Article(id=1304921614383080172, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1304921585991836085, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2026.08.006, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1756828800000, receivedDateStr=2025-09-03, revisedDate=1761148800000, revisedDateStr=2025-10-23, acceptedDate=null, acceptedDateStr=null, onlineDate=1789047157139, onlineDateStr=2026-09-10, pubDate=1787155200000, pubDateStr=2026-08-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1789047157139, onlineIssueDateStr=2026-09-10, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1789047157139, creator=13701087609, updateTime=1789047157139, updator=13701087609, issue=Issue{id=1304921585991836085, tenantId=1146029695717560320, journalId=1149653034449285133, year='2026', volume='59', issue='8', pageStart='1', pageEnd='160', issueExtLink='null', onlineDate='null', pubDate='1787155200000', pubDateStr='2026-08-20', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=1, specialIssue=null, createTime=1789047150370, creator='13701087609', updateTime=1789117776362, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1305217812939698326, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1304921585991836085, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1305217812939698327, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1304921585991836085, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=49, endPage=57, ext={EN=ArticleExt(id=1304921614588601069, articleId=1304921614383080172, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Self-healing properties of light-triggered microcapsule composite epoxy resin insulating materials, columnId=1190369066675179686, journalTitle=Insulating Materials, columnName=Material Research, runingTitle=null, highlight=null, articleAbstract=

Epoxy resin is extensively utilized in high-voltage power equipment and electronic encapsulation, but it is prone to microcracks under prolonged multi-field stresses, leading to insulation degradation and even equipment failure. Introducing self-healing microcapsules can effectively solve this problem, however conventional microcapsules have limitations such as strict triggering conditions, requiring external intervention, and the potential to damage the matrix. Therefore, this study designed a non-contact light-triggered microcapsule with urea-formaldehyde resin as the wall material and polyurethane acrylate oligomer as the core material. By embedding TiO2 and SiO2 nanoparticles with an average particle size of 200 nm into the wall material, an ultraviolet shielding layer was constructed, then the microcapsule was uniformly dispersed in the epoxy resin to prepare a composite material to achieve self-healing under natural light. The results show that the microcapsule structure remains intact at 210℃ and its thermal stability is excellent. When the mass fraction of microcapsules is 4%, the electric strength and dielectric performances of the composite materials are basically the same as those of the pure base material, with only a slight increase in tensile strength. After the damaged material is repaired, the recovery rate of tensile strength, electric strength at room temperature and high temperature, as well as volume resistivity all exceed 85%, the repair performance is excellent. This study provides a novel technical pathway to prolong the service life of epoxy resin insulating materials.

, authors=Jiameng Xu1, Wenxu Tang1, Chaolu Niu1, *, Hefei Wang1, 2, Qichang Liu1, Potao Sun1, Wenxia Sima1, authorsList=Jiameng Xu, Wenxu Tang, Chaolu Niu, Hefei Wang, Qichang Liu, Potao Sun, Wenxia Sima, authorCompany=null, correspAuthors=Chaolu Niu, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, fund=null), CN=ArticleExt(id=1304921616849330952, articleId=1304921614383080172, tenantId=1146029695717560320, journalId=1149653034449285133, language=CN, title=光触发微胶囊复合环氧绝缘材料的自修复性能, columnId=1190369066813591720, journalTitle=绝缘材料, columnName=材料研究, runingTitle=null, highlight=null, articleAbstract=

环氧树脂广泛应用于高压电力设备及电子封装,但其在长期多场应力作用下易产生微裂纹,导致绝缘劣化甚至设备故障。引入自修复微胶囊可有效改善此问题,然而传统微胶囊存在触发条件苛刻、需外部干预及可能损害基体等局限。为此,本研究设计一种以脲醛树脂为壁材、聚氨酯丙烯酸酯低聚体为芯材的非接触光触发微胶囊,通过在壁材中嵌入平均粒径为200 nm的TiO2和SiO2纳米颗粒,构建紫外屏蔽层,并将其均匀分散于环氧树脂中制得复合材料,以实现自然光照下的自主修复。结果表明:在210℃下,微胶囊结构完整,热稳定性良好。当微胶囊质量分数为4%时,复合材料的电气强度与介电性能和纯基体材料基本持平,拉伸强度小幅提升。材料受损修复后,其拉伸强度、常温和高温下的电气强度以及体积电阻率的恢复率均超过85%,修复性能良好。本研究为延长环氧树脂绝缘材料寿命提供了新的技术途径。

