Article(id=1203281644909208181, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1203281635908231645, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2025.06.013, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1722268800000, receivedDateStr=2024-07-30, revisedDate=1726761600000, revisedDateStr=2024-09-20, acceptedDate=null, acceptedDateStr=null, onlineDate=1764814300038, onlineDateStr=2025-12-04, pubDate=1750348800000, pubDateStr=2025-06-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1764814300038, onlineIssueDateStr=2025-12-04, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1764814300038, creator=13701087609, updateTime=1764814300038, updator=13701087609, issue=Issue{id=1203281635908231645, tenantId=1146029695717560320, journalId=1149653034449285133, year='2025', volume='58', issue='6', pageStart='1', pageEnd='148', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=0, articleOrder=1, issueType=-1, specialIssue=null, createTime=1764814297892, creator=13701087609, updateTime=1764815002353, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1203284590690545746, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1203281635908231645, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1203284590694740051, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1203281635908231645, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=105, endPage=114, ext={EN=ArticleExt(id=1203281645441884812, articleId=1203281644909208181, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Effect of different accelerated ageing conditions on ageing behavior of nitrile rubber for 500 kV transformer, columnId=1190369198472794288, journalTitle=Insulating Materials, columnName=Insulation Technology, runingTitle=null, highlight=

Under the high temperature conditions (90, 105, 120, and 135°C), accelerated ageing tests of nitrile rubber (NBR) were conducted in hot air, hot oil, hot air compression, and hot oil compression. The ageing mechanisms were investigated through Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA/DTG), and scanning electron microscopy (SEM), and the effects of ageing temperature, time, and deformation conditions on the ageing behavior of NBR were revealed. The results indicate that crosslinking, oxidation, and chain-breaking reactions occur during the ageing process of NBR, and the crosslinking reaction is the predominant reaction. After ageing at 120°C, grooves appear on the surface of NBR, and after ageing at 135°C, defects such as holes and damages appear on the surface. In the early stage of ageing, transformer oil has a suppressive effect on the increase of permanent deformation under compression. In the later stage of ageing, transformer oil plays a promote role for the decrease of tensile strength, and the higher the temperature, the more obvious the effect.

, articleAbstract=

Under the high temperature conditions (90, 105, 120, and 135°C), accelerated ageing tests of nitrile rubber (NBR) were conducted in hot air, hot oil, hot air compression, and hot oil compression. The ageing mechanisms were investigated through Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA/DTG), and scanning electron microscopy (SEM), and the effects of ageing temperature, time, and deformation conditions on the ageing behavior of NBR were revealed. The results indicate that crosslinking, oxidation, and chain-breaking reactions occur during the ageing process of NBR, and the crosslinking reaction is the predominant reaction. After ageing at 120°C, grooves appear on the surface of NBR, and after ageing at 135°C, defects such as holes and damages appear on the surface. In the early stage of ageing, transformer oil has a suppressive effect on the increase of permanent deformation under compression. In the later stage of ageing, transformer oil plays a promote role for the decrease of tensile strength, and the higher the temperature, the more obvious the effect.

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在高温(90、105、120、135℃)条件下,开展丁腈橡胶(NBR)的热空气、热油、热空气压缩和热油压缩加速老化试验,并通过傅里叶红外光谱、TGA/DTG和SEM探究其老化机理,揭示老化温度、时间和变形条件对NBR老化行为的影响。结果表明:NBR老化过程中会发生交联反应、氧化反应和断链反应,且以交联反应为主;120℃老化后NBR表面会出现沟槽,135℃老化后表面会出现孔洞和破损等缺陷。在老化前期,变压器油对NBR压缩永久变形具有抑制作用;在老化后期,变压器油对NBR拉伸强度的下降具有加速作用,且温度越高,效果越明显。

, articleAbstract=

在高温(90、105、120、135℃)条件下,开展丁腈橡胶(NBR)的热空气、热油、热空气压缩和热油压缩加速老化试验,并通过傅里叶红外光谱、TGA/DTG和SEM探究其老化机理,揭示老化温度、时间和变形条件对NBR老化行为的影响。结果表明:NBR老化过程中会发生交联反应、氧化反应和断链反应,且以交联反应为主;120℃老化后NBR表面会出现沟槽,135℃老化后表面会出现孔洞和破损等缺陷。在老化前期,变压器油对NBR压缩永久变形具有抑制作用;在老化后期,变压器油对NBR拉伸强度的下降具有加速作用,且温度越高,效果越明显。

