Article(id=1203281638542254559, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1203281635908231645, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2025.06.007, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1721664000000, receivedDateStr=2024-07-23, revisedDate=1726588800000, revisedDateStr=2024-09-18, acceptedDate=null, acceptedDateStr=null, onlineDate=1764814298520, onlineDateStr=2025-12-04, pubDate=1750348800000, pubDateStr=2025-06-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1764814298520, onlineIssueDateStr=2025-12-04, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1764814298520, creator=13701087609, updateTime=1764814298520, 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=52, endPage=60, ext={EN=ArticleExt(id=1203281639926374886, articleId=1203281638542254559, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Study on thermal properties of epoxy resin/micron-alumina composite dielectric based on dielectric response, columnId=1190369066675179686, journalTitle=Insulating Materials, columnName=Material Research, runingTitle=null, highlight=

Epoxy resin/micron-alumina composites are widely employed as supporting and insulating components in electrical power equipment, and their glass transition temperature and thermal expansion coefficient critically influence the long-term performance of electrical power equipment. Epoxy resin composite dielectrics containing 0%, 20%, 40%, and 60% mass fractions of micron-alumina fillers were prepared in this paper. Their thermal expansion coefficients and glass transition temperatures were calculated through numerical fitting of dielectric constant measurements at high-temperature and high-frequency. The results demonstrate that with the increase of the mass fraction of micron-alumina fillers, the thermal expansion coefficient of composite dielectrics reduces significantly, and the glass transition temperature also showing a decreasing trend. Comparative analysis between calculated values and existing experimental data reveals that the calculated value is consistent with the experimental value, confirming the scientific validity and effectiveness of dielectric spectroscopy as a methodology for evaluating the thermal properties of epoxy composite dielectrics. This approach can serves as an effective supplementary technique to conventional experimental methods for investigating the thermal characteristic of polymer.

, articleAbstract=

Epoxy resin/micron-alumina composites are widely employed as supporting and insulating components in electrical power equipment, and their glass transition temperature and thermal expansion coefficient critically influence the long-term performance of electrical power equipment. Epoxy resin composite dielectrics containing 0%, 20%, 40%, and 60% mass fractions of micron-alumina fillers were prepared in this paper. Their thermal expansion coefficients and glass transition temperatures were calculated through numerical fitting of dielectric constant measurements at high-temperature and high-frequency. The results demonstrate that with the increase of the mass fraction of micron-alumina fillers, the thermal expansion coefficient of composite dielectrics reduces significantly, and the glass transition temperature also showing a decreasing trend. Comparative analysis between calculated values and existing experimental data reveals that the calculated value is consistent with the experimental value, confirming the scientific validity and effectiveness of dielectric spectroscopy as a methodology for evaluating the thermal properties of epoxy composite dielectrics. This approach can serves as an effective supplementary technique to conventional experimental methods for investigating the thermal characteristic of polymer.

, correspAuthors=null, 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, authorCompany=null, fund=null, authors=null, authorsList=Rui SHU, Xiaoqiu NING, Bo YANG), CN=ArticleExt(id=1203281644485583457, articleId=1203281638542254559, tenantId=1146029695717560320, journalId=1149653034449285133, language=CN, title=基于介电响应的环氧树脂/微米氧化铝复合电介质热性能研究, columnId=1190369066813591720, journalTitle=绝缘材料, columnName=材料研究, runingTitle=null, highlight=

环氧树脂/微米氧化铝复合电介质在电力装备中作为支撑件和绝缘件的应用广泛,其玻璃化转变温度与热膨胀系数对设备的长期运行表现至关重要。本文制备了微米氧化铝质量分数分别为0%、20%、40%和60%的环氧树脂复合电介质,并通过高温高频介电常数的数值拟合方法,计算复合电介质的热膨胀系数和玻璃化转变温度。结果表明:随着微米氧化铝填料质量分数的增加,复合电介质的热膨胀系数显著减小,玻璃化转变温度也呈下降趋势。将计算结果与已有试验数据对比,发现计算值与试验值基本一致,证明基于介电谱测量环氧电介质热性能具有科学性和有效性,可作为研究聚合物热性能实验手段的一种有效补充。

