Article(id=1193230672056778968, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1193230615618220608, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2025.02.013, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1705420800000, receivedDateStr=2024-01-17, revisedDate=1711468800000, revisedDateStr=2024-03-27, acceptedDate=null, acceptedDateStr=null, onlineDate=1762417961372, onlineDateStr=2025-11-06, pubDate=1739980800000, pubDateStr=2025-02-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1762417961372, onlineIssueDateStr=2025-11-06, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1762417961371, creator=13701087609, updateTime=1762417961371, updator=13701087609, issue=Issue{id=1193230615618220608, tenantId=1146029695717560320, journalId=1149653034449285133, year='2025', volume='58', issue='2', pageStart='1', pageEnd='138', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1762417947916, creator=13701087609, updateTime=1762418457365, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1193232752444145866, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1193230615618220608, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1193232752444145867, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1193230615618220608, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=92, endPage=101, ext={EN=ArticleExt(id=1193230672266494170, articleId=1193230672056778968, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Effect of thermal-cooling cycling on electrical properties of epoxy resin, columnId=1192878364340924664, journalTitle=Insulating Materials, columnName=Test and Analysis, runingTitle=null, highlight=

The influence mechanism of thermal-cooling cycling times and temperature change rate on the electrical properties of epoxy resin were studied using a linear rising and cooling method. The results show that as the cycle times increases, the DC electric strength and volume resistivity of epoxy resin increase at first and then decrease, and this trend slightly increases in early cycles with the increase of temperature change rate, but decreases significantly in later cycles. The analysis indicates that thermal and cold alternating environment will promote the dynamic adjustment of chain segments in epoxy resin, making its structure more compact and regular. Although thermal expansion and cold contraction may cause micro-cracks appear on the surface of epoxy resin during early cycles, dynamic adjustment plays a dominant role, which leads to the improvment of electrical properties of epoxy resin. However, with the increase of cycle times, long-term thermal expansion and cold contraction intensifies the fracture of molecular chain segments and the expansion of micro-crack, resulting in the decrease of electrical properties of epoxy resin. With the increase of temperature change rates, the internal chain segment in epoxy resin cannot be fully adjusted, and the impact of temperature stress increases, which lead the epoxy resin more prone to deterioration.

, articleAbstract=

The influence mechanism of thermal-cooling cycling times and temperature change rate on the electrical properties of epoxy resin were studied using a linear rising and cooling method. The results show that as the cycle times increases, the DC electric strength and volume resistivity of epoxy resin increase at first and then decrease, and this trend slightly increases in early cycles with the increase of temperature change rate, but decreases significantly in later cycles. The analysis indicates that thermal and cold alternating environment will promote the dynamic adjustment of chain segments in epoxy resin, making its structure more compact and regular. Although thermal expansion and cold contraction may cause micro-cracks appear on the surface of epoxy resin during early cycles, dynamic adjustment plays a dominant role, which leads to the improvment of electrical properties of epoxy resin. However, with the increase of cycle times, long-term thermal expansion and cold contraction intensifies the fracture of molecular chain segments and the expansion of micro-crack, resulting in the decrease of electrical properties of epoxy resin. With the increase of temperature change rates, the internal chain segment in epoxy resin cannot be fully adjusted, and the impact of temperature stress increases, which lead the epoxy resin more prone to deterioration.