, correspAuthors=null, authorNote=null, correspAuthorsNote=
康举(1983-),男(满族),河北承德人,副教授,博士,主要从事电网金属材料和绝缘电介质材料的故障分析、寿命评估等研究工作。
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王振龙(1999-),男(汉族),山东滨州人,硕士生,主要研究方向为电网绝缘电介质材料的故障分析、寿命评估等;

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王振龙(1999-),男(汉族),山东滨州人,硕士生,主要研究方向为电网绝缘电介质材料的故障分析、寿命评估等;

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王振龙(1999-),男(汉族),山东滨州人,硕士生,主要研究方向为电网绝缘电介质材料的故障分析、寿命评估等;

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Journal of Polymer Science,2021,52(7):762-774., articleTitle=Study on the aging behavior and mechanism of nitrile rubber under the coupling action of multiple factors, refAbstract=null)], funds=[Fund(id=1203362950808576149, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1203281644909208181, awardId=52175286, language=CN, fundingSource=国家自然科学基金资助项目(52175286), fundOrder=null, country=null), Fund(id=1203362950905045146, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1203281644909208181, awardId=52018K22001L, language=CN, fundingSource=国网冀北电力有限公司科技项目(52018K22001L), fundOrder=null, country=null)], companyList=[AuthorCompany(id=1203362942717764449, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1203281644909208181, xref=null, ext=[AuthorCompanyExt(id=1203362942726153058, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1203281644909208181, companyId=1203362942717764449, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1. 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tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1203281644909208181, language=CN, label=图6, caption=NBR在4种老化条件下加速老化336 h前后的红外光谱, figureFileSmall=PNy4B5TZ9ADnoX5EEnWxnw==, figureFileBig=jehsrgoWScKjYr71b+Rgsg==, tableContent=null), ArticleFig(id=1203362948828864623, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1203281644909208181, language=EN, label=Fig.7, caption=TG/DTG analysis curves of NBR under different ageing conditions at 120℃, figureFileSmall=J5+1xPkgJukrco0ELw+IjA==, figureFileBig=WCcjXMTKkaHUSx/PrJFzGQ==, tableContent=null), ArticleFig(id=1203362948929527923, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1203281644909208181, language=CN, label=图7, caption=NBR在120℃不同老化条件下的TG/DTG分析曲线, figureFileSmall=J5+1xPkgJukrco0ELw+IjA==, figureFileBig=WCcjXMTKkaHUSx/PrJFzGQ==, tableContent=null), ArticleFig(id=1203362949017608312, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1203281644909208181, language=EN, label=Fig.8, caption=Changes in the internal structure of NBR during ageing process, figureFileSmall=A5byIBjJUqNVo5mwj8YQaw==, figureFileBig=QO5KVICtubDEHZI0Q/MAIg==, tableContent=null), ArticleFig(id=1203362949101494398, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1203281644909208181, language=CN, label=图8, caption=NBR老化过程中内部结构的变化, figureFileSmall=A5byIBjJUqNVo5mwj8YQaw==, figureFileBig=QO5KVICtubDEHZI0Q/MAIg==, tableContent=null), ArticleFig(id=1203362950351396993, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1203281644909208181, language=EN, label=Table 1, caption=Experimental grouping, figureFileSmall=null, figureFileBig=null, tableContent=
组别

加速老

化环境

试样类型介质试验温度/℃试验周期/h取样时间/h检测项目
1热空气I型哑铃状空气90、105、120、13533624、48、96、144、192、240、336拉伸强度
2热油25#变压器油
3热空气压缩B型圆柱体空气压缩永久变形
4热油压缩25#变压器油
), ArticleFig(id=1203362950431088771, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1203281644909208181, language=CN, label=表1, caption=

