Article(id=1210577668454618044, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1210577662121209865, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2024.08.014, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1693756800000, receivedDateStr=2023-09-04, revisedDate=1706630400000, revisedDateStr=2024-01-31, acceptedDate=null, acceptedDateStr=null, onlineDate=1766553807605, onlineDateStr=2025-12-24, pubDate=1724083200000, pubDateStr=2024-08-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1766553807605, onlineIssueDateStr=2025-12-24, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1766553807605, creator=13701087609, updateTime=1766553807605, updator=13701087609, issue=Issue{id=1210577662121209865, tenantId=1146029695717560320, journalId=1149653034449285133, year='2024', volume='57', issue='8', pageStart='1', pageEnd='147', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1766553806095, creator=13701087609, updateTime=1766563971278, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1210620298043454173, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1210577662121209865, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1210620298043454174, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1210577662121209865, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=114, endPage=121, ext={EN=ArticleExt(id=1210577668735636422, articleId=1210577668454618044, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Effect of molecular chain structure of polyethylene on its dielectric performance, columnId=1192878364340924664, journalTitle=Insulating Materials, columnName=Test and Analysis, runingTitle=null, highlight=null, articleAbstract=

In order to explore the reasons for the differences in the properties of polyethylene cable materials at home and abroad, the molecular weight distribution, long branch chain content and short branch chain content of the materials were measured by gel permeation chromatography (GPC), rotational rheological test, and self-nucleation annealing thermal classification (SSA), and the relationship between the molecular chain structure of one domestic and two imported 500 kV cross-linked polyethylene cable materials and their dielectric properties were discussed. The results show that the order of long-chain chain content in polyethylene from small to large is: domestic sample, imported B sample, imported A sample. The order of short chain content from small to large is: imported sample B, imported sample A, domestic sample. Among them, the imported sample A has higher content of long-chain chains, which is conducive to the formation of ordered molecular arrangement and crystallization, and further improve its withstand voltage level. Excessive short chain content in domestic samples can hinder the molecular crystallization, resulting in lower breakdown strength. In addition, the differences in the molecular chain structure of the three types of polyethylene have little effect on their dielectric constant, dielectric loss factor, and resistivity.

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为探究国内外聚乙烯电缆料性能差异产生的原因,本文通过凝胶渗透色谱(GPC)、旋转流变测试以及自成核退火热分级(SSA)等方法测试了材料的分子量分布、长支链含量以及短支链含量,探讨了一种国产和两种进口500 kV交联聚乙烯电缆料的分子链结构与其介电性能的关系。结果表明:聚乙烯体内长支链含量从小到大的顺序为:国产样品、进口B样品、进口A样品;短支链含量从小到大的顺序为:进口B样品、进口A样品、国产样品。其中,进口A样品中较高的长支链含量,有利于分子有序排列和结晶的形成,进而提高其耐压等级;国产样品过高的短支链含量会阻碍分子结晶,导致其击穿场强较低。此外,3种聚乙烯分子链结构的差异对其介电常数、介质损耗因数和电阻率影响不大。

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王霞(1976-),女(汉族),陕西西安人,博士,副教授,主要从事聚合物材料和测试方法的研究;

陈宇奇(1998-),男(汉族),江西九江人,硕士,主要从事聚乙烯电缆绝缘料的研究。

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王霞(1976-),女(汉族),陕西西安人,博士,副教授,主要从事聚合物材料和测试方法的研究;

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王霞(1976-),女(汉族),陕西西安人,博士,副教授,主要从事聚合物材料和测试方法的研究;

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陈宇奇(1998-),男(汉族),江西九江人,硕士,主要从事聚乙烯电缆绝缘料的研究。

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陈宇奇(1998-),男(汉族),江西九江人,硕士,主要从事聚乙烯电缆绝缘料的研究。

