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Article(id=1199641490453528620, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1199641484963181075, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2023.07.006, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1654444800000, receivedDateStr=2022-06-06, revisedDate=1670169600000, revisedDateStr=2022-12-05, acceptedDate=null, acceptedDateStr=null, onlineDate=1763946419584, onlineDateStr=2025-11-24, pubDate=1689782400000, pubDateStr=2023-07-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1763946419584, onlineIssueDateStr=2025-11-24, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1763946419584, creator=13701087609, updateTime=1763946419584, 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=32, endPage=39, ext={EN=ArticleExt(id=1199641490952650806, articleId=1199641490453528620, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Comparative analysis on heat ageing resistance of domestic and imported XLPE insulation for high voltage cables, columnId=1190369066675179686, journalTitle=Insulating Materials, columnName=Material Research, runingTitle=null, highlight=null, articleAbstract=

The domestic and imported 220 kV cross-linked polyethylene (XLPE) cable insulation were carried out accelerated thermal ageing tests at 90℃ and 135℃, and the effects of thermal ageing with different temperature and different time on the physical and chemical properties, mechanical properties, and electrical properties of XLPE insulation were investigated. The thermal ageing life of domestic and imported XLPE insulation were evaluated. The results show that the oxidation reaction induced by thermal ageing leads to the appearance of carbonyl peak in the XLPE sample, and the higher the ageing temperature, the more obvious the carbonyl peak. After ageing, the cross-linking degree of XLPE samples increases, which damages the crystal structure in the crystallization zone and decreases the crystallinity, resulting in the overall deterioration of mechanical properties. The molecular chain of the aged sample is broken and degraded, and the movement of carrier is intensified under the action of electric field, resulting in the decline of AC electric strength. The thermal ageing life evaluation shows that the thermal ageing life of domestic XLPE insulation material is greater than that of imported XLPE insualtion material. The comprehensive comparison of various properties shows that the level of domestic XLPE insulation material is equivalent to that of imported XLPE insulation material.

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对国产与进口两种220 kV电缆交联聚乙烯（XLPE）绝缘在90℃和135℃进行加速热老化试验，探究不同温度和不同时间的热老化条件对XLPE绝缘理化性能、力学性能和电气性能的影响规律，评估国产和进口XLPE绝缘的热老化寿命。结果表明：热老化引发的氧化反应导致XLPE试样中羰基峰的出现，老化温度越高，羰基峰越明显。老化后，XLPE试样的交联程度增加，破坏了结晶区的晶体结构，使结晶度下降，导致力学性能总体上出现了劣化。老化试样的分子链发生了断裂、降解，在电场作用下载流子运动加剧，致使交流电气强度下降。热老化寿命评估表明，国产XLPE绝缘料的热老化寿命大于进口XLPE绝缘料。综合对比各项性能表明，国产XLPE绝缘料与进口XLPE绝缘料水平相当。

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章彬（1974-），男（汉族），江西景德镇人，教授级高级工程师，主要从事电力电网主设备的管理。

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章彬（1974-），男（汉族），江西景德镇人，教授级高级工程师，主要从事电力电网主设备的管理。

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章彬（1974-），男（汉族），江西景德镇人，教授级高级工程师，主要从事电力电网主设备的管理。

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tableContent=null), ArticleFig(id=1217475266838971120, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199641490453528620, language=EN, label=Tab.1, caption=Appearance morphology of thermal ageing XLPE insulation samples, figureFileSmall=null, figureFileBig=null, tableContent=
XLPE未老化90℃热老化时间/天135℃热老化时间/天
144270144270
国产材料
进口材料
), ArticleFig(id=1217475266910274290, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199641490453528620, language=CN, label=表1, caption=

