Article(id=1193556934847594894, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1193556932167431095, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2025.04.006, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1713369600000, receivedDateStr=2024-04-18, revisedDate=1717257600000, revisedDateStr=2024-06-02, acceptedDate=null, acceptedDateStr=null, onlineDate=1762495748482, onlineDateStr=2025-11-07, pubDate=1745078400000, pubDateStr=2025-04-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1762495748482, onlineIssueDateStr=2025-11-07, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1762495748482, creator=13701087609, updateTime=1762495748482, 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=37, endPage=44, ext={EN=ArticleExt(id=1193556935086670226, articleId=1193556934847594894, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Research on structure and performance of polypropylene resin for DC capacitors, columnId=1190369066675179686, journalTitle=Insulating Materials, columnName=Material Research, runingTitle=null, highlight=null, articleAbstract=

High temperature liquid nuclear magnetic resonance (13CNMR), gel permeation chromatography (GPC), and differential scanning calorimetry (DSC) were used to study three kinds of polypropylene resins for DC capacitors at home and abroad with different temperature resistance grades, and analyze the effect of microstructure on electrical properties. The results show that the isotactic index, intermolecular chain defect distribution, and molecular weight characteristics jointly affect the crystallization characteristics of polypropylene, and thus affect the final high temperature dielectric properties of materials. The isotactic index of 5 units of imported polypropylene resin is greater than 97%, and the intermolecular chain stereodefect distribution is narrow (I=1.075), the weight average molecular weight is higher and the molecular weight distribution index is larger (PDI>5.6), showing excellent high temperature insulation properties (the electric strength α=533 kV/mm). While the molecular weight distribution of domestic polypropylene resin is narrow (PDI<5), the weight average molecular weight is lower, the isotactic index of 5 units is less than 97%, and the intermolecular chain stereodefect distribution is wider (I=1.106), which leads to its poor high temperature insulation performance and low electric strength (α=497 kV/mm).

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本文采用高温液体核磁(13CNMR)、凝胶渗透色谱(GPC)、差示扫描量热(DSC)法研究国内外3种不同耐温等级的直流电容器专用聚丙烯树脂,分析材料微观结构对电学性能的影响。结果表明:等规指数、分子链间缺陷分布和分子量特征共同影响聚丙烯的结晶特性,进而影响材料最终的高温介电性能。进口聚丙烯树脂的5单元等规指数大于97%,分子链间立构缺陷分布窄(I=1.075),重均分子量较高且分子量分布指数较大(PDI>5.6),表现出优异的高温绝缘性能(电气强度α=533 kV/mm)。而国产聚丙烯树脂的分子量分布窄(PDI<5),重均分子量较低,5单元等规指数小于97%以及分子链间立构缺陷分布较宽(I=1.106),进而导致其高温绝缘性能较差,电气强度较低(α=497 kV/mm)。

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苏尧天(1990-),男(汉族),河北保定人,工程师,博士,主要从事绝缘电介质材料的研究工作;

邢照亮(1988-),男(汉族),山东临沂人,高级工程师,主要从事绝缘电介质材料的研究工作。

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苏尧天(1990-),男(汉族),河北保定人,工程师,博士,主要从事绝缘电介质材料的研究工作;

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苏尧天(1990-),男(汉族),河北保定人,工程师,博士,主要从事绝缘电介质材料的研究工作;

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邢照亮(1988-),男(汉族),山东临沂人,高级工程师,主要从事绝缘电介质材料的研究工作。

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邢照亮(1988-),男(汉族),山东临沂人,高级工程师,主要从事绝缘电介质材料的研究工作。

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等规3单元特征峰 等规5单元特征峰 化学位移/×10-6
mm mmmm 21.78
mmmr 21.55
rmmr 21.33
mr mmrr 21.01
rmrr 20.85
mrmr 20.71
rr rrrr 20.31
rrrm 20.17
mrrm 20.04
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聚丙烯树脂核磁13CNMR特征峰

