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Article(id=1209857950508773655, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1209857942514438502, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2022.02.006, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1617379200000, receivedDateStr=2021-04-03, revisedDate=1620057600000, revisedDateStr=2021-05-04, acceptedDate=null, acceptedDateStr=null, onlineDate=1766382213475, onlineDateStr=2025-12-22, pubDate=1645286400000, pubDateStr=2022-02-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1766382213475, onlineIssueDateStr=2025-12-22, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1766382213475, creator=13701087609, updateTime=1766382213475, updator=13701087609, issue=Issue{id=1209857942514438502, tenantId=1146029695717560320, journalId=1149653034449285133, year='2022', volume='55', issue='2', pageStart='1', pageEnd='127', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1766382211568, creator=13701087609, updateTime=1766562990768, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1210616185499021709, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1209857942514438502, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1210616185499021710, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1209857942514438502, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=44, endPage=50, ext={EN=ArticleExt(id=1209857950802374950, articleId=1209857950508773655, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Effect of Double-layer Surface Modified Boron Nitride Nanosheet on Thermal Stability of Epoxy-based Insulating Materials, columnId=1190369066675179686, journalTitle=Insulating Materials, columnName=Material Research, runingTitle=null, highlight=null, articleAbstract=

Dopamine (DA) and 3-glycidoxypropyltrimethoxysilane (KH560) were used to double-layer surface modification of boron nitride nanosheet (BNNS), the effect of the modified BNNS on thermal stability of epoxy-based (EP) insulating materials was discussed combining FTIR, TGA, and SEM experimental test with reactive molecular dynamics simulation. The results show that both methods of grafting KH560 at the end of polydopamine (PDA) and grafting DA at the end of KH560 can modify the BNNS surface successfully, and the double-layer surface modified BNNSs have better dispersion in composites. Besides, the breakdown strength of double-layer surface modified BNNS/EP composites is higher than 31.2 kV/mm. The thermal stability of composites can be obviously improved by double-layer surface modification, the improving effect of grafting DA at the end of KH560 is optimal. The modification of double-layer covalent bond grafting long chains that grafting DA at the end of KH560 can improve the interfacial compatibility, which can enhance the interaction force between BNNN and EP matrix. Moreover, the long chain branch is beneficial to fill the void inside the materials, and so that the thermal stability of composites increases.

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使用多巴胺（DA）和3-缩水甘油氧基丙基三甲氧基硅烷（KH560）对氮化硼纳米片（BNNS）进行双层表面改性，结合FTIR、TGA、SEM实验测试和反应分子动力学模拟，探讨双层表面改性的BNNS对环氧基（EP）绝缘材料热稳定性的影响。结果表明：聚多巴胺（PDA）末端接枝KH560和KH560末端接枝DA两种双层改性方法均成功修饰BNNS表面，并且双层表面改性的BNNS在复合材料中具有更好的分散性；双层表面改性的BNNS/EP的电气强度均高于31.2 kV/mm；双层表面改性能够显著提高复合材料的热稳定性，其中KH560末端接枝DA的双层改性方法对于提升复合材料热稳定性的效果最佳。KH560末端接枝DA的双层共价键接枝长链的改性方法，有利于增强界面相容性，使得BNNS与EP基体相互作用力更大，且长支链可以填充材料内部的空隙，从而增强复合材料的热稳定性。

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吴毅（1984-），男（汉族），江苏盐城人，高级工程师，主要从事配网检修与运行管理的研究。

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吴毅（1984-），男（汉族），江苏盐城人，高级工程师，主要从事配网检修与运行管理的研究。

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吴毅（1984-），男（汉族），江苏盐城人，高级工程师，主要从事配网检修与运行管理的研究。

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different surface modification, figureFileSmall=null, figureFileBig=null, tableContent=
材料BNNS缩写BNNS/EP缩写
纯EP—EP
BNNSBNbEP
KH560改性kBNkEP
PDA改性dBNdEP
KH560末端接枝DA改性fkBNfkEP
PDA末端接枝KH560改性fdBNfdEP
), ArticleFig(id=1210905929466376589, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209857950508773655, language=CN, label=表1, caption=

