Article(id=1209928460164788351, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1209928452547933122, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2024.06.009, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1688486400000, receivedDateStr=2023-07-05, revisedDate=1694707200000, revisedDateStr=2023-09-15, acceptedDate=null, acceptedDateStr=null, onlineDate=1766399024287, onlineDateStr=2025-12-22, pubDate=1718812800000, pubDateStr=2024-06-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1766399024287, onlineIssueDateStr=2025-12-22, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1766399024287, creator=13701087609, updateTime=1766399024287, updator=13701087609, issue=Issue{id=1209928452547933122, tenantId=1146029695717560320, journalId=1149653034449285133, year='2024', volume='57', issue='6', pageStart='1', pageEnd='120', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1766399022471, creator=13701087609, updateTime=1766563931405, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1210620130816561673, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1209928452547933122, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1210620130816561674, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1209928452547933122, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=54, endPage=62, ext={EN=ArticleExt(id=1209928460462583954, articleId=1209928460164788351, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Study on ageing characteristics of FRP/RPUF interface of composite insulation cross-arm with water intrusion, columnId=1190369198472794288, journalTitle=Insulating Materials, columnName=Insulation Technology, runingTitle=null, highlight=null, articleAbstract=

In order to investigate the ageing characteristics of the FRP/RPUF interface of composite insulation cross-arm under the effect of water intrusion, FRP/RPUF interface specimens were prepared, and water intrusion and destruction process in the FRP/RPUF interface was accelerated by hygrothermal ageing method. According to the test results of water absorption, shear strength, and leakage current, the ageing characteristics of the FRP/RPUF interface under water intrusion were obtained by combining with SEM, FTIR, and TGA. The results show that water intrusion can cause moisture plasticisation of the interface, reduce the shear strength and increase the leakage current, while that destructive effects decrease with the dissipation of water; hydrolytic reaction of FRP/RPUF interface material undergoes under the effect of water, leading to the generation of local defects and the increase of impurity ions, which further destroys the mechanical and electrical properties of the interface.

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为研究水分侵入下复合绝缘横FRP/RPUF界面的老化特性,制备了FRP/RPUF界面试样,采用湿热老化方法加速水分在FRP/RPUF界面中的侵入与破坏进程;通过吸水率、剪切强度及泄漏电流测试结果,结合SEM、FTIR和TGA等表征技术,分析水分侵入下担FRP/RPUF界面的老化特性。结果表明:水分侵入会使FRP/RPUF界面受潮塑化,并使界面剪切强度降低、泄漏电流增大,但上述破坏作用会随着水分散失而减弱;水分还会使FRP/RPUF界面材料发生水解反应,造成局部缺陷,同时使杂质离子增多,进一步破坏界面的力学性能与电气性能。

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谢军(1988-),男(汉族),江苏江都人,副教授,主要从事先进电工绝缘装备及其运行特性的研究。
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颜猛(1997-),男(汉族),山东济宁人,硕士生,主要从事先进电工绝缘装备及其运行特性的研究。

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颜猛(1997-),男(汉族),山东济宁人,硕士生,主要从事先进电工绝缘装备及其运行特性的研究。