试验分组

, figureFileSmall=null, figureFileBig=null, tableContent=
组别

加速老

化环境

试样类型介质试验温度/℃试验周期/h取样时间/h检测项目
1热空气I型哑铃状空气90、105、120、13533624、48、96、144、192、240、336拉伸强度
2热油25#变压器油
3热空气压缩B型圆柱体空气压缩永久变形
4热油压缩25#变压器油
), ArticleFig(id=1203362950531752070, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1203281644909208181, language=EN, label=Table 2, caption=Mass loss rate of NBR before and after ageing at 120℃ %, figureFileSmall=null, figureFileBig=null, tableContent=
热分解过程未老化NBR热空气热油热空气压缩热油压缩
第1阶段8.836.3410.028.8910.56
第2阶段48.3044.7846.4544.7444.37
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NBR在120℃老化前后的质量损失率

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热分解过程未老化NBR热空气热油热空气压缩热油压缩
第1阶段8.836.3410.028.8910.56
第2阶段48.3044.7846.4544.7444.37
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不同加速老化条件对500 kV变压器用丁腈橡胶老化行为的影响
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王振龙 1 , 季昌国 2 , 韩哲文 2 , 林林 3 , 宋子博 2 , 康举 1
绝缘材料 | 绝缘技术 2025,58(6): 105-114
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绝缘材料 | 绝缘技术 2025, 58(6): 105-114
不同加速老化条件对500 kV变压器用丁腈橡胶老化行为的影响
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王振龙1, 季昌国2, 韩哲文2, 林林3, 宋子博2, 康举1
作者信息
  • 1.北京石油化工学院 机械工程学院,北京 102617
  • 2.国网冀北电力有限公司电力科学研究院, 北京 100045
  • 3.国网冀北电力有限公司,北京 100045
  • 王振龙(1999-),男(汉族),山东滨州人,硕士生,主要研究方向为电网绝缘电介质材料的故障分析、寿命评估等;

通讯作者:

康举(1983-),男(满族),河北承德人,副教授,博士,主要从事电网金属材料和绝缘电介质材料的故障分析、寿命评估等研究工作。
Effect of different accelerated ageing conditions on ageing behavior of nitrile rubber for 500 kV transformer
Zhenlong WANG1, Changguo JI2, Zhewen HAN2, Lin LIN3, Zibo SONG2, Ju KANG1
Affiliations
  • 1. School of Mechanical Engineering, Beijing Institute of Petrochemical Technology, Beijing 102617, China
  • 2. State Grid Jibei Electric Power Co., Ltd. Electric Power Research Institute, Beijing 100045, China
  • 3. State Grid Jibei Electric Power Co., Ltd., Beijing 100045, China
出版时间: 2025-06-20 doi: 10.16790/j.cnki.1009-9239.im.2025.06.013
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在高温(90、105、120、135℃)条件下,开展丁腈橡胶(NBR)的热空气、热油、热空气压缩和热油压缩加速老化试验,并通过傅里叶红外光谱、TGA/DTG和SEM探究其老化机理,揭示老化温度、时间和变形条件对NBR老化行为的影响。结果表明:NBR老化过程中会发生交联反应、氧化反应和断链反应,且以交联反应为主;120℃老化后NBR表面会出现沟槽,135℃老化后表面会出现孔洞和破损等缺陷。在老化前期,变压器油对NBR压缩永久变形具有抑制作用;在老化后期,变压器油对NBR拉伸强度的下降具有加速作用,且温度越高,效果越明显。

丁腈橡胶  /  交联反应  /  变压器油  /  高温加速老化  /  热油压缩

Under the high temperature conditions (90, 105, 120, and 135°C), accelerated ageing tests of nitrile rubber (NBR) were conducted in hot air, hot oil, hot air compression, and hot oil compression. The ageing mechanisms were investigated through Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA/DTG), and scanning electron microscopy (SEM), and the effects of ageing temperature, time, and deformation conditions on the ageing behavior of NBR were revealed. The results indicate that crosslinking, oxidation, and chain-breaking reactions occur during the ageing process of NBR, and the crosslinking reaction is the predominant reaction. After ageing at 120°C, grooves appear on the surface of NBR, and after ageing at 135°C, defects such as holes and damages appear on the surface. In the early stage of ageing, transformer oil has a suppressive effect on the increase of permanent deformation under compression. In the later stage of ageing, transformer oil plays a promote role for the decrease of tensile strength, and the higher the temperature, the more obvious the effect.