, authors=徐佳萌1, 唐文旭1, 牛朝露1, *, 王河飞1, 2, 刘奇昌1, 孙魄韬1, 司马文霞1, authorsList=徐佳萌, 唐文旭, 牛朝露, 王河飞, 刘奇昌, 孙魄韬, 司马文霞, authorCompany=null, correspAuthors=牛朝露, authorNote=

徐佳萌(2002-),女(汉族),河北保定人,硕士生,主要从事材料微尺度损伤的检测与抑制等的研究

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牛朝露(1999-),男(汉族),河南鹤壁人,博士生,主要从事材料微尺度损伤缺陷检测与抑制等的研究。
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徐佳萌(2002-),女(汉族),河北保定人,硕士生,主要从事材料微尺度损伤的检测与抑制等的研究

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徐佳萌(2002-),女(汉族),河北保定人,硕士生,主要从事材料微尺度损伤的检测与抑制等的研究

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光触发微胶囊复合环氧绝缘材料的自修复性能
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徐佳萌 1 , 唐文旭 1 , 牛朝露 1, * , 王河飞 1, 2 , 刘奇昌 1 , 孙魄韬 1 , 司马文霞 1
绝缘材料 | 材料研究 2026,59(8): 49-57
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绝缘材料 |材料研究 2026 , 59 (8) : 49 -57
光触发微胶囊复合环氧绝缘材料的自修复性能
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徐佳萌1, 唐文旭1, 牛朝露1, *, 王河飞1, 2, 刘奇昌1, 孙魄韬1, 司马文霞1
作者信息
  • 1重庆大学 电气工程学院,重庆 400044
  • 2国网河南省电力公司电力科学研究院,河南 郑州 450052
通讯作者:
牛朝露(1999-),男(汉族),河南鹤壁人,博士生,主要从事材料微尺度损伤缺陷检测与抑制等的研究。
作者简介:

徐佳萌(2002-),女(汉族),河北保定人,硕士生,主要从事材料微尺度损伤的检测与抑制等的研究

Self-healing properties of light-triggered microcapsule composite epoxy resin insulating materials
Jiameng Xu1, Wenxu Tang1, Chaolu Niu1, *, Hefei Wang1, 2, Qichang Liu1, Potao Sun1, Wenxia Sima1
Affiliations
  • 1School of Electrical Engineering, Chongqing University, Chongqing 400044, China
  • 2Research Institute of Electric Power Science, State Grid Henan Electric Power Company, Zhengzhou 450052, China
出版时间: 2026-08-20 doi: 10.16790/j.cnki.1009-9239.im.2026.08.006
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环氧树脂广泛应用于高压电力设备及电子封装,但其在长期多场应力作用下易产生微裂纹,导致绝缘劣化甚至设备故障。引入自修复微胶囊可有效改善此问题,然而传统微胶囊存在触发条件苛刻、需外部干预及可能损害基体等局限。为此,本研究设计一种以脲醛树脂为壁材、聚氨酯丙烯酸酯低聚体为芯材的非接触光触发微胶囊,通过在壁材中嵌入平均粒径为200 nm的TiO2和SiO2纳米颗粒,构建紫外屏蔽层,并将其均匀分散于环氧树脂中制得复合材料,以实现自然光照下的自主修复。结果表明:在210℃下,微胶囊结构完整,热稳定性良好。当微胶囊质量分数为4%时,复合材料的电气强度与介电性能和纯基体材料基本持平,拉伸强度小幅提升。材料受损修复后,其拉伸强度、常温和高温下的电气强度以及体积电阻率的恢复率均超过85%,修复性能良好。本研究为延长环氧树脂绝缘材料寿命提供了新的技术途径。

