Article(id=1304923103541350996, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1304923090710982825, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2026.04.007, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1746720000000, receivedDateStr=2025-05-09, revisedDate=1750262400000, revisedDateStr=2025-06-19, acceptedDate=null, acceptedDateStr=null, onlineDate=1789047512183, onlineDateStr=2026-09-10, pubDate=1776614400000, pubDateStr=2026-04-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1789047512183, onlineIssueDateStr=2026-09-10, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1789047512183, creator=13701087609, updateTime=1789047512183, updator=13701087609, issue=Issue{id=1304923090710982825, tenantId=1146029695717560320, journalId=1149653034449285133, year='2026', volume='59', issue='4', pageStart='1', pageEnd='144', issueExtLink='null', onlineDate='null', pubDate='1776614400000', pubDateStr='2026-04-20', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1789047509124, creator='13701087609', updateTime=1789118076681, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1305219072573071941, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1304923090710982825, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1305219072573071942, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1304923090710982825, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=54, endPage=61, ext={EN=ArticleExt(id=1304923103721706069, articleId=1304923103541350996, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Study on electrical properties degradation law of cable termination insulating oil under short-term moisture absorption, columnId=1190369198472794288, journalTitle=Insulating Materials, columnName=Insulation Technology, runingTitle=null, highlight=null, articleAbstract=

Trace moisture absorption of insulating oils in high-voltage cable terminations during on-site filling or long-term operation may cause electrical performance deterioration and even insulation breakdown. The differences in molecular structure and polarity characteristics among different types of insulating oils will lead to significant differences in the adsorption behaviors of water molecules and the degradation laws of electrical performances. In this paper, the natural water absorption of silicone oil and polyisobutylene insulating oil under different exposure time was studied. The evolution of moisture content in different temperature and humidity environments was determined by Karl Fischer titration method, and the dielectric loss factor, volume resistivity, and power-frequency breakdown voltage of the insulating oil after water absorption were tested. Through molecular dynamics and quantum chemical calculations combined with Gaussian software, the differences in the moisture absorption mechanisms of the two types insulating oils were revealed from the perspectives of microscopic dipole moment, adsorption energy, and Gibbs free energy. The results show that due to the existence of Si-O bonds and polar groups in molecular chain of silicone oil, the dipole moment is 0.69 Debye. The initial absorption rate and total moisture amount are relatively high, and its moisture absorption process conforms to the exponential growth trend, the saturated moisture content is approximately 52×10-6. The polyisobutylene has a typical non-polar C-H chain structure with a low dipole moment of 0.02 Debye, and the its moisture absorption process shows a linear upward trend. Moisture absorption will lead to a significantly increases in dielectric loss factor, decreases in volume resistivity and electric strength for the two types of insulating oils. Silicone oil fails to meet the national standard requirement for insulation strength after 2 h of exposure, while polyisobutylene maintains good insulation strength within 5 h of exposure.

, authors=Wei ZHANG1, Chenying LI1, Jingying CAO1, Xiao TAN1, Jie CHEN1, Cang BAI2, authorsList=Wei ZHANG, Chenying LI, Jingying CAO, Xiao TAN, Jie CHEN, Cang BAI, authorCompany=null, correspAuthors=null, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, fund=null), CN=ArticleExt(id=1304923105080660580, articleId=1304923103541350996, tenantId=1146029695717560320, journalId=1149653034449285133, language=CN, title=短时吸水条件下电缆终端绝缘油电性能劣化规律研究, columnId=1190369198724452531, journalTitle=绝缘材料, columnName=绝缘技术, runingTitle=null, highlight=null, articleAbstract=

