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With the rapid development of modern electrical equipment, higher requirements have been put forward for nanocomposite films with higher dielectric strength and mechanical properties. Therefore, we modified boron nitride nanosheets (BNN) with 3-aminopropyltrihydroxysilane to obtain modified BNN (aBNN), and then mixed aBNN with aramid nanofiber (ANF) to prepare dense ANF/aBNN nanocomposite films by high-temperature hot-pressing method. The thermal stability, mechanical properties and electrical insulating properties of films were characterized. The results show that with the increase of aBNN content, the thermal weight loss rate of the nanocomposite film decreases significantly. When the mass fraction of aBNN is 10%, the tensile strength, elongation at break, and toughness of the ANF/10%aBNN nanocomposite film reach the maximum value, which is 235 MPa, 14.0%, and 32.4 MPa·m1/2, respectively, it is 25%, 9.4%, and 75.1% higher than that of ANF/10%BNN, respectively. The electrical strength of ANF/10%aBNN is as high as 154 kV/mm, which is about 15% and 11.6% higher than that of pure ANF and ANF/10%BNN, respectively. And the volume resistivity reaches the maximum value of 7.94×1017 Ω·cm (tested at 60℃), which is 893% and 694% higher than that of pure ANF and ANF/10%BNN, respectively.

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随着现代电气设备的飞速发展,对具有较高电气强度和力学性能的纳米复合薄膜提出了更高的要求。为此,本文采用3-氨丙基三羟基硅烷修饰氮化硼纳米片(BNN)得到改性BNN(aBNN),然后与芳纶纳米纤维(ANF)混合,通过高温热压法制备了致密的ANF/aBNN纳米复合薄膜,并对其热稳定性、力学性能和电绝缘性能进行了表征。结果表明:随着aBNN含量的增加,纳米复合膜的热失重率明显减小。当aBNN质量分数为10%时,ANF/10%aBNN纳米复合薄膜的抗拉强度、断裂伸长率和韧性均达到最大,分别为235 MPa、14.0%和32.4 MPa·m1/2,比ANF/10%BNN分别提高了25%、9.4%和75.1%;电气强度高达154 kV/mm,比纯ANF和ANF/10%BNN分别提高了约15%和11.6%;体积电阻率(测试温度为60℃)达到最大值7.94×1017 Ω·cm,比纯ANF和ANF/10%BNN分别提高了893%和694%。

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顾臻(1989-),男(汉族),上海人,高级工程师,主要从事电力工程、绝缘技术、电能计量等工作;

卢宇(1981-),男(汉族),广东深圳人,高级工程师,主要从事电力工程、绝缘技术、电能计量等工作。

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顾臻(1989-),男(汉族),上海人,高级工程师,主要从事电力工程、绝缘技术、电能计量等工作;

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顾臻(1989-),男(汉族),上海人,高级工程师,主要从事电力工程、绝缘技术、电能计量等工作;

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卢宇(1981-),男(汉族),广东深圳人,高级工程师,主要从事电力工程、绝缘技术、电能计量等工作。

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figureFileSmall=null, figureFileBig=null, tableContent=
样品名称抗拉强度/MPa断裂伸长率/%韧性/(MPa·m1/2)
纯ANF23612.725.0
ANF/5%aBNN23813.328.2
ANF/10%aBNN23514.032.4
ANF/20%aBNN20213.624.3
ANF/10%BNN18812.818.5
文献[26]319.813.526.7
文献[27]329.614.931.0
文献[28]184.011.7514.9
), ArticleFig(id=1218964341739667687, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210620760771662364, language=CN, label=表1, caption=

本文及其他文献中纳米复合膜的抗拉强度、断裂伸长率和韧性

, figureFileSmall=null, figureFileBig=null, tableContent=
样品名称抗拉强度/MPa断裂伸长率/%韧性/(MPa·m1/2)
纯ANF23612.725.0
ANF/5%aBNN23813.328.2
ANF/10%aBNN23514.032.4
ANF/20%aBNN20213.624.3
ANF/10%BNN18812.818.5
文献[26]319.813.526.7
文献[27]329.614.931.0
文献[28]184.011.7514.9
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改性氮化硼/芳纶纳米纤维复合薄膜的制备及其性能研究
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顾臻 1 , 卢宇 2 , 周磊 1 , 张静月 1 , 李芸 2
绝缘材料 | 材料研究 2024,57(12): 20-26
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绝缘材料 | 材料研究 2024, 57(12): 20-26
改性氮化硼/芳纶纳米纤维复合薄膜的制备及其性能研究
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顾臻1, 卢宇2, 周磊1, 张静月1, 李芸2
作者信息
  • 1国网上海市电力公司,上海 200051
  • 2深圳市科陆电子科技股份有限公司,广东 深圳 518132
  • 顾臻(1989-),男(汉族),上海人,高级工程师,主要从事电力工程、绝缘技术、电能计量等工作;

