Article(id=1192878364219294027, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1192878363166523716, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2025.01.002, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1714320000000, receivedDateStr=2024-04-29, revisedDate=1718208000000, revisedDateStr=2024-06-13, acceptedDate=null, acceptedDateStr=null, onlineDate=1762333964637, onlineDateStr=2025-11-05, pubDate=1737302400000, pubDateStr=2025-01-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1762333964637, onlineIssueDateStr=2025-11-05, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1762333964637, creator=13701087609, updateTime=1762333964637, updator=13701087609, issue=Issue{id=1192878363166523716, tenantId=1146029695717560320, journalId=1149653034449285133, year='2025', volume='58', issue='1', pageStart='1', pageEnd='144', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1762333964387, creator=13701087609, updateTime=1762334342663, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1192879949821395698, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1192878363166523716, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1192879949821395699, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1192878363166523716, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=11, endPage=19, ext={EN=ArticleExt(id=1192878366119313747, articleId=1192878364219294027, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Study on effect of plasma fluorinated nano-SiO2 on surface insulating properties of epoxy resin under high temperature and moisture conditions, columnId=1190369066675179686, journalTitle=Insulating Materials, columnName=Material Research, runingTitle=null, highlight=null, articleAbstract=

With the increase of grid capacity and voltage level, the insulating properties of epoxy composite insulation materials is crucial to the safe and stable operation of electrical equipment. Long-term high temperature and high humidity will lead to a serious decline in insulating properties of materials. Nano-SiO2 was fluorinated (F-SiO2) by the plasma technology of dielectric barrier discharge (DBD) in this paper, and fluorine-containing groups were successfully grafted on the surface of nano-SiO2. The