Article(id=1210577668077121658, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1210577662121209865, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2024.08.013, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1690473600000, receivedDateStr=2023-07-28, revisedDate=1695571200000, revisedDateStr=2023-09-25, acceptedDate=null, acceptedDateStr=null, onlineDate=1766553807515, onlineDateStr=2025-12-24, pubDate=1724083200000, pubDateStr=2024-08-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1766553807515, onlineIssueDateStr=2025-12-24, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1766553807515, creator=13701087609, updateTime=1766553807515, 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=108, endPage=113, ext={EN=ArticleExt(id=1210577668345557128, articleId=1210577668077121658, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Effect of thermal⁃cooling cycling on dielectric properties of micron Al2O3 epoxy composite insulation, columnId=1192878364340924664, journalTitle=Insulating Materials, columnName=Test and Analysis, runingTitle=null, highlight=null, articleAbstract=

In order to investigate the effect of continuous changes in high and low temperatures on the epoxy composite insulation of cable terminals, micron Al2O3/epoxy composite insulation samples were prepared in this paper, and thermal-cooling cycling experiments were conducted on the samples. The changes in dielectric properties and degradation mechanism of epoxy composite insulation samples under different number of thermal-cooling cycling were analyzed through the AC breakdown, isothermal surface potential attenuation, and dielectric properties tests. The results show that during the process of thermal-cooling cycling, the cross-linked network of epoxy composite insulation deteriorates gradually under the combined action of high temperature thermal ageing and high and low temperature alternating stresses, the filler gradually separates from the matrix, microcracks and holes appear in the sample, the free volume increases, and the dielectric constant and electric strength continue to decrease. After 750 hours of thermal-cooling cycling, the AC electric strength of the sample decreases by 15.2%, the deep trap density decreases by 41%, the shallow trap density shows a fluctuating trend, and the dielectric loss factor (tanδ) firstly decreases and then slightly increases.

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为了探究高低温持续变化对电缆终端环氧复合绝缘的影响,本文制备了微米Al2O3/环氧复合绝缘试样,并对此进行了冷热循环实验。通过交流击穿、等温表面电位衰减和介电性能等测试分析了不同冷热循环次数下环氧复合绝缘试样的介电性能变化规律以及材料劣化机理。结果表明:在冷热循环过程中,环氧复合绝缘的交联网络在高温热老化和高低温交变应力的共同作用下逐渐发生劣化,填料逐渐脱离基体,试样内出现微裂纹和孔洞,自由体积不断增大,介电常数和击穿场强不断降低。其中,在经过750 h的冷热循环后,试样的交流击穿场强下降了15.2%,深陷阱密度下降了41%,浅陷阱密度呈现上下波动的趋势,介质损耗因数(tanδ)先减小后小幅增大。

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潘泽华(1992-),男(汉族),北京人,工程师,主要研究方向为高电压与绝缘技术。

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潘泽华(1992-),男(汉族),北京人,工程师,主要研究方向为高电压与绝缘技术。

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潘泽华(1992-),男(汉族),北京人,工程师,主要研究方向为高电压与绝缘技术。

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冷热循环对微米Al2O3环氧复合绝缘介电性能的影响
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潘泽华 , 任志刚 , 刘音 , 郭卫 , 李华春
绝缘材料 | 测试与分析 2024,57(8): 108-113
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绝缘材料 | 测试与分析 2024, 57(8): 108-113
冷热循环对微米Al2O3环氧复合绝缘介电性能的影响
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潘泽华, 任志刚, 刘音, 郭卫, 李华春
作者信息
  • 国网北京市电力公司电力科学研究院,北京 100192
  • 潘泽华(1992-),男(汉族),北京人,工程师,主要研究方向为高电压与绝缘技术。

Effect of thermal⁃cooling cycling on dielectric properties of micron Al2O3 epoxy composite insulation
Zehua PAN, Zhigang REN, Yin LIU, Wei GUO, Huachun LI
Affiliations
  • State Grid Beijing Electric Power Research Institute, Beijing 100192, China
出版时间: 2024-08-20 doi: 10.16790/j.cnki.1009-9239.im.2024.08.013
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为了探究高低温持续变化对电缆终端环氧复合绝缘的影响,本文制备了微米Al2O3/环氧复合绝缘试样,并对此进行了冷热循环实验。通过交流击穿、等温表面电位衰减和介电性能等测试分析了不同冷热循环次数下环氧复合绝缘试样的介电性能变化规律以及材料劣化机理。结果表明:在冷热循环过程中,环氧复合绝缘的交联网络在高温热老化和高低温交变应力的共同作用下逐渐发生劣化,填料逐渐脱离基体,试样内出现微裂纹和孔洞,自由体积不断增大,介电常数和击穿场强不断降低。其中,在经过750 h的冷热循环后,试样的交流击穿场强下降了15.2%,深陷阱密度下降了41%,浅陷阱密度呈现上下波动的趋势,介质损耗因数(tanδ)先减小后小幅增大。

