Article(id=1193556937020244377, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1193556932167431095, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2025.04.008, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1713456000000, receivedDateStr=2024-04-19, revisedDate=1714406400000, revisedDateStr=2024-04-30, acceptedDate=null, acceptedDateStr=null, onlineDate=1762495749001, onlineDateStr=2025-11-07, pubDate=1745078400000, pubDateStr=2025-04-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1762495749001, onlineIssueDateStr=2025-11-07, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1762495749001, creator=13701087609, updateTime=1762495749001, updator=13701087609, issue=Issue{id=1193556932167431095, tenantId=1146029695717560320, journalId=1149653034449285133, year='2025', volume='58', issue='4', pageStart='1', pageEnd='144', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1762495747843, creator=13701087609, updateTime=1762498255746, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1193567451108573868, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1193556932167431095, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1193567451112768173, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1193556932167431095, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=52, endPage=61, ext={EN=ArticleExt(id=1193556937246736794, articleId=1193556937020244377, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Ageing evolution of tensile and dielectric properties of ethylene propylene diene monomer self-fusing insulation, columnId=1190369066675179686, journalTitle=Insulating Materials, columnName=Material Research, runingTitle=null, highlight=null, articleAbstract=

In order to investigate the effect of combined heat-force on the performance of ethylene propylene diene monomer self-fusing insulation, ageing experiments with different temperatures and tensile rates were conducted on the ethylene propylene diene monomer self-fusing insulation, and the tensile and dielectric properties of ageing samples were characterized respectively. The results show that during the ageing process, the tensile strength and elongation at break of the sample decrease due to the gradual destruction of molecular structure and swelling of adhesive molecules, and the strong tensile stress will exacerbate the degree of ageing, make the defects gradually develop and expand, and further deteriorate the mechanical properties of the sample. With the increase of ageing time, the polar groups inside the sample increases, the steering polarisation enhances, and the polarisation loss increases. When the stretching rate gradually increases, the increasing rates of relative dielectric constant and dielectric loss factor show the trend of “slow first and fast later”. At the same time, the breakage of molecular chains and the generation of microscopic defects increase the concentration of carrier, and the larger tensile rate weakens the intermolecular forces, reduces the barrier energy level, and makes the carriers easier to migrate, resulting in a continues increase of its volume conductivity. In the later stages of ageing, the molecular chain cleavage under tensile stress is serious, and the thermal expansion of the matrix increases the free volume, leading to a decrease in electric strength. A larger tensile rate will further reduce the trap energy level inside the sample, resgreater decrease in electric strength.

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为了研究热-力联合作用对三元乙丙橡胶自熔式绝缘性能的影响,本文对三元乙丙橡胶自熔式绝缘开展了不同温度和拉伸率的老化实验,分别对老化试样的拉伸性能和介电性能进行表征。结果表明:在老化过程中,试样因分子结构逐渐被破坏及黏胶分子的溶胀作用,其拉伸强度、断裂伸长率下降,且较强的拉伸应力会加剧老化程度,使缺陷逐渐发展扩大,进一步劣化试样的力学性能。随老化时间的增加,试样内部的极性基团不断增多,转向极化增强,极化损耗增加。当拉伸率逐渐增大时,试样的相对介电常数和介质损耗因数的增大速率呈现“先慢后快”的趋势,同时分子链断裂和微观缺陷的产生使载流子的浓度增大,且较大的拉伸率使分子间作用力减弱,势垒能级降低,载流子更易迁移,导致其体积电导率持续升高。在老化后期,拉伸应力下的分子链裂解严重,基体热膨胀使自由体积增大,导致电气强度下降,较大的拉伸率会进一步降低试样内部的陷阱能级,使电气强度的下降幅度更大。

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李秀峰(1974-),女(汉族),山东青岛人,副教授,主要从事电缆料及电缆附件关键问题与技术、纳米复合电介质特性及应用、电力设备绝缘结构优化设计的研究。
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王强(1999-),男(汉族),安徽宿州人,硕士生,主要从事高电压与绝缘技术的研究。

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王强(1999-),男(汉族),安徽宿州人,硕士生,主要从事高电压与绝缘技术的研究。

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王强(1999-),男(汉族),安徽宿州人,硕士生,主要从事高电压与绝缘技术的研究。

