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In order to improve the cracking resistance of the encapsulating insulating material for dry-type air-core reactor, it is necessary to improve the toughness of the epoxy resin composite while ensuring the good electrical properties. In this paper, an epoxy glass fiber composite with good mechanical and electrical properties was obtained by adding different content of epoxy-terminated liquid nitrile butadiene rubber (ETBN), different content and partical size of Al2O3 powders to the epoxy glass fiber (EP/GF) composite, and its structure and morphology, mechanical and electrical properties were tested. The results show that when the mass fraction of ETBN, 5 μm Al2O3, and 100 nm Al2O3 is 10%, 30%, and 3%, respectively, the bending strength of the EP/GF composite reaches the highest of 291.0 MPa, which increases by 33.5% than that of the unmodified composite, and the electric strength is 24.3 kV/mm, the comprehensive properties are the best.

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为了提高干式空心电抗器包封绝缘材料的抗开裂性能,需要在保证环氧复合材料良好电气性能的同时提高其韧性。本文通过向环氧玻璃纤维(EP/GF)复合材料中加入不同含量的端环氧基液体丁腈橡胶(ETBN)、不同含量和不同粒径的Al2O3粉体,得到一种兼顾良好力学性能和电气性能的环氧玻璃纤维复合材料,并对其结构形貌、力学性能和电学性能进行测试。结果表明:当添加质量分数为10%的ETBN、质量分数为30%的5 μm Al2O3和质量分数为3%的100 nm Al2O3时,复合材料的弯曲强度最高达到291.0 MPa,比未添加填料时提升了33.5%,电气强度为24.3 kV/mm,此时EP/GF复合材料综合性能最优。

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张健(1981-),男(汉族),黑龙江哈尔滨人,教授级高级工程师,主要从事电力设备状态监测及故障诊断的研究。

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张健(1981-),男(汉族),黑龙江哈尔滨人,教授级高级工程师,主要从事电力设备状态监测及故障诊断的研究。

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张健(1981-),男(汉族),黑龙江哈尔滨人,教授级高级工程师,主要从事电力设备状态监测及故障诊断的研究。

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Keyword(id=1218111627409408182, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210560432360780160, language=CN, orderNo=2, keyword=玻璃纤维), Keyword(id=1218111627518460089, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210560432360780160, language=CN, orderNo=3, keyword=改性), Keyword(id=1218111627669455033, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