不同表面改性的BNNS和相应BNNS/EP的缩写

, figureFileSmall=null, figureFileBig=null, tableContent=
材料BNNS缩写BNNS/EP缩写
纯EP—EP
BNNSBNbEP
KH560改性kBNkEP
PDA改性dBNdEP
KH560末端接枝DA改性fkBNfkEP
PDA末端接枝KH560改性fdBNfdEP
), ArticleFig(id=1210905929558651281, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209857950508773655, language=EN, label=Tab.2, caption=Scale and shape parameters of Weibull distribution of EP and BNNS/EP nanocomposites with different surface modification, figureFileSmall=null, figureFileBig=null, tableContent=
样品Weibull参数
α/(kV/mm)β
EP28.1514.83
bEP30.4216.21
kEP30.9617.07
dEP31.2018.58
fkEP31.2922.40
fdEP32.9424.28
), ArticleFig(id=1210905929663508883, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209857950508773655, language=CN, label=表2, caption=

EP和不同表面改性BNNS/EP纳米复合材料威布尔分布的尺度参数和形状参数

, figureFileSmall=null, figureFileBig=null, tableContent=
样品Weibull参数
α/(kV/mm)β
EP28.1514.83
bEP30.4216.21
kEP30.9617.07
dEP31.2018.58
fkEP31.2922.40
fdEP32.9424.28
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双层表面改性氮化硼纳米片对环氧基绝缘材料热稳定性的影响
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吴毅 , 李志刚 , 刘智辰 , 成先文 , 杨子瑞 , 曾健
绝缘材料 | 材料研究 2022,55(2): 44-50
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绝缘材料 | 材料研究 2022, 55(2): 44-50
双层表面改性氮化硼纳米片对环氧基绝缘材料热稳定性的影响
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吴毅, 李志刚, 刘智辰, 成先文, 杨子瑞, 曾健
作者信息
  • 国网江苏省电力有限公司盐城供电分公司，江苏 盐城 224000

    • 吴毅（1984-），男（汉族），江苏盐城人，高级工程师，主要从事配网检修与运行管理的研究。

Effect of Double-layer Surface Modified Boron Nitride Nanosheet on Thermal Stability of Epoxy-based Insulating Materials
Yi WU, Zhigang LI, Zhichen LIU, Xianwen CHENG, Zirui YANG, Jian ZENG
Affiliations
  • Yancheng Power Supply Branch of State Grid Jiangsu Electric Power Co., Ltd., Yancheng 224000, China
出版时间: 2022-02-20 doi: 10.16790/j.cnki.1009-9239.im.2022.02.006
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摘要
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使用多巴胺（DA）和3-缩水甘油氧基丙基三甲氧基硅烷（KH560）对氮化硼纳米片（BNNS）进行双层表面改性，结合FTIR、TGA、SEM实验测试和反应分子动力学模拟，探讨双层表面改性的BNNS对环氧基（EP）绝缘材料热稳定性的影响。结果表明：聚多巴胺（PDA）末端接枝KH560和KH560末端接枝DA两种双层改性方法均成功修饰BNNS表面，并且双层表面改性的BNNS在复合材料中具有更好的分散性；双层表面改性的BNNS/EP的电气强度均高于31.2 kV/mm；双层表面改性能够显著提高复合材料的热稳定性，其中KH560末端接枝DA的双层改性方法对于提升复合材料热稳定性的效果最佳。KH560末端接枝DA的双层共价键接枝长链的改性方法，有利于增强界面相容性，使得BNNS与EP基体相互作用力更大，且长支链可以填充材料内部的空隙，从而增强复合材料的热稳定性。

环氧树脂  /  氮化硼纳米片  /  双层表面改性  /  复合材料  /  绝缘性能  /  热稳定性

Dopamine (DA) and 3-glycidoxypropyltrimethoxysilane (KH560) were used to double-layer surface modification of boron nitride nanosheet (BNNS), the effect of the modified BNNS on thermal stability of epoxy-based (EP) insulating materials was discussed combining FTIR, TGA, and SEM experimental test with reactive molecular dynamics simulation. The results show that both methods of grafting KH560 at the end of polydopamine (PDA) and grafting DA at the end of KH560 can modify the BNNS surface successfully, and the double-layer surface modified BNNSs have better dispersion in composites. Besides, the breakdown strength of double-layer surface modified BNNS/EP composites is higher than 31.2 kV/mm. The thermal stability of composites can be obviously improved by double-layer surface modification, the improving effect of grafting DA at the end of KH560 is optimal. The modification of double-layer covalent bond grafting long chains that grafting DA at the end of KH560 can improve the interfacial compatibility, which can enhance the interaction force between BNNN and EP matrix. Moreover, the long chain branch is beneficial to fill the void inside the materials, and so that the thermal stability of composites increases.

