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Article(id=1199641485705572886, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1199641484963181075, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2023.07.011, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1659369600000, receivedDateStr=2022-08-02, revisedDate=1664553600000, revisedDateStr=2022-10-01, acceptedDate=null, acceptedDateStr=null, onlineDate=1763946418453, onlineDateStr=2025-11-24, pubDate=1689782400000, pubDateStr=2023-07-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1763946418453, onlineIssueDateStr=2025-11-24, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1763946418453, creator=13701087609, updateTime=1763946418453, updator=13701087609, issue=Issue{id=1199641484963181075, tenantId=1146029695717560320, journalId=1149653034449285133, year='2023', volume='56', issue='7', pageStart='1', pageEnd='113', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1763946418275, creator=13701087609, updateTime=1766563596176, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1210618724747440709, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1199641484963181075, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1210618724747440710, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1199641484963181075, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=67, endPage=73, ext={EN=ArticleExt(id=1199641485948842522, articleId=1199641485705572886, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Long-term thermal ageing characteristics of natural ester impregnated silane modified insulating paper system, columnId=1190369198472794288, journalTitle=Insulating Materials, columnName=Insulation Technology, runingTitle=null, highlight=null, articleAbstract=

As a kind of environment friendly liquid dielectric with high ignition point and degradability, natural ester insulating oil is widely considered as a good substitute of mineral oil in power transformers. In order to improve the electrical and thermal ageing properties of natural ester-paper insulation system, the surface of cellulose insulation paper was modified by silane coupling agent, and the oil-paper composite insulation combinations of natural ester, traditional mineral oil, ordinary insulation paper, and silane modified insulation paper were conducted accelerated thermal ageing tests. The ageing characteristic paremeters of oil-paper during the thermal ageing of four combinations were compared and analyzed. The results show that the insulating paper modified by silane can maintain a relatively complete three-dimensional network structure of cellulose during thermal ageing, and improve the ageing resistance and electrical performance of the natural ester-paper system.

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天然酯绝缘油作为一种高燃点、可降解的环保型液体电介质，被普遍认为是矿物油在电力变压器中的良好替代品。本文以改善天然酯-纸绝缘系统的电气性能和热老化性能为目标，利用硅烷偶联剂对纤维素绝缘纸进行表面改性，并对天然酯和传统矿物油分别浸渍普通绝缘纸和硅烷改性绝缘纸的油纸复合绝缘组合进行加速热老化试验，对比分析4种组合在热老化过程中油纸的老化特征参数。结果表明：经硅烷改性的绝缘纸在热老化过程中能保持较完整的纤维素三维网状结构，并可提升天然酯-纸系统的抗老化能力和电气性能。

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卢武（1991-），男（汉族），安徽亳州人，副教授，主要从事高电压试验技术、液体放电和生物电磁方面的研究。
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郑蝶吉（1999-），女（汉族），广东湛江人，硕士生，主要从事高电压试验技术以及油纸绝缘老化机理的研究。

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郑蝶吉（1999-），女（汉族），广东湛江人，硕士生，主要从事高电压试验技术以及油纸绝缘老化机理的研究。

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郑蝶吉（1999-），女（汉族），广东湛江人，硕士生，主要从事高电压试验技术以及油纸绝缘老化机理的研究。

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tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199641485705572886, language=CN, orderNo=3, keyword=硅烷偶联剂), Keyword(id=1217475255375941645, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199641485705572886, language=CN, orderNo=4, keyword=热老化), Keyword(id=1217475255480799250, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199641485705572886, language=CN, orderNo=5, keyword=变压器)], refs=[Reference(id=1217475260484604065, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199641485705572886, doi=null, pmid=null, pmcid=null, year=2016, volume=52, issue=2, pageStart=93, pageEnd=96,102, url=null, language=null, rfNumber=[1], rfOrder=0, authorNames=王世强, 胡海燕, 刘全桢, journalName=高压电器, refType=null, unstructuredReference=王世强,胡海燕,刘全桢,等.热老化对变压器绝缘纸微观结构影响的实验研究[J].高压电器,2016,52(2):93-96,102., articleTitle=热老化对变压器绝缘纸微观结构影响的实验研究, refAbstract=null), Reference(id=1217475260589461671, tenantId=1146029695717560320, 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编号名称生厂商纯度/%
1纤维素绝缘纸亚安绝缘材料有限公司—
23-氨基丙基-三乙氧基硅烷Energy Chemical99.5
3钛酸正丁酯国药基团化学试剂有限公司97.0
4无水乙醇国药基团化学试剂有限公司99.7
5Diala S3 ZX-I矿物油壳牌公司—
6FR3天然酯绝缘油嘉吉公司—
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改性试剂与材料