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颜猛(1997-),男(汉族),山东济宁人,硕士生,主要从事先进电工绝缘装备及其运行特性的研究。

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材料FRP测试电极FRP/RPUF界面测试电极RPUF测试电极
FRP15×615×1
RPUF15×115×6
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FRP15×615×1
RPUF15×115×6
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吸收峰波数/cm-1归属
3 350-OH的伸缩振动
2 910-CH3、-CH2-中的伸展振动
1 720氨基甲酸酯和其他酯中的C=O 吸收峰
1 606苯环中的C=C骨架伸展振动
1 520氨基甲酸酯结构中N-H伸缩振动
1 221酯基中的C-O伸缩振动吸收峰
1 077脂肪族中的C-O-C吸收峰
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主要吸收峰及其对应官能团

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吸收峰波数/cm-1归属
3 350-OH的伸缩振动
2 910-CH3、-CH2-中的伸展振动
1 720氨基甲酸酯和其他酯中的C=O 吸收峰
1 606苯环中的C=C骨架伸展振动
1 520氨基甲酸酯结构中N-H伸缩振动
1 221酯基中的C-O伸缩振动吸收峰
1 077脂肪族中的C-O-C吸收峰
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水分侵入下复合绝缘横担FRP/RPUF界面的老化特性研究
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颜猛 1 , 李敏 2 , 张思刚 3 , 周哲 1 , 张宇鹏 1 , 谢军 1
绝缘材料 | 绝缘技术 2024,57(6): 54-62
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绝缘材料 | 绝缘技术 2024, 57(6): 54-62
水分侵入下复合绝缘横担FRP/RPUF界面的老化特性研究
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颜猛1, 李敏2, 张思刚3, 周哲1, 张宇鹏1, 谢军1
作者信息
  • 1华北电力大学 新能源电力系统国家重点实验室,河北 保定 071003
  • 2国网保定供电公司, 河北 保定 071066
  • 3国网兰州供电公司,甘肃 兰州 730050
  • 颜猛(1997-),男(汉族),山东济宁人,硕士生,主要从事先进电工绝缘装备及其运行特性的研究。

通讯作者:

谢军(1988-),男(汉族),江苏江都人,副教授,主要从事先进电工绝缘装备及其运行特性的研究。
Study on ageing characteristics of FRP/RPUF interface of composite insulation cross-arm with water intrusion
Meng YAN1, Min LI2, Sigang ZHANG3, Zhe ZHOU1, Yupeng ZHANG1, Jun XIE1
Affiliations
  • 1State Key Laboratory of Alternate Electrical Power System with Renewable Energy Sources, North China Electric Power University, Baoding 071003, China
  • 2State Grid Baoding Power Supply Company, Baoding 071066, China
  • 3State Grid Lanzhou Power Supply Company, Lanzhou 730050, China
出版时间: 2024-06-20 doi: 10.16790/j.cnki.1009-9239.im.2024.06.009
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为研究水分侵入下复合绝缘横FRP/RPUF界面的老化特性,制备了FRP/RPUF界面试样,采用湿热老化方法加速水分在FRP/RPUF界面中的侵入与破坏进程;通过吸水率、剪切强度及泄漏电流测试结果,结合SEM、FTIR和TGA等表征技术,分析水分侵入下担FRP/RPUF界面的老化特性。结果表明:水分侵入会使FRP/RPUF界面受潮塑化,并使界面剪切强度降低、泄漏电流增大,但上述破坏作用会随着水分散失而减弱;水分还会使FRP/RPUF界面材料发生水解反应,造成局部缺陷,同时使杂质离子增多,进一步破坏界面的力学性能与电气性能。

复合绝缘横担  /  水分侵入  /  FRP/RPUF界面  /  老化特性

In order to investigate the ageing characteristics of the FRP/RPUF interface of composite insulation cross-arm under the effect of water intrusion, FRP/RPUF interface specimens were prepared, and water intrusion and destruction process in the FRP/RPUF interface was accelerated by hygrothermal ageing method. According to the test results of water absorption, shear strength, and leakage current, the ageing characteristics of the FRP/RPUF interface under water intrusion were obtained by combining with SEM, FTIR, and TGA. The results show that water intrusion can cause moisture plasticisation of the interface, reduce the shear strength and increase the leakage current, while that destructive effects decrease with the dissipation of water; hydrolytic reaction of FRP/RPUF interface material undergoes under the effect of water, leading to the generation of local defects and the increase of impurity ions, which further destroys the mechanical and electrical properties of the interface.

