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Article(id=1198662247246561778, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1198662245069713420, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2023.01.001, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1637510400000, receivedDateStr=2021-11-22, revisedDate=1642780800000, revisedDateStr=2022-01-22, acceptedDate=null, acceptedDateStr=null, onlineDate=1763712949810, onlineDateStr=2025-11-21, pubDate=1674144000000, pubDateStr=2023-01-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1763712949810, onlineIssueDateStr=2025-11-21, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1763712949810, creator=13701087609, updateTime=1763712949810, updator=13701087609, issue=Issue{id=1198662245069713420, tenantId=1146029695717560320, journalId=1149653034449285133, year='2023', volume='56', issue='1', 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=1763712949292, creator=13701087609, updateTime=1766563309216, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1210617521154159057, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1198662245069713420, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1210617521154159058, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1198662245069713420, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=1, endPage=7, ext={EN=ArticleExt(id=1198662247611466228, articleId=1198662247246561778, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Correlation between aggregation structure of biaxially oriented polypropylene and its breakdown property, columnId=1190369066675179686, journalTitle=Insulating Materials, columnName=Material Research, runingTitle=null, highlight=null, articleAbstract=

In order to explore the correlation between the aggregation structure of biaxially oriented polypropylene (BOPP) film and its breakdown property, and promote the localization of BOPP, the properties of four kinds of BOPP samples manufactured at home and abroad were compared by optical observation, X-ray diffraction (XRD), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), impregnation, and DC breakdown experiments. The results show that the BOPP film with higher crystallinity and higher segment activation energy has a larger electric strength. Impregnating the BOPO film with benzyl toluene can change its aggregation structure and improve the electric strength of electrical weak point. Compared with similar international products, domestic BOPP films show the gap of low electric strength, small shape parameters, and many electrical weak point.

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为探究双向拉伸聚丙烯（BOPP）薄膜聚集态结构与击穿性能的关联，推动BOPP国产化，本文通过光学观测、X射线衍射（XRD）、差示扫描量热分析（DSC）、动态热机械分析（DMA）、浸渍、直流击穿等试验对国内外制造的4个BOPP薄膜试样的性能进行对比测试。结果表明：结晶度较高、链段活化能较高的BOPP薄膜具有较大的电气强度；使用苄基甲苯对BOPP薄膜进行浸渍可以改变其聚集态结构并提升电弱点电气强度；与国际同类产品相比，国产BOPP薄膜表现出电气强度低、形状参数小、电弱点较多等差距。

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刘文凤（1982-），女（汉族），天津人，教授，主要从事先进介质材料的理论与应用研究。
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马宇威（1998-），男（汉族），山西太原人，硕士生，研究方向为电容器薄膜国产化技术。

, authorsList=马宇威, 程璐, 刘宏博, 徐哲, 张卓, 邢照亮, 戴熙瀛, 刘文凤)}, authors=[Author(id=1210916721335071531, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1198662247246561778, orderNo=0, firstName=null, middleName=null, lastName=null, nameCn=null, orcid=null, stid=null, country=null, authorPic=null, dead=0, email=null, emailSecond=null, emailThird=null, correspondingAuthor=0, authorType=1, ext={EN=AuthorExt(id=1210916721477677872, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1198662247246561778, authorId=1210916721335071531, language=EN, stringName=Yuwei MA, firstName=Yuwei, middleName=null, lastName=MA, prefix=null, suffix=null, authorComment=null, nameInitials=null, affiliation=null, department=null, xref=1, address=1State Key Laboratory of Power Equipment and Electrical Insulation, Xi'an Jiaotong University, Xi'an 714009, China, bio=null, bioImg=null, bioContent=null, aboutCorrespAuthor=null), CN=AuthorExt(id=1210916721603506994, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1198662247246561778, authorId=1210916721335071531, language=CN, stringName=马宇威, firstName=宇威, middleName=null, lastName=马, prefix=null, suffix=null, authorComment=null, nameInitials=null, affiliation=null, department=null, xref=1, address=1西安交通大学 电力设备电气绝缘国家重点实验室,陕西 西安 714009, bio={"content":"