high-temperature and humid state of the material was simulated by the wet heat ageing experiment, and the surface flashover, charge dissipation characteristics and trap distribution characteristics of the samples at different ageing stages were tested. The effect of doping F-SiO2 on the wet heat ageing resistance of epoxy composites was explored, and the inhibition mechanism of F-SiO2 on the water intrusion was revealed from the molecular scale in combination with MD simulation. The experimental results show that doping F-SiO2 reduces the saturated moisture absorption of epoxy composites by 16.16%, increases the surface flashover voltage by 13.06%, and can continue to maintain high insulating properties after wet heat ageing. The simulation results show that F-SiO2 can reduce the free volume fraction of epoxy resin and the mean square displacement of water molecules, and enhance the barrier effect of epoxy composites on moisture. Plasma technology can graft fluorine elements onto the surface of nano-SiO2, effectively inhibiting the intrusion of moisture and enhancing the surface insulating properties of epoxy composites in a humid state.

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随着电网容量和电压等级的提升,环氧复合绝缘材料的绝缘性能对电气设备的安全稳定运行至关重要,长期的高温高湿状态会导致材料的绝缘性能严重下降。本文基于介质阻挡放电(Dielectric Barrier Discharge,DBD)的等离子体技术对纳米SiO2进行氟化改性(F-SiO2),成功将含氟基团接枝在纳米SiO2表面,并通过湿热老化实验模拟高温受潮状态,对不同老化阶段的试样进行沿面闪络、电荷消散特性和陷阱分布特性测试。探究了掺杂F-SiO2对环氧复合材料耐湿热老化性能的影响,并结合MD仿真模拟从分子尺度揭示了F-SiO2对水分侵入的抑制机理。实验结果表明:掺杂F-SiO2使环氧复合材料的饱和吸湿量降低了16.16%,沿面闪络电压提升了13.06%,且在湿热老化后能继续保持较高的绝缘性能。仿真结果表明:F-SiO2可以降低环氧树脂的自由体积分数和水分子的均方位移,增强了环氧复合材料对水分的阻隔作用。等离子体技术可以将氟元素接枝到纳米SiO2表面,有效抑制水分的侵入,提升环氧复合材料在受潮状态下的表面绝缘性能。

, correspAuthors=null, authorNote=null, correspAuthorsNote=
谢庆(1979-),男(汉族),四川广安人,教授,博士,主要从事高电压与绝缘技术、新型电力系统电气设备智能化的研究。
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骆立衡(1998-),男(汉族),吉林长春人,硕士生,主要从事高电压与绝缘技术的研究;

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Hebei Provincial Key Laboratory of Power Transmission Equipment Security Defense, North China Electric Power University, Baoding 071003, China