环氧树脂  /  自修复  /  自然光触发  /  微胶囊

Epoxy resin is extensively utilized in high-voltage power equipment and electronic encapsulation, but it is prone to microcracks under prolonged multi-field stresses, leading to insulation degradation and even equipment failure. Introducing self-healing microcapsules can effectively solve this problem, however conventional microcapsules have limitations such as strict triggering conditions, requiring external intervention, and the potential to damage the matrix. Therefore, this study designed a non-contact light-triggered microcapsule with urea-formaldehyde resin as the wall material and polyurethane acrylate oligomer as the core material. By embedding TiO2 and SiO2 nanoparticles with an average particle size of 200 nm into the wall material, an ultraviolet shielding layer was constructed, then the microcapsule was uniformly dispersed in the epoxy resin to prepare a composite material to achieve self-healing under natural light. The results show that the microcapsule structure remains intact at 210℃ and its thermal stability is excellent. When the mass fraction of microcapsules is 4%, the electric strength and dielectric performances of the composite materials are basically the same as those of the pure base material, with only a slight increase in tensile strength. After the damaged material is repaired, the recovery rate of tensile strength, electric strength at room temperature and high temperature, as well as volume resistivity all exceed 85%, the repair performance is excellent. This study provides a novel technical pathway to prolong the service life of epoxy resin insulating materials.