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articleId=1210577668454618044, language=EN, orderNo=4, keyword=dielectric property), Keyword(id=1218111680572216108, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210577668454618044, language=CN, orderNo=1, keyword=聚乙烯), Keyword(id=1218111680647713581, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210577668454618044, language=CN, orderNo=2, keyword=长支链), Keyword(id=1218111680744182582, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210577668454618044, language=CN, orderNo=3, keyword=短支链), Keyword(id=1218111680807097147, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210577668454618044, language=CN, orderNo=4, keyword=介电性能)], refs=[Reference(id=1218111685609574414, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210577668454618044, doi=null, pmid=null, pmcid=null, year=2020, volume=46, issue=5, pageStart=1571, pageEnd=1579, url=null, language=null, rfNumber=[1], 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articleId=1210577668454618044, language=CN, label=图8, caption=3种样品的击穿场强, figureFileSmall=HabsBwNU5cFTiL7Sy8a8lQ==, figureFileBig=Ino+g4Svv9W26WYGxxU6Cw==, tableContent=null), ArticleFig(id=1218111682602259365, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210577668454618044, language=EN, label=Table 1, caption=The test results for the molecular weight and polydispersity coefficient of the three basic resins, figureFileSmall=null, figureFileBig=null, tableContent=
项目国产样进口A进口B
Mn32 64631 45232 370
Mw151 235183 235149 330
PD4.635.834.61
), ArticleFig(id=1218111682711311280, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210577668454618044, language=CN, label=表1, caption=

3种基础树脂的分子量及多分散性系数测试结果

, figureFileSmall=null, figureFileBig=null, tableContent=
项目国产样进口A进口B
Mn32 64631 45232 370
Mw151 235183 235149 330
PD4.635.834.61
), ArticleFig(id=1218111682799391671, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210577668454618044, language=EN, label=Table 2, caption=The calculation results of the long-chain branching degree of basic resin for cross-linkable polyethylene materials, figureFileSmall=null, figureFileBig=null, tableContent=
项目国产样进口A进口B
[η]Br0.4790.5330.475
[η]lin0.5170.5880.513
g0.9260.9060.926
g0.9180.8960.918
nW0.4630.6080.463
LCB/10 0000.4290.4650.434
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可交联聚乙烯料用基础树脂长链支化度的计算结果

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项目国产样进口A进口B
[η]Br0.4790.5330.475
[η]lin0.5170.5880.513
g0.9260.9060.926
g0.9180.8960.918
nW0.4630.6080.463
LCB/10 0000.4290.4650.434
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Tm/℃110.210599.794.89085.180.575.9
SCB/10 00015.3718.7122.1125.2828.4131.5434.5337.51
L/nm7.815.894.703.963.433.022.722.46
A/%43.2222.6613.918.945.593.341.800.54
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国产样品各熔融峰对应的短支链含量和片晶厚度值

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Tm/℃110.210599.794.89085.180.575.9
SCB/10 00015.3718.7122.1125.2828.4131.5434.5337.51
L/nm7.815.894.703.963.433.022.722.46
A/%43.2222.6613.918.945.593.341.800.54
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Tm/℃111.4106100.996.191.386.581.777
SCB/10 00014.618.0721.3324.4627.5330.6333.7436.70
L/nm8.456.184.934.133.563.132.792.53
A/%44.0019.8813.108.805.924.022.681.58
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进口样品A各熔融峰对应的短支链含量和片晶厚度值

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Tm/℃111.4106100.996.191.386.581.777
SCB/10 00014.618.0721.3324.4627.5330.6333.7436.70
L/nm8.456.184.934.133.563.132.792.53
A/%44.0019.8813.108.805.924.022.681.58
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Tm/℃114.3108.9103.99994.389.484.880.1
SCB/10 00012.7216.2019.4422.5925.6328.7531.7734.72
L/nm10.557.225.584.583.903.383.002.70
A/%47.5819.7612.598.05.153.432.251.28
), ArticleFig(id=1218111684787491813, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210577668454618044, language=CN, label=表5, caption=

进口样品B各熔融峰对应的短支链含量和片晶厚度值

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Tm/℃114.3108.9103.99994.389.484.880.1
SCB/10 00012.7216.2019.4422.5925.6328.7531.7734.72
L/nm10.557.225.584.583.903.383.002.70
A/%47.5819.7612.598.05.153.432.251.28
), ArticleFig(id=1218111684921709546, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210577668454618044, language=EN, label=Table 6, caption=The εr, tanδ and ρv of three samples, figureFileSmall=null, figureFileBig=null, tableContent=
材料国产进口A进口B
εr2.1452.1582.034
tanδ5.69×10-44.43×10-44.83×10-4
ρv4.50×10146.37×10145.44×1014
), ArticleFig(id=1218111685030761454, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210577668454618044, language=CN, label=表6, caption=

