碳纳米材料表面改性碳纤维及在环氧树脂中的应用
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摘要
以N,N-二甲基甲酰胺为溶剂,通过超声的方法分别制备含多壁碳纳米管(MWCNTs)或石墨烯纳米片(GnP)的碳纳米材料表面改性剂,采用浸渍法对预处理碳纤维(CF)(去浆CF)进行改性使碳纳米材料均匀涂覆在纤维表面上,然后采用手糊成型及热压成型工艺制备环氧树脂(EP)/改性CF复合材料,利用扫描电子显微镜和电子万能试验机分析碳纳米材料表面改性剂制备条件对CF表面形貌、复丝拉伸性能的影响,在此基础上,选择各自的最佳表面改性剂制备条件,对比了含MWCNTs或GnP的表面改性剂改性CF对复合材料力学性能的影响。结果表明,碳纳米材料在表面改性剂中的分散状态直接影响CF表面碳纳米材料分布的均匀性和复合材料的性能。超声时间为2h的含MWCNTs表面改性剂和GnP质量分数为0.5%的含GnP表面改性剂对CF的改性效果较好,相应复丝的拉伸强度与去浆CF复丝相比分别提高了59.4%和70.2%,而相应复合材料的弯曲强度相对于EP/去浆CF复合材料分别提高了11.2%和41.1%,层间剪切强度分别提高了35.8%和71.3%。
Taking N,N-Dimethylformamide as solvent,surface modifying agents based on carbon nanomaterials containing multi-walled carbon nanotubes(MWCNTs) or graphene nanoplatelet(GnP) were prepared respectively by sonication. Pretreatment carbon ?ber(desizing CF) is modi?ed with the surface modifying agents by impregnation method,so that carbon nanomaterials could be uniformly coated on the surface of ?ber,and then the epoxy resin(EP)/modi?ed CF composites were prepared by hand lay-up molding and hot pressing process. The effects of preparation conditions of the surface modifying agents on the surface morphology of CF and tensile properties of multi?lament are investigated by scanning electron microscopy and electronic universal testing machine. On the basis,each optimal preparation conditions of the surface modifying agents were selected and the in?uences of the CF modi?ed by the agents containing MWCNTs or GnP on the mechanical properties of the composites were compared. The results show that the dispersion state of carbon nanomaterials in the surface modifying agents directly affects the distribution of carbon nanomaterials on the surface of CF and mechanical properties of the composites. There have better modifying results when CF are modi?ed by the surface modifying agent containing MWCNTs with ultrasonic time of 2 h or the agent containing 0.5%(mass fraction) GnP,the tensile strength of corresponding multi?laments increase by 59.4% and 70.2% respectively compared with the desizing CF,the ?exible strength of corresponding composites increase by 11.2% and 41.1% respectively and the interlaminar shear strength increase by 35.8% and 71.3% respectively compared with the EP/desizing CF composite.
Taking N,N-Dimethylformamide as solvent,surface modifying agents based on carbon nanomaterials containing multi-walled carbon nanotubes(MWCNTs) or graphene nanoplatelet(GnP) were prepared respectively by sonication. Pretreatment carbon ?ber(desizing CF) is modi?ed with the surface modifying agents by impregnation method,so that carbon nanomaterials could be uniformly coated on the surface of ?ber,and then the epoxy resin(EP)/modi?ed CF composites were prepared by hand lay-up molding and hot pressing process. The effects of preparation conditions of the surface modifying agents on the surface morphology of CF and tensile properties of multi?lament are investigated by scanning electron microscopy and electronic universal testing machine. On the basis,each optimal preparation conditions of the surface modifying agents were selected and the in?uences of the CF modi?ed by the agents containing MWCNTs or GnP on the mechanical properties of the composites were compared. The results show that the dispersion state of carbon nanomaterials in the surface modifying agents directly affects the distribution of carbon nanomaterials on the surface of CF and mechanical properties of the composites. There have better modifying results when CF are modi?ed by the surface modifying agent containing MWCNTs with ultrasonic time of 2 h or the agent containing 0.5%(mass fraction) GnP,the tensile strength of corresponding multi?laments increase by 59.4% and 70.2% respectively compared with the desizing CF,the ?exible strength of corresponding composites increase by 11.2% and 41.1% respectively and the interlaminar shear strength increase by 35.8% and 71.3% respectively compared with the EP/desizing CF composite.
