Article(id=1304923091453366706, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1304923090710982825, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2026.04.003, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1750262400000, receivedDateStr=2025-06-19, revisedDate=1755532800000, revisedDateStr=2025-08-19, acceptedDate=null, acceptedDateStr=null, onlineDate=1789047509301, onlineDateStr=2026-09-10, pubDate=1776614400000, pubDateStr=2026-04-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1789047509301, onlineIssueDateStr=2026-09-10, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1789047509301, creator=13701087609, updateTime=1789047509301, updator=13701087609, issue=Issue{id=1304923090710982825, tenantId=1146029695717560320, journalId=1149653034449285133, year='2026', volume='59', issue='4', pageStart='1', pageEnd='144', issueExtLink='null', onlineDate='null', pubDate='1776614400000', pubDateStr='2026-04-20', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1789047509124, creator='13701087609', updateTime=1789118076681, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1305219072573071941, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1304923090710982825, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1305219072573071942, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1304923090710982825, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=19, endPage=28, ext={EN=ArticleExt(id=1304923091642110387, articleId=1304923091453366706, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Effect of low temperature plasma modified SiO2 doping on electrical and mechanical properties of silicone rubber nanocomposites, columnId=1190369066675179686, journalTitle=Insulating Materials, columnName=Material Research, runingTitle=null, highlight=null, articleAbstract=

With its excellent insulating properties, silicone rubber has become the core material for key components of power equipment. In order to further improve the insulating performance of silicone rubber, the SiO2 was hydroxylated by low-temperature plasma and KH570 grafting, and doped into silicone rubber matrix to prepare SiO2/silicone rubber nanocomposites. The effect laws of different plasma modification conditions (time and frequency) on the surface morphology, surface flashover characteristics, mechanical characteristics, and surface hydrophobicity of SiO2/silicone rubber nanocomposites were systematically studied. The results show that appropriate plasma treatment time and frequency (10 min and 19 kHz) can effectively improve the surface hydrophobicity, electrical characteristics, and mechanical properties of silicone rubber. Plasma modification can effectively reduces the agglomeration of SiO2 nanoparticles in silicone rubber matrix, increase the deep trap density in composites and slow down the surface potential decay rate, thereby increasing the pollution flashover voltage of the composites. In addition, plasma modified SiO2 can significantly improve the tensile strength and hydrophobicity of SiO2/silicon rubber nanocomposites.

, authors=Tao YE, Zimo CAI, Yudi WANG, Guanxian YIN, Chun WANG, Qiang HUANG*, authorsList=Tao YE, Zimo CAI, Yudi WANG, Guanxian YIN, Chun WANG, Qiang HUANG, authorCompany=null, correspAuthors=Qiang HUANG, 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=1304923094750089688, articleId=1304923091453366706, tenantId=1146029695717560320, journalId=1149653034449285133, language=CN, title=低温等离子体改性SiO2掺杂对硅橡胶纳米复合材料电学和力学特性的影响研究, columnId=1190369066813591720, journalTitle=绝缘材料, columnName=材料研究, runingTitle=null, highlight=null, articleAbstract=

硅橡胶凭借其优异的绝缘特性,成为电力设备关键组件的核心材料。为了进一步提升硅橡胶的绝缘性能,本文使用低温等离子体和KH570接枝相结合对SiO2进行羟基化改性,将其掺杂到硅橡胶基体中制备SiO2/硅橡胶纳米复合材料,并研究不同等离子体改性条件(时间、频率)对SiO2/硅橡胶纳米复合材料表面形貌、沿面闪络特性、力学特性和表面疏水性的影响规律。结果表明:合适的等离子体处理时间和频率(10 min和19 kHz)能有效改善硅橡胶的表面疏水性、电学特性以及力学性能。等离子体改性可有效减少SiO2纳米粒子在硅橡胶基体中的团聚,增加复合材料中的深陷阱密度并减缓表面电位衰减速率,进而提升复合材料的污闪电压。此外,等离子体改性SiO2可显著提高SiO2/硅橡胶纳米复合材料的拉伸强度和疏水性。

, authors=叶涛, 蔡子默, 王禹迪, 殷关贤, 王春, 黄强*, authorsList=叶涛, 蔡子默, 王禹迪, 殷关贤, 王春, 黄强, authorCompany=null, correspAuthors=黄强, authorNote=