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Polymer Composites,2018,39(S2):945-954., articleTitle=Molecular simulation and experimental analysis on thermal and mechanical properties of carbon nanotube/epoxy resin composites with different curing agents at high-low temperature, refAbstract=null)], funds=[Fund(id=1193252932368953402, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1192878364219294027, awardId=52277147, language=CN, fundingSource=国家自然科学基金面上项目(52277147), fundOrder=null, country=null), Fund(id=1193252932423479355, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1192878364219294027, awardId=112616, language=CN, fundingSource=国创计划资助项目(112616), fundOrder=null, country=null)], companyList=[AuthorCompany(id=1193252926257853398, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1192878364219294027, xref=null, ext=[AuthorCompanyExt(id=1193252926266242007, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1192878364219294027, companyId=1193252926257853398, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1. 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项目 Si/% O/% F/%
SiO2 33.04 54.23 0
F-SiO2 22.86 43.92 17.20
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纳米SiO2氟化前后主要元素占比

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SiO2 33.04 54.23 0
F-SiO2 22.86 43.92 17.20
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等离子体氟化纳米SiO2对高温受潮状态下环氧树脂表面绝缘性能的影响研究
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骆立衡 1 , 郭骏毅 1 , 夏国巍 1 , 段祺君 3 , 尹国华 1 , 燕一博 1 , 宋景萱 1, 2 , 谢庆 1
绝缘材料 | 材料研究 2025,58(1): 11-19
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绝缘材料 | 材料研究 2025, 58(1): 11-19
等离子体氟化纳米SiO2对高温受潮状态下环氧树脂表面绝缘性能的影响研究
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骆立衡1, 郭骏毅1, 夏国巍1, 段祺君3, 尹国华1, 燕一博1, 宋景萱1, 2, 谢庆1
作者信息
  • 1.华北电力大学 河北省输变电设备安全防御重点实验室,河北 保定 071003
  • 2.华北电力大学 新能源电力系统国家重点实验室,北京 102206
  • 3.北京智慧能源研究院,北京 102209

通讯作者:

谢庆(1979-),男(汉族),四川广安人,教授,博士,主要从事高电压与绝缘技术、新型电力系统电气设备智能化的研究。
Study on effect of plasma fluorinated nano-SiO2 on surface insulating properties of epoxy resin under high temperature and moisture conditions
Liheng LUO1, Junyi GUO1, Guowei XIA1, Qijun DUAN3, Guohua YIN1, Yibo YAN1, Jingxuan SONG1, 2, Qing XIE1
Affiliations
  • 1. Hebei Provincial Key Laboratory of Power Transmission Equipment Security Defense, North China Electric Power University, Baoding 071003, China