热老化XLPE绝缘试样外观形貌

, figureFileSmall=null, figureFileBig=null, tableContent=
XLPE未老化90℃热老化时间/天135℃热老化时间/天
144270144270
国产材料
进口材料
), ArticleFig(id=1217475266985771764, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199641490453528620, language=EN, label=Tab.2, caption=Weibull distribution shape parameters of AC electric strength for domestic and imported XLPE insulation samples, figureFileSmall=null, figureFileBig=null, tableContent=
XLPE材料老化温度/℃老化时间/天
0144270
国产9011.027.076.4719.82
13511.028.278.779.71
进口9010.317.116.2222.85
13510.318.028.667.70
), ArticleFig(id=1217475267065463542, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199641490453528620, language=CN, label=表2, caption=

国产与进口XLPE绝缘试样交流电气强度Weibull分布的形状参数

, figureFileSmall=null, figureFileBig=null, tableContent=
XLPE材料老化温度/℃老化时间/天
0144270
国产9011.027.076.4719.82
13511.028.278.779.71
进口9010.317.116.2222.85
13510.318.028.667.70
), ArticleFig(id=1217475267128378104, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199641490453528620, language=EN, label=Tab.3, caption=Conversion of end-of-life duration and environmental life under equivalent working conditions, figureFileSmall=null, figureFileBig=null, tableContent=
XLPE绝缘料135℃寿命终止时长/天等效工况寿命/年
国产35.529.99
进口30.225.51
), ArticleFig(id=1217475267212264186, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199641490453528620, language=CN, label=表3, caption=

寿命终止时长与等效工况环境寿命折算

, figureFileSmall=null, figureFileBig=null, tableContent=
XLPE绝缘料135℃寿命终止时长/天等效工况寿命/年
国产35.529.99
进口30.225.51
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国产与进口高压电缆交联聚乙烯绝缘耐热老化性能对比分析
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章彬 1 , 徐曙 1 , 巩俊强 1 , 张成巍 1 , 黎小林 2 , 傅明利 2 , 侯帅 2 , 展云鹏 2
绝缘材料 | 材料研究 2023,56(7): 32-39
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绝缘材料 | 材料研究 2023, 56(7): 32-39
国产与进口高压电缆交联聚乙烯绝缘耐热老化性能对比分析
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章彬1, 徐曙1, 巩俊强1, 张成巍1, 黎小林2, 傅明利2, 侯帅2, 展云鹏2
作者信息
  • 1深圳供电局有限公司,广东 深圳 518000
  • 2南方电网科学研究院有限责任公司,广东 广州 510663

    • 章彬（1974-），男（汉族），江西景德镇人，教授级高级工程师，主要从事电力电网主设备的管理。

Comparative analysis on heat ageing resistance of domestic and imported XLPE insulation for high voltage cables
Bin ZHANG1, Shu XU1, Junqiang GONG1, Chengwei ZHANG1, Xiaolin LI2, Mingli FU2, Shuai HOU2, Yunpeng ZHAN2
Affiliations
  • 1Shenzhen Power Supply Bureau, Shenzhen 518000, China
  • 2Research Institute of China Southern Power Grid, Guangzhou 510663, China
出版时间: 2023-07-20 doi: 10.16790/j.cnki.1009-9239.im.2023.07.006
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摘要
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对国产与进口两种220 kV电缆交联聚乙烯（XLPE）绝缘在90℃和135℃进行加速热老化试验，探究不同温度和不同时间的热老化条件对XLPE绝缘理化性能、力学性能和电气性能的影响规律，评估国产和进口XLPE绝缘的热老化寿命。结果表明：热老化引发的氧化反应导致XLPE试样中羰基峰的出现，老化温度越高，羰基峰越明显。老化后，XLPE试样的交联程度增加，破坏了结晶区的晶体结构，使结晶度下降，导致力学性能总体上出现了劣化。老化试样的分子链发生了断裂、降解，在电场作用下载流子运动加剧，致使交流电气强度下降。热老化寿命评估表明，国产XLPE绝缘料的热老化寿命大于进口XLPE绝缘料。综合对比各项性能表明，国产XLPE绝缘料与进口XLPE绝缘料水平相当。

