Article(id=1193543219481899549, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1193543214067056904, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2025.03.009, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1716393600000, receivedDateStr=2024-05-23, revisedDate=1726502400000, revisedDateStr=2024-09-17, acceptedDate=null, acceptedDateStr=null, onlineDate=1762492478484, onlineDateStr=2025-11-07, pubDate=1742400000000, pubDateStr=2025-03-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1762492478484, onlineIssueDateStr=2025-11-07, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1762492478484, creator=13701087609, updateTime=1762492478484, updator=13701087609, issue=Issue{id=1193543214067056904, tenantId=1146029695717560320, journalId=1149653034449285133, year='2025', volume='58', issue='3', pageStart='1', pageEnd='157', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1762492477194, creator=13701087609, updateTime=1762498203949, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1193567233872982429, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1193543214067056904, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1193567233872982430, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1193543214067056904, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=76, endPage=86, ext={EN=ArticleExt(id=1193543220702442015, articleId=1193543219481899549, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Research on thermal ageing characteristics of graft-modified polypropylene cable insulation materials, columnId=1193543215723806988, journalTitle=Insulating Materials, columnName=Special Issue on Advanced Cable Insulation, runingTitle=null, highlight=null, articleAbstract=

To investigate the ageing characteristics and lifetime evaluation methods of graft-modified polypropylene cable insulation materials, accelerated thermal ageing tests were conducted on the samples at different temperature, and the changes in electrical and physicochemical properties of graft-modified polypropylene cables at various ageing stages were studied. The variation of key characteristic parameters, such as melting temperature, relative dielectric constant, and elongation at break with ageing time was analyzed. The results show that the melting temperature, electric strength, and elongation at break are significantly correlated with ageing time, and these parameters can be used as effective indicators for assessing the ageing degree of graft-modified polypropylene cable insulation materials.

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为探讨接枝改性聚丙烯电缆绝缘材料的老化特性及其寿命评估方法,本文通过在不同温度下进行加速热老化试验,研究了接枝改性聚丙烯电缆在不同老化阶段的电学与理化特性变化,分析了熔融温度、相对介电常数、断裂伸长率等关键特征参数与老化时间的关系。结果表明:熔融温度、电气强度、断裂伸长率等参数与老化时间呈明显相关性,可作为评估接枝改性聚丙烯电缆绝缘材料老化程度的有效指标。

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伍云健(1993-),男(汉族),湖北武汉人,副教授,主要从事固体绝缘材料改性以及老化劣化特性等方面的研究。
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褚凡武(1988-),男(汉族),湖北孝感人,高级工程师,主要从事电工绝缘材料特性测试、高压电缆试验技术等方面的研究。

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褚凡武(1988-),男(汉族),湖北孝感人,高级工程师,主要从事电工绝缘材料特性测试、高压电缆试验技术等方面的研究。

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褚凡武(1988-),男(汉族),湖北孝感人,高级工程师,主要从事电工绝缘材料特性测试、高压电缆试验技术等方面的研究。

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figureFileBig=null, tableContent=
老化温度/℃ 老化时间/天 峰值温度/℃ 熔融焓/(J/g) 结晶度/%
未老化 161.08 16.8 8.04
135 14 162.21 17.2 8.23
135 30 164.1 18.7 8.95
135 60 163.8 19.4 9.28
135 90 164.2 20.1 9.62
135 120 164.1 21.8 10.43
135 150 164.5 22.1 10.57
135 180 164.6 22.3 10.66
140 14 163.4 18.2 8.71
140 30 164.6 20.6 9.85
140 60 164.4 21.0 10.05
140 90 164.2 21.3 10.19
140 120 164.7 22.7 10.86
145 14 163.6 18.7 8.95
145 30 164.1 21.1 10.10
155 14 163.8 19.0 9.10
155 30 164.4 22.9 10.96
), ArticleFig(id=1195077330356937422, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1193543219481899549, language=CN, label=表1, caption=