    卢宇(1981-),男(汉族),广东深圳人,高级工程师,主要从事电力工程、绝缘技术、电能计量等工作。

Research on preparation and properties of modified boron nitride/aramid nanofiber composite films
Zhen GU1, Yu LU2, Lei ZHOU1, Jingyue ZHANG1, Yun LI2
Affiliations
  • 1State Grid Shanghai Electric Power Company, Shanghai 200051, China
  • 2Shenzhen Clou Electronics Co., Ltd., Shenzhen 518132, China
出版时间: 2024-12-20 doi: 10.16790/j.cnki.1009-9239.im.2024.12.003
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随着现代电气设备的飞速发展,对具有较高电气强度和力学性能的纳米复合薄膜提出了更高的要求。为此,本文采用3-氨丙基三羟基硅烷修饰氮化硼纳米片(BNN)得到改性BNN(aBNN),然后与芳纶纳米纤维(ANF)混合,通过高温热压法制备了致密的ANF/aBNN纳米复合薄膜,并对其热稳定性、力学性能和电绝缘性能进行了表征。结果表明:随着aBNN含量的增加,纳米复合膜的热失重率明显减小。当aBNN质量分数为10%时,ANF/10%aBNN纳米复合薄膜的抗拉强度、断裂伸长率和韧性均达到最大,分别为235 MPa、14.0%和32.4 MPa·m1/2,比ANF/10%BNN分别提高了25%、9.4%和75.1%;电气强度高达154 kV/mm,比纯ANF和ANF/10%BNN分别提高了约15%和11.6%;体积电阻率(测试温度为60℃)达到最大值7.94×1017 Ω·cm,比纯ANF和ANF/10%BNN分别提高了893%和694%。

改性氮化硼  /  芳纶纳米纤维  /  复合薄膜  /  力学性能  /  电气性能

With the rapid development of modern electrical equipment, higher requirements have been put forward for nanocomposite films with higher dielectric strength and mechanical properties. Therefore, we modified boron nitride nanosheets (BNN) with 3-aminopropyltrihydroxysilane to obtain modified BNN (aBNN), and then mixed aBNN with aramid nanofiber (ANF) to prepare dense ANF/aBNN nanocomposite films by high-temperature hot-pressing method. The thermal stability, mechanical properties and electrical insulating properties of films were characterized. The results show that with the increase of aBNN content, the thermal weight loss rate of the nanocomposite film decreases significantly. When the mass fraction of aBNN is 10%, the tensile strength, elongation at break, and toughness of the ANF/10%aBNN nanocomposite film reach the maximum value, which is 235 MPa, 14.0%, and 32.4 MPa·m1/2, respectively, it is 25%, 9.4%, and 75.1% higher than that of ANF/10%BNN, respectively. The electrical strength of ANF/10%aBNN is as high as 154 kV/mm, which is about 15% and 11.6% higher than that of pure ANF and ANF/10%BNN, respectively. And the volume resistivity reaches the maximum value of 7.94×1017 Ω·cm (tested at 60℃), which is 893% and 694% higher than that of pure ANF and ANF/10%BNN, respectively.