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等规3单元特征峰 等规5单元特征峰 化学位移/×10-6
mm mmmm 21.78
mmmr 21.55
rmmr 21.33
mr mmrr 21.01
rmrr 20.85
mrmr 20.71
rr rrrr 20.31
rrrm 20.17
mrrm 20.04
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样品 S(mmmm) S(mmmr) S(mrrm) 等规5单元组分含量/% 等规3单元组分含量/%
1 128.42 2.34 1 98.0 98.9
2 90.32 0.83 1 97.5 99.2
3 71.62 1.45 1 96.7 98.6
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等规指数计算结果

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样品 S(mmmm) S(mmmr) S(mrrm) 等规5单元组分含量/% 等规3单元组分含量/%
1 128.42 2.34 1 98.0 98.9
2 90.32 0.83 1 97.5 99.2
3 71.62 1.45 1 96.7 98.6
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样品 M n M w PDI
1 70 878 470 420 6.64
2 81 894 461 227 5.63
3 100 579 439 514 4.37
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不同样品特征分子量

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样品 M n M w PDI
1 70 878 470 420 6.64
2 81 894 461 227 5.63
3 100 579 439 514 4.37
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样品 熔点/℃ 结晶度/%
1 165.8 37.9
2 170.8 47.1
3 170.2 45.6
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不同试样的结晶参数

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样品 熔点/℃ 结晶度/%
1 165.8 37.9
2 170.8 47.1
3 170.2 45.6
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样品 熔融峰1温度/℃ 熔融峰2温度/℃ 结晶度/% 面积比S(熔融峰1∶2) L N L W I
1 165.0 174.5 52.2 0.71 15.7 16.7 1.063
2 173.8 180.0 66.0 0.93 26.8 28.8 1.075
3 174.5 180.1 63.4 0.98 28.3 31.3 1.106
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不同样品热分级后的结晶参数

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样品 熔融峰1温度/℃ 熔融峰2温度/℃ 结晶度/% 面积比S(熔融峰1∶2) L N L W I
1 165.0 174.5 52.2 0.71 15.7 16.7 1.063
2 173.8 180.0 66.0 0.93 26.8 28.8 1.075
3 174.5 180.1 63.4 0.98 28.3 31.3 1.106
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直流电容器专用聚丙烯树脂的结构与性能研究
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苏尧天 1 , 张翀 1 , 张兴辉 2 , 郭少玮 1 , 刘炬阳 1 , 邢照亮 1
绝缘材料 | 材料研究 2025,58(4): 37-44
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绝缘材料 | 材料研究 2025, 58(4): 37-44
直流电容器专用聚丙烯树脂的结构与性能研究
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苏尧天1, 张翀1, 张兴辉2, 郭少玮1, 刘炬阳1, 邢照亮1
作者信息
  • 1 中国电力科学研究院有限公司 先进输电技术国家重点实验室,北京 102209
  • 2 国家电网有限公司,北京 100032
  • 苏尧天(1990-),男(汉族),河北保定人,工程师,博士,主要从事绝缘电介质材料的研究工作;

    邢照亮(1988-),男(汉族),山东临沂人,高级工程师,主要从事绝缘电介质材料的研究工作。

Research on structure and performance of polypropylene resin for DC capacitors
Yaotian SU1, Chong ZHANG1, Xinghui ZHANG2, Shaowei GUO1, Juyang LIU1, Zhaoliang XING1
Affiliations
  • 1 State Key Laboratory of Advanced Power Transmission Technology, China Electric Power Reserch Institute, Beijing 102209, China
  • 2 State Grid Corporation of China, Beijing 100032, China
出版时间: 2025-04-20 doi: 10.16790/j.cnki.1009-9239.im.2025.04.006
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本文采用高温液体核磁(13CNMR)、凝胶渗透色谱(GPC)、差示扫描量热(DSC)法研究国内外3种不同耐温等级的直流电容器专用聚丙烯树脂,分析材料微观结构对电学性能的影响。结果表明:等规指数、分子链间缺陷分布和分子量特征共同影响聚丙烯的结晶特性,进而影响材料最终的高温介电性能。进口聚丙烯树脂的5单元等规指数大于97%,分子链间立构缺陷分布窄(I=1.075),重均分子量较高且分子量分布指数较大(PDI>5.6),表现出优异的高温绝缘性能(电气强度α=533 kV/mm)。而国产聚丙烯树脂的分子量分布窄(PDI<5),重均分子量较低,5单元等规指数小于97%以及分子链间立构缺陷分布较宽(I=1.106),进而导致其高温绝缘性能较差,电气强度较低(α=497 kV/mm)。