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本文采用线性升降温的方式,探究冷热循环次数和变温速率对环氧树脂电气性能的影响机制。结果表明:随着循环次数的增加,环氧树脂的直流电气强度和体积电阻率均呈先上升后下降的趋势,且这种趋势随着变温速率的增大在循环前期上升幅度较小,而在循环后期下降幅度较为显著。分析认为,冷热交替环境会促进环氧树脂内部链段动态调整,使其结构更致密规整。尽管在循环前期,热胀冷缩作用会使环氧树脂表面出现少量微裂纹,但链段动态调整占主导作用,此时环氧树脂电气性能得到提升,而随着循环次数增加,长期热胀冷缩作用加剧了分子链段的断裂,微裂纹扩展,使环氧树脂电气性能逐渐下降。随着变温速率的增大,环氧树脂内部链段无法充分调整,且所受温度应力冲击增大,环氧树脂更容易发生劣化。

, articleAbstract=

本文采用线性升降温的方式,探究冷热循环次数和变温速率对环氧树脂电气性能的影响机制。结果表明:随着循环次数的增加,环氧树脂的直流电气强度和体积电阻率均呈先上升后下降的趋势,且这种趋势随着变温速率的增大在循环前期上升幅度较小,而在循环后期下降幅度较为显著。分析认为,冷热交替环境会促进环氧树脂内部链段动态调整,使其结构更致密规整。尽管在循环前期,热胀冷缩作用会使环氧树脂表面出现少量微裂纹,但链段动态调整占主导作用,此时环氧树脂电气性能得到提升,而随着循环次数增加,长期热胀冷缩作用加剧了分子链段的断裂,微裂纹扩展,使环氧树脂电气性能逐渐下降。随着变温速率的增大,环氧树脂内部链段无法充分调整,且所受温度应力冲击增大,环氧树脂更容易发生劣化。

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周远翔(1966-),男(汉族),福建莆田人,教授,主要从事高电压技术与绝缘材料的研究。

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周远翔(1966-),男(汉族),福建莆田人,教授,主要从事高电压技术与绝缘材料的研究。

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周远翔(1966-),男(汉族),福建莆田人,教授,主要从事高电压技术与绝缘材料的研究。

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冷热循环对环氧树脂电气性能的影响
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周远翔 1, 2 , 徐景凡 1 , 朱小倩 2 , 刘轩昊 1 , 卢毅 3 , 高岩峰 3
绝缘材料 | 测试与分析 2025,58(2): 92-101
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绝缘材料 | 测试与分析 2025, 58(2): 92-101
冷热循环对环氧树脂电气性能的影响
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周远翔1, 2, 徐景凡1, 朱小倩2, 刘轩昊1, 卢毅3, 高岩峰3
作者信息
  • 1新疆大学 电气工程学院 电力系统及发电设备控制和仿真国家重点实验室风光储分室, 新疆 乌鲁木齐 830047
  • 2清华大学 电机工程与应用电子技术系 电力系统及大型发电设备安全控制和仿真国家重点实验室,北京 100084
  • 3国网冀北电力有限公司电力科学研究院,北京 100045
  • 周远翔(1966-),男(汉族),福建莆田人,教授,主要从事高电压技术与绝缘材料的研究。

Effect of thermal-cooling cycling on electrical properties of epoxy resin
Yuanxiang ZHOU1, 2, Jingfan XU1, Xiaoqian ZHU2, Xuanhao LIU1, Yi LU3, Yanfeng GAO3
Affiliations
