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Article(id=1199641486594765348, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1199641484963181075, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2023.07.007, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1658505600000, receivedDateStr=2022-07-23, revisedDate=1662652800000, revisedDateStr=2022-09-09, acceptedDate=null, acceptedDateStr=null, onlineDate=1763946418664, onlineDateStr=2025-11-24, pubDate=1689782400000, pubDateStr=2023-07-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1763946418664, onlineIssueDateStr=2025-11-24, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1763946418664, creator=13701087609, updateTime=1763946418664, 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=40, endPage=45, ext={EN=ArticleExt(id=1199641487941136947, articleId=1199641486594765348, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Dielectric spectrum analysis of ethylene propylene diene monomer for cable insulation under tensile stress, columnId=1190369066675179686, journalTitle=Insulating Materials, columnName=Material Research, runingTitle=null, highlight=null, articleAbstract=

In view of the degradation of insulating properties of ethylene propylene diene monomer (EPDM) cables caused by mechanical, electrical, and thermal stresses during operation, the dielectric spectrum of EPDM used for power cable insulation in tensile state was studied. Firstly, a tensile force applying fixture was designed, and a multi-stress dielectric spectrum testing system was built. The dielectric spectrum of EPDM under the joint action of tensile force and thermal stress was measured. The influence of tensile ratio on the dielectric loss factor of EPDM was analyzed emphatically. Then, the characteristic parameters of dielectric spectrum and their variation with tensile ratio were obtained by Cole-Cole model. The change of chemical groups of EPDM was analyzed by Fourier transform infrared spectroscopy (FTIR) from the microscopic view. Finally, the properties change mechanism of EPDM after tensile was summarized combining with carrier apparent mobility. The results show that the tensile ratio has significant influence on the complex dielectric constant and dielectric loss factor of EPDM, especially when the frequency is low, the dielectric loss factor decreases at first and then increases with the increase of tensile ratio. The analysis based on Cole-Cole model shows that the DC conductivity, relaxation strength, and relaxation peak frequency of EPDM decrease at first and then increase with the increase of tensile ratio. Combining with Fourier infrared spectroscopy, it is concluded that the EPDM molecular chain will break when the tensile ratio reaches a certain value, and the carrier mobility extracted from the depolarization current decreases at first and then increases with the increase of tensile ratio.

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针对三元乙丙橡胶（ethylene propylene diene monomer，EPDM）电缆在运行过程中常受到机械、电、热等多应力共同作用而出现绝缘性能劣化的问题，研究了电缆绝缘用EPDM在拉伸状态下的介电谱。首先设计拉伸力施加夹具，搭建多应力介电频谱测试系统，测量EPDM在拉伸力和热应力共同作用下的介电谱，重点分析拉伸比对EPDM介质损耗因数的影响，然后利用Cole-Cole模型得到介电谱特征参量及其随拉伸比变化的规律，利用傅里叶红外光谱从微观角度分析EPDM的化学基团变化，最后结合载流子视在迁移率总结EPDM拉伸后的性能变化机理。结果表明：拉伸比对EPDM的复介电常数和介质损耗因数均有明显影响，特别是频率较低时，介质损耗因数会随拉伸比的增加先减小后增大。基于Cole-Cole模型分析表明，EPDM的直流电导率、弛豫强度和弛豫峰值频率均随拉伸比的增加先减小后增大。结合傅里叶红外光谱可知，在拉伸比达到一定值后，EPDM分子链会断裂，从去极化电流中提取到的载流子迁移率也随着拉伸比的增加先减小后增大。

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雷志鹏（1983-），男（汉族），山西太原人，副教授，博士，主要从事电气绝缘放电、绝缘诊断与寿命评估、智能电器方面的研究。
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李蔚（1997-），男（汉族），湖南临湘人，硕士生，主要从事绝缘诊断与寿命评估方面的研究。

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李蔚（1997-），男（汉族），湖南临湘人，硕士生，主要从事绝缘诊断与寿命评估方面的研究。