epoxy resin  /  boron nitride nanosheet  /  double-layer surface modification  /  composite materials  /  insulating properties  /  thermal stability
吴毅, 李志刚, 刘智辰, 成先文, 杨子瑞, 曾健. 双层表面改性氮化硼纳米片对环氧基绝缘材料热稳定性的影响. 绝缘材料, 2022 , 55 (2) : 44 -50 . DOI: 10.16790/j.cnki.1009-9239.im.2022.02.006
Yi WU, Zhigang LI, Zhichen LIU, Xianwen CHENG, Zirui YANG, Jian ZENG. Effect of Double-layer Surface Modified Boron Nitride Nanosheet on Thermal Stability of Epoxy-based Insulating Materials[J]. Insulating Materials, 2022 , 55 (2) : 44 -50 . DOI: 10.16790/j.cnki.1009-9239.im.2022.02.006
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0 引言
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环氧树脂（EP）因具有优异的绝缘性、化学稳定性和力学性能，被广泛应用于制造电力设备和微电子器件[1-2]。随着特高压输电和微电力电子器件等技术的快速发展，高电压、大容量、小型化的电力设备和高度集成化的电子器件成为电力领域的主流研究方向[3]。但在大容量、小型化设备或高集成电子电路中，热量积累问题更为严重，导致局部温度急剧上升。而固体介质长时间暴露在高温下，会使材料造成永久性损伤甚至绝缘失效，缩短电力设备或电子器件的使用寿命[4-5]。因此，探索具有高热稳定性的新型绝缘材料非常必要。
目前，对环氧树脂、聚酰亚胺和聚碳酸酯等聚合物绝缘热老化的研究报道较多，其研究结果表明，聚合物长时间处于高温环境中，会对绝缘造成不可逆损害，同时导致绝缘材料的力学性能等也有所降低[6-8]。近年来纳米技术的发展为开发高性能新型材料提供了新思路。ZHANG Hua等[9]采用重力混合方法制备了氮化硼纳米片（BNNS）/EP复合材料，实现了5%～40%范围内的可控BNNS质量分数，提高了复合材料的导热系数，同时保持了较低的介质损耗。基于纳米粒子在环氧树脂纳米复合材料的分散程度和分布，发现掺入BNNS的复合材料热稳定性提升效果明显比掺入SiO2和Al2O3的好[10-12]。已有研究[13-14]表明，纳米填料表面改性有利于提高复合材料的性能。王楠等[15]制备了聚多巴胺（PDA）修饰的BNNS，石倩等[16]制备表儿茶素非共价键改性BNNS，结果均表明复合材料的热稳定性有所提高。LEE J H等[17]、WENG Ling等[18]研究了硅烷化BNNS对复合材料热力学性能影响，结果表明，经表面硅化处理的复合材料热力学性能均显著提高，归因于BNNS表面的成功硅化，有助于BNNS在环氧基体中均匀分散，并增强界面结合强度。
为了进一步提高复合材料性能，研究人员提出对纳米填料进行双层表面改性。YU Bin等[19]通过空气加热法制备了羟基化的h-BN（BNO)，然后共价接枝（3-异氰丙基）三乙氧基硅烷，结果表明，添加3%的BNO使EP纳米复合材料的初始热解温度比纯EP提高了42.7℃；而接枝（3-异氰丙基）三乙氧基硅烷的BNO更加显著提高了复合材料的热稳定性和热氧化抗性。YANG Dan等[20]、ZHANG Chunli等[21]使用PDA末端接枝硅烷偶联剂对BNNS进行双层非共价键表面改性，增强了BNNS与环氧基的相容性，在改善复合材料防腐性能和导热性能方面具有突出的优势。上述研究表明，双层表面改性纳米填料对复合材料性能提升具有更大的潜力，但目前针对双层表面改性对复合材料绝缘性能和热稳定性的研究结论尚不完善。
基于此，本研究以多巴胺（DA）和硅烷偶联剂（KH560）为改性剂，提出KH560末端接枝DA双层共价键表面改性BNNS的方法，测试其改性程度及其相应复合材料的电气强度，并从宏观实验和微观仿真两种时空尺度探讨双层表面改性的BNNS对环氧基复合材料热稳定性的影响。