composite cross-arm  /  moisture instrusion  /  FRP/RPUF interface  /  ageing characteristics
颜猛, 李敏, 张思刚, 周哲, 张宇鹏, 谢军. 水分侵入下复合绝缘横担FRP/RPUF界面的老化特性研究. 绝缘材料, 2024 , 57 (6) : 54 -62 . DOI: 10.16790/j.cnki.1009-9239.im.2024.06.009
Meng YAN, Min LI, Sigang ZHANG, Zhe ZHOU, Yupeng ZHANG, Jun XIE. Study on ageing characteristics of FRP/RPUF interface of composite insulation cross-arm with water intrusion[J]. Insulating Materials, 2024 , 57 (6) : 54 -62 . DOI: 10.16790/j.cnki.1009-9239.im.2024.06.009
随着复合材料生产工艺的发展,以高性能纤维增强复合材料(fiber reinforced polymer,FRP)为基础制造复合绝缘横担替代传统钢制横担已成为可能。相比传统钢制横担,复合绝缘横担凭借着优良的经济性和安全性、机械强度高、质量轻等优点得到了快速推广,并应用至超、特高压工程中[1-3]
复合绝缘横担基本结构同复合绝缘子类似,其FRP芯棒外部加装硅橡胶伞裙以增大爬电距离。相比于复合绝缘子,复合绝缘横担一般呈水平布置,且荷载较大,为提高经济效益,保证机械强度,复合绝缘横担FRP芯棒多采用宽径空心结构。为防止FRP芯棒内壁因湿气侵入等原因发生闪络,一般在FRP芯棒内填充SF6、N2等干燥气体,但该方式易发生气体泄漏,且检测维护难度较大[4-5]。为此,可在FRP芯棒内部填充硬质聚氨酯泡沫(rigid polyurethane foam,RPUF)[6-7],构成聚氨酯填充型复合绝缘横担。故相较于复合绝缘子,复合绝缘横担除具有FRP/硅橡胶护套外,还具有FRP/RPUF界面[7],界面结构如图1所示。
界面处物理化学性能相对较差,是复合绝缘结构中的薄弱环节[8-9]。界面处常因电场畸变引起局部放电,甚至造成界面击穿等严重事故,威胁复合绝缘设备的运行安全[10-12]。对于复合绝缘横担,增加的FRP/RPUF界面及RPUF生产过程中可能出现的发泡不均匀等[13]现象使界面问题变得更加复杂。
目前,针对复合绝缘横担FRP/RPUF界面老化的研究相对较少,多数研究主要集中在复合绝缘子的FRP/硅橡胶界面上。其中,CHENG Li等[14]通过水煮实验发现了FRP/硅橡胶界面的粘结等级与界面泄漏电流存在对应关系。段明明等[15]运用GB/T 177—1989中的压剪强度试验方法评估了复合绝缘子FRP/硅橡胶界面的力学性能,并证明压剪试验可以准确地反映界面老化程度。聂章翔等[16]分析了FRP/硅橡胶界面的水煮老化特性,并提出泄漏电流的变化可以有效地表征界面的老化程度。杨昌建等[17]通过水煮老化实验,使用傅里叶红外光谱、热失重等分析方法,发现水分侵入绝缘子芯棒与金具压接界面后会影响界面的摩擦力和配位键。这些研究为界面老化问题提供了一定的理论基础。
复合绝缘横担运行时间尚短,相关研究尚处于起步阶段,因复合绝缘横担的基本结构与复合绝缘子类似,故借鉴复合绝缘子的相关研究结论,可有效保障FRP/硅橡胶护套等传统界面的性能。然而近年来却多次出现FRP/RPUF界面失效事故:2013年,昆明特高压基地出现复合横担因内绝缘击穿导致线路失压事故;亦有多条超、特高压线路因复合横担内绝缘局部缺陷,未通过淋雨冲击实验。经分析,水分侵入是界面故障发生的重要原因[18-19]。但水分侵入下FRP/RPUF界面的老化机理尚未明确,给复合绝缘横担安全运行带来极大隐患。
