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Article(id=1304923109807649150, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1304923090710982825, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2026.04.005, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1744732800000, receivedDateStr=2025-04-16, revisedDate=1749484800000, revisedDateStr=2025-06-10, acceptedDate=null, acceptedDateStr=null, onlineDate=1789047513677, onlineDateStr=2026-09-10, pubDate=1776614400000, pubDateStr=2026-04-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1789047513677, onlineIssueDateStr=2026-09-10, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1789047513677, creator=13701087609, updateTime=1789047513677, 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=39, endPage=46, ext={EN=ArticleExt(id=1304923110000587135, articleId=1304923109807649150, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Effect of cross-linking reaction conditions on thermal-oxidative ageing characteristics of polyethylene cable insulation, columnId=1190369066675179686, journalTitle=Insulating Materials, columnName=Material Research, runingTitle=null, highlight=null, articleAbstract=

The thermal-oxidative ageing characteristics of cross-linked polyethylene (XLPE) are the critical factor affecting the operational life of cable insulation, but its internal relationship with XLPE cross-linking reaction conditions are still lacking in research. In this paper, seven types of XLPE samples were prepared by precisely controlling the cross-linking reaction temperature and time. Combined with Fourier transform infrared spectroscopy, tensile test, and gel content measurement, the influence law and mechanism of cross-linking reaction conditions on the thermal-oxidative ageing characteristics of XLPE cable insulation were investigated. The results show that the cross-linking reaction conditions directly affect the residual antioxidant content and the cross-linking structure in XLPE, while the thermal-oxidative ageing resistance of XLPE is dominated by the residual antioxidant content, which is also synergistically influenced by the cross-linking structure.When the cross-linking reaction temperature is too low or the time is too short, the cross-linking structure of XLPE is incomplete; when the cross-linking reaction temperature is too high or the time is too long, the cross-linking structure of XLPE will not be significantly improved, while the residual antioxidant content in XLPE will decreases. Both the two cases will lead to a decrease in thermal-oxidative ageing resistance of XLPE. The XLPE prepared under the cross-linking reaction temperature of 170℃ and reaction time of 16 min exhibits excellent thermal-oxidative ageing resistance, which is due to the high residual antioxidant content of XLPE under the cross-linking reaction condition and the perfect cross-linking structure. The research result provides a theoretical support for optimizing thethermal-oxidative ageing resistance of XLPE cable insulation.

, authors=Peigao ZHANG1, *, Xiangliang ZHANG2, Xiaozili HUANG3, authorsList=Peigao ZHANG, Xiangliang ZHANG, Xiaozili HUANG, authorCompany=null, correspAuthors=Peigao ZHANG, 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=1304923111665725844, articleId=1304923109807649150, tenantId=1146029695717560320, journalId=1149653034449285133, language=CN, title=交联反应条件对聚乙烯电缆绝缘热氧老化特性影响的研究, columnId=1190369066813591720, journalTitle=绝缘材料, columnName=材料研究, runingTitle=null, highlight=null, articleAbstract=

交联聚乙烯（XLPE）的热氧老化特性是影响电缆绝缘运行寿命的关键因素，但其与XLPE交联反应条件的内在关联尚缺乏研究。本文精确调控交联反应温度和时间制备7种XLPE试样，结合傅里叶红外光谱、拉伸测试和凝胶含量测试，探讨交联反应条件对交联聚乙烯电缆绝缘热氧老化特性的影响规律与机理。结果表明：交联反应条件直接影响XLPE中剩余抗氧剂含量和交联结构，而XLPE的耐热氧老化性能由剩余抗氧剂含量主导，也受交联结构的协同影响。交联反应温度过低、时间过短会导致XLPE交联结构不完善；交联反应温度过高、时间过长不能明显提升XLPE的交联结构，反而会降低XLPE中剩余抗氧剂的含量，两种情况均会导致XLPE的耐热氧老化性能降低。交联反应温度为170℃且反应时间为16 min条件下制备的XLPE试样具有优异的耐热氧老化性能，这源于该交联反应条件下XLPE较高的剩余抗氧剂含量，同时交联结构较完善。该研究结果为XLPE电缆绝缘耐热氧老化性能的优化提供了理论支撑。