环氧复合绝缘  /  微米Al2O3  /  冷热循环  /  介电性能

In order to investigate the effect of continuous changes in high and low temperatures on the epoxy composite insulation of cable terminals, micron Al2O3/epoxy composite insulation samples were prepared in this paper, and thermal-cooling cycling experiments were conducted on the samples. The changes in dielectric properties and degradation mechanism of epoxy composite insulation samples under different number of thermal-cooling cycling were analyzed through the AC breakdown, isothermal surface potential attenuation, and dielectric properties tests. The results show that during the process of thermal-cooling cycling, the cross-linked network of epoxy composite insulation deteriorates gradually under the combined action of high temperature thermal ageing and high and low temperature alternating stresses, the filler gradually separates from the matrix, microcracks and holes appear in the sample, the free volume increases, and the dielectric constant and electric strength continue to decrease. After 750 hours of thermal-cooling cycling, the AC electric strength of the sample decreases by 15.2%, the deep trap density decreases by 41%, the shallow trap density shows a fluctuating trend, and the dielectric loss factor (tanδ) firstly decreases and then slightly increases.

epoxy composite insulation  /  micron Al2O3  /  thermal⁃cooling cycling  /  dielectric properties
潘泽华, 任志刚, 刘音, 郭卫, 李华春. 冷热循环对微米Al2O3环氧复合绝缘介电性能的影响. 绝缘材料, 2024 , 57 (8) : 108 -113 . DOI: 10.16790/j.cnki.1009-9239.im.2024.08.013
Zehua PAN, Zhigang REN, Yin LIU, Wei GUO, Huachun LI. Effect of thermal⁃cooling cycling on dielectric properties of micron Al2O3 epoxy composite insulation[J]. Insulating Materials, 2024 , 57 (8) : 108 -113 . DOI: 10.16790/j.cnki.1009-9239.im.2024.08.013
电缆终端绝缘套管通常采用环氧树脂复合绝缘作为单一的绝缘介质装配到电缆线路的末端[1]。在电缆实际运行时,较大的负载电流会导致绝缘温度升高,最高可达90℃,短时过载下的绝缘温度则更高[2-4]。然而,环境温度可能比导体温度低得多,如在中国北方冬季,温度可低至-40℃[5-6]。随着电缆负载电流的不断变化,电缆终端环氧绝缘会经历极高温度和极低温度的连续变化,其绝缘性能将不断劣化[7-9]。因此,研究冷热循环对环氧复合绝缘的影响及其机理对电缆的安全稳定运行具有重要意义。
