Characterization and properties of SiO2-coated graphene/bismaleimide composites
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摘要: 采用硅烷偶联剂乙烯基三甲氧基硅烷(VTMO)改性石墨烯(GE),利用溶胶-凝胶法在GE表面包覆SiO2微球,得到SiO2包覆改性石墨烯(SiO2@(VTMO-GE)),以二烯丙基双酚A(BBA)和双酚A双烯丙基醚(BBE)为活性稀释剂,4,4′-二氨基二苯甲烷型双马树脂(MBMI)为单体,制备MBMI-BBA-BBE(MBAE)树脂基体;同时,以SiO2@(VTMO-GE)为增强体,采用原位聚合法制备SiO2@(VTMO-GE)/MBAE复合材料。对VTMO-GE及包覆效果进行表征和分析,研究SiO2@(VTMO-GE)增强体与SiO2@(VTMO-GE)/MBAE复合材料性能之间的关系。结果表明:VTMO成功改性GE,且SiO2微球均匀包覆在VTMO-GE表面;SiO2@(VTMO-GE)提高了SiO2@(VTMO-GE)/MBAE复合材料性能。当SiO2@(VTMO-GE)掺杂量为2.0wt%时,SiO2@(VTMO-GE)/MBAE复合材料的冲击强度和弯曲强度达到最大,分别为23.0 kJ/m2和157.4 MPa,较聚合物基体分别提高了150%和58%;在频率为102~104 Hz范围内,介电常数较为平稳,约为70.0;介电损耗约为3.7×10−3,耐热性能随SiO2@(VTMO-GE)掺杂量的增加有所提高。SiO2@(VTMO-GE)/MBAE复合材料具有优异的综合性能,为其进一步应用奠定了基础。Abstract: The silane coupling agent vinyl trimethoxysilane (VTMO) was used to modify graphene (GE), and SiO2 microspheres were coated on the surface of graphene by sol-gel method to obtain SiO2-coated modified graphene (SiO2@(VTMO-GE)). The 4,4′-diaminodiphenyl methane bismaleimide-diallyl bisphenol A-bisphenol A bisallyl ether (BBA-BBE-MBMI, MBAE) matrix was synthesized from BBA, BBE and MBMI, in which BBA and BBE were used as reactive diluents and MBMI was used as the monomer. The MBAE modified by SiO2-coated graphene (SiO2@(VTMO-GE)/MBAE) composites were prepared by in-situ polymerization with SiO2@(VTMO-GE) as the reinforcement. The effect of SiO2@(VTMO-GE) on the properties of the SiO2@(VTMO-GE)/MBAE composite was studied by characterizing and analyzing the VTMO-GE and the coating effect. The results show that GE is successfully modified by VTMO, and SiO2 microspheres are uniformly coated on the surface of VTMO-GE. The SiO2@(VTMO-GE) component improves global properties of the SiO2@(VTMO-GE)/MBAE composite. The impact strength and bending strength of the SiO2@(VTMO-GE)/MBAE composite reach the maximum of 23.0 kJ/m2 and 157.4 MPa, respectively, which are 150% and 58% higher than that of the MBAE, when the content of SiO2@(VTMO-GE) is 2.0wt%. The dielectric constant and the dielectric loss are about 70.0 and 3.7×10–3 in the frequency range of 102–104 Hz, while the heat resistance enhances with the increase of SiO2@(VTMO-GE) amount. The SiO2@(VTMO-GE)/MBAE composite exhibits excellent global properties and lays the foundation for further application.