交联聚乙烯  /  热老化  /  理化性能  /  力学性能  /  电气性能

The domestic and imported 220 kV cross-linked polyethylene (XLPE) cable insulation were carried out accelerated thermal ageing tests at 90℃ and 135℃, and the effects of thermal ageing with different temperature and different time on the physical and chemical properties, mechanical properties, and electrical properties of XLPE insulation were investigated. The thermal ageing life of domestic and imported XLPE insulation were evaluated. The results show that the oxidation reaction induced by thermal ageing leads to the appearance of carbonyl peak in the XLPE sample, and the higher the ageing temperature, the more obvious the carbonyl peak. After ageing, the cross-linking degree of XLPE samples increases, which damages the crystal structure in the crystallization zone and decreases the crystallinity, resulting in the overall deterioration of mechanical properties. The molecular chain of the aged sample is broken and degraded, and the movement of carrier is intensified under the action of electric field, resulting in the decline of AC electric strength. The thermal ageing life evaluation shows that the thermal ageing life of domestic XLPE insulation material is greater than that of imported XLPE insualtion material. The comprehensive comparison of various properties shows that the level of domestic XLPE insulation material is equivalent to that of imported XLPE insulation material.

cross-linked polyethylene  /  heat ageing  /  physical and chemical properties  /  mechanical properties  /  electrical properties
章彬, 徐曙, 巩俊强, 张成巍, 黎小林, 傅明利, 侯帅, 展云鹏. 国产与进口高压电缆交联聚乙烯绝缘耐热老化性能对比分析. 绝缘材料, 2023 , 56 (7) : 32 -39 . DOI: 10.16790/j.cnki.1009-9239.im.2023.07.006
