Article(id=1241795755275522357, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1241795749348967189, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2021.08.008, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1602777600000, receivedDateStr=2020-10-16, revisedDate=1608739200000, revisedDateStr=2020-12-24, acceptedDate=null, acceptedDateStr=null, onlineDate=1773996779507, onlineDateStr=2026-03-20, pubDate=1629388800000, pubDateStr=2021-08-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1773996779507, onlineIssueDateStr=2026-03-20, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1773996779507, creator=13701087609, updateTime=1773996779507, updator=13701087609, issue=Issue{id=1241795749348967189, tenantId=1146029695717560320, journalId=1149653034449285133, year='2021', volume='54', issue='8', pageStart='1', pageEnd='114', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1773996778094, creator=13701087609, updateTime=1773997690758, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1241799577397953390, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1241795749348967189, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1241799577397953391, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1241795749348967189, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=45, endPage=51, ext={EN=ArticleExt(id=1241795755619455296, articleId=1241795755275522357, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Mechanical Properties and Water Tree Characteristics of XLPE/OMMT Nanocomposite Dielectrics, columnId=1190369066675179686, journalTitle=Insulating Materials, columnName=Material Research, runingTitle=null, highlight=null, articleAbstract=

In order to study the influence of crosslinking behavior on the mechanical properties and water tree characteristics of nanocomposite dielectrics, we prepared two nanocomposites of polyethylene/montmorillonite (PE/OMMT) and crosslinked polyethylene/montmorillonite (XLPE/OMMT) by melt blending, and their tensile properties, dynamic mechanical properties, and water tree ageing characteristics were tested. The results show that the OMMT in XLPE plays a role of physical crosslinked point and stress dispersion, which increases the tensile strength and toughness of nanocomposites. The homogeneously dispersed OMMT of lamellar heat resistance and physical support functions improves the storage modulus of nanocomposite at high temperature. The water tree initiation time of the nanocomposites is short, and the OMMT layer is beneficial to buffer the impact of expansion and deformation of water molecules on the molecular chain, so that the growth length of water tree is smaller. The three-dimensional network structure after crosslinking enhances the ability to withstand deformation of nanocomposites, thus the nanocomposites have better resistance to water tree.

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为了研究交联行为对纳米复合电介质力学性能和水树枝特性的影响,采用熔融共混的方法分别制备了聚乙烯/蒙脱土(PE/OMMT)和交联聚乙烯/蒙脱土(XLPE/OMMT)两种纳米复合材料,并对其拉伸性能、动态力学性能和水树枝老化特性进行测试。结果表明:有机化蒙脱土(OMMT)加入到XLPE中起到物理交联点和应力分散的作用,使纳米复合材料的拉伸强度增大、韧性增强。均匀分散的OMMT片层阻热和物理支撑的双重作用提高了纳米复合材料高温区的储能模量。纳米复合材料的水树枝引发时间较短,OMMT片层有利于缓冲水分子的伸缩变形对分子链的冲击,水树枝生长长度较小。而交联后形成的三维网状结构使纳米复合材料承受形变的能力增强,具有更优的抗水树枝性能。

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李秀峰(1974-),女(汉族),山东青岛人,副教授,博士,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的研究。
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杨云梦(1996-),女(汉族),山东泰安人,硕士生,主要从事高电压与绝缘技术的研究。

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杨云梦(1996-),女(汉族),山东泰安人,硕士生,主要从事高电压与绝缘技术的研究。

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试样弹性模量/MPa屈服强度/MPa屈服应变/%
PE161.09.50.61
PE/OMMT-1%192.610.10.63
PE/OMMT-2%232.010.70.65
PE/OMMT-3%169.89.80.63
XLPE108.48.90.54
XLPE/OMMT-1%116.59.00.55
XLPE/OMMT-2%118.79.10.57
XLPE/OMMT-3%113.19.00.54
), ArticleFig(id=1245062204811231825, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1241795755275522357, language=CN, label=表1, caption=

