Article(id=1193543216340369684, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1193543214067056904, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2025.03.004, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1723996800000, receivedDateStr=2024-08-19, revisedDate=1729440000000, revisedDateStr=2024-10-21, acceptedDate=null, acceptedDateStr=null, onlineDate=1762492477736, onlineDateStr=2025-11-07, pubDate=1742400000000, pubDateStr=2025-03-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1762492477736, onlineIssueDateStr=2025-11-07, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1762492477736, creator=13701087609, updateTime=1762492477736, updator=13701087609, issue=Issue{id=1193543214067056904, tenantId=1146029695717560320, journalId=1149653034449285133, year='2025', volume='58', issue='3', pageStart='1', pageEnd='157', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1762492477194, creator=13701087609, updateTime=1762498203949, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1193567233872982429, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1193543214067056904, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1193567233872982430, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1193543214067056904, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=35, endPage=41, ext={EN=ArticleExt(id=1193543216562667798, articleId=1193543216340369684, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Effects of liquid additives on processing characteristics and physical properties of high-voltage cable insulation materials, columnId=1193543215723806988, journalTitle=Insulating Materials, columnName=Special Issue on Advanced Cable Insulation, runingTitle=null, highlight=null, articleAbstract=

The researches on the effect of liquid additives on the improvement of processing characteristics and physical properties of crosslinked polyethylene (XLPE) insulation materials for high-voltage cables are insufficient. In this paper, liquid crosslinking agents and antioxidants were taken as research objects. The effects and mechanisms of liquid additives on the scorch resistance, gel content, crosslinking by-products, thermodynamic and dielectric properties of XLPE were discussed. The results show that the liquid cross-linking agent 2,5-dimethyl-2,5-bis(tert-butyl peroxide)hexane with a high decomposition temperature and long-chain alkyl groups involved in crosslinking reaction can simultaneously enhance the scorch resistance and gel content of XLPE insulation materials, and reduce the content of crosslinking by-products. Meanwhile, the liquid antioxidants α-tocopherol and sorbitol exhibit excellent compatibility, they can form temperature-dependent proton transfer interactions, which can improve the anti-scorch performance of XLPE without compromising its gel content. Additionally, these liquid crosslinking agent and antioxidants can improve the breakdown performance of XLPE insulation while maintaining its thermodynamic properties. This study proves the feasibility of applying liquid additives to XLPE insulation for high-voltage cable.

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液体添加剂对提升高压电缆交联聚乙烯绝缘材料加工特性和物理性能影响的研究尚不充分。本文以液体交联剂和抗氧剂为研究对象,探讨液体添加剂对交联聚乙烯抗焦烧性能、凝胶含量、交联副产物含量、热力学和介电性能的影响及其机理。结果表明:液体交联剂2,5-二甲基-2,5-双(过氧化叔丁基)己烷具有较高分解温度和参与交联的长链烷基,可同时提升交联聚乙烯绝缘材料的抗焦烧性能和凝胶含量,并降低交联副产物含量。而液体抗氧剂α-生育酚和山梨醇具有良好的相容性,二者可形成具有温度依赖性的质子转移反应,可以在保证材料凝胶含量的前提下提升材料的抗焦烧性能。此外,液体交联剂和抗氧剂能够提升交联聚乙烯绝缘的击穿性能,同时保证热力学性能。该研究证明了液体添加剂应用至高压电缆交联聚乙烯绝缘中具有可行性。

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任想(1990-),男(汉族),湖北黄冈人,高级工程师,主要从事架空输电线路及电力电缆运维、电力设备碳排放评价、冲击电压计量的研究。
, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=o/glARYQLhSIbvyojnZPaQ==, magXml=IhUUqQ7/i1eVjzo8Y3hUaA==, pdfUrl=null, pdf=cd/P/qqltQN4Y07RtAASOQ==, pdfFileSize=2622722, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=VXWlT6qPh937ag04Q2hzoA==, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=MvtTDC9AFON19g5Ttjdviw==, mapNumber=null, authorCompany=null, fund=null, authors=

张耀东(1987-),男(汉族),湖北武汉人,高级工程师,主要从事电力电缆运维的研究。

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张耀东(1987-),男(汉族),湖北武汉人,高级工程师,主要从事电力电缆运维的研究。