高压电缆终端绝缘油在现场灌装或长期运行条件下的微量吸水可能导致其电气性能劣化甚至发生绝缘击穿故障。不同类型绝缘油在分子结构、极性特性上的差异会导致其对水分子的吸附行为及电性能劣化规律显著不同。本文研究硅油与聚异丁烯两种绝缘油在不同暴露时间下的自然吸水情况,采用卡尔费休滴定法测定不同温湿度环境下的水分含量演变,并测试吸水后绝缘油的介质损耗因数、体积电阻率及工频击穿电压;结合Gaussian软件进行分子动力学与量子化学计算,从微观偶极矩、吸附能及吉布斯自由能角度揭示两类绝缘油的吸水机制差异。结果表明:硅油因分子链中存在Si-O键及极性基团,偶极矩为0.69 Debye,初期吸水速率与总吸水量较高,其吸水过程符合指数增长规律,饱和含水量约为52×10-6;聚异丁烯为典型非极性C-H链结构,偶极矩为0.02 Debye,吸水过程呈线性上升趋势。吸水会导致两种绝缘油的介质损耗因数明显增大、体积电阻率降低、电气强度下降,硅油在暴露2 h后即不满足国标绝缘强度要求,而聚异丁烯在暴露5 h内仍具有较好的绝缘强度。

, authors=张伟1, 李陈莹1, 曹京荥1, 谭笑1, 陈杰1, 柏仓2, authorsList=张伟, 李陈莹, 曹京荥, 谭笑, 陈杰, 柏仓, authorCompany=null, correspAuthors=null, authorNote=

张伟(1989-),女(汉族),黑龙江宝清人,高级工程师,博士,主要从事线缆设备评价、电缆材料研究等方面的工作。

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张伟(1989-),女(汉族),黑龙江宝清人,高级工程师,博士,主要从事线缆设备评价、电缆材料研究等方面的工作。

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张伟(1989-),女(汉族),黑龙江宝清人,高级工程师,博士,主要从事线缆设备评价、电缆材料研究等方面的工作。

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(a) 硅油 (b) 聚异丁烯

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短时吸水条件下电缆终端绝缘油电性能劣化规律研究
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张伟 1 , 李陈莹 1 , 曹京荥 1 , 谭笑 1 , 陈杰 1 , 柏仓 2
绝缘材料 | 绝缘技术 2026,59(4): 54-61
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绝缘材料 |绝缘技术 2026 , 59 (4) : 54 -61
短时吸水条件下电缆终端绝缘油电性能劣化规律研究
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张伟1, 李陈莹1, 曹京荥1, 谭笑1, 陈杰1, 柏仓2
作者信息
  • 1国网江苏省电力有限公司电力科学研究院,江苏 南京 211103
  • 2国网江苏省电力有限公司,江苏 南京 210000
作者简介:

张伟(1989-),女(汉族),黑龙江宝清人,高级工程师,博士,主要从事线缆设备评价、电缆材料研究等方面的工作。

Study on electrical properties degradation law of cable termination insulating oil under short-term moisture absorption
Wei ZHANG1, Chenying LI1, Jingying CAO1, Xiao TAN1, Jie CHEN1, Cang BAI2
Affiliations
  • 1State Grid Jiangsu Electric Power Co., Ltd. Research Institute, Nanjing 211103, China
  • 2State Grid Jiangsu Electric Power Co., Ltd., Nanjing 210000, China
出版时间: 2026-04-20 doi: 10.16790/j.cnki.1009-9239.im.2026.04.007
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高压电缆终端绝缘油在现场灌装或长期运行条件下的微量吸水可能导致其电气性能劣化甚至发生绝缘击穿故障。不同类型绝缘油在分子结构、极性特性上的差异会导致其对水分子的吸附行为及电性能劣化规律显著不同。本文研究硅油与聚异丁烯两种绝缘油在不同暴露时间下的自然吸水情况,采用卡尔费休滴定法测定不同温湿度环境下的水分含量演变,并测试吸水后绝缘油的介质损耗因数、体积电阻率及工频击穿电压;结合Gaussian软件进行分子动力学与量子化学计算,从微观偶极矩、吸附能及吉布斯自由能角度揭示两类绝缘油的吸水机制差异。结果表明:硅油因分子链中存在Si-O键及极性基团,偶极矩为0.69 Debye,初期吸水速率与总吸水量较高,其吸水过程符合指数增长规律,饱和含水量约为52×10-6;聚异丁烯为典型非极性C-H链结构,偶极矩为0.02 Debye,吸水过程呈线性上升趋势。吸水会导致两种绝缘油的介质损耗因数明显增大、体积电阻率降低、电气强度下降,硅油在暴露2 h后即不满足国标绝缘强度要求,而聚异丁烯在暴露5 h内仍具有较好的绝缘强度。