Bin ZHANG, Shu XU, Junqiang GONG, Chengwei ZHANG, Xiaolin LI, Mingli FU, Shuai HOU, Yunpeng ZHAN. Comparative analysis on heat ageing resistance of domestic and imported XLPE insulation for high voltage cables[J]. Insulating Materials, 2023 , 56 (7) : 32 -39 . DOI: 10.16790/j.cnki.1009-9239.im.2023.07.006
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0 引言
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XLPE因具有原材料来源丰富、价格低廉、电气性能优异、介质损耗和介电常数较小等优点，作为电缆绝缘在中高压输配电网络中得到了广泛应用[1-3]。在电缆运行过程中，XLPE绝缘寿命会受到热老化的影响。高压电缆正常工作温度可达到90℃，若线路发生故障，工作温度最高甚至能够达到250℃[4-5]。热老化过程会改变XLPE绝缘的微观结构与理化性能，进而对其力学性能与电气性能造成影响[6]。因此，XLPE绝缘的热老化特性是其绝缘性能的重要指标。
国内外研究人员对XLPE电缆绝缘的热老化特性进行了很多研究[7-9]。文献[10-11]研究发现热老化会缩短XLPE绝缘寿命，降低XLPE绝缘的电气性能与力学性能。欧阳本红等[12]提出了一种基于空间电荷分布评估XLPE绝缘老化的方法。刘继平等[13]分别在125℃和150℃高温下对XLPE绝缘进行了700 h的热老化试验，分析了热裂解在热老化过程中对XLPE绝缘性能变化的作用机理。李欢等[14]研究了XLPE电缆绝缘的热老化特性，老化温度分别设置为100℃和160℃，结果表明老化温度较高时，XLPE绝缘材料的热性能、力学性能大幅下降。胡丽斌等[15]研究发现羰基指数能够反映绝缘老化程度，热老化时间越长，XLPE绝缘老化越严重。目前XLPE电缆绝缘老化的研究主要针对的是XLPE绝缘的老化特性，关于XLPE电缆绝缘热老化过程的劣化机理研究较少，且缺少对国产与进口XLPE电缆绝缘热老化特性差异的研究，导致国产XLPE绝缘的性能优化方向不清楚。
本文选取90℃和135℃两个老化温度对XLPE绝缘进行热老化试验，研究不同温度、不同时间的热老化对国产220 kV XLPE电缆绝缘理化性能、力学性能和电气性能的影响规律，并与进口的相同电压等级绝缘料的性能进行对比分析，评估国产和进口XLPE绝缘的热老化寿命。
1 试验
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1.1 试样制备及老化试验
高压电缆用交联聚乙烯绝缘材料分别由国内某公司提供的110 kV绝缘料和北欧化工生产的LE401S XLPE绝缘料。采用平板硫化机在180℃、15 MPa的条件下热压15 min获得尺寸为100 mm×100 mm×1 mm的试样，然后进行热老化试验。设置热老化温度分别为90℃和135℃，热老化取样间隔为168 h（7天），即最大热老化时长为1 680 h（70天）[16-17]。此外，设置未进行热老化处理的交联聚乙烯试样作为对照组。加速热老化试验箱采用YC-450A型电热恒温箱，额定功率为1 600 W，热老化箱容积为71 L，可实现50～250℃温度范围内的数字式温控调节，采用IEC 60216-1:2013规定的II类强制通风条件（换气160次/h）。
1.2 测试方法
采用Nicolet公司iS10型号傅里叶红外光谱仪测试老化前后XLPE绝缘试样的红外光谱（FTIR），波数范围为600～4 000 cm-1，分辨率为0.4 cm-1。采用热老化烘箱对交联聚乙烯材料进行90℃和135℃的加速热老化试验，每7天取样1次进行FTIR分析，每种热老化温度下共取样10次。采用Mettler Toledo®公司DSC 1/1100 SF型DSC分析仪测试老化试样的结晶、熔融特性，温度范围为20～600℃，升温速率为10 K/min。体积电导率采用三电极法测试，测试直流场强为10 kV/mm，测试环境温度分别为30、60、90℃，测试时间为600 s，采样率为1次/s。选取测试结果最后30个数据点的算术平均值作为试样的平均电导电流，然后进行体积电导率计算。测试试样在90℃和135℃下热老化不同时间后的交流电气强度，试验在90℃的绝缘油中进行。