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张耀东(1987-),男(汉族),湖北武汉人,高级工程师,主要从事电力电缆运维的研究。

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Journal of Applied Polymer Science,2023,140(20):e53844., articleTitle=An efficient strategy triggered crosslinking of polyethylene and its application in degassing-free ultrahigh voltage power cables, refAbstract=null)], funds=[Fund(id=1195077033354077174, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1193543216340369684, awardId=521532220002, language=CN, fundingSource=国网湖北省电力有限公司科技项目(521532220002), fundOrder=null, country=null)], companyList=[AuthorCompany(id=1195077029604369346, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1193543216340369684, xref=null, ext=[AuthorCompanyExt(id=1195077029612757955, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1193543216340369684, companyId=1195077029604369346, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=State Grid Hubei Electric Power Co., Ltd. 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label=Table 1, caption=Detailed formulas and naming of all samples, figureFileSmall=null, figureFileBig=null, tableContent=
试样 交联剂含量/份 抗氧剂含量/份
DCP DHBP 抗氧剂300 α-生育酚 山梨醇
PE-A 1.8 0 0.2 0 0
PE-B 1.8 0 0 0.1 0.1
PE-X 0 1.8 0.2 0 0
PE-Y 0 1.8 0 0.1 0.1
PE-Z 0 1.6 0 0.1 0.1
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试样的详细配方与命名

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试样 交联剂含量/份 抗氧剂含量/份
DCP DHBP 抗氧剂300 α-生育酚 山梨醇
PE-A 1.8 0 0.2 0 0
PE-B 1.8 0 0 0.1 0.1
PE-X 0 1.8 0.2 0 0
PE-Y 0 1.8 0 0.1 0.1
PE-Z 0 1.6 0 0.1 0.1
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试样 PE-A PE-B PE-X PE-Y PE-Z
凝胶含量/% 85.2 86.1 87.3 88.6 86.5
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XLPE试样的凝胶含量

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试样 PE-A PE-B PE-X PE-Y PE-Z
凝胶含量/% 85.2 86.1 87.3 88.6 86.5
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试样 PE-A PE-B PE-X PE-Y PE-Z
熔点/℃ 105.5 104.7 107.1 106.3 105.6
结晶度/% 31.4 30.1 32.3 31.9 32.8
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XLPE试样的熔点和结晶度

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试样 PE-A PE-B PE-X PE-Y PE-Z
熔点/℃ 105.5 104.7 107.1 106.3 105.6
结晶度/% 31.4 30.1 32.3 31.9 32.8
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试样 拉伸强度/MPa 断裂伸长率/%
PE-A 24.29 592.61
PE-B 24.38 601.18
PE-X 24.85 629.52
PE-Y 25.13 636.04
PE-Z 24.67 633.07
), ArticleFig(id=1195077033005949939, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1193543216340369684, language=CN, label=表4, caption=

XLPE试样的拉伸强度和断裂伸长率

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试样 拉伸强度/MPa 断裂伸长率/%
PE-A 24.29 592.61
PE-B 24.38 601.18
PE-X 24.85 629.52
PE-Y 25.13 636.04
PE-Z 24.67 633.07
), ArticleFig(id=1195077033064670196, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1193543216340369684, language=EN, label=Table 5, caption=Weibull parameters for breakdown characteristics of XLPE samples, figureFileSmall=null, figureFileBig=null, tableContent=
试样 α/(kV/mm) β
PE-A 487.67 11.82
PE-B 494.43 12.77
PE-X 498.85 12.13
PE-Y 509.38 13.75
PE-Z 511.92 13.91
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XLPE试样击穿特性的Weibull参数

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试样 α/(kV/mm) β
PE-A 487.67 11.82
PE-B 494.43 12.77
PE-X 498.85 12.13
PE-Y 509.38 13.75
PE-Z 511.92 13.91
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液体添加剂对高压电缆绝缘材料加工特性和物理性能的影响
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张耀东 , 任想
绝缘材料 | 先进电缆绝缘专题 2025,58(3): 35-41
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绝缘材料 | 先进电缆绝缘专题 2025, 58(3): 35-41
液体添加剂对高压电缆绝缘材料加工特性和物理性能的影响
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张耀东, 任想
作者信息
  • 国网湖北省电力有限公司电力科学研究院,湖北 武汉 430012
  • 张耀东(1987-),男(汉族),湖北武汉人,高级工程师,主要从事电力电缆运维的研究。