接枝改性PP熔融过程的DSC测试结果

, figureFileSmall=null, figureFileBig=null, tableContent=
老化温度/℃ 老化时间/天 峰值温度/℃ 熔融焓/(J/g) 结晶度/%
未老化 161.08 16.8 8.04
135 14 162.21 17.2 8.23
135 30 164.1 18.7 8.95
135 60 163.8 19.4 9.28
135 90 164.2 20.1 9.62
135 120 164.1 21.8 10.43
135 150 164.5 22.1 10.57
135 180 164.6 22.3 10.66
140 14 163.4 18.2 8.71
140 30 164.6 20.6 9.85
140 60 164.4 21.0 10.05
140 90 164.2 21.3 10.19
140 120 164.7 22.7 10.86
145 14 163.6 18.7 8.95
145 30 164.1 21.1 10.10
155 14 163.8 19.0 9.10
155 30 164.4 22.9 10.96
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接枝改性聚丙烯电缆绝缘材料热老化特性研究
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褚凡武 1 , 徐明忠 1 , 张伟 1 , 邓凯 1 , 彭超 1 , 伍云健 2 , 张丹枫 2
绝缘材料 | 先进电缆绝缘专题 2025,58(3): 76-86
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绝缘材料 | 先进电缆绝缘专题 2025, 58(3): 76-86
接枝改性聚丙烯电缆绝缘材料热老化特性研究
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褚凡武1, 徐明忠1, 张伟1, 邓凯1, 彭超1, 伍云健2, 张丹枫2
作者信息
  • 1 中国电力科学研究院有限公司,湖北 武汉 43070
  • 2 湖北工业大学,湖北 武汉 430068
  • 褚凡武(1988-),男(汉族),湖北孝感人,高级工程师,主要从事电工绝缘材料特性测试、高压电缆试验技术等方面的研究。

通讯作者:

伍云健(1993-),男(汉族),湖北武汉人,副教授,主要从事固体绝缘材料改性以及老化劣化特性等方面的研究。
Research on thermal ageing characteristics of graft-modified polypropylene cable insulation materials
Fanwu CHU1, Mingzhong XU1, Wei ZHANG1, Kai DENG1, Chao PENG1, Yunjian WU2, Danfeng ZHANG2
Affiliations
  • 1 China Electric Power Research Institute, Wuhan 4300070, China
  • 2 Hubei University of Technology, Wuhan 430068, China
出版时间: 2025-03-20 doi: 10.16790/j.cnki.1009-9239.im.2025.03.009
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为探讨接枝改性聚丙烯电缆绝缘材料的老化特性及其寿命评估方法,本文通过在不同温度下进行加速热老化试验,研究了接枝改性聚丙烯电缆在不同老化阶段的电学与理化特性变化,分析了熔融温度、相对介电常数、断裂伸长率等关键特征参数与老化时间的关系。结果表明:熔融温度、电气强度、断裂伸长率等参数与老化时间呈明显相关性,可作为评估接枝改性聚丙烯电缆绝缘材料老化程度的有效指标。

接枝改性聚丙烯  /  电缆绝缘材料  /  热老化  /  性能评估  /  老化特性

To investigate the ageing characteristics and lifetime evaluation methods of graft-modified polypropylene cable insulation materials, accelerated thermal ageing tests were conducted on the samples at different temperature, and the changes in electrical and physicochemical properties of graft-modified polypropylene cables at various ageing stages were studied. The variation of key characteristic parameters, such as melting temperature, relative dielectric constant, and elongation at break with ageing time was analyzed. The results show that the melting temperature, electric strength, and elongation at break are significantly correlated with ageing time, and these parameters can be used as effective indicators for assessing the ageing degree of graft-modified polypropylene cable insulation materials.