1 实验方法与仿真细节
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1.1 主要原材料
环氧树脂（E51）、无水乙醇（EtOH）、甲基四氢苯酐固化剂（MTHPA），分析纯，常州市润翔化工有限公司；2,4,6-三（二甲氨基甲基）苯酚促进剂（DMP-30），分析纯，上海阿拉丁生化科技股份有限公司；氮化硼纳米片（500 nm），上海纳欧纳米技术有限公司；盐酸多巴胺、3-（2,3-环氧丙氧）丙基三甲氧基硅烷（KH560）、三羟甲基氨基甲烷（Tris-HCl）缓冲液，分析纯，上海麦克林生化科技有限公司；四氢呋喃（THF），分析纯，天津市科密欧化学试剂有限公司。
1.2 氮化硼纳米片表面改性
KH560末端接枝DA共价键双层表面改性BNNS方法：①将0.2 g KH560和2 g羟基化的BNNS加入EtOH/H2O溶液（EtOH和H2O的质量比为1∶1）中，在70℃下磁力搅拌8 h，再使用EtOH清洗和真空抽滤，将滤纸上的固体放在70℃真空箱中干燥24 h，得到KH560单层改性的BNNS（kBN）；②然后将一定量kBN加入DA/THF溶液（0.5%DA）中，在60℃下磁力搅拌6 h，再使用EtOH清洗和真空抽滤，将滤纸上的固体放在70℃真空箱中干燥24 h，得到KH560末端接枝DA双层表面改性的BNNS（fkBN）。
PDA末端接枝KH560非共价键双层表面改性BNNS方法：①向300 mL的缓冲溶液（pH=8.5，250 mL Tris-HCl缓冲液+50 mL的无水乙醇）中加入2 g BNNS，使用冷水浴超声1 h保证BNNS均匀分散在溶液里，再称取0.8 g盐酸多巴胺加入上述溶液中，然后在60 ℃下磁力搅拌12 h，再使用EtOH清洗和真空抽滤，将滤纸上的固体放在70℃真空箱中干燥24 h，得到PDA单层改性的BNNS（dBN）；②重复①的磁力搅拌过程后，将KH560加入搅拌后的溶液中，在60℃下磁力搅拌12 h，再使用EtOH清洗和真空抽滤，将滤纸上的固体放在70℃真空箱中干燥24 h，得到PDA末端接枝KH560双层表面改性的BNNS（fdBN）。
1.3 BNNS/EP复合材料制备
使用EP、固化剂和促进剂的质量比为100∶80∶1，BNNS的质量分数为前三者总质量的3%，复合材料的制备流程：①将适量EP放在60℃的油浴中30 min，再按上述质量比例向EP中加入BNNS，保持60℃油浴，对该混合物依次执行30 min的电动搅拌（1 000 r/min）和1 h的分散乳化（5 000 r/min）；②称取适量的MTHPA加入上述溶液中，再使用电动搅拌（1 000 r/min）1 h；③称取适量DMP-30加入上述溶液中，再使用电动搅拌（1 000 r/min）20 min；④将上述溶液放至真空箱中抽真空脱泡2 h，再使用注射器将脱泡后的溶液注入模具；⑤将模具放入真空箱内，抽真空1 min，设置真空箱温度与时间为：80℃下预固化2 h，120℃下固化2 h后再升温至150℃并保持2 h，固化结束后取出样品自然冷却至常温。不同表面改性的BNNS和相应BNNS/EP的缩写如表1所示。
1.4 测试与表征
采用赛默飞世尔科技公司的NICOLET iS10型FTIR进行分子结构分析，扫描范围为4 000～400 cm-1，扫描次数为32，分辨率为4 cm-1。采用耐驰科学仪器商贸有限公司的STA 449-F5型同步热分析仪对氮化硼纳米片和复合材料样品进行热重分析，测试温度范围为30～800℃，氮气气氛，升温速率为10℃/min。采用赛默飞世尔科技公司的Apreo S型SEM观察样品形貌及填料的分散情况，样品经喷金处理，工作电压为10 kV。使用吉林省华博科技工业有限公司的HJC-100kV型计算机控制的线性升压实验装置，1 kV/s线性匀速升压。
1.5 仿真模型与计算方法
分子模型的建立与计算采用仿真软件（LAMMPS）和反应力场（ReaxFF）[14,22]。以双酚A型缩水甘油醚（DGEBA）和甲基四氢邻苯二甲酸酐（MTHPA）为环氧树脂和固化剂分子，模型包括24个DGEBA和48个MTHPA分子，BNNS模型尺寸为28.4 Å×29.5 Å，包括175个N原子和B原子，如图1所示。热老化过程模拟细节：采用正则系综（NVT），温度以105 K/ps恒定速率使模拟系统从300 K升至2 400 K，系统维持2 400 K的温度150 ps，仿真步长为0.1 fs；文献[23]表明高温只会加速反应速率而不会改变反应机制。
