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Article(id=1199642732063977820, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1199642729207660562, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2023.11.008, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1682179200000, receivedDateStr=2023-04-23, revisedDate=1684857600000, revisedDateStr=2023-05-24, acceptedDate=null, acceptedDateStr=null, onlineDate=1763946715607, onlineDateStr=2025-11-24, pubDate=1700409600000, pubDateStr=2023-11-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1763946715607, onlineIssueDateStr=2025-11-24, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1763946715607, creator=13701087609, updateTime=1763946715607, updator=13701087609, issue=Issue{id=1199642729207660562, tenantId=1146029695717560320, journalId=1149653034449285133, year='2023', volume='56', issue='11', pageStart='1', pageEnd='116', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1763946714927, creator=13701087609, updateTime=1766563708953, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1210619197772657229, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1199642729207660562, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1210619197772657230, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1199642729207660562, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=47, endPage=52, ext={EN=ArticleExt(id=1199642732365967709, articleId=1199642732063977820, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Effect of antioxidant types in transformer oil on thermal ageing performance of insulating paper, columnId=1190369198472794288, journalTitle=Insulating Materials, columnName=Insulation Technology, runingTitle=null, highlight=null, articleAbstract=

In order to study the effect of antioxidant types in transformer oil on the thermal ageing performance of insulating paper, antioxidants T501, T531, and DBP were added to the insulation system composed of naphthenic mineral oil and insulating paper, and the antioxidant mass fraction was 0.4%. The heat ageing test was carried out at 130℃ for 600 h. The moisture and furfural content in the insulating oil, the moisture content and polymerization degree in the insulating paper were determined every 120 h. At the same time, the aged insulating paper was characterized by FTIR, XRD, SEM, and EDS. The results show that the addition of antioxidant T501 and T531 have little effect on the deterioration of insulating paper, and the deterioration of insulating paper in the oil with antioxidant DBP is aggravate in the late ageing stage. Since the antioxidant T531 has a combination of neutralization and hydrolysis, it inhibits the degradation process of cellulose, and the ageing degree of T351 insulating paper is the lightest.

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为研究变压器油中添加抗氧化剂对绝缘纸热老化性能的影响，向环烷基矿物油、绝缘纸组成的绝缘体系中分别添加T501、T531、DBP 3种抗氧化剂，抗氧化剂质量分数均为0.4%，在130℃下进行热老化试验，老化时长为600 h。每隔120 h测定绝缘油中水分含量和糠醛含量、绝缘纸中水分含量与聚合度，同时对老化绝缘纸进行FTIR、XRD、SEM、EDS表征。结果表明：添加抗氧化剂T501、T531对绝缘纸的劣化影响较小，添加抗氧化剂DBP的油中绝缘纸在老化后期劣化程度加剧；由于T531抗氧化剂具有中和、水解双重作用，对纤维素的降解起到抑制作用，T531绝缘纸的老化程度最轻。

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胡学超（1987-），男（汉族），内蒙古呼和浩特人，高级工程师，博士，硕士生导师，主要从事绝缘电介质材料、电化学储能、电力用油及设备状态感知等研究与应用工作。

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胡学超（1987-），男（汉族），内蒙古呼和浩特人，高级工程师，博士，硕士生导师，主要从事绝缘电介质材料、电化学储能、电力用油及设备状态感知等研究与应用工作。

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胡学超（1987-），男（汉族），内蒙古呼和浩特人，高级工程师，博士，硕士生导师，主要从事绝缘电介质材料、电化学储能、电力用油及设备状态感知等研究与应用工作。