nitrile rubber  /  crosslinking reaction  /  transformer oil  /  high-temperature accelerated ageing  /  hot oil compression
王振龙, 季昌国, 韩哲文, 林林, 宋子博, 康举. 不同加速老化条件对500 kV变压器用丁腈橡胶老化行为的影响. 绝缘材料, 2025 , 58 (6) : 105 -114 . DOI: 10.16790/j.cnki.1009-9239.im.2025.06.013
Zhenlong WANG, Changguo JI, Zhewen HAN, Lin LIN, Zibo SONG, Ju KANG. Effect of different accelerated ageing conditions on ageing behavior of nitrile rubber for 500 kV transformer[J]. Insulating Materials, 2025 , 58 (6) : 105 -114 . DOI: 10.16790/j.cnki.1009-9239.im.2025.06.013
丁腈橡胶(NBR)是丙烯腈和丁二烯乳液共聚物,其分子式见式(1)[1-3],由于它含有极性物质——丙烯腈,使其具有耐高低温、耐油、耐磨和耐腐蚀等性能[4-5]。因此,NBR被广泛应用于对耐油性能要求苛刻的工作环境中,其中包括变压器行业,主要用于减震垫和密封圈[6]
然而,由于NBR还含有大量的不饱和双键丁二烯单元(式(1)),并且在变压器的应用环境中,往往受到高温、氧气、变压器油、机械载荷等多种环境因素的协同作用[7-9],加速NBR老化,使之出现硬化、脆化、龟裂及变形等问题,导致其各项性能大幅下降,直至失效,极大地影响变压器的稳定运行[10]。因此,评价环境因素对NBR老化过程的影响,对促进NBR在电力行业中的应用具有重要意义。
由于NBR在实际工作环境下的老化速率较慢,通常采用高温加速老化试验来研究NBR的老化规律[11-15]。ZHAO J等[13]对NBR进行高温加速老化试验,研究NBR的热氧化老化过程,发现交联发生在整个老化过程中,而链断裂则在老化后期发生并与交联竞争,交联密度几乎以恒定的速率增加,而交联度的增加速率在老化后期放缓。LIU X等[15]对比研究了NBR在空气、商业润滑油和基础油介质中老化前后挥发性组分和化学结构的变化,发现基础油由于屏障作用和氧气的消耗,可以保护橡胶免受严重的氧化和交联,而商业润滑油会与NBR中的添加剂反应,渗透到橡胶中,促进橡胶的氧化和交联,加速NBR老化。ZHAO Q等[16]模拟了空气和液压油环境,研究NBR在自由状态和压缩状态下的老化行为和降解机理,发现压缩应力和油介质均减缓了NBR的老化。纵观已有文献,国内外学者在NBR加速老化试验和老化机理方面开展了大量工作,但是已有工作大多只分析单一条件对NBR老化的影响,对实际工况中多因素作用下NBR的老化行为和机理鲜有涉及。
因此,本研究对NBR在高温(90、105、120、135℃)条件下进行热空气、热油、热空气压缩、热油压缩加速老化试验,并通过傅里叶红外光谱、热失重(TGA)和扫描电镜(SEM)来探究老化机理,揭示老化温度、时间和变形条件对NBR老化行为的影响。
试验材料为NBR,江苏神马电力股份有限公司生产,规格为30 mm×20 mm,用于现役500 kV油浸式变压器。参照GB/T 528—2009(等同于ISO 37:2005)进行拉伸试样制备及拉伸试验,拉伸试样采用I型哑铃状试样,总长度为115 mm(其中试验长度为25 mm),端部宽度为25 mm,狭窄部分长度和宽度分别为33 mm和6 mm,厚度为2 mm。参照GB/T 7759.1—2015(等同于ISO 815-1:2008)进行压缩永久变形试样制备及压缩试验,压缩试样采用B型圆柱体试样,直径为13 mm,高度为6.5 mm。拉伸试样和压缩试样均通过橡胶切片机或压片机进行裁切制备。