, articleAbstract=

环氧树脂/微米氧化铝复合电介质在电力装备中作为支撑件和绝缘件的应用广泛,其玻璃化转变温度与热膨胀系数对设备的长期运行表现至关重要。本文制备了微米氧化铝质量分数分别为0%、20%、40%和60%的环氧树脂复合电介质,并通过高温高频介电常数的数值拟合方法,计算复合电介质的热膨胀系数和玻璃化转变温度。结果表明:随着微米氧化铝填料质量分数的增加,复合电介质的热膨胀系数显著减小,玻璃化转变温度也呈下降趋势。将计算结果与已有试验数据对比,发现计算值与试验值基本一致,证明基于介电谱测量环氧电介质热性能具有科学性和有效性,可作为研究聚合物热性能实验手段的一种有效补充。

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舒锐(1993-),男(汉族),四川南充人,讲师,主要从事电气工程、电工材料与绝缘技术研究。

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舒锐(1993-),男(汉族),四川南充人,讲师,主要从事电气工程、电工材料与绝缘技术研究。

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舒锐(1993-),男(汉族),四川南充人,讲师,主要从事电气工程、电工材料与绝缘技术研究。

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(a) 氧化铝质量分数为0% (b) 氧化铝质量分数为60%

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氧化铝质量分数/%温度/℃εfα/Hz
01203.5950
1403.573 000
1603.5575 000
201203.8480
1403.826 500
1603.80110 000
401204.6483
1404.628 000
1604.60140 000
601205.0990
1405.079 500
1605.05160 000
), ArticleFig(id=1203362948929527922, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1203281638542254559, language=CN, label=表1, caption=

环氧树脂复合电介质的介电拟合参数

, figureFileSmall=null, figureFileBig=null, tableContent=
氧化铝质量分数/%温度/℃εfα/Hz
01203.5950
1403.573 000
1603.5575 000
201203.8480
1403.826 500
1603.80110 000
401204.6483
1404.628 000
1604.60140 000
601205.0990
1405.079 500
1605.05160 000
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基于介电响应的环氧树脂/微米氧化铝复合电介质热性能研究
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舒锐 1 , 宁晓秋 2 , 杨波 1
绝缘材料 | 材料研究 2025,58(6): 52-60
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绝缘材料 | 材料研究 2025, 58(6): 52-60
基于介电响应的环氧树脂/微米氧化铝复合电介质热性能研究
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舒锐1, 宁晓秋2, 杨波1
作者信息
  • 1.西南交通大学 希望学院,四川 成都 610400
  • 2.海南电网有限责任公司三亚变电运检分公司,海南 三亚 572000
  • 舒锐(1993-),男(汉族),四川南充人,讲师,主要从事电气工程、电工材料与绝缘技术研究。

Study on thermal properties of epoxy resin/micron-alumina composite dielectric based on dielectric response
Rui SHU1, Xiaoqiu NING2, Bo YANG1
Affiliations
  • 1. Hope College, Southwest Jiaotong University, Chengdu 610400, China
  • 2. Sanya Substation Operation and Inspection Branch of Hainan Power Grid Co., Ltd., Sanya 572000, China
出版时间: 2025-06-20 doi: 10.16790/j.cnki.1009-9239.im.2025.06.007
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环氧树脂/微米氧化铝复合电介质在电力装备中作为支撑件和绝缘件的应用广泛,其玻璃化转变温度与热膨胀系数对设备的长期运行表现至关重要。本文制备了微米氧化铝质量分数分别为0%、20%、40%和60%的环氧树脂复合电介质,并通过高温高频介电常数的数值拟合方法,计算复合电介质的热膨胀系数和玻璃化转变温度。结果表明:随着微米氧化铝填料质量分数的增加,复合电介质的热膨胀系数显著减小,玻璃化转变温度也呈下降趋势。将计算结果与已有试验数据对比,发现计算值与试验值基本一致,证明基于介电谱测量环氧电介质热性能具有科学性和有效性,可作为研究聚合物热性能实验手段的一种有效补充。