直流电容器  /  聚丙烯  /  等规指数  /  立构缺陷分布  /  分子量

High temperature liquid nuclear magnetic resonance (13CNMR), gel permeation chromatography (GPC), and differential scanning calorimetry (DSC) were used to study three kinds of polypropylene resins for DC capacitors at home and abroad with different temperature resistance grades, and analyze the effect of microstructure on electrical properties. The results show that the isotactic index, intermolecular chain defect distribution, and molecular weight characteristics jointly affect the crystallization characteristics of polypropylene, and thus affect the final high temperature dielectric properties of materials. The isotactic index of 5 units of imported polypropylene resin is greater than 97%, and the intermolecular chain stereodefect distribution is narrow (I=1.075), the weight average molecular weight is higher and the molecular weight distribution index is larger (PDI>5.6), showing excellent high temperature insulation properties (the electric strength α=533 kV/mm). While the molecular weight distribution of domestic polypropylene resin is narrow (PDI<5), the weight average molecular weight is lower, the isotactic index of 5 units is less than 97%, and the intermolecular chain stereodefect distribution is wider (I=1.106), which leads to its poor high temperature insulation performance and low electric strength (α=497 kV/mm).

DC capacitor  /  polypropylene  /  isotactic index  /  stereodefect distribution  /  molecular weight
苏尧天, 张翀, 张兴辉, 郭少玮, 刘炬阳, 邢照亮. 直流电容器专用聚丙烯树脂的结构与性能研究. 绝缘材料, 2025 , 58 (4) : 37 -44 . DOI: 10.16790/j.cnki.1009-9239.im.2025.04.006
Yaotian SU, Chong ZHANG, Xinghui ZHANG, Shaowei GUO, Juyang LIU, Zhaoliang XING. Research on structure and performance of polypropylene resin for DC capacitors[J]. Insulating Materials, 2025 , 58 (4) : 37 -44 . DOI: 10.16790/j.cnki.1009-9239.im.2025.04.006