2 结果与讨论
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2.1 热老化对XLPE理化性能的影响
经加速热老化后的XLPE绝缘试样外观形貌特征如表1所示。从表1可以看出，在135℃下，国产和进口XLPE绝缘试样色泽均发生明显变化，由白色透明状逐渐转变为黄色非透明状；而老化至70天时，XLPE绝缘试样色泽均变为暗红色，进口XLPE绝缘试样颜色深于国产绝缘试样。相较90℃下，XLPE绝缘试样色泽改变并不显著。因此色泽由白色改变为黄色乃至暗红色和试样透明度下降是XLPE绝缘热老化的典型外观形貌特征。
XLPE绝缘在热老化过程中，分子链段会发生“自由基链式反应”，其反应过程如图1所示。XLPE绝缘分子主链在加热、富氧条件下，可经氧化反应形成自由基，并同时生成过氧化产物；进一步地，过氧化产物对XLPE绝缘分子主链引发质子转移反应，进而导致分子主链产生更多的自由基。最终在上述链式反应的作用下，XLPE绝缘发生分子链断裂和交联点被破坏，导致绝缘内部形成大量缺陷，绝缘性能大幅下降。因此，不同热老化时间下XLPE绝缘中的羰基含量是反映绝缘热老化程度的重要理化性能指标。对90℃和135℃下热老化不同时间的国产XLPE绝缘试样进行FTIR测试，结果如图2所示。
从图2可以看出，国产XLPE绝缘试样均在波数为2 750～3 000 cm-1处出现明显的特征峰，对应碳氢键的伸缩振动等。图2中右侧为FTIR在波数为1 700～1 800cm-1的局部放大图，观察可见，与未老化XLPE绝缘试样相比，老化XLPE绝缘试样在波数为1 720 cm-1处出现特征峰，对应羰基-C=O的伸缩振动，表明XLPE在热老化过程中产生了羰基。老化温度为90℃时，羰基特征峰仅呈现小幅增大趋势；而老化温度为135℃时，随老化天数的增加，羰基特征峰显著增强，表明随着热老化程度加深，XLPE绝缘内部羰基含量增多。
通过计算国产与进口XLPE绝缘在90℃和135℃下老化不同时间后的羰基指数研究XLPE绝缘热老化的特点。两种XLPE绝缘试样的羰基指数随时间和温度的变化关系如图3所示。从图3可以看出，国产XLPE绝缘试样的羰基指数随着热老化时间的延长而增加。未老化时，国产XLPE试样中的羰基指数非常低，仅为0.82。135℃下老化14天后，羰基指数增加至1.24，相比未老化时增加了51.2%。135℃下老化70天后，羰基指数急剧增加至2.77，相比未老化时增加了237.8%。90℃下老化14天后，羰基指数没有明显变化。90℃下老化70天后，羰基指数增加至1.04，相比未老化时增加了26.8%，仍小于135℃下老化14天的羰基指数。这是由于随着温度升高，分子活性增强，加快了XLPE绝缘的氧化反应，此外，在高温下氧气扩散更快，增加了XLPE绝缘分子链间的氧气含量，因此高温催化了XLPE绝缘分子链的“自由基链式反应”。由国产与进口XLPE绝缘试样的羰基指数变化情况可知，国产和进口XLPE绝缘料的羰基指数变化趋势一致，此外，90℃下国产XLPE绝缘料的羰基指数较进口XLPE绝缘料更低，135℃下老化前中期，国产XLPE绝缘料与进口XLPE绝缘料的羰基指数相差不大，并且在老化70天后，国产料羰基指数更低。
XLPE绝缘的结晶度（Χc）可以反映其内部结构与相关理化性能，计算式如式（1）所示。
ΔXc=ΔHΔH0
式（1）中：∆H为被测试样的熔融焓，单位为J/g；∆H0为100%结晶时试样的熔融焓，取值为287.3 J/g。
图4为热老化温度分别为90℃和135℃时国产和进口XLPE绝缘试样的结晶度随老化时间的变化规律。从图4可以看出，90℃下XLPE绝缘试样老化前后的熔融结晶特性变化不大。刚开始老化时结晶度有些许上升，这是由于重结晶导致的，老化重结晶临界时间结束后，结晶度开始下降。未老化时的国产XLPE绝缘试样结晶度为31.43%，90℃下老化70天后试样的结晶度略有下降，为30.43%。135℃下老化国产XLPE绝缘试样的熔融焓随着老化时间的增加显著降低，老化14天时XLPE绝缘试样的结晶度降低至20.39%，而老化70天时结晶度发生显著下降，结晶度只有6.71%，可见135℃的老化条件下结晶度的下降速率远大于90℃时。对比90℃和135℃下国产与进口XLPE绝缘试样结晶度的变化情况，表明国产和进口XLPE绝缘试样的结晶度变化趋于一致，经过长期热老化后国产XLPE绝缘料的结晶度均略高于进口XLPE绝缘料，说明国产XLPE绝缘的内部微观结构更为稳定。