电缆终端  /  硅油  /  聚异丁烯  /  微水  /  介电性能

Trace moisture absorption of insulating oils in high-voltage cable terminations during on-site filling or long-term operation may cause electrical performance deterioration and even insulation breakdown. The differences in molecular structure and polarity characteristics among different types of insulating oils will lead to significant differences in the adsorption behaviors of water molecules and the degradation laws of electrical performances. In this paper, the natural water absorption of silicone oil and polyisobutylene insulating oil under different exposure time was studied. The evolution of moisture content in different temperature and humidity environments was determined by Karl Fischer titration method, and the dielectric loss factor, volume resistivity, and power-frequency breakdown voltage of the insulating oil after water absorption were tested. Through molecular dynamics and quantum chemical calculations combined with Gaussian software, the differences in the moisture absorption mechanisms of the two types insulating oils were revealed from the perspectives of microscopic dipole moment, adsorption energy, and Gibbs free energy. The results show that due to the existence of Si-O bonds and polar groups in molecular chain of silicone oil, the dipole moment is 0.69 Debye. The initial absorption rate and total moisture amount are relatively high, and its moisture absorption process conforms to the exponential growth trend, the saturated moisture content is approximately 52×10-6. The polyisobutylene has a typical non-polar C-H chain structure with a low dipole moment of 0.02 Debye, and the its moisture absorption process shows a linear upward trend. Moisture absorption will lead to a significantly increases in dielectric loss factor, decreases in volume resistivity and electric strength for the two types of insulating oils. Silicone oil fails to meet the national standard requirement for insulation strength after 2 h of exposure, while polyisobutylene maintains good insulation strength within 5 h of exposure.