随着国家新型电力系统建设规划的稳步推进,高压干式直流支撑电容器作为多电平换流器的核心组件之一,市场需求量急剧增长。我国高压干式直流支撑电容器的研发和制造起步较晚,现阶段虽有厂家完成了样机生产,但是性能与进口产品相比仍有差距,无法实现工程应用。双向拉伸聚丙烯(BOPP)薄膜由于具有低介质损耗、高电气强度、易于加工成型等优点,是高压电干式直流支撑电容器的核心部件,其电气强度直接决定了电容器的设计场强和储能密度[1-2]。国产和进口BOPP薄膜的差距主要体现在国产BOPP薄膜的电气强度和耐温等级偏低,长期使用过程中性能不稳定,电容器容易失效从而引发事故。影响国产BOPP薄膜性能的主要因素是薄膜的微观凝聚态结构,该结构主要由树脂特性和拉膜工艺共同决定[3-5]。目前,国产BOPP薄膜的生产线工艺较为成熟,采用进口聚丙烯树脂拉制的薄膜能完全满足应用需求。但是聚丙烯树脂原料在国内仍然属于“卡脖子”技术,因此成为了国产BOPP薄膜以及电容器性能与国外产品有差距的主要原因。
进口电工级高端聚丙烯树脂具有等规度较高(>99%(萃取法))、灰分含量较低(<20×10-6)等特点,用其制备的薄膜材料通常具有较高的结晶度以及较少的内部结构缺陷,从而保障了其高电气强度和耐温特性[6]。通过近年来的探索,国内厂家逐步掌握了高等规度和低灰分聚丙烯树脂的制备工艺,产品的各项指标性能已经达到同级别进口聚丙烯树脂的水平[7]。但是,采用国产聚丙烯树脂制备的电容器BOPP薄膜性能仍然无法达到进口水平,在耐电压强度和耐温特性上仍和进口BOPP薄膜存在较大差距,主要原因为在生产过程中成膜不稳定、良品率低。
目前对国产电工级BOPP薄膜的研究主要集中在薄膜微观结构对其电气性能的影响方面[8-10],但是对聚丙烯树脂本身结构的差异性研究不够深入,国产和进口聚丙烯树脂间的结构和性能差别仍然不明确。本文选取了一种国产牌号和两种进口牌号的电工级薄膜用聚丙烯树脂原材料进行对比表征,系统分析国产和进口电工级聚丙烯树脂的微观结构和性能差异。
不同耐温等级的进口电工级聚丙烯树脂为样品1(最高适用温度为85℃)和样品2(最高适用温度为105℃);国产电工级聚丙烯树脂为样品3,牌号为LB03F,中国石油天然气股份有限公司兰州石化公司;所有原材料灰分含量均为20×10-6(高温煅烧法)。
高温液体核磁共振仪,型号为AVANCE III HD 400,德国Bruker公司;差示扫描量热仪,型号为DSC-Q2000,美国TA公司;高温凝胶渗透色谱仪,型号为PL-GPC220,美国Agilent公司;偏光显微镜,型号为DM2700P,美国Leica公司;宽频介电谱仪,型号为Concept40,德国Novocontrol GmbH公司;灵敏电流计,型号为6517B,美国Keithley公司;直流击穿测试设备,型号为HCDJC,北京华测试验仪器有限公司。
采用高温核磁共振碳谱13CNMR对树脂的等规指数进行表征。将一定质量的聚丙烯样品在120℃下溶解在氘代四氯乙烷溶剂中进行测试,测试频率为400 MHz,扫描次数为7 000~9 000次。
将聚丙烯样品在160℃下、三氯苯中充分溶解后配置成浓度为1 mg/mL的聚合物溶液,采用高温凝胶渗透色谱仪对溶液进行表征。仪器温度为150℃,进样体积为200 μL。通过校正曲线,将洗脱时间转化为分子量,得到分子量分布曲线。
采用DSC法测试树脂的结晶度。用分析天平(精度为0.1 mg)称取质量为7.0~8.0 mg的样品,首先快速升温到230℃消除热历史后以20℃/min的速率降温到40℃,然后以10℃/min的升温速率升温至230℃后得到曲线。通过升温曲线得到熔融峰温度。对升温曲线的熔融峰进行处理,计算得到结晶度。计算公式如式(1)所示。
X C = Δ H m Δ H m , 0 × 100 %
式(1)中:X C为样品结晶度;ΔH m为样品的熔融焓,所取面积温度为120~190℃;ΔH m,0为聚丙烯α晶体100%结晶时的熔融焓,取值为209 J/g。
采用DSC法进行测试:①将样品升温至200℃,恒温5 min以消除热历史;②将样品以20℃/min的速率降温至30℃,恒温2 min;③将样品以20℃/min的速率升温至169℃,恒温15 min后重复步骤②;④分别以8个温度从高到低进行连续退火,8个温度分别为169、165、161、157、153、149、145、141℃,在每个温度下恒温15 min;⑤重复步骤②。热分级完成后,以10℃/min的速率将样品升温至200℃,记录最终的SSA熔融曲线。