此针对上述问题,本文通过湿热老化实验加速水分在FRP/RPUF界面的侵入及破坏进程,通过对界面材料的吸水率、界面力学性能、界面电气性能及界面材料微观理化测试结果,分析水分侵入下复合绝缘横担FRP/RPUF界面老化特性,并研究FRP/RPUF界面老化机理。
本文制备了FRP/RPUF界面试样,其中FRP是型号为3240的电工绝缘环氧玻璃纤维板材,其规格为100 mm×100 mm×10 mm,板材表面含有厚度约为2 mm的环氧树脂层,下层为环氧玻璃纤维交织结构,板材特性与实际工程应用中复合绝缘横担纤维增强复合绝缘FRP近似,符合实验材质要求且便于试样制作。RPUF为双组分组合料,其中A组分为以二苯基甲烷二异氰酸酯(MDI)为基体的混合物(亨斯迈(5005));B组分为组合多元醇及助剂混合物(型号为HYW1018-2,河北聚久复合材料有限公司)。采用人工浇注成型发泡工艺,在实验室制备FRP/RPUF界面试样,制备流程如图2所示。制备前使用超声波清洗机清洗FRP板并烘干。同时按照 1∶1的质量比称取RPUF的A、B组分备用。为保证FRP/RPUF界面具有较好的粘接性能,将FRP板在电热鼓风干燥箱中加热至40℃,同时采用水浴加热锅将称量好的A、B组分料预热至25℃。RPUF的制备采用人工一步法浇注成型发泡工艺,将上述称量好且预热好的A、B组分料混合,采用高速电动搅拌器搅拌30 s,至混合料发白、膨胀时迅速倒入固定有FRP的模具中,等待其填满模具,封装模具同时放入电热鼓风烘箱中,在80℃下固化8 h。固化结束后,待其自然降温冷却后,将模具拆除,得到整块的FRP/RPUF界面试样。最终切割后的FRP/RPUF界面试样尺寸为15 mm×10 mm×16 mm,FRP和RPUF的厚度为8 mm,尺寸误差为0.5 mm。
基于湿热老化实验实现水分加速侵入及破坏。可采用水煮法实现湿热老化,水煮时温度设置为100℃。由文献[20]可知,材料此时不会因高温发生分解。在水浴锅中进行实验,使用的水为去离子水,实验时定期换水及加水,以保证电导率稳定。湿热老化时间分别为0、12、60、108、156、204、252 h。
为分析吸水率变化特性,制备了单一的FRP和RPUF试样,尺寸分别与FRP/RPUF界面试样中对应部分一致,并对其进行湿热老化实验,加速水分的侵入进程。对经不同湿热老化时间的试样,采用称重法分析界面材料的吸水率。测试时,首先对试样进行干燥处理,并记录原始质量,然后进行湿热老化实验。老化至规定时间后取出试样,擦去表面水分并称重。各组测试包含5个试样,吸水率取平均值。
复合绝缘横担FRP/RPUF界面为双层介质粘结合界面,通过剪切强度测试可直观分析界面结合强度,进而表征界面力学性能[15]。参考文献[21]设计了FRP/RPUF界面剪切测试夹具,其基本结构如图3所示。
测试时,利用上述夹具固定试样,并对试样FRP端施加与界面表面平行载荷,直至RPUF和FRP分离。采用万能试验机(BOS-100KNM型,厦门搏仕检测设备有限公司)施加载荷,其最大载荷为100 kN。载荷施加方式为位移控制方式,载荷加载速率设为2 mm/min[22]。实验过程中记录最大载荷,采用最大载荷除以界面面积即为试样界面的剪切强度。
研究表明,界面泄漏电流可有效反映复合绝缘子FRP/硅橡胶界面的电气性能[17-20]。故本文根据FRP/RPUF界面试样的结构特点,搭建了四电极电流测试平台,在避免表面电流对测试结果影响的同时,实现同步且独立地对通过FRP/RPUF界面、FRP和RPUF的电流进行测试。四电极结构示意图及电流测试回路如图4所示,其中电极材质为黄铜。