张静等[10]研究了冷热循环对电缆附件与本体之间的界面压力的影响。结果表明,长期冷热循环后的硅橡胶材料在测试温度下其弹性模量发生明显上升,电缆附件产生不可恢复的形变,界面压力降低,界面密封性能下降。周益扬[11]分别研究了高温、低温、湿热、高低温循环以及湿热低温循环对硅橡胶材料性能的影响,发现高低温循环对硅橡胶的影响最为严重,可大幅降低硅橡胶的力学性能。殷实鉴[12]对超导磁体封装用环氧树脂进行了冷热循环实验,并通过微观结构观察揭示了其性能退化的机制。然而,目前关于冷热循环对电缆终端环氧绝缘介电性能影响的研究还很少。
本研究制备微米Al2O3/环氧复合绝缘试样,并设计冷热循环实验,以模拟电缆在实际运行条件下负载电流波动叠加环境温度变化所导致的高低温持续作用过程。通过交流击穿测试、等温表面电位衰减测试(ISPD)以及介电性能测试分析环氧复合绝缘的冷热循环介电特性,并采用扫描电子显微镜(SEM)和热膨胀测试研究环氧复合绝缘的冷热循环微观特性及劣化机理。希望能为电缆实际运行时的环氧复合绝缘状态评估提供理论支撑。
双酚A型环氧树脂(E51),南通星辰合成材料有限公司;甲基四氢苯酐(MTHPA),阿拉丁试剂(上海)有限公司;微米Al2O3粒径为2 μm,深圳晶材化工有限公司。
取适量的E51、MTHPA、微米Al2O3(质量比为100∶38∶300),放置于THINKY MIXER ARE-310型搅拌机中,在2 000 r/min的转速下混合15 min,之后放入超声波清洗机中以100 W的功率处理30 min。然后,将混合物再次放入搅拌机中,在2 000 r/min的转速下混合15 min,2 200 r/min的转速下脱气15 min。最后,将混合物缓慢倒入不锈钢板模具中,固化程序为:80℃/2 h+120℃/2 h+150/4 h。
冷热循环实验的温度为-50℃和120℃。升温和降温速率分别为9℃/min和3℃/min。单次冷热循环持续15 h,总共进行50次的冷热循环实验,共750 h。
采用直径为25 mm的球-球电极,在室温下以 1 kV/s的升压速率进行交流击穿测试。
采用热膨胀仪(L75型,德国林赛斯公司)测试试样的相对伸长量随温度的变化。试样为圆柱形,高度和直径分别为20 mm和6 mm。测试温度为30~150℃,升温速率为2℃/min。
使用扫描电子显微镜(VE9800型,日本KEYENCE公司)观察样品的断裂面微观形貌。为了保证良好的成像效果,在样品的断裂面处进行喷金处理。
参考文献[9]中的等温表面电位衰减(ISPD)实验的平台设置和测试条件。针电极和栅电极分别施加-12 kV和-8 kV的直流电压,电压持续施加3 min。测试时间为5 h,温度为80℃。
在室温下,采用电桥对试样进行工频介电常数和介质损耗因数(tanδ)的测试。
微米Al2O3/环氧复合绝缘试样在冷热循环过程中的交流击穿场强变化如图1所示。从图1可以看出,随着冷热循环次数增加,交流击穿场强整体呈现出下降的趋势,且在经历10次冷热循环后便出现了大幅下降。在经过50次的冷热循环后,交流击穿场强从初始的35.14 kV/mm下降到29.81 kV/mm,下降了15.2%,表明试样的绝缘性能出现了一定程度的劣化。
由ISPD测试结果计算出不同冷热循环次数下微米Al2O3/环氧复合绝缘的浅陷阱和深陷阱的能级特性及其密度分布结果,分别如图23所示。由击穿场强曲线与深陷阱密度曲线的相似变化趋势可得,冷热循环过程中的击穿场强变化主要由深陷阱调制。从图3可以看出,深陷阱密度随冷热循环次数的变化较为显著,随着冷热循环次数的增加,深陷阱密度总体上单调下降,其中50次冷热循环后的深陷阱密度(1.75×1018 C/m3)相比初始状态试样(2.95×1018 C/m3)降低了41%。浅陷阱密度则上下波动。
其中,在经过10次冷热循环后,深陷阱密度出现了大幅下降,而浅陷阱密度出现小幅增加,这可导致载流子的浓度和迁移率增大,该结果对应图1中交流击穿场强出现的大幅下降。这表明在经过10次冷热循环后,样品即出现了严重的劣化,缺陷大幅增加。
对比经过20次和30次冷热循环的结果,从图3可以看出,深陷阱的密度出现了下降,这意味着材料中载流子的浓度增加,而迁移率下降,这一现象对应图1中该阶段的交流击穿场强无明显变化。这是由于在制备试样的过程中,大量微米Al2O3的存在使得体系非常黏稠,复合材料在高温固化时,固化剂和基体难以进行充分接触和反应。但在经过10次冷热循环后,微裂纹逐渐形成,体系结构逐渐松散,于是在高温下,固化剂和其他小分子继续参与固化反应(后固化)[13-15],从而使得试样的局部交联度增大,因此延缓了试样的劣化程度。
随着后固化的逐渐完成,由于高温热老化和填料与基体之间的持续拉伸收缩,试样的劣化程度逐渐加深。试样内的低密度区域增多,深陷阱密度进一步降低,浅陷阱密度逐渐增大,最终导致交流击穿场强的持续降低。
相对介电常数是描述材料在电场中极化的宏观参数,而tanδ则是电介质在被施加电压时所消耗的有功功率和无功功率的比值[16-18]图4为不同冷热循环次数下试样的相对介电常数和tanδ的变化。从图4可以看出,随着冷热循环次数的增加,试样的相对介电常数不断降低,从初始的6.11降低至冷热循环50次后的5.82,下降了4.75%。而tanδ则先大幅降低,随后小幅升高。tanδ从初始的6.4×10-3大幅降低至第20次冷热循环后的2.0×10-3,经过50次冷热循环后tanδ再升高为3.3×10-3,产生了48.4%的降幅。