叶涛(1984-),男(汉族),海南万宁人,高级工程师,主要从事应急管理、保供电管理、配网管理、配电自动化等工作

, correspAuthorsNote=
黄强(1981-),男(汉族),海南文昌人,工程师,主要从事电网规划和配电运维的工作。
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叶涛(1984-),男(汉族),海南万宁人,高级工程师,主要从事应急管理、保供电管理、配网管理、配电自动化等工作

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叶涛(1984-),男(汉族),海南万宁人,高级工程师,主要从事应急管理、保供电管理、配网管理、配电自动化等工作

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Beijing: University of Chemical Technology Beijing,2023., articleTitle=Study on reinforcing silicone rubber with layered clay modified nano-silica composites, refAbstract=null)], funds=null, companyList=[AuthorCompany(id=1304923094938833369, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304923091453366706, xref=null, ext=[AuthorCompanyExt(id=1304923094947221978, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304923091453366706, companyId=1304923094938833369, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=Wenchang Power Supply Bureau of Hainan Power Grid Co., Ltd., Wenchang 571300, China), AuthorCompanyExt(id=1304923094955610587, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304923091453366706, companyId=1304923094938833369, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, 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Trap parameters of SiO2/silicone rubber nanocomposites

, figureFileSmall=null, figureFileBig=null, tableContent=
试样Ea/eVNa/(×1016 cm-3·eV-1)
SIR0.8313.263
SiO2-0 min0.9124.539
SiO2-5 min0.9214.389
SiO2-10 min0.9255.326
SiO2-15 min0.9194.688
), ArticleFig(id=1304923099749700135, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304923091453366706, language=CN, label=表1, caption=

SiO2/硅橡胶纳米复合材料的陷阱参数

, figureFileSmall=null, figureFileBig=null, tableContent=
试样Ea/eVNa/(×1016 cm-3·eV-1)
SIR0.8313.263
SiO2-0 min0.9124.539
SiO2-5 min0.9214.389
SiO2-10 min0.9255.326
SiO2-15 min0.9194.688
), ArticleFig(id=1304923099850363432, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304923091453366706, language=EN, label=Table 2, caption=

Trap parameters of SiO2/silicone rubber nanocomposites

, figureFileSmall=null, figureFileBig=null, tableContent=
试样Ea/eVNa/(×1016 cm-3·eV-1)
SIR0.8313.263
SiO2-0 kHz0.8924.641
SiO2-18 kHz0.9194.655
SiO2-19 kHz0.9255.364
SiO2-20 kHz0.9094.839
), ArticleFig(id=1304923099930055209, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1304923091453366706, language=CN, label=表2, caption=

SiO2/硅橡胶纳米复合材料的陷阱参数

, figureFileSmall=null, figureFileBig=null, tableContent=
试样Ea/eVNa/(×1016 cm-3·eV-1)
SIR0.8313.263
SiO2-0 kHz0.8924.641
SiO2-18 kHz0.9194.655
SiO2-19 kHz0.9255.364
SiO2-20 kHz0.9094.839
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低温等离子体改性SiO2掺杂对硅橡胶纳米复合材料电学和力学特性的影响研究
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叶涛 , 蔡子默 , 王禹迪 , 殷关贤 , 王春 , 黄强 *
绝缘材料 | 材料研究 2026,59(4): 19-28
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绝缘材料 |材料研究 2026 , 59 (4) : 19 -28
低温等离子体改性SiO2掺杂对硅橡胶纳米复合材料电学和力学特性的影响研究
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叶涛(1984-),男(汉族),海南万宁人,高级工程师,主要从事应急管理、保供电管理、配网管理、配电自动化等工作

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叶涛, 蔡子默, 王禹迪, 殷关贤, 王春, 黄强*
作者信息
  • 海南电网有限责任公司文昌供电局,海南 文昌 571300
通讯作者:
黄强(1981-),男(汉族),海南文昌人,工程师,主要从事电网规划和配电运维的工作。
作者简介:

叶涛(1984-),男(汉族),海南万宁人,高级工程师,主要从事应急管理、保供电管理、配网管理、配电自动化等工作

Effect of low temperature plasma modified SiO2 doping on electrical and mechanical properties of silicone rubber nanocomposites
Tao YE, Zimo CAI, Yudi WANG, Guanxian YIN, Chun WANG, Qiang HUANG*
Affiliations
  • Wenchang Power Supply Bureau of Hainan Power Grid Co., Ltd., Wenchang 571300, China
出版时间: 2026-04-20 doi: 10.16790/j.cnki.1009-9239.im.2026.04.003
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硅橡胶凭借其优异的绝缘特性,成为电力设备关键组件的核心材料。为了进一步提升硅橡胶的绝缘性能,本文使用低温等离子体和KH570接枝相结合对SiO2进行羟基化改性,将其掺杂到硅橡胶基体中制备SiO2/硅橡胶纳米复合材料,并研究不同等离子体改性条件(时间、频率)对SiO2/硅橡胶纳米复合材料表面形貌、沿面闪络特性、力学特性和表面疏水性的影响规律。结果表明:合适的等离子体处理时间和频率(10 min和19 kHz)能有效改善硅橡胶的表面疏水性、电学特性以及力学性能。等离子体改性可有效减少SiO2纳米粒子在硅橡胶基体中的团聚,增加复合材料中的深陷阱密度并减缓表面电位衰减速率,进而提升复合材料的污闪电压。此外,等离子体改性SiO2可显著提高SiO2/硅橡胶纳米复合材料的拉伸强度和疏水性。

等离子体  /  硅橡胶  /  沿面闪络  /  表面电荷积聚

With its excellent insulating properties, silicone rubber has become the core material for key components of power equipment. In order to further improve the insulating performance of silicone rubber, the SiO2 was hydroxylated by low-temperature plasma and KH570 grafting, and doped into silicone rubber matrix to prepare SiO2/silicone rubber nanocomposites. The effect laws of different plasma modification conditions (time and frequency) on the surface morphology, surface flashover characteristics, mechanical characteristics, and surface hydrophobicity of SiO2/silicone rubber nanocomposites were systematically studied. The results show that appropriate plasma treatment time and frequency (10 min and 19 kHz) can effectively improve the surface hydrophobicity, electrical characteristics, and mechanical properties of silicone rubber. Plasma modification can effectively reduces the agglomeration of SiO2 nanoparticles in silicone rubber matrix, increase the deep trap density in composites and slow down the surface potential decay rate, thereby increasing the pollution flashover voltage of the composites. In addition, plasma modified SiO2 can significantly improve the tensile strength and hydrophobicity of SiO2/silicon rubber nanocomposites.