  • 1The Wind Solar Storage Division of State Key Laboratory of Control and Simulation of Power System and Generation Equipment, School of Electrical Engineering, Xinjiang University, Urumqi 830047, China
  • 2State Key Laboratory of Control and Simulation of Power Systems and Generation Equipment, Department of Electrical Engineering, Tsinghua University, Beijing 100084, China
  • 3Research Institute of State Grid Jibei Electric Power Co., Ltd., Beijing 100045, China
出版时间: 2025-02-20 doi: 10.16790/j.cnki.1009-9239.im.2025.02.013
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本文采用线性升降温的方式,探究冷热循环次数和变温速率对环氧树脂电气性能的影响机制。结果表明:随着循环次数的增加,环氧树脂的直流电气强度和体积电阻率均呈先上升后下降的趋势,且这种趋势随着变温速率的增大在循环前期上升幅度较小,而在循环后期下降幅度较为显著。分析认为,冷热交替环境会促进环氧树脂内部链段动态调整,使其结构更致密规整。尽管在循环前期,热胀冷缩作用会使环氧树脂表面出现少量微裂纹,但链段动态调整占主导作用,此时环氧树脂电气性能得到提升,而随着循环次数增加,长期热胀冷缩作用加剧了分子链段的断裂,微裂纹扩展,使环氧树脂电气性能逐渐下降。随着变温速率的增大,环氧树脂内部链段无法充分调整,且所受温度应力冲击增大,环氧树脂更容易发生劣化。

冷热循环  /  环氧树脂  /  线性升降温  /  变温速率  /  电气性能

The influence mechanism of thermal-cooling cycling times and temperature change rate on the electrical properties of epoxy resin were studied using a linear rising and cooling method. The results show that as the cycle times increases, the DC electric strength and volume resistivity of epoxy resin increase at first and then decrease, and this trend slightly increases in early cycles with the increase of temperature change rate, but decreases significantly in later cycles. The analysis indicates that thermal and cold alternating environment will promote the dynamic adjustment of chain segments in epoxy resin, making its structure more compact and regular. Although thermal expansion and cold contraction may cause micro-cracks appear on the surface of epoxy resin during early cycles, dynamic adjustment plays a dominant role, which leads to the improvment of electrical properties of epoxy resin. However, with the increase of cycle times, long-term thermal expansion