综合考虑NBR在变压器中的实际工作环境以及25#变压器油的特性等因素,参照GB/T 2941—2006(等同于ISO 23529:2004)和H/GT 2887—2018,选择4组加速老化温度进行试验,老化温度分别为90、105、120、135℃,加速老化试验周期为336 h。按照“前紧后疏”的取样原则,分别取第24、48、96、144、192、240、336 h老化后的试样进行检测,具体试验分组如表1所示。对NBR在4种条件下(热空气、热油、热空气压缩以及热油压缩)进行加速热老化试验,其中热空气压缩和热油压缩试验组中的试样放置于压缩永久变形装置中,压缩装置符合GB/T 7759.1—2015(等同于ISO 815-1:2008)标准要求,保证试样上下表面均匀受力;热油和热油压缩试验组试样需完全浸没在25#变压器油中(该变压器油的性能指标符合IEC 60296:2020标准要求)。
表1所示试验条件,对拉伸试样进行老化试验,达到取样时间后,分别随机取出3个试样,在室温下放置24 h后,采用MTS-CET400型微型电子万能试验机在室温下进行拉伸测试,拉伸速度为500 mm/min,获得试样的拉伸强度,取平均值并求标准差。
选取3个尺寸一致的B型圆柱体试样放入压缩装置中,通过限制器保持25%的压缩率,按照表1所列方案进行热空气压缩和热油压缩老化试验,达到取样时间后取出压缩装置,立即解除压缩并将试样取出置于木板上,在室温下恢复30 min,然后使用YJC106型数显橡胶测厚仪测量每个试样中心部位的高度,即恢复高度(h1),每个试样测量5次,取平均值并求标准差,采用式(1)计算压缩永久变形(C)。
C=h0-h1h0-hs×100%
式(1)中:h0为试样原始高度,mm;h1为试样恢复后的高度,mm;hs为压缩装置限制器高度,mm。
采用配备衰减全反射(ATR)附件的Nicolet iS50型傅里叶变换红外光谱仪对NBR老化前后的化学结构进行表征,波数为4 000~700 cm-1,分辨率为2 cm-1,扫描次数为32次。
采用SDT-650型同步热分析仪(TGA)测试NBR的热分解特性,温度范围为室温~600℃,升温速率为5℃/min,环境气氛为氮气,氮气流量为100 mL/min。
通过TESCAN CLARA型扫描电子显微镜(SEM)观察拉伸试样断口形貌与压缩试样的表面形貌,观察前对试样进行喷金处理。
图1是NBR在不同条件下老化后的拉伸强度变化曲线。从图1可以看出,在热空气老化条件下,试样的拉伸强度在90℃老化温度下呈上升趋势;在105、120、135℃老化温度下,老化前期(0~96 h)拉伸强度略有上升,而在老化后期拉伸强度呈下降趋势。需要说明的是,135℃热空气条件下的老化试样在第288 h后即出现明显的脆化,性能严重下降,故未测试第336 h的拉伸强度,下文在热油中的试验同理。在热油老化条件下,试样的拉伸强度在90℃老化温度下呈现上升趋势,在105℃老化温度下呈现轻微的下降趋势,而在120℃和135℃老化温度下均呈明显的下降趋势,且在135℃老化温度下老化192 h后试样的拉伸强度已经趋于稳定。结果表明,在热油老化条件下,温度越高,NBR的拉伸强度下降得越快。对比图1(a)图1(b)可知,在相同温度下老化相同时间后,NBR在热油条件下的拉伸强度下降程度比热空气条件下的更大,可以推断变压器油具有加速NBR老化的作用。
NBR无论是热空气还是热油条件下的拉伸强度在90℃老化温度下均呈上升趋势,这是由于这个温度下NBR老化程度较轻,有部分分子链发生交联反应并生成交联结构,分子链间相对滑移的难度增加,提高了NBR的抗拉伸能力[7,16-17]。随着老化温度的升高,NBR的拉伸强度下降,这是因为更高的温度导致橡胶发生氧化反应、断链反应,破坏了NBR分子链的连接,使得分子链逐步降解。此外,对于在变压器油中的试样,由于变压器油在高温下会发生氧化降解,产生的氧化产物如羟基(-OH)、酮基(-C=O)、羧基(-COOH)等,与油分子共同侵入橡胶内部,使大分子链结构之间的作用力减弱,导致大分子链结构解缠,加速了NBR的老化,使得拉伸强度下降更严重[18-20]。综上,老化初期,高温会提高NBR的拉伸强度,随着老化时间的延长,拉伸强度降低。温度越高,拉伸强度下降速率越快,且变压器油起到了加速老化的作用。