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李蔚（1997-），男（汉族），湖南临湘人，硕士生，主要从事绝缘诊断与寿命评估方面的研究。

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编号吸光度
k=1.0k=1.2k=1.4k=1.6k=1.8
10.0600.0690.0650.0670.063
20.2890.2710.2740.2550.266
30.2090.2000.2030.1790.181
40.1650.1670.1710.1690.185
51.2001.2601.2401.2501.340
60.2630.2630.2510.2480.252
), ArticleFig(id=1217475264133644978, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199641486594765348, language=CN, label=表1, caption=

120℃时不同拉伸比下EPDM特征基团吸光度

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编号吸光度
k=1.0k=1.2k=1.4k=1.6k=1.8
10.0600.0690.0650.0670.063
20.2890.2710.2740.2550.266
30.2090.2000.2030.1790.181
40.1650.1670.1710.1690.185
51.2001.2601.2401.2501.340
60.2630.2630.2510.2480.252
), ArticleFig(id=1217475264246891193, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199641486594765348, language=EN, label=Tab.2, caption=Dielectric spectra characteristic parameters of EPDM with different tensile ratios at 120℃, figureFileSmall=null, figureFileBig=null, tableContent=
kΔετ/sασdc/(S/m)
1.021.002.290.649.90×10-14
1.212.647.500.744.70×10-14
1.410.8513.080.793.34×10-14
1.611.1012.330.793.30×10-14
1.814.890.990.661.20×10-13
), ArticleFig(id=1217475264326582973, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199641486594765348, language=CN, label=表2, caption=

120℃时不同拉伸比下EPDM的介电谱特征参数

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kΔετ/sασdc/(S/m)
1.021.002.290.649.90×10-14
1.212.647.500.744.70×10-14
1.410.8513.080.793.34×10-14
1.611.1012.330.793.30×10-14
1.814.890.990.661.20×10-13
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电缆绝缘用三元乙丙橡胶在拉伸状态下的介电频谱分析
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李蔚 1 , 何庆辉 1 , 门汝佳 1 , 李媛媛 1 , 雷志鹏 1 , 王伟 2 , 杨冬冬 2
绝缘材料 | 材料研究 2023,56(7): 40-45
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绝缘材料 | 材料研究 2023, 56(7): 40-45
电缆绝缘用三元乙丙橡胶在拉伸状态下的介电频谱分析
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李蔚1, 何庆辉1, 门汝佳1, 李媛媛1, 雷志鹏1, 王伟2, 杨冬冬2
作者信息
  • 1太原理工大学 电气与动力工程学院,山西 太原 030024
  • 2国网山西省电力公司电力科学研究院,山西 太原 030012

    • 李蔚（1997-），男（汉族），湖南临湘人，硕士生，主要从事绝缘诊断与寿命评估方面的研究。

通讯作者:

雷志鹏（1983-），男（汉族），山西太原人，副教授，博士，主要从事电气绝缘放电、绝缘诊断与寿命评估、智能电器方面的研究。
Dielectric spectrum analysis of ethylene propylene diene monomer for cable insulation under tensile stress
Wei LI1, Qinghui HE1, Rujia MEN1, Yuanyuan LI1, Zhipeng LEI1, Wei WANG2, Dongdong YANG2
Affiliations
  • 1College of Electrical and Power Engineering, Taiyuan University of Technology, Taiyuan 030024, China
  • 2State Grid Shanxi Electric Power Research Institute, Taiyuan 030012, China
出版时间: 2023-07-20 doi: 10.16790/j.cnki.1009-9239.im.2023.07.007
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摘要
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针对三元乙丙橡胶（ethylene propylene diene monomer，EPDM）电缆在运行过程中常受到机械、电、热等多应力共同作用而出现绝缘性能劣化的问题，研究了电缆绝缘用EPDM在拉伸状态下的介电谱。首先设计拉伸力施加夹具，搭建多应力介电频谱测试系统，测量EPDM在拉伸力和热应力共同作用下的介电谱，重点分析拉伸比对EPDM介质损耗因数的影响，然后利用Cole-Cole模型得到介电谱特征参量及其随拉伸比变化的规律，利用傅里叶红外光谱从微观角度分析EPDM的化学基团变化，最后结合载流子视在迁移率总结EPDM拉伸后的性能变化机理。结果表明：拉伸比对EPDM的复介电常数和介质损耗因数均有明显影响，特别是频率较低时，介质损耗因数会随拉伸比的增加先减小后增大。基于Cole-Cole模型分析表明，EPDM的直流电导率、弛豫强度和弛豫峰值频率均随拉伸比的增加先减小后增大。结合傅里叶红外光谱可知，在拉伸比达到一定值后，EPDM分子链会断裂，从去极化电流中提取到的载流子迁移率也随着拉伸比的增加先减小后增大。