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articleId=1199642732063977820, language=CN, label=图8, caption=DBP绝缘纸老化600 h的EDS分析, figureFileSmall=AMsXCmGF6H+t8Y/aOv5Z0w==, figureFileBig=EkwA5aRT08S6VWyq+46Pvg==, tableContent=null), ArticleFig(id=1217475516051935295, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199642732063977820, language=EN, label=Tab.1, caption=Correlation fitting between DP of insulating paper and furfural contents in oil, figureFileSmall=null, figureFileBig=null, tableContent=
纸样关系式相关系数
空白纸DP=-36.957×lnCfur+257.990.944 7
T501纸DP=-31.747×lnCfur+254.210.938 2
T531纸DP=-61.604×lnCfur+235.450.948 1
DBP纸DP=-64.221×lnCfur+255.140.888 1
), ArticleFig(id=1217475516148404292, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199642732063977820, language=CN, label=表1, caption=

油中糠醛含量与绝缘纸聚合度的相关性关系拟合

, figureFileSmall=null, figureFileBig=null, tableContent=
纸样关系式相关系数
空白纸DP=-36.957×lnCfur+257.990.944 7
T501纸DP=-31.747×lnCfur+254.210.938 2
T531纸DP=-61.604×lnCfur+235.450.948 1
DBP纸DP=-64.221×lnCfur+255.140.888 1
), ArticleFig(id=1217475516311982154, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199642732063977820, language=EN, label=Tab.2, caption=The relative crystallinity of insulating papers, figureFileSmall=null, figureFileBig=null, tableContent=
绝缘纸强度Crl/%
IamI002
新纸3933 17587.62
空白纸(120 h)6263 94184.12
空白纸(360 h)6103 79283.91
空白纸(600 h)6573 64781.99
T501纸(600 h)6733 93882.91
T531纸(600 h)5363 18183.15
DBP纸(600 h)5853 01280.58
), ArticleFig(id=1217475516500725838, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199642732063977820, language=CN, label=表2, caption=

绝缘纸相对结晶度计算结果

, figureFileSmall=null, figureFileBig=null, tableContent=
绝缘纸强度Crl/%
IamI002
新纸3933 17587.62
空白纸(120 h)6263 94184.12
空白纸(360 h)6103 79283.91
空白纸(600 h)6573 64781.99
T501纸(600 h)6733 93882.91
T531纸(600 h)5363 18183.15
DBP纸(600 h)5853 01280.58
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变压器油中抗氧化剂类型对绝缘纸热老化性能的影响
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胡学超 1, 2 , 薛守洪 1, 2 , 孙利强 1, 2 , 吴立霞 1 , 刘江 1 , 朱志平 3
绝缘材料 | 绝缘技术 2023,56(11): 47-52
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绝缘材料 | 绝缘技术 2023, 56(11): 47-52
变压器油中抗氧化剂类型对绝缘纸热老化性能的影响
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胡学超1, 2, 薛守洪1, 2, 孙利强1, 2, 吴立霞1, 刘江1, 朱志平3
作者信息
  • 1内蒙古电力(集团)有限责任公司内蒙古电力科学研究院分公司,内蒙古 呼和浩特 010020
  • 2内蒙古自治区新型电力系统智能电网企业重点实验室,内蒙古 呼和浩特 010020
  • 3长沙理工大学 化学化工学院,湖南 长沙 410114

    • 胡学超（1987-），男（汉族），内蒙古呼和浩特人，高级工程师，博士，硕士生导师，主要从事绝缘电介质材料、电化学储能、电力用油及设备状态感知等研究与应用工作。