plasma  /  silicone rubber  /  surface flashover  /  surface charge accumulation
叶涛, 蔡子默, 王禹迪, 殷关贤, 王春, 黄强. 低温等离子体改性SiO2掺杂对硅橡胶纳米复合材料电学和力学特性的影响研究. 绝缘材料, 2026 , 59 (4) : 19 -28 . DOI: 10.16790/j.cnki.1009-9239.im.2026.04.003
Tao YE, Zimo CAI, Yudi WANG, Guanxian YIN, Chun WANG, Qiang HUANG. Effect of low temperature plasma modified SiO2 doping on electrical and mechanical properties of silicone rubber nanocomposites[J]. Insulating Materials, 2026 , 59 (4) : 19 -28 . DOI: 10.16790/j.cnki.1009-9239.im.2026.04.003
硅橡胶(silicone rubber,SR)作为一种高性能弹性体材料,凭借其优异的耐高低温特性、化学稳定性、抗臭氧性、电绝缘性能和憎水性等特点,已成为电力设备关键组件的核心材料,特别是在硅橡胶复合绝缘子的制备中发挥着重要作用[1-3]。然而,由于硅橡胶复合绝缘子的运行环境复杂,长时间运行容易导致绝缘子老化、绝缘性能下降,最终导致电力系统发生故障。已有研究表明,绝缘子表面局部放电和沿面闪络是引起绝缘子老化的主要原因[4-5]。因此,研究人员一直致力于研究如何提升复合绝缘子的沿面闪络特性[6-7]
已有研究表明,硅橡胶的表面物化特性和电学特性会直接影响其沿面闪络特性。例如,硅橡胶良好的表面憎水性表明其沿面闪络特性较好。因此,研究人员致力于研究通过改善硅橡胶的表面特性和电学特性从而提升其沿面闪络电压[8]。研究表明,在硅橡胶中掺杂纳米粒子能够有效改善硅橡胶的介电特性、表面疏水性和力学特性等[9-10]。高文欣等[11]通过掺杂氮化硼(BN)纳米粒子制备BN/硅橡胶复合材料,结果表明复合材料的疏水性以及表面电荷积聚特性得到改善,从而提升了复合材料的沿面闪络特性和抗老化特性。周远翔等[12]将不同接枝类型的纳米TiO2掺杂到硅橡胶中,加强了硅橡胶基体的界面作用,提高了复合材料的直流闪络电压。陈炳强等[13]以气相SiO2为补强填料,研究其对室温硫化硅橡胶力学性能的影响,结果表明硅橡胶的拉伸模量随SiO2用量的增加而增大,但过量的SiO2会造成其体系分散不均匀,最终导致硅橡胶的拉伸模量降低。曾玉等[14]通过机械混合和平板硫化的方法制备了石墨烯/Mxene/硅橡胶柔性复合材料,结果表明加入1.2份石墨烯和0.8份Mxene时,复合材料的拉伸强度增加至680 kPa,弹性模量为605 kPa。
然而,由于纳米粒子制备工艺要求较高以及具有高比表面积和表面活性,其容易在聚合物基体中分散不均匀从而发生团聚现象,这种现象不仅会影响聚合物的物理化学特性,而且纳米粒子团聚处也更易积聚电荷,造成聚合物局部击穿甚至发生闪络[15-16]。因此,改善纳米粒子在聚合物中的团聚现象有利于提升绝缘材料的性能。赵艳芳等[17]将KH550作为改性剂,改善了多壁碳纳米管在硅橡胶中的分散性,提升了复合材料的整体性能。荆素航等[18]采用硅烷偶联剂对纳米SiO2进行表面改性,显著改善了纳米SiO2在环氧树脂中的分散状态。
等离子体因其低功耗、高效率的特点,可根据应用需求在纳米粒子表面接枝相应的官能团,减少其在基体中的团聚,近年来常被用作纳米粒子改性的重要手段[19-21]。姜楠等[22]利用等离子体羟基化改性SiO2粒子,再掺杂到绝缘纸中,有效提高了绝缘纸的绝缘性能。MI Y等[23]使用大气压双极纳秒脉冲电介质势垒放电(DBD)+H2O低温等离子体羟基化改性氮化硼纳米片(BNNS),并将其添加到环氧树脂中制备复合材料,结果表明复合材料在保持原有绝缘性能的基础上,导热性能提高了67%,延长了复合材料的使用寿命。
本文通过低温等离子体活化与硅烷偶联剂接枝相结合的方法对纳米SiO2进行表面改性,将其掺杂到硅橡胶基体中制备SiO2/硅橡胶纳米复合材料,并系统考察不同等离子体处理条件对复合材料疏水性、力学性能及沿面闪络特性的影响。
