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Article(id=1190369199278096541, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1190365079976640655, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2025.07.016, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1727539200000, receivedDateStr=2024-09-29, revisedDate=1730563200000, revisedDateStr=2024-11-03, acceptedDate=null, acceptedDateStr=null, onlineDate=1761735733097, onlineDateStr=2025-10-29, pubDate=1752940800000, pubDateStr=2025-07-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1761735733097, onlineIssueDateStr=2025-10-29, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1761735733097, creator=13701087609, updateTime=1761735733097, updator=13701087609, issue=Issue{id=1190365079976640655, tenantId=1146029695717560320, journalId=1149653034449285133, year='2025', volume='58', issue='7', pageStart='1', pageEnd='150', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=1, specialIssue=null, createTime=1761734750980, creator=13701087609, updateTime=1761735924323, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1190370001430348320, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1190365079976640655, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1190370001430348321, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1190365079976640655, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=136, endPage=142, ext={EN=ArticleExt(id=1190369199563309216, articleId=1190369199278096541, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Comparative study on surface modification of two types of epoxy resins: charge accumulation suppression and flashover performance improvement, columnId=1190369198472794288, journalTitle=Insulating Materials, columnName=Insulation Technology, runingTitle=null, highlight=

In order to suppress surface charge accumulation on the insulation in HVDC wall bushings and improve their flashover performance, the epoxy resins used for the supporting insulator and the tube body were surface fluorinated under the same conditions using a fluorine/nitrogen mixture. The results show that fluorine atoms are introduced into the surface layers of two types of epoxy resins by the substitution for hydrogen atoms and the addition to carbon-carbon double bonds, forming C-F bonds. The fluorination is accompanied by chain breaking, which mainly occurs at the crosslinking sites. Due to the difference in epoxy value, two types of epoxy resins show different crosslinking densities. SEM imaging shows that they have different thicknesses of the fluorinated layer and surface morphologies. Surface potential decay and surface conductivity measurements reveal that the fluorination increases surface conductivity of two types of epoxy resins and inhibits their surface charge accumulation to different degrees. Flashover tests show that their DC flashover voltages are significantly increased by the fluorination to almost the same degree.

, articleAbstract=

In order to suppress surface charge accumulation on the insulation in HVDC wall bushings and improve their flashover performance, the epoxy resins used for the supporting insulator and the tube body were surface fluorinated under the same conditions using a fluorine/nitrogen mixture. The results show that fluorine atoms are introduced into the surface layers of two types of epoxy resins by the substitution for hydrogen atoms and the addition to carbon-carbon double bonds, forming C-F bonds. The fluorination is accompanied by chain breaking, which mainly occurs at the crosslinking sites. Due to the difference in epoxy value, two types of epoxy resins show different crosslinking densities. SEM imaging shows that they have different thicknesses of the fluorinated layer and surface morphologies. Surface potential decay and surface conductivity measurements reveal that the fluorination increases surface conductivity of two types of epoxy resins and inhibits their surface charge accumulation to different degrees. Flashover tests show that their DC flashover voltages are significantly increased by the fluorination to almost the same degree.

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为了抑制高压直流穿墙套管内绝缘的表面电荷积聚、改善其闪络性能，使用氟/氮混合气体在相同条件下对套管支撑绝缘子用环氧树脂和管体用环氧树脂进行了表面氟化改性对比研究。结果表明：氟原子通过取代氢原子和加成碳-碳双键分别引入到两种环氧树脂的表层并形成C-F键。氟化伴随有断链发生，断链主要发生在交联点。由于环氧值的不同，两种环氧树脂显现出不同的交联密度。SEM图像显示两种环氧树脂有不同的氟化层厚度和表面形貌。表面电位衰减测试和表面电导率测量表明氟化不同程度地增加了两种环氧树脂的表面电导率，抑制了它们的表面电荷积聚。闪络试验表明氟化显著地提高了两种环氧树脂的直流闪络电压，且提升幅度相当。