图4可知,FRP/RPUF界面测试电极除与界面部分接触外,还与FRP材料与RPUF材料接触,故该电极测得的电流除包含通过界面处的电流,还有部分通过FRP和RPUF的电流。因此,需根据测试电极与各材料间的接触面积对通过FRP/RPUF界面处的电流进行换算[23],FRP及RPUF材料与各测试电极间的接触面积如表1所示。
具体的换算关系如式(1)所示。
ib'=ib-16ia+16ic
式(1)中:iaibic分别为通过FRP、FRP/RPUF界面和RPUF测试电极的电流;ib'为经换算后通过界面的实际电流。
采用扫描电子显微镜(SEM,Quanta 250 FEG型,FEI)观测不同老化程度的FRP/RPUF界面试样微观形貌变化特性。
采用傅里叶红外光谱仪(FTIR,NICOLET-IN10型)对经过压剪分离后的FRP/RPUF界面进行FTIR测试,分析不同老化程度FRP/RPUF界面试样分子化学键结构及活性基团的变化规律,测试时波数范围为4 000~600 cm-1
采用热重分析仪(PerkinElmer-STA6000型)对FRP和RPUF材料进行热失重分析(TGA),实验温度范围为50~650℃,升温速率设定为20℃/min。
对试样共进行252 h的湿热老化实验,实验过程中试样吸水率变化规律如图5所示。从图5可以看出,随着湿热老化时间的增加,FRP试样的吸水率先快速上升,然后在湿热老化90 h时趋于饱和,最终稳定在1.09%左右;RPUF试样的吸水率逐渐增大,且至湿热老化252 h未见明显饱和现象。
综上,在同一湿热老化时间下,RPUF材料的吸水率远高于FRP材料,表明水分更易经过RPUF侵入FRP/RPUF界面。
为分析剪切强度变化特性,对湿热老化不同时间的FRP/RPUF界面试样进行剪切强度测试。考虑到实验结果分散性,各湿热老化时间下包含10个界面试样,对每个试样在相同条件下进行压剪测试并求其平均值。不同湿热老化时间下FRP/RPUF界面剪切强度测试结果如图6所示。从图6可以看出,随着湿热老化时间的增加,FRP/RPUF界面平均剪切强度逐渐下降,在湿热老化252 h后,界面平均剪切强度为109.69 N/cm2,较未老化时166.16 N/cm2降低了33.98%,表明水分侵入会严重影响FRP/RPUF界面的力学性能。这可归因为水分对界面的塑化和水解作用。
为进一步分析水分侵入对界面的破坏作用,采用干燥箱对经不同湿热老化时间的试样进行烘干处理,以去除界面处水分对剪切强度的影响。经烘干后,剪切强度结果如图7所示。
对比图67可以看出,水分烘干后,各组试样的平均剪切强度均有所提升,但仍低于未湿热老化的样品。水分侵入FRP、RPUF等高分子聚合物中,会使高分子聚合物基体产生溶胀和塑化作用,进而使得基体内分子结构间距和自由体积增大,导致界面材料软化增塑,影响界面力学性能,使得界面剪切强度降低。但塑化作用是物理破坏作用,当水分消失之后,塑化作用的效果减弱,因此FRP/RPUF界面力学性能有所恢复。但即使水分完全烘干,界面的力学性能也难以完全恢复,这表明水分侵入会使FRP/RPUF界面产生不可逆转的破坏作用。
综上,水分侵入FRP/RPUF界面后会影响界面力学性能,并使界面剪切强度逐渐降低。
对湿热老化至规定时间的试样进行电流测试,测结果如图8所示。从图8可以看出,未老化试样的电流基本稳定,无明显的吸收现象。对试样进行湿热老化后,通过FRP材料、RPUF材料和FRP/RPUF界面的电流均出现吸收现象,即包含极化电流。且随着湿热老化时间的增加,吸收现象越明显。这可能是由于水在电场的作用下发生了偶极子转向极化,且随着湿热老化时间的增加,试样含水量增多,松弛极化程度加深。而对于未湿热老化的试样,其内部松弛极化较微弱,故电流无明显吸收现象。
