的提高,试样的玻璃化转变温度逐渐上升,均达到130℃以上,其中T145试样的玻璃化转变温度达到最大值141.0℃。玻璃化转变温度受相邻交联点的平均链长与柔性所影响,相邻交联点的平均链长越短,交联程度越高,分子更难运动,玻璃化转变温度也越高。当后固化温度较低时,环氧树脂整体交联不充分;随着后固化温度的提高,环氧树脂交联逐渐形成广泛的三维网络,体系刚性达到最佳,热稳定性也最佳。可见,随着后固化温度的提高,环氧浸渍纸材料整体的固化程度逐渐完整。
图2(a)2(b)分别给出了环氧浸渍纸材料(T145)与纯环氧树脂材料的介质损耗因数(tanδ)。由图2可知,环氧浸渍纸材料的tanδ大于纯环氧树脂材料的tanδ,且在低频范围比较明显,这是由于皱纹纸含有大量的羟基,引入了更多偶极子使得tanδ变高。另一方面,由于皱纹纸上的羟基与水分子会形成氢键,氢键的存在会导致环氧浸渍纸中的水分难以去除,这可能也是tanδ变高的原因之一。
相较于纯环氧材料,环氧浸渍纸材料在1~10 Hz出现了一个损耗峰,这是在低频区域可以观察到的界面极化(IP)。这种弛豫机制也被称为Maxwell-Wagner-Sillars效应[18-19],是由于空间电荷在两种具有不同介电常数的界面处积累,从而形成了能够跟随低频和高温外电场变化的偶极子。
随着温度的升高,可以在高频域与中间频域分别观察到βα弛豫,其中β弛豫源于主链极性侧基的重新定向,比如羟基或羰基侧基的蠕动[17]。在玻璃化转变温度附近,纯环氧树脂与环氧浸渍纸材料均出现一个明显的弛豫峰(α弛豫),这与环氧树脂从玻璃态到高弹态的转变有关[18],它对应于主链的微布朗节段运动,主要是由垂直附着在主聚合物分子链上的偶极子重新排列造成的扭型构象改变所致。
为更好地展现不同弛豫随温度的变化情况,测试了环氧浸渍纸材料在不同温度下的复介电常数虚部,结果如图3所示。复介电常数的实部ε'和虚部ε''分别与响应电流的容性分量和阻性分量有关。其中,实部与电容量相关,表征电介质在外部电场作用下产生内部反向电场的能力;而虚部则与介电运动产生的焦耳热直接相关,用于衡量介电响应过程的能量损耗[19]。从图3可以看出,随着温度上升,IP弛豫峰逐渐变得明显,到150℃时,在高频段以α弛豫为主。随着温度上升,α与IP弛豫峰均向高频移动,这是因为温度升高可以促进分子链段运动,极性基团在高频电场作用下更容易转向[20]
为对比不同固化温度对介电弛豫过程的影响,图4展示了不同固化温度下环氧浸渍纸材料的复介电常数虚部对比图。从图4可以看出,T140与T145的α弛豫峰在更低的频率段出现,这是由于随着固化程度的增加,环氧分子链段结合更紧密,交联程度更高,分子迁移率降低,更难跟随电场转向[21],这与2.1节中的DSC温度所对应。另一方面,环氧浸渍纸材料IP弛豫峰的频率随着后固化温度的升高呈现先下降后升高的规律。其中,T140的IP弛豫峰比其他样品的频率更低,这表明皱纹纸形成的界面相互作用增加[22],积聚的界面电荷更加难以运动,相应地,T140具有最低的介质损耗。
皱纹纸由具有羟基的纤维素构成,而羟基可以与酸酐进行反应进而参与环氧树脂的固化过程[23-24],上述羟基的存在会促进环氧树脂的固化反应,产生更多热量。环氧树脂/酸酐固化体系在固化过程中会产生残余应力,且越接近固化物中心,产生的残余应力越大[25-26]。由于皱纹纸处在固化体系的中心,且其内部的羟基促进了反应进行,使固化反应放出更多热量加剧了这种现象,从而促进了缺陷的产生。这与图4中T145试样IP弛豫峰相较于T140出现升高的现象吻合。
图5图6分别显示了环氧浸渍纸材料的tanδε'随固化温度和频率变化的趋势。从图5可以看出,在低频区环氧浸渍纸材料的tanδ随后固化温度的升高先减小后增大,而在高频区不同样品的tanδ趋于相同。在低频范围内,电导损耗占主导地位[27],由于T140的界面作用更强,降低了电导损耗,T140的tanδ最低。在高频范围内,极化损耗占主导地位。可以看出,tanδ在频率为104~105 Hz时达到最低值,之后随着频率的升高tanδ逐渐增大,在高频范围内发生了较大的损耗。