epoxy resin  /  self-healing  /  natural light-trigger  /  microcapsules
徐佳萌, 唐文旭, 牛朝露, 王河飞, 刘奇昌, 孙魄韬, 司马文霞. 光触发微胶囊复合环氧绝缘材料的自修复性能. 绝缘材料, 2026 , 59 (8) : 49 -57 . DOI: 10.16790/j.cnki.1009-9239.im.2026.08.006
Jiameng Xu, Wenxu Tang, Chaolu Niu, Hefei Wang, Qichang Liu, Potao Sun, Wenxia Sima. Self-healing properties of light-triggered microcapsule composite epoxy resin insulating materials[J]. Insulating Materials, 2026 , 59 (8) : 49 -57 . DOI: 10.16790/j.cnki.1009-9239.im.2026.08.006
环氧树脂因其优异的绝缘性能广泛应用于电子封装与电力设备绝缘[1-3]。然而,在实际运行中,绝缘材料在温度、电磁及应力等多场耦合下易产生损伤,加剧电场畸变,长期累积可导致绝缘失效,缩短设备寿命[4-5]。传统损伤检测手段难以实现对绝缘早期微损伤的实时监测[6-11],且停机更换或整体修复成本高昂。
受生物体自修复机制的启发,国内外学者致力于通过功能化改性实现绝缘材料自修复。目前自修复技术主要分为本征型以及外援型[9-11]两类体系,其中外援型微胶囊自修复技术因其制备过程对基体性能影响较小且修复效率较高而备受关注[12-13]。然而现有微胶囊体系的修复剂固化过程往往需要苛刻的外部触发条件,包括高温[14-16]、水分[17-18]、酸碱性[19-20]等。其中,高温响应型微胶囊需要外部加热触发,但高温会加速基体材料老化;pH响应型微胶囊则面临所需酸性或碱性的触发条件腐蚀材料等问题。上述修复体系可能对基体材料产生负面影响,限制了微胶囊型自修复复合材料在电力设备绝缘领域的实际工程应用。
针对上述问题,本研究提出一种光响应型微胶囊体系,通过在其外壳嵌入平均粒径约为200 nm的TiO2和SiO2颗粒形成具有紫外屏蔽功能的脲醛树脂结构,可有效保护芯材;芯材为聚氨酯丙烯酸酯低聚体,可在自然光触发下发生固化,实现非接触式修复。采用扫描电子显微镜、红外光谱和热重分析对微胶囊的形貌、化学结构及热稳定性进行系统表征。将不同质量分数的微胶囊掺入环氧树脂中制备复合绝缘材料,研究掺杂浓度对复合材料电气强度、介电性能和力学性能的影响,确定适宜的掺杂浓度并验证其修复性能。
二月桂酸二丁基锡(DBTDL)、甲基丙烯酸羟乙酯(HEMA)、间苯二酚、稀释剂苯乙烯均购自上海麦克林生化科技股份有限公司;三乙醇胺购自国药集团化学试剂有限公司;阿拉伯树胶购自西格玛奥德里奇(上海)贸易有限公司。疏水性TiO2纳米颗粒、双亲性SiO2纳米颗粒均购自达西浓纳米科技(常州)有限公司;异佛尔酮二异氰酸酯(IPDI)、氯化铵、尿素、柠檬酸、甲醛、光引发剂184均购自上海易恩化学技术有限公司;氢氧化钠购自成都市科隆化学品有限公司;去离子水购自苏州威立特环保科技有限公司;环氧树脂(E-51)、甲基六氢邻苯二甲酸酐固化剂(MHHPA)均购自广州市忠高化工有限公司;2,4,6-三(二甲氨基甲基)苯酚购自广东元丰化学科技有限公司。
以脲醛树脂为壁材基体,掺杂疏水性TiO2和双亲性SiO2纳米颗粒对其进行功能化改性,并以含丙烯酰氧基的聚氨酯丙烯酸酯低聚体作为芯材。该芯材可在自然紫外光照射下发生聚合固化,具备光响应特性,且无需额外条件,避免了外部触发条件对基体材料的潜在影响。脲醛树脂壁材经济性好,致密性与韧性优于聚氨酯,能够有效保护芯材并隔绝基体。TiO2纳米颗粒具有亲油疏水性,靠近壁材内侧,对紫外光具有一定的吸收作用[21];双亲性SiO2纳米颗粒靠近壁材外侧,可实现对外部紫外光的反射[22],且能增强外壳的机械强度[23],两种纳米颗粒赋予了微胶囊外壳紫外光屏蔽性能,防止内部修复剂在长期储存过程中提前固化,确保了微胶囊修复性能的长期稳定性。