马宇威（1998-），男（汉族），山西太原人，硕士生，研究方向为电容器薄膜国产化技术。

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马宇威（1998-），男（汉族），山西太原人，硕士生，研究方向为电容器薄膜国产化技术。

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unstructuredReference=万荣根.绝缘油和聚丙烯薄膜相互作用的研究[D].西安:西安交通大学,1987., articleTitle=绝缘油和聚丙烯薄膜相互作用的研究, refAbstract=null)], funds=[Fund(id=1210916727408423063, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1198662247246561778, awardId=5500-202058455A-0-0-00, language=CN, fundingSource=国家电网有限公司科技项目(5500-202058455A-0-0-00), fundOrder=null, country=null)], companyList=[AuthorCompany(id=1210916721129550623, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1198662247246561778, xref=1, ext=[AuthorCompanyExt(id=1210916721137939232, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1198662247246561778, companyId=1210916721129550623, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1State Key Laboratory of Power Equipment and Electrical Insulation, Xi'an Jiaotong University, Xi'an 714009, China), AuthorCompanyExt(id=1210916721142133537, tenantId=1146029695717560320, 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figureFileSmall=x1nq1AIFJg/nEQowN/W+vw==, figureFileBig=gwiLPXfCQZqErmsCSKNDwQ==, tableContent=null), ArticleFig(id=1210916726766694517, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1198662247246561778, language=EN, label=Tab.1, caption=Weibull distribution parameters of DC breakdown test for BOPP films, figureFileSmall=null, figureFileBig=null, tableContent=
参数BOPP-ABOPP-BBOPP-CBOPP-D
α563.8619.4599.7650.7
β7.38.39.210.4
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BOPP薄膜直流击穿试验的Weibull参数

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参数BOPP-ABOPP-BBOPP-CBOPP-D
α563.8619.4599.7650.7
β7.38.39.210.4
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参数BOPP-ABOPP-BBOPP-CBOPP-D
α566.7591.9568.7574.0
β13.310.313.814.0
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BOPP薄膜浸渍后直流击穿试验的Weibull参数

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参数BOPP-ABOPP-BBOPP-CBOPP-D
α566.7591.9568.7574.0
β13.310.313.814.0
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双向拉伸聚丙烯薄膜聚集态结构与击穿特性的关联
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马宇威 1 , 程璐 1 , 刘宏博 1 , 徐哲 1 , 张卓 2 , 邢照亮 2 , 戴熙瀛 2 , 刘文凤 1
绝缘材料 | 材料研究 2023,56(1): 1-7
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绝缘材料 | 材料研究 2023, 56(1): 1-7
双向拉伸聚丙烯薄膜聚集态结构与击穿特性的关联
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马宇威1, 程璐1, 刘宏博1, 徐哲1, 张卓2, 邢照亮2, 戴熙瀛2, 刘文凤1
作者信息
  • 1西安交通大学 电力设备电气绝缘国家重点实验室,陕西 西安 714009
  • 2全球能源互联网研究院有限公司,北京 102209

    • 马宇威（1998-），男（汉族），山西太原人，硕士生，研究方向为电容器薄膜国产化技术。

通讯作者:

刘文凤（1982-），女（汉族），天津人，教授，主要从事先进介质材料的理论与应用研究。
Correlation between aggregation structure of biaxially oriented polypropylene and its breakdown property
Yuwei MA1, Lu CHENG1, Hongbo LIU1, Zhe XU1, Zhuo ZHANG2, Zhaoliang XING2, Xiying DAI2, Wenfeng LIU1
Affiliations
  • 1State Key Laboratory of Power Equipment and Electrical Insulation, Xi'an Jiaotong University, Xi'an 714009, China
  • 2Global Energy Interconnection Research Institute Co., Ltd., Beijing 102209, China
出版时间: 2023-01-20 doi: 10.16790/j.cnki.1009-9239.im.2023.01.001
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摘要
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为探究双向拉伸聚丙烯（BOPP）薄膜聚集态结构与击穿性能的关联，推动BOPP国产化，本文通过光学观测、X射线衍射（XRD）、差示扫描量热分析（DSC）、动态热机械分析（DMA）、浸渍、直流击穿等试验对国内外制造的4个BOPP薄膜试样的性能进行对比测试。结果表明：结晶度较高、链段活化能较高的BOPP薄膜具有较大的电气强度；使用苄基甲苯对BOPP薄膜进行浸渍可以改变其聚集态结构并提升电弱点电气强度；与国际同类产品相比，国产BOPP薄膜表现出电气强度低、形状参数小、电弱点较多等差距。