将一定质量的聚丙烯粒子在230℃下熔融,然后在玻璃片上压制成厚度小于5 μm的薄片并置于偏光热台中直接进行观察。热态初始温度为230℃,以10℃/min的速率降温到110℃,在该温度下观察样品不同结晶时间的结晶形貌。
采用灵敏电流计测试树脂样品的直流体积电阻率,测试参考GB/T 31838.2—2019相关要求。将样品平整置于电极装置检测盒内,两面接触导电橡胶电极。测试条件为:直流电压为1 000 V、极化时间大于500 s、测量次数为3次,测试温度为85℃。采用直流击穿设备测试材料在85℃下的电气强度,将平均厚度为0.02 mm的样品浸没到绝缘油中进行测试,升压速率为200 V/s。采用Weibull分布对数据进行分析,以失效概率为63.2%处的特征击穿值作为材料的电气强度值。采用接触三电极法在测试温度为85℃、测试频率为10~105 Hz下对样品进行介电性能测试,样品为圆片,直径为20 mm,对圆片两面进行喷金处理。
高温核磁共振法测试得到的等规指数是指聚丙烯分子链构象中连续3个(mm)或者5个(mmmm)甲基(-CH3)在分子链同一侧结构所占整体的含量,计算方法为对应特征峰的积分面积占所有峰积分面积的总和,用等规3单元和等规5单元组分含量表示。其核磁特征峰化学位移如表1所示[11],计算公式如(2)~(3)所示。对于高等规聚丙烯树脂,核磁测试所得特征峰通常包括mmmm、mmmr和rmmr 3个特征峰。
等规 3 单元 组分 含量 = S ( m m ) S ( m m ) + S ( m r ) + S ( r r ) × 100 %
等规 5 单元 组分 含量 = S ( m m m m ) S ( m m ) + S ( m r ) + S ( r r ) × 100 %
式(2)~(3)中:S(mm)为核磁谱图中mmmm,mmmr和rmmr 3个特征峰对应的积分面积S(mmmm)、 S(mmmr)和S(rmmr)之和;S(mr)为mmrr、rmrr和 mrmr 3个特征峰对应的积分面积S(mmrr)、S(rmrr)和S(mrmr)之和;S(rr)为rrrr、rrrm和mrrm 3个特征峰对应的积分面积S(rrrr)、S(rrrm)和S(mrrm)之和。
图1为不同样品的高温核磁共振碳谱(13CNMR),表2为计算得到的等规5单元和3单元组分的含量。
图1表2可以看出,国产聚丙烯树脂(试样3)无论是等规5单元还是等规3单元组分的含量,都较进口树脂试样1和试样2偏低;而对于进口树脂,具有较高耐温等级的试样2,其等规3单元组分含量略高于试样1。等规聚丙烯分子链可视为一个连续的等规聚丙烯序列,该序列会被偶尔出现的缺陷中断。由于这些缺陷的存在,使得分子链中的等规链段长度(又称等规序列长度)变短。具有较长等规链段长度的PP树脂通常其凝聚态结构也具有良好的规整性,进而提升树脂的结晶特性和电学特性。但值得注意的是,高温核磁共振法仅能分辨出树脂中分子链平均缺陷的数量,不能确定最终树脂的微观凝聚态结构,因此需要结合其他表征手段进行进一步解析。等规度差异的来源通常来自树脂合成过程中的催化剂种类和工艺方法。国产树脂较低的等规度说明其催化剂对单体插入的选择性仍然较低,且合成工艺仍然不稳定,导致体系中小分子含量仍然较多,从而影响最终产品的性能。
图2为不同样品的分子量分布曲线,表3为相关特征分子量数据。从图2可以看出,进口聚丙烯(样品1和样品2)尽管耐温等级不同,却具有基本一致的分子量分布特征,其差别在于试样1的数均分子量较低。而表3可以看出,进口聚丙烯(样品1和样品2)的特点是分子量分布较宽(PDI分别为6.64和5.63),尤其是高分子量(>1 100 000)和低分子量(<100 000)部分占比明显高于国产树脂。该分子量分布特征满足BOPP基料工艺的基本需求,即较宽的分子量分布为树脂提供了良好的成膜特性,分子量较高的分子链保证了树脂的熔体强度[12-13]。国产树脂由于分子量分布较窄,在加工过程中易发生破膜现象,生产稳定性较差。