当极化电流衰减完毕时(加压时间为600 s), 电流基本稳定,此时的电流可认为是泄漏电流。 从图8可以看出,随着湿热老化时间的增加,通过FRP/RPUF界面的泄漏电流逐渐增大,且通过FRP、RPUF的泄漏电流也呈上述规律。这是因为水分侵入后,材料的电导率增大,导致泄漏电流值逐渐增大。
为进一步分析泄漏电流增大的原因,对各试样进行干燥处理,并测量干燥后通过FRP材料、RPUF材料和FRP/RPUF界面的电流,结果如图9所示。从图9可以看出,电流基本保持稳定,仅FRP材料老化252 h时的电流出现上升趋势。出线该现象的原因是FRP试样在干燥后,试样内部的水分几乎完全散失,在进行电流测试时,试样水分的散失已经进入到一个稳定、缓慢的状态,水分散失不再对泄漏电流的变化造成巨大影响。但是,试样长时间处于加压状态,使试样发热温度升高,从而导致电流上升[16]
综合图89可知,水分干燥后,各试样的吸收现象均明显减弱,且泄漏电流值也明显减小。但与未湿热老化的试样相比,经湿热老化处理并将水分烘干后,通过各部分的电流仍存在一定的吸收现象。对该现象可做如下解释:对试样烘干后,水分散失使得偶极子转向极化减弱,进而使得电流的吸收现象减弱。但水分侵入界面后,会使FRP/RPUF界面和材料内部产生局部缺陷,进而引起空间电荷极化,空间电荷极化是慢极化,所以测得电流也会有一定的吸收现象,但这种吸收现象不如偶极子转向极化(水分存在时)明显。
图10为湿热老化过程中,各试样烘干前后泄漏电流变化结果。从图10可以看出,经湿热老化后即使水分完全烘干,通过各部分的泄漏电流也随着湿热老化时间的增加而增大。这表明,经湿热老化后泄漏电流增大的原因除了吸湿受潮使得电导率增大外,还有其他原因。
综上,水分侵入FRP/RPUF界面后会影响界面电气性能,并使界面泄漏电流逐渐增大。
图11为不同湿热老化时长下FRP/RPUF界面的SEM测试结果。从图11可以看出,未老化试样FRP/RPUF界面处粘接紧密;RPUF内部泡孔孔壁基本光滑,没有明显坍塌现象;FRP切面平整、质地紧密,无纤维裸露和粉化现象。当湿热老化60 h时,FRP/RPUF界面处有轻微裂纹出现;RPFU部分泡孔坍塌,泡孔部分断裂;FRP中玻璃纤维及环氧树脂贴合度下降。当湿热老化108 h时,FRP/RPUF界面处裂纹进一步扩大;RPFU泡孔坍塌数量增多;FRP切面部分粗糙化、质地松散。当湿热老化204 h时,FRP/RPUF界面处开始出现脱粘现象;RPFU泡孔坍塌严重,泡孔壁整体断裂;FRP切面粗糙程度加深。当湿热老化252 h时,FRP/FPUF界面出现严重脱粘现象;RPUF泡孔结构遭到严重破坏,出现明显破损和坍塌现象,且相邻泡孔发生贯通现象;FRP切面变得粗糙,粉化严重且玻璃纤维出现裸露现象。
综上,水分侵入界面后,会导致RPFU部分的泡孔坍塌和断裂,使得FRP中的玻璃纤维和环氧树脂贴合度下降,同时在FRP/RPUF界面处会出现轻微裂纹。这些缺陷导致界面的力学性能下降,剪切强度降低。随着湿热老化程度的加深,RPFU中的泡孔会遭到更严重的破坏,FRP中的环氧树脂会出现孔洞,并且纤维逐渐裸露,而界面处会出现严重的脱粘现象,甚至可能形成长缝样的缺陷。上述变化导致界面的力学性能严重下降,剪切强度进一步降低。由于这些缺陷是不可逆的,即使将湿热老化后的FRP/RPUF界面试样完全烘干,其界面力学性能也难以完全恢复,这与2.2节中实验结果一致。
此外,界面处及界面材料中出现的局部缺陷易产生空间电荷极化,使固体材料电导性能提高,这也解释了2.3节中对湿热老化试样烘干处理后电流变化的原因。