PE、XLPE及纳米复合材料的弹性形变参数

, figureFileSmall=null, figureFileBig=null, tableContent=
试样弹性模量/MPa屈服强度/MPa屈服应变/%
PE161.09.50.61
PE/OMMT-1%192.610.10.63
PE/OMMT-2%232.010.70.65
PE/OMMT-3%169.89.80.63
XLPE108.48.90.54
XLPE/OMMT-1%116.59.00.55
XLPE/OMMT-2%118.79.10.57
XLPE/OMMT-3%113.19.00.54
), ArticleFig(id=1245062204911895123, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1241795755275522357, language=EN, label=Tab.2, caption=The plastic deformation parameters of PE, XLPE, and nanocomposites, figureFileSmall=null, figureFileBig=null, tableContent=
试样

拉伸强度

/MPa

断裂伸长率

/%

断裂能

/(J/m2)

PE11.0558.34.28
PE/OMMT-1%11.3565.55.63
PE/OMMT-2%13.7595.66.48
PE/OMMT-3%11.4484.35.68
XLPE15.4469.75.71
XLPE/OMMT-1%16.2527.26.15
XLPE/OMMT-2%17.7474.26.57
XLPE/OMMT-3%16.3441.46.40
), ArticleFig(id=1245062204995781208, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1241795755275522357, language=CN, label=表2, caption=

PE、XLPE及纳米复合材料的塑性形变参数

, figureFileSmall=null, figureFileBig=null, tableContent=
试样

拉伸强度

/MPa

断裂伸长率

/%

断裂能

/(J/m2)

PE11.0558.34.28
PE/OMMT-1%11.3565.55.63
PE/OMMT-2%13.7595.66.48
PE/OMMT-3%11.4484.35.68
XLPE15.4469.75.71
XLPE/OMMT-1%16.2527.26.15
XLPE/OMMT-2%17.7474.26.57
XLPE/OMMT-3%16.3441.46.40
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XLPE/OMMT纳米复合电介质力学性能和水树枝特性研究
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杨云梦 1 , 许庆重 1 , 邓繁盛 1 , 董芸滋 1 , 李秀峰 1 , 崔锡静 2
绝缘材料 | 材料研究 2021,54(8): 45-51
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绝缘材料 | 材料研究 2021, 54(8): 45-51
XLPE/OMMT纳米复合电介质力学性能和水树枝特性研究
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杨云梦1, 许庆重1, 邓繁盛1, 董芸滋1, 李秀峰1, 崔锡静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浙江万马股份有限公司,浙江 杭州 311305
  • 杨云梦(1996-),女(汉族),山东泰安人,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,博士,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的研究。
Mechanical Properties and Water Tree Characteristics of XLPE/OMMT Nanocomposite Dielectrics
Yunmeng YANG1, Qingzhong XU1, Fansheng DENG1, Yunzi DONG1, Xiufeng LI1, Xijing CUI2
Affiliations
  • 1College of Electrical and Electronic Engineering, Shandong University of Technology, Zibo 255000, China
  • 2Zhejiang Wanma Co., Ltd., Hangzhou 311305, China
出版时间: 2021-08-20 doi: 10.16790/j.cnki.1009-9239.im.2021.08.008
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为了研究交联行为对纳米复合电介质力学性能和水树枝特性的影响,采用熔融共混的方法分别制备了聚乙烯/蒙脱土(PE/OMMT)和交联聚乙烯/蒙脱土(XLPE/OMMT)两种纳米复合材料,并对其拉伸性能、动态力学性能和水树枝老化特性进行测试。结果表明:有机化蒙脱土(OMMT)加入到XLPE中起到物理交联点和应力分散的作用,使纳米复合材料的拉伸强度增大、韧性增强。均匀分散的OMMT片层阻热和物理支撑的双重作用提高了纳米复合材料高温区的储能模量。纳米复合材料的水树枝引发时间较短,OMMT片层有利于缓冲水分子的伸缩变形对分子链的冲击,水树枝生长长度较小。而交联后形成的三维网状结构使纳米复合材料承受形变的能力增强,具有更优的抗水树枝性能。