, figureFileSmall=null, figureFileBig=null, tableContent=
编号名称生厂商纯度/%
1纤维素绝缘纸亚安绝缘材料有限公司—
23-氨基丙基-三乙氧基硅烷Energy Chemical99.5
3钛酸正丁酯国药基团化学试剂有限公司97.0
4无水乙醇国药基团化学试剂有限公司99.7
5Diala S3 ZX-I矿物油壳牌公司—
6FR3天然酯绝缘油嘉吉公司—
), ArticleFig(id=1217475259322781819, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199641485705572886, language=EN, label=Tab.2, caption=Detection method for feature parameter of samples, figureFileSmall=null, figureFileBig=null, tableContent=
样品测试功能测试方法/设备设备型号相关参数
绝缘纸纤维结构光学显微镜BX53M放大倍数×800
元素分布电子场发射扫描电镜JSM-7800F放大倍数×1 000 000
抗张强度智能电子拉力机XLW(PC)

拉伸速度

5 mm/min

击穿电压圆柱型电极结构IEC 60243-1:2013—
相对介电常数宽频介电仪Concept 80电极直径：40 mm
绝缘油酸度酸碱滴定法Metrohm 848—
油中溶解气体气相色谱仪LX-3200E—
击穿电压全自动绝缘油介电强度测试仪SKJD-06击穿次数：6次
油中糠醛含量液相色谱仪LCMS 1260-6470进样精度：<0.25%
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样品各特征参量检测方法

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样品测试功能测试方法/设备设备型号相关参数
绝缘纸纤维结构光学显微镜BX53M放大倍数×800
元素分布电子场发射扫描电镜JSM-7800F放大倍数×1 000 000
抗张强度智能电子拉力机XLW(PC)

拉伸速度

5 mm/min

击穿电压圆柱型电极结构IEC 60243-1:2013—
相对介电常数宽频介电仪Concept 80电极直径：40 mm
绝缘油酸度酸碱滴定法Metrohm 848—
油中溶解气体气相色谱仪LX-3200E—
击穿电压全自动绝缘油介电强度测试仪SKJD-06击穿次数：6次
油中糠醛含量液相色谱仪LCMS 1260-6470进样精度：<0.25%
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样品类型相关系数尺度参数β/kV形状参数α
O1P10.98748.726 712.214 0
O1P20.97950.408 913.649 4
O2P10.95456.331 515.416 7
O2P20.96356.869 417.252 5
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不同样品组合中绝缘油的击穿电压统计参数

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样品类型相关系数尺度参数β/kV形状参数α
O1P10.98748.726 712.214 0
O1P20.97950.408 913.649 4
O2P10.95456.331 515.416 7
O2P20.96356.869 417.252 5
), ArticleFig(id=1217475259834486923, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199641485705572886, language=EN, label=Tab.4, caption=Statistical parameters of breakdown voltage of insulating paper in different combinations of samples, figureFileSmall=null, figureFileBig=null, tableContent=
样品类型相关系数尺度参数β/kV形状参数α
O1P10.94516.236 339.406 8
O1P20.96016.998 941.023 0
O2P10.94716.425 946.645 3
O2P20.95917.113 150.368 2
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不同样品组合中绝缘纸的击穿电压统计参数

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样品类型相关系数尺度参数β/kV形状参数α
O1P10.94516.236 339.406 8
O1P20.96016.998 941.023 0
O2P10.94716.425 946.645 3
O2P20.95917.113 150.368 2
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天然酯浸渍硅烷改性绝缘纸系统的长期热老化特性研究
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郑蝶吉 1 , 王哲铭 1 , 赵文彬 1 , 闵宇霖 2 , 彭伟 3 , 卢武 1
绝缘材料 | 绝缘技术 2023,56(7): 67-73
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绝缘材料 | 绝缘技术 2023, 56(7): 67-73
天然酯浸渍硅烷改性绝缘纸系统的长期热老化特性研究
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郑蝶吉1, 王哲铭1, 赵文彬1, 闵宇霖2, 彭伟3, 卢武1
作者信息
  • 1上海电力大学，电气工程学院，上海 200090
  • 2上海电力大学，环境与化学工程学院，上海 200090
  • 3国网上海市电力公司，上海 200122