  • 2. State Key Laboratory of Alternate Electrical Power System with Renewable Energy Sources, North China Electric Power University, Beijing 102206, China
  • 3. Beijing Smart Energy Research Institute, Beijing 102209, China
出版时间: 2025-01-20 doi: 10.16790/j.cnki.1009-9239.im.2025.01.002
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随着电网容量和电压等级的提升,环氧复合绝缘材料的绝缘性能对电气设备的安全稳定运行至关重要,长期的高温高湿状态会导致材料的绝缘性能严重下降。本文基于介质阻挡放电(Dielectric Barrier Discharge,DBD)的等离子体技术对纳米SiO2进行氟化改性(F-SiO2),成功将含氟基团接枝在纳米SiO2表面,并通过湿热老化实验模拟高温受潮状态,对不同老化阶段的试样进行沿面闪络、电荷消散特性和陷阱分布特性测试。探究了掺杂F-SiO2对环氧复合材料耐湿热老化性能的影响,并结合MD仿真模拟从分子尺度揭示了F-SiO2对水分侵入的抑制机理。实验结果表明:掺杂F-SiO2使环氧复合材料的饱和吸湿量降低了16.16%,沿面闪络电压提升了13.06%,且在湿热老化后能继续保持较高的绝缘性能。仿真结果表明:F-SiO2可以降低环氧树脂的自由体积分数和水分子的均方位移,增强了环氧复合材料对水分的阻隔作用。等离子体技术可以将氟元素接枝到纳米SiO2表面,有效抑制水分的侵入,提升环氧复合材料在受潮状态下的表面绝缘性能。

等离子体氟化  /  环氧复合材料  /  湿热老化  /  水分扩散  /  分子动力学

With the increase of grid capacity and voltage level, the insulating properties of epoxy composite insulation materials is crucial to the safe and stable operation of electrical equipment. Long-term high temperature and high humidity will lead to a serious decline in insulating properties of materials. Nano-SiO2 was fluorinated (F-SiO2) by the plasma technology of dielectric barrier discharge (DBD) in this paper, and fluorine-containing groups were successfully grafted on the surface of nano-SiO2. The high-temperature and humid state of the material was simulated by the wet heat ageing experiment, and the surface flashover, charge dissipation characteristics and trap distribution characteristics of the samples at different ageing stages were tested. The effect of doping F-SiO2 on the wet heat ageing resistance of epoxy composites was explored, and the inhibition mechanism of F-SiO2 on the water intrusion was revealed from the molecular scale in combination with MD simulation. The experimental results show that doping F-SiO2 reduces the saturated moisture absorption of epoxy composites by 16.16%, increases the surface flashover voltage by 13.06%, and can continue to maintain high insulating properties after wet heat ageing. The simulation results show that F-SiO2 can reduce the free volume fraction of epoxy resin and the mean square displacement of water molecules, and enhance the barrier effect of epoxy composites on moisture. Plasma technology can graft fluorine elements onto the surface of nano-SiO2, effectively inhibiting the intrusion of moisture and enhancing the surface insulating properties of epoxy composites in a humid state.