老化不同阶段XLPE结晶度的下降由不同原因引起。XLPE是由LDPE在高温与交联剂DCP作用下发生交联反应形成的。部分PE分子链交联形成网状结构，产生非晶区；另一部分PE分子链未发生交联。在老化开始阶段，高温会引发PE分子链游离端基的交联反应，提升绝缘交联度，进而降低了XLPE绝缘的结晶度；随老化时间增加，XLPE绝缘的交联结构被破坏，使结晶度下降速度减缓；在老化42～70天时，XLPE绝缘结晶度大幅下降，此时晶体结构在长期高温作用下被破坏，XLPE绝缘结晶度大幅降低。
2.2 热老化对XLPE力学性能的影响
进一步测试了国产和进口XLPE绝缘试样热老化后的力学性能变化规律，结果如图5～6所示。从图5～6可以看出，力学性能的变化规律与结晶度的变化规律类似。在90℃下，国产XLPE绝缘试样老化初期的断裂伸长率略有上升，从未老化试样的688.9%上升到729.9%，最大拉伸强度也略有上升。老化时间为56天时，断裂伸长率下降到601.1%。老化时间为70天时，试样的断裂伸长率为501.2%，最大拉伸强度从24.6 MPa下降到17.6 MPa，下降了28.5%。在135℃下，国产XLPE绝缘试样的断裂伸长率和最大拉伸强度下降迅速，老化14天时，断裂伸长率下降至564.9%，老化28天时断裂伸长率下降至368.6%，接近断裂伸长率下降50%的寿命终点，最大拉伸强度由24.6 MPa下降到20.5 MPa。根据曲线估计，XLPE绝缘试样寿命终止时间为35.5天。老化42天时断裂伸长率已低于原断裂伸长率的50%，到达寿命终点，最大拉伸强度为14.5 MPa，下降了41%。老化70天时，断裂伸长率为82.45%，仅为未老化试样的12%，最大拉伸强度为6.3 MPa，仅为未老化试样的26%。从图5～6还可以看出，国产和进口XLPE绝缘试样的断裂伸长率与最大拉伸强度均随老化时间降低，当老化温度为90℃时，国产与进口XLPE绝缘试样的断裂伸长率无明显差别，但国产XLPE绝缘试样的最大拉伸强度在热老化过程中较进口XLPE绝缘试样更大；当老化温度为135℃时，国产XLPE绝缘试样虽然断裂伸长率在老化过程中略小于进口XLPE绝缘试样，但其最大拉伸强度较大，在135℃下老化70天后，国产与进口XLPE绝缘试样的断裂伸长率已无明显差距，而国产XLPE绝缘试样的最大拉伸强度仍更大，表明经过长期热老化后国产XLPE绝缘试样的力学性能优于进口XLPE绝缘。
在90℃下，XLPE结晶区仍保持较为完整的结构，对自由基R·和O2的氧化反应有一定的阻碍作用，因此，XLPE绝缘试样的力学性能未发生大幅下降。在135℃下，XLPE绝缘试样进入黏流态，分子链变得无序分散，使得自由基R·和O2的氧化反应加剧，分子结构更多地被破坏，致使XLPE绝缘试样的力学性能大幅降低。
有研究指出，在老化初期键合作用强于断键，而在老化中后期断键作用强于键合[18]。90℃下国产XLPE绝缘试样老化初期的分子链断裂点与部分不完全交联PE分子链的交联反应较强，使XLPE绝缘交联度提升，网状结构更加坚固，同时晶体结构破坏性较小，因此老化初期力学性能提升。同样地，在135℃老化初期，XLPE绝缘的交联度有一定提高，力学性能下降速度较慢；而在老化中后期，XLPE绝缘晶体与交联结构在高温作用下破坏严重，使其力学性能快速下降。
2.3 热老化对XLPE电气性能的影响
为进一步分析热老化对交联聚乙烯电气性能的影响，测试了90℃和135℃下热氧老化不同时间的XLPE绝缘试样交流电气强度，得到63.2%失效概率下的电气强度如图7(a)所示。从图7(a)可以看出，除90℃下老化14天的国产XLPE绝缘试样电气强度略有上升外，其余绝缘试样的电气强度相比未老化绝缘试样均有不同程度的下降，表明热老化会降低XLPE绝缘试样的电气性能，且高温下老化试样电气强度的下降幅度明显大于低温下的老化试样。未老化试样的电气强度为30.7 kV/mm，135℃老化70天后试样的电气强度仅为22.3 kV/mm，下降了27.4%。未老化试样在不同温度下均保持了较高的电气强度；经热老化后，电气强度下降幅度较大，归因于在氧气和热的作用下XLPE发生热氧老化降解。随着老化温度的升高，试样在热氧老化过程中与氧气接触更充分且容易造成试样内部的大分子链断裂、降解，非晶区的分子链更易受热氧老化的影响，甚至形成局部缺陷，成为诱发击穿的薄弱点，进而导致电气强度降低。