环氧树脂  /  微米氧化铝填料  /  热膨胀系数  /  玻璃化转变温度  /  介电响应

Epoxy resin/micron-alumina composites are widely employed as supporting and insulating components in electrical power equipment, and their glass transition temperature and thermal expansion coefficient critically influence the long-term performance of electrical power equipment. Epoxy resin composite dielectrics containing 0%, 20%, 40%, and 60% mass fractions of micron-alumina fillers were prepared in this paper. Their thermal expansion coefficients and glass transition temperatures were calculated through numerical fitting of dielectric constant measurements at high-temperature and high-frequency. The results demonstrate that with the increase of the mass fraction of micron-alumina fillers, the thermal expansion coefficient of composite dielectrics reduces significantly, and the glass transition temperature also showing a decreasing trend. Comparative analysis between calculated values and existing experimental data reveals that the calculated value is consistent with the experimental value, confirming the scientific validity and effectiveness of dielectric spectroscopy as a methodology for evaluating the thermal properties of epoxy composite dielectrics. This approach can serves as an effective supplementary technique to conventional experimental methods for investigating the thermal characteristic of polymer.

epoxy resin  /  micro alumina filler  /  thermal expansion coefficient  /  glass transition temperature  /  dielectric response
舒锐, 宁晓秋, 杨波. 基于介电响应的环氧树脂/微米氧化铝复合电介质热性能研究. 绝缘材料, 2025 , 58 (6) : 52 -60 . DOI: 10.16790/j.cnki.1009-9239.im.2025.06.007
Rui SHU, Xiaoqiu NING, Bo YANG. Study on thermal properties of epoxy resin/micron-alumina composite dielectric based on dielectric response[J]. Insulating Materials, 2025 , 58 (6) : 52 -60 . DOI: 10.16790/j.cnki.1009-9239.im.2025.06.007