由于国产树脂和进口树脂立构规整性和分子量的差异性会对其最终的凝聚态结构造成影响,本文采用DSC法研究了不同树脂的结晶特性,结果如图3所示,表4为通过曲线计算得到的样品结晶参数。从图3表4可以看出,试样1具有最低的结晶温度(165.8℃)和结晶度(37.9%),因此其只能应用于制备低耐温等级薄膜。样品3和样品2对比,熔融峰温度相近,但是样品3的结晶度偏低。值得注意的是,样品1尽管平均等规指数和样品2接近,但是其结晶度却显著偏低,甚至低于等规指数更低的试样3,这说明平均等规指数不是决定树脂最终结晶度的充分条件。
为了进一步分析造成上述差异的原因,采用DSC法对不同试样进行了连续自成核退火热分级(SSA)。图4为不同样品热分级后的DSC曲线,采用Peakfit 4.12软件对曲线进行分峰拟合处理,采用热力学方法按Gibbs-Thomson方程(式(4))计算片晶厚度,用片晶厚度来描述BOPP树脂样品结晶序列长度的多分散性[14]
T = T m 0 ( 1 - 2 σ e Δ H m l )
式(4)中:T为各级分熔点,K;l为片晶厚度,nm; T m 0为聚丙烯平衡熔点,取值为460.7 K;σ 为表面自由能,取值为0.049 6 J/m2;Δ m为标准熔融热焓,取值为1.84×108 J/m3
样品的数均晶片厚度(L N)、重均晶片厚度(L W)和晶片厚度分布系数(I)计算公式如式(5)~(7)所示。
L N = n 1 L 1 + n 2 L 2 + . . . n i L n n 1 + n 2 + . . . n i = f i L i
L W = n 1 L 1 2 + n 2 L 2 2 + . . . n i L n 2 n 1 + n 2 + . . . n i = f i L i 2 f i L i
I = L W L N
式(5)~(7)中:ni为不同晶片厚度分子链的数量;fi为不同晶片厚度分子链所占比例;L 1 、L 2 ......Ln为热分级后不同的晶片厚度。
初始熔融行为相同的不同PP样品,经过逐步等温结晶热分级处理后其熔融行为表现出不同。这是因为在不同等温热处理过程中,具有不同等规序列分布的分子链具有不同的结晶能力。材料的熔融温度越高,相应的其晶片厚度越大,对应的分子链等规度越高,而熔融热焓代表了一定厚度片晶的含量,通过熔融热焓的比值可以计算出片晶含量的比、晶片厚度和晶片厚度分布参数。
图4可以看出,所有样品都出现了2个明显的熔融峰,其分别代表具有不同晶片厚度结晶的熔融焓变化。对曲线进行分峰处理得到的结晶参数如表5所示。从表5可以看出,对于进口树脂,试样2的L WL N以及结晶度均显著高于样品1,这说明尽管二者的平均等规指数接近,但是由于样品1的数均分子量比样品2低,导致其在结晶过程中形成的晶片厚度小于样品2,从而造成了二者结晶度的显著不同。此外,从表5熔融峰面积比可得出结论,试样2的高结晶组分含量高于样品1,这说明样品2对应分子链的高等规度组分相对含量较高,而中低等规度组分含量较低。以上结构差异均会导致二者具有不同的耐温和耐电压特性。国产树脂样品3和进口树脂样品2相比,二者具有接近的L WL N,但样品3的I值较高,这说明国产树脂具有较高的晶片厚度分布系数,体系中存在着较多不同立构缺陷的分子链,从而使其立构缺陷分布过宽,造成和进口树脂的凝聚态结构差异和性能差异。
不同树脂的结晶性差异还可以通过其等温结晶形貌进行直接观测。图5为不同树脂样品熔融后在110℃时的等温结晶POM照片。聚丙烯在POM下会显示出典型的十字消光图像,呈现球晶形貌。从图5可以看出,在同样结晶时间下(结晶时间为50 s),样品2生成的球晶平均尺寸较大(约为60 μm)推测其有较快的结晶速率。样品1由于分子量较低,形成的球晶尺寸也较小(约为35 μm),该结果和DSC测试结果相吻合。样品3和样品1相比,尽管样品3平均等规指数较低,但是由于其分子量分布较窄,立构缺陷分布较宽,导致其在相同结晶时间(结晶时间为20 s)下所形成的球晶尺寸只略大于样品1,但是随着等温结晶趋于完善(结晶时间为50 s),样品3球晶尺寸逐渐接近样品2。
以上结果表明,PP树脂的结晶度不仅取决于分子链的平均立构规整性,还和分子量分布以及分子链缺陷分布密切相关,在平均等规指数接近的情况下(国产和进口树脂相比),具有高分子量(>1 100 000)组分占比,宽分子量分布且立构缺陷分布较窄的分子链结构容易形成球晶,在相同结晶时间内球晶尺寸生长较快,生成的球晶尺寸较大,结晶度较高。