    • 郑蝶吉（1999-），女（汉族），广东湛江人，硕士生，主要从事高电压试验技术以及油纸绝缘老化机理的研究。

通讯作者:

卢武（1991-），男（汉族），安徽亳州人，副教授，主要从事高电压试验技术、液体放电和生物电磁方面的研究。
Long-term thermal ageing characteristics of natural ester impregnated silane modified insulating paper system
Dieji ZHENG1, Zheming WANG1, Wenbin ZHAO1, Yulin MIN2, Wei PENG3, Wu LU1
Affiliations
  • 1School of Electric Engineering, Shanghai University of Electric Power, Shanghai 200090, China
  • 2School of Environmental and Chemical Engineering, Shanghai University of Electric Power, Shanghai 200090, China
  • 3State Grid Shanghai Municipal Electric Power Company, Shanghai 200122, China
出版时间: 2023-07-20 doi: 10.16790/j.cnki.1009-9239.im.2023.07.011
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摘要
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天然酯绝缘油作为一种高燃点、可降解的环保型液体电介质，被普遍认为是矿物油在电力变压器中的良好替代品。本文以改善天然酯-纸绝缘系统的电气性能和热老化性能为目标，利用硅烷偶联剂对纤维素绝缘纸进行表面改性，并对天然酯和传统矿物油分别浸渍普通绝缘纸和硅烷改性绝缘纸的油纸复合绝缘组合进行加速热老化试验，对比分析4种组合在热老化过程中油纸的老化特征参数。结果表明：经硅烷改性的绝缘纸在热老化过程中能保持较完整的纤维素三维网状结构，并可提升天然酯-纸系统的抗老化能力和电气性能。

天然酯  /  油纸绝缘  /  硅烷偶联剂  /  热老化  /  变压器

As a kind of environment friendly liquid dielectric with high ignition point and degradability, natural ester insulating oil is widely considered as a good substitute of mineral oil in power transformers. In order to improve the electrical and thermal ageing properties of natural ester-paper insulation system, the surface of cellulose insulation paper was modified by silane coupling agent, and the oil-paper composite insulation combinations of natural ester, traditional mineral oil, ordinary insulation paper, and silane modified insulation paper were conducted accelerated thermal ageing tests. The ageing characteristic paremeters of oil-paper during the thermal ageing of four combinations were compared and analyzed. The results show that the insulating paper modified by silane can maintain a relatively complete three-dimensional network structure of cellulose during thermal ageing, and improve the ageing resistance and electrical performance of the natural ester-paper system.