3种样品的εr、tanδρv

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材料国产进口A进口B
εr2.1452.1582.034
tanδ5.69×10-44.43×10-44.83×10-4
ρv4.50×10146.37×10145.44×1014
), ArticleFig(id=1218111685114647538, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210577668454618044, language=EN, label=Table 7, caption=Breakdown characteristic parameters of three samples, figureFileSmall=null, figureFileBig=null, tableContent=
材料α/(kV/mm)β
国产105.132.6
进口A130.720.2
进口B108.145.0
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3种样品的击穿特征参数

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材料α/(kV/mm)β
国产105.132.6
进口A130.720.2
进口B108.145.0
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聚乙烯分子链结构差异对其介电性能的影响
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王霞 , 陈宇奇 , 陈润邦 , 吴锴
绝缘材料 | 测试与分析 2024,57(8): 114-121
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绝缘材料 | 测试与分析 2024, 57(8): 114-121
聚乙烯分子链结构差异对其介电性能的影响
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王霞, 陈宇奇, 陈润邦, 吴锴
作者信息
  • 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 710049
  • 王霞(1976-),女(汉族),陕西西安人,博士,副教授,主要从事聚合物材料和测试方法的研究;

    陈宇奇(1998-),男(汉族),江西九江人,硕士,主要从事聚乙烯电缆绝缘料的研究。

Effect of molecular chain structure of polyethylene on its dielectric performance
Xia WANG, Yuqi CHEN, Runbang CHEN, Kai WU
Affiliations
  • State Key Laboratory of Electric Insulation and Power Equipment, Xi′an Jiaotong University, Xi′an 710049, China
出版时间: 2024-08-20 doi: 10.16790/j.cnki.1009-9239.im.2024.08.014
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为探究国内外聚乙烯电缆料性能差异产生的原因,本文通过凝胶渗透色谱(GPC)、旋转流变测试以及自成核退火热分级(SSA)等方法测试了材料的分子量分布、长支链含量以及短支链含量,探讨了一种国产和两种进口500 kV交联聚乙烯电缆料的分子链结构与其介电性能的关系。结果表明:聚乙烯体内长支链含量从小到大的顺序为:国产样品、进口B样品、进口A样品;短支链含量从小到大的顺序为:进口B样品、进口A样品、国产样品。其中,进口A样品中较高的长支链含量,有利于分子有序排列和结晶的形成,进而提高其耐压等级;国产样品过高的短支链含量会阻碍分子结晶,导致其击穿场强较低。此外,3种聚乙烯分子链结构的差异对其介电常数、介质损耗因数和电阻率影响不大。

聚乙烯  /  长支链  /  短支链  /  介电性能

In order to explore the reasons for the differences in the properties of polyethylene cable materials at home and abroad, the molecular weight distribution, long branch chain content and short branch chain content of the materials were measured by gel permeation chromatography (GPC), rotational rheological test, and self-nucleation annealing thermal classification (SSA), and the relationship between the molecular chain structure of one domestic and two imported 500 kV cross-linked polyethylene cable materials and their dielectric properties were discussed. The results show that the order of long-chain chain content in polyethylene from small to large is: domestic sample, imported B sample, imported A sample. The order of short chain content from small to large is: imported sample B, imported sample A, domestic sample. Among them, the imported sample A has higher content of long-chain chains, which is conducive to the formation of ordered molecular arrangement and crystallization, and further improve its withstand voltage level. Excessive short chain content in domestic samples can hinder the molecular crystallization, resulting in lower breakdown strength. In addition, the differences in the molecular chain structure of the three types of polyethylene have little effect on their dielectric constant, dielectric loss factor, and resistivity.