为进一步分析水分侵入对界面材料的破坏作用,对FRP/RPUF界面处进行了FTIR测试,结果如图12所示,其中主要吸收峰及其对应官能团如表2所示。从图12可以看出,湿热老化后,材料界面处在波数为1 720、1 520、1 221、1 077 cm-1的吸收峰高度均出现下降。这些变化归因于界面处RPUF中的氨基甲酸酯和其他酯基的水解,导致这些基团对应的吸收峰高度下降。而在3 350 cm-1和2 910 cm-1处的吸收峰高度上升,其归因于上述基团水解产生-COOH和-OH,使得-OH浓度增加,从而对应特征峰(3 350 cm-1)高度增加。此外,水解反应会导致聚合物的大分子链断裂,比如在C=O、C-O或C-O-C等化学键处断裂,使形成的化合物带有-CH3或-CH2-,从而造成其对应波数2 910 cm-1处的吸收峰高度增加。
综上,水分侵入后,水分会使FRP/RPUF界面材料发生水解反应。水解反应使得RPUF材料中的氨基甲酸酯和其他酯基分解、大分子链断裂,进而导致RPUF材料中泡孔坍塌、孔壁断裂,产生局部缺陷。水解反应还会使FRP材料中的环氧树脂基体分解,使环氧树脂基体内部产生孔洞,并影响环氧树脂与玻璃纤维包裹紧密程度。在上述水解作用下,FRP/RPUF界面力学性能下降。而水解反应不可逆,因此即使将试样完全烘干,其界面力学性能也难以完全恢复,这与2.2节中实验结果一致。
此外,水解除产生局部缺陷外,还会导致界面杂质离子增多,又进一步提高了界面的电导性能。最终,在界面及材料内部的局部缺陷及杂质离子的共同作用下,界面及材料的电导增大,泄漏电流增大。故FRP/RPUF界面经湿热老化后即使水分完全烘干,泄漏电流仍增大。
图13为各试样RPUF、FRP材料的热失重分析结果。由图13可知,相较于未湿热老化试样,湿热老化后试样中RPUF、FRP材料的残留率均高于未老化试样。从图13(a)RPUF材料的热重分析结果可以看出,各样品均在200~300℃迅速分解,且经湿热老化后的试样残留率高于未老化试样。分析可知,RPUF达到热分解温度时,首先是氨基甲酸酯基团C-O键断裂,并分解成多元醇及异氰酸酯,在高温下上述分解物形成小分子气体逸出,并最终残留碳和大分子组合物[18]。而由前文分析结果可知,水分侵入后RPUF材料中的氨基甲酸酯和酯基等主要大分子基团发生水解,从而使RPUF剩余质量分数增加,故TGA测试结果最终残留率增大。TGA测试结果进一步表明,RPUF材料在水分作用下氨基甲酸酯基团分解。
从图13(b)FRP试样的热失重曲线可以看出,在100~300℃,未老化试样发生的热失重主要是由于材料内自由水的挥发,而湿热老化试样的热失重主要是侵入FRP试样的水分蒸发造成的。对于所有试样在300~650℃温度范围内发生的热失重,因为玻璃纤维在850℃以下不发生分解[24],所以主要是环氧树脂基体分解导致的,剩余质量为玻璃纤维的质量。试样的玻璃纤维质量分数均在83%左右,热失重过程中分解的主要部分为环氧树脂,其占比在17%左右。对比不同湿热老化时间试样的热失重曲线可知,未湿热老化的试样残留率最低,说明相同质量下,未老化试样环氧树脂相对含量最大,湿热老化试样的环氧树脂相对含量有所下降。该结果表明水分侵入FRP/RPUF界面后,界面处会发生环氧树脂分解。而湿热老化252 h试样的环氧树脂相对含量最低,说明环氧树脂分解最为严重。即表明,随着湿热老化时间的增加,FRP材料内环氧树脂分解程度增大。
综上,TGA结果表明,水分侵入FRP/RPUF界面后,会使界面处RPUF材料大分子基团断裂、FRP材料中环氧树脂基体分解,最终破坏FRP/RPUF界面性能,使剪切强度下降、泄漏电流增加。
SEM、FTIR和TGA测试结果表明,水分侵入FRP/RPUF界面后,导致界面性能下降的主要原因是水解作用使界面处大分子链断裂和小分子逸出。FRP/RPUF界面老化机理如图14所示。