graft-modified polypropylene  /  cable insulation materials  /  thermal ageing  /  performance evaluation  /  ageing characteristics
褚凡武, 徐明忠, 张伟, 邓凯, 彭超, 伍云健, 张丹枫. 接枝改性聚丙烯电缆绝缘材料热老化特性研究. 绝缘材料, 2025 , 58 (3) : 76 -86 . DOI: 10.16790/j.cnki.1009-9239.im.2025.03.009
Fanwu CHU, Mingzhong XU, Wei ZHANG, Kai DENG, Chao PENG, Yunjian WU, Danfeng ZHANG. Research on thermal ageing characteristics of graft-modified polypropylene cable insulation materials[J]. Insulating Materials, 2025 , 58 (3) : 76 -86 . DOI: 10.16790/j.cnki.1009-9239.im.2025.03.009
电力电缆在建筑、交通、发电以及石化等领域起着至关重要的作用[1-2]。目前,交联聚乙烯(XLPE)是应用最广泛的电缆绝缘材料,然而XLPE的生产过程复杂,存在能耗大、效率低、难以回收等问题。随着“双碳”目标的提出,绿色低碳电缆绝缘材料的发展成为重要趋势。聚丙烯(PP)由于其良好的耐热性、绝缘性和可回收性[3],成为替代传统热固性电缆绝缘材料的选择。然而,PP结构中存在叔碳原子,容易发生链式氧化反应,导致性能下降[4-5]。因此,深入研究聚丙烯材料的老化特性对评估其作为电缆主绝缘的可行性至关重要。
目前,国内外已经有大量学者进行了电缆绝缘材料老化方面的研究。段玉兵等[6]对高压XLPE电缆绝缘进行了加速热老化试验,发现XLPE绝缘会产生羰基、碳碳双键等官能团,其数量随着老化温度的升高而增加。王兵等[7]对退役电缆进行了加速老化试验,发现羰基指数和介电常数随着老化进行而增大。ZHAO Y F等[8]研究了XLPE电缆的电热联合老化,发现电缆形态的变化会抵消外部应力的影响,阻碍进一步降解发生。P QUENNEHEN等[9]研究发现聚氯乙烯电缆的主要老化机制为热稳定剂的脱氢反应。CHEN J等[10]对不同运行时间的XLPE电缆进行了测试,研究发现XLPE绝缘的介电常数和介质损耗因数随运行时间的增加先减小后增大,交流电气强度上升。H YAHYAOUI等[11]对高压直流XLPE电缆开展老化试验,发现绝缘材料的体积电阻率在老化前后保持不变。YU J Z等[12]研究了运行时间对电缆传导电流的影响,发现陷阱密度、空间电荷积累阈值和活化能都随运行时间的增加而增大。
常规的聚丙烯材料具有硬度高、结晶度高、柔韧性低等缺点,不能直接作为电缆绝缘材料[13]。近年来为了满足电缆绝缘材料的性能需求,提升PP综合性能的改性技术成为了研究热点。目前,主要的改性方式包括共混改性、共聚改性和接枝改性[14]。陈鸿等[15]对比了两种改性PP的结构与性能,发现共混改性PP的力学性能更优异但交流电气强度相对共聚改性更低。文献[16-17]研究表明采用化学接枝改性的PP材料绝缘性能明显优于共混改性。其中接枝苯乙烯能显著提升的交流电气强度[18]和热氧老化性能[19];接枝马来酸酐能提高PP与无机材料的相容性[20],同时引入大量的深陷阱提升PP电气特性[21];接枝受阻酚基团能提高PP的抗氧化能力和机械强度[22-23]
由于国内PP电缆绝缘材料的研究起步较晚,目前还没有实际工况下的老化试样,对于PP电缆绝缘的老化研究主要采用加速老化试验和仿真的研究方法。樊林禛等[18]对接枝2.5%~10%质量分数苯乙烯(St)的PP材料的电性能进行了研究,发现交流电气强度随着接枝含量的升高而提升。胡世勋等[14]对改性PP的性能进行了测试,发现相较于XLPE材料,改性PP具有更高的热稳定性和绝缘性能。PENG C等[24]进行了热重-气相色谱(TG-GC)分析,发现接枝改性PP电缆绝缘材料相较于纯PP具有更高的热分解温度。尽管PP老化研究深入,但对成品PP电缆绝缘材料的老化研究仍较缺乏。