在DBTDL催化下,控制条件使IPDI的高活性异氰酸酯基团优先与HEMA的羟基反应,生成末端含丙烯酰氧基的预聚物。将22.5 g IPDI与0.04 g DBTDL混合,在55℃和机械搅拌的条件下缓慢滴加12.5 g HEMA,滴加完毕后升温至65℃反应5.5 h;随后加入15 g稀释剂和1.5 g光引发剂184,最终获得光固化型预聚体,制备过程如图1(a)所示。为保障微胶囊在受损时能有效释放修复剂,对预聚体的黏度进行检测。参照GB/T 10247—2008[24]相关要求,在23℃恒温下使用数字式黏度计测定预聚体黏度,量取40 mL预聚体进行测试,重复操作3次后取平均值,最终测得光固化型预聚体的黏度为1 436.32 mPa·s,表明其具有一定的流动性。
使用纯度为99%的尿素与质量分数为38%的甲醛溶液按质量比为45∶100混合。用三乙醇胺调节体系pH至碱性(pH=8.5±0.2),使混合液在温度为60℃、转速为550 r/min条件下反应1.5 h。反应结束自然冷却至25℃后,用柠檬酸将pH调节至中性(pH=7.0±0.2),得到体系性能状态稳定的脲醛树脂预聚体溶液,制备过程如图1(b)所示。
将0.5 g TiO2与0.5 g SiO2纳米颗粒及8 g阿拉伯树胶分散于150 mL去离子水中,加入25 mL聚氨酯丙烯酸酯低聚体作为芯材,将混合溶液在温度为60℃、转速为750 r/min条件下乳化50 min,形成水包油乳液。随后向乳液中加入脲醛树脂预聚体、间苯二酚和氯化铵,用柠檬酸调节pH至4.0~4.5,再在70℃水浴中以300 r/min的转速进行原位缩聚反应,通过羟甲基与氨基的脱水缩合形成交联结构。反应结束后,用浓度为0.1 mol/L的NaOH溶液将体系pH调节至7.0±0.2,继续保温45 min以使壁材充分交联固化。最终产物经去离子水和乙醇洗涤,过滤并真空干燥10 h,得到微胶囊粉末,其制备流程如图1(c)所示。
微胶囊复合环氧绝缘材料制备过程如图2所示。以E51环氧树脂为基体,与甲基六氢邻苯二甲酸酐(MHHPA)及催化剂2,4,6-三(二甲氨基甲基)苯酚按质量比为100∶85∶2混合,将混合物在温度为50℃、转速为450 r/min条件下机械搅拌30 min后,分别加入不同质量分数(0%、2%、4%、6%、8%)的微胶囊,继续搅拌30 min使其均匀混合。经真空脱泡1 h后,注入预置于加热台的金属模具中(尺寸为20 mm×20 mm×1 mm),按照固化程序95℃/3 h+110℃/3 h完成固化。固化后冷却至室温进行脱模、清洗,制得不同微胶囊掺杂浓度的复合环氧绝缘材料。
采用高分辨扫描电子显微镜(SEM,TM-4000 Plus型)观测微胶囊表面形貌;通过傅里叶变换红外光谱仪(FTIR,Nicolet iS50型)对微胶囊进行特征峰分析;利用同步热分析仪(TG-DSC,TA SDT Q600型)检测微胶囊的热稳定性;通过宽频介电谱仪(Novocontrol concept 80型)分析复合环氧绝缘材料的介电性能;采用万能拉力试验机(ZQ-990A型)对复合环氧绝缘材料进行拉伸实验,测试其力学性能。
采用高分辨扫描电子显微镜(SEM)观察微胶囊的微观形貌,结果如图3所示。从图3可以看出,微胶囊表面包覆的脲醛树脂层具有粗糙的组织特征,主要表现为局部突起和凹陷,显著提高了微胶囊的比表面积,有利于增强其与环氧树脂基材的界面相互作用[25]。粒度分析结果如图4所示,从图中可以看出微胶囊的粒径分布符合宽分布正态分布规律,平均粒径为180.20 μm,标准差为45.67 μm(方差为2 085.75 μm2),约70%颗粒粒径集中在135~225 μm范围内,整体呈显著集中分布特征。
通过傅里叶红外光谱(FTIR)对芯材及微胶囊的基团构成进行分析,结果如图5所示。