BOPP  /  聚集态结构  /  绝缘击穿

In order to explore the correlation between the aggregation structure of biaxially oriented polypropylene (BOPP) film and its breakdown property, and promote the localization of BOPP, the properties of four kinds of BOPP samples manufactured at home and abroad were compared by optical observation, X-ray diffraction (XRD), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), impregnation, and DC breakdown experiments. The results show that the BOPP film with higher crystallinity and higher segment activation energy has a larger electric strength. Impregnating the BOPO film with benzyl toluene can change its aggregation structure and improve the electric strength of electrical weak point. Compared with similar international products, domestic BOPP films show the gap of low electric strength, small shape parameters, and many electrical weak point.

BOPP  /  aggregation structure  /  insulation breakdown
马宇威, 程璐, 刘宏博, 徐哲, 张卓, 邢照亮, 戴熙瀛, 刘文凤. 双向拉伸聚丙烯薄膜聚集态结构与击穿特性的关联. 绝缘材料, 2023 , 56 (1) : 1 -7 . DOI: 10.16790/j.cnki.1009-9239.im.2023.01.001
Yuwei MA, Lu CHENG, Hongbo LIU, Zhe XU, Zhuo ZHANG, Zhaoliang XING, Xiying DAI, Wenfeng LIU. Correlation between aggregation structure of biaxially oriented polypropylene and its breakdown property[J]. Insulating Materials, 2023 , 56 (1) : 1 -7 . DOI: 10.16790/j.cnki.1009-9239.im.2023.01.001
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0 引言
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高压电力电容器广泛应用于电力系统的输变电各环节，承担着直流支撑、交直流滤波、无功补偿等重要作用[1-2]。双向拉伸聚丙烯薄膜（BOPP）由于具有低介质损耗、高电气强度、易于加工成型等优点，是电力电容器最广泛应用的绝缘介质[3]。BOPP的击穿特性是决定电容器性能的最重要因素之一，其电气强度直接决定了电容器的设计场强和储能密度 [4-5]。