环氧树脂是分子主链含有两个以上环氧基聚合物的统称,其固化物具有良好的电气绝缘性能、力学性能与热性能,常作为支撑件与绝缘件用于高压输变电设备[1-6]。在使用中为了进一步增强环氧树脂的力学性能,通常向环氧树脂中加入大量微米氧化铝填料制成环氧树脂/微米氧化铝复合电介质[2,7]。填料的引入改变了环氧树脂的介观结构,使得复合电介质的机械强度得到改善[7]。然而机械强度变化的同时,复合电介质的热性能也会因填料的加入而变化。
绝缘材料的热性能关键参数包括热导率、热膨胀系数、玻璃化转变温度与热分解温度等[7-8]。热膨胀系数与玻璃化转变温度共同影响着环氧复合电介质的长期使用性能[9-10]。温度升高,环氧复合材料的宏观性能下降[10-11],当温度高于其玻璃化转变温度时,环氧复合材料性能会急剧下降。因此,通常情况下材料的玻璃化转变温度决定设备运行温度的上限[9]。而热膨胀系数与其他绝缘件及运行环境的不匹配可能会导致设备因温度变化而开裂,造成损坏。
目前部分学者对环氧复合材料的热性能展开了研究,宁晓秋等[8]制备了不同质量分数的环氧树脂/微米氧化铝复合电介质,通过试验研究了填料含量对复合材料介电常数与玻璃化转变温度的影响规律。L M MCGRATH等[12]通过试验获得了微米氧化铝填料对不同环氧树脂交联体系热性能和力学性能的影响规律。刘云鹏等[13]向环氧树脂中加入微米氮化硼填料制备环氧树脂/微米氮化硼复合材料,探究了填料对复合材料电性能和热性能参数的影响。上述研究均通过试验直接提取复合材料的热参数,发现填料含量会影响复合材料的热性能,但并未从复合材料的微观与介观的角度进行验证与分析[8,12-13],因而影响了进一步对复合电介质热性能变化内在机制的深入探索。
聚合物的玻璃化转变过程和热膨胀行为与分子和原子的运动状态有关,而环氧树脂的介电响应同样与分子和原子的运动状态相关。因此,聚合物的介电响应与玻璃化转变过程和热膨胀行为必然存在一定联系。目前,部分学者通过对环氧树脂在高温下的介电谱进行数值计算与分析获得了部分与分子或分子链运动相关的热性能参数[14-18]。李明儒等[14]研究发现,环氧树脂在高频区域的介电常数随着温度上升存在一个转折,并认为转折点对应的温度与玻璃化转变温度有关。翟进乾等[15]研究发现,环氧微米复合电介质分子链松弛运动活化能与玻璃化转变温度呈线性相关。林生军等[16]研究发现,环氧树脂分子链松弛特征频率与温度遵循Vogel-Fulcher-Tammann公式,并发现拟合参数Vogel温度与实测玻璃化转变温度相差约50 K。LI Mingru等[17]和HUANG Yin等[18]研究发现,环氧树脂在高频区域的介电常数与温度存在函数关系,并通过一系列公式推导与变换,计算了电介质在橡胶态的热膨胀系数。由此可知,通过介电响应求取电介质的玻璃化转变温度与热膨胀系在数理论上是可行的,但目前该方法在环氧复合电介质中的有效性与科学性还需进一步验证。
本研究制备了环氧树脂/微米氧化铝复合电介质,测取了复合材料的宽带介电谱,通过对介电响应的分析与计算,求取复合电介质的玻璃化转变温度与热膨胀系数,从介电响应的角度分析氧化铝填料对环氧复合电介质热膨胀系数和玻璃化转变温度的影响,研究成果有助于理解环氧树脂/微米氧化铝复合电介质宏观性能与介观结构的关联。
E51型环氧树脂,环氧值为0.525 eq/100 g,南通星辰合成材料有限公司;甲基四氢苯酐固化剂,常州市润祥化工有限公司;苯酚促进剂,上海阿拉丁生化科技股份有限公司;球形微米氧化铝填料,粒径为20 μm,泰安盛源粉体有限公司。
将脱模剂均匀涂抹在模具表面,然后将模具放入130℃烘箱预热2 h。称取100 g环氧树脂加入三口烧瓶中,将烧瓶加热至50℃,随后称取m g微米氧化铝填料倒入三口烧瓶,保持三口烧瓶的温度为50℃、真空度>0.08 MPa,搅拌30 min并脱气。之后称取80 g固化剂与1 g促进剂加入三口烧瓶,在50℃、真空度>0.08 MPa条件下搅拌30 min并脱气。将烧瓶内混合物倒入预热完毕的模具进行加热固化,固化程序为80℃/2 h+140℃/12 h,固化结束使模具自然冷却至室温,开模取出试样。用无水乙醇和去离子水将试样清洗干净后放入50℃烘箱干燥备用。所制试样为圆片,直径为50 mm、厚度为1 mm。
制样中,微米氧化铝质量(m)的计算公式如式(1)所示。
x=m100+80+1+m
式(1)中:x为复合电介质中微米氧化铝填料的质量分数,本文x分别为0%、20%、40%和60%;m为微米氧化铝填料的质量,g;100、80和1分别为环氧树脂、固化剂与促进剂的质量。
使用VEG800S型扫描电子显微镜观测微米氧化铝填料在环氧树脂中的分散情况,观测前将试样截断,对断面喷镀导电电极。