, articleAbstract=

为了抑制高压直流穿墙套管内绝缘的表面电荷积聚、改善其闪络性能，使用氟/氮混合气体在相同条件下对套管支撑绝缘子用环氧树脂和管体用环氧树脂进行了表面氟化改性对比研究。结果表明：氟原子通过取代氢原子和加成碳-碳双键分别引入到两种环氧树脂的表层并形成C-F键。氟化伴随有断链发生，断链主要发生在交联点。由于环氧值的不同，两种环氧树脂显现出不同的交联密度。SEM图像显示两种环氧树脂有不同的氟化层厚度和表面形貌。表面电位衰减测试和表面电导率测量表明氟化不同程度地增加了两种环氧树脂的表面电导率，抑制了它们的表面电荷积聚。闪络试验表明氟化显著地提高了两种环氧树脂的直流闪络电压，且提升幅度相当。

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安振连（1963-），男（汉族），江苏徐州人，教授，主要从事高压绝缘和导体材料的表层改性和相关介电性能等研究。
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杨知非（1990-），男（汉族），河南许昌人，工程师，博士，主要从事变压器类设备绝缘状态检测、监测、运行可靠性评估的研究；

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杨知非（1990-），男（汉族），河南许昌人，工程师，博士，主要从事变压器类设备绝缘状态检测、监测、运行可靠性评估的研究；

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杨知非（1990-），男（汉族），河南许昌人，工程师，博士，主要从事变压器类设备绝缘状态检测、监测、运行可靠性评估的研究；

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试样HMFHMXRFXR
表面电导率/S<6.2×10-202.4×10-16<6.2×10-201.7×10-15
), ArticleFig(id=1190960555008606522, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1190369199278096541, language=CN, label=表1, caption=

两种环氧试样氟化前后在室温下高纯氮气中的表面电导率

, figureFileSmall=null, figureFileBig=null, tableContent=
试样HMFHMXRFXR
表面电导率/S<6.2×10-202.4×10-16<6.2×10-201.7×10-15
), ArticleFig(id=1190960555105075515, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1190369199278096541, language=EN, label=Table 2, caption=Statistical results of DC flashover voltages of the virgin and surface fluorinated epoxy samples, figureFileSmall=null, figureFileBig=null, tableContent=
试样数据数特征闪络电压V0/kV形状因子β平均闪络电压/kV
HM2039.9954.1339.62
FHM2043.4252.9342.99
XR2040.0158.6439.67
FXR2043.4549.4843.01
), ArticleFig(id=1190960555176378684, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1190369199278096541, language=CN, label=表2, caption=

环氧原试样和表面氟化试样的直流闪络电压统计结果

, figureFileSmall=null, figureFileBig=null, tableContent=
试样数据数特征闪络电压V0/kV形状因子β平均闪络电压/kV
HM2039.9954.1339.62
FHM2043.4252.9342.99
XR2040.0158.6439.67
FXR2043.4549.4843.01
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两种环氧树脂表面改性的比较研究：电荷积聚抑制与闪络性能改善
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杨知非 1 , 董曼玲 1 , 詹振宇 1 , 王鑫 2 , 郑含博 3 , 安振连 2
绝缘材料 | 绝缘技术 2025,58(7): 136-142
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绝缘材料 | 绝缘技术 2025, 58(7): 136-142
两种环氧树脂表面改性的比较研究：电荷积聚抑制与闪络性能改善
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杨知非1, 董曼玲1, 詹振宇1, 王鑫2, 郑含博3, 安振连2
作者信息
  • 1.国网河南省电力公司电力科学研究院，河南 郑州 450099
  • 2.同济大学 电气工程系，上海 201804
  • 3.广西大学 电气工程学院，广西 南宁 530004

    • 杨知非（1990-），男（汉族），河南许昌人，工程师，博士，主要从事变压器类设备绝缘状态检测、监测、运行可靠性评估的研究；

通讯作者:

安振连（1963-），男（汉族），江苏徐州人，教授，主要从事高压绝缘和导体材料的表层改性和相关介电性能等研究。
Comparative study on surface modification of two types of epoxy resins: charge accumulation suppression and flashover performance improvement
Zhifei YANG1, Manling DONG1, Zhenyu ZHAN1, Xin WANG2, Hanbo ZHENG3, Zhenlian AN2
Affiliations
  • 1. State Grid Henan Province Electric Power Corporation Research Institute, Zhengzhou 450099, China
  • 2. Department of Electrical Engineering, Tongji University, Shanghai 201804, China
  • 3. College of Electrical Engineering, Guangxi University, Nanning 530004, China
出版时间: 2025-07-20 doi: 10.16790/j.cnki.1009-9239.im.2025.07.016
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摘要
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为了抑制高压直流穿墙套管内绝缘的表面电荷积聚、改善其闪络性能，使用氟/氮混合气体在相同条件下对套管支撑绝缘子用环氧树脂和管体用环氧树脂进行了表面氟化改性对比研究。结果表明：氟原子通过取代氢原子和加成碳-碳双键分别引入到两种环氧树脂的表层并形成C-F键。氟化伴随有断链发生，断链主要发生在交联点。由于环氧值的不同，两种环氧树脂显现出不同的交联密度。SEM图像显示两种环氧树脂有不同的氟化层厚度和表面形貌。表面电位衰减测试和表面电导率测量表明氟化不同程度地增加了两种环氧树脂的表面电导率，抑制了它们的表面电荷积聚。闪络试验表明氟化显著地提高了两种环氧树脂的直流闪络电压，且提升幅度相当。

环氧树脂  /  环氧值  /  直接氟化  /  表面物化特征  /  表面电性能  /  表面电荷积聚  /  直流闪络

In order to suppress surface charge accumulation on the insulation in HVDC wall bushings and improve their flashover performance, the epoxy resins used for the supporting insulator and the tube body were surface fluorinated under the same conditions using a fluorine/nitrogen mixture. The results show that fluorine atoms are introduced into the surface layers of two types of epoxy resins by the substitution for hydrogen atoms and the addition to carbon-carbon double bonds, forming C-F bonds. The fluorination is accompanied by chain breaking, which mainly occurs at the crosslinking sites. Due to the difference in epoxy value, two types of epoxy resins show different crosslinking densities. SEM imaging shows that they have different thicknesses of the fluorinated layer and surface morphologies. Surface potential decay and surface conductivity measurements reveal that the fluorination increases surface conductivity of two types of epoxy resins and inhibits their surface charge accumulation to different degrees. Flashover tests show that their DC flashover voltages are significantly increased by the fluorination to almost the same degree.