, authors=张培高1, *, 张向亮2, 黄小自立3, authorsList=张培高, 张向亮, 黄小自立, authorCompany=null, correspAuthors=张培高, authorNote=

张向亮（1987-），男（汉族），江西九江人，高级工程师，主要从事轨道交通保护、高低压电缆系统的研究。

, correspAuthorsNote=
张培高（1986-），男（汉族），四川宜宾人，讲师，主要从事电力设备状态监测与故障诊断、高低压电缆系统的研究；
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张向亮（1987-），男（汉族），江西九江人，高级工程师，主要从事轨道交通保护、高低压电缆系统的研究。

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张向亮（1987-），男（汉族），江西九江人，高级工程师，主要从事轨道交通保护、高低压电缆系统的研究。

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交联反应条件对聚乙烯电缆绝缘热氧老化特性影响的研究
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张培高 1, * , 张向亮 2 , 黄小自立 3
绝缘材料 | 材料研究 2026,59(4): 39-46
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绝缘材料 |材料研究 2026 , 59 (4) : 39 -46
交联反应条件对聚乙烯电缆绝缘热氧老化特性影响的研究
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张向亮（1987-），男（汉族），江西九江人，高级工程师，主要从事轨道交通保护、高低压电缆系统的研究。

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张培高1, *, 张向亮2, 黄小自立3
作者信息
  • 1泸州职业技术学院，四川　泸州　646000
  • 2湖州学院，浙江　湖州　313000
  • 3桂林赛盟检测技术有限公司，广西　桂林　541004
通讯作者:
张培高（1986-），男（汉族），四川宜宾人，讲师，主要从事电力设备状态监测与故障诊断、高低压电缆系统的研究；
作者简介:

张向亮（1987-），男（汉族），江西九江人，高级工程师，主要从事轨道交通保护、高低压电缆系统的研究。

Effect of cross-linking reaction conditions on thermal-oxidative ageing characteristics of polyethylene cable insulation
Peigao ZHANG1, *, Xiangliang ZHANG2, Xiaozili HUANG3
Affiliations
  • 1Luzhou Vocational & Technical College, Luzhou 646000, China
  • 2Huzhou College, Huzhou 313000, China
  • 3Guilin CEMT Technology Co., Ltd., Guilin 541004, China
出版时间: 2026-04-20 doi: 10.16790/j.cnki.1009-9239.im.2026.04.005
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摘要
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交联聚乙烯（XLPE）的热氧老化特性是影响电缆绝缘运行寿命的关键因素，但其与XLPE交联反应条件的内在关联尚缺乏研究。本文精确调控交联反应温度和时间制备7种XLPE试样，结合傅里叶红外光谱、拉伸测试和凝胶含量测试，探讨交联反应条件对交联聚乙烯电缆绝缘热氧老化特性的影响规律与机理。结果表明：交联反应条件直接影响XLPE中剩余抗氧剂含量和交联结构，而XLPE的耐热氧老化性能由剩余抗氧剂含量主导，也受交联结构的协同影响。交联反应温度过低、时间过短会导致XLPE交联结构不完善；交联反应温度过高、时间过长不能明显提升XLPE的交联结构，反而会降低XLPE中剩余抗氧剂的含量，两种情况均会导致XLPE的耐热氧老化性能降低。交联反应温度为170℃且反应时间为16 min条件下制备的XLPE试样具有优异的耐热氧老化性能，这源于该交联反应条件下XLPE较高的剩余抗氧剂含量，同时交联结构较完善。该研究结果为XLPE电缆绝缘耐热氧老化性能的优化提供了理论支撑。