交联  /  纳米复合电介质  /  拉伸强度  /  储能模量  /  水树枝

In order to study the influence of crosslinking behavior on the mechanical properties and water tree characteristics of nanocomposite dielectrics, we prepared two nanocomposites of polyethylene/montmorillonite (PE/OMMT) and crosslinked polyethylene/montmorillonite (XLPE/OMMT) by melt blending, and their tensile properties, dynamic mechanical properties, and water tree ageing characteristics were tested. The results show that the OMMT in XLPE plays a role of physical crosslinked point and stress dispersion, which increases the tensile strength and toughness of nanocomposites. The homogeneously dispersed OMMT of lamellar heat resistance and physical support functions improves the storage modulus of nanocomposite at high temperature. The water tree initiation time of the nanocomposites is short, and the OMMT layer is beneficial to buffer the impact of expansion and deformation of water molecules on the molecular chain, so that the growth length of water tree is smaller. The three-dimensional network structure after crosslinking enhances the ability to withstand deformation of nanocomposites, thus the nanocomposites have better resistance to water tree.

crosslinking  /  nanocomposite dielectric  /  tensile strength  /  storage modulus  /  water tree
杨云梦, 许庆重, 邓繁盛, 董芸滋, 李秀峰, 崔锡静. XLPE/OMMT纳米复合电介质力学性能和水树枝特性研究. 绝缘材料, 2021 , 54 (8) : 45 -51 . DOI: 10.16790/j.cnki.1009-9239.im.2021.08.008
Yunmeng YANG, Qingzhong XU, Fansheng DENG, Yunzi DONG, Xiufeng LI, Xijing CUI. Mechanical Properties and Water Tree Characteristics of XLPE/OMMT Nanocomposite Dielectrics[J]. Insulating Materials, 2021 , 54 (8) : 45 -51 . DOI: 10.16790/j.cnki.1009-9239.im.2021.08.008