polyethylene  /  long branched chain  /  short branched chain  /  dielectric property
王霞, 陈宇奇, 陈润邦, 吴锴. 聚乙烯分子链结构差异对其介电性能的影响. 绝缘材料, 2024 , 57 (8) : 114 -121 . DOI: 10.16790/j.cnki.1009-9239.im.2024.08.014
Xia WANG, Yuqi CHEN, Runbang CHEN, Kai WU. Effect of molecular chain structure of polyethylene on its dielectric performance[J]. Insulating Materials, 2024 , 57 (8) : 114 -121 . DOI: 10.16790/j.cnki.1009-9239.im.2024.08.014
聚乙烯电缆因其良好的电气性能、耐化学性和耐热性,在电力输配领域被广泛应用[1]。然而随着电力系统的不断发展,对电缆料的性能要求也越来越高,其中包括更高的电压等级、更低的能量损耗和更长的使用寿命等。因此研究聚乙烯绝缘料的分子链结构与其宏观介电性能的关系,对研发新型高压电缆绝缘料具有重要的指导意义。
国内外研究团队针对基础树脂分子链结构对介电性能的影响进行了广泛而深入的研究。如通过调控聚合物的结构和合成方法,同时利用分子模拟以及先进的材料表征技术,探索不同分子链结构对介电性能的影响及其他优化材料性能[2]。罗军等[3]通过流变参数表征材料的长支链含量,进而确定长支链含量对材料耐压等级的影响。A T LORENZO等[4]探究了短支链对材料结晶性能的影响。以上研究为优化聚合物材料的介电性能提供了理论基础和实验指导,但关于分子链结构与介电性能的关系研究仍不全面。
本文选取一种国产和两种进口的500 kV电压等级的交联聚乙烯电缆料,通过凝胶渗透色谱(GPC)、旋转流变测试以及自成核退火热分级(SSA)等方法测试材料的分子量分布、长支链含量以及短支链含量。最终确定3种电缆料的长支链和短支链含量对材料耐压等级、介电损耗和电导的影响。
选用万马电缆料厂生产的500 kV高压交流电缆绝缘用可交联聚乙烯粒料,以及分别来自北欧化工和陶氏化学的两种进口500 kV高压交流电缆绝缘用可交联聚乙烯粒料作为试样。为论述方便,将万马、北欧和陶氏生产的3种粒料在文中依次标注为国产样、进口A、进口B。
北欧化工公司和陶氏化学公司对外仅提供成品可交联料,不提供用于高压交流可交联料生产的基础树脂,因此仅能对其生产的成品可交联料进行提纯后开展性能分析。为了保证实验的一致性也对国产样品进行了相同的处理。获取基础树脂的步骤如下:首先,将粒状材料放入温度为120℃的平板硫化机中进行模压处理,形成厚度约为0.15 mm的薄片。随后,将薄片切割成边长为15 mm的正方形试样,并将其浸泡在装有无水乙醇的烧杯中,在65℃条件下搅拌约5 h。取出试样并使用无水乙醇清洗3~5次。在70℃的真空环境中进行干燥后进行称重。然后,将3种萃取后的样品使用平板硫化机在180℃、16 MPa下压成厚度为0.2 mm的试样。再将3种试样剪成尺寸为0.5 mm×0.5 mm的颗粒,以增大与二甲苯试剂的接触面积。最后,将试样和二甲苯置于磨口瓶,放入110℃烘箱内进行24 h的萃取,之后再将包裹试样的不锈钢网包取出,置于110℃真空烘箱中烘焙24 h。
按照ASTM D6474-2012和SH/T1759—2007,采用AgilentPL-GPC220型高温凝胶色谱仪测定以上3种萃取后聚乙烯试样的相对分子质量与分子量分布,溶剂为1,2,4-三氯苯(TCB),测量温度为150℃,流量为1.0 mL/min。
使用HAAKE MARS型旋转流变仪对样品进行流变性能测试。首先对试样进行动态应变扫描,以确定样品的线性黏弹性能范围,然后在线性黏弹性能范围内进行动态流变测试。在测试频率10 rad/s、温度为150℃的条件下,进行动态应变扫描实验,范围为1%~100%,记录并观察储能模量(G΄)随应变变化的趋势。接着,对试样进行动态频率扫描实验,在150℃的温度下对样品施加小振幅剪切力,应变设定为1%。在频率扫描范围0.1~100 rad/s记录并观察储能模量(G′)、损耗模量(G″)和复数黏度(η*)等黏弹性参数随频率变化的情况。