图5(a)可以看出,波数为3 326.23 cm-1处的N-H峰和波数为2 243.56 cm-1处的NCO峰表明芯材中存在氨基甲酸基团。从图5(b)可以看出,波数为1 109.82 cm-1处的Si-O伸缩振动峰和波数为665.23 cm-1处的Ti-O晶格振动峰证实了TiO2和SiO2纳米颗粒的成功掺杂。此外,波数为3 375.92 cm-1处的N-H峰、波数为1 702.95 cm-1处的C=O峰以及1 469.96 cm-1处的C-N峰与脲醛树脂特征一致,表明已形成完整的脲醛树脂壁结构包裹芯材。
对微胶囊进行同步热分析,结果如图6所示。从图6可以看出,初始阶段(50~210.82℃)的质量损失率为5.32%,归因于微胶囊表面水分的挥发。在温度为210.82~400.43℃内,微胶囊的残留率显著下降,归因于壁材破裂及芯材逐步发生热降解。温度进一步升高到550℃,残余有机组分持续热分解并形成碳质残留物,最终微胶囊的残留率为7.21%。DSC曲线在温度为230.78℃处出现吸热峰,该温度与失重起始温度210.82℃较为接近,归因于壁材熔融;在温度为350~400℃内的强放热峰对应质量快速下降阶段,该温度远高于自然光固化温度,表明微胶囊光照修复过程不会出现壁材熔化、芯材热泄漏等问题,热稳定性良好。在复合环氧绝缘材料高温固化过程中,其结构完整性和功能性不会受到显著影响。
为验证壳体的紫外屏蔽性能,以防止微胶囊芯材提前固化,在波长为200~800 nm范围内采用紫外-可见分光光度法(UV-Vis)对其进行测试实验。为确保数据可靠性,每个样品重复测试3次并取平均值。测试结果表明,纯脲醛树脂壳体在紫外光关键作用波段(波长为250~400 nm)的平均吸光度仅为0.23,紫外阻隔能力较弱,无法有效屏蔽外界紫外光;而纳米复合壳体在该波段的平均吸光度达到了0.96,紫外光吸收性能良好,可显著降低芯材与紫外光的接触概率,进而避免芯材提前发生固化反应。
根据GB/T 1408.1—2016相关要求[26],搭建工频击穿试验平台对微胶囊复合环氧绝缘材料的电气强度进行测试,测试平台如图7所示。样品置于板-板电极间,浸入绝缘油以防止沿面放电。采用1 kV/s恒定升压速率加压直至样品击穿。
为减少偶然误差,对5组不同掺杂浓度的样品分别进行9次重复试验,并采用双参数Weibull模型进行统计分析,以63.2%累积失效概率所对应的电气强度作为特征电气强度,计算公式如式(1)所示[27]
P(U)=1-exp-Eηβ×100%
式(1)中:E为实测电气强度,kV/mm;P(U)为累积击穿概率;η为特征电气强度;β表征击穿数据的离散性。
图8为微胶囊复合环氧绝缘材料电气强度的Weibull分布图。
图8可以看出,纯环氧树脂的电气强度为31.58 kV/mm,低浓度微胶囊掺杂可提高复合材料的电气强度,当微胶囊质量分数为2%时,复合材料的电气强度为32.28 kV/mm,与纯环氧树脂相比提升了2.22%。这归因于微胶囊引入的电荷陷阱能够降低电子迁移率、缩短载流子平均自由程,从而有效增强样品的绝缘性能[28]。当微胶囊质量分数为4%时,复合材料的电气强度(31.12 kV/mm)与纯环氧树脂性能相当,差异约为1%。随着微胶囊浓度的进一步增加,复合材料的绝缘性能显著劣化,当微胶囊的质量分数为6%时,复合材料的电气强度为30.28 kV/mm;当微胶囊的质量分数为8%时,复合材料的电气强度为29.66 kV/mm,相较于纯环氧树脂下降了6.08%,表明过量微胶囊可能形成内部缺陷,成为电场集中点,导致复合材料的电气强度降低。
利用宽频介电谱仪研究微胶囊浓度对复合材料介电特性的影响,结果如图9所示。在微胶囊相同掺杂浓度下,复合材料的介电常数整体呈现随频率增加而单调递减的趋势,这归因于在高频条件下弛豫极化效应被削弱。而在相同频率(50 Hz)下,微胶囊质量分数为0%、2%、4%、6%、8%时,复合材料的介电常数分别为4.09、4.15、4.21、4.33、4.54。微胶囊在低浓度(2%)时,复合材料的介电常数与纯环氧树脂接近,而微胶囊在高浓度(8%)时,复合材料的介电常数显著上升。一方面是由于微胶囊中液态修复剂与环氧基体形成的固-液界面引入缺陷态,增加漏电流与介质损耗;另一方面脲醛树脂壳层与环氧基体形成的互穿网络可限制链段运动,抑制偶极子极化,从而提升介电性能。在微胶囊低浓度下缺陷效应与网络增强作用相互平衡,介电常数变化不大;在微胶囊高浓度下界面缺陷占主导,导致漏电流增大和介电常数升高。