三元乙丙橡胶  /  拉伸  /  介电频谱  /  Cole-Cole模型  /  红外光谱  /  去极化电流

In view of the degradation of insulating properties of ethylene propylene diene monomer (EPDM) cables caused by mechanical, electrical, and thermal stresses during operation, the dielectric spectrum of EPDM used for power cable insulation in tensile state was studied. Firstly, a tensile force applying fixture was designed, and a multi-stress dielectric spectrum testing system was built. The dielectric spectrum of EPDM under the joint action of tensile force and thermal stress was measured. The influence of tensile ratio on the dielectric loss factor of EPDM was analyzed emphatically. Then, the characteristic parameters of dielectric spectrum and their variation with tensile ratio were obtained by Cole-Cole model. The change of chemical groups of EPDM was analyzed by Fourier transform infrared spectroscopy (FTIR) from the microscopic view. Finally, the properties change mechanism of EPDM after tensile was summarized combining with carrier apparent mobility. The results show that the tensile ratio has significant influence on the complex dielectric constant and dielectric loss factor of EPDM, especially when the frequency is low, the dielectric loss factor decreases at first and then increases with the increase of tensile ratio. The analysis based on Cole-Cole model shows that the DC conductivity, relaxation strength, and relaxation peak frequency of EPDM decrease at first and then increase with the increase of tensile ratio. Combining with Fourier infrared spectroscopy, it is concluded that the EPDM molecular chain will break when the tensile ratio reaches a certain value, and the carrier mobility extracted from the depolarization current decreases at first and then increases with the increase of tensile ratio.