液体硅橡胶(A/B胶),德国瓦克国际集团有限公司;粒径为20 nm的纳米二氧化硅(SiO2)、盐酸(浓度为0.1 mol/L)、乙醇(浓度为99%),上海麦克林生化科技有限公司;KH570硅烷偶联剂(纯度为97%),上海阿拉丁科技有限公司。
本文搭建的等离子体处理平台如图1所示,实验平台包含气路部分、等离子体处理部分、波形检测部分。气路部分主要由氮气源、气体流量控制器以及前驱物组成;等离子体处理部分主要由等离子体反应釜以及调压器和等离子体发生器组成;实验通过示波器监测外加电压和放电波形。其中气体流量控制器流量规格为5SLM,等离子体电源输出电压为0~30 kV,通过调压器控制。等离子体处理装置的上下电极直径为50 mm,反应釜由石英玻璃制成,其直径为120 mm。示波器的电压范围为100~240 V,频率为50~60 Hz。
等离子体改性材料的操作步骤为:首先,确保气路部分各装置之间已通过软管连接,检查气密性是否良好;确保处理部分各设备接线安全无误;将定量的材料放进反应釜后,确保反应釜放置在电极正中间。接着,通过气体流量控制器将氮气流量调至设定值,通入装有前驱物的洗气瓶,使氮气携带前驱物蒸气进入等离子体反应釜;持续通气1 min,以确保腔内气氛稳定。最后,打开等离子体电源,调整到预设参数后,开始处理并实时监测材料放电状态及示波器波形变化。
等离子体处理SiO2纳米粒子:将待处理的SiO2纳米粒子均匀置于等离子体反应釜中,确保其表面充分暴露,每次处理的样品质量固定为0.2 g;向装置通入1 min N2及前驱物,主要用于对SiO2进行物理清洗和表面活化;之后启动等离子体发生器的电源,电源工作电压设置为60 V,放电电压为30 kV,工作频率分别为18、19、20 kHz,处理时间分别为0、5、10、15 min;处理结束后关闭等离子体源继续保持惰性气体吹扫以稳定SiO2表面状态,避免受到污染。
先配制去离子水/无水乙醇混合溶液,然后用精密数字天平称取质量为3.0 g充分干燥的纳米SiO2粒子加入上述混合溶液中,其中各组分用量按m(纳米粒子,g)V(去离子水,mL)V(乙醇,mL)=1∶5∶3进行配置。再向混合溶液中加入0.15 mL盐酸溶液将溶液的pH值调节至4~5,再加入0.6 g硅烷偶联剂KH570充分水解后得到悬浮液。将悬浮液用磁力搅拌机搅拌30 min,之后置于70℃恒温水浴振荡器中振荡60 min,使偶联剂充分和SiO2纳米粒子表面的羟基进行缩合反应。最后将悬浮液进行超声处理,过滤后放入鼓风烘干箱中干燥48 h得到改性SiO2纳米粉末,将干燥后的SiO2纳米粉末研磨以确保完全分散。SiO2纳米粒子的改性流程如图2所示。
将液体硅橡胶A/B组分按质量比为1∶1混合,搅拌均匀作为基体,再加入质量分数为5%的改性SiO2纳米粒子到硅橡胶基体溶液中充分搅拌均匀,将混合溶液放入真空箱脱泡20 min后,缓慢倒进模具中,将模具水平放置在平板硫化仪内,平板硫化仪上、下板温度均设定为160℃,压力为15 MPa,硫化10 min后,取出模具并放入水中冷却,待充分冷却后,取下压好的样片,制得SiO2/硅橡胶纳米复合材料,制备流程如图3所示。
等温表面电位衰减(ISPD)测量系统如图4所示,该系统由电晕放电、恒温加热、表面电位测量、数据采集系统4个部分构成,其中电晕放电、恒温加热、表面电位测量系统放置在一个有机玻璃制成的恒温箱体中,确保箱体内部恒温恒湿。
测试前,将环境湿度调节至30%,温度维持25℃,然后对试样进行预处理:用酒精清洁试样表面,两面贴覆接地锡箔纸,置于80℃烘箱中处理24 h以消除残余电荷和表面水分。测试时,先用电极系统对试样进行2 min电晕充电,完成后立即将静电探头移至试样上方,开始实时监测表面电位。
闪络电压测试系统如图5所示,主要由交流电压源、电容分压器(1 000∶1)、保护电阻、指型电极、罗氏线圈和数字示波器等设备组成。
测试时,首先对试样进行彻底清洁和干燥,以去除表面原有污染物;随后使用硅藻土、高岭土、氯化钠和纯水配制污染液,质量比为8∶8∶2∶200。将污染液充分搅拌,保证材料溶解完全,密度均匀,用定量涂刷法对试样表面进行涂污,之后静置自然晾干,完成试样涂污制备过程;最后使用雾化器将涂污后的试样表面打湿,再将其固定于指型电极中,保证指型电极下平面紧贴试样污秽面,上、下电极最近距离保持为1 cm,采用逐步升压的方式对试样进行加压直至发生沿面闪络,同一试样测试15组数据,结果取平均值。