210560432360780160, language=CN, orderNo=4, keyword=力学性能)], refs=[Reference(id=1218111631301722389, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210560432360780160, doi=null, pmid=null, pmcid=null, year=2019, volume=null, issue=null, pageStart=null, pageEnd=null, url=null, language=null, rfNumber=[1], rfOrder=0, authorNames=聂洪岩, journalName=null, refType=null, unstructuredReference=聂洪岩.过电压下干式空心电抗器匝间绝缘失效机理研究[D].哈尔滨:哈尔滨工业大学,2019., articleTitle=过电压下干式空心电抗器匝间绝缘失效机理研究, refAbstract=null), Reference(id=1218111631398191386, 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干式空心电抗器用环氧玻璃纤维复合材料协同增韧改性及性能研究
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张健 1 , 刘贺千 1 , 朱勇行 2 , 李中原 1 , 杨洪达 1 , 赵春明 3
绝缘材料 | 材料研究 2024,57(7): 43-50
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绝缘材料 | 材料研究 2024, 57(7): 43-50
干式空心电抗器用环氧玻璃纤维复合材料协同增韧改性及性能研究
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张健1, 刘贺千1, 朱勇行2, 李中原1, 杨洪达1, 赵春明3
作者信息
  • 1国网黑龙江省电力有限公司电力科学研究院,黑龙江 哈尔滨 150030
  • 2哈尔滨理工大学 工程电介质及其应用教育部重点实验室,黑龙江 哈尔滨 150080
  • 3国网吉林省电力有限公司电力科学研究院,吉林 长春 130021
  • 张健(1981-),男(汉族),黑龙江哈尔滨人,教授级高级工程师,主要从事电力设备状态监测及故障诊断的研究。

Study on synergistic toughening modification and performance of epoxy glass fiber composite materials for dry-type air-core reactor
Jian ZHANG1, Heqian LIU1, Yonghang ZHU2, Zhongyuan LI1, Hongda YANG1, Chunming ZHAO3
Affiliations
  • 1State Grid Heilongjiang Electric Power Company Limited Electric Power Research Institute, Harbin 150030, China
  • 2Key Laboratory of Engineering Dielectrics and Its Application, Ministry of Education, Harbin University of Science and Technology, Harbin 150080, China
  • 3State Grid Jilin Electric Power Company Limited Electric Power Research Institute, Changchun 130021, China
出版时间: 2024-07-20 doi: 10.16790/j.cnki.1009-9239.im.2024.07.006
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为了提高干式空心电抗器包封绝缘材料的抗开裂性能,需要在保证环氧复合材料良好电气性能的同时提高其韧性。本文通过向环氧玻璃纤维(EP/GF)复合材料中加入不同含量的端环氧基液体丁腈橡胶(ETBN)、不同含量和不同粒径的Al2O3粉体,得到一种兼顾良好力学性能和电气性能的环氧玻璃纤维复合材料,并对其结构形貌、力学性能和电学性能进行测试。结果表明:当添加质量分数为10%的ETBN、质量分数为30%的5 μm Al2O3和质量分数为3%的100 nm Al2O3时,复合材料的弯曲强度最高达到291.0 MPa,比未添加填料时提升了33.5%,电气强度为24.3 kV/mm,此时EP/GF复合材料综合性能最优。