EPDM  /  tensile  /  dielectric spectroscopy  /  Cole-Cole model  /  FTIR  /  depolarization current
李蔚, 何庆辉, 门汝佳, 李媛媛, 雷志鹏, 王伟, 杨冬冬. 电缆绝缘用三元乙丙橡胶在拉伸状态下的介电频谱分析. 绝缘材料, 2023 , 56 (7) : 40 -45 . DOI: 10.16790/j.cnki.1009-9239.im.2023.07.007
Wei LI, Qinghui HE, Rujia MEN, Yuanyuan LI, Zhipeng LEI, Wei WANG, Dongdong YANG. Dielectric spectrum analysis of ethylene propylene diene monomer for cable insulation under tensile stress[J]. Insulating Materials, 2023 , 56 (7) : 40 -45 . DOI: 10.16790/j.cnki.1009-9239.im.2023.07.007
正文
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0 引言
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三元乙丙橡胶（ethylene propylene diene monomer，EPDM）电缆大量运用于中、高压电缆领域，特别是在煤矿、核电站、船舶等领域应用广泛[1]。这是因为EPDM与其他塑料类绝缘材料相比，在恶劣环境下也能保持良好的稳定性，如我国煤矿综采工作面采煤机拖拽电缆均采用乙丙橡胶作为绝缘[2]。然而，采煤机拖拽电缆的运行环境极其恶劣，电缆正常运行时除经受由电流产生的热应力，还要承受不断变化的拉伸和挤压等机械应力作用，导致电缆故障时有发生。采煤机拖拽电缆一旦出现故障，轻则影响生产，重则可能导致人身触电，甚至电缆着火或者发生瓦斯爆炸事故。因此，分析和评估采煤机电缆用EPDM在运行环境下的介电性能，不仅对于掌握电缆的运行状态具有重要意义，而且可为何时修复或更换接近使用寿命期限或存在故障隐患的电缆提供参考。
目前评估电缆绝缘劣化状态的方法有很多，主要有回复电压法（recovery voltage method，RVM）、极化去极化电流（polarization and depolarization current，PDC）法、频域介电谱（frequency-domain dielectric spectroscopy，FDS）法、介电响应法、差示热量扫描法、拉伸实验、红外光谱法等。其中频域介电谱法为无损测量，可在较低电压下实现，且携带信息丰富，已被广泛应用于电缆状态评估领域。周利军等[3]通过对XLPE电缆实部频谱进行数学变换得出新的谱图，提取了损耗峰的峰值频率来表征电缆绝缘的劣化状态。王昊月等[4]针对XLPE电缆在用超低频0.1 Hz介损检测电缆局部老化灵敏度不高的情况下，发现高压频域介电谱对局部老化反应灵敏，提出联合两种方法对电缆老化状态进行评估。
在多应力共同作用下的电缆劣化研究中，何华琴等[5]研究了温度和压强对乙丙橡胶基复合材料工频介电性能的影响，发现温度对不同压强下三元乙丙橡胶基复合材料的相对介电常数具有显著影响，在压力确定的条件下，复合材料的相对介电常数随温度升高而减小，介质损耗因数随温度升高而增大；在固定温度下，乙丙橡胶的相对介电常数随压强增大而增大，介质损耗因数随压强增大无变化。HE H等[6]测量了硅橡胶在单热应力、单拉伸力以及两种应力联合老化后的介电频谱，结果表明在单拉伸力以及两种应力联合的情况下，硅橡胶的介质损耗因数和相对介电常数均增大。综上所述，目前针对EPDM在拉伸应力作用下的介电频谱研究较少，导致无法掌握采煤机拖拽电缆绝缘运行中经受拉力时的绝缘性能变化规律。
针对以上问题，本文以采煤机拖拽电缆用EPDM绝缘为研究对象，搭建温度和拉伸比可控的介电谱测量系统，测量EPDM在不同拉伸比和温度共同作用下的介电频谱；然后基于经直流电导修正的单弛豫Cole-Cole模型对介电谱进行拟合，得到相应的介电谱特征参量；最后结合傅里叶红外光谱分析EPDM介电谱受拉伸比和温度影响的机理。
1 试验