Effect of antioxidant types in transformer oil on thermal ageing performance of insulating paper
Xuechao HU1, 2, Shouhong XUE1, 2, Liqiang SUN1, 2, Lixia WU1, Jiang LIU1, Zhiping ZHU3
Affiliations
  • 1Inner Mongolia Power (Group) Co., Ltd., Inner Mongolia Power Research Institute Branch, Hohhot 010020, China
  • 2Inner Mongolia Enterprise Key Laboratory of New Power System Smart Grid, Hohhot 010020, China
  • 3School of Chemistry and Chemical Engineering, Changsha University of Science and Technology, Changsha 410114, China
出版时间: 2023-11-20 doi: 10.16790/j.cnki.1009-9239.im.2023.11.008
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摘要
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为研究变压器油中添加抗氧化剂对绝缘纸热老化性能的影响，向环烷基矿物油、绝缘纸组成的绝缘体系中分别添加T501、T531、DBP 3种抗氧化剂，抗氧化剂质量分数均为0.4%，在130℃下进行热老化试验，老化时长为600 h。每隔120 h测定绝缘油中水分含量和糠醛含量、绝缘纸中水分含量与聚合度，同时对老化绝缘纸进行FTIR、XRD、SEM、EDS表征。结果表明：添加抗氧化剂T501、T531对绝缘纸的劣化影响较小，添加抗氧化剂DBP的油中绝缘纸在老化后期劣化程度加剧；由于T531抗氧化剂具有中和、水解双重作用，对纤维素的降解起到抑制作用，T531绝缘纸的老化程度最轻。

油纸绝缘  /  热老化  /  抗氧化剂  /  微观形貌

In order to study the effect of antioxidant types in transformer oil on the thermal ageing performance of insulating paper, antioxidants T501, T531, and DBP were added to the insulation system composed of naphthenic mineral oil and insulating paper, and the antioxidant mass fraction was 0.4%. The heat ageing test was carried out at 130℃ for 600 h. The moisture and furfural content in the insulating oil, the moisture content and polymerization degree in the insulating paper were determined every 120 h. At the same time, the aged insulating paper was characterized by FTIR, XRD, SEM, and EDS. The results show that the addition of antioxidant T501 and T531 have little effect on the deterioration of insulating paper, and the deterioration of insulating paper in the oil with antioxidant DBP is aggravate in the late ageing stage. Since the antioxidant T531 has a combination of neutralization and hydrolysis, it inhibits the degradation process of cellulose, and the ageing degree of T351 insulating paper is the lightest.