交联聚乙烯(XLPE)以其优异的电气性能和力学性能而广泛应用于电力电缆绝缘层[1-2]。电力电缆在运行过程中,由于受到电、热、力等联合作用[3],绝缘层会发生一系列物理化学变化,导致其电气性能、力学性能及其他性能逐渐劣化,进而影响电缆的使用寿命[4]。因此,对电缆的绝缘性能提出了更高要求。
聚合物纳米复合材料因其独特的结构和优异的综合性能,为电气绝缘材料的研究提供了新的思路[5]。纳米粒子的掺入可改善复合材料的电气强度、耐电晕、耐树枝化等电气性能。冯军强等[6]利用溶胶-凝胶法制备了银/聚乙烯醇(Ag/PVA)纳米复合材料,发现当Ag含量为0.04%时,均匀分散在PVA中的Ag微粒阻碍了电子的定向运动,有效地提高了纳米复合材料的电气强度。何恩广等[7]研究了纳米二氧化钛(TiO2)填料对变频电机电磁线绝缘性能的影响。结果发现,改性后的电磁线经过电晕破坏,析出的纳米TiO2微粉层可以改善电场分布,并在绝缘层表面形成电子和紫外线屏障,捕获电晕放电产生的电荷,从而提高电磁线的耐电晕性能。R KURNIANTO等[8]在XLPE中掺杂氧化镁(MgO)粒子,研究不同MgO含量对水树枝老化的影响。结果表明,当MgO质量分数为2%时,纳米复合材料空间电荷的分布得到显著改善,水树枝抑制效果最佳。
电力设备绝缘在使用过程中也可能受到外界机械应力破坏而发生一系列物理化学变化,纳米粒子不仅可提高复合材料的电气性能,而且也会对力学性能产生影响。影响纳米复合材料性能的因素很多,包括纳米颗粒的尺寸、掺杂量等。J CHO等[9]研究了纳米粒子尺寸对复合材料力学性能的影响,发现随着粒径的减小,复合材料的弹性模量和拉伸强度逐渐增加。王娟等[10]研究了碳纳米管(CNTs)分散增强氮化铝(AlN)基复合材料的力学性能,结果表明,在1 750℃的烧结温度下,随着CNTs质量分数的增加,AlN-CNTs复合材料的抗弯强度和断裂韧性先上升后下降,当CNTs质量分数为1%时,复合材料的力学性能最佳。V KAVITHA等[11]验证了纳米黏土对XLPE基体力学性能的增强作用,提出其力学性能的改善归因于纳米黏土在XLPE基体中的分散状态。
纳米粒子在聚合物基体中的分散状态是决定复合材料性能优劣的关键因素,而交联过程又会影响纳米粒子在复合体系中的分散情况,从而改变其微观结构,进而影响宏观性能,但目前关于交联行为对纳米复合材料力学性能及抗水树枝性能的相关研究相对较少。为探讨纳米粒子填充量和交联行为对复合材料力学性能和抗水树枝性能的影响,本研究采用熔融共混的方法分别制备了聚乙烯/蒙脱土(PE/OMMT)和交联聚乙烯/蒙脱土(XLPE/OMMT)纳米复合材料,分析交联行为和OMMT填充量对纳米复合材料弹性形变和塑性形变等力学性能的影响,研究力学性能的改变对水树枝的抑制机理。
聚乙烯(PE),牌号为2220H,熔体流动速率为(2.0±0.2)g/10 min,扬子石化-巴斯夫有限责任公司;35 kV交联聚乙烯绝缘料(XLPE),采用牌号为2220H的聚乙烯树脂与交联剂(DCP)和抗氧剂熔融混合造粒而得,南京中超新材料股份有限公司;纳米蒙脱土(MMT),片晶厚度约为1 nm,横向长度约为30 nm,浙江丰虹粘土化工有限公司。
采用质量分数为1%的二甲基氢化牛脂季铵盐对MMT进行表面改性处理,得到有机化蒙脱土(OMMT)。将OMMT与聚乙烯按照2∶8的质量比在开放式炼塑机上熔融共混,得到OMMT含量为20%的母料。
PE/OMMT纳米复合试样的制备:将OMMT母料分别按5%、10%、15%的质量分数与PE料粒熔融共混,得到OMMT含量为1%、2%、3%的PE/OMMT纳米复合材料,混炼温度为100℃。出料后在温度为175℃、压力为15 MPa的平板硫化机上预热 3 min,加压5 min成型,加压冷却至室温,制得厚度分别为1、3、5 mm的试样若干。
XLPE/OMMT纳米复合试样制备:制备过程与PE/OMMT纳米复合试样相同。出料后在温度为175℃、压力为15 MPa的平板硫化机上预热3 min,加压15 min成型,加压冷却至室温,制得各种厚度的试样若干。