使用微机控制电子万能试验机(型号为E42.503,美特斯工业系统(中国)有限公司)测试试样的拉伸性能;使用界面张力仪(型号为SL200KB,上海梭伦信息科技有限公司)测试试样的静态接触角。
首先采用SBC-12型离子溅射仪对试样进行喷金处理10 min,并使用场发射扫描电镜(SEM,型号为QUANTA-450-FEG,FEI公司)观察SiO2纳米粒子在硅橡胶中的分散情况。使用红外显微成像系统(型号为Spotlight 400,美国PerkinElmer公司)对试样进行红外光谱(FTIR)测试。
为了研究等离子体处理时间对SiO2纳米粒子的影响,对处理频率为19 kHz不同处理时间(5、10、15 min)的SiO2纳米粒子进行红外光谱测试,结果如图6所示。从图6可以看出,未处理的SiO2在3 450 cm-1处存在明显的-OH伸缩振动宽峰,在1 100 cm-1处为Si-O-Si的反对称伸缩振动峰,在880 cm-1附近为Si-O-Si键的对称伸缩振动峰。经等离子体羟基化处理后,在3 450 cm-1处-OH的伸缩振动峰增强,说明试样中与羟基相关的振动基团含量增加,间接表明SiO2表面羟基化程度提高。随着等离子体处理时间的增加,-OH振动峰的峰值先升高后降低,在处理时间为10 min时-OH振动峰的峰值达到最高,随后-OH振动峰峰值降低的原因可能是由于过度处理,导致表面弱结合羟基和物理吸附水减少,且部分硅醇基可能发生脱水缩合反应,重新形成Si-O-Si键,从而使-OH振动峰强度下降,但仍高于未处理SiO2中的羟基含量。
图7为纯硅橡胶和SiO2/硅橡胶纳米复合材料在处理频率为19 kHz、不同等离子体处理时间下的SEM表面形貌图。
图7可以看出,纯硅橡胶表面相对光滑平整,无任何杂质。随着SiO2纳米粒子的掺杂,硅橡胶表面出现较多团聚粒子,使得SiO2/硅橡胶复合材料表面变得不平整,如图7(b)所示。随着等离子体处理的SiO2纳米粒子加入,复合材料表面团聚粒子显著减少,但依旧有少量粒子团聚在硅橡胶基体,如图7(c)所示。但是随着等离子体处理时间继续增加,SiO2纳米粒子的分散更加均匀,虽然还有极少数粒子团聚但复合材料表面相对平整光滑,如图7(d)图7(e)所示。根据实验结果可以推断:经偶联剂KH570处理后的SiO2,其等离子体处理时间越长,表面-OH含量越多,官能团接枝率越高,最终促进了SiO2纳米粒子在硅橡胶基体中的分散。上述结果表明,等离子体处理10 min的SiO2在硅橡胶基体中的分散状态最佳。
图8为SiO2/硅橡胶纳米复合材料在处理时间为10 min、不同处理频率下的SEM表面形貌图。
图8可以看出,等离子体处理频率可直接影响SiO2纳米粒子在复合材料中的分散特性。等离子体电源频率为18 kHz时,由于反应釜中产生的等离子体不均匀,SiO2纳米粒子的改性处理并不充分,导致SiO2纳米粒子在硅橡胶基体中分散不均匀,有较大的团聚粒子出现,并且复合材料的表面不平整。当等离子体电源频率为19 kHz时,产生的等离子体相对均匀,SiO2纳米粒子得到了充分改性,因此其在硅橡胶基体中分散相对均匀,复合材料的表面光滑平整。当等离子体电源频率为20 kHz时,等离子体改性SiO2的效果下降,复合材料中又出现少量团聚现象。综合来看,等离子体处理时间控制在10 min、电源频率控制在19 kHz时对SiO2的改性效果最佳,同时SiO2在硅橡胶基体中分散也相对较好。
为探究等离子体处理时间和频率对SiO2/硅橡胶纳米复合材料表面疏水性的影响,本文采用静态水接触角测试对不同处理条件下样品的疏水性能进行表征。
对处理频率为19 kHz、不同等离子体处理时间的SiO2/硅橡胶纳米复合材料进行5次疏水角测量,每次选择不同位置,并对测试结果取平均值,结果如图9所示。从图9可以看出,随着等离子体处理时间增加,SiO2/硅橡胶纳米复合材料的疏水角呈现出先增大后减小再增大的趋势,在等离子体处理时间为10 min时,复合材料的疏水角达到最大值(133.0°),相比纯硅橡胶试样(97.2°)提升了36.8%。
对处理时间为10 min、不同等离子体处理频率下的SiO2/硅橡胶纳米复合材料进行疏水角测量,结果如图10所示。从图10可以看出,随着等离子体处理频率的增加,复合材料的疏水角呈现先增大后减小的趋势。其中等离子体处理频率为19 kHz时,复合材料的疏水角达到最大值(133.0°),比纯硅橡胶材料提升了36.8%。该变化趋势可归因于等离子体对纳米粒子表面形貌与表面能的协同调控。一方面,经硅烷偶联剂和低温等离子体处理的SiO2粒子可有效填充硅橡胶表面空隙和孔洞,使填料与基体形成致密的网状结构,改善硅橡胶的疏水性能;另一方面,经表面改性的SiO2粒子携带大量疏水性有机基团,在与硅橡胶基体复合时可降低其表面自由能,进一步增强材料对水分子的排斥能力[24]