plasma fluorination  /  epoxy composites  /  hygrothermal ageing  /  moisture diffusion  /  molecular dynamics
骆立衡, 郭骏毅, 夏国巍, 段祺君, 尹国华, 燕一博, 宋景萱, 谢庆. 等离子体氟化纳米SiO2对高温受潮状态下环氧树脂表面绝缘性能的影响研究. 绝缘材料, 2025 , 58 (1) : 11 -19 . DOI: 10.16790/j.cnki.1009-9239.im.2025.01.002
Liheng LUO, Junyi GUO, Guowei XIA, Qijun DUAN, Guohua YIN, Yibo YAN, Jingxuan SONG, Qing XIE. Study on effect of plasma fluorinated nano-SiO2 on surface insulating properties of epoxy resin under high temperature and moisture conditions[J]. Insulating Materials, 2025 , 58 (1) : 11 -19 . DOI: 10.16790/j.cnki.1009-9239.im.2025.01.002
近年来,环氧复合绝缘材料在电力领域得到了广泛应用,包括变压器、断路器、绝缘子等[1-2],能够有效地提高电气设备的耐潮湿性、绝缘性能和抗短路能力,从而确保电力系统的安全性和稳定性。在实际工况下,环氧复合绝缘材料常常面临特殊环境下的挑战,比如高温和高湿条件。在高湿度环境下,材料容易吸收水分,导致材料内部湿度增加,从而引发严重的吸湿劣化问题[3-4]
研究认为,环氧树脂材料中的水分扩散行为会导致其介质损耗上升,介电常数升高,从而使内部电场分布极不均匀而产生局部放电、闪络放电甚至是绝缘击穿等故障[4-6],因此环氧树脂材料的耐湿热性能难以满足大多数的实际工程应用。通过物理方法或化学方法向环氧树脂基体中添加填料,可以提高环氧树脂的电学、热学性能和力学性能[7-9]。其中,微纳米SiO2因其成本低廉、热学和力学性能优良,成为制备环氧树脂复合材料的常用填料。作为无机纳米填料,SiO2可以有效地抑制水分的侵蚀,但其与环氧树脂结合强度不高,界面效应也较差,难以在高温受潮状态下保持较高的绝缘性能[10]
含氟有机物难溶于水[11],且碳氟化合物被视为极具稳定性和惰性的化学物质,使其在各种化学环境中都表现出卓越的耐受性[12-13]。因此从理论上来看,采用氟化技术对环氧树脂及复合材料进行改性,可以提升绝缘材料面对潮湿、高温等恶劣环境时的预期性能。等离子体氟化技术是近年来的研究热点之一,可以用来对材料表面进行氟化处理,通常能够在几纳米至几十纳米的深度范围内实现氟化[14],同时氟化填料改性环氧树脂相关的技术也较为成熟[15-17]。杜伯学等[18]对聚酰亚胺薄膜进行直接氟化处理,使得薄膜表面形成氟化屏蔽层,抑制了电荷注入,减少了空间电荷积累。詹振宇等[19]通过等离子体在环氧样品表面接枝氟元素,显著提升了材料的闪络电压。但在湿热环境下,对环氧复合绝缘材料的填料进行氟化改性以增强复合绝缘材料的耐湿热老化性能的相关研究较少,因此研究氟化填料对环氧复合材料阻止水分扩散的效果具有重要的科学价值。
本文采用等离子体氟化纳米SiO2的方法,调节环氧复合材料在受潮状态下的表面绝缘性能,并对掺杂SiO2和氟化SiO2(F-SiO2)的环氧复合材料进行加速湿热老化处理。通过对不同老化阶段的样品进行沿面闪络和电荷消散特性测试,研究湿热老化后F-SiO2对环氧复合材料闪络电压及表面电荷消散的影响,并通过不同老化时间样品质量的变化情况,探究F-SiO2对环氧复合材料内部水分扩散的影响规律。最后,结合微观表征和分子动力学仿真,从微观结构变化的角度解释等离子体氟化SiO2对环氧树脂复合材料在高温受潮状态下表面绝缘性能的影响机制。
本文通过DBD等离子体放电氟化处理粒径为50 nm的SiO2,步骤如下:首先,将适量干燥后的纳米SiO2均匀涂覆在DBD反应釜表面,并将该反应釜放置在上下两金属电极之间。其次,通过调节气体流量计,设定Ar的流速为2.5 L/min,CF4的流速为0.4 L/min,并将混合气体均匀引入到反应釜中。其中,Ar用作保护气体,CF4则是氟源气体。随后,待气流稳定后,启动等离子体激励器电源,并将激励器电压调至6 kV,频率设定为50 kHz。此时,反应釜内将形成稳定的等离子体放电,从而使CF4气体及纳米SiO2表面产生大量活性基团,进而将含氟基团接枝在填料表面上。等离子体介质阻挡放电过程如图1所示。