完好的FRP/RPUF界面是依靠两种材料分子之间的吸附力粘接形成的。当水分侵入FRP/RPUF界面后,其塑化作用使得基体内分子结构间距和自由体积增大,导致界面材料软化增塑,影响界面力学性能,使界面的剪切强度降低。此外,水分侵入后还会发生水解作用。水解反应会使RPUF材料的酯基和大分子链分解,进而导致泡孔坍塌和孔壁断裂,形成缺陷[23]。对于FRP材料,水解反应会使环氧树脂基体分解,产生孔洞,并影响与玻璃纤维的紧密结合。在塑化和水解作用的共同作用下,FRP/RPUF界面力学性能下降,界面剪切强度降低。
由于水解作用使得材料分解,在界面产生极性基团,这些基团在电场中容易产生热激发载流子。增加了界面处的载流子密度,提高了界面电导率,并增加了界面泄漏电流。同时,水具有强极性,其本身的电离会释放大量的载流子。此外,界面中存在的杂质和游离小分子也会为界面提供额外的载流子。因此,水分子的强极性特性以及与界面材料的水解反应共同作用,对界面电气性能的劣化过程起着重要的影响。
(1)相同条件下,RPUF的吸水率远高于FRP,水分更易通过RPUF侵入FRP/RPUF界面,水分侵入后会使界面材料受潮并塑化,进而导致界面力学性能下降。当水分消失后,塑化作用的效果减弱,FRP/RPUF界面力学性能有所恢复。
(2)水分侵入后,FRP/RPUF界面材料会发生水解,使RPUF中的酯基分解、大分子链断裂,FRP中环氧树脂基体分解;在水解作用下,界面材料内部产生泡孔坍塌、纤维裸露等现象,使界面处局部脱粘、杂质离子数目增多。
(3)水分侵入后,材料受潮、塑化作用及水解反应等因素会共同影响FRP/RPUF界面力学及电气性能,并使FRP/RPUF界面剪切强度降低、泄漏电流增大。
  • 国家自然科学基金资助项目(52007065)
  • 中央高校基本科研业务费专项资金资助项目(2022MS071)
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2024年第57卷第6期
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doi: 10.16790/j.cnki.1009-9239.im.2024.06.009
  • 接收时间:2023-07-05
  • 首发时间:2025-12-22
  • 出版时间:2024-06-20
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  • 收稿日期:2023-07-05
  • 修回日期:2023-09-15
基金
国家自然科学基金资助项目(52007065)
中央高校基本科研业务费专项资金资助项目(2022MS071)
作者信息
    1华北电力大学 新能源电力系统国家重点实验室,河北 保定 071003
    2国网保定供电公司, 河北 保定 071066
    3国网兰州供电公司,甘肃 兰州 730050

通讯作者:

谢军(1988-),男(汉族),江苏江都人,副教授,主要从事先进电工绝缘装备及其运行特性的研究。
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https://castjournals.cast.org.cn/joweb/jycl/CN/10.16790/j.cnki.1009-9239.im.2024.06.009
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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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