电缆绝缘  /  交联聚乙烯  /  交联反应条件  /  热氧老化  /  剩余抗氧剂含量

The thermal-oxidative ageing characteristics of cross-linked polyethylene (XLPE) are the critical factor affecting the operational life of cable insulation, but its internal relationship with XLPE cross-linking reaction conditions are still lacking in research. In this paper, seven types of XLPE samples were prepared by precisely controlling the cross-linking reaction temperature and time. Combined with Fourier transform infrared spectroscopy, tensile test, and gel content measurement, the influence law and mechanism of cross-linking reaction conditions on the thermal-oxidative ageing characteristics of XLPE cable insulation were investigated. The results show that the cross-linking reaction conditions directly affect the residual antioxidant content and the cross-linking structure in XLPE, while the thermal-oxidative ageing resistance of XLPE is dominated by the residual antioxidant content, which is also synergistically influenced by the cross-linking structure.When the cross-linking reaction temperature is too low or the time is too short, the cross-linking structure of XLPE is incomplete; when the cross-linking reaction temperature is too high or the time is too long, the cross-linking structure of XLPE will not be significantly improved, while the residual antioxidant content in XLPE will decreases. Both the two cases will lead to a decrease in thermal-oxidative ageing resistance of XLPE. The XLPE prepared under the cross-linking reaction temperature of 170℃ and reaction time of 16 min exhibits excellent thermal-oxidative ageing resistance, which is due to the high residual antioxidant content of XLPE under the cross-linking reaction condition and the perfect cross-linking structure. The research result provides a theoretical support for optimizing thethermal-oxidative ageing resistance of XLPE cable insulation.