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1.1 试样制备
根据GB/T 7594.8—1987相关要求，选用DCJ30M型乙丙橡胶胶片制作试样。首先将乙丙橡胶胶片置于120℃的模具上预热1 min，然后在165℃和10 MPa压力下热压硫化15 min得到乙丙橡胶试样。完成以后，将试样放入温度为80℃的真空干燥箱静置48 h以消除硫化产生的副产物和机械应力。最后将试样裁剪成长为180 mm、宽为60 mm的长方形样片用于后续试验，试样厚度约为1.0 mm。在试验前，用酒精擦拭试样表面并静置12 h，消除可能存在的表面电荷和表面污渍。
1.2 介电频谱测量方法
图1为介电频谱测量系统图。试验所用仪器为NOVOCONTROL Concept 80宽频介电阻抗谱测量系统，测量电压为3 V，测量频率为10-2～106 Hz。试验中将测量端的两极经屏蔽线分别引入温控箱中，温控箱的控温精度为±1℃。测量时，为使测量结果稳定以及不同试样的温度和拉伸比控制准确和保持一致性，先将试样拉伸到一定的拉伸比，并置于温控箱中，待温控箱温度达到设定温度后稳定30 min再进行测量。
分别测量不同温度和拉伸比条件下EPDM的介电频谱，温度分别设置为60、90、120℃，拉伸比分别设置为1.0、1.2、1.4、1.6、1.8。
拉伸夹具如图2所示，拉伸夹具由金属滑轨、对位聚苯酚（polyphenylene，PPL）夹板和滑台、电极台组成。PPL夹板和滑台可以在温度为300℃以下仍保证试样的力学性能，并将试样加持牢固。使用PPL夹板夹紧试样后，调节滑轨上的旋钮移动PPL滑台，使试样拉伸固定长度，完成对拉伸比的控制。电极台中的电极为黄铜圆柱电极，直径为25 mm，固定在可调高度的不锈钢板上。
1.3 红外光谱
使用Nicolet iS5型傅里叶变换红外光谱测试仪对不同拉伸比的乙丙橡胶样品进行红外光谱测试，通过样品表面的反射信号获得样品表层有机成份的结构信息。扫描次数为10次，分辨率为4 cm-1。
2 试验结果
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2.1 介电频谱
图3为EPDM在不同拉伸比和不同温度下的介电频谱图。由图3(a)可以看出，复介电常数实部（即相对介电常数）随频率的减小而增大，主要是因为在高频条件下，极化来不及建立导致的。在相同温度下，除60℃、k=1.0条件下的实部数据外，随着拉伸比的增加，EPDM的复介电常数实部均呈现出先减小后增大的变化规律。在拉伸比为1.4和1.6时，不同温度和不同频率下EPDM的复介电常数实部非常相似，说明在1.4～1.6拉伸比范围附近，复介电常数实部存在一个极小值。当拉伸比达到1.8时，复介电常数实部明显增大，甚至超过了未拉伸EPDM试样的复介电常数实部。
从图3(b)可以看出，不同拉伸比下EPDM的介质损耗因数也有类似的规律。不同的是，温度升高到90℃以后，低频区域出现了损耗峰。在90℃、拉伸比为1.0和1.8下，以及120℃、所有拉伸比下，在低频区域均出现了明显的损耗峰。这是因为在频率很低时，电导损耗很大，淹没了偶极子转向极化损耗峰；当频率增加时，电导损耗减小，偶极子转向极化得以显示出来。与此同时，温度的升高可使损耗峰向高频移动，于是损耗峰在高温下与电导损耗分离。
图4为120℃时损耗峰值频率与拉伸比的关系。从图4可以看出，损耗峰值频率会先随着拉伸比的增大先减小后增大，在拉伸比为1.4～1.6附近出现极小值，进一步表明1.4～1.6的拉伸比为EPDM性能变化的转折点。
为进一步分析低频下EPDM的介质损耗因数与拉伸比的关系，选取频率为0.1 Hz和0.01 Hz，不同温度下的介质损耗因数随拉伸比的变化进行分析，结果如图5所示。从图5可以看出，在120℃和拉伸比为1.0～1.4时，0.1 Hz和0.01 Hz的介质损耗因数均呈单调递减的趋势；当拉伸比达到1.6后，介质损耗因数开始增大；在拉伸比为1.8时介质损耗因数迅速增大。该变化规律与损耗峰值频率的变化规律基本相同。在其他温度下，如果不考虑未拉伸（即拉伸比为1.0）情况，EPDM的介质损耗因数随拉伸比的变化趋势与120℃时类似。不同温度下，拉伸比为1.4时的介质损耗因数总是低于未拉伸EPDM的介质损耗因数。
2.2 红外光谱