modified boron nitride  /  aramid nanofibers  /  composite film  /  mechanical properties  /  electrical performance
顾臻, 卢宇, 周磊, 张静月, 李芸. 改性氮化硼/芳纶纳米纤维复合薄膜的制备及其性能研究. 绝缘材料, 2024 , 57 (12) : 20 -26 . DOI: 10.16790/j.cnki.1009-9239.im.2024.12.003
Zhen GU, Yu LU, Lei ZHOU, Jingyue ZHANG, Yun LI. Research on preparation and properties of modified boron nitride/aramid nanofiber composite films[J]. Insulating Materials, 2024 , 57 (12) : 20 -26 . DOI: 10.16790/j.cnki.1009-9239.im.2024.12.003
绝缘纳米材料由于具有质量轻、易加工和柔韧性好的特点,已广泛应用于先进的电子和电力设备,如绝缘栅双极晶体管、电动汽车、电力变压器和牵引电动机等[1]。其中,氮化硼具有较高的介电常数和面内导热系数,是绝缘和导热应用中的理想材料。氮化硼纳米片(BNN)是一种结构类似石墨烯的二维纳米填料,但其电绝缘性却远高于石墨烯,是构建高介电聚合物复合材料的理想填料[2-4]。HUANG X Y等[5]以多面体低聚硅氧烷功能化氮化硼纳米管为填料,制备了具有较好介电和导热性能的环氧纳米复合材料。K SATO等[6]以5种不同等级的片状六方氮化硼和芳香族聚酰亚胺为原料,成功制备了一系列无机/有机复合薄膜,该复合薄膜具有较高的热稳定性和热扩散率。然而,由于BNN表面光滑,化学惰性高,其与聚合物基体的相容性较差,导致制备的复合材料力学性能较差[7-13]。芳纶纤维(AF)因其高的电绝缘性、热稳定性和机械强度而成为商用绝缘纸的常用材料[14-16]。近年来的研究表明,AF可以化学劈裂成具有高长宽比、大比表面积和优异力学性能的芳纶纳米纤维(ANF)[17-19]。此外,由于纳米纤维表面具有丰富的极性基团,易于与无机纳米材料结合,是制备绝缘纳米复合薄膜的理想材料。许多研究人员致力于通过将ANF与无机填料(如蒙脱土和云母)结合来提高复合材料的绝缘性能[20-24]。目前,关于将改性BNN与ANF有机结合制备具有良好电绝缘性能和力学性能的复合纳米材料的报道仍较少。
本文采用3-氨丙基三羟基硅烷修饰BNN,并与ANF混合形成均匀的悬浮液,通过热压法制备致密的ANF/aBNN纳米复合薄膜,并对其热稳定性、力学性能和电绝缘性能进行表征,希望所制备的纳米复合膜能在现代电气设备、绝缘纸等领域推广使用。
芳纶纳米纤维(ANF),山东聚芳新材料股份有限公司;六方氮化硼(h-BN)粉末(直径<150 nm,纯度为99.8%)、3-氨丙基三羟基硅烷(APS),上海阿拉丁生化科技有限公司;氢氧化钾(KOH,纯度为95%)、二甲亚砜(DMSO,纯度为99.5%)、乙醇(纯度为99.7%)、异丙醇(IPA,纯度为99.7%),天津凯瑞思精细化工有限公司。
AXIS SUPRA+型能谱仪,深圳市科时达电子科技有限公司;AL-Y3500型X射线衍射仪(XRD),丹东奥龙射线仪器集团有限公司;JEM-7401型扫描电子显微镜(SEM),日本电子株式会社;IRTracer-100型傅里叶变换红外光谱仪(FTIR),日本岛津公司;NETZSCH DSC-200F3型差示扫描量热仪(DSC),德国耐施仪器公司;TFW-11型电子万能试验机,上海拓丰仪器科技有限公司;GEST-121A型全自动绝缘高电阻测量仪,北京冠测精电仪器设备有限公司;AHDZ-10/100型电气强度测试仪,中山市嘉仕电子科技有限公司;JEM-120i型透射电镜,日本电子株式会社;HS-TGA-101型热重分析仪,上海和晟仪器科技有限公司。
将100 mg BNN均匀分散于100 mL乙醇和0.1 mL APS的混合溶液中,在60℃下搅拌24 h后,真空过滤得到颗粒状产物。然后用乙醇洗涤产物5次,去除未反应的APS。最后,将改性后的BNN分散于DMSO溶液中,超声处理3 h,得到均匀的改性BNN(aBNN)悬浮液。
参考YANG M等[25]的方法制备芳纶纳米纤维分散体:将20 mL去离子水、1.0 g ANF 和1.5 g KOH 加入500 mL DMSO中,在室温下磁力搅拌10 h,得到暗红色的ANF悬浮液,质量分数为2 mg/mL。