cable insulation  /  cross-linked polyethylene  /  cross-linking reaction condition  /  thermal-oxidative ageing  /  residual antioxidant content
张培高, 张向亮, 黄小自立. 交联反应条件对聚乙烯电缆绝缘热氧老化特性影响的研究. 绝缘材料, 2026 , 59 (4) : 39 -46 . DOI: 10.16790/j.cnki.1009-9239.im.2026.04.005
Peigao ZHANG, Xiangliang ZHANG, Xiaozili HUANG. Effect of cross-linking reaction conditions on thermal-oxidative ageing characteristics of polyethylene cable insulation[J]. Insulating Materials, 2026 , 59 (4) : 39 -46 . DOI: 10.16790/j.cnki.1009-9239.im.2026.04.005
正文
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0　引言
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交联聚乙烯（cross-linked polyethylene，XLPE）作为高压电缆的主绝缘材料，在运行过程中长期承受着高温作用，不可避免地发生热老化而对材料造成不可恢复的损伤，甚至导致材料击穿失效[1-3]。XLPE通常是由电缆绝缘料经过复杂的交联反应形成，而交联反应条件是决定其结构与组成的关键因素[1,4]。因此，开展交联反应条件对XLPE电缆绝缘热氧老化特性影响的研究具有重要意义。
热氧老化特性是XLPE电缆绝缘领域研究的热点内容。XLPE热氧老化过程涉及复杂的反应，主要包括自由基引发、增长和终止反应[3,5]，会直接导致XLPE大分子链断裂，生成小分子链和羰基等产物，从而影响XLPE的聚集态结构[6-9]，最终表现为材料宏观性能的劣化甚至失效[8-12]。
当前，大量的研究聚焦于XLPE热氧老化特性影响因素的分析，在提升其耐热氧老化性能方面取得显著成果。抗氧剂作为材料抗老化的重要添加剂，其含量越多，反应活性越高，越有利于提升材料的耐热氧老化性能[13-15]。氧气是热氧老化的关键因素，氧气浓度越高，抗氧剂消耗越快，XLPE的结构和性能劣化越明显[16-17]。此外，老化温度对XLPE的热氧老化特性和性能劣化有显著的影响，温度越高，XLPE热氧老化反应越剧烈，性能劣化越快[7,18-20]。也有研究表明，在温度频变环境下的热氧老化比恒温环境下的热氧老化对XLPE绝缘的结构破坏更加严重[21]。可见，当前针对高压电缆XLPE热氧老化特性方面已开展大量的研究，但忽略了交联反应条件对XLPE热氧老化特性的影响。
基于上述分析，本文开展交联反应条件对XLPE热氧老化特性的影响及其机理研究。首先精确调控交联反应温度、时间制备7种XLPE试样，采用加速热老化方法制备不同的老化试样，然后通过傅里叶红外光谱和拉伸测试，全面分析交联反应温度和时间对XLPE热氧老化特性的影响规律，结合凝胶含量测试、傅里叶红外光谱和抗氧剂作用原理，揭示交联反应温度和时间对XLPE热氧老化特性的影响机理，为XLPE电缆绝缘耐热氧老化性能的优化提供理论基础。
1　实验
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1.1　主要原材料
选择某国产110 kV高压电缆绝缘用低密度聚乙烯（LDPE）作为基础树脂；过氧化二异丙苯（dicumyl peroxide，DCP）和抗氧剂300购于上海麦克林生化科技有限公司。
1.2　试样制备
取适量LDPE、DCP和抗氧剂300加入密炼机，保持118℃的腔体温度和24 r/min的转速，熔融共混8 min后得到绝缘料。再取适量绝缘料，在120℃的硫化机中预热8 min，然后在不同温度和时间下热压交联，压力始终保持16 MPa，热交联后再水冷至室温制得XLPE试样。最后将XLPE试样放置在真空干燥箱中脱气，温度为70℃，时间为18 h。其中DCP和抗氧剂添加量分别为1.8份和0.2份。
交联反应温度分别设置为165、170、175、180℃，保持交联反应时间为12 min不变，制得的试样分别命名为W165、W170、W175、W180；交联反应时间分别设置为12、16、20、24 min，保持交联反应温度为170℃不变，制得的试样分别命名为W170、T16、T20、T24。
热氧老化试样制备：将上述XLPE试样悬挂在鼓风恒温老化箱中，在135℃下进行加速热老化处理，热老化时间分别为168、672、1 536、1 656、1 776、1 896、2 016、2 136 h。
1.3　测试方法
采用Nicolet iS10型傅里叶红外光谱仪测试XLPE试样中羰基与抗氧剂含量，试样厚度为1 mm，选择反射模式，测量波数为1 600～3 600 cm-1，分辨率为0.4 cm-1。