通讯作者:

任想(1990-),男(汉族),湖北黄冈人,高级工程师,主要从事架空输电线路及电力电缆运维、电力设备碳排放评价、冲击电压计量的研究。
Effects of liquid additives on processing characteristics and physical properties of high-voltage cable insulation materials
Yaodong ZHANG, Xiang REN
Affiliations
  • State Grid Hubei Electric Power Co., Ltd. Electric Power Research Institute, Wuhan 430012, China
出版时间: 2025-03-20 doi: 10.16790/j.cnki.1009-9239.im.2025.03.004
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液体添加剂对提升高压电缆交联聚乙烯绝缘材料加工特性和物理性能影响的研究尚不充分。本文以液体交联剂和抗氧剂为研究对象,探讨液体添加剂对交联聚乙烯抗焦烧性能、凝胶含量、交联副产物含量、热力学和介电性能的影响及其机理。结果表明:液体交联剂2,5-二甲基-2,5-双(过氧化叔丁基)己烷具有较高分解温度和参与交联的长链烷基,可同时提升交联聚乙烯绝缘材料的抗焦烧性能和凝胶含量,并降低交联副产物含量。而液体抗氧剂α-生育酚和山梨醇具有良好的相容性,二者可形成具有温度依赖性的质子转移反应,可以在保证材料凝胶含量的前提下提升材料的抗焦烧性能。此外,液体交联剂和抗氧剂能够提升交联聚乙烯绝缘的击穿性能,同时保证热力学性能。该研究证明了液体添加剂应用至高压电缆交联聚乙烯绝缘中具有可行性。

高压电缆  /  交联聚乙烯  /  液体添加剂  /  加工特性  /  物理性能

The researches on the effect of liquid additives on the improvement of processing characteristics and physical properties of crosslinked polyethylene (XLPE) insulation materials for high-voltage cables are insufficient. In this paper, liquid crosslinking agents and antioxidants were taken as research objects. The effects and mechanisms of liquid additives on the scorch resistance, gel content, crosslinking by-products, thermodynamic and dielectric properties of XLPE were discussed. The results show that the liquid cross-linking agent 2,5-dimethyl-2,5-bis(tert-butyl peroxide)hexane with a high decomposition temperature and long-chain alkyl groups involved in crosslinking reaction can simultaneously enhance the scorch resistance and gel content of XLPE insulation materials, and reduce the content of crosslinking by-products. Meanwhile, the liquid antioxidants α-tocopherol and sorbitol exhibit excellent compatibility, they can form temperature-dependent proton transfer interactions, which can improve the anti-scorch performance of XLPE without compromising its gel content. Additionally, these liquid crosslinking agent and antioxidants can improve the breakdown performance of XLPE insulation while maintaining its thermodynamic properties. This study proves the feasibility of applying liquid additives to XLPE insulation for high-voltage cable.