本研究通过不同温度下的加速热老化试验,获取接枝苯乙烯改性PP成品电缆绝缘在不同老化阶段的电学和理化特性,并探究适用于接枝改性PP电缆绝缘材料老化的特征参数。通过深入了解其老化过程及性能变化,为PP电缆绝缘材料的使用与推广提供参考。
本研究使用的聚丙烯电缆由清华大学研制、宁波东方电缆股份有限公司生产,使用电缆切片机(JQB-II型,嘉兴市凯博实验仪器有限公司)将电缆沿径向切割制成长度约为15 cm的样段,再通过电缆切片机将样段沿轴向切割,制成厚度分别为1 mm和0.3 mm的样条,制样过程如图1所示。再将其裁切成尺寸为30 mm×30 mm的样片用于各项电学性能及理化性能测试。使用压片机(KST01型,山东卡斯特有限公司)压制成符合GB/T 2951.11—2008要求的哑铃试样,用于力学性能测试。
根据GB/T 2951.12—2008,采用烘箱(101-00BS型,绍兴市苏珀仪器有限公司)对PP电缆绝缘试样在135、140、145、155℃下进行热老化试验。
采用高分辨场发射扫描电子显微镜(SEM,SU8010型,日本日立公司)观察试样的表面形貌,放大倍数为100~1 000倍。测试前将PP电缆绝缘材料剪切成尺寸为5 mm×5 mm的样片,然后对其表面进行喷金处理。
采用差示扫描量热仪(TGA/DSC 3+型,瑞士Mettler Toledo公司)开展材料热重分析,N2气氛。以10℃/min的速率由30℃升温至600℃获得PP的TGA曲线。以10℃/min的速率升温至200℃,保温3 min,然后以10℃/min的速率降温至30℃,获得结晶曲线;再以10℃/min的速率升温至200℃获得熔融曲线。
采用电子式万能试验机(MTS CMT4000型,美特斯工业系统(中国)有限公司)测试PP试样的力学性能。依据GB/T 22078.1—2008以及GB/T 2951.11—2008规定的具体试验方法,分别制备5A型哑铃试样,拉伸速度设置为25 mm/min,每种材料测试5个试样,对其拉伸强度、断裂伸长率取中位数作为最终结果。
采用宽频介电谱仪(Concept80型,德国NovoControl公司)测量1~106 Hz下材料的相对介电常数及介质损耗因数。圆型薄片试样的厚度为1 mm,直径为40 mm。为保证试样与测试电极接触优良,测试前在试样两面均匀涂抹上导电银浆并低温烘干。各类试样均进行5次测试,取中值为测试结果。
采用直径为1.5 cm的球-球电极测试试样的交流电气强度。将试样置于绝缘油中以避免表面放电,升压速率为1 kV/s,每种试样测试10个点的电气强度,并基于威布尔(Weibull)分布模型进行分析。
采用多功能X射线衍射仪(Empyrean锐影系列,荷兰马尔文帕纳科公司)对PP薄片试样进行扫描,实验靶材为Cu靶,波长为0.154 nm,管电压为40 kV,管电流为40 mA,扫描范围为5°~30°。
采用光电子能谱仪(PHI 5000 VersaProbe Ⅲ型,日本ULVAC-PHI公司)对PP试样表面元素组成及化学状态进行分析。测试前对试样进行表面清洁处理,通过小面积扫描模式获得试样表面元素的全谱图,通过C 1s、O 1s特征峰对PP试样的氧化程度及C-O、C=O的含量进行半定量分析。
140℃下不同老化阶段试样外观如图2所示。从图2可以看出,未老化时试样表面光滑,呈现乳白色;在140℃下老化14天后试样颜色变深呈现微黄,且表面粗糙程度增大;老化120天后发生明显黄化现象,试样表面出现肉眼可见裂纹,试样变为淡棕褐色质地,明显变硬变脆。
不同温度下老化不同时间的试样微观形貌如图3所示。从图3(a)可以看出,未老化时接枝改性PP电缆绝缘材料表面较为光滑,没有明显瑕疵。从图3(b)(g)(h)(i)可以看出,随着老化温度的升高,老化相同时间的试样表面粗糙程度增加。