and cold contraction intensifies the fracture of molecular chain segments and the expansion of micro-crack, resulting in the decrease of electrical properties of epoxy resin. With the increase of temperature change rates, the internal chain segment in epoxy resin cannot be fully adjusted, and the impact of temperature stress increases, which lead the epoxy resin more prone to deterioration.

thermal-cooling cycling  /  epoxy resin  /  linear thermal-cooling  /  temperature change rate  /  electrical properties
周远翔, 徐景凡, 朱小倩, 刘轩昊, 卢毅, 高岩峰. 冷热循环对环氧树脂电气性能的影响. 绝缘材料, 2025 , 58 (2) : 92 -101 . DOI: 10.16790/j.cnki.1009-9239.im.2025.02.013
Yuanxiang ZHOU, Jingfan XU, Xiaoqian ZHU, Xuanhao LIU, Yi LU, Yanfeng GAO. Effect of thermal-cooling cycling on electrical properties of epoxy resin[J]. Insulating Materials, 2025 , 58 (2) : 92 -101 . DOI: 10.16790/j.cnki.1009-9239.im.2025.02.013
环氧树脂(EP)作为一种常用的电气绝缘材料,具备优良的电气性能和力学性能,广泛应用于高压直流电缆组合预制式电缆接头、干式变压器、SF6绝缘子等电气设备中[1-2]。我国寒冷地区的极端低温可达到-40℃[3],运行于寒冷地区的高压直流电缆在设备停机、负载需求减少或系统调整等情况下由负载状态转变为空载状态时,其温度会逐渐降低至环境温度。此时,一旦高压直流电缆再次进入负载状态,电缆及其接头又将经受温度的剧烈变化。长期高低温交替的工况会给高压直流电缆环氧绝缘件的安全稳定运行带来新挑战[4]
目前,国内外学者已经开展温度变化对电力设备绝缘影响的研究。金海云等[5]研究发现冷热循环老化会降低室温硫化硅橡胶(RTV)的绝缘性能,主要原因是循环过程中材料的交联网络遭到破坏。王凯琳等[6]研究发现,产生温差时,绝缘子泄漏电流会随时间的推移先增大,直至达到一个新的平衡状态后开始减小,且这种趋势随着温差的增大愈加明显。张静等[7]、王子康等[8-9]研究表明,冷热循环的老化温度及老化时间是电缆接头绝缘界面压力的主要影响因素。在冷热循环过程中,电缆附件绝缘界面压力呈先增大后减小的趋势,其原因是硅橡胶材料的弛豫特性和带材的迅速失效。
此外,针对冷热循环对环氧树脂及其复合材料电气性能和力学性能的影响也已有一些研究。任银银等[10]研究发现在冷热循环过程中,环氧树脂基碳纤维增强复合材料的拉伸强度呈先降低再升高再降低的变化趋势。CHEN X W等[11]研究发现,在冷热循环过程中环氧树脂的介电常数和介质损耗因数总体上增大,而弯曲性能因后固化先增大,随后由于分子链断裂、树脂基体老化和水解等现象而逐渐减小。
综上所述,关于环氧树脂的研究大多聚焦于冷热循环对环氧树脂及其复合材料力学性能的影响,对电气性能的研究较少,且关于变温速率对其性能影响的研究也非常缺乏。因此,本研究对环氧树脂进行冷热循环处理,针对不同循环次数和变温速率下的样品进行电气性能测试,并结合理化性能测试结果,系统性地探究冷热循环对环氧树脂电气性能的影响机制,为进一步优化环氧材料的设计和应用提供理论基础。