环氧树脂  /  玻璃纤维  /  改性  /  力学性能

In order to improve the cracking resistance of the encapsulating insulating material for dry-type air-core reactor, it is necessary to improve the toughness of the epoxy resin composite while ensuring the good electrical properties. In this paper, an epoxy glass fiber composite with good mechanical and electrical properties was obtained by adding different content of epoxy-terminated liquid nitrile butadiene rubber (ETBN), different content and partical size of Al2O3 powders to the epoxy glass fiber (EP/GF) composite, and its structure and morphology, mechanical and electrical properties were tested. The results show that when the mass fraction of ETBN, 5 μm Al2O3, and 100 nm Al2O3 is 10%, 30%, and 3%, respectively, the bending strength of the EP/GF composite reaches the highest of 291.0 MPa, which increases by 33.5% than that of the unmodified composite, and the electric strength is 24.3 kV/mm, the comprehensive properties are the best.

epoxy resin  /  glass fiber  /  modified  /  mechanical property
张健, 刘贺千, 朱勇行, 李中原, 杨洪达, 赵春明. 干式空心电抗器用环氧玻璃纤维复合材料协同增韧改性及性能研究. 绝缘材料, 2024 , 57 (7) : 43 -50 . DOI: 10.16790/j.cnki.1009-9239.im.2024.07.006
Jian ZHANG, Heqian LIU, Yonghang ZHU, Zhongyuan LI, Hongda YANG, Chunming ZHAO. Study on synergistic toughening modification and performance of epoxy glass fiber composite materials for dry-type air-core reactor[J]. Insulating Materials, 2024 , 57 (7) : 43 -50 . DOI: 10.16790/j.cnki.1009-9239.im.2024.07.006
近年来,随着经济快速发展,城乡居民用电量逐年提升,对电网的供电可靠性要求也越来越高。干式空心电抗器作为一种使用率极高的电感器件,在电力系统中起着无功补偿、限制短路电流、抑制高次谐波的重要作用[1],对保证电力供应的安全可靠性具有重要意义。目前我国电网中电力设备服役年限普遍较长,干式空心电抗器长时间运行经常会发生一些故障[2]。经过调查,干式空心电抗器发生故障的主要原因有:生产制造工艺的缺陷、匝间短路故障、包封绝缘开裂等[3-4],其中,由于干式空心电抗器长期暴露在外界环境中,因包封绝缘开裂、受潮、过热等引起的故障占比较高,根本原因是绝缘材料受到损坏[5-6]
干式空心电抗器绕包绝缘使用的环氧树脂浸渍玻璃纤维复合材料是通过特殊工艺热压固化成型,具有较好的力学性能和绝缘性能[7]。然而干式空心电抗器在运行过程中,长期受到热应力、机械应力、电应力等多因素联合作用,容易导致包封绝缘材料开裂失效,进而影响匝间绝缘,对设备安全可靠运行造成影响,所以绝缘材料的抗开裂性能极大程度影响着干式空心电抗器的使用寿命。因此需要对环氧/玻璃纤维(EP/GF)复合材料进行改性研究,提升包封绝缘复合材料的抗开裂能力。