采用5KNCMT-4503型拉力机测试XLPE试样的力学性能，将试样裁剪为哑铃状，厚度为1 mm，拉伸速率为100 mm/min，通过计算机自动生成应力-应变曲线，再根据式（1）计算XLPE试样的断裂伸长率。
EBA=L-L0L0×100%
式（1）中：EBA为断裂伸长率，%；L为试样拉伸断裂时的标线长度；L0为试样拉伸前的标线长度。
采用凝胶萃取法测试XLPE试样的交联度，将试样切成直径为0.5 mm的片状并放入不锈钢网袋，将网袋放入煮沸的二甲苯溶液中，保持温度为110℃，时间为24 h，然后取出网袋，在110℃的真空烘箱中放置24 h进行干燥。每个试样测试5次，取平均值作为最终交联度。交联度（M）计算方法如式（2）所示。
M=m2-m0m1-m0×100%
式（2）中：m0为网袋质量；m1为萃取前网袋和试样的质量；m2为干燥后网袋和试样的质量。
2　结果与讨论
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2.1　交联反应温度对XLPE热氧老化特性的影响
通过XLPE中羰基浓度随老化时间的变化规律，能够有效评估XLPE的热氧老化特性。采用比尔-朗伯定律可以定量计算XLPE中的羰基浓度，如式（3）所示。
CC=O=Aα
式（3）中：CC=O为羰基浓度；A为波数为1 712 cm-1处羰基特征峰的吸光度；α为羰基的摩尔吸收系数，其值为300 mol-1·L·cm-1。
不同交联反应温度下XLPE试样中羰基浓度随老化时间的变化规律如图1所示。从图1可以看出，在老化初期（672 h之前），4种试样的羰基浓度和增加速率相差不大，羰基浓度均低于0.5 mol/L；在老化中后期（672～2 136 h），W165和W180试样的羰基浓度明显高于W170和W175试样，尤其在老化1 896 h时，W170和W175试样的羰基浓度分别为2.2 mol/L和2.0 mol/L，而W165和W180试样此时的羰基浓度均大于8.0 mol/L。这表明交联反应温度过高或过低，均会对XLPE的耐热氧老化性能造成负面影响。从图1还可以看出，4种试样的羰基浓度均呈现先缓慢增加再突然快速增加的变化趋势，这表明XLPE的耐热氧老化性能存在临界点，临界点所对应的时间称为耐老化临界时间，试样的耐老化临界时间越长，表明其耐热氧老化性能越好。从图1中插图可知，W165、W170、W175、W180试样的临界耐老化时间分别为1 776、1 896、1 896、1 656 h，表明随着交联反应温度升高，XLPE试样的耐老化临界时间会出现1个峰值，对应的试样具有更好的耐热氧老化性能，而交联反应温度过高或过低均会削弱XLPE的耐热氧老化性能。
进一步采用断裂伸长率表征XLPE的耐热氧老化性能，断裂伸长率越低，说明其内部网络结构越不完善。而在老化过程中，断裂伸长率突变越早，表明老化对XLPE内部分子链破坏越严重，即试样的耐热氧老化性能越差。图2为4种XLPE试样的断裂伸长率随老化时间的变化规律。
从图2可以看出，W165和W170试样的断裂伸长率呈现先升高后缓慢下降再突然快速下降的趋势；而W175和W180试样的断裂伸长率呈现缓慢下降再突然快速下降的趋势。未老化时，W165、W170、W175、W180试样的断裂伸长率分别为585%、596%、624%、613%，W165试样的断裂伸长率明显低于其他试样，这与其内部不完善的交联结构相关。而老化168 h之前，W165和W170试样的断裂伸长率呈现略微升高的趋势，这是由于其内部剩余过氧化物或者自由基在热作用下继续交联导致。随着老化时间的增加，4种XLPE试样的断裂伸长率均出现临界点，由图2插图可知，其对应的临界时间与羰基浓度曲线的临界时间基本一致，表明老化过程中确实存在临界状态，且XLPE试样的断裂伸长率临界时间随交联反应温度的变化也会出现1个峰值。
结合图1和图2可知，XLPE的耐热氧老化性能存在临界点，交联反应的温度过高或者过低均会缩短XLPE的耐老化临界时间，削弱XLPE试样的耐热氧老化性能。
2.2　交联反应时间对XLPE热氧老化特性的影响
不同交联反应时间的XLPE试样中羰基浓度随老化时间的变化规律如图3所示。
从图3可以看出，在老化初期（672 h之前），4种XLPE试样的羰基浓度和增加速率相差不大；在老化中后期（672～2 136 h），相同老化时间下4种XLPE试样的羰基浓度从小到大依次为T16、W170、T20、T24，在老化1 896 h时，W170、T16、T20、T24试样的羰基浓度分别为2.2、1.4、2.5、9.1 mol/L；在老化2 016 h时，W170、T20、T24试样的羰基浓度均大于9.0 mol/L，远高于T16试样，表明交联反应时间过长或过短均会对XLPE的耐热氧老化性能造成负面影响。
从图3还可以看出，4种XLPE试样的羰基浓度均呈现先缓慢增加再快速增加的变化趋势。W170、T16、T20、T24试样的耐老化临界时间分别为1 896、2 016、1 896、1 776 h，表明随着交联反应时间的增加，XLPE试样的临界耐老化时间也会出现1个峰值，而交联反应时间过长或过短均会削弱XLPE的耐热氧老化性能。