在实际工业应用中，低概率下的电气强度也会造成事故的发生，因此有必要对1%失效概率下试样的电气强度进行分析。图7(b)为失效概率为1%时XLPE绝缘试样的电气强度随老化时间的变化。当老化温度为90℃时，两种XLPE绝缘试样在1%失效概率下的电气强度均在老化时间为14和42天明显下降。相比之下，国产XLPE绝缘试样在老化前、后失效概率为1%时的电气强度更高。当老化温度升高到135℃时，老化后的两种XLPE绝缘试样1%失效概率下的电气强度都表现出明显的下降，但国产XLPE绝缘试样的电气强度仍高于相同老化时间下的进口XLPE绝缘试样。
国产与进口XLPE绝缘试样交流电气强度Weibull分布的形状参数如表2所示。从表2可以看出，老化14天与42天试样的形状参数较小，这是因为在热老化过程中，XLPE绝缘试样的劣化存在分散性，使其电气强度也具有更大的分散性，而在老化70天时，所有试样的劣化均达到较为严重的程度，此时所有试样的电气强度分散性变小。
在30℃和90℃环境下测试热老化处理后国产和进口XLPE绝缘试样的体积电导率，结果如图8所示。从图8(a)可以看出，30℃环境下未老化的国产和进口XLPE绝缘试样体积电导率分别为2.77×10-15 S/m和1.98×10-15 S/m，满足国标规定的220 kV高压交流电缆交联聚乙烯绝缘常温体积电导率的要求。经90℃热老化70天后，在30℃环境下国产和进口XLPE绝缘试样的体积电导率分别上升至1.42×10-14 S/m和1.33×10-14 S/m，相较于未老化试样分别上升了412.3%和617.1%，且体积电导率逐渐趋于稳定。相比于90℃热老化，135℃热老化使XLPE绝缘试样的体积电导率显著上升；135℃热老化70天后，国产和进口XLPE绝缘试样在30℃环境下体积电导率分别上升至2.14×10-13 S/m和3.22×10-13 S/m，相较于未老化试样上升了两个数量级，表明135℃热老化对XLPE绝缘试样的体积电导率造成较大影响。对比国产和进口XLPE绝缘试样的体积电导率随老化温度和时间的变化，在老化温度为90℃条件下，进口XLPE绝缘试样的体积电导率均略小于国产XLPE绝缘试样，而在老化温度为135℃条件下，老化28天后进口XLPE绝缘试样的体积电导率均超过国产XLPE绝缘试样，且有进一步上升趋势，表明国产XLPE绝缘试样具有更优异的耐热氧老化特性。
从图8(b)可以看出，相较于30℃测试环境温度，提高测试环境温度明显提高了绝缘试样的体积电导率，这与载流子运动加速密切相关。国产XLPE绝缘试样在90℃下的体积电导率随热老化时长的变化趋势与30℃测试环境温度的结果相一致。相较于未老化的XLPE绝缘试样，135℃热老化处理70天后体积电导率提高了1个数量级，而相较于相同老化时间的90℃热老化处理，135℃热老化处理后的体积电导率提高不足1个数量级。
2.4 热老化寿命评估
根据上文中试样的力学性能随老化时间变化的规律可知，老化温度为135℃时，国产XLPE绝缘试样的寿命终止时间为35.5天，基于IEC 60216-1:2013要求，将热加速老化采用的II类强制通风条件（换气160次/h），折算为I类强制通风条件（换气20次/h）折算方法如式（2）所示[16]。
τ1=8⋅τ0
式（2）中：τ0为135℃下的真实热老化时间；τ1为折算为I类强制通风条件下的热老化时间。
基于Arrhenius公式，将老化温度为135℃的热加速老化时间折算为90℃工况温度下的等效热老化时间，如式（3）～（4）所示。
τ2τ1=exp-EaR⋅T135exp-EaR⋅T90
τ2=τ1⋅expEaR⋅1T90-1T135
式（3）～（4）中：τ2为90℃下的等效热老化时间；R为理想气体常数，约为8.314 472 J/(mol·K）；Ea为试验活化能，取典型值为100 kJ/mol；T90与T135为热力学温度，即T90=363.15 K，T135=408.15 K。