本研究树脂基体选用双酚A型环氧树脂E-51,固化剂选用甲基六氢邻苯二甲酸酐,促进剂选用N,N-二甲基苄胺。首先,按照质量比100∶85∶2称取环氧树脂、固化剂和促进剂放入烧杯中,并搅拌30 min使其充分混合。搅拌结束后放入60℃真空干燥箱中真空脱气1 h。随后,将混合物倒入模具中,放入鼓风干燥箱中,在100、120、140、160℃温度下分别固化2 h。最后,将固化完成的样品自然冷却至室温,获得厚度为(200±20)μm的试验样品。
首先,将制备好的环氧树脂样品进行烘干预处理,并对其分组和编号。将样品分批置于紧凑型快速温变高低温试验箱(CTE-SE7506-10LW型)中进行冷热循环试验。由于电缆的运行温度为70℃左右,设置试验箱内温度从室温(20℃)降至-40℃,停留60 min,然后再从-40℃升至70℃,停留60 min,最后从70℃降至室温,完成1个循环周期。在上一周期的最后阶段不进行保温,直接进行下一循环周期试验,冷热循环过程如图1所示。
为了研究不同变温速率对环氧树脂性能的影响,将样品分为4组,采用线性升降温的方式,分别以1、4、7、10℃/min的变温速率进行冷热循环试验。同时,为了探究不同循环次数对样品的影响,本研究选择15、30、45、60次循环后的样品作为研究对象,并将它们分别标记为n15、n30、n45和n60。在后续讨论中,冷热循环前期是指进行了15次和30次冷热循环,而冷热循环后期指是进行了45次和60次冷热循环。
使用Gemini SEM 500型高分辨率蔡司场发射扫描电子显微镜(SEM)观察样品表面的微观形貌,扫描电压为15 kV,观测倍数为20 000倍,样品表面进行喷铂处理。采用VERTEX 70 V型傅里叶变换红外光谱仪(FTIR)对样品进行红外光谱测试,波数为4 500~650 cm-1。使用Q 5000 IR型差示扫描量热仪(DSC)研究样品的热性能,测试温度为30~250℃,升温速率为10℃/min,降温速率为30℃/min,测试环境为氮气。
(1)直流击穿测试:按照GB/T 1408—2016《绝缘材料电气强度试验方法》开展直流击穿测试。测试中使用球-板电极,其中球电极直径为20 mm,板电极直径为25 mm,电极材料为不锈钢。为了防止沿面闪络的发生,测试过程中将试样和球-板电极完全浸没在变压器油中。测试环境为室温,样品厚度为200 μm,升压速率为500 V/s。
(2)空间电荷测试:采用电声脉冲法(PEA)测量空间电荷[12]。外施电场强度为-20 kV/mm,极化时间为40 min,去极化时间为10 min,采样时间间隔为3 s。测试在室温下进行,每组测试3次。
(3)表面电位衰减测试:采用表面电位衰减法(ISPD),通过电晕放电充电的方式在材料表面沉积一定量的电荷,在等温条件下测试绝缘材料表面电位的衰减情况。针电极和栅极分别施加-8 kV和 -3 kV电压,给样品充电10 min,充至表面电位接近 3 kV。充电完成后,将样品移至静电探头下方进行测试,静电探头距离样品2 mm,测试8 h,测试在室温下进行。
(4)体积电阻率测试:根据GB/T 31838—2019《固体绝缘材料介电和电阻特性》,使用三电极法测试试样的电导电流。测试外施电场为25 kV/mm,极化时间为30 min,中心电极半径为10 mm。测试在室温下进行,每组测试3次。测试得到电导电流后根据公式ρ=(IE-1S-1)-1计算环氧树脂的体积电阻率ρ,其中I为电导电流,E为外施电场强度,S为中心电极的面积。
试验过程发现,随着变温速率的增大,样品表面的凹凸变形现象逐渐加剧。选择1℃/min和10℃/min冷热循环处理后样品的表面形貌图作为典型进行对比,如图2所示。从图2可知,未经处理的环氧树脂表面光滑平整,而经冷热循环处理后,样品表面出现两种主要的损伤类型:表面凹凸变形和微裂纹。随着循环次数的增加,样品表面微裂纹逐渐增多且加深。经10℃/min冷热循环处理60次后,环氧树脂样品表面凹凸变形处出现了很深的裂纹。
分析认为,微裂纹的形态、深度和大小主要受循环时间的影响,而表面凹凸变形则主要受变温速率的影响。在高温固化后,环氧树脂内会存在残余应力,冷热循环过程中的热胀冷缩作用也会导致应力的积累。当这两种应力共同作用超过环氧树脂所能承受的应力阈值时,微裂纹就会形成[13]。变温速率增大会进一步加剧样品表面凹凸变形和微裂纹的形成,这可能是因为快速的热胀冷缩导致环氧树脂所受应力增大[14]。随着循环次数的增加,局部凹凸变形加剧,当超过一定值后,凹凸区域将会形成更多且更深的微裂纹。