oil-paper insulation  /  thermal ageing  /  antioxidant  /  micromorphology
胡学超, 薛守洪, 孙利强, 吴立霞, 刘江, 朱志平. 变压器油中抗氧化剂类型对绝缘纸热老化性能的影响. 绝缘材料, 2023 , 56 (11) : 47 -52 . DOI: 10.16790/j.cnki.1009-9239.im.2023.11.008
Xuechao HU, Shouhong XUE, Liqiang SUN, Lixia WU, Jiang LIU, Zhiping ZHU. Effect of antioxidant types in transformer oil on thermal ageing performance of insulating paper[J]. Insulating Materials, 2023 , 56 (11) : 47 -52 . DOI: 10.16790/j.cnki.1009-9239.im.2023.11.008
正文
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0 引言
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矿物油浸式变压器以矿物绝缘油和纤维素纸作为主要的绝缘材料。绝缘油是原油经过蒸馏、裂化等复杂的工艺加工而成的一种油品，主要元素为C、H，还有少量的S、Cl和极少量的金属元素，烃类主要成分包括烷烃（占比>50%）、环烷烃（占比为10%～40%）、芳香烃（占比为5%～15%）。绝缘纸以木浆为原料用牛皮纸加工的方法制成，主要成分包括纤维素、半纤维素、木质素等。其中矿物绝缘油在变压器运行时起到绝缘、散热、熄弧和传递故障信息载体的作用，而绝缘纸主要起到机械支撑与阻隔高低压绕组间电气连接的作用[1-2]。
油纸绝缘在运行过程中易受温度、水分、氧气、电场等因素的影响，不可避免地会发生老化，造成变压器内部绝缘性能下降。工程上通过定期检测变压器油的各项指标来分析评判绝缘油的老化程度，对老化严重的绝缘油采取换油、吸附、净化、再生处理等措施可以很大程度上缓解绝缘油的老化。而绝缘纸通常只会在变压器停电吊检期间才可以取样检测，且绝缘纸劣化导致的绝缘性能下降存在不可逆、危害大、修复成本高的特点，因此绝缘纸的性能劣化被认为是导致变压器设备故障和失效最主要的因素之一[3-5]。
通常在变压器油投入运行前都会向其中添加一定含量的抗氧化剂2，6-二叔丁基对甲酚（T501）以提高油纸绝缘的抗氧化性能，延长其使用寿命。T501的作用机制为T501分子中的羟基能提供氢原子，与油中的活性自由基和过氧化物反应生成稳定的化合物，中断油的链锁反应，属于自由基抑制剂[6]。T501作为一种酚类抗氧化剂在常温下稳定性好，但在高温下其抗氧化性能会下降，老化产物会进一步加速油纸劣化，影响油纸绝缘性能。相较于T501，胺类抗氧化剂N-苯基-1-萘胺（T531）具有更好的热稳定性，是一种常用的油品添加剂。此外，由于2，6-二叔丁基苯酚（DBP）与T501性质类似，也有向变压器油中添加DBP以提高油纸绝缘的抗氧化性[7-8]。因此，研究变压器油中添加抗氧化剂类型对绝缘纸性能的影响，对于提高油纸绝缘的热稳定性具有重要意义，试验结果可以为变压器油中抗氧化剂的选型提供参考。
本文向4组油浸纸试样中添加不同类型的抗氧化剂进行加速热老化试验，得到了不同老化时长的油纸绝缘，然后测量油纸中微量水分、油中糠醛含量、绝缘纸聚合度（degree of polymerization，DP），同时使用FTIR、SEM、EDS、XRD观察绝缘纸表面的微观形貌和结构特征变化，判断各组绝缘纸的老化程度，研究不同类型抗氧化剂对绝缘纸性能劣化的影响。
1 试验
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1.1 油样的制备