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Key words:
- bismaleimide /
- graphene /
- SiO2 /
- mechanical properties /
- dielectric properties
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表 1 SiO2@(乙烯基三甲氧基硅烷-石墨烯)/4′4-二氨基二苯甲烷型双马来酰亚胺-二烯丙基双酚-双酚A二烯丙基醚(SiO2@(VTMO-GE)/MBAE)复合材料的编号
Table 1. Number of SiO2@(vinyl trimethoxysilane- graphene)/4,4′-diaminodiphenyl methane bismaleimide-diallyl bisphenol A-bisphenol A bisallyl ether(SiO2@(VTMO-GE)/MBAE) composites
No. Component Mass fraction of SiO2@(VTMO-GE)/wt% A0 MBAE 0 A1 SiO2@VTMO-GE/MBAE 0.5 A2 SiO2@VTMO-GE/MBAE 1.0 A3 SiO2@VTMO-GE/MBAE 1.5 A4 SiO2@VTMO-GE/MBAE 2.0 A5 SiO2@VTMO-GE/MBAE 3.0 表 2 SiO2@(VTMO-GE)/MBAE复合材料的热失重数据
Table 2. Thermogravimetry data of SiO2@(VTMO-GE)/MBAE composites
No. Td/℃ Td5/℃ Td10/℃ A1 401 412 426 A2 404 416 425 A3 404 416 427 A4 410 418 429 A5 411 419 432 Notes: Td—Thermal decomposition temperature; Td5—Temperature at 5% mass loss; Td10—Temperature at 10% mass loss. -
[1] KOTROTSOS A, TSOKANAS P, TSANTZALIS S, et al. Healing of carbon fiber reinforced plastics by dies-alder based polymer: Effects of healing agent concentration and curing cycle[J]. Journal of Applied Polymer Science,2019,136(19):47478. doi: 10.1002/app.47478 [2] 董慧民, 喻彪, 闫丽, 等. 双马来酰亚胺/聚醚砜福相树脂固化中相形貌与化学流变性能[J]. 航空材料学报, 2018, 38(6):64-70.DONG Huimin, YU Biao, YAN Li, et al. Phase morphology and chemical rheological properties of bismaleimide/polyethersulfone phase-facies cured[J]. Journal of Aeronautical Materials,2018,38(6):64-70(in Chinese). [3] 刘振, 贾园, 赵春宝, 等. 改性MoS2/双马来酰亚胺树脂的制备及性能研究[J]. 中国钼业, 2019(2):37-40.LIU Zhen, JIA Yuan, ZHAO Chunbao, et al. Preparation and properties of modified MoS2/bismaleimide resin[J]. China Molybdenum Industry,2019(2):37-40(in Chinese). [4] 周如金, 王翔, 王钧, 等. 苯并噁嗪增韧改性双马来酰亚胺树脂的制备与研究[J]. 玻璃钢/复合材料, 2018(12):21-27. doi: 10.3969/j.issn.1003-0999.2018.12.004ZHOU Rujin, WANG Xiang, WANG Jun, et al. Preparation and study of benzooxazine toughened modified bismaleimide resin[J]. Fiber Reinforced Plastics/Composites,2018(12):21-27(in Chinese). doi: 10.3969/j.issn.1003-0999.2018.12.004 [5] 朱金华, 刘晓辉, 赵颖, 等. 增韧改性氰酸酯/双马来酰亚胺/烯丙基双酚A树脂体系粘接性能研究[J]. 化学与黏合, 2016, 38(3):176-179.ZHU Jinhua, LIU Xiaohui, ZHAO Ying, et al. Study on bonding properties of toughened modified cyanate/bismaleimide/allyl bisphenol A resin system[J]. Chemistry and Adhesion,2016,38(3):176-179(in Chinese). [6] 吕燕, 常刚, 黄春江, 等. 双马来酰亚胺树脂增韧改性剂的合成[J]. 热固性树脂, 2014, 29(6):51-55.LV Yan, CHANG Gang, HUANG Chunjiang, et al. Synthesis of bismaleimide resin toughening modifier[J]. Thermosetting Resin,2014,29(6):51-55(in Chinese). [7] 张冬丽. 导热/介电聚合物基复合材料结构与性能研究[D]. 北京: 北京科技大学, 2019.ZHANG Dongli. Study on structure and properties of thermal/dielectric polymer matrix composites[D]. Beijing: Beijing University of Science and Technology, 2019(in Chinese). [8] BALANDIN A A, GHOSH S, BAO W Z, et al. Superior thermal conductivity of single-layer graphene[J]. Nano Letters,2008,8(3):902-907. doi: 10.1021/nl0731872 [9] BOLOTIN K I, SIKES K J, JIANG Z, et al. Ultrahigh electron mobility in suspended graphene[J]. Solid State Communications,2008,146(9-10):351-355. doi: 10.1016/j.ssc.2008.02.024 [10] 程江龙, 刘延磊, 吴胜明, 等. 原位改性法制备功能化石墨烯/聚甲基丙烯酸甲酯复合材料及其性能研究[J]. 青岛科技大学学报(自然科学版), 2018, 39(1):84-89.CHENG Jianglong, LIU Yanlei, WU Shengming, et al. Preparation of functionalized graphene/polymethyl methacrylate composites by in-situ modification and their properties[J]. Journal of Qingdao University of Science and Technology (Natural Science Edition),2018,39(1):84-89(in Chinese). [11] 韩乔乔, 周智勇, 陈磊. 石墨烯增强碳纤维环氧复合材料界面性能研究[J]. 