natural ester  /  oil-paper insulation  /  silane coupling agent  /  thermal ageing  /  transformer
郑蝶吉, 王哲铭, 赵文彬, 闵宇霖, 彭伟, 卢武. 天然酯浸渍硅烷改性绝缘纸系统的长期热老化特性研究. 绝缘材料, 2023 , 56 (7) : 67 -73 . DOI: 10.16790/j.cnki.1009-9239.im.2023.07.011
Dieji ZHENG, Zheming WANG, Wenbin ZHAO, Yulin MIN, Wei PENG, Wu LU. Long-term thermal ageing characteristics of natural ester impregnated silane modified insulating paper system[J]. Insulating Materials, 2023 , 56 (7) : 67 -73 . DOI: 10.16790/j.cnki.1009-9239.im.2023.07.011
正文
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0 引言
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绿色高效是“双碳”目标下以新能源为主体的新型电力系统的三大特征之一，采用环境友好型绝缘油替代传统矿物绝缘油已成为绿色电工装备技术研发领域的趋势。现有研究表明，使用天然酯替代矿物油可以在一定程度上提升油中绝缘纸的寿命[1]，然而天然酯电力变压器在长期运行过程中，油纸绝缘系统会受到电场、温度、水分等因素的共同作用而发生老化降解[2-4]，其中劣化的绝缘油可以采用过滤或更换新油等方法进行处理，而绝缘纸的老化是不可逆的，且难以进行绝缘纸更换操作[5-7]，因此天然酯变压器在长期使用过程中的绝缘纸老化问题仍需进一步研究。
调控纤维素绝缘纸的电气性能与传热性能是提高油纸绝缘强度的根本和关键[8-9]，目前国内外针对纤维素绝缘纸的电气性能与传热性能调控的方法主要分为纳米改性[10-13]、化学改性和物理掺杂。纳米改性技术是通过调控绝缘油和纤维素纸板的电导率和介电常数来改善油和纸中的电场分布不均匀程度，从而提高油纸绝缘的电气性能[14]。化学改性技术主要是通过氰乙基化[15]、乙酰化[16]等方法将纤维素中具有极强亲水性的羟基置换成更为稳定的化学基团，从而达到降低纤维素的亲水性并提高其抗热老化性能的目的[17-18]。物理掺杂技术则是通过添加热稳定剂与绝缘纸老化产生的低分子量酸发生中和反应，从而抑制纤维素的进一步降解[19]。现阶段国内外在探索调控绝缘纸电气性能与传热性能方面开展了大量研究，并取得了丰富的成果[14]，但在调控过程中增强油纸复合绝缘系统某一性能的同时不可避免地会对油纸绝缘系统的其他性能造成负面影响，特别是绝缘纸的抗张强度等力学性能会受到较大影响。因此亟需寻找一种既能提升油纸绝缘系统的电气性能和抗热老化性能，又能保证绝缘纸机械强度的改性方法。
烷氧基硅烷由于其能在水解后通过Si-O-Si键缩聚成一种三维结构的包覆层附着于材料表面，可以在不改变材料微观结构的情况下提高其力学性能和电气性能，已经被广泛应用于木材、棉织物或纺织品行业中以提升其耐热性能和抗张强度[18-20]。本研究利用烷氧基硅烷对纤维素绝缘纸表面进行改性，并对天然酯与改性前后的绝缘纸构成的复合绝缘进行加速热老化试验，研究天然酯-纸绝缘系统的绝缘性能、力学性能等特性在长期热老化条件下的变化规律，验证硅烷偶联剂对天然酯-纸绝缘抗老化性能的改性效果。
1 试验
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1.1 主要原材料
绝缘纸改性及热老化试验用到的相关材料以及试剂如表1所示。油-纸绝缘试品组合分为4组：矿物油+普通绝缘纸（以下简称O1P1）、矿物油+改性绝缘纸（以下简称O1P2）、天然酯+普通绝缘纸（以下简称O2P1）和天然酯+改性绝缘纸（以下简称O2P2）。
1.2 试验流程
1.2.1 绝缘纸改性处理