high-voltage cable  /  crosslinked polyethylene  /  liquid additives  /  processing characteristics  /  physical properties
张耀东, 任想. 液体添加剂对高压电缆绝缘材料加工特性和物理性能的影响. 绝缘材料, 2025 , 58 (3) : 35 -41 . DOI: 10.16790/j.cnki.1009-9239.im.2025.03.004
Yaodong ZHANG, Xiang REN. Effects of liquid additives on processing characteristics and physical properties of high-voltage cable insulation materials[J]. Insulating Materials, 2025 , 58 (3) : 35 -41 . DOI: 10.16790/j.cnki.1009-9239.im.2025.03.004
高压电缆是我国电力输送的关键设备,而交联聚乙烯(XLPE)作为电缆主绝缘材料,其物理性能决定了电网运行的安全性与可靠性[1-2]。XLPE绝缘材料的物理性能不仅取决于加工工艺和基料,同时也受添加剂配方的影响[3-5]。液体添加剂具有良好的相容性和稳定性[6-7],将其应用至高压电缆XLPE绝缘材料是提升其加工性和物理性能的潜在策略。
高压电缆XLPE绝缘材料通常是通过向低密度聚乙烯中加入交联剂和抗氧剂等添加剂后,再经历熔融、挤出、交联和脱气等过程制得,故其主要的添加剂是交联剂和抗氧剂[3]。而添加剂对XLPE绝缘材料的加工性、力学性能、热学性能以及电学性能均有显著的影响[4,8-9]。当前针对添加剂对高压电缆XLPE绝缘材料性能的影响已开展众多研究并取得有益的进展。
交联剂直接决定XLPE绝缘的加工性和力学性能等。过氧化二异丙苯(DCP)作为高压电缆XLPE绝缘制造过程中常用的交联剂,其含量影响绝缘材料的抗焦烧性能和交联程度,其中含量过高对提升XLPE交联程度没有显著作用,但会明显降低XLPE的抗焦烧性能[9-11],这是因为含量过高会产生过多的交联副产物,进而会对XLPE电学性能造成严重的负面影响[12-13]。鉴于过氧化叔丁基异丙苯(TBCP)和二叔丁基过氧化物(DTBP)等交联剂在聚烯烃中的研究结果,液体交联剂能够协同提升绝缘料的加工特性,故液体交联剂作为DCP替代品具有可行性[14-16]
抗氧剂不仅影响XLPE绝缘材料的加工性,同时会对XLPE绝缘的耐老化性和电学性能产生显著的影响。当前应用的抗氧剂多为固态,尽管采用多种固态抗氧剂配合使用能够在一定程度上提升材料性能,但其与低密度聚乙烯熔体的相容性较差,使得最终XLPE材料的宏观性能仍具有不稳定性[9,17]。液体抗氧剂包括单一的茶多酚、石榴籽提取物以及复合液体抗氧剂,在低密度聚乙烯和超高密度聚乙烯等聚烯烃合成中,不仅能够保证交联程度,同时能够保证耐老化性能,表明液体添加剂具有提升绝缘料宏观性能的潜力[6-7,18-21]
为了揭示液体添加剂对高压电缆XLPE绝缘材料加工特性和物理性能的影响,本文采用液体交联剂(2,5-二甲基-2,5-双(过氧化叔丁基)己烷,DHBP)和液体抗氧剂(α-生育酚和山梨醇)作为XLPE绝缘材料的添加剂,分别测试二者对XLPE材料抗焦烧性能、凝胶含量、脱气特性、力学性能、耐老化性和介电性能等的影响,进而探讨其作用机理,为高性能高压电缆XLPE绝缘的添加剂研发提供理论基础与数据支撑。
选用青岛汉缆股份有限公司生产的220 kV高压电缆绝缘用低密度聚乙烯(LDPE)作为基料;交联剂DCP和DHBP的生产厂家为上海阿拉丁生化科技股份有限公司;抗氧剂300(固态)、α-生育酚和山梨醇的生产厂家为上海麦克林生化科技有限公司。
使用密炼机在温度为115℃、转速为25 rad/min的条件下将LDPE、交联剂、抗氧剂熔融共混10 min,得到的混合材料称为绝缘料,用来测试材料的抗焦烧性能。
取适量的绝缘料加入不锈钢模具中,放入硫化机,在120℃下预热8 min,再在180℃、15 MPa下热压15 min,然后保持压力的同时使用水循环冷却至室温,获得XLPE试样,最后将试样放在70℃的真空条件下干燥12 h,以充分排出其交联副产物。