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ageing conditions, figureFileSmall=hqIgX3ahBjvA/t9FCgIZQw==, figureFileBig=tJrGzLc+PO70Xl12SnrAaA==, tableContent=null), ArticleFig(id=1195072121920557597, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1193556937020244377, language=CN, label=图8, caption=不同热-力老化条件下EPDM自熔式绝缘的击穿特性, figureFileSmall=hqIgX3ahBjvA/t9FCgIZQw==, figureFileBig=tJrGzLc+PO70Xl12SnrAaA==, tableContent=null), ArticleFig(id=1195072121987666463, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1193556937020244377, language=EN, label=Table 1, caption=Activation energy of EPDM self-fusing insulation under different thermal-force ageing, figureFileSmall=null, figureFileBig=null, tableContent=
试样 活化能/eV
老化前 老化168 h 老化336 h 老化504 h
未拉伸 0.77 0.75 0.73 0.71
拉伸率 105% 0.75 0.73 0.70
110% 0.73 0.72 0.70
115% 0.71 0.71 0.70
), ArticleFig(id=1195072122155438625, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1193556937020244377, language=CN, label=表1, caption=

不同热-力老化条件下EPDM自熔式绝缘的活化能

, figureFileSmall=null, figureFileBig=null, tableContent=
试样 活化能/eV
老化前 老化168 h 老化336 h 老化504 h
未拉伸 0.77 0.75 0.73 0.71
拉伸率 105% 0.75 0.73 0.70
110% 0.73 0.72 0.70
115% 0.71 0.71 0.70
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试样 老化前 老化168 h 老化336 h 老化504 h
E 0/(kV/mm) β E 0/(kV/mm) β E 0/(kV/mm) β E 0/(kV/mm) β
未拉伸 30.0 11.9 27.4 11.3 25.9 10.4 24.4 9.6
拉伸率 105% 27.3 11.1 25.6 10.2 24.1 9.5
110% 26.8 11.0 25.1 9.9 23.7 9.0
115% 26.3 10.8 24.5 9.9 23.1 9.0
), ArticleFig(id=1195072122298044966, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1193556937020244377, language=CN, label=表2, caption=

不同热-力老化条件下EPDM自熔式绝缘的特征参数

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试样 老化前 老化168 h 老化336 h 老化504 h
E 0/(kV/mm) β E 0/(kV/mm) β E 0/(kV/mm) β E 0/(kV/mm) β
未拉伸 30.0 11.9 27.4 11.3 25.9 10.4 24.4 9.6
拉伸率 105% 27.3 11.1 25.6 10.2 24.1 9.5
110% 26.8 11.0 25.1 9.9 23.7 9.0
115% 26.3 10.8 24.5 9.9 23.1 9.0
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三元乙丙橡胶自熔式绝缘拉伸性能和介电性能的老化演变规律
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王强 1 , 李昊泽 1 , 李秀峰 1 , 丁志鹏 1 , 白鑫宇 1 , 刘迪 1 , 王靖然 2
绝缘材料 | 材料研究 2025,58(4): 52-61
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绝缘材料 | 材料研究 2025, 58(4): 52-61
三元乙丙橡胶自熔式绝缘拉伸性能和介电性能的老化演变规律
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王强1, 李昊泽1, 李秀峰1, 丁志鹏1, 白鑫宇1, 刘迪1, 王靖然2
作者信息
  • 1 山东理工大学 电气与电子工程学院,山东 淄博 255000
  • 2 国网淄博桓台供电公司,山东 淄博 256400
  • 王强(1999-),男(汉族),安徽宿州人,硕士生,主要从事高电压与绝缘技术的研究。

通讯作者:

李秀峰(1974-),女(汉族),山东青岛人,副教授,主要从事电缆料及电缆附件关键问题与技术、纳米复合电介质特性及应用、电力设备绝缘结构优化设计的研究。
Ageing evolution of tensile and dielectric properties of ethylene propylene diene monomer self-fusing insulation
Qiang WANG1, Haoze LI1, Xiufeng LI1, Zhipeng DING1, Xinyu BAI1, Di LIU1, Jingran WANG2
Affiliations
  • 1 College of Electric and Electronic Engineering, Shandong University of Technology, Zibo 255000, China
  • 2 State Grid Zibo Huantai Power Supply Company, Zibo 256400, China
出版时间: 2025-04-20 doi: 10.16790/j.cnki.1009-9239.im.2025.04.008
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为了研究热-力联合作用对三元乙丙橡胶自熔式绝缘性能的影响,本文对三元乙丙橡胶自熔式绝缘开展了不同温度和拉伸率的老化实验,分别对老化试样的拉伸性能和介电性能进行表征。结果表明:在老化过程中,试样因分子结构逐渐被破坏及黏胶分子的溶胀作用,其拉伸强度、断裂伸长率下降,且较强的拉伸应力会加剧老化程度,使缺陷逐渐发展扩大,进一步劣化试样的力学性能。随老化时间的增加,试样内部的极性基团不断增多,转向极化增强,极化损耗增加。当拉伸率逐渐增大时,试样的相对介电常数和介质损耗因数的增大速率呈现“先慢后快”的趋势,同时分子链断裂和微观缺陷的产生使载流子的浓度增大,且较大的拉伸率使分子间作用力减弱,势垒能级降低,载流子更易迁移,导致其体积电导率持续升高。在老化后期,拉伸应力下的分子链裂解严重,基体热膨胀使自由体积增大,导致电气强度下降,较大的拉伸率会进一步降低试样内部的陷阱能级,使电气强度的下降幅度更大。

三元乙丙橡胶自熔式绝缘  /  热-力联合老化  /  拉伸性能  /  介电性能

In order to investigate the effect of combined heat-force on the performance of ethylene propylene diene monomer self-fusing insulation, ageing experiments with different temperatures and tensile rates were conducted on the ethylene propylene diene monomer self-fusing insulation, and the tensile and dielectric properties of ageing samples were characterized respectively. The results show that during the ageing process, the tensile strength and elongation at break of the sample decrease due to the gradual destruction of molecular structure and swelling of adhesive molecules, and the strong tensile stress will exacerbate the degree of ageing, make the defects gradually develop and expand, and further deteriorate the mechanical properties of the sample. With the increase of ageing time, the polar groups inside the sample increases, the steering polarisation enhances, and the polarisation loss increases. When the stretching rate gradually increases, the increasing rates of relative dielectric constant and dielectric loss factor show the trend of “slow first and fast later”. At the same time, the breakage of molecular chains and the generation of microscopic defects increase the concentration of carrier, and the larger tensile rate weakens the intermolecular forces, reduces the barrier energy level, and makes the carriers easier to migrate, resulting in a continues increase of its volume conductivity. In the later stages of ageing, the molecular chain cleavage under tensile stress is serious, and the thermal expansion of the matrix increases the free volume, leading to a decrease in electric strength. A larger tensile rate will further reduce the trap energy level inside the sample, resgreater decrease in electric strength.