环氧纳米SiO2复合材料的制备流程如下:首先,将适量双酚A型环氧树脂、甲基四氢邻苯二甲酸酐固化剂称量后加入烧杯中,设置搅拌速率为300 r/min,在60℃下搅拌10 min,再添加适量的 2,4,6-三(二甲氨基甲基)苯酚促进剂,控制环氧树脂、固化剂、促进剂的质量比为100∶80∶1。然后添加适量的50 nm SiO2粉末,控制SiO2的质量分数为3%,继续搅拌20 min,使各组分充分混合。在80℃下抽真空,以去除共混物中的气泡,并将混合物浇注至模具,进一步脱泡处理后升温至120℃固化 2 h,初步固化完成,再在120℃下后固化10 h。确保环氧树脂与酸酐等充分固化,使得环氧复合材料固化物基本达到最大交联度[20],得到的环氧复合材料分别命名为SiO2-EP和F-SiO2-EP。
考虑到本文所用环氧树脂的玻璃化转变温度、高压绝缘设备中环氧复合材料的运行温度以及阿伦尼乌斯“十度法则”,在特定的温度范围内,每升高10℃,反应速率或过程速率大约增加1倍。故本文使用水煮的方法模拟材料的高温受潮状态,将环氧复合材料试样置于去离子水中,并通过电加热板加热至90℃进行加速老化[21]。每间隔1 d取出样片,吸干表面水分后称重。同时,对老化0、5、10、15、20 d的样片进行微观表征及电学性能测试。
图2为环氧树脂复合材料沿面闪络测试平台。在温度为25℃的腔体内部进行负极性直流沿面闪络测试,采用针-针电极配置模拟产生极不均匀的电场。电极尖端曲率半径为0.2 mm,电极间距为7 mm。使用高压直流电源,采用匀速升压法增加电压,加压速率为100 V/s,直到发生闪络放电。为确保实验结果的可靠性,对每种样品取5个试样,分别进行15次闪络实验,并计算平均值作为结果。
图3为表面电位衰减测试平台。首先,将高压直流电源的电压调节至-7 kV,并在距离样片中心上方7 mm处使用充电针对样片充电60 s;其次,使用电容探头在样片上方2 mm处对表面电位进行采集,持续30 min。最后,对采集完成的数据进行归一化处理。
进一步基于等温电流衰减法(isothermal surface potential decay,ISPD)[22],利用电位衰减曲线即可计算得到材料表面的陷阱分布情况。绝缘材料陷阱能级(H ET)与陷阱能级密度(D ET)满足如式(1)~(2)所示关系20
H E T = k B T l n ( ν a t e t )
D E T = t ε 0 ε r Q l d f s p ( t ) d t
式(1)~(2)中:f sp(t)为表面电位衰减函数;k B为玻尔兹曼常数;T为绝对温度;v ate为电子逃逸频率;Q为元电荷量;l为样片厚度;ε 0ε r分别为真空介电常数和相对介电常数;t表示时间。
表面电位衰减曲线满足双指数函数分布,因此f sp(t)可表示为式(3),根据计算结果即可得到复合材料表面的陷阱能级分布曲线。
f s p ( t ) = A e - t u + B e - t v
式(3)中,ABuv为双指数函数的拟合参数。
本文对等离子体氟化改性前后的纳米SiO2进行傅里叶变换红外光谱(FTIR)测试和X射线光电子能谱测试(XPS),结果如图4所示。从图4(a)可以看出,氟化前后的纳米SiO2均在808 cm-1和1 100 cm-1处出现属于Si-O-Si与Si-O键的伸缩振动峰,而氟化后的纳米SiO2在570 cm-1附近出现了C-F2的特征峰,在1 216 cm-1处出现了C-F键的特征峰,说明在纳米SiO2表面成功接枝了含氟基团。
图4(b)可以看出,纳米SiO2在530 eV处存在O 1s峰,在153 eV与104 eV处存在Si 2s与Si 2p特征峰;F-SiO2在687 eV处出现了F 1s特征峰,在832 eV处还出现了F元素的俄歇峰。使用Avantage软件对C元素和F元素进行分峰处理后得到图4(c)图4(d)。如图4(c)所示,C的分峰图主要包含C-F2、C-F、C-O和C-C 4个峰,分别出现在292.0、288.5、285.8、284.7 eV。如图4(d)所示,F的分峰图为1个单峰,出现在688.5 eV附近。分析认为,作为氟源气体的CF4在等离子体改性过程中电离生成含氟自由基,以-CF2和-CF为主要形式接枝在纳米SiO2表面。
通过XPS测试结果获取SiO2氟化前后的主要元素含量占比,如表1所示。
表1可知,F-SiO2表面F元素占比达到17.20%,而Si元素和O元素占比相比SiO2有明显的下降。结合FTIR和XPS谱图可以看出,等离子体氟化技术可以有效地将氟元素接枝到纳米SiO2表面,增加含氟基团的数量。
环氧复合材料的吸湿规律可以根据吸湿量随老化时间的变化趋势进行分析。本文中,最长老化时间为20 d,且每隔1 d对样片进行一次质量记录,利用式(4)即可计算复合材料的吸湿量。
η = m t - m 0 m 0 × 100 %
式(4)中:η为样片吸湿量;mt为老化时间为t时的样片质量;m 0为初始样片质量。