epoxy resin  /  epoxy value  /  direct fluorination  /  surface physicochemical characteristics  /  surface electrical properties  /  surface charge accumulation  /  DC flashover
杨知非, 董曼玲, 詹振宇, 王鑫, 郑含博, 安振连. 两种环氧树脂表面改性的比较研究：电荷积聚抑制与闪络性能改善. 绝缘材料, 2025 , 58 (7) : 136 -142 . DOI: 10.16790/j.cnki.1009-9239.im.2025.07.016
Zhifei YANG, Manling DONG, Zhenyu ZHAN, Xin WANG, Hanbo ZHENG, Zhenlian AN. Comparative study on surface modification of two types of epoxy resins: charge accumulation suppression and flashover performance improvement[J]. Insulating Materials, 2025 , 58 (7) : 136 -142 . DOI: 10.16790/j.cnki.1009-9239.im.2025.07.016
正文
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0 引言
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我国能源分布与地区经济发展的极不平衡决定了我国必须大范围地调配电力资源，凸显了我国对输送容量大、输电距离远、输电损耗小、控制灵活便捷的特高压直流输电技术的迫切需求。在高压直流输电工程中必须使用穿墙套管连接直流场和换流变压器，直流穿墙套管被比作系统的咽喉，其可靠性关系到整个输电系统的安全稳定运行。由于传统的油浸纸电容式结构的穿墙套管存在燃烧和爆炸的风险，新建的换流站的直流穿墙套管均为环氧芯体/SF6气体复合绝缘结构或纯SF6气体绝缘结构。与直流GIS/GIL的绝缘子表面易于积聚电荷类似，直流穿墙套管的环氧芯体或支撑绝缘子也容易积聚电荷。此外，由于穿墙套管的环氧管体为绝缘体，电荷还会在套管管体内壁上积聚。因此，直流穿墙套管的电荷积聚问题比GIS/GIL的情形更加复杂。这些绝缘表面积聚的电荷会畸变电场，可能引起套管内部闪络或击穿[1-3]。
绝缘子的表面电荷积聚主要起因于其体传导、表面传导及电极放电引起的气相传导[4-6]。每种电荷积聚机制的具体贡献取决于内因（绝缘自身和表面的电性能、绝缘和电极的形状等）和外因（施加的电压和气氛等）[6]。提高绝缘子的体电阻率或体绝缘性能可阻止电荷经体内到达绝缘子表面[7]，采用非线性电导材料对绝缘子进行改性也能实现对其表面电荷的调控[8]，合理地设置屏蔽电极和悬浮电极、优化绝缘子形状同样能有效降低电极放电，减少经气相到达绝缘子的电荷[9-13]。而绝缘子表面传导对其电荷积聚的影响复杂，并非表面电阻率越大，电荷积聚越少；相反，适当地减小表面电阻率有利于抑制电荷积聚，提高直流闪络电压[4,14]。等离子体处理或等离子体气相沉积可适当提高环氧绝缘的表面传导，抑制其表面电荷积聚，经处理后其直流闪络性能得到明显的改善[15-17]。半导电性或非线性导电的物理涂层同样由于能抑制环氧绝缘的电荷积累，可以提高其闪络电压[4,18]。然而，由于某些原因，这些表面改性方法至今尚未得到实际应用。直接氟化作为一种极为有效的材料表面化学改性方法被用于抑制环氧绝缘的表面电荷积聚，以改善其直流闪络性能[19]，现已取得了不少有益的成果[20-24]。
近年来，直接氟化方法已应用到GIS环氧绝缘子的表面改性，使其直流闪络性能显著提升[25]。研究表明，绝缘子氟化层的性能与其材料本身有关[26]，而至今几乎没有关于环氧树脂的表面氟化改性与材料本身关联性的深入研究。为了有效抑制高压直流穿墙套管支撑绝缘子和管体的表面电荷积聚，改善其闪络性能，本文对绝缘子用环氧树脂和管体用环氧树脂进行直接氟化改性，对比研究氟化层的物化特征和基本电性能，探究直接氟化对环氧树脂直流闪络性能的提升作用。
1 试验
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1.1 试样制备与直接氟化