图3为经过1℃/min和10℃/min冷热循环处理后样品表面的红外光谱图。环氧树脂的红外光谱特征峰主要有:3 450 cm-1处羟基-OH的伸缩振动特征峰,3 000~2 800 cm-1处C-H的伸缩振动特征峰,1 732 cm-1处饱和醛、酮、酸中C=O的伸缩振动特征峰,1 250~1 050 cm-1处芳香醚的R-O对称伸缩振动特征峰,以及1 180~1 045 cm-1处酸酐C-O的开链特征峰。
图3可知,在1 250~1 050 cm-1处的特征峰强度均随循环次数增加呈现先增大后减小的趋势。在进行15次和30次冷热循环后,环氧树脂的后固化反应导致酸酐和环氧树脂发生开环反应,产生更多的C-O,进而导致1 250~1 050 cm-1范围内的特征峰强度增大[15]。随着循环次数的增加,形成的微裂纹和微孔会逐渐渗入氧气,导致环氧树脂主链中的芳香醚结构发生氧化反应,破坏了R-O-Ph结构,使1 250~1 050 cm-1范围内的特征峰强度开始减小。同时,环氧树脂发生氧化分解生成C=O,使得1 732 cm-1处的特征峰强度逐渐增大。值得一提的是,经10℃/min冷热循环处理60次后,由于微孔扩大和微裂纹的严重扩展使更多的氧气能够渗入材料中且分子链中邻苯环碳原子上的C-H键发生断裂,最终使1 250~1 050 cm-1处芳香醚的R-O特征峰和3 000~2 800 cm-1处C-H特征峰的吸收强度明显减小。此外,由于经10℃/min冷热循环处理45~60次后,试样表面会形成较多且深的微裂纹和微孔,在此循环期间的冷却阶段,空气中的水分子会通过裂纹和微孔渗入试样内部,当再次升温时,高温和水分子的共同作用会引发环氧树脂的水解反应,导致经10℃/min冷热循环处理60次后的样品-OH特征峰略微增强[16-17]
玻璃化转变温度是非晶态材料从高弹态转变为玻璃态的临界温度,它取决于材料的交联度、自由体积、分子结构和排列方式等因素[18]。在分子结构方面,玻璃化转变温度主要受相邻交联点的平均链长影响,相邻交联点的平均链长越短,分子越难运动,玻璃化转变温度越高[19]
图4为经1℃/min和10℃/min冷热循环处理后环氧树脂的DSC曲线。
图4可知,随着循环次数的增加,环氧树脂的玻璃化转变温度呈现先上升后下降的趋势。在冷热循环前期,高温使环氧树脂发生热膨胀,分子链间距增大,为聚合链的运动提供足够的空间,而在低温收缩过程中,调整好的分子链被拉回到更紧凑的状态。反复循环能够不断调整链段分布,使得环氧树脂的内部结构变得更加致密规整,同时环氧树脂发生后固化反应,因此在冷热循环前期,环氧树脂的玻璃化转变温度随着循环次数的增加而升高。但随着循环次数的继续增加,冷热循环前期出现的微裂纹和微孔会进一步扩展、表面凹凸变形加剧,并且伴随聚合物分子链断裂等问题,导致环氧树脂玻璃化转变温度降低。此外,较小的变温速率可以给环氧树脂提供更充足的时间,使其内部分子链能够进行更多的微小运动,形成更致密的结构。因此,在冷热循环次数相同的条件下,1℃/min冷热循环处理的样品玻璃化转变温度高于10℃/min冷热循环处理的样品。
在直流电场作用下,当载流子获取足够的能量可以克服电场势垒并穿越材料时[20-21],就会发生直流击穿。图5为冷热循环处理后环氧树脂的直流电气强度折线图。从图5可以看出,经过冷热循环处理的样品在不同变温速率下的直流电气强度均呈先上升后下降的趋势,并在冷热循环30次时达到最大值。未经冷热循环处理的样品直流电气强度为366.6 kV/mm,经1、4、7、10℃/min冷热循环处理30次后,环氧树脂的电气强度分别上升了16.3%、14.3%、13.3%和10.8%。随后,环氧树脂的直流电气强度开始下降,经过60次冷热循环处理后,环氧树脂的直流电气强度分别下降至390.6、373.2、372.2、359.5 kV/mm。
根据自由体积击穿理论,聚合物的电气强度取决于平均自由行程,而平均自由行程与自由体积的大小有关[22]。在冷热循环前期,环氧树脂内部链段调整重排,形成更致密规整的结构,使其自由体积减小。在外施电场的作用下,载流子在自由行程内无法获得足够能量来克服势垒,从而提高了样品的直流电气强度。尽管在冷热循环处理30次之前已经出现微裂纹,但由于材料整体结构仍然紧密排列,冷热循环处理前期样品的直流电气强度仍然高于未经处理的样品。然而,冷热循环达到30次后,随着循环次数的增加,环氧树脂链段断裂使其内部自由体积增大,微裂纹增多并扩展,且表面凹凸变形加剧导致局部场强增大,两者共同作用使载流子在较低的电场下就能获得足够的能量来克服势垒,最终导致直流电气强度逐渐降低。同时,较大的变温速率会导致环氧树脂内部链段调整不充分,微裂纹较多,并且表面凹凸变形更加严重。因此,在较大变温速率冷热循环处理前期,环氧树脂的直流电气强度上升幅度较小,而在冷热循环处理后期下降更为显著。