图2(a)为未老化NBR拉伸断口形貌,可以看到填充剂和其他助剂均匀地分布在橡胶基体中。图2(b)~(e)分别为NBR在4种加速老化条件下老化336 h后的拉伸断口形貌,在120℃热空气条件下老化336 h后,断口表面明显粗糙,出现颗粒团聚(如图2(b)所示);在120℃热油条件下老化336 h后,颗粒团聚比较少,但出现孔洞,呈现为韧脆混合断裂的特征(如图2(c)所示);在135℃热空气条件下老化336 h后,断口表面出现明显的沟壑和孔洞,以及长条状的聚集物,呈现出明显的脆性断裂特征(如图2(d)所示);在135℃热油条件下老化336 h后,颗粒物聚集和凹坑数量明显增多(如图2(e)所示)。上述结果表明,NBR在老化过程中,会产生孔洞、颗粒物聚集、破损等缺陷,并且随着温度的升高,缺陷越严重,脆化现象越明显[19]
图3为NBR在不同条件下老化后的压缩永久变形曲线。从图3可以看出,在热空气压缩和热油压缩下,随着温度的升高和老化时间的延长,NBR的压缩永久变形均随之增大,并且趋势相同:即试验前期(0~96 h)增速较快,试验后期(120~336 h)趋于平缓。对比图3(a)3(b)可知,在相同温度下在热油中的压缩永久变形明显小于在热空气中的压缩永久变形。
橡胶的压缩永久变形主要受其分子链恢复能力的影响,橡胶在受到压缩力作用时,如果发生交联反应,则因新形成的交联键对橡胶网络结构的固定作用使得橡胶部分或完全不能恢复[21]。受压缩时交联反应发生的原因是,当NBR受到压缩力作用时,分子链之间的距离会变小,并使NBR内部温度升高,从而促进交联反应的进行。因此,交联反应导致NBR在老化过程中压缩永久变形的增加,并且在热空气中比热油中的交联反应更加明显。这是由于热油压缩试样完全沉浸在25#变压器油中,有效阻止了空气与NBR的接触,另外25#变压器油中添加了一些助剂,如抗氧化剂等,这些助剂会渗入NBR中,阻碍NBR分子与氧发生反应,改变橡胶的结构和性能,增加了橡胶的柔软度[21-22],导致交联反应的程度降低,使老化后压缩永久变形的程度减轻。但是随着老化时间的延长,溶胀到达平衡后,加之交联结构的增加以及链断裂逐渐增多[18],导致压缩永久变形逐渐上升。综合以上原因,使得热油压缩试样的恢复高度高于热空气压缩试样。因此,NBR在热油中的压缩永久变形要低于热空气中的压缩永久变形。温度越高,NBR的压缩永久变形越高,变压器油在一定程度上减缓了压缩永久变形的增加。
图4(a)为未老化NBR表面形貌,可以看出表面有轻微的孔洞和沟槽。图4(b)~(e)为NBR在4种加速老化条件下老化336 h后的压缩试样表面形貌。在120℃热空气条件下老化后,NBR经过压缩后,分子链沿特定方向排列,导致取向发生变化,从而产生明显的沟槽(如图4(b)所示);在120℃热油条件下老化后,沟槽深度比较浅,但表面突起异物明显增多(如图4(c)所示)[23]。在135℃空气条件下老化后,试样表面有明显的孔洞缺陷和突起物(如图4(d)所示);在135℃热油条件下老化后,试样表面出现大面积的破损和孔洞(如图4(e)所示)[24-25]。综上,温度越高,对NBR的表面形貌破坏程度越大,由轻微的沟槽到明显的孔洞缺陷,此外变压器油会加重对NBR表面形貌的破坏。
图5为25#变压器油经135℃老化前后的红外光谱,其中2 924 cm-1和2 857 cm-1处的吸收峰分别对应-CH2的不对称和对称伸缩振动峰;2 955 cm-1处为油介质特有的尖峰,即R-CH3结构的不对称伸缩振动峰;1 458 cm-1处为-CH2的变形振动峰,1 371 cm-1处为-CH3的变形振动峰[26-27]