使用Concept 80型宽带介电谱仪测量试样宽温域与宽频域的介电谱,测试温度为20~160℃,步长为20℃,频率为10-1~106 Hz。试验中试样两面施加1 V的交流电压。测试前需对试样两面喷镀导电电极,电极直径分别为30 mm与40 mm。
使用差示扫描量热仪(DSC,型号为DSC822E)测量试样的玻璃化转变温度,升温速率为10℃/min,测试气氛为氮气。
图1为环氧微米氧化铝复合电介质断面经扫描电子显微镜放大1 000倍的微观形貌。从图1可以看出,不加微米氧化铝填料的试样断面光洁,内部不存在固化过程产生的缺陷。加入质量分数为60%微米氧化铝填料的试样内部微观形貌与纯环氧树脂存在很大差异。大量的填料充盈在试样断面,且微米粒子间存在重叠现象。由于所加填料的质量分数较大,导致复合材料内不可避免地出现部分区域填料分布不均,这种现象在高掺杂含量的环氧复合电介质中较为常见[18]
图2为环氧复合电介质在20℃的宽频域介电谱。从图2(a)可以看出,随着微米氧化铝填料质量分数的增加,在20℃下复合电介质的介电常数(复介电常数实部)不断增大。从图2(b)可以看出,填料的加入导致复合电介质的介质损耗因数(复介电常数虚部)增大。这是因为氧化铝填料的引入增强了电介质体内的电子极化、原子极化与界面极化[8,15-16]。多种极化的增强导致复合电介质的介电常数与介质损耗因数随着填料质量分数的增加而增大。
图2还可以看出,虽然在20℃时,不同环氧复合电介质的介电常数与介质损耗因数存在差异,但并未观测到明显的松弛极化现象,无法展开电介质介电松弛的分析与计算,也无法获得与分子和原子运动相关的参数。研究表明[15-18],高温下环氧树脂的松弛行为更易于研究与观察,因此本文对高温下环氧树脂复合电介质的介电常数进行测试与分析。
图3为环氧复合电介质宽温域的介电常数。从图3可以看出,相较于纯环氧树脂,复合电介质在低频区域的介电常数对温度更敏感,高频区域介电常数的变化难以观测与对比。研究表明,环氧树脂在高频区域的介电常数与分子和原子的运动状态有关[15-18],在低频区域的介电常数与聚合物内的电荷积聚和杂质离子有关[16,19]。因此若想获得环氧树脂复合电介质与分子和原子运动相关的热性能参数,需要对高温区域的介电谱展开拟合计算,提取高频区域的松弛与极化参数。
常用的介电谱拟合计算方法包括Cole-Cole(C-C)公式、Cole-David(C-D)公式、Havriliak-Negami(H-N)公式及3种公式的变形[15-18,20-22],其中H-N公式经参数变换可转换为C-C与C-D公式,因此具有较强的普适性,在环氧树脂的拟合与计算中应用广泛[15-18]。因此本文选择H-N函数对试样在高温下的介电谱进行拟合计算。每一个独立的松弛极化过程,可用一个H-N函数进行描述,由于图3中环氧树脂在高温下的高频与低频区域分别存在一个松弛极化过程,因此需要使用两个H-N函数对两个松弛极化过程分别描述。通常情况,环氧树脂中位于高频区域的松弛过程一般记为松弛过程α,而低频区域的松弛过程一般记为松弛过程δ,因此本文使用的H-N函数具体如式(2)所示。
ε*=ε+Δεα[1+(iωτα)βα]γα+Δεδ[1+(iωτδ)βδ]γδ
式(2)中:ε*为复介电常数;ε为高频区域的介电常数,主要由电子与原子位移极化构成,数值约等于光频介电常数;ω为角频率,数值上等于2πff为测试频率;τατδ为松弛过程α与δ的松弛时间,等于1/2πfα与1/2πfδfαfδ为松弛过程α与δ的特征频率;Δεα与Δεδ分别为松弛过程α与δ的松弛强度;βγ为图形系数,0<β≤1,0<γ×β≤1。
在玻璃化转变温度以下,环氧树脂的松弛过程受到抑制,无法进行精确的拟合。而图3中当温度大于120℃时,可观测到环氧树脂复合电介质明显的松弛极化现象,因此本文仅针对120℃、140℃与160℃ 3个温度下的测试曲线进行拟合。
图4为使用H-N函数对160℃下纯环氧树脂介电常数进行拟合的结果。从图4可以看出,计算结果与试验值接近,证明拟合参数选择适宜,计算结果科学可信。所有试样在高温下的介电拟合曲线见图3中黑色实线。由于电介质的热性能与高频介电常数ε和特征频率fα有关,为了便于计算,将不同试样在3个温度下的εfα表1中列出,随后基于拟合得到的εfα,计算环氧树脂复合电介质的热膨胀系数与玻璃化转变温度。
随着温度上升,聚合物在热膨胀的作用下体积变大,密度减小,该物理现象可用式(3)表示[11,17]
ρ=ρ0[1-αf(T-T0)]
式(3)中:ρ为聚合物在T温度下的密度,kg/m3ρ0为聚合物在T0温度下的密度,kg/m3αf为热膨胀系数,K-1
研究发现,克劳修斯公式能将介电常数与聚合物的密度有效关联,如式(4)所示22-24