本文分别使用套管支撑绝缘子用树脂原料和管体用树脂原料制备支撑绝缘环氧试样和管体环氧试样。这两种试样均为双酚A二缩水甘油醚（DGEBA）环氧树脂和甲基四氢苯酐（MTHPA）固化体系。支撑绝缘环氧试样的原料为亨斯迈先进材料公司生产的环氧值为0.26 mol/100 g的CT5531型环氧树脂和HY5533-1型酸酐固化剂，配方中树脂和固化剂的质量比为100∶48，固化条件为130℃、28 h。管体环氧试样的原料为上海雄润树脂有限公司生产的环氧值为0.52 mol/100 g的HE-3301A型环氧树脂和HE-3301B型酸酐固化剂，配方中树脂和固化剂的质量比为100∶85，固化条件为120℃、10 h。两种环氧试样的厚度均为2 mm，制备过程相似。在实验室首先将树脂和固化剂均匀混合、脱气，然后真空浇注入不锈钢模具中，在相应固化条件下固化，得到环氧试样。
两种环氧试样的直接氟化在实验室反应釜中在相同的条件下进行。使用的反应气为氟气体积浓度为12.5%的氟气/氮气混合气体，氟化压力、温度、时间分别为0.1 MPa、55℃、30 min。下文中为了简化记述，将由亨斯迈原料制备的支撑绝缘环氧试样和由雄润原料制备的管体环氧试样分别称为试样HM和试样XR，而它们氟化后得到的氟化试样分别被称为试样FHM和试样FXR。
1.2 测试与表征
1.2.1 氟化层的物化特征表征
采用衰减全反射红外光谱法（ATR-IR）分析两种环氧试样氟化前后的表层化学结构。使用扫描电子显微镜（SEM）观察氟化引起的试样表面形貌变化，确定所形成的氟化层厚度，为降低入射电子束在试样表面积聚对成像的影响，测试前在SEM试样上溅射一层薄的金层。
1.2.2 表面电导率与表面电位衰减测量
采用标准三电极法测量表面电导率，评价两种环氧树脂氟化前后的表面基本电学性能；通过表面电位衰减测量评价直接氟化对两种环氧树脂表面电荷积聚的影响。考虑到GIS/GIL中的干燥SF6气氛，为避免环境湿度的影响，表面电导率和表面电位衰减测量均在充有0.1 MPa高纯氮气的接地不锈钢桶中进行，桶内的温度为室温。表面电导率测量数据在施加500 V直流电压6 min时读取。表面电位测量使用图1所示的试样电晕充电和表面电位测量系统。首先采用栅控电晕充电法对已在不锈钢桶中静置60 min以上的试样进行电晕充电，充电结束后将试样立即（5 s的滞后）转至静电探头下方，表面电位由静电电位计（Monroe 244A型）测得，并通过多功能电表（Keithley 6514型）将数据传递到计算机存储。
1.2.3 直流闪络试验
使用图2所示的指形电极/片状试样组合评价两种环氧试样氟化前后的直流闪络性能。将两个半径为30 mm的完全相同的304不锈钢指形电极固定在试样上，两电极尖端的间距为10 mm。闪络试验在充有0.1 MPa SF6气体的不锈钢试验腔中进行。当试样在腔中静置60 min以上时，对其施加直流电压，直流电压的升压方式为阶梯式：首先将电压匀速（1.6 kV/s）升至第一个台阶（36.0 kV），随后的每个台阶高均为1.0 kV，所有台阶的持续时间均为5 min，直至发生闪络。直流高压由阻容分压器（1 000∶1）测量。对每种氟化或未氟化试样取20个样品进行闪络试验。
2 实验结果与分析
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2.1 氟化层的物化特征
图3为两种环氧试样氟化前后的ATR-IR图谱。从图3可以看出，氟化前，试样HM和试样XR的ATR-IR图谱均显示了酸酐固化双酚A型环氧树脂的典型吸收峰[21]：O-H伸缩振动（3 500 cm-1）、亚甲基和甲基的C-H伸缩振动（2 964～2 874 cm-1）、酯基中C=O伸缩振动（1 730 cm-1）、苯环中C=C伸缩振动（1 508 cm-1、1 608 cm-1）、甲基不对称变形振动（1 458 cm-1）、苯环的C-H面内弯曲振动（1 178 cm-1）、脂肪醚C-O-C伸缩振动（1 042、1 230、1 290 cm-1）、苯环的C-H面外弯曲振动（827 cm-1）。然而，由于原料不同，这两种环氧试样在特征吸收峰的相对强度上存在明显的不同，如原料环氧值较高的试样XR比试样HM有明显较强的C=O相对吸收强度，这也表明试样XR比试样HM有更高的固化交联密度。