cable termination  /  silicone oil  /  polyisobutylene  /  trace moisture  /  dielectric property
张伟, 李陈莹, 曹京荥, 谭笑, 陈杰, 柏仓. 短时吸水条件下电缆终端绝缘油电性能劣化规律研究. 绝缘材料, 2026 , 59 (4) : 54 -61 . DOI: 10.16790/j.cnki.1009-9239.im.2026.04.007
Wei ZHANG, Chenying LI, Jingying CAO, Xiao TAN, Jie CHEN, Cang BAI. Study on electrical properties degradation law of cable termination insulating oil under short-term moisture absorption[J]. Insulating Materials, 2026 , 59 (4) : 54 -61 . DOI: 10.16790/j.cnki.1009-9239.im.2026.04.007
随着新型电力系统建设的加速推进,高压交联聚乙烯(XLPE)电缆凭借其较高的载流能力、优异的绝缘性能及敷设灵活性,在城市电网升级改造中发挥着重要作用。当前,我国110 kV及以上电压等级的XLPE电力电缆户外终端普遍采用充油套管结构,以确保电缆与空气之间的绝缘过渡,并提升电缆运行的安全性与可靠性[1]。相较于传统的油纸绝缘,油式电缆终端在绝缘介质构成及应用方式上具有显著差异。传统油纸绝缘终端依赖于油-纸复合介质,其绝缘特性来源于纤维素纸的吸油浸润效应,使得油体与固体绝缘协同作用形成多层介电屏障,从而提升油纸绝缘终端的整体耐压水平[2]。然而,油式终端采用单一液态绝缘介质,无固体绝缘材料的辅助支撑,其绝缘性能完全取决于所填充绝缘油的电气性能及物理化学特性。尽管其无纸化设计有效规避了纸材老化导致的绝缘劣化风险,并简化了终端结构,但也对绝缘油的纯净度、介质损耗、局部放电抑制能力等提出了更高要求[3]。因此,如何确保油式终端在现场安装施工及长期运行中的绝缘稳定性,成为高压电缆终端设计与运行维护的关键问题之一。
目前,高压电缆终端的绝缘填充介质主要包括硅油与聚异丁烯(polyisobutylene,PIB)。硅油的主要成分为聚甲基硅氧烷,其分子主链由交替排列的硅(Si)与氧(O)原子构成(-Si-O-Si-),侧链为甲基(-CH3)等有机基团,具有优异的热稳定性和较低的介质损耗;聚异丁烯由异丁烯单体聚合而成,其主链结构由饱和碳-碳(C-C)单键组成,并带有高密度甲基侧链(-CH(CH3)2),形成完全非极性的线性高分子结构[4]。这两类合成绝缘油在黏度、击穿电压、介质损耗因数及吸水特性等方面与传统矿物绝缘油存在显著差异,因此,其在长期运行中的电气稳定性及环境适应性备受关注。
近年来,围绕绝缘油的多场耦合作用机制及服役寿命评估具有较为系统性的研究成果。在复合绝缘体系水分迁移机理方面,研究表明硅油-硅橡胶界面存在明显的水分重分布现象,硅油相含水量随相对湿度呈线性增长,其饱和含水量表现出指数型温度依赖性[5-6],而硅橡胶相则表现出非线性吸湿特性且温度稳定性显著。另外在温度梯度驱动下水分由硅橡胶向硅油迁移的动力学过程也有相关报道[7]。针对硅油等合成油的老化表征,基于傅里叶红外光谱特征峰与微水含量的协同监测方法被证实可有效评估硅油的老化程度[8]。在老化条件方面,有研究在90℃热老化工况下分析了硅油介电性能的演变特征,结果表明其劣化过程与水分参与的自催化氧化反应相关[9]。此外,还有研究对不同老化路径下硅油的老化行为进行对比,发现热老化后再施加电应力与电-热联合老化对硅油的整体老化效果影响基本一致[10]。在介电响应微观机制层面,天然酯绝缘油含水率对其介电温/频谱特征的影响规律已有较为充分研究,通过频域介电谱(10-2~103 Hz)实验分析表明,绝缘油的介质损耗因数在全频段呈现先升高后降低的非单调特性,油浸纸的介质损耗因数则随频率升高持续降低,而绝缘油和油浸纸的相对介电常数均随频率升高呈降低趋势[10-14]