ε-1ε+2=ρNA3ε0Mαe
式(4)中:ρ为聚合物的密度,kg/m3ε为高频区域的光频介电常数;NA为阿伏伽德罗常数,其值为6.02×1023ε0为真空介电常数,其值为8.85×10-12 F/m;M为相对分子质量;αe为电子极化率。
式(3)代入式(4),并对温度求一阶导数,可得式(5)
ddT(ε-1ε+2)=-αfρ0NA3ε0Mαe
然后,结合式(3)、(4)和(5),可得式(6)
ε-1ε+2=TddT(ε-1ε+2)-(1αf+T0)ddT(ε-1ε+2)
针对式(6),以T为横轴,以(ε-1/ε+2)为纵轴作图并进行线性拟合。因为T0通常远小于1/αf,在式(6)中计算热膨胀系数αf时可近似忽略,所以线性拟合后的斜率与截距比值的绝对值即为材料的热膨胀系数。由于介电拟合时所拟合数据为高温下材料进入橡胶态的数据,所求得的热膨胀系数为聚合物橡胶态的热膨胀系数。
图5(a)式(6)的线性拟合曲线,计算发现各试样的线性回归系数R2均大于0.99,表明数据拟合良好,(ε-1/ε+2)与T存在很强的线性关系。经式(6)计算得到试样的热膨胀系数见图5(b),可以发现纯环氧树脂的热膨胀系数最大,为1.93×10-4 K-1,随着填料质量分数的增加,复合电介质的热膨胀系数不断下降,当填料质量分数为20%、40%和60%时,复合电介质的热膨胀系数分别为1.70×10-4、1.19×10-4、9.99×10-5 K-1
在热的作用下,物质的体积会发生膨胀。对于环氧树脂而言,其体积的增加主要来源于分子热运动和自由体积膨胀的贡献。然而,微米级的氧化铝填料由于其陶瓷材料的特性,其体积变化仅受分子热运动的影响,因为氧化铝内部并不存在显著的自由体积,导致环氧树脂与氧化铝之间在热膨胀系数上的自然差异。
当氧化铝添加到环氧树脂中时,如图6所示,氧化铝会分布在环氧树脂分子的周围。随着温度的升高,环氧树脂分子趋向于膨胀,但由于周围氧化铝填料的存在,其热膨胀系数相对较小,未能与环氧树脂同步膨胀,反而对环氧树脂分子的膨胀行为产生了抑制作用,从而导致复合电介质的热膨胀系数下降。随着氧化铝质量分数的增加,使得有机环氧树脂分子的膨胀行为受到更强的抑制。因此,填料质量分数的增加导致复合电介质的热膨胀系数持续下降。研究表明[12-13],向环氧树脂中掺入热膨胀系数较小的填料,确实能够降低复合电介质的热膨胀系数,这一结果与图5的计算结果以及上述分析相符。
环氧树脂分子链松弛极化的特征频率与温度存在确定的函数关系。林生军等[16]与HUANG Yin等[18]发现环氧树脂大分子链松弛极化的特征频率与温度的函数关系符合Vogel-Fulcher-Tammann公式,见式(7)。通过式(7)的拟合计算可求得函数中的常数Vogel温度,该温度数值上比环氧树脂的玻璃化转变温度低约50 K。因此,通过对环氧复合电介质松弛极化特征频率与温度关系的拟合与计算,也可近似求得复合电介质的玻璃化转变温度。
fα=fα0e(-DαTα0T-Tα0)
式(7)中:fα0为温度趋向于无穷大时的松弛峰频率,Hz;Dα为松弛过程α的活化能系数;Tα0为松弛过程α的Vogel温度,K。
环氧复合电介质在高温下大分子链松弛极化的特征频率fαT0/(T-T0)的拟合曲线见图7(a)。从图7(a)可以看出,经Vogel-Fulcher-Tammann公式拟合后各曲线的线性回归系数均大于0.99。拟合得到的Vogel温度加50 K即为试样的玻璃化转变温度,计算得到环氧复合电介质的玻璃化转变温度见图7(b)。从图7(b)可以看出,纯环氧树脂的玻璃化转变温度最高,为114.85℃。随着填料质量分数的增加,复合电介质的玻璃化转变温度不断下降,当填料质量分数为20%、40%和60%时,复合电介质的玻璃化转变温度分别为106.85、100.85、96.85℃。
玻璃化转变温度计算结果显示,微米氧化铝填料的引入降低了复合电介质的玻璃化转变温度,不利于维持良好的耐热性能,该结论与文献[8]和[15]已报道的结论相近。宁晓秋等[8]研究发现,大量填料的引入会增大体系黏度,阻碍环氧树脂与固化剂分子的流动,降低复合电介质的交联度,从而降低复合电介质的玻璃化转变温度。而复合电介质玻璃化转变温度的下降不利于电力设备长期稳定的运行,因此后续研究有必要针对环氧复合电介质的工艺进行改性,降低体系黏度,增强有机分子的流动性,从而增大交联度,提升复合电介质的耐热性能。