试样的配方如表1所示,根据相关文献[5,9-10]选择交联剂与抗氧剂含量,其中PE-A为对照组。
采用转矩流变仪(RM-200C型,哈普电气技术有限责任公司),依据GB/T 16584—1996测试绝缘料的转矩以判断其抗焦烧性能。将40 g绝缘料倒入转矩流变仪腔体内,腔体的温度为140℃,转速为60 rad/min,记录转矩随时间变化的曲线,转矩稳定时结束测试。
采用凝胶萃取法测试XLPE的凝胶含量。依据JB/T 10437—2004,将不锈钢滤网折成网包(称量质量并记为m 0),再称取0.3 g试样放入网包(称量质量并记为m 1),封口后放入装有二甲苯溶液的圆底烧瓶中,在140℃下回流萃取10 h,然后将网包取出并在140℃真空条件下干燥6 h(称量质量并记为m 2),试样凝胶含量(C gel)的计算方法如式(1)所示。每种试样同时测试5组并取平均值作为凝胶含量的最终结果。
C g e l = m 2 - m 0 m 1 - m 0 × 100 %
采用热重分析仪(TG/SDTA 851e型,梅特勒-托利多公司)测试XLPE试样的交联副产物含量。称取5 mg未脱气的XLPE试样放入氧化铝坩锅中,起始温度设置为50℃,升温到600℃,其中升温速率为10℃/min,测试环境为氮气,记录试样质量随温度变化的曲线。
采用差示扫描量热仪(822e型,梅特勒-托利多公司)测试XLPE试样的熔融-结晶特性。称取约 5 mg的XLPE试样加入铝坩埚中并封盖,温度为从30℃升温至150℃,升温速率为10℃/min,然后恒温3 min,再降温至30℃,降温速率为10℃/min,然后再恒温3 min,获得试样的结晶曲线。随后再从30℃升温至150℃,升温速率为10℃/min,获得二次升温曲线。根据式(2)计算试样的结晶度(X c)。
X c = Δ H m Δ H 100 × 100 %
式(2)中:∆H m为XLPE试样的熔融焓;∆H 100为XLPE结晶度为100%时的熔融焓,其值为287.3 J/g。
采用差示扫描量热仪测试XLPE绝缘试样的氧化诱导期以表征其耐老化性能。依据GB/T 17391—1998,称取0.5 mg的试样放入铝坩埚,并将坩埚放入测试腔体内,然后在氮气气氛下将温度从30℃升至200℃,在200℃保持5 min,然后关闭氮气阀门同时向腔体内通入氧气,保持该测试温度与氧气气氛,直至曲线上出现明显的放热峰时结束测试。整个测试过程中氮气和氧气的流量均恒定为50 mL/min。
采用拉力机(5KNCMT-4503型,美特斯工业系统(中国)有限公司深圳分公司)测试XLPE试样的力学性能。依据GB/T 1040.1—2018,将厚度为 1 mm的试样裁成哑铃状,拉伸速率为100 mm/min,记录测试过程中的应力-应变曲线。试样的拉伸强度和断裂伸长率分别通过式(3)式(4)计算。
T S = F A
式(3)中:T S表示拉伸强度,MPa;F表示试样拉伸断裂时的应力,N;A表示试样的横截面积,mm2
E B A = L - L 0 L 0 × 100 %
式(4)中:E BA表示断裂伸长率,%;L表示试样拉伸断裂时的标线长度,mm;L 0表示试样拉伸前的标线长度,mm。
采用击穿试验装置(HJC-100 kV型,华博科技工业有限公司)测试XLPE试样的直流电气强度。测试采用直径为25 mm的球-球铜电极,在纯净变压器油中进行。以1 kV/s的升压速率连续升压,直至试样击穿,记录击穿时刻的电压。由于XLPE试样的电气强度具有分散性,对每个试样进行16次有效测试。采用两参数威布尔(Weibull)分布来表征在某电场强度下试样被击穿的概率( P ( E b ; α ,   β )),如式(5)所示。
P E b ; α ,   β = 1 - e x p - E b α β
式(5)中:E b表示电气强度,kV/mm;α表示尺度参数,即击穿概率为63.2%时的电气强度,kV/mm;β表示形状参数,表征试样测试结果的分散程度。
5种XLPE绝缘材料的转矩随时间的演变曲线如图1所示。从图1可以看出,曲线均先从M点下降到N点,然后再呈现继续上升的变化趋势,直至转矩达到稳定。通常认为M点到N点的间隔时间越久,材料的抗焦烧性能越好[22]。而材料最终转矩的大小与其交联程度相关。