2 表征分析
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图2为原始BNNS和表面改性BNNS的FTIR图谱。从图2可以看出，BN曲线上的两个最为明显的特征峰分别为1 402 cm-1处B-N键的面内伸缩振动峰和811 cm-1处B-N-B键的面外弯曲振动峰。从fkBN曲线上可见，1 110 cm-1处为Si-O键的伸缩振动峰，910 cm-1处为B-O键的伸缩振动峰，以及在3 571～3 625 cm-1间出现氨基的伸缩振动峰，说明BNNS表面共价键链接的KH560末端成功接枝了DA；从fdBN曲线上发现，在3 420～3 588 cm-1间是氨基、羟基的特征峰，2 929 cm-1和2 862 cm-1处的KH560亚甲基的非对称伸缩振动和对称伸缩振动峰，以及865 cm-1处KH560环氧基的伸缩振动峰，表明BNNS表面附着的PDA末端接枝了KH560。
图3是原始BNNS和表面改性BNNS的热重分析（TGA）曲线。
从图3可以看出，fkBN在高于250℃时才出现明显的失重现象，与kBN相比，fkBN的失重率更高，说明KH560接枝BNNS后接枝DA成功。对于fdBN样品，质量残留率约为89.36%，其失重率大于dBN，这部分是KH560的接枝量。通过上述分析可知，4种不同的改性方法都成功实现BNNS的表面处理。
图4是EP和不同表面改性BNNS/EP纳米复合材料的断面SEM图像。从图4可以看出，纯EP的断面呈多河流状，而且表面较光滑，这属于典型的脆性断裂现象；未经表面改性的BNNS/EP纳米复合材料断面中的BNNS出现小范围团聚，说明其与EP基体的相容性不理想，而经表面改性的BNNS/EP纳米复合材料断面变得更加粗糙，在复合材料中表现出良好的分散性；对比单层改性和双层改性样品的图像发现，双层接枝改性的BNNS被EP基体更加均匀包裹，说明其分散性更好。
3 性能分析
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3.1 电气强度
使用威布尔分布表征6种样品的电气强度，如式（1）所示，计算结果如图5和表1所示。
PF=1-e-(Eα)β
式（1）中：PF表示在电场强度E下的累计失效概率；E为样品击穿时的场强；α为尺度参数，表示绝缘击穿概率为63.2%时的电气强度；β为形状参数，表示击穿电压的分布范围，β值越大说明击穿电压值的分散性越小。
从图5可以看出，掺入BNNS的复合材料电气强度均高于纯EP（28.15 kV/mm），其中fkEP和fdEP复合材料的电气强度均大于31.2 kV/mm，比kEP、dEP复合材料的高，主要源于经过双层表面改性的BNNS能够改善界面处的陷阱特性，有利于更好地抑制复合材料空间电荷的注入和内部偶极子的极化作用。由表2可知，双层表面改性的BNNS/EP电气强度分散性较小，说明复合材料界面相容性好，改性后的BNNS能够更好地分散在基体中。上述分析表明掺杂BNNS后的环氧基纳米复合材料具有良好的电气强度。
3.2 热稳定性
EP和不同表面改性BNNS/EP纳米复合材料的热重分析实验结果如图6所示。
从图6可以看出，纯EP和BNNS/EP纳米复合材料均呈现出相似的失重趋势，表明BNNS的掺入没有改变EP的热分解机制。经表面改性处理的BNNS/EP纳米复合材料由于部分功能化官能团活性较大易分解，先于EP分子热分解，该反应过程吸收了部分热量，可以延缓EP分子的热分解。对比不同样品热重分析曲线可以发现，纯EP进入快速热失重的温度较低，且达到残留质量平稳的温度大约为499℃，明显低于掺入BNNS的纳米复合材料，这说明纳米复合材料热稳定性高于纯EP，需要更高的热分解温度与更长的热分解时间；其中双层接枝改性的纳米复合材料热稳定性提升程度更为明显，由fkEP纳米复合材料的热重分析曲线可见，其在500℃下的残留率为16.79%、800℃下的残留率为7.88%，远高于其他BNNS/EP纳米复合材料。
引入耐热指数温度（THRI）进一步表征BNNS/EP纳米复合材料的热稳定性，计算方法如式（2）[24]，结果如图7所示。
THRI=0.49[T5+0.6(T30-T5)]
式（2）中：T5表示热失重5%时的温度；T30表示热失重30%时的温度。