自成核实验的目的是确定初始自成核温度(Ts),而选择Ts时必须满足以下条件:①该温度必须足够高,可使几乎所有聚合物晶体都能达到熔融状态[5];②该温度必须足够低,仍保留产生晶核的记忆,即结晶热历史未完全消除。
(1)自成核(SN)实验的步骤如下:①将样品升温到160℃,并保持恒温3 min,以消除任何热历史。②将样品降温至0℃。③将样品升温至预设的自成核温度,并保持恒温5 min。④将样品再次降温至0℃。⑤将样品再次升温至160℃,并记录熔融曲线。所有的升温和降温速率均设置为10℃/min。
(2)连续自成核退火热(SSA)实验的步骤如下:①进行与SN实验中的步骤①~④相同的操作。在其中的步骤③中,使用的Ts即为最佳自成核温度。②将样品升温至下一个自成核温度,该温度比上一个自成核温度低5℃,并保持恒温5 min。③重复步骤①和②,依次进行直到涵盖样品的整个熔融温度范围。④最后将样品升温至160℃,并记录熔融曲线。
将3种可交联聚乙烯绝缘料(国产料、进口A、进口B)使用平板硫化机在180℃、16 MPa下制备XLPE试样,试样厚度分别为0.2 mm和0.5 mm。之后将试样置于70℃烘箱内热处理12 h以除去交联副产物。
交流击穿实验采用HJC-100kV型电压击穿试验仪对厚度为0.2 mm的XLPE试样进行工频击穿实验;工频下XLPE试样的介电常数和介质损耗因数采用2821型西林电桥进行测试;体积电阻率利用实验室自制的三电极系统,通过美国吉时利公司的6517B型静电计来测试[6]
对于可交联聚乙烯绝缘料,未清洗时材料中含有大量的交联剂。清洗后,材料中几乎不含交联剂则未生成凝胶。3种样品在二甲苯中萃取后均无肉眼可见的固态物,故认为交联剂已清洗干净。3种基础树脂的分子量分布曲线如图1所示,根据实验结果提取基础树脂的数均分子量(Mn)、重均分子量(Mw)及多分散性系数(PD)列于表1中。
小分子量短碳链的含量主要影响数均分子量Mn,而高分子量长碳链的含量主要影响重均分子量Mw,多分散性系数PD=Mw/Mn,用来表征高聚物分子量分布的宽度。当聚合物分子链接近均匀链长时,其PD值趋向于1,因此高的多分散性系数意味着聚合物分子量分布的“纯度”不好,即长、短分子链组分混杂。
图1表1可知,国产树脂的高分子量长链含量比进口样品A的少,而小分子量分子链含量相对接近。国产树脂和进口树脂B的分布曲线十分接近,分子量分布比较集中,PD值较小。
如长支链支化分子链的链长与聚合物主链相当,可根据高温凝胶色谱的实验结果来表征聚乙烯树脂的长支链支化度(LCB[8]。基础树脂中每10 000个主链碳原子上的长支链个数(LCB/10 000)可由式(1)得到[9]
LCB/10000=nw×1.4×105MW
式(1)中,nw为三功能分支点的数量,即基础树脂试样中长支链的数量。
再根据nw和描述聚合物支化度即分支因子g之间的关系(式(2)[8])及特性黏度ηBrηlin与分支因子g的关系方程(式(3)[8])可计算出3种聚乙烯树脂的长链支化度,其中ηBrηlin和分子量的关系可根据马克-霍温克方程(式(4))得到。
g=6nw0.52+nwnwln(2+nw+nw2+nw-nw)-1
gB=g'=ηBrηlin
η=KMα
式(2)~(4)中:ηBr为支链分子特性黏度;ηlin为具有相同分子量的直链分子的特性黏度;M为试样分子量;K、α分别为与溶剂、试样温度相关的常数,通过GPC实验得到,本研究取K=1.75×10-4α=0.67。
式(4)中代入Mv可计算得到聚乙烯树脂的ηBr,代入Mw可计算得到ηlin。而分支因子g的定义为支链聚合物分子均方回转半径Rg2Br与具有相同分子量的直链聚合物分子均方回转半径Rg2lin的比值。由于在同一溶剂下,支链聚合物分子和直链聚合物分子的溶胀性能存在差异,均方回转半径不同,因此取gB=g′B通常介于0.8~1.0[9],本文中B取值为0.9。根据式(1)~(4)依次计算出3种聚乙烯树脂的g′、gnwLCB/10 000,各参数的计算结果如表2所示。
表2可以看出,进口树脂A的长支链支化度LCB/10 000明显高于国产树脂,而进口树脂B的长链支化度与国产树脂非常接近,这与GPC实验的结果吻合,进口树脂A的Mn低而Mw高,具有更宽的分子量分布(高PD值)。
在低应变范围内,聚合物熔体通常呈线性黏弹性,这意味着聚合物的储能模量(G′)、损耗模量(G″)与应变(γ)无关。在测试期间,聚合物熔体内部的分子链缠绕结构保持完整,未发生破坏[10]