在实际运行环境中,电缆终端绝缘油不可避免地会受到湿度影响,而水分的引入将显著改变油介质的物理化学特性和电气性能。研究表明,水分的存在可能导致油介质的介质损耗增加、体积电阻率降低,并可能促使局部放电发生,从而影响电缆终端的绝缘可靠性[15-18]。值得注意的是,在电缆终端的现场安装过程中,绝缘油的灌装作业通常在露天环境下进行,且施工过程中油液开封后若未能及时灌装,可能会吸收空气中的水分,从而影响其绝缘性能[19-21]。目前的研究大多关注长期老化以及大量进水后绝缘油的绝缘以及介电特性变化,绝缘油短时吸水特性以及短时吸水条件下绝缘强度的变化目前还未有报道。因此,研究高压电缆终端常用绝缘油的短时吸水特性,并系统评估吸水后的电气性能变化,对于优化终端绝缘设计、提高运行可靠性以及完善状态监测与维护策略具有重要意义。
本文研究不同环境温度和暴露时间下两类绝缘油的水分含量变化规律;针对吸水后的绝缘油,测试其体积电阻率、介质损耗因数、电气强度等介电参数,研究各参数变化情况,并通过量子化学方法计算绝缘油的微观结构与吸附能参数,分析水分对绝缘油电气性能的影响机理。相关研究结果可为高压电缆终端绝缘油的选型、运行监测及寿命评估提供数据参考。
硅油,型号为AK50,德国Wacker公司;聚异丁烯,型号为PB400,韩国Daelim公司。
吸水性测试采用卡尔费休滴定法进行。为研究温度对绝缘油吸水行为的影响,试验分别在3种恒温恒湿条件下进行,温度分别为25、40、60 ℃(温度波动范围为±0.5 ℃),相对湿度控制在(65 ± 3)%。温度控制采用高精度恒温油浴锅,以确保油样在整个暴露过程中始终处于稳定的温度环境中。具体试验过程为:将500  mL待测绝缘油样置于洁净的标准烧杯中,敞口暴露于设定环境下,分别在暴露3、24、48、72、96、120  h时进行取样。使用专用取样器从油杯中抽取油样后,立即注入密封性良好的取样瓶中并旋紧瓶盖,以避免样品在转移过程中受环境温度变化或二次吸潮的影响。所有测试操作均在同一平台上完成,确保不同温度工况下数据的准确性与可比性。
电气强度参照GB/T 507—2002相关要求搭建实验系统进行测试,测试电路如图1所示。电源采用工频电压发生器连续升压,升压速率为1 kV/s;电极包含两种类型(如图2所示):椭球形电极(曲率半径为25 mm)构建稍不均匀电场,针-板电极(针尖曲率半径为0.3 mm)构建极不均匀电场,电极间距均为2.5 mm,电极材料为黄铜,经加工及抛光处理。测试时,每次击穿后立即更换油样以消除碳化产物对测试结果的影响,针对每种暴露时间的油样,重复进行5次击穿试验,取5次试验结果的算术平均值作为该状态下的击穿电压值。绝缘油的介质损耗因数与体积电阻率是衡量其绝缘品质的关键参数,采用符合IEC 60247:2004要求的介损及体积电阻率测试仪。
硅油与聚异丁烯在不同暴露时间下的含水量变化趋势如图3所示。从图3可以看出,硅油在整个暴露周期内的含水量呈现初期显著上升后期饱和的变化趋势,在25℃下硅油的含水量由初期的约31×10-6逐渐上升至52×10-6左右,表明硅油具有较强的吸湿性,且其吸湿过程具有明显的扩散特征。在40℃和60℃条件下,整个暴露周期内硅油的含水量都有所上升,且上升速率比25℃下更快。相比之下,聚异丁烯的含水量始终维持在较低水平,在暴露时间范围内其吸水行为接近线性过程,未出现显著的上升或饱和趋势。在25℃下,聚异丁烯的含水量仅从初期的约24×10-6上升至29×10-6左右,且上升速度较为缓慢,吸湿能力明显弱于硅油。