进一步采用断裂伸长率表征不同交联反应时间下XLPE试样的耐热氧老化性能，结果如图4所示。从图4可以看出，W170试样的断裂伸长率呈现先缓慢升高后缓慢下降再突然快速下降的趋势，而T16、T20、T24试样的断裂伸长率呈现先基本不变后缓慢下降再突然快速下降的趋势。未老化时，W170、T16、T20、T24试样的断裂伸长率分别为596%、622%、622%和620%，W170试样的断裂伸长率明显低于其他试样，这与其内部不完善的交联结构相关。随着老化时间的延长，4种XLPE试样的断裂伸长率也均出现临界点，由图4插图可知，其对应的临界时间与羰基浓度曲线的临界时间基本一致，且XLPE试样的断裂伸长率临界时间随交联反应时间的变化也存在1个峰值。
结合图3和图4，进一步证明XLPE的耐热氧老化性能存在临界点，交联反应时间过长或过短均会降低XLPE试样的耐热氧老化性能。
基于图1和图3的测试结果可知，XLPE的耐热氧老化性能受交联反应温度和时间的影响，故绘制交联反应温度-反应时间-临界时间的数据图，如图5所示。从图5可以看出，交联反应温度为170℃、交联反应时间为16 min处XLPE试样的临界时间最大，表明该交联反应条件下的XLPE试样具有最佳的耐热氧老化性能。此外，交联反应条件对于XLPE的耐热氧老化性能具有显著影响，即交联反应的温度过高或过低、交联反应时间过长或过短均会削弱XLPE的耐热氧老化性能。
2.3　交联反应条件对XLPE热氧老化特性的影响机制
由上述分析可知，交联反应温度和时间均会影响XLPE试样的热氧老化性能。为了深入讨论其影响机制，进一步从交联结构和组成成分两个方面进行分析。
测试不同交联反应温度下XLPE试样的交联度随老化时间的变化曲线，结果如图6所示。从图6可以看出，未老化时，W165、W170、W175、W180试样的交联度分别为82.9%、84.8%、86.2%、85.7%，随着交联反应温度的升高，交联度呈现先上升然后基本不变的趋势，表明交联反应温度过高对XLPE的交联结构基本无提升作用。对比XLPE试样交联度在整个老化周期的变化规律，在老化672 h之前，W165和W170试样的交联度均先略上升后再缓慢下降，而W175和W180试样的交联度直接缓慢下降，表明未老化时W165和W170试样的交联结构并不完善；在老化672～2 136 h时，4种XLPE试样的交联度均呈现先缓慢下降再突然快速下降的趋势。从图6插图可以看出，4种XLPE交联度的临界时间分别为1 776、1 896、1 896、1 656 h，与XLPE羰基浓度的临界时间一致，但临界点处不同试样的交联度并不同，W165、W170、W175、W180试样的临界交联度分别为79%、81.5%、81.4%、82.2%。
测试不同交联反应时间下XLPE试样的交联度随老化时间的变化曲线，结果如图7所示。从图7可以看出，未老化时，W170、T16、T20、T24试样的交联度分别为84.8%、86.0%、86.1%、86.0%，随着交联反应时间的增加，试样的交联度呈现先上升随后基本不变的趋势，表明交联反应时间过长对XLPE试样的交联结构也没有提升作用。
对比XLPE试样交联度在整个老化周期的变化规律，在老化672 h之前，W170试样的交联度先略有增加后降低，而T16、T20、T24试样的交联度基本不变，表明未老化时W170试样的交联结构并不完善；在老化672～2 136 h时，4种XLPE试样的交联度均呈现先缓慢下降后快速下降的趋势。从图7插图可以看出，4种XLPE交联度的临界时间分别为1 896、2 016、1 896、1 776 h，与其耐老化临界时间基本一致，但临界点处不同试样的交联度并不同，W170、T16、T20、T24试样的临界交联度分别为81.5%、81.6%、81.4%、77.6%，表明XLPE的交联度数值不能作为耐热氧老化性能临界点的判据。
综上可知，交联反应温度过低、交联反应时间过短，使得XLPE内部的交联结构不完善，表现为交联度较低，这也是其断裂伸长率在老化初期较小的原因。但交联反应温度过高、交联反应时间过长并未使得XLPE交联度提高，表明该条件对进一步完善交联结构贡献不大。然而，上述分析表明，交联反应温度过高、交联反应时间过长的XLPE试样耐热氧老化性能仍存在差异，说明交联结构是否完善不是影响XLPE耐热氧老化性能的唯一因素。
抗氧剂作为XLPE交联过程和耐热氧老化性能的关键添加剂，其作用机理如图8所示。在交联反应过程中，抗氧剂中的酚羟基会与LDPE自由基发生还原反应，如图8中的路径I所示，因此交联过程中会消耗一定抗氧剂；而在长期老化过程中，抗氧剂会与自由基发生反应，起到延缓老化进程的作用，如图8中的路径II所示。
通过图8可知，交联反应和热氧老化反应过程中均会消耗抗氧剂，当交联反应条件选择不恰当时，抗氧剂将大量消耗，使得XLPE中剩余抗氧剂含量减少，进而显著影响其耐热氧老化性能。当老化过程中XLPE中无抗氧剂或者含量极少时，无法有效延缓老化反应，XLPE会快速老化，此时为XLPE耐热氧老化性能的临界点。因此，剩余抗氧剂含量在交联反应条件对XLPE耐热氧老化性能的影响方面具有关键作用。