试验用油为45#环烷基基础油，其中不含任何抗氧化剂，分装为320 g/份，放入500 mL磨口试剂瓶中备用。准确称取T501、T531、DBP 3种抗氧化剂各1.28 g分别添加到试验油中，在低于60℃条件下进行水浴加热，使抗氧化剂充分溶解于油中，组成抗氧化剂质量分数为0.4%的油样和空白油样。试验用纸为亚安绝缘材料厂生产的绝缘牛皮纸，不添加任何热稳定剂，将试验纸裁剪成尺寸为10 cm×10 cm×2 mm，在60℃的条件下干燥48 h，每瓶油样中放入两张绝缘纸（为方便区分，将各组油浸纸分别称为空白纸、T501纸、T531纸、DBP纸）。普通铜线作为加速老化的催化剂，铜的添加量参照ASTM D1394相关要求，铜与油质量比为0.058∶1，即18.6 g/份，烘干后放入磨口玻璃瓶中。
1.2 老化试验及表征方法
由于变压器实际运行时绝缘油的温度普遍不会超过80℃，局部过热时不会超过90℃[9]，通常加速老化试验温度一般设定为120～140℃，因此本文热老化温度设定为中间值130℃。为降低称量过程中空气、水分的影响，再次将称好后的油样放入温度为60℃、压力为-0.1 MPa的真空干燥箱中脱气脱水48 h，然后在烘箱中进行加速热老化，取样时间点为120、240、360、480、600 h。待油样冷却至室温后测定油纸中水分含量和油中糠醛含量，将绝缘纸取出后，使用正己烷在75℃下进行索氏提取除油，参照GB/T 29305—2012相关要求测试纸样聚合度[10]，然后进行微观形貌表征。
2 结果与分析
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2.1 油纸中水分变化
变压器在运行过程中，水分会由外部环境侵入内部，油纸老化过程也会产生水分。水分在变压器油中的含量虽少，但对油纸绝缘的性能有很大影响，水分还会参与纤维素的老化降解反应，加速绝缘纸力学性能的劣化。实际变压器纸样中水分难以检测，对油中含水量的检测就是油纸绝缘系统的一个重要指标。
图1为4组油样中的微水含量测试结果。从图1可以看出，所有油样中含水量随老化时间的延长均呈现先下降后上升的趋势，并在第360 h时达到最小值。在老化前期（0～360 h），由于抗氧化剂含量充足，油老化生成的水分较少，而且由于高温下水分蒸发和绝缘纸的吸附作用，主要表现为水分从绝缘油中迁移到绝缘纸和磨口瓶上部空间，使得油中水分含量呈现缓慢下降的趋势。随着老化时间延长，抗氧化剂逐渐被消耗，油老化生成的水分增多，且绝缘纸经历长时间老化后发生分解，绝缘纸的表层结构被破坏，吸附在绝缘纸中的水分释放出来进入绝缘油中，进一步加速绝缘油老化，因此油中水分迅速上升。其中由于胺类抗氧化剂T531水解会消耗水分，所以加入T531的油中水分含量相对偏低[11]。
图2为4组绝缘纸的样水分含量测试结果。从图2可以看出，所有绝缘纸的水分含量在老化过程中均呈现波动变化。由于绝缘纸在老化初期劣化严重，且生成大量水分，使水分含量上升。在老化后期，绝缘纸发生老化分解产生水分，且绝缘纸的表层结构被破坏，纤维素无定形区率先分解，吸附在绝缘纸中的水分又释放出来，使绝缘纸中水分含量均呈上升趋势。
2.2 油中糠醛含量
糠醛，其化学式为C5H4O2，在变压器油中具有中等溶解能力，在纤维素的降解过程中产生，可以间接反映绝缘纸的老化情况。
图3为4组变压器油中糠醛含量随老化时间的变化情况。从图3可以看出，各组油中糠醛含量呈现上升趋势，对比各组油中糠醛含量差异：空白油老化240 h后糠醛含量开始增加，T501油和T531油老化480 h后糠醛含量迅速增加，说明绝缘纸在老化初期没有发生严重劣化，抗氧化剂的加入延缓了糠醛的生成时间；相较于抗氧化剂T501与T531，DBP的热分解产物对纤维素老化有催化作用，会加速糠醛的生成，导致油中糠醛含量高于这两组油样，推测出现波动的原因是糠醛在高温下发生分解[12]。老化600 h后，空白油中糠醛含量最大，T531油中糠醛含量最小，糠醛含量从大到小排序为空白油、DBP油、T501油、T531油。
2.3 绝缘纸聚合度
绝缘纸的主要成分是α-纤维素，其化学式为(C6H10O5)n，其中n是聚合度（DP）。纤维素是由 β-D-葡萄糖基通过1,4-β糖苷键结合构成的长链高聚合碳氢化合物，其老化过程宏观体现为绝缘纸聚合度的变化。