目前电工领域用高端BOPP薄膜是我国的一项“卡脖子”技术，在特高压直流输电领域使用的电容器薄膜基本被国外垄断，国产薄膜性能与进口薄膜之间存在较大差距，主要体现在电气强度偏低。BOPP薄膜的宏观性能如击穿特性、力学特性等是由微观的聚集态结构决定的。聚丙烯作为一种典型的半结晶聚合物，其内部为晶区与非晶区共存的复杂两相结构，在双向拉伸过程中又伴随着聚集态结构的进一步变化，包括晶型转变、结晶度上升、球晶变形、取向态结构出现等[6-7]。目前针对BOPP薄膜的系统研究主要集中在性能的测试与分析。例如，LU J Y等[8]针对BOPP薄膜的结晶特性和击穿特性进行了一系列实验，结果显示结晶度越大、拉伸强度越高、厚度越大的薄膜具有越高的电气强度；XIONG J等[9]选取同步拉伸和异步拉伸两种方法制备的BOPP薄膜作为研究对象，对其形貌结构、力学与电学性能进行了全面测试表征，结果表明双向同步拉伸的薄膜性能更优；程璐等[10]提出了一种多段式Weibull分布的分析方法，结果表明多段式Weibull分布更适用于研究BOPP薄膜的击穿行为，虽然单一的Weibull分布常用于表征电介质的电气强度，但对于实际装置而言，低场强击穿区的弱点更直接地影响电容器整机的运行性能，因此必须考虑这些电弱点的强度与分布规律。另外还有部分工作针对纳米复合双向拉伸聚丙烯薄膜进行相关研究[11]。
以上研究总结了部分影响BOPP薄膜直流击穿特性的因素，然而对于其击穿特性和聚集态结构之间的关系尚缺乏系统性的研究。本文选取4种国内外市场占有率较大的BOPP薄膜作为研究对象，系统研究薄膜击穿特性和微观形貌之间的联系，建立微观性能参数与宏观电气性能之间的关联，为优化BOPP制造和加工工艺，提升国产化水平提供数据和理论参考。
1 试验
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1.1 主要原材料
选取北欧化工生产的HC300BF型电容器薄膜专用聚丙烯粒料，其灰分小于20×10-6，由沸腾正庚烷抽提法测得其等规指数为98.5%，由凝胶渗透色谱法（GPC）测得其分子量分散指数（PDI）为4。测试使用的BOPP薄膜样品由国内外4个厂家生产，分别命名为BOPP-A、BOPP-B、BOPP-C、BOPP-D，其中BOPP-D由国外厂商制造，其余均由国内厂商制造。
1.2 试验与表征
1.2.1 结构与形貌表征
采用OLYMPUS型光学显微镜观察薄膜表面的粗化形态，放大倍数为400倍。采用Bruker D8 Advance A25型X射线衍射仪对样品的晶型进行表征，测试的衍射角为10°～30°。采用METTLER DSC 822型差示扫描量热仪测试BOPP的熔融行为，测试样品量约为5 mg，将样品置于标准铝坩埚内，在氮气保护下从室温加热至200℃熔融，升温速率设置为10℃/min。
1.2.2 动态力学性能测试
采用METTLER DMA/SDTA型动态热机械分析仪对BOPP进行测试，试样的有效尺寸为9 mm×3.1 mm，温度为-40～40℃，升温速率为3℃/min。
1.2.3 浸渍试验
真空浸渍是传统油浸式电容器的生产环节之一，目的是填补膜间气隙，增强设备耐局部放电能力，优化散热条件等。本文通过浸渍试验辅助研究BOPP薄膜中的电弱点分布。将薄膜裁剪后放入盛有苄基甲苯的玻璃瓶中并使之完全浸没，瓶口密封后将玻璃瓶置于80℃真空干燥烘箱内，浸渍时间为24 h。处理结束后将薄膜取出并在无水乙醇中润洗以清除表面浸渍剂残留，擦拭干净后在室温下干燥备用。
1.2.4 直流击穿试验
将薄膜表面用无水乙醇擦拭后，固定在直径为25 mm的球形黄铜电极间进行测试，电极系统浸没于变压器油当中以防止沿面闪络。测试时以1 kV/s的速率升压，直至薄膜试样击穿，并用Weibull分布对数据进行分析。
2 结果与讨论
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2.1 表面形貌分析
BOPP薄膜的聚集态结构是由PP分子链在一定条件下堆叠形成的结晶区和无定形区并存的形态，其中结晶区分子链具有长程有序结构且排列紧密，无定形区分子链则仅具有短程有序结构且排列较松散。为研究BOPP薄膜的聚集态结构，首先采用光学显微镜对4种BOPP薄膜试样的表面形貌进行观察，结果如图1所示。