从图3还可以看出，55℃、30 min氟化使酸酐固化双酚A环氧树脂的所有特征吸收峰显著降低甚至消失，在940～1 340 cm-1波数范围内出现了强的C-F吸收带。这表明氟原子通过取代氢原子和加成苯环进入环氧树脂表层。在氟化试样的ATR-IR图谱中，伴随原C=O吸收峰的显著降低，在高波数侧（1 767 cm-1）出现了新的C=O吸收峰。C=O吸收峰的变化实际是由于氟同时“攻击”了环氧固化交联网络中的其他化学键，尤其是交联点（酯基中）的 C-O键，形成了易于在大气中水解为羧基的氟化酰基（-COF）[24]。这个新C=O吸收峰不仅有水解生成的羧基的贡献，还有伴随生成的交联产物的贡献。需要指出的是，在红外的分析精度内两种氟化试样的ATR-IR图谱没有本质的不同，但这不意味着它们的表面化学结构相同。另外，与试样FHM的ATR-IR图谱相比，试样FXR的ATR-IR图谱中可明显地看到试样XR的特征吸收峰，这意味着试样FXR的氟化层应比试样FHM薄许多。
图4为两种表面氟化环氧试样断面和表面的SEM图像。
从图4(a)和(b)可以看出，正如根据ATR-IR分析所推测的，试样FXR的氟化层比试样FHM的氟化层薄许多，前者厚度仅为后者厚度的三分之一。这是因为试样HM的环氧原料比试样XR具有较低的环氧值或较大的分子量，所以试样HM具有较低的交联密度，氟气更容易进入其内部形成较厚的氟化层。从图4(c)可以看出，氟化没有引起套管管体XR环氧试样表面发生明显的变化，放大4万倍下试样FXR的表面仍如同原试样或氟化前（未显示）一样平整；而从图4(d)可见，相同放大倍数下的图像显示氟化使套管支撑绝缘HM环氧试样表面出现了凹坑和裂缝，这再次说明氟化层的物理特征与环氧材料本身有关。环氧试样表面形貌的变化是氟原子引入和断链引起的表层内应力及氟化反应放热等综合作用的结果。通常来说，由于氟化易引起交联处C-O断键，交联密度高的环氧试样氟化时表面易出现裂纹[27]。然而，交联密度较高的XR环氧试样氟化后表面裂纹反而较少，这一异常现象意味着氟化引起环氧试样表面形貌的变化不仅与树脂原料的环氧值有关，还与其他方面有关。从树脂生产厂家获悉，该套管管体用XR环氧树脂为“接枝改性的双酚A二缩水甘油醚”，氟化后试样表面几乎不出现裂纹应该是由于双酚A二缩水甘油醚接枝改性的结果。
2.2 氟化层的基本电性能与表面电荷积聚
如1.2.2节中所述，为避免环境湿度对氟化层基本电性能测量和表面电位衰减测量的影响，这些测量均在充有0.1 MPa高纯氮气的接地不锈钢桶中进行。表1给出了两种环氧试样氟化前后在室温下的表面电导率测量结果。从表1可以看出，两种环氧试样氟化前在高纯氮气中均具有极低的无水分吸附影响的本征表面电导率（低于仪器的测量下限6.2×10-20 S），氟化显著地增加了它们的表面电导率，管体XR环氧试样表面电导率的增幅比支撑绝缘HM环氧试样更大，试样FXR的表面电导率比试样FHM高了约一个数量级。
图5为两种环氧试样表面氟化前后在室温下高纯氮气中的表面电位衰减。在表面电位测量前，试样在-10 kV的针电压和-2 kV的栅电压下被充电了5 min。从图5可以看出，由于这两种环氧树脂具有优异的体绝缘和表面绝缘，这两种未氟化试样的表面电位在室温下的3 000 s观测时间内几乎不衰减，具有与栅电压相近的表面电位。然而，与未氟化试样相比，这两种氟化试样的表面电位表现出明显或快速的衰减。直接氟化是表面修饰方法，不会改变材料的体性质，氟化试样的表面电位衰减肯定是由于表面传导，试样FXR比试样FHM更快的表面电位衰减显然是由于表1所示前者具有较高的表面电导率。表面电位衰减结果表明直接氟化有效地抑制了两种环氧绝缘的表面电荷积聚，尤其是套管管体XR环氧绝缘的电荷积聚抑制效果更加显著。
表层中引入电负性最强的氟原子会成为化学深陷阱中心，而氟原子引入产生的结构缺陷及断键导致的结构紊乱等会成为物理浅陷阱[19]。因此，直接氟化引起环氧树脂表面传导的增加是其表层结构变化和组成变化或物理浅陷阱和化学深陷阱相互竞争的结果[19]。试样FXR比试样FHM具有更高的表面电导率或更快的表面电位衰减是由于其氟化层的结构紊乱度更高或浅陷阱更多，这主要是因为如图3中红外结果所述，管体XR环氧树脂比支撑绝缘HM环氧树脂的交联密度高，交联点断链引起的结构紊乱度高。
2.3 直流闪络性能改善
氟化引起的环氧树脂表面电性能的变化会影响其闪络性能。为评价这一性能变化，如1.2.3节所述，对每种氟化或未氟化环氧试样，在0.1 MPa SF6气中使用指形电极/片状试样组合进行20个样品的闪络试验。使用两参数威布尔统计分析测得的闪络电压数据，结果如图6所示，4种试样直流闪络电压的威布尔统计参数及平均值如表2所示。