为进一步研究两种绝缘油在暴露过程中含水量的变化趋势,引入拟合函数进行数据处理。针对聚异丁烯的吸湿特性,采用最小二乘法进行线性拟合,拟合函数为式(1)。
Cw-PIB(t, T)=(0.000164T+0.0342)+(0.0075t+24.07)
式(1)中:Cw-PIB为聚异丁烯的含水量;t为暴露时间;T为环境温度。
硅油的吸水过程表现出明显的非线性规律,且在前期暴露过程中水分含量迅速上升,随后趋于稳定。基于其典型的动态变化特征,采用单指数衰减函数对实验数据进行非线性拟合,拟合函数为式(2)。
Cw-so(t, T)=C0(T)+A(T)e-t/t1
式(2)中:Cw-so表示硅油的吸水量;t1为吸水动力学过程的时间常数,表征硅油吸水量由快速增长阶段向稳定阶段过渡的特征时间,在25℃下t1为44.1 h; C0(T)和A(T)分别表示与温度有关的常数,其中C0(T)=-0.08T+58.5,A(T)=-0.083 5T-25.48。
根据模型计算出半饱和吸水时间,硅油在前48 h内已基本完成主要吸水过程,而聚异丁烯的吸水量呈线性上升。该特性反映了硅油初期对环境水分的快速吸收能力,在绝缘系统长期运行以及安装施工过程中需注意初期受潮风险。
介质损耗因数(tanδ)是表征绝缘材料在交流电场下能量损耗的重要参数,其反映了材料极化滞后所带来的介质损耗能力。介质损耗因数的计算公式如式(3)所示。
tanδ=ε/ε'
式(3)中:ε′为介电常数实部,表示材料储存电能的能力,即电容效应;ε″为介电常数虚部,表示材料中电能材料的损耗,即电阻效应。
在交流电场中,油中的极性杂质(如水分)会显著增加ε″,从而导致tanδ升高。通常,绝缘油的tanδ越低,表示其介质损耗越小,电绝缘性能越好。
硅油及聚异丁烯介质损耗因数随暴露时间的变化关系如图4所示。从图4可以看出,硅油和聚异丁烯的tanδ随着暴露时间的增加均呈上升趋势,表明水分子的渗入导致绝缘油极化过程加剧,能量损耗显著增加。但聚异丁烯的介质损耗因数上升程度略低于硅油。
体积电阻率(ρv)是衡量绝缘油电性能的重要参数,其计算公式如式(4)所示。
ρv=RS/L
式(4)中:R为绝缘油的电阻值;S为电极面积;L为电极间距。
硅油以及聚异丁烯体积电阻率随暴露时间的变化关系如图5所示。
图5可以看出,随着暴露时间的增加,硅油与聚异丁烯的体积电阻率均呈现下降趋势,表明水分的引入导致绝缘油的导电性增强,绝缘性能下降。相较于硅油,聚异丁烯表现出较好的电绝缘稳定性,其初始体积电阻率高达4.136×1013 Ω·m,且在整个暴露过程中下降幅度较小,表明聚异丁烯对水分子的扩散和导电通道形成具有更强的抑制作用。
综合介质损耗因数与体积电阻率的结果可知,硅油在暴露初期对水分较敏感,介质损耗因数上升与体积电阻率下降较明显;而聚异丁烯则表现出更强的吸水抑制能力与绝缘稳定性,表明其适用于对电绝缘要求较高且存在潮湿环境的长期应用场景。
击穿电压是衡量绝缘材料在外加电场作用下承受最大电压而不发生电气击穿的能力,反映材料的电气强度。硅油及聚异丁烯在不同暴露时间下的击穿电压测试结果如图6所示。从图6可以看出,随着暴露时间的增加,两种绝缘油的击穿电压均呈现下降的趋势,但下降幅度和变化速率存在显著差异。其中硅油的击穿电压在暴露周期内下降幅度超过了60%,相比之下,聚异丁烯的击穿电压下降幅度在40%左右。值得注意的是,依据国标对绝缘油电气强度的基本要求,绝缘油在2.5 mm间隙距离下的击穿电压应不低于40  kV,其中硅油仅在吸湿前(暴露时间为0  h)满足标准要求,暴露2 h即迅速降至标准以下;而聚异丁烯表现出较优的稳定性,其击穿电压在暴露5 h内均满足国标要求。该结果表明,绝缘油在使用与储存过程中对水分控制至关重要,尤其是对于硅油类材料,短时暴露于潮湿环境可能导致其击穿性能迅速下降,存在显著的绝缘风险。相较之下,聚异丁烯具备更好的吸水抑制能力和绝缘稳定性,在应对微水侵入时具有更大的安全裕度。由此可见,微量水分的持续渗入会削弱绝缘油的电气强度,且短时吸湿行为亦可能使其无法满足标准要求,在实际应用中应加强对环境湿度的管控和油品密封管理,以确保电力设备运行的绝缘可靠性。