采用如图1(a)所示的表面改性方法对纤维素绝缘纸进行改性处理，具体改性过程如下：将绝缘纸裁剪后浸泡在含有摩尔体积浓度为0.2 M的3-氨基丙基-三乙氧基硅烷（APES）的500 mL无水乙醇溶液中，并加入5 mL正硅酸四丁酯（C16H36O4SiO）作为催化剂，浸泡时间为5天。硅烷偶联剂对纤维素改性的化学反应式如图1(b)所示，其改性机理可以分为两个步骤[21]：
（1）3-氨基丙基-三乙氧基硅烷通过水解得到相应的硅烷醇，释放出游离的醇分子，水解物质通过硅烷醇和纤维素羟基之间的氢键吸附在纤维素表面；
（2）通过化学缩合反应将Si-O-C键接枝到纤维素表面，形成硅氧烷桥，并在纤维素表面构成三维网络的包覆层。
为了验证3-氨基丙基-三乙氧基硅烷的改性效果，对绝缘纸表面形貌和元素分布进行检测，结果如图1(c)所示，可以明显观察到经3-氨基丙基-三乙氧基硅烷改性后的绝缘纸纤维颜色加深，边界轮廓更明显，并且在SEM能谱图以及元素含量变化表可以看到，通过改性后绝缘纸表面存在大量的Si和N元素，表明改性后绝缘纸表面存在一定的Si-O-Si键，而且在Si-O-Si三维网络表面成功接枝了部分-NH2基团。
1.2.2 加速热老化试验方案
为了更好地模拟实际变压器中油纸复合绝缘系统的老化过程，本文参照IEC 62332-2:2014的相关要求，设计了如下样品预处理与热老化试验流程：
（1）将尺寸均为15 cm×15 cm×0.15 mm的普通和改性纤维素绝缘纸样品与绝缘纸板混合，分别放入大容量磨口玻璃瓶中，置于真空烘箱（温度为90℃，压强为50 Pa）中进行48 h干燥处理，保证绝缘纸和绝缘纸板样品中的含水量控制在0.5%以内，经过干燥处理后，每个玻璃瓶中绝缘纸样品质量为20 g，绝缘纸板样品质量为80 g。
（2）将同样经过脱气和干燥处理后的780 mL绝缘油与步骤（1）中100 g绝缘纸和绝缘纸板样品混合，在40℃的真空环境中进行24 h的充分浸渍。
（3）根据上述IEC标准相关要求，裁剪出若干个表面积为9.8 cm2（尺寸为0.05 cm×4.65 cm×2 cm）的铜片以及钢片，并按照钢片与铜片各1个的数量，分别放入步骤（2）中装有浸渍完全的油-纸绝缘样品的磨口玻璃瓶中。
（4）将装有油-纸绝缘样品以及固体金属材料的玻璃瓶在氮气环境中抽真空再进行密封。
（5）将密封完成的玻璃瓶置于温度为145℃的老化烘箱中进行为期35天的热老化试验，期间定期取样进行特征参数检测，测量次数均在3次以上，取测量平均值作为测量结果。
（6）将取出的样品静置至室温，用无水乙醇充分清洗纸张表面的油渍后烘干密封存放备用。
1.3 测试参数与方法
在热老化过程中，对4种油纸绝缘组合进行定期检测纤维表面的微观形貌及油纸老化特征参数，相关检测方法如表2所示。
本文参照IEC 60243-1:2013相关要求，使用如图2所示的试验装置对纤维素绝缘纸的工频击穿电压进行测试。选用规格为50 kVA/50 kV的测试变压器作为电压输出，采用金属支架以及密封性较好的不锈钢腔体进行电极的固定以及绝缘油的盛放。击穿试验使用的电极装置由两个黄铜圆柱体组成，电极的直径与高度均为25 mm。测量过程中对绝缘纸样品施加上升速率为500 V/s的工频交流电压，直至发生绝缘纸样品短时快速击穿。
2 结果与讨论
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2.1 绝缘油老化特征参数对比
2.1.1 油中酸值含量
图3为不同油纸绝缘样品组合中测得的油中酸值随老化时间的变化趋势。从图3中可知，两种天然酯-纸绝缘样品的油中酸值均随着老化时间的增加而显著增大，这是由于天然酯在老化过程中会产生大量易溶于油中的高分子量酸，而矿物油老化后烃类分解产生的碳氧酸等属于低分子量酸，易被吸附于绝缘纸表面，导致矿物油中酸值含量较低。同时，经过35天热老化后，含有普通绝缘纸的天然酯酸值是浸渍改性绝缘纸的天然酯酸值的两倍以上，这是因为3-氨基丙基-三乙氧基硅烷呈弱碱性，可以与老化过程中油中的氢离子发生中和反应，其中氨基氮上的孤电子对会与氢离子结合形成一个共价键，氮从三价变成胺盐，导致浸渍改性绝缘纸的天然酯酸值较低[7]。
2.1.2 油中糠醛浓度
变压器绝缘油中的呋喃成分均来自于绝缘纸分解，因此，通过对油中糠醛浓度的监测可以有效的观察变压器内固体绝缘材料的老化状态。图4为不同油纸绝缘样品组合中的油中糠醛浓度随老化时间的变化趋势。