对比图1曲线可知,PE-A和PE-B的抗焦烧时间分别为216 s和259 s,其抗焦烧性能相近;PE-X和PE-Y的抗焦烧时间分别为298 s和341 s,明显优于前述两种XLPE绝缘材料的抗焦烧性能。而PE-Z的抗焦烧时间为377 s,说明其抗焦烧性能最佳。与文献[22]中进口220 kV绝缘料(抗焦烧时间约为210 s)相比,本研究使用液体添加剂制备的绝缘料具有更好的抗焦烧性能。
5种XLPE试样的凝胶含量测试结果如表2所示。从表2可以看出,PE-B的凝胶含量高于PE-A,PE-Y的凝胶含量高于PE-X,而PE-X和PE-Y的凝胶含量均高于PE-A和PE-B。此外,PE-Z的凝胶含量低于PE-Y但与PE-X相近。文献[22]中的进口绝缘料完全交联后的凝胶含量约为82%,因此本研究中的绝缘料完全交联后的凝胶含量满足要求。
对于高压电缆XLPE绝缘材料加工特性而言,期望其抗焦烧性能好且其交联程度高。对比5种绝缘材料的加工特性,发现PE-Z同时具有良好的抗焦烧性能和凝胶含量,一方面是由于DHBP的分解温度(140℃)比DCP的分解温度(120℃)更高,在较低温度下有利于延缓大分子自由基的形成,抑制预交联反应;另一方面是由于α-生育酚和山梨醇具有更好的分散性和相容性,且α-生育酚和山梨醇之间在较低温度下会形成有效的质子转移反应,如图2所示[20-21],从而提升了酚羟基利用率,也有利于抑制预交联反应,故PE-Z具有良好的抗焦烧性能。
相比于DCP,DHBP是长链烷基过氧化物,在交联网络中能够作为连接桥架[23],如图3所示,保证了更高的交联密度,使得凝胶含量有所提升;同时,单位质量的DHBP热分解形成的过氧化物自由基更多,能够引发生成更多低密度聚乙烯自由基,也在一定程度上提升了交联效率。此外,α-生育酚和山梨醇在高温下的质子转移作用会被削弱,故对交联反应的抑制作用较小,进而有利于保证较高的凝胶含量。因此,PE-Z具有良好的抗焦烧性能和较高的凝胶含量。
进一步分析5种未脱气XLPE试样的交联副产物含量,其热重分析曲线如图4所示。质量损失越多表明交联副产物越多,在实际加工过程中对脱气时间的要求也就越高。从图4可以看出,PE-A和PE-B的质量损失明显大于其他3种试样,这是因为DCP交联反应(如图5所示)产生的多种副产物在升温过程中会挥发,而DHBP引发交联反应的副产物较少。由图3图5可知,DHBP本体会参与到交联反应中,使得其交联副产物较少,故PE-X、PE-Y和PE-Z的质量损失较低,脱气时间要求较低。
由上述数据可知,添加液体交联剂(DHBP)和抗氧剂(α-生育酚和山梨醇),可以同时保证XLPE绝缘材料良好的抗焦烧性能和较高的凝胶含量,并有效降低交联副产物的含量,表明液体添加剂有利于提升XLPE绝缘材料的加工性能。
5种XLPE试样的熔融-结晶特性曲线如图6所示,为了避免试样热历史的影响,选取二次升温曲线作为试样的熔融曲线。
5种XLPE试样的熔点和结晶度统计结果如表3所示。从表3可以看出,PE-X、PE-Y和PE-Z的熔点和结晶度略高于PE-A和PE-B。这是由于DHBP的长链烷基有利于促进结晶,使得材料结晶度增加。但PE-X、PE-Y和PE-Z的凝胶含量较高,即交联程度较高,这在一定程度上会抑制结晶,因此,5种XLPE试样的熔点和结晶度相近。
采用氧化诱导期表征XLPE试样的耐热老化性能,结果如图7所示,图中热流上升曲线的切线与初期水平曲线的切线的交点所对应的时间即氧化诱导期。从图7可以看出,PE-A和PE-B试样的氧化诱导期分别为11.70 min和11.92 min,PE-X和PE-Y绝缘试样的氧化诱导期分别为12.74 min和14.53 min,而PE-Z绝缘试样的氧化诱导期为13.64 min。通过对比发现,添加DHBP的XLPE试样氧化诱导期略高于添加抗氧剂300的试样,这是因为抗氧剂300的熔点为160℃左右,与XLPE试样的相容性差,所以抗氧剂300在试样内部的分散不均匀,容易导致XLPE绝缘内部形成缺陷,而DHBP具有良好的相容性与分散性。
此外,在XLPE热氧老化过程中,除了酚羟基具有清除自由基功能外,抗氧剂300中的硫元素和山梨醇的羟基均能与自由基发生终止反应,抑制热氧老化过程[9,20-21],其中单位质量的山梨醇的羟基数量较多。综上可知,在抗氧剂含量相同的情况下,抗氧剂在XLPE绝缘中的分布状态越均匀,越有利于提升材料的耐热老化性能。