图6为经10℃/min冷热循环处理后环氧树脂的空间电荷分布。由图6可知,未经处理的环氧树脂样品在极化过程中有同极性电荷注入。经过冷热循环处理的样品空间电荷积聚量呈先减小后增大的趋势。这是因为冷热循环处理能改善试样内部链段分布,使其结构缺陷减少,陷阱密度降低,从而导致空间电荷积聚量减小。然而,随着冷热循环的进行,微裂纹的增多和扩展、分子链的断裂反应以及化学降解的发生,引入了更多的陷阱,导致冷热循环后期样品内部空间电荷积聚量增大。
去极化过程可以更直观地反映环氧树脂内部的空间电荷积聚量和陷阱的分布。图7为不同变温速率下冷热循环处理60次样品去极化过程中空间电荷积聚量随时间变化的曲线。由图7可知,冷热循环60次后,随着变温速率的增大,环氧树脂内空间电荷积聚量增多。这是由于在冷热循环后期,环氧树脂出现微裂纹、分子链断裂等缺陷,引入了更多能够捕获载流子的陷阱,进而使空间电荷更容易积聚[23]。此外,随着变温速率的增大,环氧树脂与氧气和水分子的反应加剧,劣化程度增加,同样引入了更多的陷阱。
为了研究冷热循环处理后聚合物内部陷阱的分布特性,可通过ISPD法推导计算出陷阱能级(ET)和陷阱密度(Ntrap),计算公式如式(1)~(3)所示[24]
ET=kBTln(νATEt)
Qs(t)=tε0εrqeLdϕs(t)dt
Ntrap=-Qs(t)2df(ET)δ(ET, t)
式(1)~(3)中:kB为玻尔曼兹常数;νATE为逃逸频率,取值为1012T为绝对温度;Qs(t)为电荷密度;ε0为真空介电常数;εr为相对介电常数;ϕs(t)为试样表面电位;qe为电子电荷量;L为试样厚度;f为费米狄拉克分布函数;δ为狄拉克函数。
图8为冷热循环处理后环氧树脂的陷阱密度能级分布曲线,所有曲线均有2个峰,分别代表浅陷阱中心和深陷阱中心。
图8可以看出,未经冷热循环处理的样品可能由于内部结构缺陷的原因存在大量浅陷阱[25]。随着冷热循环次数的增加,环氧树脂的浅陷阱密度呈先减小后增大的趋势,且随着变温速率的增大,冷热循环前期浅陷阱密度减小幅度较小,而循环后期增幅较大。分析认为,冷热循环前期,链段调整改善了试样内部结构,减少了结构缺陷,使环氧树脂浅陷阱密度减小[26]。随着冷热循环次数的增加,试样表面微裂纹扩展、表面凹凸变形更加严重,并伴随分子链的断裂[27],因此60次冷热循环处理后样品中浅陷阱密度增大。而较快的变温速率使链段调整不充分,且表面劣化更严重,因此,较快变温速率冷热循环处理的环氧树脂浅陷阱密度在循环前期减小幅度较小,循环后期增幅更较大。
图9为冷热循环处理后环氧树脂的体积电阻率折线图。
图9可知,随着冷热循环次数的增加,环氧树脂的体积电阻率呈现先上升后下降的趋势。同时,随着变温速率的增大,体积电阻率在冷热循环前期提升幅度较小,而在冷热循环后期下降的幅度较大。未经处理的环氧树脂体积电阻率为5.10×1015 Ω·m。在1、4、7、10℃/min变温速率下,经过30次冷热循环处理后,样品的体积电阻率分别上升至1.10×1016、1.07×1016、9.81×1015、8.95×1015 Ω·m,随后开始下降,经60次冷热循环处理后,体积电阻率分别下降至6.61×1015、6.31×1015、6.15×1015、4.87×1015 Ω·m。
聚合物材料的体积电阻率可表示为ρ=(n·q·μ-1,其中n表示载流子的浓度,q表示载流子的带电量,μ表示载流子的迁移率[28]。通常在载流子类型不变的情况下,电导率的大小主要取决于载流子的迁移率和浓度。载流子的浓度主要受杂质和添加剂的影响,而载流子的迁移率则与自由体积相关[29]。在冷热循环前期,具有较高交联度和更致密结构的环氧树脂自由体积较小,对电荷的束缚能力更强,导致载流子的迁移率降低,从而使得体积电阻率升高[30-31]。随着冷热循环进行至30次以后,环氧树脂内部链段断裂,自由体积增大,对载流子的束缚能力减弱,体积电阻率逐渐降低。此外,在冷热循环前期,较小的变温速率使聚合物具有更致密规整的结构,因此,随着变温速率减小,环氧树脂的体积电阻率随循环次数增加提升幅度变大。而在冷热循环后期,随着变温速率增大,环氧树脂中的微裂纹增多,自由体积变大,因此体积电阻率随循环次数增加的降低幅度随变温速率的增大而增大。