将微胶囊复合环氧绝缘材料浇筑制备成哑铃状,用于拉伸性能测试。拉伸应力σ由式(2)计算。
σ=Pbd
式(2)中:P为拉伸载荷,N;b为样品断裂面长度,mm;d为样品断裂面宽度,mm。定制哑铃型模具的拉伸截面对应样品断裂面长度b为10 mm,样品断裂面宽度d为2 mm。
不同掺杂浓度复合材料的载荷-位移曲线如图10所示。将图10中的最大载荷代入式(2)中,可得样品的拉伸强度。计算结果表明,微胶囊质量分数为2%的复合材料拉伸性能最优,拉伸强度为54.86 MPa,较纯环氧树脂的拉伸强度(47.65 MPa)提高了15.13%。微胶囊质量分数为4%时,复合材料的拉伸强度为50.21 MPa,较纯环氧树脂提高了5.37%。这归因于固化过程中,环氧预聚物渗入脲醛外壳微观结构,构成物理互穿聚合物网络。同时,脲醛树脂的胺基、亚胺基与环氧固化产生的羟基形成氢键,增强了界面结合,且微胶囊可填充固化缺陷、抑制裂纹扩展,从而改善力学性能[29]。然而,随微胶囊掺杂浓度进一步增大,易发生团聚,而团聚体会破坏环氧树脂基体的结构连续性,在受力过程中形成局部应力集中区域,诱发应力畸变与萌生微裂纹,最终导致复合材料的拉伸强度显著降低。
微胶囊内封装的修复组分为聚氨酯丙烯酸酯低聚体,其分子末端修饰有丙烯酰氧基团。在光引发剂的作用下,可受紫外光辐照诱导而引发自由基聚合反应,实现光固化交联,其自修复机制如式(3)所示。在紫外光辐照下,体系中所含的光引发剂(PI)吸收光能,由基态跃迁至激发态(PI*),产生具有高反应活性的自由基(R)。该活性自由基可结合修复剂分子(M)中的碳-碳双键,引发连续的链式加成聚合,促使分子链不断增长并相互交联,最终形成三维网络状固态聚合物。在聚合反应进程中,增长链的活性末端可能通过链转移反应将活性中心迁移至其他分子,或经由双基终止、偶合终止等链终止途径结束链增长,从而完成修复过程[30-31]
PI紫外PI*PI*RR+MR-MR-M+MR-MM*R-MM+nMR-MnR-Mn+R-MiR-Mn+i-R
综合上述试验,相较于纯环氧树脂,当微胶囊质量分数≥6%时,复合材料的电气强度下降超过4%,介电常数显著上升,拉伸强度大幅降低,严重影响基体材料的性能,制约材料实际应用可行性。
当微胶囊质量分数为2%时,复合材料的电气性能与力学性能略有提升,但过低浓度可能导致损伤区域与微胶囊接触概率不足,影响修复效果。为在保障修复效能的同时减少对基体性能影响,进一步对比了微胶囊质量分数为2%与4%样品的自修复性能。
将样品划分为3种不同状态进行对比分析:未经任何处理的完好样品定义为原始状态;在不同掺杂浓度的样品表面预制宽度与深度分别约为100 μm与200 μm的十字形机械损伤,并采用乙醇冲洗以清除溢出的修复剂,此状态记为损伤状态;另有一组样品在引入相同规格的划痕后不作清洗处理,使其在24 h自然光下完成自主修复过程,即为自修复后状态。基于图7所示的工频击穿试验平台,对各状态下不同微胶囊掺杂浓度样品的电气强度进行测试,室温(25℃)条件下的测试结果如图11(a)所示。从图11(a)可以看出,损伤状态下因电场畸变,所有样品的电气强度均显著下降;修复后,微胶囊质量分数为4%的样品电气强度恢复至28.63 kV/mm,绝缘恢复率达到了91.32%,而微胶囊质量分数为2%的样品电气强度仅恢复至26.86 kV/mm,恢复率为82.75%,表明质量分数为2%的微胶囊与损伤区域的有效接触概率不足,致使修复剂释放效率降低,最终削弱自修复效能。
为评估高温环境下的修复性能,在80℃绝缘油中对样品进行电气强度试验,结果如图11(b)所示。从图11(b)可以看出,微胶囊质量分数为2%和4%样品的绝缘恢复率分别为78.61%和88.02%,均低于室温下的恢复率,降幅分别为4.14%和3.30%。这可能是由于在高温下修复剂的反应速率提升,导致修复剂尚未反应就已部分固化。微胶囊质量分数为2%的复合材料恢复率降幅较为显著,微胶囊质量分数为4%的复合材料因微胶囊分布密度更高,在高温条件下仍保持较优良的修复效果,且具有更高的稳定性。