图6可以看出,随着后固化温度的升高,环氧浸渍纸材料的介电常数也呈现先降低后升高的趋势,这主要是因为环氧树脂与皱纹纸的界面相互作用阻碍了极性基团的移动,导致该区域的分子链段转向困难,使T140的介电常数最低,而T145则因为后固化温度过高在界面区域产生了固化不完全等缺陷,导致界面作用下降,介电常数升高,这与tanδ的变化趋势相对应。
击穿性能是衡量绝缘材料电气强度的重要指标。图7为不同后固化温度处理后环氧浸渍纸材料的直流击穿强度Weibull分布图,表2为统计得到的直流击穿强度具体数值。从图7表2可以看出,随着测试温度的提高,各样品的直流击穿强度均呈现下降的趋势。温度的升高会引起电介质内部电流增大,从而加速热平衡的破坏过程。以T140为例,测试温度为110℃时的直流击穿强度相较于测试温度为90℃时下降了17%左右。
随着后固化温度的升高,环氧浸渍纸材料的击穿强度呈现先上升后下降的趋势。其中,T140具有最高的击穿强度。环氧树脂的直流击穿强度受到分子链交联程度与界面强度的共同影响[28-29]。在高压下,电子与分子链发生碰撞,导致分子链不断断裂,增大了环氧浸渍纸的缺陷,最终导致整体击穿。交联程度越高的样品,需要破坏更多的分子链,而玻璃化转变温度能在一定程度上反映分子间的交联程度。因此,随着环氧浸渍纸材料交联程度的上升,其击穿强度也相应上升。另一方面,随着皱纹纸的加入,由于丰富的羟基会引起界面区域固化速率的增大,导致形成缺陷,而绝缘材料的击穿往往是从绝缘的薄弱点发生和发展,使得环氧浸渍纸材料的直流击穿强度呈现先上升后下降的趋势。可见,在固化温度等工艺的选择中,需要关注皱纹纸引入的影响。
本文对经过不同后固化温度处理后的环氧浸渍纸进行绝缘性能研究,讨论了固化温度对环环氧浸渍纸电气性能的影响并分析其机理,得出以下结论:
(1)在一定的温度范围内,随着后固化温度的提高,环氧浸渍纸的玻璃化转变温度也随之提高。
(2)环氧树脂与皱纹纸会引起界面极化,从而影响环氧浸渍纸的介电特性。
(3)由于界面与交联程度的共同影响,后固化温度为140℃的环氧浸渍纸材料具有最高的直流击穿强度。
  • 国家自然科学基金资助项目(52207032)
  • 国家自然科学基金资助项目(92266110)
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doi: 10.16790/j.cnki.1009-9239.im.2023.12.016
  • 接收时间:2023-07-30
  • 首发时间:2025-11-24
  • 出版时间:2023-12-20
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  • 收稿日期:2023-07-30
  • 修回日期:2023-09-04
基金
国家自然科学基金资助项目(52207032)
国家自然科学基金资助项目(92266110)
作者信息
    1浙江工业大学 信息工程学院,浙江 杭州 310023
    2清华大学 电机系 新型电力系统运行与 控制全国重点实验室,北京 100084
    3国网新乡供电公司, 河南 新乡 453002
    4国网综合能源服务集团有限公司,北京 100032

通讯作者:

周远翔(1966-),男(汉族),福建莆田人,教授,博士,主要从事高电压技术与绝缘材料的研究。
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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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