研究表明材料的表面电荷积聚和陷阱分布特性与其沿面闪络电压有直接的关系,因此本文研究了不同等离子处理条件对SiO2/硅橡胶纳米复合材料表面电荷积聚和陷阱分布特性的影响。
图11为SiO2/硅橡胶纳米复合材料在为处理频率为19 kHz、不同等离子体处理时间下的表面电位衰减曲线。从图11可以看出,所有试样的表面电位数值随着时间的增加分为两个阶段衰减:前期衰减迅速,后期衰减缓慢并且在10 000 s后逐渐接近于零。其中,等离子体改性处理的SiO2/硅橡胶纳米复合材料表面电位相比于未处理的硅橡胶前期衰减速率明显降低。随着等离子体处理时间的增加,复合材料表面电位的衰减速率先降低后升高,当等离子体处理时间为10 min时,试样的表面电位衰减速率达到最低。
图11的表面电位衰减曲线进行拟合分析,计算得到SiO2/硅橡胶纳米复合材料的表面电子陷阱分布特性,结果如图12所示,相应参数如表1所示。从图12表1可以看出,经过SiO2掺杂后,复合材料的陷阱能级(Ea)和陷阱密度(Na)明显升高,其中等离子体处理时间为10 min时,复合材料的陷阱能级和能级密度达到最高。经等离子体改性的SiO2在硅橡胶基体里引入了大量的深陷阱,当深陷阱占主导地位时,复合材料表面陷阱中的电子需要相当多的能量才能脱陷,因此,电子在复合材料表面移动更困难,这也对应了复合材料的表面电位衰减曲线的变化趋势。
等离子体处理频率对SiO2/硅橡胶纳米复合材料表面的电荷消散也有直接的影响,图13为SiO2/硅橡胶纳米复合材料在处理时间为10 min、不同等离子体处理频率下的表面电位衰减曲线。从图13可以看出,所有试样的表面电位随测量时间的增加均呈现先快速衰减后缓慢衰减的变化过程。随着等离子体处理频率的增加,试样表面电位的衰减速率先降低再升高。等离子体处理频率为19 kHz时,试样表面电位的衰减速率最低。
图13的表面电位衰减曲线进行拟合分析,计算得到SiO2/硅橡胶纳米复合材料表面电子陷阱分布特性,结果如图14所示,相应参数如表2所示。从图14表2可以看出,等离子体处理频率对SiO2的改性效果直接影响SiO2/硅橡胶纳米复合材料表面的电荷消散,其中处理频率为19 kHz时等离子体产生比较均匀,对SiO2纳米粒子的改性比较充分,使其在基体中的分散效果较好,引入较多的深陷阱限制了表面电荷的移动。实验结果表明,合适的处理频率可以有效地改善SiO2纳米粒子在硅橡胶基体里的分散效果,改善团聚现象,对提升复合材料的电学性能有积极作用。
本文测试了不同等离子体处理条件对SiO2/硅橡胶纳米复合材料污闪电压的影响,其中处理频率为19 kHz、不同等离子处理时间对SiO2/硅橡胶纳米复合材料污闪电压的影响如图15所示。
图15可以看出,SiO2/硅橡胶纳米复合材料的污闪电压随等离子体处理时间的增加呈现先增大后减小的趋势。当等离子体处理时间为10 min时,复合材料的污闪电压最大(8.29 kV),相比纯硅橡胶试样提升了33%。整体来看,采用适当的等离子体处理时间对SiO2改性有利于提升SiO2/硅橡胶纳米复合材料的污闪电压,改善硅橡胶的绝缘性能。
处理时间为10 min、不同等离子体处理频率对SiO2/硅橡胶纳米复合材料污闪电压的影响如图16所示。从图16可以看出,复合材料的污闪电压随等离子体处理频率的增加呈先增大后减小的变化趋势。相同污秽条件下,处理频率为19 kHz时,复合材料的污闪电压达到最大值(8.29 kV),相比纯硅橡胶试样的污闪电压提升了33%。这一现象与前文中材料的表面电荷积聚特性实验结果相吻合,表明适宜的等离子体处理频率能够有效地对SiO2纳米粒子进行改性,从而显著提高SiO2/硅橡胶纳米复合材料的污闪电压。
根据前文表面疏水角的测试结果可知,SiO2经过改性处理可在硅橡胶表面形成纳米粗糙结构,水分更难在基体表面铺展成导电水膜,从而可抑制泄漏电流,降低污闪风险。
进一步分析表明,通过调控等离子体处理的时间和频率,可以实现对纳米SiO2粒子的羟基化改性,进而促进其在硅橡胶基体中的均匀分散。这种改性可以增加SiO2/硅橡胶纳米复合材料的陷阱能级与陷阱密度,从而有效提升污闪电压。