将135℃寿命终止时长τ0代入式（2）与式（4）得到等效工况寿命τ2，结果如表3所示。从表3可以看出，国产XLPE绝缘试样比进口XLPE绝缘试样具有更长的热老化寿命。
3 机理分析
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XLPE绝缘微观结构的变化会影响其整体宏观性能。在经过高温热氧老化处理后，不论是国产还是进口的XLPE绝缘试样，XLPE的分子链都会发生氧化反应，产生很多的游离基。部分游离基会继续交联，提升XLPE绝缘试样的力学性能，但随着老化时间的推移，更多的游离基会更倾向于破坏分子链，导致XLPE稳定有序的晶区结构被损坏，聚合物总体结晶度降低。
同样地，高温老化造成的分子链分解也会促使载流子自由程的增加，载流子活动变得更加激烈，载流子数量增多、迁移速率加快，使得XLPE绝缘试样的电流密度增加，导致体积电导率上升了数个数量级。由于非晶区的脆弱性，该部分的分子链更容易发生断裂形成物理缺陷区域，其在强电场下会成为诱发击穿的薄弱点，引起电场畸变进而降低了XLPE绝缘的电气强度。但是因为国产XLPE绝缘试样有着更稳定的内部微观结构，致使其受热氧老化的影响相较于进口XLPE绝缘试样更小，所以国产XLPE绝缘试样保持着更加优异的宏观性能，更直观的表现就是其热老化终止寿命更长。
4 结论
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（1）对XLPE绝缘试样进行加速热老化试验，发现热老化过程中XLPE绝缘试样色泽由白色变为黄色乃至暗红色且试样透明度下降。此外，老化后XLPE绝缘的晶体结构被破坏，结晶度下降，交联度提高，相同处理条件下，国产XLPE绝缘的结晶度高于进口XLPE。
（2）在90℃下，国产XLPE绝缘试样的力学性能先升高后降低；而在135℃下老化，由于分子结构遭到破坏，老化试样的力学性能大幅降低，但国产XLPE绝缘试样的力学性能优于进口的XLPE绝缘试样。
（3）热氧老化过程致使XLPE绝缘的大分子链断裂、降解，形成局部物理缺陷区域，进而降低了XLPE绝缘的交流电气强度。在相同热老化条件下，国产XLPE绝缘试样的交流电气强度略优于进口XLPE绝缘试样。
（4）国产XLPE绝缘试样比进口XLPE绝缘试样具有更长的热老化寿命，说明国产220 kV XLPE绝缘料具有较好的耐热老化性能，可为我国实现220 kV高压电缆绝缘料的国产化替代奠定关键基础。
基金
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  • 南方电网公司科技项目(SZKJXM20190588)
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参考文献 引证文献
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2023年第56卷第7期
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doi: 10.16790/j.cnki.1009-9239.im.2023.07.006
  • 接收时间：2022-06-06
  • 首发时间：2025-11-24
  • 出版时间：2023-07-20
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  • 收稿日期：2022-06-06
  • 修回日期：2022-12-05
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南方电网公司科技项目(SZKJXM20190588)
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    1深圳供电局有限公司,广东 深圳 518000
    2南方电网科学研究院有限责任公司,广东 广州 510663
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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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