图3(c)可以看出,在老化中期,材料表面出现较多细微且分散的裂纹,长度为约1 μm。随着老化时间的延长,材料表面的裂纹逐渐发展延伸并连接在一起,且深度明显加深,长度可达8 μm,如图3(d)所示。当材料发生黄化现象后,材料表面存在肉眼可见的裂纹,如图3(e)(f)所示,裂痕明显且较深,PP电缆绝缘材料表面出现明显断层。
通过热失重分析测得接枝改性PP电缆绝缘材料在140℃下老化不同时间的TG曲线,如图4所示。将接枝改性PP电缆绝缘材料热重分析中失重5%时对应温度(T 5%)作为热分解温度,由图4可知,未老化试样的热分解温度为395.95℃。
接枝改性PP电缆绝缘材料在不同老化温度下的热分解温度随老化时间的变化趋势如图5所示。从图5可以看出,随着热老化时间的增加,热分解温度都呈现出先小幅度上升后保持稳定再明显下降的趋势。
分析该现象的原因,在热老化过程中抗氧化剂逐渐消耗直至耗尽,空气中的氧气开始与接枝改性PP反应。PP分子链上的叔碳原子断裂形成自由基,与氧气反应进一步产生羰基、羧基,形成链式氧化反应。一旦链式氧化反应发生,PP电缆绝缘材料开始迅速降解,性能也随之发生明显变化,热分解温度迅速下降至310℃左右。
在老化末期,宏观上PP电缆绝缘材料发生黄化现象,材料硬度增加,表面粗糙程度增大直至出现明显裂纹。由于热分解温度在末期的明显下降发生在黄化后,此时PP电缆绝缘材料在力学和电学性能方面已经完全不能满足绝缘要求。因此热分解温度的上升适合作为PP电缆绝缘材料初期老化阶段的判断标准。
通过DSC测试得到接枝改性PP电缆绝缘材料在140℃下老化不同时间的熔融曲线,如图6所示。从图6可以看出,改性PP的熔融峰峰值对应温度在老化开始后有一个明显的上升,之后随着老化时间的延长熔融峰峰值对应温度向低温方向移动。
接枝改性PP电缆绝缘材料的熔融温度随老化时间的变化趋势如图7所示。从图7可以看出,试样在135、140、145℃下老化时,其熔融温度随着老化时间的延长先发生小幅度的上升,在发生黄化现象后其熔融温度迅速下降;在155℃下老化时,由于老化温度更接近接枝改性PP的熔融温度,其熔融温度变化较为明显,在老化初期升高了13℃,之后随着老化时间的延长,熔融温度缓慢下降,在发生黄化现象后迅速下降,但最终熔融温度依旧高于材料在未老化时的熔融温度,由此可以推断在接近熔点的温度下进行老化会使PP电缆绝缘材料的热学性质发生较大改变。
通过DSC分析获得不同老化温度、不同老化时间下接枝改性PP电缆绝缘材料的熔融焓,根据结晶度和熔融焓之间的关系式[25],可以计算试样的结晶度,如式(1)所示。
X c = Δ H Δ H 0 × 100 %
式(1)中:X c表示聚合物结晶度;ΔH表示熔融焓;ΔH 0表示完全结晶时的熔融焓,PP的ΔH 0为209 J/g[26]
试样在140℃下老化不同时间的结晶曲线如图8所示,在不同老化温度下老化30天的结晶曲线如图9所示,对应测试数据列于表1
表1可以看出,PP试样的结晶度随老化时间的延长呈现不同程度的上升,且老化温度越高,老化30天后的结晶度上升越显著。这是由于接枝改性影响了PP的结晶过程使其熔融焓降低[14],同时苯乙烯接枝的苯环结构也会抑制大分子的规则排列降低材料的结晶度[27]。此外,电缆的制造过程也会对其结晶度造成影响,一方面电缆制造时需加入抗氧化剂、稳定剂、阻燃剂等,这些添加剂会干扰PP的分子链排列,进而降低材料的结晶度;另一方面,电缆的加工过程包含挤出后的冷却阶段,绝缘材料在离开机头后要立即冷却防止由于重力引发的形变[28],冷却阶段的低温结晶过程会降低结晶度[29]。因此接枝改性PP的熔融焓显著低于均聚PP(约为96.5 J/g)[30]。在老化初期,PP继续结晶,结构逐渐稳定,结晶度增加,从而导致PP绝缘材料的热分解温度和熔融温度在老化初期小幅上升。随着老化过程的进行,结晶度的变化幅度逐渐减小,热分解温度和熔融温度也随之稳定[31]
不同老化温度下试样的断裂伸长率随老化时间的变化趋势如图10所示。