对不同拉伸比处理后的EPDM样片进行红外光谱测试。测量了120℃下经不同拉伸比预拉伸72 h后EPDM试样在500～4 000 cm-1范围内的红外光谱，结果如图6所示。表1为120℃时不同拉伸比下EPDM特征基团的吸光度。图6和表1中的编号1为羟基-OH的伸缩振动吸收峰；编号2、3、4、6分别为-CH2-（亚甲基）的不对称伸缩振动峰、对称伸缩振动峰、弯曲振动吸收峰以及骨架振动峰；编号5为其他物质干扰。
从图6可以看出，随着拉伸比的变化，-CH2-的不对称伸缩振动峰以及其他物质的吸光度变化较大。由表1中主要特征基团的吸光度可知，-OH基团在整个拉伸比范围内的变化没有规律可循，而-CH2-基团在吸光度k小于1.4时，其振动峰吸光度变化不大，说明EPDM内部分子结构未发生破坏。所以此时介电性能的变化主要还是物理层面因素导致的。当k大于1.4时，-CH2-的除弯曲以外所有振动峰的吸光度较未拉伸时都降低，说明乙丙橡胶的分子链交联度降低，分子链确实发生了断裂。编号5处的杂质干扰峰1 000～1 100 cm-1明显增加，这是由拉伸时析出的添加物（填料补剂、加工助剂、抗氧化剂）覆盖在试样表面导致的[5]。因此，乙丙橡胶的介电性能受化学结构改变的影响，即小分子链的断裂和杂质的析出均对极化有一定的促进作用。
3 分析与讨论
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3.1 基于直流电导率修正的Cole-Cole模型
EPDM的介电频谱主要取决于电极极化（属于麦克斯韦-瓦格纳界面极化效应的一种）、电导率以及偶极子转向极化[7]。通过对图3(a)和(b)进行乘积处理可以得到复介电常数虚部随频率的变化图，对曲线的横纵坐标取双对数坐标，计算1 Hz以下复介电常数虚部与频率的关系，可以得出复介电常数虚部在低频下的斜率均大于-1，说明存在电极极化[8]。然而，当频率逐渐增大时，载流子无法移动到电极界面，不能形成极化，极化程度减弱[9-10]。
较低频段下EPDM损耗的变化主要是由极化损耗和电导损耗共同作用引起的。较高频段下损耗来源包括节段链的旋转运动（α弛豫）与甲基侧基的取向运动（β弛豫），它们在100℃左右的弛豫峰值频率通常在105～106 Hz[11]。由于虚部频谱图在106 Hz附近并未出现弛豫峰，说明拉伸力的施加并未对α和β弛豫过程有明显影响，与此同时，因为介电常数虚部仅出现了1个弛豫峰，所以可以采用经直流电导率修正的单弛豫Cole-Cole模型对频谱图进行拟合[12]，其公式如式（2）所示。
εcc*ω=ε∞+σdcjε0ω+Δε1+(jωτ)α
式（2）中：ε∞为光频介电常数；σdc为直流电导率，其在高温和低频下占主导地位，所以需要剔除其影响；ε0为真空介电常数；ω为角速度，计算公式为ω=2π/T，T为周期；Δε为弛豫强度；τ为弛豫时间常数；α为形状参数。
图7为在120℃、k为1.8时EPDM复介电常数虚部拟合图，拟合度为0.999 39，可以看出该模型可以很好地拟合EPDM的弛豫过程。表2为经Cole-Cole模型拟合得到的温度为120℃时不同拉伸比下EPDM的介电谱特征参数。
基于Cole-Cole模型提取的直流电导率、弛豫强度以及弛豫时间常数归一化值与拉伸比的关系如图8所示。从图8可以看出，3个参数均与拉伸比有着很强的相关性。弛豫强度和直流电导率随着拉伸比的增加先减小后增大。相反，弛豫时间常数随着拉伸比的增加先增大后减小，说明弛豫峰首先向低频移动，再反向高频移动。
3.2 拉伸机理分析
电导率σ的计算公式[14]如式（3）所示。
σ=en0μ
式（3）中：e为电荷电量；n0为载流子浓度；μ为载流子迁移率。
根据测量的去极化电流，可采用式（4）计算不同拉伸比下EPDM的去极化电荷量随时间的变化（Qd(t)）[15]。
Qdt=∫0tId(t)dt
式（4）中，Id(t)为去极化电流随时间的变化值，因此载流子迁移率可用式（5）表示。
μt=2εQdt2×dQdtdt
结合上述公式，最终得出载流子迁移率在不同拉伸比情况下随时间变化的曲线。
图9为EPDM在电场强度为3 kV/mm下极化600 s后，通过去极化电流得到的载流子视在迁移率。通过对图片进行双对数坐标处理可知，随着时间的增加，迁移率趋于稳定，而随着拉伸比的增加，载流子迁移率先减小后增加，极小值出现在拉伸比为1.2附近，而3.1节中由介电谱计算得到的电导率极小值在1.4附近，这是因为在式（3）中，电导率不仅受载流子迁移率的影响，还与载流子浓度有关。