ethylene propylene diene monomer self-fusing insulation  /  combined thermal-force ageing  /  tensile properties  /  dielectric properties
王强, 李昊泽, 李秀峰, 丁志鹏, 白鑫宇, 刘迪, 王靖然. 三元乙丙橡胶自熔式绝缘拉伸性能和介电性能的老化演变规律. 绝缘材料, 2025 , 58 (4) : 52 -61 . DOI: 10.16790/j.cnki.1009-9239.im.2025.04.008
Qiang WANG, Haoze LI, Xiufeng LI, Zhipeng DING, Xinyu BAI, Di LIU, Jingran WANG. Ageing evolution of tensile and dielectric properties of ethylene propylene diene monomer self-fusing insulation[J]. Insulating Materials, 2025 , 58 (4) : 52 -61 . DOI: 10.16790/j.cnki.1009-9239.im.2025.04.008
交联聚乙烯电缆因其优异的电气性能和力学性能,广泛应用于我国城市电网中[1]。得益于电缆的大量使用和铺设长度的增加,电缆附件的应用和发展越来越受到业界的关注。通常冷缩式电缆附件绝缘采用硅橡胶(SR)或三元乙丙橡胶(EPDM)经加热高温硫化(温度约为180℃)制得。利用橡胶的高弹性,将其套接在电缆本体绝缘上,当外界环境温度变化时,热胀冷缩产生的“呼吸效应”会造成界面压力下降,导致电缆的电气性能失效。新型EPDM自熔式电缆附件,采用EPDM绝缘自粘带与电缆XLPE绝缘低温熔融粘合形成“无物理界面”的复合层,通过EPDM自熔式绝缘粘合特性消除绝缘界面的气隙,同时粘合力保证了界面压力及密封性能,此“无物理界面”结构可以较好地解决传统冷缩式附件易产生活动界面的问题[2-3],从而降低沿面爬电等事故的发生概率。
电缆附件长期运行过程中,绝缘层容易发生热氧老化。目前学者们已开展大量实验,探究热氧老化对绝缘材料性能的影响。王若丞等[4]针对110 kV预制式接头SR绝缘老化后的各项性能进行测试,发现随着老化温度的升高和时间的增加,试样的力学性能和介电性能均下降。HU Q C等[5]对硫化制得的EPDM在120℃下的热氧老化降解现象进行研究,发现随着老化时间的增加,EPDM的羟基和羰基含量以及羰基指数均呈上升趋势。但在实际工作环境下,电缆附件绝缘层的老化诱因是非单一性的,为模拟实际情况下的绝缘老化过程,很多学者设计了多因素老化实验。LIU Y等[6]研究发现在电应力和机械应力共同作用下,随老化时间的增加,附件SR的力学性能和介电性能显著下降,而附件EPDM的力学性能和介电性能则基本稳定。LI C J等[7]对EPDM密封材料分别进行了热氧老化和压缩状态下的热氧老化实验,发现在压缩程度较大时EPDM的降解速度更快。
由于电缆附件在运行过程中,线芯负载发热会导致绝缘温升以及附件制作过程中存在自粘带拉伸绕包应力,为了探究这二者对EPDM自熔式绝缘长期性能的影响,本文模拟实际运行工况,对热-力联合老化作用下,EPDM自熔式绝缘拉伸性能和介电性能的老化演变规律进行研究。研究结果可为新型自熔式接头的界面性能稳定性研究提供实验依据。
EPDM绝缘自粘带,美国3M公司,由EPDM基体、胶黏剂、填料SiO2、炭黑和抗氧剂复合而成。
万能试验机(型号为UTM2103),深圳三思纵横科技股份有限公司;高精密高压电容电桥(型号为QS87)、耐压测试仪(型号为FYJK-50),上海杨高电器有限公司;高阻计(型号为ZC36),上海第六电表厂有限公司。
本课题组设计了一种能够保持材料固定拉伸率的实验装置,如图1所示,装置两侧使用夹具固定试样,通过左侧的拉伸控制杆可以操纵活动夹具在滑轨上移动,从而改变试样的拉伸程度,达到实验所需不同拉伸率的要求。
新型自熔式接头在实际工程安装时,EPDM绝缘自粘带是通过半重叠绕包在电缆本体上,实验时为模拟实际绕包工艺情况,取一定长度的EPDM绝缘自粘带,按照图2的示意图进行排列,再将按顺序叠放的自粘带置于模板上,最后将模板放在温度为120℃、压力为15 MPa的平板硫化机中预热3 min,加压5 min成型,待试样冷却至室温,制得厚度为1 mm的EPDM自熔式绝缘试样若干。