图5是不同冷热循环次数下试样断裂面的微观形貌。从图5可以看出,试样为初始状态时,基体与填料间结合较为紧密。在10次冷热循环后,试样断裂面处出现了明显的微裂纹和孔洞。随着冷热循环次数的增加,试样断裂面处的微裂纹逐渐增多,孔洞逐渐增大,试样结构逐渐疏松,劣化逐渐加重。这是因为在冷热循环过程中,高温会导致试样交联网络逐渐劣化,分子链断裂,进而产生微裂纹。且在高低温交变应力作用下,由于环氧基体与Al2O3填料不同的热膨胀系数使得界面处于不断的拉伸和压缩状态,界面结合程度逐渐变差[19-20],填料从基体中脱落,进而产生孔洞和裂纹。
对于大多数聚合物而言,在玻璃化转变温度前后存在两种不同的线膨胀系数。其中在玻璃化转变温度以下,热膨胀主要与分子的热运动有关;在玻璃化转变温度以上,热膨胀不仅会受到分子热运动的影响,还与材料内自由体积的膨胀有关。因此,玻璃化转变温度前后的线膨胀系数之差可以反应出试样内自由体积的相对大小[21-22]
图6是试样在冷热循环过程中的相对伸长量随温度的变化曲线。曲线的拐点对应的温度为试样的玻璃化转变温度,通过求取玻璃化转变温度前后的曲线斜率并作差,可以得到试样的线膨胀系数之差,结果如图7所示。从图7可以看出,随着冷热循环次数的增加,试样自由体积不断增大,且在10次冷热循环后便出现了大幅增加,在冷热循环后期,试样自由体积的增幅逐渐减缓。结合SEM的结果可知,在高温热老化和高低温应力的作用下,分子链断裂,界面逐渐脱离,试样内产生微裂纹和孔洞,进而导致自由体积增大。
常温下,环氧复合绝缘处于玻璃态,材料的极化主要由电子位移极化和界面极化组成。环氧复合绝缘中含有大量微米Al2O3,引入了大量的有机-无机界面。空间电荷容易在界面处积累,进而导致界面极化作用增强,使得环氧复合绝缘的介电常数增大[23-25]。而在冷热循环过程中,结合试样的介电常数结果和SEM图像可以判断,由于基体与填料界面处不断地拉伸与压缩,界面逐渐受损,填料逐渐脱离,界面结合程度逐渐变差,其极化过程减弱,从而导致介电常数降低,产生的松弛损耗更少。同时,试样内自由体积增大,分子链段完成极化转向的空间增大,损耗进一步降低[26-28]。因此,tanδ首先出现一定程度下降。随着冷热循环次数的增加,在高温热老化以及高低温应力作用下,分子链段逐渐断裂,产生了大量游离的小分子,进而参与到极化过程中,损耗增加。因此,在冷热循环后期,相对介电常数降幅逐渐减缓,而损耗则有所增大。
(1)在经过750 h的冷热循环后,复合绝缘试样的交流击穿场强降低了15.2%,深陷阱密度下降了41%。浅陷阱密度呈现上下波动的趋势,介电常数逐渐降低,tanδ先大幅降低后小幅增大。
(2)在冷热循环过程中,试样持续承受高温热老化以及高低温应力的作用。在高温的作用下,交联网络逐渐劣化,分子链逐渐断裂。在高低温交变应力的作用下,环氧基体与微米Al2O3不同的热膨胀系数使得有机-无机界面处于不断的拉伸和压缩状态,界面结合程度逐渐减弱。因此,在多次冷热循环后,有机-无机界面逐渐脱离,试样内产生了大量的微裂纹和孔洞,自由体积不断增大,进而导致介电常数和交流击穿场强降低。
  • 国家电网公司科技项目(5500-202311526A-3-2-ZN)
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2024年第57卷第8期
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doi: 10.16790/j.cnki.1009-9239.im.2024.08.013
  • 接收时间:2023-07-28
  • 首发时间:2025-12-24
  • 出版时间:2024-08-20
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  • 收稿日期:2023-07-28
  • 修回日期:2023-09-25
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国家电网公司科技项目(5500-202311526A-3-2-ZN)
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    国网北京市电力公司电力科学研究院,北京 100192
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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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