从图1可以看出，4种薄膜试样表面均出现BOPP特有的环形圈状结构的粗化形态，这是双向拉伸过程中发生的β向α晶型转变导致的。聚丙烯的β晶密度大于α晶，双向拉伸过程中晶型转化导致薄膜的表面分子链堆叠形态和体积发生变化，进而形成大量细密的“火山口”形貌结构[12-13]。
虽然国产与进口BOPP薄膜具有相同的环形结晶，但是结晶环的尺寸与分布差异显著。对每个样品的环形圈数量与直径进行统计，统计面积约为6 mm2，结果如图2所示。从图2可知，进口BOPP-D薄膜表面的环形结构数量远多于国产薄膜且分布较致密，其晶环总数达670个以上，晶环直径为50～150 μm，而国产薄膜的晶环数量则总体偏少且直径分布范围较广，如BOPP-A薄膜的晶环总数仅170个左右，直径为0～250 μm。粗化环形态与加工过程中的冷却辊温度、拉伸比等设定有关，良好的表面形态无论对于油浸式电容器的浸渍特性，或是干式电容器的金属化膜蒸镀特性都具有显著的提升作用[14-15]。
2.2 结晶特性
BOPP的结晶特性是其聚集态结构的重要组成部分，采用X射线衍射法（XRD）和差示扫描量热法（DSC）获取BOPP薄膜的结晶参数。首先通过XRD测试表征薄膜的晶型，结果如图3所示。薄膜试样的衍射峰数量与其厚度有关，本研究薄膜试样的厚度均控制在6 μm左右，因而各试样的出峰数量均相同[16]。衍射图中的3个衍射峰分别对应于α晶型的（110）、（040）、（130）晶面，未发现有β晶的衍射峰。通常挤出的聚丙烯厚片中含有一定量β晶，但是在双向拉伸过程会诱导β晶向α晶转变，因此在BOPP薄膜中仅观察到α晶的存在。
采用DSC测试了4种BOPP薄膜试样从室温至195℃的熔融曲线，结果如图4所示。图中4种试样均在约170℃的位置出现1个放热主峰。聚丙烯常见的晶型包括α晶、β晶、γ晶等，3种晶型分别对应的熔点约为167、145、150℃，由此可以推断4种BOPP薄膜DSC曲线中的放热峰来自于α晶的熔融过程，与XRD表征结果一致。进一步选取DSC曲线的极值点作为试样熔融温度Tm，发现4种试样的Tm分布在168～173℃，其中国外生产的BOPP-D薄膜的Tm最高，达到172.6℃，比国内薄膜高出约4℃，这是BOPP-D薄膜的片晶厚度较大所致。片晶厚度对熔点的影响与结晶的表面能有关，BOPP-D薄膜的片晶厚度更大，表明其结晶更完善，单位体积内晶体的表面能更低，熔点更高[17]。
此外，4种BOPP薄膜的DSC曲线在170℃主峰左侧，大约164℃附近出现了1个侧峰，因为该峰为双向拉伸过程取向态结构形成导致的，所以仅存在于BOPP中，而在聚丙烯粒料以及热压聚丙烯薄膜的DSC熔融曲线中较为罕见[18]。在双向拉伸过程中，力与温度的共同作用导致聚丙烯分子重结晶，其中沿拉伸方向的分子链段会定向排列，产生局部有序的取向结构进而增大分子间作用力，在熔融时这些分子间作用力产生的能量得以释放进而形成侧峰[18-20]。
进一步通过对熔融峰的面积进行积分，根据式（1）计算出各样品的结晶度Xc[21]。
Xc=ΔHmΔHm,0
式（1）中：Xc为试样的结晶度；ΔHm为试样的熔融焓；ΔHm,0为聚丙烯α晶体100%结晶的熔融焓，其值为209 J/g。
计算得到BOPP-A、BOPP-B、BOPP-C、BOPP-D薄膜的结晶度Xc分别为46.16%、51.81%、49.00%、54.25%。可以发现，进口BOPP-D薄膜的结晶度显著高于3种国产BOPP薄膜，结合2.1中光学观测的结果，BOPP-D薄膜具有较高的粗化环密度，这主要是由于表面的晶环结构本质是晶型转化过程中产生的，密集的晶环结构意味着表面生成的α晶体含量较多，因而结晶度较高。而BOPP薄膜不同的结晶形态主要是由双向拉伸工艺中的拉伸温度、模式、拉伸比例和速率决定的，因此合理优化拉伸工艺可以对BOPP薄膜的结晶形态进行调控，最终获得理想的表面结晶形态。
2.3 非晶区链段运动特性
非晶区的结构和性能对聚丙烯薄膜的电学性能同样具有重要影响，通常电弱点主要分布于无定形区，而无定形区分子链的排列和运动对载流子的传输过程有显著影响[22]。因此研究聚丙烯薄膜中非晶区的分子链段运动特性具有重要意义。采用动态热机械分析仪测试4种BOPP薄膜试样在1、5、10、20 Hz下链段的松弛响应，得到1 Hz下的储能模量和各频率下的损耗模量温谱图分别如图5、图6所示。