图4为4组绝缘纸的聚合度（DP）随老化时间的变化情况。从图4可以看出，4组绝缘纸的DP随着老化时间延长而降低，在老化初期（0～120 h）受温度影响较大，聚合度下降较快，在老化中期（120～360 h），聚合度下降速率趋于平缓，在老化后期（360～600 h），由于抗氧化剂被消耗，直接导致老化产物增多，对绝缘纸的破坏进一步加深，聚合度下降速率加快。老化600 h后，绝缘纸的DP从大到小排序为T531纸、T501纸、空白纸、DBP纸。
由于油中糠醛只在纤维素中葡萄糖单体断键开环的过程中产生，而绝缘纸聚合度DP表示的是纤维素分子中葡萄糖单体的整体数目，二者之间存在近似对数关系[13]，关系式如式（1）所示。
DP=a×lnCfur+b
式（1）中：DP为绝缘纸聚合度；Cfur为油中糠醛含量；a、b为系数。
将油中糠醛含量与绝缘纸DP按照式（1）进行相关拟合，结果见表1。从表1可以看出，空白纸、T501纸、T531纸相关系数均接近1，说明油中糠醛含量变化与绝缘纸DP的变化具有一致性；DBP油中糠醛含量波动变化，与绝缘纸聚合度的相关性较差。
2.4 FTIR分析
绝缘纸在外界应力作用下会发生一系列的老化反应，产生CO、CO2、糠醛等物质并溶解于绝缘油中，因此必定伴随官能团的变化，利用红外光谱可以从分子水平解释绝缘纸的老化过程。
新纸和老化600 h空白纸的红外光谱如图5所示。
从图5可以看出，新纸在波数为3 500～3 100 cm-1区间出现了1个吸收峰平台，这是纤维素分子中O-H的伸缩振动吸收峰和纤维素中的-OH与相邻羟基中的H形成H-O-H的伸缩振动吸收峰；在波数为2 889 cm-1左右的吸收峰是甲基或亚甲基中C-H的伸缩振动吸收峰；在波数为1 427 cm-1、1 366 cm-1左右的吸收峰是甲基或亚甲基的面内弯曲振动吸收峰；在波数为1 160 cm-1左右的吸收峰是纤维素中C-O-C糖苷键的不对称伸缩振动引起的；在波数为1 055 cm-1、1 033 cm-1左右的吸收峰是纤维素中仲醇羟基的吸收峰；在波数为897 cm-1左右的吸收峰是β-D葡萄糖的特征吸收峰[14-15]。对比老化600 h空白绝缘纸红外光谱可以看出，在波数为3 500～3 100 cm-1纤维素分子中O-H的伸缩振动吸收峰强度减弱，说明绝缘纸发生老化，纤维素分子中的-OH含量减少，在绝缘纸老化过程中氢键遭到破坏；在波数为1 160 cm-1和897 cm-1处的吸收峰强度减弱，说明纤维素糖苷键C-O-C的结构遭到破坏，数量减少；同时发现在波数1 723 cm-1处出现了C=O的伸缩振动吸收峰，说明纤维素在老化后产生了醛、酮或酸类物质。
2.5 XRD分析
X射线衍射可以表征纤维素的物理结构中具有规则链状的晶体区和无序的非晶体区（无定形区）。纤维素的结晶度是指纤维素分子中晶体结构占纤维素总体的百分数，结晶度的大小对绝缘纸的物理性能影响很大，结晶度较高的纤维素分子弹性很大，组成绝缘纸的机械强度好。
图6为绝缘纸的XRD测试结果。从图6可以看出，绝缘纸老化前后的晶体结构中均存在结晶区（002峰）和非结晶区（001峰），纤维素的晶体类型并无变化。参照L SEGAL[16]介绍的方法计算各组绝缘纸的相对结晶度（Crl），计算公式如式（2）所示。
Crl=[(I002-Iam)/I002]×100%
式（2）中：I002为绝缘纸老化前后晶体结构中的结晶区（002）；Iam为特定峰位衍射峰强度。
表2为绝缘纸相对结晶度计算结果。从表2可以看出，随着老化时间延长，相较于新纸，空白组绝缘纸结晶度有所下降，说明纤维素分子结构遭到破坏。比较老化600 h各组绝缘纸相对结晶度的大小，结晶度从大到小顺序为T531纸、T501纸、空白纸、DBP纸。
2.6 绝缘纸SEM及EDS表征
绝缘纸中纤维素形态上表现为相互缠绕的管束结构。通过对微观下纤维素的形态和表面断裂情况进行分析，可以在一定程度上为宏观判断绝缘纸的机械强度、老化情况提供依据。所有纸样在SEM测试前需进行喷金处理以增强纤维素表面的导电性。
图7为放大1 000倍绝缘纸的扫描电镜图。从图7可以看出，新纸的纤维比较完整、排列紧密、表面光滑，几乎没有纤维断裂或损坏；老化600 h后，纤维表面变得粗糙，粗细不均匀，纤维与纤维之间的“孔洞”明显增多。与空白绝缘纸和DBP绝缘纸相比，T501绝缘纸和T531绝缘纸的纤维较为完整和光滑，说明这两组绝缘纸的劣化程度相对较小。DBP绝缘纸的纤维表面出现明显的断裂现象，几乎没有明显的纤维结构，劣化程度最大。