对处理频率为19 kHz、不同等离子体处理时间下SiO2/硅橡胶纳米复合材料的力学性能进行测试,同一试样测试5组取平均值,结果如图17所示。从图17可以看出,随着等离子体处理时间的增加,SiO2/硅橡胶纳米复合材料的拉伸强度逐渐提高,当等离子体处理时间为10 min时,复合材料的拉伸强度达到最大值(6.27 MPa),较纯硅橡胶提升了36.6%。随着等离子体处理时间继续增加到15 min,复合材料的拉伸强度开始减小,说明等离子体处理时间过长会影响SiO2纳米粒子在硅橡胶基体里的分散性及二者的相互作用,但其拉伸强度依然达到5.78 MPa,较未处理硅橡胶提升了25.9%。
分析认为复合材料拉伸强度的提高归因于SiO2作为硅橡胶体系的典型补强填料,可与聚硅氧烷链段产生氢键,从而提高材料的力学性能。本文对纳米SiO2进行低温等离子体活化(羟基化)后,再采用硅烷偶联剂KH570进行表面有机化改性,使得补强效果更好。此外,纳米SiO2粒径小、比表面积大,表面与硅橡胶基体的结合能力强,可依靠化学键、氢键等在两种组分间发挥协同作用,显著提高硅橡胶材料的力学性能[25]
图18为处理时间为10 min、不同处理频率对SiO2/硅橡胶纳米复合材料力学性能的影响。
图18可以看出,随着等离子体处理频率的增大,SiO2/硅橡胶纳米复合材料的拉伸强度呈现先增大后减小的趋势。当等离子体处理频率为19 kHz时,复合材料的拉伸强度达到最大值(5.19 MPa),较纯硅橡胶提升了13%。结合SEM结果可知,适宜的等离子体处理频率可有效活化SiO2纳米粒子表面-OH,再经过硅烷偶联剂KH570的修饰,SiO2纳米粒子经水解缩合反应,在硅橡胶基体间构建稳定的共价键网络,该化学桥联作用可有效改善SiO2纳米粒子在硅橡胶基体中的分散性,有利于提升SiO2/纳米复合材料的拉伸强度。
总体来看,经等离子体改性的SiO2纳米粒子制备的SiO2/硅橡胶纳米复合材料具备更好的力学性能,当等离子体处理时间为10 min、处理频率为19 kHz时,SiO2/硅橡胶纳米复合材料的拉伸特性最好。
本文采用等离子体技术和KH570接枝相结合对SiO2纳米粒子进行羟基化改性,将其掺杂到硅橡胶基体中,制备SiO2/硅橡胶纳米复合材料,并系统研究了不同处理条件对其微观形貌、电学特性、力学特性以及疏水性的影响,主要结论如下:
(1)等离子体羟基化处理显著提升了SiO2纳米粒子的表面羟基含量,改善了其在硅橡胶基体中的分散性。当等离子体处理时间为10 min、处理频率为19 kHz时,SiO2纳米粒子的分散效果最佳,团聚现象显著减少。
(2)等离子体改性后SiO2/硅橡胶纳米复合材料的表面电位衰减速率减缓,深陷阱密度增加。污闪电压测试表明,在合适的等离子体处理时间和频率下(10 min和19 kHz),复合材料的污闪电压明显提升。
(3)等离子体改性显著提高了SiO2/硅橡胶纳米复合材料的拉伸强度和疏水性。当等离子体处理时间为10 min、处理频率为19 kHz时,SiO2/硅橡胶纳米复合材料的拉伸强度和疏水性最佳。

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2026年第59卷第4期
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doi: 10.16790/j.cnki.1009-9239.im.2026.04.003
  • 接收时间:2025-06-19
  • 首发时间:2026-09-10
  • 出版时间:2026-04-20
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  • 收稿日期:2025-06-19
  • 修回日期:2025-08-19
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    海南电网有限责任公司文昌供电局,海南 文昌 571300

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黄强(1981-),男(汉族),海南文昌人,工程师,主要从事电网规划和配电运维的工作。
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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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