参照GB/T 3512—2014相关要求进行热氧老化实验,选取100℃作为加速热氧老化实验温度,在此温度下设置168、336、504 h 3个时间变量。EPDM自熔式绝缘是采用EPDM绝缘自粘带在一定拉伸率下重叠绕包,并在低温下熔融粘合而成,因此选用105%、110%和115% 3个拉伸率进行实验。其中,拉伸率的定义如式(1)所示。
ε = L - L 0 L 0 × 100 %
式(1)中:ε是拉伸率;L是试样拉伸后的长度;L 0是未拉伸试样的初始长度。
制备不同热-力联合老化条件下的试样以供性能测试。
拉伸性能测试:根据GB/T 528—2009相关要求对不同老化条件下的试样进行拉伸实验,拉伸试样为哑铃试片,拉伸速率为(500±50)mm/min,每组测试5个试样,结果取平均值。
介电常数和介质损耗因数:对各老化阶段的试样进行介电性能测试,试样厚度为1 mm,测试电压为1 kV,测试频率为50 Hz,测试温度分别为25、40、60、80、90℃。
电导-温度特性:测量不同试样的体积电阻率(其倒数是体积电导率),试样厚度为1 mm,实验电压设置为1 kV,测量温度分别为25、40、60、80、90℃。
击穿特性:对各试样的电气强度进行测试,试样厚度为1 mm,升压速率为2 kV/s。每组选取3个试样,每个试样测试5个击穿点,共采集15个电气强度数据,并通过威布尔(Weibull)分布函数进行分析。
对不同老化条件下的EPDM自熔式绝缘进行拉伸测试,拉伸强度和断裂伸长率的变化规律如图3所示。
图3可知,与老化前相比,在老化初期(168 h),未拉伸试样的拉伸强度和断裂伸长率小幅下降;在老化后期(504 h),试样的拉伸强度和断裂伸长率下降速度加快,当老化时间达到504 h时,拉伸性能的衰减幅度最大,拉伸率为115%的试样,拉伸强度和断裂伸长率较老化前分别下降了56.29%和45.75%。在老化初期,EPDM基体中因化学键断裂所产生的游离基会在高温下重新键合,试样的微观结构遭到的破坏程度较低[8],对拉伸性能的影响较小。但EPDM分子链对热氧环境较为敏感[9],随着老化时间的增加,试样与氧气间的接触越来越充分,老化带来的影响逐渐由试样表层向内部发展[10]。老化后期,在高温作用下,EPDM自熔式绝缘内部的大分子链发生断裂,分子结构受到破坏加剧,微观缺陷增多[11];同时,在老化过程中黏胶溶胀了EPDM基体,减弱了分子间作用力[12],导致试样抵御形变的能力变差,因此拉伸强度下降更严重。在长期老化过程中,EPDM分子主链被破坏,材料的柔性随之减弱[13],与聚合物柔性成正相关的断裂伸长率也降低[11]。因此,试样的拉伸性能随老化程度的加深不断变差。
无论老化前期还是后期,对各试样施加应力时,其拉伸性能均呈下降趋势,且在老化后期(504 h)下降更为明显,拉伸率为105%时,试样的拉伸强度和断裂伸长率较老化前分别下降了39.40%和34.74%。由于EPDM基体在热老化过程中形成的微小孔隙缺陷[14]会在较强的机械应力下逐渐发展扩大,成为局部薄弱点[15]。在长时间的外力作用下,此薄弱点逐渐发展,导致SiO2填料-橡胶基体界面发生脱粘[16],出现微观裂纹和裂缝。拉伸率的增大也使EPDM分子结构遭到的破坏逐渐累积,最终导致试样的拉伸性能降幅更大,可见,较强的外施应力会促进老化进程,加剧试样劣化程度。
各试样相对介电常数随温度的变化规律如图4所示。从图4可以看出,在不同老化环境下,各试样的相对介电常数随温度升高均呈现先增大后减小的变化趋势。这是因为弛豫过程与热运动有关,当温度升高时,分子热运动增强,弛豫时间减少,弛豫极化更容易建立[17-18],极化增强,导致相对介电常数增大;但温度继续升高时,分子热运动加剧反而阻碍了链端单元、分子链段沿电场方向的定向排列[19],极化减弱,导致相对介电常数减小[20]
图4(a)可知,与老化前相比,在相同温度下,老化168 h的未拉伸试样相对介电常数的变化率较小;而老化504 h后,试样相对介电常数的增幅有所升高。热氧老化作用使EPDM分子链发生断裂降解,并生成含有羰基等极性基团的老化产物[21],偶极子的转向极化率增大,导致试样的相对介电常数随老化时间的增加而增大。