从图5～6可以看出，随着温度升高，4种BOPP薄膜的储能模量有所下降，同时损耗模量曲线出现了松弛峰。这一松弛过程对应于聚丙烯的玻璃化转变过程。玻璃化转变温度是高分子链开始旋转或冻结的温度，在玻璃化转变温度以下非晶区链段与链间自由体积都被“冻结”，而在玻璃化转变温度以上，链段开始运动。
由图5～6可知，4种薄膜试样中进口BOPP-D薄膜的储能模量显著高于国产薄膜，同时BOPP-D薄膜的玻璃化转变温度也最高，达到约16℃，比国产试样高出6℃左右。在半结晶聚合物中，晶区对非晶区的分子链段运动有限制作用，进口BOPP-D薄膜的结晶度最高，因而相较于国产薄膜拥有较高的储能模量与玻璃化转变温度。
此外，从图6还可以看出，不同频率下4种薄膜试样的玻璃化转变温度均呈现出随试验频率的增大而右移的现象，这是因为试验频率增大等效于观测时间变短，使得同一弛豫过程在较高温度下才能观测到。为进一步定量表征链段运动能力，在本文的测试频率与温度下，将测试结果近似按照式（2）拟合计算链段运动的活化能[23]，拟合结果如图7所示。
lnf=lnf0-ΔH/kTg
式（2）中：f为交变作用力的频率；f0为指前因子；k为Boltzmann常数；Tg为玻璃化转变温度；ΔH为链段运动活化能。
从图7拟合计算得到BOPP-A、BOPP-B、BOPP-C、BOPP-D薄膜的链段运动活化能分别为9.13、10.04、9.94、10.59 eV。相比3种国产试样，进口BOPP-D薄膜显示出最高的链段运动活化能，这一方面与进口薄膜较高的结晶度对非晶区链段运动的抑制作用有关，另一方面进口薄膜更好的分子链段定向排列也可以对自身运动起到一定的限制作用。
2.4 直流击穿特性分析
BOPP薄膜的击穿特性是其作为电容器介质材料最重要的性能之一。击穿性能的表征是一个统计学概念，尺度参数影响电容器的整体设计水平，形状参数决定裕度与可靠性。因此高端电容器介质薄膜要求同时兼具较高的电气强度即尺度参数与较低的离散程度即形状参数。为了能够全面掌握BOPP薄膜的击穿特性，本研究利用浸渍剂小分子能够被非晶区捕获这一特性，对BOPP进行浸渍处理以改变薄膜的聚集态结构，通过对浸渍前后的薄膜试样进行直流击穿试验以及Weibull统计分析，获得聚集态结构对击穿性能的影响规律。
双参数的Weibull分布可以表示为式（3）。
PE=1-exp [-(E/α)β]
式（3）中：E为测试得到的直流电气强度；P(E)为累积击穿概率；α为尺度参数，代表累积击穿概率为63.2%时对应的电气强度，是电介质击穿性能的主要评估依据；β为形状参数，代表数据的分散性，β越大表明击穿时外施场强的范围越小，材料可靠性越高。
图8为4种薄膜试样浸渍前直流电气强度的Weibull分布图，对应的尺度参数和形状参数列于表1中。从图8和表1可以看到，进口BOPP-D薄膜无论是α还是β都明显优于国产薄膜，其中α达到650.7 kV/mm，相比最低的BOPP-A薄膜高了15.41%。更重要的是进口薄膜的β高，达到10.4，高于3种国内薄膜的水平。较高的β值表明薄膜的可靠性高，这对于电容器的裕量设计具有重要意义。
将薄膜的结晶度Xc、直流电气强度α、链段运动活化能进行比对发现这三者具有一定关联性，结果如图9所示。从图9可以看出，结晶度越大的薄膜，链段运动活化能越大，同时直流电气强度也越高。
一般聚丙烯的击穿发生在分子链排列松散或存在结构缺陷的非晶区中，然而非晶区分子链段的活动性会受到结晶区的阻碍，因而结晶度较大的薄膜其链段运动的活化能也越高。分子链段运动性越强，则需要更大的自由体积为其提供空间，在强电场下电子挣脱分子链的束缚进入自由体积后，更容易在电场作用下加速获得足够能量并撞击分子链断裂引发绝缘失效[24]。因此链段运动活化能较高的薄膜材料其电气强度也越高。
对图8中击穿数据进行进一步分析可以发现，国外BOPP-D薄膜的击穿数据拟合程度较高，而国产薄膜的击穿数据拟合程度相对较低，其中BOPP-A薄膜的拟合程度最低，这可能与其内部的电弱点较多有关。