从图6和表2可以看出，试样HM和试样XR累计闪络概率为63.2%时的威布尔特征闪络电压V0及平均闪络电压非常相近，表明两种环氧树脂的闪络性能几乎相同。值得注意的是，不管是支撑绝缘HM环氧试样还是管体XR环氧试样，氟化均改善了它们的闪络性能，使它们的特征直流闪络电压分别提升了8.58%和8.60%，二者的提升率也非常相近。从表2还可以看出，所有试样的闪络电压威布尔分布具有大的形状因子，表明闪络电压的离散性小。而且，氟化没有明显地改变闪络电压的离散性。
氟化引起的环氧绝缘闪络性能的改善是由于其表面基本电性能的变化，即表面电导率的增大。表面电导率增大对直流闪络电压的提升应该有两方面的影响[21]。一方面，表面电导率增大有利于抑制电极放电引起的试样表面电荷积累，因而有利于直流闪络电压的提升；另一方面，由于试样表面的电流流线不平行，表面电流会向指形电极尖端汇聚，表面电导率增大会增大电极尖端附近的电场，从而不利于闪络电压的提升。因此，氟化引起的环氧绝缘直流闪络性能的改善是这两方面影响相互竞争的结果。另外需要说明的是，标准三电极法和通常的表面电位衰减测量评价的是绝缘材料在“低电场下的电性能”，而发生在高电场下的闪络应直接关联于绝缘材料在“高电场下的电性能”，环氧绝缘在高电场下的表面电性能存在强的非线性特性[26]。试样FXR和试样FHM在低电场下的表面电性能差异明显，而它们的直流闪络性能几乎相同，这可能是因为它们的氟化层在高电场下具有相近的电性能。
3 结论
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（1）相同的氟化处理在两种环氧树脂上形成了厚度显著不同的氟化层，套管管体用环氧树脂由于高的环氧值等，其氟化层厚度仅为套管支撑绝缘用环氧树脂氟化层厚度的三分之一。氟化层的表面形貌不仅关联于树脂原料的环氧值，还密切关联于其分子结构。
（2）直接氟化显著地增大了两种环氧树脂的表面电导率，因此有效抑制了它们的表面电荷积聚。氟化后原料环氧值较高的套管管体用环氧树脂的表面电导率的增幅更大，对表面电荷积聚的抑制效果更加显著。
（3）由于对表面电荷积聚的抑制，直接氟化显著地提高了两种环氧树脂的直流闪络电压。闪络发生在高电场下，氟化层在高电场下的电性能可能具有强的非线性特性。
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2025年第58卷第7期
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doi: 10.16790/j.cnki.1009-9239.im.2025.07.016
  • 接收时间：2024-09-29
  • 首发时间：2025-10-29
  • 出版时间：2025-07-20
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  • 收稿日期：2024-09-29
  • 修回日期：2024-11-03
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    1.国网河南省电力公司电力科学研究院，河南 郑州 450099
    2.同济大学 电气工程系，上海 201804
    3.广西大学 电气工程学院，广西 南宁 530004

通讯作者:

安振连（1963-），男（汉族），江苏徐州人，教授，主要从事高压绝缘和导体材料的表层改性和相关介电性能等研究。
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https://castjournals.cast.org.cn/joweb/jycl/CN/10.16790/j.cnki.1009-9239.im.2025.07.016
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2种不同金属材料的力学参数
科
Family		 属数
Number of
genus		 种数
Number of
species		 占总种数比例
Percentage of
total species (%)		 属
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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