从物理角度来看，在拉伸应力较小（k小于1.4）时，相当于材料在垂直方向上被挤压，使得绝缘内部间隙在垂直方向上减小[16]，导致跃迁的势垒增大，载流子跃迁更难以实现，从而载流子的迁移率降低，最终导致直流电导率降低，与从介电谱提取的直流电导率规律一致。当k大于1.4时，结合红外光谱图法可知，当EPDM超过其弹性范围后，分子链开始断裂、微孔开始增加，在水平方向上的间隙和自由体积增大，其对载流子跃迁的影响超过了在垂直方向上挤压对载流子的影响，导致载流子迁移率升高，从而使得直流电导率反而增加。
图10为分子链拉伸以及橡胶分子链网络拉伸断裂示意图[17]。在外部拉伸应力作用下，聚合物的内部形态结构会发生改变。在一定的弹性范围内，拉伸形变不会破坏EPDM分子链的结构[16]，反而因为拉伸之后分子链取向趋于有序化，即取向受到拉伸的限制（如图10(a)所示），导致极性基团活性降低，发生偶极子取向极化的概率减小[18]。因此，试样的极化强度减小，Δε弛豫强度可反映介质的极化强度，所以呈现出先减小的规律；在拉伸比为1.0～1.4时，松弛弛豫峰均随着拉伸比的增加向低频移动，即τ增大。
当拉伸比为1.4～1.8时，形变将超出EPDM可承受的弹性范围，如图10(b)所示，EPDM内部部分分子链发生断裂，极性分子增多，且分子链相互之间受到的束缚减小，自由体积增大，分子的转向极化在电场的作用下变得更容易，极化过程更容易建立[19]，导致松弛弛豫峰整体向高频移动，即τ减小；极化强度增大，Δε增加。这也是EPDM的弛豫峰值随频率先减小后增大的原因。
4 结论
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（1）拉伸比对EPDM的复介电常数和介质损耗因数均有明显的影响。经Cole-Cole模型提取的直流电导率、弛豫强度和弛豫时间常数等参数均与拉伸比有着较强的相关性，其中直流电导率和弛豫强度随着拉伸比的增加先减小后增大，而弛豫时间常数随着拉伸比的增加先增大后减小。
（2）在弹性范围内，EPDM主要官能团无明显变化，当超出弹性范围后，-CH2-的除弯曲以外的所有振动峰的吸光度均随着拉伸比的增加而降低，而拉伸造成的杂质析出导致杂质吸光度增加。
（3）随着拉伸比的增加，从去极化电流提取出的载流子迁移率在稳定阶段先减小后增大，与介电谱提取的直流电导率变化规律相一致。
基金
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  • 国家自然科学基金资助项目(51977137)
  • 山西省重点研发计划项目(202102040201001)
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2023年第56卷第7期
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doi: 10.16790/j.cnki.1009-9239.im.2023.07.007
  • 接收时间：2022-07-23
  • 首发时间：2025-11-24
  • 出版时间：2023-07-20
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  • 收稿日期：2022-07-23
  • 修回日期：2022-09-09
基金
国家自然科学基金资助项目(51977137)
山西省重点研发计划项目(202102040201001)
作者信息
    1太原理工大学 电气与动力工程学院,山西 太原 030024
    2国网山西省电力公司电力科学研究院,山西 太原 030012

通讯作者:

雷志鹏（1983-），男（汉族），山西太原人，副教授，博士，主要从事电气绝缘放电、绝缘诊断与寿命评估、智能电器方面的研究。
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2种不同金属材料的力学参数
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Family		 属数
Number of
genus		 种数
Number of
species		 占总种数比例
Percentage of
total species (%)		 属
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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