电弱点对实际电容器的设计生产有巨大影响，也是国产薄膜与进口薄膜的主要差距之一。本文设计了24 h浸渍试验，将薄膜溶胀并改变薄膜聚集态结构，利用弱极性小分子只能与结晶不完善的晶区或非晶区缔合并填补在非晶区中微观电弱点这一特性，研究浸渍之后电弱点的强度变化规律[25]。对浸渍试验后的4种薄膜进行直流击穿测试，结果如图10所示，对应的尺度参数和形状参数列于表2中。
从图10和表2可知，在浸渍后各薄膜的电气强度之间的差距有所减小，同时各样品的β均有所提升，BOPP-A、BOPP-B、BOPP-C、BOPP-D薄膜试样的形状参数分别从7.3、8.3、9.2和10.4提升到13.3、10.3、13.8和14.0。β的提升对应于击穿数据的集中化分布，这表明通过浸渍方式使得薄膜结构的均一化水平得到提升，实验结果与上述设计思路一致。同时观察浸渍后电气强度的Weibull分布图发现国产BOPP-A、BOPP-C薄膜低击穿场强区的电气强度高于Weibull拟合直线，而浸渍前低击穿场强区的电气强度却低于拟合直线，这表明浸渍后局部电弱点被填补，电弱点的电气强度有所提升。
3 结论
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通过对部分国产的BOPP薄膜与进口薄膜进行对比测试，主要是到以下结论：
（1）从微观形态上看，进口BOPP薄膜的表面粗化环密度较大，分布较为集中，同时结晶度也高于国产薄膜。
（2）进口薄膜直流击穿试验的尺度参数与形状参数均大于国产薄膜，同时电弱点分布较少。具有高结晶度、高链段运动活化能的薄膜直流电气强度较高。
（3）浸渍试验会改变BOPP薄膜的聚集态结构，对局部缺陷的电气强度有提升作用，同时使得薄膜均一程度提高，形状参数增大。
基金
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  • 国家电网有限公司科技项目(5500-202058455A-0-0-00)
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2023年第56卷第1期
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doi: 10.16790/j.cnki.1009-9239.im.2023.01.001
  • 接收时间：2021-11-22
  • 首发时间：2025-11-21
  • 出版时间：2023-01-20
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  • 收稿日期：2021-11-22
  • 修回日期：2022-01-22
基金
国家电网有限公司科技项目(5500-202058455A-0-0-00)
作者信息
    1西安交通大学 电力设备电气绝缘国家重点实验室,陕西 西安 714009
    2全球能源互联网研究院有限公司,北京 102209

通讯作者:

刘文凤（1982-），女（汉族），天津人，教授，主要从事先进介质材料的理论与应用研究。
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2种不同金属材料的力学参数
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Number of
species		 占总种数比例
Percentage of
total species (%)		 属
Genus		 种数
Number of
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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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