图10为冷热循环处理过程中环氧树脂的链段动态调整和表面形貌示意图。在冷热循环30次之前,冷热循环处理使环氧树脂高温下松弛的分子链在低温下重新排列,反复循环后其链段紧密排列,且后固化反应使其交联度提高[32]。尽管表面出现了微裂纹和凹凸变形,但裂纹数量较少且变形不严重,因此整体上环氧树脂的性能得到了提升。随着冷热循环次数的增加,环氧树脂分子链在长期热胀冷缩作用下会发生氧化断裂,主要表现为微裂纹扩展、微孔逐渐扩大以及表面凹凸变形,导致环氧树脂的电气性能逐渐下降。此外,微孔和微裂纹也会进一步促进氧气和空气中水分子的渗入。经过10℃/min冷热循环处理60次后,环氧树脂表面严重劣化,甚至发生了水解反应。
冷热循环处理过程中环氧树脂的断键机理如图11所示。由图11可知,环氧树脂的主链发生氧化断裂,使主链上的仲醇氧化为酸,同时在苯环旁的醚基与酯基之间的C-H处也发生氧化反应,断键产生醛、醚等物质[33]。水解反应使较活泼的C-O键发生断裂,可能会生成羟基或酸[34]。此外,较快的变温速率会导致环氧树脂链段的动态调整不充分,并且快速的热胀冷缩更容易促使微裂纹和表面凹凸变形的产生。
通过对冷热循环处理后的环氧树脂微观结构和直流电气性能的研究,总结了冷热循环对环氧树脂电气性能的影响机理,得到主要结论如下:
(1)冷热循环处理使环氧树脂表面出现微裂纹和凹凸变形。随着循环时间的增加,微裂纹逐渐扩展、表面凹凸变形加剧,从而导致环氧树脂绝缘性能劣化。此外,较快的变温速率也会加剧环氧树脂绝缘性能的劣化。
(2)经过冷热循环处理后,随着循环次数的增加,环氧树脂的直流电气强度和体积电阻率呈现先上升后下降的趋势,空间电荷积聚量呈先减小后增大的趋势。
(3)冷热循环处理能够使环氧树脂高温下松弛的分子链在低温下重新排列,形成致密规整的网络结构,从而提升其电气性能。然而,随着冷热循环次数增加,微裂纹扩展和表面凹凸变形加剧,内部分子链断裂,导致环氧树脂电气性能逐渐下降。变温速率越快,对材料的绝缘性能越不利,较快的变温速率会导致链段调整不充分,限制冷热循环前期环氧树脂电气性能的提升。冷热循环后期环氧树脂性能劣化严重是因为快速温度变化产生较大应力,加剧了表面凹凸变形程度。
  • 国家电网有限公司科技项目(5500-202214108A-1-1-ZN)
参考文献 引证文献
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2025年第58卷第2期
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doi: 10.16790/j.cnki.1009-9239.im.2025.02.013
  • 接收时间:2024-01-17
  • 首发时间:2025-11-06
  • 出版时间:2025-02-20
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  • 收稿日期:2024-01-17
  • 修回日期:2024-03-27
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国家电网有限公司科技项目(5500-202214108A-1-1-ZN)
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    1新疆大学 电气工程学院 电力系统及发电设备控制和仿真国家重点实验室风光储分室, 新疆 乌鲁木齐 830047
    2清华大学 电机工程与应用电子技术系 电力系统及大型发电设备安全控制和仿真国家重点实验室,北京 100084
    3国网冀北电力有限公司电力科学研究院,北京 100045
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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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