从图7可以看出，5种BNNS/EP纳米复合材料的THRI都高于纯EP，其中kEP、fEP、fkEP和fdEP 4种纳米复合材料的THRI分别为188.5、187.2、190.5、186.3℃，说明双层接枝改性的纳米复合材料热稳定性优于单层改性纳米复合材料，且fkEP纳米复合材料的THRI最高，比纯EP提高了12%。可知，耐热指数温度的表征结果与热重分析实验一致，均说明双层表面改性能够更好地提高复合材料的导热性能，且KH560末端接枝DA的双层共价键改性方法对环氧树脂复合材料热稳定性的提升效果最好。
为了从微观尺度深入探讨双层表面改性BNNS对EP复合材料热稳定性的影响机制，采用反应分子动力学模拟高温下BNNS/EP复合材料的热裂解过程。选取模拟过程中环氧分子初始热解温度（TI）、初始热解时间（tI）和完全热解时间（tF）来综合表征复合模型的热稳定性，参数值越大说明复合模型的热稳定性越好，结果如图8所示。从图8可以看出，BNNS/EP复合模型的TI、tI和tF均高于纯EP模型，说明掺杂BNNS能够提升复合模型的热稳定性。fkEP纳米复合模型的TI为1 569.7 K、tI为12.2 ps、tF为149.2 ps，均高于其他模型，说明其热稳定性最佳。这主要是由于BNNS自身的良好热性能以及双层共价键表面改性使得界面结合强度高，同时增加接枝分子链长度能有效填充材料自由空隙，限制分子链的热运动。
进一步计算不同模型在玻璃化转变温度（Tg）以下时的体积热膨胀系数（CTE），Tg的计算选用密度-温度法，CTE的计算根据式（3），计算结果如图9所示。
CTE=1V0(∂V∂T)P
式（3）中：V是体系在温度T下的体积；V0是模拟盒子在初始温度的体积；P代表恒压过程。
从图9可以看出，掺杂双层表面改性BNNS的复合模型热膨胀系数均低于其他模型，其中fkEP和fdEP的热膨胀系数分别为1.66×10-4/K和1.73×10-4/K，热膨胀系数越小，分子链热运动越弱，材料热稳定性越好，说明fkEP纳米复合模型的热稳定性最好。上述仿真结果与实验结果一致。
综上可知，双层表面改性的BNNS/EP复合材料的热稳定性更好，其中fkEP热稳定性最佳，这是由于KH560末端接枝DA双层共价键改性的BNNS在基体中具有更好的分散性和结合强度，使复合材料的结构更为致密，限制了分子链的热运动；同时BNNS表面接枝亲和性好的长链，有利于填充复合材料内部分子链间的空隙，使材料内部不易形成微孔或缝隙等缺陷。
4 结论
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（1）PDA末端接枝KH560和KH560末端接枝DA均成功修饰了BNNS表面，经双层表面改性的BNNS在复合材料中具有更好的分散性，且其相应的复合材料具有良好的电气强度。
（2）实验测试和分子模拟均表明，两种经KH560和DA双层表面改性的BNNS/EP复合材料均具有更好热稳定性，其中KH560末端接枝DA的双层共价键表面改性效果最佳。
（3）双层表面改性能够有效增强界面相容性和结合强度，限制分子链的热运动，同时亲和性好的长支链易填充至材料内部空隙，减少材料内部的缺陷，从而达到提升复合材料热稳定性的效果。
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2022年第55卷第2期
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doi: 10.16790/j.cnki.1009-9239.im.2022.02.006
  • 接收时间：2021-04-03
  • 首发时间：2025-12-22
  • 出版时间：2022-02-20
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  • 收稿日期：2021-04-03
  • 修回日期：2021-05-04
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    国网江苏省电力有限公司盐城供电分公司，江苏 盐城 224000
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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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