XLPE试样的拉伸曲线测试结果如图8所示,计算得到其拉伸强度和断裂伸长率如表4所示。从表4可以看出,5种XLPE试样的拉伸强度相近,约为24~25 MPa;PE-A和PE-B的断裂伸长率在600%左右,而其他XLPE试样的断裂伸长率均在630%左右,说明添加DHBP的XLPE试样断裂伸长率略高于添加DCP的试样。这是由于添加DHBP的XLPE交联程度略高,且添加DHBP的XLPE内部存在长链烷基作为桥梁。
通过上述分析可知,与传统的固体交联剂和抗氧剂相比,液体添加剂仍可以有效保证XLPE绝缘的力学性能和耐热老化性能。
测试5种XLPE试样在室温条件下的直流击穿特性,结果如图9所示,对测试结果采用两参数威布尔(Weibull)分布函数处理,结果如表5所示。
图9表5可以看出,PE-A和PE-B试样的电气强度分别为487.67 kV/mm和494.43 kV/mm,PE-X和PE-Y试样的电气强度分别为498.85 kV/mm和509.38 kV/mm,上述数据表明,添加α-生育酚和山梨醇的XLPE试样具有更高的电气强度和击穿稳定性,这一方面是由于抗氧剂300在电场作用下更容易发生解离,导致载流子浓度增加,另一方面是由于抗氧剂300的熔点高,分散不均匀,更容易使XLPE内部形成缺陷,而液体抗氧剂具有良好的相容性与稳定性。
对比PE-A和PE-X、PE-B和PE-Y试样的电气强度可以发现,添加DHBP交联剂的XLPE电气强度更高,这一方面是由于DHBP引发交联反应后生成的交联副产物量远低于DCP引发交联生成的交联副产物,使得XLPE体内杂质少;另一方面是DHBP本体参与交联反应增加了XLPE的交联密度,有利于保证材料的电气强度[23]
综合上述绝缘试样的加工特性、热力学性能和介电性能,发现添加较低含量的液体交联剂(DHBP)以及液体抗氧剂(α-生育酚和山梨醇),能够提升XLPE绝缘料的抗焦烧性能,增加XLPE的凝胶含量并降低交联副产物的含量,且在保证热力学性能的同时,提升了绝缘性能,这表明液体添加剂在高压电缆交联聚乙烯绝缘材料中的应用具有可行性与科学性。
(1)液体交联剂DHBP具有较高分解温度,有利于提升XLPE绝缘材料的抗焦烧性能,而DHBP的长链烷基参与交联反应且在交联网络中充当桥梁,可提升XLPE交联密度并降低交联副产物含量。
(2)液体抗氧剂α-生育酚和山梨醇具有更高的相容性,二者在较低温度下形成有效的质子转移反应,而在高温下该反应被抑制,因此可在保证凝胶含量的同时提升XLPE绝缘材料的抗焦烧性能。
(3)液体添加剂能否保证XLPE绝缘材料的热力学性能并提升击穿特性,取决于交联密度的提升、交联副产物的降低以及液体抗氧剂的稳定性与相容性。
  • 国网湖北省电力有限公司科技项目(521532220002)
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doi: 10.16790/j.cnki.1009-9239.im.2025.03.004
  • 接收时间:2024-08-19
  • 首发时间:2025-11-07
  • 出版时间:2025-03-20
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  • 收稿日期:2024-08-19
  • 修回日期:2024-10-21
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国网湖北省电力有限公司科技项目(521532220002)
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    国网湖北省电力有限公司电力科学研究院,湖北 武汉 430012

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任想(1990-),男(汉族),湖北黄冈人,高级工程师,主要从事架空输电线路及电力电缆运维、电力设备碳排放评价、冲击电压计量的研究。
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

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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