近年来,国内外较多学者对环氧/玻璃纤维(EP/GF)复合材料开展了改性研究。谢志鹏[8]将羧甲基-β-环糊精和端羧基液体丁腈橡胶加入到环氧树脂中形成三元复合材料,结果表明增加羧甲基-β-环糊精含量能有效提高复合材料的热稳定性,但是会导致复合材料的弯曲模量下降。胡光凯等[9]将端氨基液体丁腈橡胶加入到环氧树脂中,发现当端氨基液体丁腈橡胶质量分数为20%时,复合材料的综合力学性能较纯环氧树脂体系有所提高,这是因为胶体粒子融入环氧树脂基体中,引入了深陷阱,改善了固化物的力学性能。王聪等[10]以纳米黏土改性环氧树脂与固化剂混合胶液为基体,以三维正交机织玻璃纤维物为增强体,制备了性能更优异的EP/GF复合材料,结果表明当黏土的质量分数为1%时,复合材料的弯曲强度有较大提升。曾强等[11]采用液晶增韧改性环氧树脂,研究发现当液晶与环氧树脂的质量比为3∶100时,复合材料的弯曲强度提高了87%,同时再掺杂适量的Al2O3时,复合材料的介电常数提升了2.5倍。M A TARAWNEH等[12]制备了壁碳纳米管(MWCNTs)增强橡胶增韧的环氧树脂,将其与传统橡胶增韧的环氧树脂进行力学性能对比测试,结果表明在添加质量分数为1%的MWCNTs后,复合材料的弯曲模量提高了125%,弯曲强度提高了20%。M T RIAZ等[13]用表面改性过的SiO2纳米颗粒改性环氧树脂,结果表明SiO2能引入深陷阱,进而改善复合材料的电学性能。G J WITHERS等[14]利用纳米黏土改性EP/GF复合材料,并对改性后的复合材料进行力学性能测试,发现改性后复合材料的拉伸强度提高了11.7%。
上述关于EP/GF复合材料的改性研究更多的关注于单一性能的提升,而干式空心电抗器包封绝缘的EP/GF复合材料要求具有较好的弯曲强度,并且保证良好的电气性能。基于此,本文采用端环氧基丁腈橡胶(ETBN)与微纳米Al2O3共掺的形式对EP/GF复合材料进行协同改性,制备多元改性的EP/GF复合材料,以期在有效提升复合材料弯曲强度的同时保证其仍具有良好的绝缘性能,实现干式空心电抗器包封绝缘整体性能的提升,并延长使用寿命。
环氧树脂(EP):型号为E51,工业级,国都化工(昆山)有限公司;无碱玻璃纤维布(GF):型号为7628,工业级,河间市中驰嘉业材料有限公司;端环氧基丁腈橡胶(ETBN),工业级,靖江市通高化工有限公司;促进剂:2,4-二甲基咪唑,分析纯,江苏源邦化工有限公司;固化剂:双氰胺,分析纯,上海麦克林生化科技有限公司;稀释剂:N,N-二甲基甲酰胺(DMF),工业级,山东千祥化工有限公司;Al2O3粉体,粒径分别为1、5、10 μm和100 nm,比斯利新材料(苏州)有限公司。
胶液制备:将固化剂、促进剂分别按质量分数3%、1%加入到一定质量的环氧树脂中,在混合物中加入适量的DMF使其溶解,配置成胶液,将胶液装入三口瓶用磁力搅拌器以恒温恒转速(温度为60℃,转速为1 000 r/min)搅拌2 h后取出;将裁剪好的玻璃纤维布(尺寸为16 cm×16 cm)浸渍在配好的胶液中,放入80℃真空烘箱中进行抽真空处理,排泡30 min,取出晾晒10 min后待用。
预固化:将浸渍有胶液的玻璃纤维布晾晒至不悬挂胶液,之后放入160℃的鼓风烘箱中预固化 90 s,得到预固化层压板。
热压成型:将预固化层压板叠放在一起(8层为1组),用钢板压紧固定,并在钢板上喷涂脱模剂,再放入平板硫化机中先在160℃下预热30 min,之后加压至8 MPa热压3 h,制备得到厚度为1 mm未改性的EP/GF复合材料,图1为试样制备流程图。
再次制备:第1步,在原有胶液配比基础上加入质量分数分别为10%、20%、30%、40%、50%的ETBN,根据测试结果选出力学性能最好的一组;第2步,在第1步最优改性方案基础上再加入质量分数分别为10%、20%、30%、40%、50%,粒径分别为1、5、10 μm的Al2O3粉体,选出力学性能最好的一组;第3步,在第2步最优改性方案基础上再加入质量分数分别为1%、3%、5%粒径为100 nm的Al2O3粉体,制备出多组待测EP/GF复合材料。
红外光谱(FTIR)测试采用德国布鲁克公司生产的Bruker-EQUINOX 55型红外光谱仪,使用反射模式,测试波长为500~4 000 cm-1
扫描电镜(SEM)测试采用日本日立高新技术公司生产的SU8020型电镜,测试前先将待测试样放入液氮中20 min进行脆断处理,之后贴于导电胶上,再将试样断面进行喷金处理。
弯曲强度测试采用深圳市新三思材料检测有限公司生产的CMT5205型万能试验机,按照GB/T 2571—1995要求进行测试,试样尺寸为100 mm×20 mm×1 mm。
电气强度采用桂林电器科学研究院有限公司公司生产的HT-5/20型击穿测试系统,使用圆柱形电极进行测试,测试环境为室温、油浴,升压方式为逐级升压,试样尺寸为40 mm×40 mm×1 mm,每种试样各测试10次,击穿电压取Weibull分布失效概率为63.2%的特征失效电压。