图4(b)可知,与未拉伸状态相比,拉伸率较低(105%)的试样,相对介电常数略微增大。应力较小时,EPDM自熔式绝缘的橡胶基体仍具有较好的弹性,拉伸后的分子链由卷曲状态变为伸展状态,见图5右侧[22-24],应力并不会对分子结构造成破坏[25],此时相对介电常数的变化主要是热老化引起的。另外,在60℃时,拉伸率为105%的拉伸试样的相对介电常数为2.80,略低于未拉伸试样的介电常数2.82。这是因为少量分子链因拉伸作用其取向趋于有序化,使得部分极性基团的活性下降[22,26],偶极子取向极化略有减弱,导致相对介电常数减小。由图4(d)可知,当拉伸率较大(115%)时,相对介电常数的增幅变大。随着应力的增强,热塑性橡胶基体形变逐渐超出可承受的弹性范围,见图5右侧,一方面,较强的应力作用加速了分子链裂解反应(主链断裂、氧化),EPDM分子结构的破坏程度加剧[23],分子链段的对称性降低进而产生宏观偶极距[19];另一方面,分子链断裂导致链间束缚减弱,在电场作用下转向极化更易发生[22]。这些原因均会导致介质极性增强,分子极化率增加,相对介电常数增大[27]。另外,黏胶在试样内部发生的溶胀现象使分子间作用力减弱,且黏胶小分子充当了偶极子,极化率增强,相对介电常数进一步增大。可见,随着拉伸率的增加,相对介电常数增大速率呈现“先慢后快”的变化规律。
图6是各EPDM自熔式绝缘老化试样介质损耗因数随温度的变化规律。
图6可以看出,各试样的介质损耗因数随温度升高均存在“先减小后增大”的变化规律。在25℃下,黏胶的存在会增大“橡胶-黏胶”体系的黏度,此时的损耗主要由松弛极化提供,温度升高后,分子热运动增强,尽管极性分子的转向极化能及时跟上交变电场的变化,但黏胶分子对转向极化的束缚力减弱,极化损耗有所降低[20,28];而随着温度继续升高,EPDM自熔式绝缘中的黏胶小分子会充当杂质离子增加电导,进而导致电导损耗增大,介质损耗因数再次升高。
图6(a)可知,相较于老化前,在老化初期,未拉伸试样的介质损耗因数仅增大6.26%;而老化后期的试样增幅却达到了36.90%。老化时间越长,试样内部EPDM分子链的降解越严重,一方面,在热氧老化过程中,EPDM分子链断裂与氧接触,生成羰基等极性基团,在外电场作用下极性基团参与极化,使介质损耗持续增大[29];另一方面,分子链发生降解,断裂的分子链段充当了载流子,使载流子增多,电导增大,电导损耗增加[24]。因为试样的介质损耗由极化损耗和电导损耗两部分组成,所以在老化后期,介质损耗因数增大更明显。
图6(b)(d)可以看出,在老化后期,与未拉伸试样相比,拉伸率为105%和110%的试样,其介质损耗因数略有增大,但在60℃时,拉伸试样的介质损耗因数略小于未拉伸试样的数值,这是由于试样处于低拉伸率时,分子链上的部分极性基团活性降低,偶极子发生转向极化的概率减小[26],极化损耗减少,导致介质损耗因数减小。而拉伸率为115%时,试样的介质损耗因数显著增大,这是由于在较高的拉伸率下,极化过程更容易建立[22],导致极化损耗增加;同时,高拉伸率还会引起电导率升高,增加电导损耗[23],从而使介质损耗因数增大。因此,介质损耗因数的增幅随应力的增强也呈现“先慢后快”的变化趋势。
不同老化条件下的EPDM自熔式绝缘,其体积电导率-温度的拟合关系如图7所示。体积电导率主要受载流子浓度和迁移率的影响[30],其中活化能可以从一定程度上反映载流子的迁移水平,活化能越低,载流子的迁移率越高,即越容易跃迁参与导电。活化能可通过式(2)进行计算,结合图7计算各试样的活化能列于表1中。
式(2)中:μ 0是活化能;B是lnγ v~(1 000/T)拟合直线的斜率;γ v是体积电导率;T是开氏温度;k是玻尔兹曼常数。
μ 0 = B k
图7可知,各试样的体积电导率大小都与温度的变化呈正相关。分子的热运动能力随温度升高逐渐增强,载流子在受热状态下所受的束缚力减弱,易于参与导电[19],从而使试样的体积电导率增长。如图7(a)所示,与老化前相比,随老化时间的增加,试样的体积电导率逐渐增大。在热老化环境下,EPDM分子链发生裂解形成短链,易在电场下发生电离,形成离子电导充当载流子,增加了载流子的浓度[19]。并且在热老化过程中,试样内部会形成微小孔洞、裂纹等物理缺陷和极性基团等化学缺陷,使活化能降低[31],载流子的迁移率提高。这两方面原因导致EPDM自熔式绝缘的体积电导率随老化的进行不断增大,绝缘性能随之变差。
根据图7(b)(d)可知,拉伸率从105%增加到115%时,试样体积电导率的增幅不断变大,在拉伸率为115%,老化时间为504 h时,增幅高达51.9%。可见,老化过程中施加较强的应力,会加剧EPDM分子结构的破坏[23],使分子链之间的间隙变大,分子间作用力随之减小[32],载流子迁移时受到的阻碍减小,迁移率增大。同时,EPDM与SiO2填料间的界面结合力变差,界面发生脱粘,部分SiO2颗粒受到的束缚力减弱,充当了导电载流子,使载流子的浓度增加[19]。因此,高拉伸率状态下试样的体积电导率增幅较大。