为更全面地评价微胶囊质量分数为4%的复合材料综合修复效能,进一步对其损伤前后的拉伸强度与体积电阻率进行测试,重复进行5次平行测试以减小随机误差,结果如图12所示。从图12可以看出,微胶囊质量分数为4%的复合材料在原始状态下拉伸强度为51.26 MPa,优于纯环氧树脂的47.36 MPa。损伤后两类材料的拉伸强度分别下降至30.52 MPa和28.33 MPa。经自修复后,微胶囊质量分数为4%的样品的拉伸强度恢复至43.76 MPa,恢复效率达到了85.37%。在原始状态下,纯环氧树脂的体积电阻率为1.15×1015 Ω·cm,微胶囊质量分数为4%的复合材料的体积电阻率为7.8×1014 Ω·cm,表明微胶囊的引入导致其本征绝缘性能略有下降。损伤后,两者的电阻率分别降至7.1×1014 Ω·cm与6.3×1014 Ω·cm。经自修复过程,微胶囊质量分数为4%的复合材料的体积电阻率显著回升至7.5×1014 Ω·cm,恢复至其原始水平的96.2%,表明修复剂有效填充了损伤通道,重建了材料的绝缘完整性。
选取微胶囊质量分数为4%的复合试样与纯环氧树脂,分别在其表面制造划痕进行材料修复性能的验证试验,结果如图13所示。从图13可以看出,经24 h自然光引发固化后,掺有微胶囊的试样的损伤通道实现了填充闭合,并且修复后划痕宽度缩减了20%~30%,具有良好的修复响应。
本研究针对传统微胶囊激发条件严苛、易损伤基体等问题,开发了一种非接触光触发微胶囊增强的环氧树脂复合绝缘体系,并对其电气强度、介电性能和力学性能进行了研究,得出主要结论如下:
(1)所制备光触发微胶囊呈规则球形,平均粒径为180.20 μm,在温度为210.82℃时质量损失率仅为5.32%,表明具有良好的热稳定性。
(2)随微胶囊掺杂浓度增加,复合材料的电气强度与拉伸强度均呈先上升后下降的趋势,介电常数单调上升。当微胶囊质量分数为4%时,复合材料的拉伸强度提高约5.37%,电气强度与介电常数均未发生显著变化,表明该含量下复合材料的绝缘性能未受明显影响。
(3)微胶囊质量分数为4%的复合材料在自然光照射下损伤电气强度恢复率达到了91.32%,体积电阻率回升至原来水平的96.2%,拉伸强度的恢复效率达到了85.37%;在80℃高温环境中电气强度恢复率仍可达到88.02%。基于壁材内部纳米颗粒的紫外屏蔽特性,保证微胶囊完整状态下芯材稳定;微胶囊破裂后,修复剂可在自然光照下发生原位固化,克服了传统修复体系对外部刺激的依赖。

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2026年第59卷第8期
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doi: 10.16790/j.cnki.1009-9239.im.2026.08.006
  • 接收时间:2025-09-03
  • 首发时间:2026-09-10
  • 出版时间:2026-08-20
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  • 收稿日期:2025-09-03
  • 修回日期:2025-10-23
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    1重庆大学 电气工程学院,重庆 400044
    2国网河南省电力公司电力科学研究院,河南 郑州 450052

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牛朝露(1999-),男(汉族),河南鹤壁人,博士生,主要从事材料微尺度损伤缺陷检测与抑制等的研究。
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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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