3种树脂不同的微观凝聚态结构对其电学性能会产生显著影响。采用直流体积电阻率和宽带介电技术表征了3种聚丙烯样品在85℃下的电学性能差异。图6(a)为3种聚丙烯样品在极化时间为400~1 000 s的直流体积电阻率。从图6(a)可以看出,试样1和试样2的体积电阻率分别为1.5×1015 Ω·m和1.1×1015 Ω·m,都高于试样3的体积电阻率(4×1014 Ω·m),表明具有较宽分子链间缺陷分布的PP树脂绝缘性能较差,也表明由于较低的传输活化能,电荷载流子更倾向于在分子链的缺陷之间迁移[15]。链间缺陷的存在也可以通过高温下树脂的介电特性来证明。图6(b)为3种聚丙烯样品在85℃下的宽频介电谱图。从图6(b)可以看出,所有样品介电常数都呈现相同的变化趋势,在测试频率范围内,介电常数约为2.4,表现较好的稳定性。而从介质损耗因数的变化规律来看,样品3表现出一定差别,其在低频下介质损耗因数较高,随着测试频率的变化,其介质损耗因数下降较快并产生波动。具有较宽立构缺陷分布的国产树脂介质损耗来源于电荷载流子迁移的电导损耗[16-19]。这表明树脂间结晶度差异并不是影响树脂电学性能差异的根本原因,立构缺陷分布具有更大影响,这是由于分子链内部缺陷在外加电场和温度场作用更易于引发载流子的迁移。
图7为3种聚丙烯样品在85℃下直流电气强度的Weibull分布曲线,其中双参数分布可表示为式(8)
P E = 1 - e x p - E / α β
式(8)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越大表明电气强度的分散性越小,材料的可靠性越高。
图7可以看出,样品2具有最高的特征电气强度(533 kV/mm)和β值,表明样品2较高的立构规整度和较窄的立构缺陷分布赋予了样品较规整的内部结构,材料内部缺陷较少,因此具备优异的高温击穿特性。样品3的电气强度最低(497 kV/mm),表明样品3内部较多的缺陷结构降低了材料整体的击穿能垒。值得注意的是,尽管样品1的结晶度是3种样品中最低的,但其电气强度较样品2并无显著差异,且高于样品3。这再次说明结晶度不是决定树脂电学性能的直接参数,分子链间的等规缺陷分布和分子量分布共同影响了样品的微观凝聚态结构,进而决定了其最终的电学性能。
采用13CNMR、GPC以及DSC技术并结合电学性能测试,对国内外3种不同耐温等级的直流电容器专用聚丙烯树脂进行结构和性能解析。研究发现树脂的耐温性能和电学性能与其内部的凝聚态结构有关,单一结晶度指标不能直接反映树脂的电学性能。最终结果表明,具有较高等规指数、较宽分子量分布以及较窄等规缺陷分布的聚丙烯树脂结晶结构更完善、内部缺陷更少,从而赋予了其更加优异的高温介电性能。
  • 国家电网公司科技项目(5500-202255488A-2-0-KJ)
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2025年第58卷第4期
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doi: 10.16790/j.cnki.1009-9239.im.2025.04.006
  • 接收时间:2024-04-18
  • 首发时间:2025-11-07
  • 出版时间:2025-04-20
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  • 收稿日期:2024-04-18
  • 修回日期:2024-06-02
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国家电网公司科技项目(5500-202255488A-2-0-KJ)
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    1 中国电力科学研究院有限公司 先进输电技术国家重点实验室,北京 102209
    2 国家电网有限公司,北京 100032
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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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