针织工业, 2019(1):1-3. doi: 10.3969/j.issn.1000-4033.2019.01.001HAN Qiaoqiao, ZHOU Zhiyong, CHEN Lei. Study on interface properties of graphene reinforced carbon fiber epoxy composites[J]. Knitting Industry,2019(1):1-3(in Chinese). doi: 10.3969/j.issn.1000-4033.2019.01.001 [12] 贾海鹏, 苏勋家, 侯根良, 等. 石墨烯/聚合物纳米复合材料制备与微波吸收性能研究进展[J]. 化工学报, 2012, 63(6):1663-1668. doi: 10.3969/j.issn.0438-1157.2012.06.001JIA Haipeng, SU Xunjia, HOU Genliang, et al. Progress in preparation and microwave absorption properties of graphene/polymer nanocomposites[J]. Journal of Chemical Industry and Engineering,2012,63(6):1663-1668(in Chinese). doi: 10.3969/j.issn.0438-1157.2012.06.001 [13] 林金堂. 基于化学气相沉积石墨烯/PEDOT-PSS共混复合材料的导电薄膜[J]. 复合材料学报, 2018, 35(1):180-184.LIN Jintang. Conductive film based on chemical vapor deposited graphene/PEDOT-PSS blended composites[J]. Acta Materiae Compositae Sinica,2018,35(1):180-184(in Chinese). [14] 叶国锐, 晏义伍, 曹海琳. 氧化石墨烯改性玄武岩纤维及其增强环氧树脂复合材料性能[J]. 复合材料学报, 2014, 31(6):1402-1408.YE Guorui, YAN Yiwu, CAO Hailin. Graphene oxide modified basalt fiber and its properties of reinforced epoxy resin composites[J]. Acta Materiae Compositae Sinica,2014,31(6):1402-1408(in Chinese). [15] CHEN Z Y, GUO L L, YAN H X, et al. Amino functionalization of graphene/graphene-like MoSe2 hybrids as lubricant additives for bismaleimide composites: Preparation, mechanical and tribological properties[J]. Composites Part B: Engineering,2019,61:263-271. [16] LERF A, HE H, FORSTER M, et al. Structure of graphite oxide revisited[J]. The Journal of Physical Chemistry B,1998,102(23):4477-4482. doi: 10.1021/jp9731821 [17] 李闯, 李伟, 王明宇, 等. 功能化氧化石墨烯改性双马树脂及其复合材料[J]. 材料工程, 2018, 46(12):48-53. doi: 10.11868/j.issn.1001-4381.2017.000494LI Chuang, LI Wei, WANG Mingyu, et al. Functionalized graphene oxide modified double horse resin and its composite material[J]. Materials Engineering,2018,46(12):48-53(in Chinese). doi: 10.11868/j.issn.1001-4381.2017.000494 [18] CHEN Y F, WU Y Z, DAI G Q, et al. Effect of functionalized graphene on mechanical properties and dielectric constant of bismaleimide composites[J]. Journal of Materials Science: Materials in Electronics,2019,30:6234-6241. doi: 10.1007/s10854-019-00926-9 [19] 宋鲁彬, 郭章新, 李忠贵, 等. 含缺陷的石墨烯对增强树脂基复合材料力学性能的影响[J]. 高压物理学报, 2018, 32(6):40-49.SONG Lubin, GUO Zhangxin, LI Zhonggui, et al. Effect of graphene containing defects on mechanical properties of reinforced resin matrix composites[J]. Chinese Journal of High Pressure Physics,2018,32(6):40-49(in Chinese). [20] HAO F, FANG D N, XU Z P, et al. Mechanical and thermal transport properties of graphene with defects[J]. Applied Physics Letters,2011,99(4):041901. [21] ZHANG G L, LU S C, KE Y C. Effects of silica nanoparticles on tribology performance of poly(epoxy resin-bismaleimide)-based nanocomposites[J]. Polymer Engineering and Science,2019,59(2):274-283. doi: 10.1002/pen.24901 [22] MARTIN R, ZHAO Y H, KEWES G, et al. Silver nanowires with optimized silica coating as versatile plasmonic resonators[J]. Scientific Reports,2019,9(1):3859. doi: 10.1038/s41598-019-40380-5 [23] 中国国家标准化管理委员会. 树脂浇筑体性能试验方法: GB/T 2567—2008[S]. 北京: 中国标准出版社, 2009.Standardization Administration of the People’s Republic of China. Test methods for properties of resin casting boby: GB/T 2567—2008[S]. Beijing: China Standards Press, 2009(in Chinese). [24] NAN C W. Physics of inhomogeneous inorganic materials[J]. Progress in Materials Science,1993,37(1):1-116. [25] 胡济珠, 董岚, 卢婷玉, 等. 高热导率的聚偏氟乙烯/石墨烯复合材料[J]. 集成技术, 2019, 8(1):15-23.HU Jizhu, DONG Lan, LU Tingyu, et al. High thermal conductivity polyvinylidene fluoride/graphene composites[J]. Integration Technology,2019,8(1):15-23(in Chinese).