图2为3种基础树脂在150℃下的储能模量与应变γ的关系。由图2可知,在应变参数<10%时,基础树脂均处于线性黏弹区[11]。为得到3种材料的零剪切黏度η0(剪切速率为零时的黏度),进一步对基础树脂进行动态频率扫描,得到复数黏度(η*)随角频率(ω)的变化关系,如图3所示。图3中以最小角频率值对应的η*值作为样品的零剪切黏度η0。国产树脂、进口树脂A和进口树脂B的η0分别为1.58×105、1.92×105、1.71×105
在聚合物中,高长支链含量会导致分子链之间形成更多的物理缠结点,从而使整体结构更加稳定,η0也就更大。进口A较高的η0与GPC测试的计算结果相符,进一步验证了A样品中长支链的含量较高的事实。综上,长支链含量从小到大的顺序为:国产样、进口B、进口A。
选择最佳自成核温度(Ts)时,确保样品中的聚合物晶体达到高度熔化状态,但仍保留一定的结晶热历史。在后续的降温过程中,残留的记忆效应会引发晶核形成,从而使样品中的晶核密度大幅增加。这会对样品的后续结晶行为产生影响,具体表现为结晶峰的位置逐渐向高温区移动,样品的结晶特性会在降温过程中发生变化[12]
46分别为3种基础树脂在不同热处理温度下的结晶和熔融曲线。以国产样品为例,根据图4的结果可以看到国产样品在高于110℃下测试时, 表现出的结晶和熔融行为与在160℃下的相同,即结晶峰和熔融峰的形状和位置都没有发生变化,说明样品在高于110℃下进行等温热处理时,是处于完全熔融态,所以结晶和熔融行为都不受影响。而样品在低于110℃下测试时,发现其结晶和熔融行为均表现出明显的不同。以Ts为109℃时为例,当样品从109℃降温时,立即发生了结晶行为,说明在109℃恒温处理后依然有少量晶体残余。这些现象说明样品此时的热处理温度使样品处于部分熔融态,并未完全熔化。综上所述,国产样品只有在110℃热处理时,才满足自成核的要求,所以110℃是国产样品的最佳自成核温度。同理由图56可以得到进口A、进口B试样的最佳自成核温度分别为110℃和114℃。
此外,在进行高于各自的最佳自成核温度的测试时,3种样品表现出的结晶和熔融行为与在160℃下的相同。具体而言,结晶峰和熔融峰的形状和位置在高于最佳自成核温度下和160℃下均未发生变化,这表明升、降温过程对样品的结晶状态没有明显的影响。该结果的一致性间接说明了实验中多次升降温对于材料交联度的影响较小。
在这项研究中,为了确保实验的可靠性,本文严格保持了多次升、降温实验中的升温速率、降温速率、保持时间等实验条件的一致性。这有助于排除实验条件变化可能引起的误差,能够更可靠地比较不同测试条件下样品的性质。
在确定了最佳的自成核温度后,对3种基础树脂进行SSA实验,以获取样品的短支链结构信息。图7列出了SSA实验后的3种基础树脂的熔融曲线。由图7可见,3种样品都体现了明显的多峰熔融特征。依据SSA热分级的理论,这些熔融峰是晶体中厚度不一的片晶受热熔融产生的。从分子链的角度上来看,链端上分布着各个长度的亚甲基序列,为一条长的分子链分割成长度不一的短链段。这些短链段在不同的温度下完成结晶和不同的温度下熔融,最终形成多峰熔融现象。
根据SSA热分级曲线和式(5)可得到样品的短支链比例(SCB/10 000,基础树脂中每10 000个主链碳原子上的短支链个数)[13]
Tm=-1.55SCB/10000+134
式(5)中,Tm为各个熔融峰对应的温度。
由Gibbs-Thomson公式(式(6))计算各个熔融峰对应的片晶厚度(L[14],计算结果如表35所示。
L=2σTm0ΔzΔHTm0-Tm
式(6)中:Tm0代表平衡熔融点,取399 K;表面自由能σ=5.0 kJ/mol;熔融焓ΔH=8.2 kJ/mol;Δz指聚乙烯里每个重复单元(亚甲基-CH2-)的尺寸,Δz=0.254 nm。
表35SCB/10 000表示短支链含量,L表示片晶厚度,A表示峰面积占整个面积的比例。从表3~5可以看出,国产样品的各个熔融峰的熔点和对应的片晶的厚度均低于进口A和进口B的。一般地,温度最高的熔融峰对应的分子链结构最为规整,最能反映样品的结晶能力。以温度最高的熔融峰作为主峰可以看到,国产样品的主峰熔点最低,峰面积占整个面积的比例较小,短支链含量较高,片晶厚度较小,因此结晶能力相对较差。而进口B样品的结晶能力最好,进口A样品次之。但由于进口A样品有较高的长支链含量,可以有效地阻碍电场中的电荷运动,从而减缓电场梯度的增长速度,推断进口A较进口B具有更高的击穿场强。