图10可以看出,在不同老化温度下,试样的断裂伸长率在老化初期(14天内)都出现了一次明显的下降;在老化中期断裂伸长率随着老化时间的延长缓慢下降,这一趋势在老化温度较低(135℃、140℃)时更明显;在老化末期断裂伸长率迅速下降。
在145℃和155℃下老化的材料有硬化的现象发生,其中155℃下的硬化现象最为明显。在老化的最终阶段会发生黄化现象,发生黄化现象前,断裂伸长率相比未老化试样下降30%左右,发生黄化现象后,材料硬度明显增大且质地变脆,在施加较小应力的情况下就会发生断裂。
不同老化温度下接枝改性PP绝缘材料的拉伸强度随老化时间的变化趋势如图11所示。从图11可以看出,在老化初期拉伸强度出现小幅度的下降,之后随老化时间的延长变化不明显,在黄化现象发生后,材料变硬变脆,拉伸强度迅速下降。
接枝改性PP在140℃下老化不同时间的介电常数如图12所示。从图12可以看出,在黄化现象发生前(老化120天以内),试样的介电常数会随着老化的进行发生小幅度的上升,且随频率变化程度极小。在黄化现象发生后介电常数大幅上升,且随频率变化明显。
根据物质的介电常数可以判别高分子材料的极性大小。通常,相对介电常数大于3.6的为极性物质;相对介电常数在2.8~3.6的为弱极性物质;相对介电常数小于2.8的为非极性物质。由于PP材料为非极性分子聚合物,其内部主要的极化方式为电子位移极化,其他极化形式占比很少,使得PP相对介电常数随频率的变化相对较小。
在黄化现象发生前,材料的介电常数在低频区域显著高于高频区域,黄化现象发生后,介电常数随频率的升高显著下降。这一变化归因于黄化过程中,PP长链断裂生成极性较强的小分子,使得材料的主要极化方式由电子位移极化转变为极性分子转向极化。极性分子转向极化对频率响应较为敏感,在高频区域难以发生,导致介电常数随频率升高而下降。
接枝改性PP电缆绝缘材料在140℃下老化不同时间的介质损耗因数(tanδ)随频率的变化趋势如图13所示。
图13可以看出,在黄化现象发生前,试样的tanδ较低且随频率变化不明显。黄化现象发生后,tanδ随频率变化明显,且相较黄化前明显增大,同时tanδ在低频和高频区域均显著升高,且低频区域上升更为明显。低频区域的显著上升可归因于接枝改性引入的界面区域以及材料内部缺陷的增多[18],导致载流子在迁移过程中更容易被陷阱或界面捕获,形成空间电荷积聚并引发空间电荷极化。空间电荷极化主要影响低频区域的介电性能[32],这一结果与实验测试结果一致。高频区域的介质损耗因数升高则与黄化过程中极性小分子含量增加相关,极性分子转向极化在高频下难以完全响应,但仍会引起一定的介质损耗。
接枝改性PP在不同老化温度下的交流电气强度随老化时间的变化趋势如图14所示。从图14可以看出,未老化试样的电气强度可以达到80 kV/mm(试样厚度为0.3 mm)。随着老化时间的增加,接枝改性PP的电气强度在较低老化温度下呈现缓慢提升、缓慢降低、急速降低3个阶段。在缓慢提升和缓慢降低阶段,交流电气强度的变化值相对较小;而在急速降低阶段,电气强度降低50%以上,试样的绝缘性能急剧下降。
接枝改性PP在140℃下老化不同时间的XRD测试结果如图15所示。从图15可以看出,未老化试样表现出α晶型的5个典型特征衍射峰,即分别位于2θ为14.17°、16.95°、18.63°、21.23°、21.92°处的衍射峰,对应于聚丙烯晶型的(110)、(040)、(130)、(111)、(131)晶面。相较于未老化的PP试样,老化后的试样衍射峰有轻微增强,未出现新的衍射峰,说明老化过程中PP存在进一步的结晶过程,但PP的晶型并未发生改变。此外,未老化试样在2θ=20°处存在一个峰(图中阴影区域),随着老化的进行,该峰峰值逐渐减小直至消失。推测是在电缆的生产过程中添加的抗氧化剂,随着老化的进行逐渐消耗导致的衍射峰变化。
对在140℃下老化不同时间的PP试样进行XPS测试,获得了C1s和O1s图谱并进行分峰处理,分别如图16图17所示。根据分峰结果可以获得元素不同价态的含量比例[33-34],从而对材料的老化过程进行进一步分析。