首先,将一定量的aBNN用超声仪均匀分散在DMSO溶剂中。然后缓慢滴入一定量的ANFs悬浮液,辅助机械搅拌4 h。制备的ANF/aBNN分散体经过直径为47 mm、孔径为0.2 μm的多孔尼龙膜,真空过滤得到ANF/aBNN复合薄膜。将复合膜浸泡在大量去离子水中24 h,去除DMSO溶剂。然后将ANF/aBNN纳米复合膜在130℃、-0.01 MPa压力下真空干燥20 min。最后在25 MPa、230℃下压制5 min,得到ANF/aBNN纳米复合膜。其中,aBNN的质量分数分别为5%、10%、20%、30%时的纳米复合膜分别命名为ANF/5% aBNN、ANF/10%aBNN、ANF/20%aBNN、ANF/30% aBNN。另外制备含10%BNN的样品命名为ANF/10%BNN,进行对比研究。
采用扫描电镜和透射电镜对样品进行形貌观察;采用X射线衍射仪和傅里叶变换红外仪对ANF/aBNN纳米复合膜的结构进行分析;采用热重分析仪分析薄膜的热性能,氮气气氛,温度为20~800℃,升温速率为10℃/min;采用电子万能试验机对ANF/aBNN纳米复合膜进行拉伸试验,拉伸速率为1 mm/min;采用电气强度测试仪测试ANF/aBNN纳米复合膜的电气强度;采用全自动绝缘高电阻测量仪测试ANF/aBNN纳米复合膜的绝缘电阻,电阻仪测试范围为100 kΩ~10 TΩ。所有样品被裁剪为长20 mm,宽10 mm的矩形条。
为了使BNN均匀分散,采用3-氨丙基三羟基硅烷对其表面进行改性,得到带正电的aBNN,BNN改性前后的透射电镜图像如图1所示。从图1可以看出,改性前的BNN出现了明显的团聚现象,改性后的aBNN分散更为均匀。用XPS和FTIR测定了BNNs和aBNN的化学结构,结果如图2所示。
图2(a)可以看出,aBNN中出现了Si2p的结合能;从图2(b)可以看出,aBNN在1 125 cm-1、491 cm-1处分别出现了Si-O-Si的拉伸对称吸收峰和Si-O吸收峰,在1 340 cm-1处出现了一个强峰,对应B-N键的面内拉伸振动。以上结果表明,BNN被APS成功改性为aBNN。
为了进一步研究aBNN与ANF之间的相互作用类型,对不同aBNN含量的ANF/aBNN纳米复合膜进行了FTIR分析,结果如图3所示。从图3可以看出,随着aBNN含量的增加,1 399 cm-1处的单峰向1 393 cm-1较低波数移动,826 cm-1处的单峰向824 cm-1较低波数移动,这是由aBNN的B-N键面内、面外弯曲振动与ANF上芳香环共振引起的,结果表明在纳米复合膜中,aBNN与ANF之间存在很强的相互作用。
图4为热压前后ANF/aBNN纳米复合膜的表面和截面形貌。从图4(a)(c)可以看到,热压前的复合膜表面结构不致密,截面图显示复合膜具有明显间隙的多层结构。复合膜经热压后,表面的芳纶纳米纤维紧密结合,增强了界面结合力(图4(b)),同时层与层之间紧密结合,薄膜内部分层得到改善(图4(d))。致密的结构有助于提高纳米复合膜的力学性能和电气绝缘性能。
图5为不同aBNN含量下ANF/aBNN纳米复合膜的XRD图谱。从图5可以看出,纯ANF在(110)、(200)和(004)晶面处出现了衍射峰,而复合纳米材料的衍射峰和晶面与纯ANF相似,这表明aBNN的引入不会破坏ANF的取向结晶度。在26.8°和41.7°处的衍射峰对应aBNN纳米片的(002)和(100)晶面。当向ANF基体中添加aBNN时,随着aBNN含量的增加,复合材料在26.7°~60.0°的2θ范围内出现的特征衍射峰强度明显增强。其原因是硅烷键在复合材料中起着分子桥的作用,无机填料通过共价键与有机聚合物基体紧密结合。
图6为不同aBNN含量下ANF/aBNN纳米复合膜的TGA曲线。从图6可以看出,纳米复合膜的初始质量损失出现在100~120℃处,此时纳米复合膜的降解率约为2%。在此阶段,纳米复合膜释放分子间结合水,造成较小的质量损失。纳米复合膜的热解温度主要在538~600℃。800℃时,aBNN质量分数分别为0%和30%的纳米复合膜残留率分别约为45%和64%,随着aBNN含量的增加,纳米复合膜的残留率增大,质量损失明显减小,说明aBNN的添加可以增强复合材料的热稳定性。