图2为EP/GF复合材料弯曲强度随ETBN含量的变化规律。从图2可以看出,随着ETBN含量的增加,EP/GF复合材料的弯曲强度呈现先上升后下降的趋势,纯EP/GF复合材料的弯曲强度为217.9 MPa,当添加的ETBN质量分数为10%时,复合材料的弯曲强度最大,达到了239.0 MPa,此时复合材料的韧性最好,相比未添加ETBN的EP/GF复合材料弯曲强度提升了9.7%。这一现象可以用“孔洞剪切屈服”理论解释[15]:当加入适量ETBN后,ETBN颗粒的空化会在EP分子的柔性区域引入大量的空隙,空隙受到外力作用时会发生形变,起到缓冲作用[16]。此时,ETBN颗粒所在位置形成了剪切屈服,当受到外力作用时,集中的外力会发散到ETBN颗粒所在位置的周围基体上,使环氧基体在受到外力作用时可以形成更多的形变缓冲区域,可以提高EP/GF复合材料的韧性,并且在ETBN质量分数为10%时提升效果最优;当ETBN含量更高时,复合材料内部分子链段交联密度降低,剪切屈服强度降低,导致其韧性下降。
为了保证EP/GF复合材料优异的力学性能,需要进一步掺杂Al2O3微米颗粒。本研究在固定质量分数为10%的ETBN基础上,再添加不同含量、不同粒径的微米Al2O3构成多元网络,从而起到协同增韧的效果。图3为在质量分数为10%的ETBN基础上添加不同含量、不同粒径微米Al2O3的EP/GF复合材料的弯曲强度。从图3可以看出,随着粒径为1、5、10 μm的Al2O3含量的增加,EP/GF复合材料的弯曲强度都呈先上升后下降的趋势,其中填充质量分数为30%的5 μm Al2O3时,EP/GF复合材料的弯曲强度最大,韧性最好。
图4为在质量分数为10%的ETBN及质量分数为30% 5 μm Al2O3基础上添加不同含量粒径为100 nm Al2O3的EP/GF复合材料的弯曲强度。从图4可以看出,当掺杂少量100 nm Al2O3时,EP/GF复合材料的弯曲强度变化不大,这是由于纳米粒子主要是改善复合材料的电气性能,对其力学性能的影响不大。当添加质量分数为3%的100 nm Al2O3时,EP/GF复合材料的弯曲强度为291.0 MPa,比纯EP/GF复合材料提升了33.5%。
微米Al2O3作为一种无机填料,能填补引入ETBN颗粒形成的空隙,并且作为应力的集中点,在受到外力时,可诱发周围环氧树脂基体的屈服形变,吸收外力产生的能量,从而起到缓冲作用,阻挡裂纹的延伸[17];并且微米Al2O3颗粒比表面积大,表面活性点位多,容易发生交联,进一步增加了微粒与环氧树脂基体的接触面积,在受到外力作用时,吸收能量,抑制裂纹延伸,这种作用在5 μm Al2O3质量分数为30%时最显著。
图5为EP/GF复合材料在不同改性阶段时的红外光谱图。从图5可以看出,改性最后波数为914 cm-1附近的环氧基特征峰基本消失,说明EP中的环氧基团基本全部打开并参与固化反应;加入ETBN后,波数为3 500 cm-1附近EP中羟基的宽吸收峰消失,进一步说明ETBN作为胶黏剂已经固化完全。波数为3 358 cm-1附近为EP分子中苯环被取代的吸收峰,说明ETBN的加入引入了少量酚基在苯环上,而苯环的吸收峰较弱,可能是因为ETBN的分子链与EP分子链存在纠缠作用,包裹着苯环。波数为3 187 cm-1处为-NH2特征吸收峰;波数为2 237cm-1附近的-C≡N吸收峰变弱,主要有两方面原因:一方面是因为-C≡N含量少,另一方面可能是因为-C≡N参与固化反应,修饰结合物的网络结构所致。综上所述,ETBN、微纳米Al2O3的引入不只是简单的物理共混,还存在有机化合物之间的化学反应。通过对比4种试样的红外光谱可知,改性后EP/GF复合材料化学结构的改变,是因为ETBN与EP发生化学反应。
为了更好地解释添加ETBN和Al2O3对EP/GF复合材料力学性能的影响,对不同改性阶段的EP/GF复合材料断面进行SEM测试,结果如图6所示。
图6(a)可以看出,纯EP/GF复合材料的断面整齐,裸露着较多的玻璃纤维束,表面均匀附着少量环氧树脂小颗粒。从图6(b)(d)可以看出,当添加质量分数为10%的ETBN、质量分数为30%的5 μm Al2O3、质量分数为3%的100 nm Al2O3后,复合材料表面原本裸露的玻璃纤维束紧密粘合在一起,这是改性后EP/GF复合材料弯曲性能提升的重要原因。ETBN和Al2O3作为填料,一方面能和环氧树脂分子形成较多的海岛结构,受外力作用时能发散外力,起到缓冲作用;另一方面ETBN和Al2O3颗粒作为“黏合剂”,在环氧玻璃纤维体系中共同形成立体式交叉互联的网络结构,能够填补玻璃纤维束与束之间的缝隙,提高界面结合力,界面由脆性结构转变为韧性结构,使EP/GF复合材料的韧性增强。