表1中的活化能反映了载流子参与导电时克服势垒所需的能量大小。根据图5的示意图可知,EPDM自熔式绝缘的自由体积在老化过程中会发生变化。长时间的热氧老化使橡胶基体在高温环境下的热膨胀现象愈发严重[23],同时老化后期的EPDM分子链裂解反应加剧,材料内部的自由体积增大[24],载流子运动所需克服的势垒减小,各试样的活化能随老化时间的增加逐渐下降[33]。而拉伸应力的增强,不仅进一步扩大了自由体积空间[24],也使大分子链在热应力作用下更容易断裂,分子间作用力持续降低,对载流子的束缚力减弱[34],导致试样的活化能不断降低。并且,自由体积的增大为黏胶的溶胀过程提供了有利条件[35],一方面,溶胀减弱了分子间的作用力[36];另一方面,溶胀效应同样也引起自由体积的增加[37],使活化能减小。
采用Weibull分布函数分析了不同老化条件下EPDM自熔式绝缘的工频击穿特性,结果如图8所示。
对应的尺寸参数E 0和形状参数β列于表2,其中,E 0反映电气强度的大小,β反映数据的分散程度。由图8(a)表2可知,在未拉伸状态下,与老化前的试样相比,在老化初期,试样的E 0下降了8.67%,β下降了5.04%;当老化时间逐渐增加到504 h时,E 0下降了18.67%,β下降了19.33%。在老化后期,EPDM分子链裂解严重,能产生更多的游离基和小分子等产物[24],这些产物易发生电离产生自由电子[19];另外,根据自由体积击穿理论,聚合物内部自由体积增大会增加电子运动的平均自由行程[38]。使得更多电子在运动过程中积攒更强能量,撞击破坏分子链,从而导致热老化过程中EPDM自熔式绝缘的电气强度下降[24],数据的分散性增大。
图8(b)(d)可以看出,与未拉伸试样相比,当拉伸率从105%逐步升高到115%时,老化504 h试样的变化率E 0不断减小。拉伸过程会降低试样内部的陷阱能级[25],有利于自由电子的迁移[32]。并且,老化所引发的EPDM分子链裂解反应,使原先规整的分子结构变得松散无序[19],经拉伸后,链间距离发生变化,自由体积显著增大[24]。同时,填料-基体的两相分离会诱导界面处的裂纹、裂缝等微观缺陷增多[11],局部导电通道易于发展[34]。以上变化致使拉伸状态下试样的电气强度下降,数据分散性变大。由前面分析可知,黏胶在老化过程中发生溶胀会引起试样内部自由体积增大[37],由自由体积击穿理论可知,这也会导致试样在较低的电气强度下会发生击穿[24]
(1)随老化时间的增加,EPDM自熔式绝缘分子结构的破坏程度加重,导致拉伸性能不断下降,且较强的拉伸应力作用会导致局部弱点的产生,从而加剧其劣化程度。
(2)热老化过程中生成的极性基团会增强极化,使试样的介电常数增大,介质损耗因数增大,应力较强时会加速分子链裂解,减小链间束缚力,导致介质极性增强,介电常数和介质损耗因数的增大速率随拉伸率增加呈“先慢后快”的变化规律。
(3)在长期老化过程中,较强的拉伸应力作用会破坏试样的分子结构,引发界面脱粘,另外在热-力联合老化过程中自由体积得到扩充,载流子更易迁移,导致其体积电导率持续升高,活化能降低。
(4)热氧老化导致的分子链裂解和自由体积增大,拉伸应力导致的微观缺陷增多,以及黏胶的溶胀效应共同造成了EPDM自熔式绝缘电气强度的下降。
  • 山东省自然科学基金资助项目(ZR2023ME129)
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2025年第58卷第4期
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doi: 10.16790/j.cnki.1009-9239.im.2025.04.008
  • 接收时间:2024-04-19
  • 首发时间:2025-11-07
  • 出版时间:2025-04-20
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  • 收稿日期:2024-04-19
  • 修回日期:2024-04-30
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山东省自然科学基金资助项目(ZR2023ME129)
作者信息
    1 山东理工大学 电气与电子工程学院,山东 淄博 255000
    2 国网淄博桓台供电公司,山东 淄博 256400

通讯作者:

李秀峰(1974-),女(汉族),山东青岛人,副教授,主要从事电缆料及电缆附件关键问题与技术、纳米复合电介质特性及应用、电力设备绝缘结构优化设计的研究。
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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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