图7为ANF/aBNN和ANF/BNN纳米复合膜的应力-应变曲线,表1为本文及其他文献中纳米复合膜的抗拉强度、断裂伸长率和韧性。由于ANF之间的范德华力、氢键以及分子链上的共价键作用,ANF表现出良好的机械强度和韧性,从表1可以看出,其抗拉强度、断裂伸长率和韧性分别为236 MPa、12.7%和25.0 MPa·m1/2。当薄膜中BNN的质量分数为10%时,ANF/10%BNN纳米复合膜变脆,抗拉强度和韧性分别降低至188 MPa、12.8%和18.5 MPa·m1/2,这可能是因为BNN相对于ANF具有脆性,BNN易使ANF发生滑移。对于ANF/aBNN纳米复合膜,当aBNN质量分数为10%时,ANF/10%aBNN纳米复合膜的抗拉强度、断裂伸长率和韧性均达到最大,分别为235 MPa、14.0%和32.4 MPa·m1/2,比ANF/10%BNN纳米薄膜分别提高了25%、9.4%和75.1%,表现出更高的机械强度。这是因为与BNN相比,改性后的aBNN带正电荷,可以更好地与带负电荷的ANF结合,有助于提高复合膜的强度。另外,由表1可以看到,本文制备的ANF/10%aBNN纳米复合薄膜与其他文献相比,也具有更优的机械强度。
图8为纳米复合膜的电气强度随温度的变化曲线。从图8可以看到,随着温度的升高,纳米复合膜的电气强度均呈现先增大后减小的趋势。当测试温度为100℃时,所有样品的电气强度均达到最大值,其中纯ANF、ANF/10%BNN、ANF/10%aBNN的电气强度分别为134、138、154 kV/mm。与纯ANF和ANF/10%BNN相比,ANF/10%aBNN的电气强度分别提高了约14.9%和11.6%,说明将BNN改性为aBNN后,有助于提高纳米复合材料的电气强度。
图9为纳米复合膜的体积电阻率随温度的变化曲线。由图9可知,随着温度的升高,纳米复合膜的体积电阻率均先升高后降低。当测试温度为60℃时,所有样品的体积电阻率均达到最大值。此温度下,纯ANF、ANF/10%BNN、ANF/10%aBNN的体积电阻率分别为8.00×1016、1.00×1017、7.94×1017 Ω·cm,ANF/10%aBNN的体积电阻率比纯ANF、ANF/10% BNN分别提高了893%和694%,说明将BNN改性为aBNN后,有助于提高纳米复合材料的体积电阻率。这是由于aBNN本身具有二维结构和较高的电气强度,可以填补分子链之间的空隙,并与ANF形成氢键,使得整个体系的结构结合更加紧密,减少了自由体积,有效削弱了分子链的运动,从而防止纳米复合膜在强电场作用下被击穿,提高了纳米复合膜的绝缘性能。
本文用3-氨丙基三羟基硅烷修饰BNN得到改性aBNN,然后与ANF混合,采用高温热压法制备致密的ANF/aBNN纳米复合薄膜,得到以下结论:
(1)aBNN的添加可以增强复合薄膜的热稳定性,随着aBNN含量的增加,纳米复合膜的热失重率明显减小。
(2)aBNN的添加有助于提高复合膜的机械强度,随着aBNN含量的增加,抗拉强度、断裂伸长率和韧性均先增大后减小。当aBNN质量分数为10%时复合薄膜具有最优的力学性能,抗拉强度、断裂伸长率和韧性分别达到235 MPa、14.0%和32.4 MPa·m1/2
(3)复合薄膜的绝缘性能良好,随着温度的升高,纳米复合膜的电气强度均呈现先增大后减小的趋势。当测试温度为60℃时,电气强度和体积电阻率分别达到154 kV/mm和7.94×1017 Ω·cm。
  • 深圳市科技计划项目(KCXFZ202012211734131 27)
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2024年第57卷第12期
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doi: 10.16790/j.cnki.1009-9239.im.2024.12.003
  • 接收时间:2024-03-21
  • 首发时间:2025-12-24
  • 出版时间:2024-12-20
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  • 收稿日期:2024-03-21
  • 修回日期:2024-06-12
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深圳市科技计划项目(KCXFZ202012211734131 27)
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    1国网上海市电力公司,上海 200051
    2深圳市科陆电子科技股份有限公司,广东 深圳 518132
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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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