从图4可以看出，在热老化初期和中期，所有样品组合的油中糠醛浓度均随老化时间的增加而显著增大，其中天然酯中糠醛浓度明显小于相同条件下的矿物油中糠醛浓度，这是由于天然酯中的添加剂[22]会消耗一定量的糠醛，而且天然酯中的含水饱和度高于矿物油，造成纤维素中的水分向天然酯迁移，显著降低了固体绝缘的降解速率。在热老化后期，各样品组合中糠醛浓度变化较小甚至出现轻微下降的趋势，这是由于随着老化时间的增加，油纸中的部分化合物会与糠醛发生反应从而消耗部分糠醛。同时随着老化时间的增加，纤维素降解速率会有所下降，糠醛的生成速度也减慢，当其生成速率接近并低于消耗速率时，就会发生波动并出现下降的趋势。相比于天然酯-普通纸绝缘系统，天然酯-改性纸绝缘系统中的油中糠醛产量减少了15%，间接证明了硅烷改性对于延缓天然酯-纸绝缘老化的积极作用。
2.1.3 油中溶解气体
油纸复合绝缘系统在热老化过程中会产生各种特征气体，其中CO2与CO含量比值可以作为反映绝缘纸老化的表征量，甲烷与乙炔的含量变化则可作为绝缘油老化的表征量。依照IEC 60567-2011相关要求，对热老化过程中油中溶解气体进行定期检测，结果如图5所示。由于C2H2与H2属于放电时的特征气体，没有出现明显变化，因此文中没有进行单独分析。
从图5(a)可以看出，随着热老化的进行，所有样品组合的油中CO2与CO含量比值均先快速上升至最大值，然后缓慢降低并逐渐趋于稳定。对使用同一种绝缘油的样品组合而言，含改性绝缘纸组合的油中CO2与CO含量比值的峰值比含普通绝缘纸的组合更大，且到达峰值所需要的老化时间更长。这一现象间接证明了在相同的热老化条件下，改性绝缘纸的降解程度和速率明显低于普通绝缘纸。由图5(b)和图5(c)可知，含有改性绝缘纸的绝缘油溶解的烃类气体含量均明显低于含有普通绝缘纸的绝缘油，而且随着老化程度的加深，这两种情况下低分子烃类气体的含量差异逐渐增大。这一现象间接证明了在相同的热老化条件下，含有改性绝缘纸的组合中绝缘油老化程度和速率更低。在热老化35天时，相比于矿物油-普通纸绝缘系统，天然酯-改性纸绝缘系统中油中溶解烃类气体如乙烯以及甲烷的生成量下降了40%以上，间接证实了硅烷改性对于延缓天然酯-纸绝缘老化的积极作用。
2.1.4 绝缘油的击穿电压
依照IEC 60156-2018相关要求，利用2.5 mm的球型电极间隙对绝缘油进行工频击穿电压测试。图6为4种不同油纸绝缘样品组合中绝缘油在老化过程中的击穿电压变化趋势图。从图6可以看出，在整个加速热老化过程中，天然酯和矿物油的击穿电压均保持在45～60 kV浮动，没有出现持续下降或者增长趋势，这与先前的研究[23-24]结论一致。且在相同老化条件下，天然酯和矿物油的击穿电压无明显差异。对使用同一种绝缘油的样品组合而言，将普通绝缘纸替换为改性绝缘纸并不会显著影响绝缘油的击穿特性，这证明使用硅烷改性技术对绝缘纸进行表面调控的同时，并不会降低绝缘油的电气性能。
图7为热老化过程中绝缘油的击穿电压威布尔分布图，图中的离散点为击穿试验实际的测试值，中间直线为威布尔（Weibull）分布拟合曲线，两边的曲线为95%置信区间分界线。4种不同油纸绝缘样品组合的击穿电压统计参数如表3所示，其中尺度参数β对应绝缘油击穿电压的大小，形状参数α说明实际试验测量数据的分散情况。从表3可以看出，4组数据的相关系数均大于0.94，说明击穿电压的数据符合两参数威布尔分布。而且在老化过程中，4种组合中O2P2组的数据分散性最小。
2.2 绝缘纸老化特征参数
2.2.1 绝缘纸的抗张强度
抗张强度是横向绝缘纸机械强度的重要指标，变压器在长期运行过程中会受到各种应力的作用，因此在老化过程中机械强度的保持显得十分关键。图8为热老化过程中绝缘纸抗张强度的变化趋势。
从图8可以看出，在相同试验条件下，浸渍天然酯的绝缘纸拉伸强度明显大于浸渍矿物油的绝缘纸拉伸强度，证明天然酯能在一定程度上减缓纤维素的降解速度。这是由于天然酯的含水量饱和度较高，能促使纤维素中的水分向油中迁移。同时，矿物油在老化过程中会产生易被绝缘纸吸收的低分子量酸，天然酯老化过程中产生的高分子量油酸不仅不会促进纤维素纸的降解，而且能与纤维素中的-OH基团发生酯化反应，使得纤维素结构更加稳定。
浸渍天然酯的两种绝缘纸中，在经过35天的热老化之后，普通绝缘纸的抗张强度下降了47.8%，而改性绝缘纸仅下降了10%左右，其表现出更好的拉伸性能。这是由于硅烷偶联剂发生化学缩合后形成的硅氧烷桥有助于纤维素表面形成硅氧烷桥包覆层，而且硅烷中的有机官能团能提高硅烷与纤维素的相容性，增强基体与材料之间的界面粘合力，强化了纤维素的大分子链。另外，氨基可在老化过程中与水分发生反应，降低水分对于纤维素纸的影响，延缓纤维素绝缘纸抗张强度的下降速率。因此运用硅烷偶联剂对纤维素纸进行改性处理可以显著提升纤维素绝缘纸的拉伸性能。