硅油与聚异丁烯在吸水特性上表现出较大差异,源于两者分子结构中有无极性基团。为进一步从分子层面验证两种材料在吸水特性上的差异,本文通过Gaussian软件对两种绝缘油的分子单元微观结构以及能量参数进行计算,两种绝缘油经过优化后的分子结构如图7所示。硅油分子主链为Si-O键结构,其对水分子具有较强的偶极-偶极吸引作用,而聚异丁烯为典型的非极性C-H链结构,该结构仅能依赖范德华力对水分进行物理吸附。计算过程中使用基于RB3LYP泛函与6-311G(D)基组对硅油分子进行结构优化与参数计算,结果表明其偶极矩为0.69 Debye,显示出明显的分子极性;而聚异丁烯模型在相同计算方法下所得偶极矩仅为0.02 Debye,近似于非极性分子。这种偶极矩的数量级差异直接决定了分子在吸附水分子时的亲和能力与吸附势能的不同。
进一步通过式(5)对硅油和聚异丁烯的吸附能进行计算。
Eads=Et-(EO+EH)
式(5)中:Eads为吸附能;Et为吸附体总能量;EOEH分别为绝缘油分子(硅油/聚异丁烯)与水分子的孤立能量。
通过计算得出,硅油与水的吸附能为-0.062 5 eV,聚异丁烯与水的吸附能为-0.031 3 eV,负的吸附能表明吸附过程是能量释放过程,即热力学自发过程。计算结果显示,硅油具有更强的吸附能力,对水分子的捕获能力更高。
同时,吸附过程的热力学特性也可通过Gibbs自由能变化进行描述,如式(6)所示。
ΔGH-TΔS
式(6)中:ΔG为Gibbs自由能;ΔH为焓变;ΔS为熵变。
通过计算得出,硅油-水体系的ΔG为-2 302.77 kcal/mol,聚异丁烯-水体系的ΔG为-587.84 kcal/mol,均表现为自发吸附,但硅油-水体系的自由能下降幅度更大,表明硅油与水结合后的状态在热力学上更加稳定。
此外,考虑分子间作用力,不同绝缘油与水分子构成的偶极-偶极相互作用势能Ud可用式(7)表示。
Ud=-2μOμH4πε0r3
式(7)中:μOμH分别为绝缘油分子和水分子的偶极矩;ε0为真空介电常数;r为分子间距离。
由于硅油分子偶极矩远大于聚异丁烯,其与水分子的相互作用势能明显更大,从而解释了硅油吸水量与吸水速率均高于聚异丁烯的现象。
进一步分析两种绝缘油的吸水量随时间的变化情况可知,硅油的吸水过程更符合准指数增长规律,而聚异丁烯的吸水过程则表现出较好的线性关系,反映了其稳定的缓慢吸水趋势。这种差异不仅体现在吸水量的绝对值,更体现在后续电性能变化的演化速率与机制。
在电性能方面,tanδ作为衡量极化滞后损耗的主要参数,其演化与极性分子含量密切相关。根据经典的Debye单极化弛豫模型,吸湿后的极性介质中介质损耗分量ε(ω)可表示为式(8)。
ε(ω)=(εs-ε)1+(ωτ)2
式(8)中:εs是静态介电常数;ε是高频极限介电常数;τ是极化弛豫时间;ω为外加电场角频率。
由式(8)可知,吸水后绝缘油极性增强,导致εs上升、τ降低,进而使ε在工频区域迅速增加,引发绝缘油的tanδ快速增大。进一步地,若考虑系统中多个极化机制并存(如界面极化、偶极转向极化等),可将介电响应扩展为多弛豫型模型,ε*(ω)为复介电常数,如式(9)所示。
ε*(ω)=ε+εs-ε1+(jωτ)1-α
式(9)中:α为分布因子,介于0~1之间,描述弛豫时间的分布宽度;j为虚数单位。
水分子引入使得极化路径更加复杂,增大了α值,表现为介质损耗因数的带宽扩展及峰值位移。上述推导说明了短时间微量吸水即可使绝缘油在宏观上产生显著的介电响应变化,且其幅度与极性程度呈正相关。
与此同时,水分的掺杂也显著影响绝缘油的导电行为,特别是体积电阻率的演化趋势。在热激发载流子迁移机制下,体积电导率σ可表达为Arrhenius关系,如式(10)所示。