对3种样品进行材料介电常数(εr)、介质损耗因数(tanδ)和体积电阻率(ρv)测试,实验结果列于表6。由表6可见,3种可交联料XLPE试样的εr和tanδ差异较小且均满足作为高压电缆交联聚乙烯绝缘材料的性能要求[15]
对3种XLPE试样击穿场强特征参数进行测试,如图8所示,具体结果列于表7表7α为尺度参数,为失效概率为63.2%时的击穿场强;β为形状参数,β越大,试样的一致性越好。由表7可知进口B的产品一致性较好,国产交联聚乙烯绝缘料制得XLPE的尺度参数低于进口A、B样品,这说明国产绝缘料在交流击穿场强测试中逊色于进口产品。而交流击穿场强与结晶度成正相关,与熔融曲线和片晶厚度测试的结果一致,故认为国产样品的结晶度较低。
已有研究表明,相对较高的长支链含量被认为能够促使分子链在电场中形成更有序的排列和更稳定的电场结构,这有助于提高击穿电压[16]。同时长支链的存在可能通过电场调制效应可增强分子链的有序性,减小电场集中度,从而降低击穿概率。此外,长支链可以通过影响周围电场的分布,使局部电场场强发生变化,从而减缓电荷在电场中的运动,增加电子的自由程,最终提高击穿电压。
SSA实验中不同的熔融峰是源于不同厚度的片晶结构,这表明了分子链上存在着不同宽度的可结晶序列[17]。分子链上的小支链可把长的分子链划分为长短不一的亚甲基序列,试样不同的Ts下规整排列的晶区,构成了不同厚度的片晶。而较高的短支链含量,会降低分子链结构的规整度,从而使结晶能力下降[18]。此外,短支链的存在可能使得分子链在电场中更容易受到扭曲和变形,导致电场在分子链的周围形成较强的梯度,增加了击穿的风险。
国产样品较低的长支链含量和较高的短支链含量使其击穿场强略低。而进口样A较高的击穿场强得益于较高的长支链含量,其较低的形状参数可能使相对较高的短支链含量导致分子链的不规则性增加,从而使产品的一致性较差。国产样品的尺寸参数与进口样B的尺寸参数相近,说明两者的击穿场强已无明显差距,为了提高国产产品一致性可以考虑进一步降低其短支链含量。
(1)3种聚乙烯长支链含量由小到大的顺序为:国产样品、进口B样品、进口A样品;短支链含量由小到大的顺序为:进口B样品、进口A样品、国产样品。
(2)聚乙烯的长短支链含量差异对其介电常数、介质损耗因数和电阻率影响较小。
(3)聚乙烯基础树脂中较高的长支链含量可通过增加分子间的空间限制、促进晶核形成以及提高结晶温度等方式来整体提高树脂的结晶能力,进而提高材料的耐压等级。较高的短支链含量降低了树脂分子之间的相互作用,使得晶核的形成机会减少,导致其结晶能力降低。
(4)国产样品的分子量分布和长支链含量与进口料B已无明显差异,为提升国产电联料的产品性能,有待进一步降低短支链含量。
  • 国家自然科学基金资助项目(52077171)
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2024年第57卷第8期
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doi: 10.16790/j.cnki.1009-9239.im.2024.08.014
  • 接收时间:2023-09-04
  • 首发时间:2025-12-24
  • 出版时间:2024-08-20
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  • 收稿日期:2023-09-04
  • 修回日期:2024-01-31
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国家自然科学基金资助项目(52077171)
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    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 710049
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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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