从绝缘纸的聚合度测试结果和微观形貌表征可以得知，绝缘纸老化600 h后，添加抗氧化剂DBP的绝缘纸劣化程度最大，而添加抗氧化剂T501和T531对绝缘纸劣化起到了抑制作用。为探究DBP绝缘纸老化600 h对表面侵蚀性介质的影响，进一步对该绝缘纸进行EDS分析，结果如图8所示。
从图8可以看出，老化600 h后的DBP纸样表面中检测出微量铜元素，说明老化绝缘纸对油中游离的微量铜离子具有吸附作用。铜作为催化剂能促进油的自由基链式反应，产生更多的H+和极性自由基，链式反应如式（3）所示[17]。
H+在热应力和微量水分的作用下，会破坏纤维素分子中葡萄糖单体的配糖键，形成不稳定的游离葡萄糖，游离葡萄糖很容易脱水开环生成多种杂环化合物（例如2-呋喃甲醛、5-甲基-2-呋喃甲醛等），最终直接导致纤维素大分子裂解严重，变压器油中糠醛含量升高，绝缘纸聚合度降低。
而T531作为一种胺类化合物呈弱碱性，可以中和老化油中的H+，生成铵盐，从而可以抑制纤维素的降解，反应式如式（4）所示[18]。
3 结论
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（1）油纸绝缘中含水量在老化前期存在溶解与吸附的动态平衡，在老化后期纤维素分解导致油纸中水分含量上升；绝缘纸的聚合度与油中糠醛含量存在近似对数关系，但糠醛在高温下不稳定，对于老化严重的油纸，二者相关性较差。
（2）在老化过程中纤维素分子中的-OH被破坏，糖苷键C-O-C断裂，绝缘纸的相对结晶度降低，表面纤维结构断裂严重；EDS分析表明绝缘纸对油中铜离子具有一定吸附作用，会加速油纸老化。
（3）绝缘纸老化程度从大到小顺序为DBP纸、空白纸、T501纸、T531纸，其中DBP由于自身分解反而会加速油纸老化，而T531抗氧化剂由于具有良好的热稳定性以及消耗油中的水分和H+，对绝缘纸的老化起到抑制作用。
基金
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  • 内蒙古自治区自然科学基金资助项目(2021BS05 005)
  • 内蒙古电力科学研究院自筹科技项目(2021-ZC-10)
  • 内蒙古电力科学研究院自筹科技项目(2021-ZC-03)
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2023年第56卷第11期
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doi: 10.16790/j.cnki.1009-9239.im.2023.11.008
  • 接收时间：2023-04-23
  • 首发时间：2025-11-24
  • 出版时间：2023-11-20
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  • 收稿日期：2023-04-23
  • 修回日期：2023-05-24
基金
内蒙古自治区自然科学基金资助项目(2021BS05 005)
内蒙古电力科学研究院自筹科技项目(2021-ZC-10)
内蒙古电力科学研究院自筹科技项目(2021-ZC-03)
作者信息
    1内蒙古电力(集团)有限责任公司内蒙古电力科学研究院分公司,内蒙古 呼和浩特 010020
    2内蒙古自治区新型电力系统智能电网企业重点实验室,内蒙古 呼和浩特 010020
    3长沙理工大学 化学化工学院,湖南 长沙 410114
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2种不同金属材料的力学参数
科
Family		 属数
Number of
genus		 种数
Number of
species		 占总种数比例
Percentage of
total species (%)		 属
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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