根据文献[12],将压制好的厚度为5 mm的试样裁剪成长度为15 mm、宽度为10 mm的长方体。采用针尖曲率半径为(5±1)μm的钢针在试样侧面扎一个直径为2 mm的圆孔,针尖部分与接地电极距离保持在2 mm左右,扎针角度为30°。将钢针拔出后,利用注射器向圆孔内注入少量AgNO3溶液,浸没过针尖部分,再将钢针插入,预留针尖部分溶液作为水针电极,钢针尖与试样针孔尖长度大约为2 mm,在钢针末端接高压电极,将导电铝箔粘贴在试样底部作为接地极,在线观察水树枝的试样,如图1所示。为防止扎针过程中的残余应力,将试样和钢针同时放入70℃的烘箱中加热2 h,采用专用模具将针电极匀速插入,恒温2 h后,将试样取出自然冷却至室温。
力学性能测试:根据GB/T 1040—2006采用深圳三思纵横公司的CMT4503型万能试验机,对试样进行拉伸性能测试,拉伸速率为(250±50)mm/min,实验温度为(23±2)℃。
动态力学分析(DMA):采用美国TA仪器公司的Q800型动态热机械分析仪,使样品在程序控制温度下,施加随时间变化的交变力,研究样品的动态力学行为,得到其储能模量和损耗因子tanδ随温度变化的关系。实验温度为25~100℃,频率为 1 Hz,施加0.1 N的作用力。
水树枝老化实时观测系统主要由高压发生器、显微镜、照相机与计算机组成[12],如图2所示。将试样放入二甲基硅油中,防止发生沿面闪络。实验条件电压为5 kV、频率为6 kHz,AgNO3溶液浓度为0.1 mol/L,加压时间为14~21天。用显微镜从上端实时观察针尖部分的水树枝生长情况,放大倍数为45倍,设置每20 min拍照一次,并通过图像采集软件将观察到的水树枝图像显示在电脑屏幕上。观察PE、XLPE及纳米复合材料中水树枝引发情况和生长状况,统计其引发时间和实时生长长度。
拉伸试验能够清楚地反映材料受力后所发生的弹性、塑性与断裂3个变形阶段的基本特征[13],其应力-应变曲线可以反映材料的大形变特性[14],一般分为两个部分:弹性变形区和塑性变形区[15]。对PE、XLPE及纳米复合材料进行拉伸性能测试,其弹性形变参数如表1所示,塑性形变参数如表2所示。
表1中可以看出,在弹性变形区,随着OMMT含量的增加,两种纳米复合试样的弹性模量、屈服强度和屈服应变均出现先增大后减小的趋势。PE/OMMT-2%纳米复合试样的弹性模量最大,达到232.0 MPa,屈服强度为10.7 MPa。而交联后,无论是XLPE还是纳米复合材料,弹性形变参数均呈下降趋势,尤其是XLPE/OMMT-2%纳米复合试样的弹性模量下降程度最大,下降率为48.84%,远超XLPE的下降率32.67%。通过SEM对纳米复合试样脆断面形貌观察发现,当OMMT质量分数为2%时,OMMT与PE基体树脂的界面结合较好,OMMT片层堆积较少,无明显的微观缺陷,在PE基体中实现了均匀剥离分散[16],其大的比表面积与聚合物基体之间形成了较强的界面作用力,对分子链段运动的束缚增强[17],使弹性模量增大,抗形变能力增强。弹性模量和屈服强度也与复合材料的结晶度密切相关[18]。加入OMMT后,晶体形态由球晶型变成沿片层表面生长的横穿晶,晶体尺寸减小,堆砌紧密,交联后试样非晶区域面积明显增加[19],其结构的差异在宏观上导致了弹性模量和屈服强度的不同[20]。交联形成的网状结构限制了分子链段的运动,影响了聚乙烯结晶,使无定形区增多[21],分子链活动的自由空间增大,导致材料屈服应变减小。可见,OMMT的填充改性对试样弹性形变参数的影响程度优于交联。
在聚合物材料的拉伸行为超过材料的屈服点之后继续施加载荷,便进入了材料的塑性形变阶段。从材料出现不均匀形变到被拉断,可得到拉伸强度、断裂伸长率和断裂能等特征参数,如表2所示。