对不同改性阶段的EP/GF复合材料进行电气强度测试,结果如图711所示。从图7可以看出,随着ETBN掺杂量的增加,EP/GF复合材料的电气强度逐渐下降,当ETBN质量分数超过10%时,EP/GF复合材料的电气强度下降速率变快。未掺杂ETBN时,环氧分子固化后具有较多的刚性基团,可以阻止载流子的移动,抑制产生二次载流子,电气强度较高。随着ETBN含量增加,电气强度逐渐降低,这是由于ETBN柔性长链分子质量比环氧分子质量大,会引入大量分子质量较大的自由体,减少环氧分子中的刚性基团,增加载流子产生概率,进而产生二次载流子,出现类似于雪崩的现象,降低了复合材料的电气强度[18]。为了保证复合材料的电气性能,并且根据ETBN质量分数为10%时复合材料的弯曲性能最优,选择ETBN质量分数为10%。
在EP/GF复合材料中添加质量分数为10%的ETBN基础上,再添加粒径分别为1、5、10 μm的 Al2O3并测试复合材料的电气强度。从图810可以看出,随着不同粒径的微米Al2O3掺杂量的增加,复合材料的电气强度逐渐降低,这是因为大量掺杂微米Al2O3虽然能大幅提升材料的力学性能,但同时也会引入较多的缺陷,并且可能造成团聚现象的发生,导致电气强度降低。
为了使改性后EP/GF复合材料仍具有较好的电气性能,在EP/GF复合材料中添加质量分数为10%的ETBN、质量分数为30%的5 μm Al2O3基础上再添加100 nm的Al2O3粉体并测试复合材料的电气强度。从图11可以看出,随着100 nm Al2O3掺杂量的增加,EP/GF复合材料的电气强度先升高后降低,当添加质量分数为3%的100 nm Al2O3时,EP/GF复合材料的电气强度最好,此时EP/GF复合材料的电气强度为24.3 kV/mm。这是因为掺杂少量纳米Al2O3时,Al2O3纳米颗粒会在环氧基体中引入深陷阱,捕获电荷,束缚电荷运功,使得电荷难以热激发,同时能够降低载流子的迁移率,抑制电荷流动,提升EP/GF复合材料的电气强度[19-21]。同时,填料含量增加会提升各物质间的界面结合强度,少量纳米Al2O3的引入会在EP/GF复合材料内部产生少许小型通道,当施加电压时,有助于电荷的消散,提升复合材料的击穿电压。随着Al2O3掺杂量的增加,一方面,电荷通道间互相重叠,提升了载流子的含量[22-24];另一方面,Al2O3掺杂过多容易发生团聚现象,对电荷的束缚能力降低,使得EP/GF复合材料的电气强度下降。
(1)在EP/GF复合材料中协同掺杂ETBN和微米Al2O3填料时,随着ETBN、微米Al2O3含量的增加,EP/GF复合材料的弯曲强度呈现先上升后下降的趋势,这一现象可以用“孔洞剪切屈服”理论解释;并且微米Al2O3填料的粒径大小对EP/GF复合材料的弯曲强度也有影响。
(2)在EP/GF复合材料中掺杂少量的100 nm Al2O3能够改善复合材料的电气性能,这是因为100 nm Al2O3粒径小,会在EP基体中引入深陷阱,束缚电荷运动,降低载流子的迁移率,抑制电荷移动,提升EP/GF复合材料的电气强度。
(3)当添加质量分数为10%的ETBN、质量分数为30%的5 μm Al2O3和质量分数为3%的100 nm Al2O3时,EP/GF复合材料的综合性能最优,此时电气强度为24.3 kV/mm,弯曲强度最高达到291.0 MPa,比未添加填料时提升了33.5%。
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2024年第57卷第7期
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doi: 10.16790/j.cnki.1009-9239.im.2024.07.006
  • 接收时间:2023-07-23
  • 首发时间:2025-12-24
  • 出版时间:2024-07-20
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  • 收稿日期:2023-07-23
  • 修回日期:2023-09-07
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国家电网有限公司总部科技项目(5108-202218280A-2-338-XG)
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    1国网黑龙江省电力有限公司电力科学研究院,黑龙江 哈尔滨 150030
    2哈尔滨理工大学 工程电介质及其应用教育部重点实验室,黑龙江 哈尔滨 150080
    3国网吉林省电力有限公司电力科学研究院,吉林 长春 130021
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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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