图5为掺杂SiO2和F-SiO2的环氧复合材料在不同湿热老化阶段的吸湿量。从图5可以看出,F-SiO2对环氧复合材料吸湿量变化趋势的影响不大,但会直接影响环氧复合材料的饱和吸湿量。在老化初期,3种环氧复合材料的吸湿量明显增加,基本符合Fick扩散定律,即材料中的吸湿量与老化时间的平方根成线性关系,其中F-SiO2-EP的初期吸湿量要略高于SiO2-EP。随着老化时间增加,3种环氧复合材料的吸湿量增加逐渐变慢直至达到饱和,其中 F-SiO2-EP先于SiO2-EP达到饱和,饱和吸湿量约为0.83%,低于SiO2-EP的饱和吸湿量(约为0.99%),F-SiO2-EP饱和吸湿量较SiO2-EP饱和吸湿量降低了16.16%,说明经过等离子体氟化的SiO2比未氟化的SiO2在抑制水分侵入方面表现出显著优势,含氟基团能有效抑制水分扩散,并对侵入环氧复合材料内部的水分子具有一定的束缚作用。
湿热老化后,环氧复合材料的内部电场分布变得极不均匀,可能导致局部放电、闪络放电甚至绝缘击穿等问题[23]。本文对不同老化阶段的环氧复合材料进行了直流沿面闪络测试,结果如图6所示,旨在探究湿热老化对环氧复合材料电气绝缘性能的影响。
图6可以看出,在老化前SiO2-EP环氧复合材料的闪络电压为9.11 kV,SiO2-EP环氧复合材料的闪络电压为10.3 kV,其闪络电压较SiO2-EP提升了13.06%。分析认为,纳米SiO2具有较高的绝缘性能,掺杂纳米SiO2可以提高复合材料整体的绝缘性能,并且其表面羟基也有助于增强纳米SiO2与环氧基体的结合。而经过等离子体氟化处理的纳米SiO2表面接枝了含氟基团,赋予纳米SiO2表面更高的活性,对提升环氧复合材料整体的绝缘性能效果更加显著。
老化初期,SiO2-EP和F-SiO2-EP复合材料在老化5 d时闪络电压略微提升,随着湿热老化持续发展,两种复合材料的闪络电压均呈现下降趋势,其中F-SiO2-EP复合材料的闪络电压在湿热老化过程中一直高于SiO2-EP复合材料,并且F-SiO2-EP复合材料在湿热老化过程中闪络电压下降幅度较小,比较稳定。这是由于F-SiO2-EP复合材料受到SiO2表面含氟基团的影响,在湿热老化水分侵入过程中具有一定的抑制作用。而在老化20 d时EP的闪络电压出现略微上升,这是由于环氧树脂经过长时间湿热老化后,水分渗入与析出达到平衡,环氧树脂吸收的水分逐渐在材料内部分布均匀,减少了局部电场集中和电荷积累现象。
为了研究湿热老化对SiO2-EP和F-SiO2-EP复合材料闪络性能的影响机理,本文采用ISPD法测试了不同老化阶段环氧复合材料的表面电位衰减特性,并对环氧复合材料表面陷阱分布的变化规律进行了计算分析。
图7为环氧复合材料在不同湿热老化阶段的电位衰减特性曲线和陷阱特性分布曲线。从图7(a)(c)的电位衰减曲线可以看出,SiO2-EP复合材料消散最快的阶段分别出现在老化初期(老化5 d)和老化后期(老化20 d),在1 800 s内表面电荷消散了40%左右,而F-SiO2-EP复合材料在1 800 s内表面电荷仅消散了20%和15%。在老化中期(老化10 d和15 d)时,两种复合材料消散速率相差不大,其中老化10 d的SiO2-EP和F-SiO2-EP复合材料在1 800 s内表面电荷分别消散了20%和7%左右。可见,在不同老化阶段F-SiO2-EP复合材料的表面电位衰减速率要显著低于SiO2-EP复合材料,说明F-SiO2-EP复合材料受湿热老化的影响要明显低于SiO2-EP复合材料。
图7(d)(f)的陷阱分布曲线可以看出, F-SiO2-EP复合材料的陷阱曲线更集中,其对应的闪络电压变化幅度也较小。老化后环氧复合材料表面深陷阱的能级与密度整体均呈现不同程度的下降,其中F-SiO2-EP复合材料的下降幅度明显低于SiO2-EP复合材料。老化初期(老化5 d),环氧复合材料的陷阱能级和陷阱密度均呈现下降趋势,SiO2-EP复合材料的陷阱密度下降了20%左右,而 F-SiO2-EP复合材料的陷阱密度下降了12%。随着老化程度的加深,SiO2-EP和F-SiO2-EP复合材料的陷阱能级和陷阱密度均略有上升,符合表面电荷消散规律。
分析认为,老化初期(老化5 d)时,环氧复合材料以材料表面对水分子的吸附与水解作用为主,渗透作用则相对较弱,材料表面吸附水分子后,会钝化一些表面陷阱,减少陷阱密度。老化中期(老化10 d和15 d)时,水分子已经充分侵蚀材料表面并逐层渗透到复合材料内部,在湿热环境中环氧树脂和纳米SiO2之间的界面在湿热环境中可能发生劣化和水解反应,导致界面处的化学键断裂和不均匀性增加,这些界面破坏会产生新的陷阱,使陷阱密度和能级增加。当老化程度进一步加深(老化20 d),复合材料已经达到饱和吸湿,环氧树脂和纳米SiO2之间的界面趋于稳定,这一阶段主要以水分子与环氧树脂间的水解反应过程为主,已有的缺陷逐渐被填充,因此在老化后期深陷阱能级与密度会再次略有升高。
本文利用Material Studio(MS)软件构建了环氧树脂DGEBA、固化剂MTHPA以及一次交联的DGEBA-MTHPA单体分子,如图8(a)(c)所示,并对DGEBA和MTHPA单体模型进行结构优化。在Amorphous Cell模块中,设置模型温度为580 K,密度为0.6 g/cm3,DGEBA和MTHPA的反应摩尔比约为2∶1,构建1个纯环氧模型和2个分别掺杂SiO2、F-SiO2填料的复合模型,如图8(d)(f)所示。
利用交联程序进行多级交联处理,得到交联度为90%的掺杂SiO2、F-SiO2的环氧树脂模型。通过退火脚本[24]对经过弛豫处理的3种环氧模型进行580~270 K退火处理,选取300 K时的模型进行后续计算。