图5可以看出,经过135℃高温加速老化后,变压器油中部分官能团的吸收峰发生明显的变化:-CH2的不对称和对称伸缩振动峰、R-CH3的不对称伸缩振动峰、-CH2的变形振动峰和-CH3的变形振动峰的峰面积均明显增大,且老化时间越长,峰面积越大。这是由于随着老化的进行,变压器油分子链会降解,油中的碳-氢键受到高温、氧气等环境因素的影响而发生断裂和降解,导致碳-氢键含量增加27-28,从而使得红外光谱中-CH2的不对称和对称伸缩振动峰面积增大。在25#变压器油老化的过程中,氧化产物如羟基(-OH)、酮基(-C=O)、羧基(-COOH)等会逐渐积累,这些氧化产物会逐渐渗入NBR试样内部,取代NBR中的某些添加剂,使大分子链结构解缠。
图6为NBR在4种老化条件下加速老化336 h前后的全反射红外光谱图。从图6可以看出,以未老化NBR的红外光谱为例,2 913 cm-1和2 842 cm-1处的吸收峰分别为-CH2-的不对称和对称伸缩振动峰;2 233 cm-1处的特征峰为氰基(-CN)的伸缩振动峰;1 725 cm-1处为C=O的伸缩振动峰;1 423 cm-1处为-CH2-的弯曲振动峰;954 cm-1处的尖峰为反式 (1,4)-CH=CH-的变形振动峰[28]
与未老化NBR相比,NBR老化后,2 913 cm-1、2 842 cm-1处-CH2的吸收峰和2 233 cm-1处-CN的吸收峰峰值明显降低,表明有其他基团产生且橡胶分子链发生交联反应和氧化反应[29-30]。对比图6中4种老化温度下的红外光谱发现,老化温度越高,-CH2的不对称和对称伸缩振动峰峰值下降得越多。954 cm-1处反式(1,4)-CH=CH-的变形振动峰峰值也出现明显降低,表明C=C发生断裂,产生了新的氧化物。1 725 cm-1处的C=O伸缩振动峰峰值降低,说明-C=O-基团浓度降低,这是由于NBR中的部分添加剂在老化过程中逐渐渗出所致。综上表明,高温会降低-CH2-的不对称和对称伸缩振动峰峰值和-CH=CH-的变形振动峰峰值,NBR在老化过程中发生了交联反应和氧化反应:-CN发生交联反应,如式(3)所示32;NBR中的不饱和键(-CH=CH-)发生氧化反应,形成羟基(-OH)和羰基(-C=O)等含氧官能团,如式(4)所示31;自由基也发生交联反应,如式(5)所示[20]
通过对比图6(a)中不同老化条件下-CH=CH-的吸收峰发现,在热油条件下的吸收峰峰值明显高于热空气条件下,印证了变压器油可有效隔绝NBR与氧气的接触,抑制了-CH=CH-峰值的降低。
NBR在120℃不同条件下老化前后的热重分析曲线如图7所示。从图7可以看出,未老化NBR和老化336 h NBR的热分解过程均表现为两个失重阶段:第1阶段(约150~300℃)为缓慢失重阶段,主要是热氧老化过程中增塑剂等低分子物质挥发及吸附水失重;第2阶段(约350~500℃)为快速失重阶段,主要为NBR主链及其交联产物在高温下裂解,这是NBR最主要的分解反应,分解速率最快[21,33-34]。不同老化条件下,两个阶段热分解的质量损失率如表2所示。从表2可以看出,第1阶段未老化NBR的质量损失率为8.83%,在热空气、热油、热空气压缩、热油压缩条件下老化336 h后的质量损失率分别为6.34%、10.02%、8.89%、10.56%,与未老化NBR相比总体上表现为质量损失增加;第2阶段未老化NBR的质量损失率为48.3%,在热空气、热油、热空气压缩、热油压缩条件下老化336 h后的质量损失率分别为44.78%、46.45%、44.74%、44.37%,与未老化NBR相比表现为质量损失降低。
在低温段(第1阶段),老化试验后样品的质量损失率增大,结合红外光谱结果(图6),主要是由于样品在老化试验过程中发生氧化降解生成低分子物质挥发,如一氧化碳、二氧化碳、醛类化合物等;热油条件比热空气条件下(包括:热油vs热空气、热油压缩vs热空气压缩)的质量损失率大,说明热油条件比热空气条件更能抑制物质的挥发;压缩条件比不压缩条件下的质量损失率大(包括:热空气压缩vs热空气、热油压缩vs热油),表明压缩条件下更能抑制物质的挥发。高温段(第2阶段)的质量损失变化再次表明,NBR老化过程中伴随着高分子链的断链。