表2可以看出,两种纳米复合材料的拉伸强度随着OMMT含量的增加呈现先增大后减小的趋势,在2%添加量时达到峰值。这是由于均匀分散的OMMT片层通过离子键与基体树脂连接,当其中某一大分子链受到应力时,可通过OMMT将应力传递到其他分子链上,起到应力分散的作用,有利于复合材料拉伸强度的提高。但当OMMT质量分数大于2%时,过多的OMMT在基体中分散不均匀,部分发生团聚,基体与OMMT之间的界面上发生相分离可能使形态发生变化[22],诱导微观裂纹。裂纹使材料受到应力作用时易沿此处发展,致使其力学性能下降。在OMMT质量分数相同的情况下,交联后的纳米复合试样拉伸强度增加。XLPE/OMMT-2%试样的拉伸强度高达17.7 MPa,比PE/OMMT-2%增加了29.20%。交联形成了键能较强的交联键,且交联反应使晶片之间缠结的分子链结构增多[23],同时OMMT在体系中作为物理交联点,能够防止链段分子的滑移,因此其拉伸强度较高。
断裂能用来表征材料的韧性,断裂能越大,表明材料韧性越好,发生脆性断裂的可能性越小[5]。加入OMMT后,纳米复合材料的断裂能明显上升,这是因为一方面当受到外加应力时,OMMT片层发生形变,片层的缓冲作用有利于吸收更多的能量。另一方面,纳米粒子与聚合物基体的界面作用力可以抑制粒子周围分子链段的运动,从而提高材料的断裂韧度[24]。交联后,纳米复合材料的断裂能进一步提高,这是因为交联形成较强分子间力,使OMMT片层在裂纹扩展过程中成为应力传递的阻碍,同时界面作用增强,物理缠结分子链结构增多,微观结构更加密实,进一步阻碍了裂纹的发展。因此交联后的纳米复合材料增强、增韧作用明显增大。
动态热力学方法可以测定在周期振动力下,材料随时间、温度或频率变化的动态粘弹性能[15]。对各试样在25~100℃温度区间进行动态力学性能测试,获得PE、XLPE及纳米复合材料交联前后的结构变化规律。储能模量、损耗因子随温度的变化曲线如图3所示。从图3(a)可以看出,PE、XLPE及纳米复合材料试样的储能模量随温度升高都呈下降趋势。这是因为在较低温度时,分子链段处于被束缚位置,不易发生扩散运动,分子链的主价键和次价键所形成的内聚力使材料具有较高的机械强度[23],所以起始储能模量较大。随着温度的升高,分子热运动能量增加,分子中原子的振动强度和振幅增大,较多分子链段开始短程的扩散运动[23],微晶体开始熔化,所以储能模量随温度升高呈现下降的趋势。当温度高于90℃时,添加OMMT的PE/OMMT纳米复合材料储能模量均高于PE。而交联后,无论XLPE还是XLPE/OMMT纳米复合材料,储能模量均低于交联前,分析认为,均匀分散的OMMT片层会对周围聚合物链段的分子运动产生约束,从而延缓聚合物链段的松弛[5],加上大长厚比OMMT片层的阻热作用,导致PE/OMMT纳米复合材料的储能模量较大。交联后纳米复合试样的储能模量下降,说明交联过程影响OMMT的分散状态,OMMT的片层阻热作用减弱,片层外的分子链发生形变,消耗了较多的能量,从而使储能模量减小。当温度超过100℃时,晶体已经全部熔化[5],纳米复合材料的储能模量依然高于纯基体树脂,说明在高温段OMMT的片层阻热和物理支撑对储能模量的作用明显。
图3(b)可以看出,试样的损耗因子tanδ随温度的升高都呈现先增大后减小的趋势,在50~90℃之间出现峰值,是力学松弛中的α松弛[25]。目前普遍认为α松弛与升温过程中分子链的运动有密切关系[26]。与基体树脂相比,两种纳米复合材料的损耗峰值温度升高,当OMMT质量分数为2%时,PE/OMMT-2%的损耗因子峰值最高。分散良好的OMMT片层对分子链段的运动形成束缚,使分子链的刚性增加,损耗峰值温度向高温移动。与交联前相比,交联后XLPE和纳米复合试样的tanδ峰值均呈下降趋势,损耗峰值温度向低温方向移动。OMMT粒子在体系中起到物理交联点的作用,在交联反应后,晶片之间形成大量缠结分子链[23],进一步限制了分子链段的运动,所以tanδ峰值减小。但交联拉近了硅酸盐片层的层间距[16],OMMT片层堆叠改变了纳米复合材料的内部结构,增加了微观缺陷,界面作用力减弱,所以损耗峰值温度向低温方向移动。
水树枝老化是纳米复合材料微观结构变化在宏观上的体现。通过对纳米复合材料力学性能的测试,发现添加2%质量分数的OMMT时,复合材料的力学性能最佳。因此将OMMT质量分数为2%的纳米复合材料作为优选配方进行水树枝老化研究。分别对PE、PE/OMMT-2%、XLPE和XLPE/OMMT-2%试样进行水树枝实时观测,发现随着老化时间的增加,沿电场方向和垂直主电场方向水树枝生长长度不断增大,第14天以后生长逐渐缓慢,到第21天时进入滞长期,水树枝生长长度趋于稳定,因此选取14天作为老化试验时间。图4为各试样水树枝生长形态。图5为水树枝的引发时间和生长长度的关系。