自由体积以“孔穴”的形式分散于材料内部,并为分子提供活动空间,因而分子链才可能发生运动[25]。自由体积理论认为:固态和液态物质的体积V t由两个部分组成:一部分是分子占据的体积V o,另一部分是分子未占据的体积V f,即自由体积。
本文引入自由体积分数(FFV)来表示自由体积的相对大小,其表达式为式(5),其中F FV为自由体积分数。
F F V = V f V o + V f
使用Atom Volumes & Surfaces模块对降温到300 K且经过200 ps NPT系综处理的环氧树脂交联体系模型计算Connolly surface,如图9所示,其中灰色为构建Connolly曲面外表面,蓝色为内表面。
利用式(5)可以计算出每个模型的FFV,取平均值后结果如图10(a)所示,观察发现,掺杂F-SiO2可以降低环氧体系的自由体积分数。这是由于 F-SiO2填料与环氧树脂基体界面间的结合紧密,结构不容易由于水分的侵入而被破坏。通过纳米SiO2对复合材料中自由体积的占据,可以减少水分子的入侵,降低水分对环氧基体内部的腐蚀作用。自由体积的减小使水分子具有更小的运动空间,使分子在体系中更难迁移。
均方位移(Mean square displacement,MSD)表征动力学过程中体系粒子位移平方的平均值,水分子在微观体系中的质心移动可以用均方位移进行描述[26],均方位移的定义为式(6)
D M S = 1 3 N i = 0 N - 1 R i t - R i 0 2
式(6)中: D M S表示均方位移;Ri(t)和Ri(0)分别表示系统内任何原子Ri在时间t和初始时的位移矢量。
MS软件中,分子轨迹文件记录了体系的运动状态(如速度和位置等)信息,通过计算分子轨迹文件的均方位移,结果如图10(b)所示。
图10(b)可知,掺杂F-SiO2的环氧树脂体系的均方位移低于掺杂SiO2的环氧树脂体系。这是由于含氟基团与水的极性相差很大,导致两者之间的界面张力很大,从而抑制F-SiO2在水中的分散,而且自由体积的减小会使水分子的运动空间更小,水分子在体系内更难迁移,从而降低了水分子的MSD,增加了水分子向环氧复合材料内部扩散的难度,增强了复合材料对水分的阻隔作用。因此掺杂F-SiO2的环氧树脂疏水性更优。
本文利用等离子体技术对纳米SiO2进行氟化改性,以增强掺杂SiO2的环氧复合材料在高温受潮状态下的表面绝缘性能。通过对掺杂SiO2和F-SiO2的环氧复合材料的吸湿量、闪络电压和表面电荷陷阱分布等电学性能参数进行测试,并结合微观表征和MD仿真,解释了等离子体氟化SiO2对水分的阻隔作用及高温受潮状态下表面绝缘性能的影响机制,得到如下主要结论:
(1)利用等离子体技术对SiO2进行氟化改性可以将氟元素接枝到纳米SiO2表面,减少表面羟基的数量,增强了纳米SiO2与环氧基体的结合程度,从而增强了环氧复合材料在高温受潮状态下的表面绝缘性能。
(2)通过湿热老化实验发现,F-SiO2-EP复合材料吸湿量有所下降,说明氟化技术可以增强环氧复合材料对水分的阻隔作用。复合材料中水分含量的减少,降低了对环氧基体的腐蚀作用,从而提高了闪络电压等电气性能,增强了环氧复合材料在高温受潮状态下的表面绝缘性能。
(3)利用MD仿真模拟发现,氟化SiO2可以降低环氧复合材料内部的自由体积分数,以此抑制水分的侵入,从而降低了水分子在复合材料中的均方位移,增强了F-SiO2-EP复合材料对水分的阻隔作用。
  • 国家自然科学基金面上项目(52277147)
  • 国创计划资助项目(112616)
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2025年第58卷第1期
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doi: 10.16790/j.cnki.1009-9239.im.2025.01.002
  • 接收时间:2024-04-29
  • 首发时间:2025-11-05
  • 出版时间:2025-01-20
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  • 收稿日期:2024-04-29
  • 修回日期:2024-06-13
基金
国家自然科学基金面上项目(52277147)
国创计划资助项目(112616)
作者信息
    1.华北电力大学 河北省输变电设备安全防御重点实验室,河北 保定 071003
    2.华北电力大学 新能源电力系统国家重点实验室,北京 102206
    3.北京智慧能源研究院,北京 102209

通讯作者:

谢庆(1979-),男(汉族),四川广安人,教授,博士,主要从事高电压与绝缘技术、新型电力系统电气设备智能化的研究。
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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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