为了进一步研究抗氧剂含量的影响，通过傅里叶红外光谱测试不同XLPE试样的剩余抗氧剂含量，波数为3 510 cm-1处是抗氧剂300的特征峰。考虑到最初制样添加的抗氧剂含量是一致的，为了有效定量分析，本文以未老化W165试样的剩余抗氧剂含量为基准，对其他XLPE试样的抗氧剂含量进行归一化处理，结果如图9和图10所示。从图9和图10可以看出，所有试样的剩余抗氧剂含量曲线呈现3个阶段，老化168 h之前，抗氧剂迅速消耗，主要用于捕捉自由基和分解过氧化物，延缓老化进程；在老化168～1 656 h时，随着老化时间增加，抗氧剂消耗速度减缓，虽然含量有所下降，但仍持续发挥抗老化作用，延缓材料老化；在老化1 656～2 136 h时，抗氧剂快速消耗至几乎耗尽，材料失去保护，老化反应加速[22-23]。
由图9和图10插图可以看出，剩余抗氧剂含量也存在临界点，7种试样的剩余抗氧剂含量临界时间从小到大依次为W180、T24、T20、W175、W165、W170、T16，这与羰基浓度的临界时间基本一致。综上可知，T16试样的耐热氧老化性能最佳。
7种试样剩余抗氧剂含量临界时间所对应的剩余抗氧剂含量均为0.18±0.02，由此可知，当XLPE的剩余抗氧剂含量低于一定值时，XLPE材料基本失去耐热氧老化性能。XLPE试样临界点处的交联度是不同的，但临界点处剩余抗氧剂含量基本一致，侧面表明剩余抗氧剂含量是XLPE试样耐热氧老化性能的主导因素。由此可以推测，XLPE中剩余抗氧剂含量能够作为其耐热氧老化性能的评估标准。
结合XLPE试样的交联度和剩余抗氧剂含量综合分析，未老化时，W165和W170试样中剩余抗氧剂含量明显较高，但由于其交联度低，交联结构不完善，导致试样的耐热老化性能不佳。虽然其他5种试样的交联度均为85%左右，但其相应的起始剩余抗氧剂含量及其临界时间和羰基浓度临界时间不同，从小到大依次为W180、T24、T20、W175、T16。这是由于交联剂和抗氧剂含量相同的情况下，XLPE的交联度是有上限的，即交联度达到一定值后并不会随交联反应时间和温度的增加而增加，但在高温下，XLPE试样中仍会存在一定大分子自由基，随着抗氧剂小分子不停扩散运动，抗氧剂不断被大分子自由基消耗，导致剩余抗氧剂含量减少。
综上所述，交联反应温度和时间对XLPE的耐热氧老化性能均有显著的影响，交联反应温度过低、交联反应时间过短会导致XLPE交联结构不完善，在一定程度上降低XLPE的耐热氧老化性能；而交联反应温度过高、交联反应时间过长不会完善XLPE的交联结构，但会明显降低XLPE中剩余抗氧剂含量，进而导致其耐热氧老化性能下降。交联反应温度为170℃且反应时间为16 min的XLPE试样具有优异的耐热氧老化性能。
3　结论
收起
（1）交联反应温度和时间直接影响XLPE中剩余抗氧剂含量和交联结构，进而影响其耐热氧老化性能，其中，XLPE的耐热氧老化性能由剩余抗氧剂含量主导，同时也受交联结构的协同作用。
（2）交联反应温度低且反应时间短，会导致XLPE交联结构不完善，降低其耐热氧老化性能；而过度提高反应温度或延长反应时间，尽管能在一定程度上完善交联结构，但会降低XLPE中剩余抗氧剂含量，显著降低其耐热氧老化性能。
（3）交联反应温度为170℃且反应时间为16 min的XLPE试样具有优异的耐热氧老化性能，这源于该条件下XLPE不仅具有较高的剩余抗氧剂含量，同时交联结构较完善。

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2026年第59卷第4期
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doi: 10.16790/j.cnki.1009-9239.im.2026.04.005
  • 接收时间：2025-04-16
  • 首发时间：2026-09-10
  • 出版时间：2026-04-20
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  • 收稿日期：2025-04-16
  • 修回日期：2025-06-10
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    1泸州职业技术学院，四川　泸州　646000
    2湖州学院，浙江　湖州　313000
    3桂林赛盟检测技术有限公司，广西　桂林　541004

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张培高（1986-），男（汉族），四川宜宾人，讲师，主要从事电力设备状态监测与故障诊断、高低压电缆系统的研究；
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2种不同金属材料的力学参数
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genus		 种数
Number of
species		 占总种数比例
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total species (%)		 属
Genus		 种数
Number of
species		 占总种数比例
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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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