根据上文试验结果,绘制NBR在老化过程中的内部结构变化示意图,如图8所示。图8(a)~(d)为NBR在热空气中老化过程内部结构变化示意图,首先自由链发生交联后加入网络结构,交联度和交联密度均增加(图8(a)图8(b));随后几乎没有新链加入交联结构,但交联点逐步增加,网络变得越来越紧密,形成一个刚性网络,这个过程中NBR内部的添加剂会不断向外逸出(图8(b)图8(c));最后NBR发生氧化反应,氧化通过自由基的重组诱导了额外的交联,此外氧化还会导致网络中的链断裂,特别是在高温老化条件下,羰基数量增多。由于交联链的两端几乎不可能同时从网络中断裂,链的断裂一般形成非自由链的悬垂链(图8(c)图8(d))。
图8(a)~(c)8(e)为NBR在热油中老化过程内部结构变化示意图,老化前期与热空气中老化过程相同,不同之处在于随着NBR内部添加剂的溢出及外部变压器油分子的渗入,导致NBR交联的网格结构改变,油分子的渗入减小了橡胶内大分子链间的相互作用,使分子链发生溶胀以及大分子链的结构解缠,橡胶软化,导致NBR拉伸强度降低。总结变压器油对NBR老化过程的影响为:在老化前期,油介质会在试样表面形成封闭环境,隔绝NBR与氧气接触,减缓了NBR的氧化和交联过程;在老化中后期,由于变压器油也发生降解,降解产物会逐渐渗入NBR内部,取代NBR中的某些添加剂,使大分子链结构解缠,导致NBR拉伸强度降低(如图1(b)所示),同时由于交联反应速率相对热空气中减缓,使得分子链能保留较多恢复能力,导致在热油中NBR的压缩永久变形相对较低(如图2(b)所示)。
(1)老化温度越高,NBR老化速率越快。在试验时间(336 h)内,90℃老化温度下拉伸强度随老化时间的延长呈上升趋势;其他老化温度下,在热空气中老化前期拉伸强度略有上升、老化后期呈下降趋势,在热油中拉伸强度整体呈下降趋势,且温度越高,下降速率越明显。压缩永久变形随着老化时间和温度的增加而增大。
(2)NBR在120℃老化后表面会出现沟槽,在135℃老化后表面会出现孔洞和破损等缺陷,随着老化温度的升高,缺陷更严重、脆化现象更加明显,且变压器油会使孔洞、破损等缺陷更加严重。
(3)NBR老化过程中会发生交联反应、氧化反应和断链反应,以交联反应为主。高温下变压器油也会发生降解,产生的氧化物会渗入NBR内部,导致NBR的拉伸强度降低。
  • 国家自然科学基金资助项目(52175286)
  • 国网冀北电力有限公司科技项目(52018K22001L)
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2025年第58卷第6期
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doi: 10.16790/j.cnki.1009-9239.im.2025.06.013
  • 接收时间:2024-07-30
  • 首发时间:2025-12-04
  • 出版时间:2025-06-20
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  • 收稿日期:2024-07-30
  • 修回日期:2024-09-20
基金
国家自然科学基金资助项目(52175286)
国网冀北电力有限公司科技项目(52018K22001L)
作者信息
    1.北京石油化工学院 机械工程学院,北京 102617
    2.国网冀北电力有限公司电力科学研究院, 北京 100045
    3.国网冀北电力有限公司,北京 100045

通讯作者:

康举(1983-),男(满族),河北承德人,副教授,博士,主要从事电网金属材料和绝缘电介质材料的故障分析、寿命评估等研究工作。
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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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