图4可以看出,4种试样的水树枝由针孔通道及针尖向四周发射状生长,其纵向截面呈半圆形。从图5可以看出,添加OMMT的纳米复合材料水树枝生长长度在沿电场方向和垂直主电场方向都有一定程度的减小。与PE和XLPE相比,纳米复合试样水树枝的引发时间缩短为2天,但相同时间下水树枝的生长长度明显减小。PE/OMMT-2%试样在第14天的水树枝沿电场方向和垂直主电场方向的长度分别为38.62 μm和43.57 μm,而XLPE/OMMT-2%试样分别仅为31.58 μm和35.94 μm。
添加OMMT的纳米复合试样水树枝引发时间缩短,这是由于OMMT的加入在非晶区中引入了较多的杂质离子,在电化学作用下成为诱导水树枝引发的因素[12]。电场力使材料内部的水分子沿电场方向发生形变,对材料施加交变的挤压力,使内部发生形变,当形变超过材料本身的弹性极限时,分子链将发生应力断裂,形成微观裂纹,从而引发水树枝[27]。从红外光谱的研究发现,水树枝老化后试样的羰基指数明显增加[28],表明在水树枝形成过程中,产生了大量游离的羰基化合物R-C-(=O)O-阴离子,伴随着聚合物基体分子链的热降解,局部区域电化学降解作用进一步加重。加入OMMT后,纳米复合材料的韧性增加(见表2断裂能),片层有利于缓冲水分子的伸缩形变对分子链的冲击,并且OMMT局部片层堆积的空间效应提高了复合材料的抗氧化性,进一步阻碍水气分子穿过聚合物基体,阻挡了水与内部分子链的结合,从而延缓了水树枝的生长。而交联后的复合材料,交联密度增加,微观结构密实,交联键的键能大于范德华力,不易断裂;同时交联形成的三维网状结构,其应力分散的作用使纳米复合材料可承受较大的形变,不易形成微观裂纹,水树枝的生长得到抑制,因而交联后的纳米复合材料抑制水树枝的效果更优。
(1)OMMT与基体之间形成的较强界面作用力和交联形成的三维网状结构,限制了分子链段的运动,两者的协同作用有效提高了XLPE/OMMT纳米复合材料的拉伸强度,使复合材料的韧性增强,断裂能增大。
(2)纳米复合材料的储能模量随温度的升高而降低。均匀分散的OMMT片层起到阻热和物理支撑作用,可显著提高纳米复合材料高温区的储能模量。
(3)抗水树枝性能与材料力学性能的改善密切相关。加入OMMT后,纳米复合材料的韧性增强,水分子伸缩形变对分子链的冲击得到缓冲。三维网状结构能够有效分散纳米复合材料受到的形变应力,使得XLPE/OMMT纳米复合材料具有更优的抗水树枝性能。
  • 山东省自然科学基金面上项目(ZR2019MEE100)
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2021年第54卷第8期
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doi: 10.16790/j.cnki.1009-9239.im.2021.08.008
  • 接收时间:2020-10-16
  • 首发时间:2026-03-20
  • 出版时间:2021-08-20
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  • 收稿日期:2020-10-16
  • 修回日期:2020-12-24
基金
山东省自然科学基金面上项目(ZR2019MEE100)
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浙江万马股份有限公司,浙江 杭州 311305

通讯作者:

李秀峰(1974-),女(汉族),山东青岛人,副教授,博士,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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