σ=σ0e-Ea/kT
式(10)中:σ0为指前因子,与载流子浓度相关;Ea为电导活化能;k为玻尔兹曼常数。
体积电阻率为体积电导率的倒数,即式(11)。
ρv=1σ=σ0eEa/kT
水分子作为极性杂质,不仅会引入自由极化离子,还可通过弱化分子间作用力和破坏局域势阱结构,降低电子/空穴跃迁所需的激发能垒Ea,进而降低了绝缘油的体积电阻率。
水分的引入不仅会使绝缘油的介电性能显著劣化,微量水分在油中还起到了自由电荷载流子的供给源作用,促进局部导电通道形成,进而降低油品的绝缘特性。随着水分在油中逐渐富集,局域电场分布趋于复杂,局部过高的电场强度促使水分子在界面区域发生重排与集聚,演变为纳米尺度的水团结构。根据“小桥”理论,这些水团在一定条件下可以通过界面吸附和电场诱导排列形成水桥,充当临时性的低电阻路径,从而显著降低了绝缘油的整体击穿耐受能力。结合本文的击穿试验结果可知,在初期吸水阶段,尽管总体含水量未达到饱和,但绝缘油的击穿电压已出现明显下降,且局部体积电阻率与介质损耗因数均发生明显劣化,进一步验证了“小桥”理论关于水桥形成对绝缘系统性能劣化的早期影响机制。
本文对高压电缆终端用硅油及聚异丁烯绝缘油在暴露0~120 h内的吸水特性进行了研究,通过介电性能、击穿电压测试与分子动力学计算,分析了两者在吸水特性、电性能演变及微观机理上的差异,主要结论如下:
(1)硅油的饱和含水量高于聚异丁烯,硅油在整个暴露周期内含水量呈现初期显著上升后期饱和的指数函数变化趋势,在25℃下的饱和含水量约为52×10-6,而聚异丁烯的含水量始终维持在较低水平,在暴露0~120 h内其吸水行为接近线性过程,未出现显著的加速或饱和趋势。
(2)硅油及聚异丁烯吸水后的介电性能以及电气强度均出现了明显劣化。随着含水量的上升,两种绝缘油的介质损耗因数增大,体积电阻率降低,并且硅油在暴露2 h后击穿电压就不满足国标要求,而聚异丁烯在吸水初期表现出更优的稳定性,其击穿电压在暴露5 h内均满足国标要求。
(3)两种绝缘油的分子动力学计算结果表明,硅油分子中含有极性基团,偶极矩为0.69 Debye,而聚异丁烯分子为非极性碳氢链结构,偶极矩仅为0.02 Debye,主要依赖范德华力吸附水分。硅油与水的吸附能为-0.062 5 eV,聚异丁烯与水的吸附能为-0.031 3 eV,进一步说明硅油分子体系对水分子的吸收能力更强。

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2026年第59卷第4期
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doi: 10.16790/j.cnki.1009-9239.im.2026.04.007
  • 接收时间:2025-05-09
  • 首发时间:2026-09-10
  • 出版时间:2026-04-20
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  • 收稿日期:2025-05-09
  • 修回日期:2025-06-19
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    1国网江苏省电力有限公司电力科学研究院,江苏 南京 211103
    2国网江苏省电力有限公司,江苏 南京 210000
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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
栓菌属 Trametes 5 2.39
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