2.2.2 绝缘纸的击穿电压
4种样品组合中绝缘纸击穿电压随老化时间的变化趋势如图9所示。
从图9可以看出，所有样品组合中纤维素纸的击穿电压随老化时间增加均呈现出下降的趋势。与浸渍矿物油中老化的绝缘纸不同的是，浸渍天然酯中的绝缘纸击穿电压在老化前期出现大幅波动。当热老化时间达到35天时，浸渍天然酯中的改性绝缘纸击穿电压相比普通绝缘纸提高了37.8%，这是由于硅烷经水解后形成的Si-O-Si网络结构裹覆于纤维素分子表面，使得放电通到沿着包覆层表面发展，间接增大了放电距离，从而延缓了绝缘材料的击穿。上述现象充分表明对绝缘纸进行硅烷改性处理能显著提高其电气强度。
4种不同油纸绝缘样品组合热老化过程中绝缘纸的交流击穿电压数据威布尔分布如图10所示，其威布尔参数如表4所示。从表4可以看出，4组数据的相关系数均大于0.94，说明试验测试的击穿电压数据符合威布尔分布。改性绝缘纸的形状参数α以及尺度参数β稍有改善，其中O2P2的组合击穿电压分布较窄，对应于形状参数α较大。
2.2.3 绝缘纸的介电性能
图11为加速热老化条件下4种油纸绝缘样品组合中绝缘纸在工频处的介电常数以及介质损耗因数变化规律。从图11中可以看出，两种绝缘纸的介电常数以及介质损耗因数均随着老化时间增加而增大。同一老化条件下，相比于普通绝缘纸，改性绝缘纸始终保持较低的介电常数和介质损耗因数，且随着老化时间的增加，改性前后的绝缘纸介电常数差值出现缓慢增大的趋势。在热老化35天时，浸渍天然酯中的改性绝缘纸相对介电常数相比于普通绝缘纸减少了18.9%，介质损耗因数相比于普通绝缘纸减少了9.2%，证明经硅烷改性的天然酯-纸绝缘系统中绝缘纸的介电性能在老化过程中得到了显著提升。
3 结论
收起
（1）使用硅烷改性技术可以有效提升油纸绝缘系统中绝缘油的抗老化能力。对使用同一种绝缘油的样品组合而言，将普通绝缘纸替换为改性绝缘纸并不会显著影响绝缘油的击穿特性，证明使用硅烷改性技术在增强绝缘油抗老化能力的同时，并不会降低绝缘油的电气性能。
（2）硅烷偶联剂对天然酯-纸的绝缘性能具有良好的改性效果，可以在不降低绝缘油电气性能的条件下，调控绝缘纸的理化性能和电气性能，显著提升复合绝缘系统中固体绝缘材料的电气强度和力学性能，并延缓油纸绝缘的老化降解速度。
基金
收起
  • 国家自然科学基金资助项目(51707113)
  • 上海市“晨光计划”项目(21CGA63)
文献
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2023年第56卷第7期
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doi: 10.16790/j.cnki.1009-9239.im.2023.07.011
  • 接收时间：2022-08-02
  • 首发时间：2025-11-24
  • 出版时间：2023-07-20
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  • 收稿日期：2022-08-02
  • 修回日期：2022-10-01
基金
国家自然科学基金资助项目(51707113)
上海市“晨光计划”项目(21CGA63)
作者信息
    1上海电力大学，电气工程学院，上海 200090
    2上海电力大学，环境与化学工程学院，上海 200090
    3国网上海市电力公司，上海 200122

通讯作者:

卢武（1991-），男（汉族），安徽亳州人，副教授，主要从事高电压试验技术、液体放电和生物电磁方面的研究。
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2种不同金属材料的力学参数
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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
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