在2.4与2.5中,基于介电响应拟合计算分别计算了环氧复合电介质的热膨胀系数与玻璃化转变温度,从计算结果中发现微米氧化铝填料对热性能参数的影响规律与已报道的规律相符。但本文的研究成果与通过热学试验直接测量的实验结果相比是否一致还需要进行对比验证。本文以DSC试验获得试样的玻璃化转变温度,并与前文的计算结果进行对比,同时选择已报道文献的试验数据作为共同对照组。
图8为环氧复合电介质的DSC曲线。从图8可以发现,氧化铝质量分数为0%、20%、40%和60%的试样玻璃化转变温度的试验值分别为110.25、107.12、97.49、96.17℃。将图7中基于介电响应计算求得的环氧复合电介质玻璃化转变温度与图8通过DSC试验求得的玻璃化转变温度进行对比,同时选用文献[8]与文献[15]的数据作为共同对照组,结果如图9所示。
图9可以发现,本文基于介电响应拟合参数通过Vogel-Fulcher-Tammann公式计算的玻璃化转变温度与DSC试验获得的玻璃化转变温度基本相同。对于纯环氧树脂,玻璃化转变温度通过Vogel-Fulcher-Tammann公式的计算值为114.85℃,而DSC测得的试验结果为110.25℃,二者非常接近。同时发现文献[8]和[15]的试验值分别为111.48℃和112.15℃,与本文的计算值与试验值均相差不大。通过Vogel温度计算的玻璃化转变温度与众多试验值吻合,证明基于介电拟合求取环氧复合电介质玻璃化转变温度的方法是科学有效的。
图10为本文热膨胀系数计算值与已报道的试验数据对比。从图10可以看出,本文基于介电拟合计算求得的热膨胀系数与文献[12]基于试验获得的热膨胀系数基本相同。对于纯环氧树脂,本文的热膨胀系数计算值为1.93×10-4 K-1,而文献[12]的试验值为2.01×10-4 K-1。而对于微米氧化铝质量分数为60%的试样,虽然文献[12]并未给出具体的试验值,但作者对不同试样微米氧化铝质量分数与热膨胀系数的关系进行了线性拟合,发现填料质量分数与复合电介质的热膨胀系数存在线性关系。因此可通过拟合曲线近似推断微米氧化铝质量分数为60%时试样的热膨胀系数。通过图10的对比证明了基于介电响应计算环氧树脂及其复合电介质热膨胀系数的方法具有科学性和准确性,可将其视为一种测量环氧树脂热膨胀系数的有效方法。
通过上述讨论可知,基于介电响应测取环氧树脂热性能参数是一种科学有效的方法,未来可开发专用的计算与分析软件,在介电谱测试的同时,直接获取材料与分子和原子运动相关的热参数,如热膨胀系数和玻璃化转变温度,有助于加速我国高端实验设备的自主化进程。
本文制备了含有微米氧化铝填料质量分数分别为0%、20%、40%和60%的环氧树脂/微米氧化铝复合电介质,通过对高温下介电常数进行拟合与计算,求取了复合电介质的热膨胀系数与玻璃化转变温度,发现计算得到的热膨胀系数与玻璃化转变温度均随着微米氧化铝填料质量分数的增加而下降。将本文环氧复合电介质热膨胀系数与玻璃化转变温度的计算值与试验值进行对比发现,计算值与试验值基本吻合,证明基于介电谱测量环氧电介质热性能具有科学性和有效性,可作为研究聚合物热性能实验手段的一种有效补充,有助于加速我国实验装备的自主化进程。
  • 四川省第一批现场工程师专项培养计划项目(教职成厅函{2023}6号)
  • 四川省民办教育协会2023年研究课题(MBXH23YB448)
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doi: 10.16790/j.cnki.1009-9239.im.2025.06.007
  • 接收时间:2024-07-23
  • 首发时间:2025-12-04
  • 出版时间:2025-06-20
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  • 收稿日期:2024-07-23
  • 修回日期:2024-09-18
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四川省第一批现场工程师专项培养计划项目(教职成厅函{2023}6号)
四川省民办教育协会2023年研究课题(MBXH23YB448)
作者信息
    1.西南交通大学 希望学院,四川 成都 610400
    2.海南电网有限责任公司三亚变电运检分公司,海南 三亚 572000
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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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