图16可以看出,黄化现象发生前,随着老化的进行,碳氧单键的相对含量逐渐升高。黄化现象发生后,碳氧双键的相对含量升高。从图17可以看出,在黄化现象发生前,前期碳氧单键和碳氧双键的相对含量开始几乎保持不变,后期碳氧双键的相对含量略有上升。黄化现象发生后,碳氧单键和碳氧双键的相对含量出现了反转,碳氧双键的相对含量大幅上升,远高于碳氧单键的相对含量。在黄化现象发生前,PP分子链保持完整,碳碳单键的含量基本稳定,因此可以通过对应峰值来判断氧元素的相对含量。老化初期,氧元素主要以碳氧单键的形式存在于PP试样中:空气中的氧气与PP长链上的叔碳原子反应,取代氢元素生成碳氧单键。随着老化进程加剧,黄化现象出现,一方面更多的叔碳原子被氧元素取代,进一步生成碳氧单键;另一方面,部分已有的碳氧单键经历进一步氧化,转化为碳氧双键。碳氧双键的形成伴随PP长链的断裂,导致碳碳单键的绝对含量减少。同时链断裂产生了末端羰基和羟基结构,使得碳氧双键和碳氧单键的绝对含量均显著升高,从而反映出材料氧化程度的加深。
(1)随着老化程度的加深,接枝改性PP表面粗糙程度逐渐增加,裂纹逐渐连接并出现明显断层现象,因此微观观察可以为绝缘状态的评估提供有力支持。
(2)在老化过程中,接枝改性PP的熔融温度呈先上升后下降的趋势,可作为电缆全周期的寿命评估指标;热分解温度在老化开始阶段有明显的上升,可作为初期老化阶段的评估指标。
(3)老化过程中,接枝改性PP的断裂伸长率呈现出明显的三段式变化,因此可作为评估材料老化程度的可靠指标,推荐使用断裂伸长率下降40%作为绝缘失效的判断依据;拉伸强度的变化趋势不明显,不适合作为评估指标。
(4)在接枝改性PP发生黄化现象前,相对介电常数呈现小幅上升趋势,虽可作为材料老化状态的辅助判断依据,但受变化幅度限制,不推荐作为独立的有效评估指标;电气强度随老化时间延长呈显著下降趋势,且线性相关性较强,能够更准确地反映材料老化程度,适合作为评估材料老化的有效指标。
(5)在黄化现象发生前,氧元素主要以碳氧单键的形式存在于材料中,并且随着老化的进行碳氧单键含量逐渐上升。黄化现象发生后,碳氧双键含量显著增加。含氧化学键的相对含量可作为寿命评估指标。
  • 中国电力科学研究院研究开发基金项目(SZ83-22-004)
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doi: 10.16790/j.cnki.1009-9239.im.2025.03.009
  • 接收时间:2024-05-23
  • 首发时间:2025-11-07
  • 出版时间:2025-03-20
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  • 收稿日期:2024-05-23
  • 修回日期:2024-09-17
基金
中国电力科学研究院研究开发基金项目(SZ83-22-004)
作者信息
    1 中国电力科学研究院有限公司,湖北 武汉 43070
    2 湖北工业大学,湖北 武汉 430068

通讯作者:

伍云健(1993-),男(汉族),湖北武汉人,副教授,主要从事固体绝缘材料改性以及老化劣化特性等方面的研究。
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https://castjournals.cast.org.cn/joweb/jycl/CN/10.16790/j.cnki.1009-9239.im.2025.03.009
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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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