引文
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[2]Kim K J,Kim J,Yu W R,et al.Improved tensile strength of carbon fibers undergoing catalytic growth of carbon nanotubes on their surface[J].Carbon,2013,54:258-267.
[3]Li Fei,Liu Yu,Qu Chengbing,et al.Enhanced mechanical properties of short carbon fiber reinforced polyethersulfone composites by graphene oxide coating[J].Polymer,2015,59:155-165.
[4]Zhang Han,Liu Yi,Kuwata M,et al.Improved fracture toughness and integrated damage sensing capability by spray coated CNTs on carbon fibre prepreg[J].Composites Part A:Applied Science and Manufacturing,2015,70:102-110.
[5]张庆波,眭凯强,刘丽.碳纤维电泳沉积碳纳米管对界面性能的影响[J].材料科学与工艺,2015,23(1):45-50.Zhang Qingbo,Sui Kaiqiang,Liu Li.The influence of carbon fiber reinforcement composite by electrophoretic deposition carbon nanotubes on interfacial property of carbon fiber surface[J].Materials Science and Technology,2015,23(1):45-50.
[6]陈师.电泳沉积法制备CNT/CF及其复合材料界面微观力学行为的拉曼研究[D].上海:东华大学,2016.Chen Shi.Preparration of CNT/CF by EPD and raman study on interfacial micro-mechanical properties of their composites[D].Shanghai:Donghua University,2016.
[7]郑林宝,王延相,陈纪强,等.CF-CNTs多尺度增强体的制备及CF-CNTs/环氧树脂复合材料力学性能[J].复合材料学报,2017(11):50-58.Zheng Linbao,Wang Yanxiang,Chen Jiqiang,et al.Preparation of CF-CNTs multi-scale reinforcement and mechanical properties of CF-CNTs/epoxy composites[J].Acta Materiae Compositae Sinica,2017(11):50-58.
[8]张舒.基于上浆法的界面设计及其对CFRP界面性能影响研究[D].哈尔滨:哈尔滨工业大学,2014.Zhang Shu.Investigation on interphase design based on sizing process and its effect on interfacial properties of CFRP[D].Harbin:Harbin Institute of Technology,2014.
[9]李娜,王志平,刘刚,等.含碳纳米管上浆剂的制备及对碳纤维/环氧树脂复合材料界面的影响[J].高分子材料科学与工程,2015,31(3):147-152.Li Na,Wang Zhiping,Liu Gang,et al.Fabrication of sizing agent containing multi-walled carbon nanotubes and effect on carbon fibers/epoxy resin composite interface[J].Polymer Materials Science&Engineering,2015,31(3):147-152.
[10]王昊,颜春,徐海兵,等.碳纤维表面改性剂的研究进展[J].热固性树脂,2016,31(3):65-69.Wang Hao,Yan Chun,Xu Haibing,et al.Research progress of carbon fiber sizing agent[J].Thermosetting Resin,2016,31(3):65-69.
[11]Cha J,Jin S,Shim J H,et al.Functionalization of carbon nanotubes for fabrication of CNT/epoxy nanocomposites[J].Materials&Design,2016,95:1-8.
[12]Qin W,Vautard F,Drzal L T,et al.Mechanical and electrical properties of carbon fiber composites with incorporation of graphene nanoplatelets at the fiber-matrix interphase[J].Composites Part B,2015,69:335-341.
[13]张清杰.官能化碳纳米管/碳纤维多尺度增强环氧树脂基复合材料基础研究[D].北京:北京化工大学,2016.Zhang Qingjie.The fundamental research on the functionalized carbon nanotube/carbon fiber multi-scale reinforced expoxy composites[D].Beijing:Beijing University of Chemical Technology,2016.
[14]于倩倩,陈刚,郑志才,等.酸化石墨烯改性环氧树脂及其碳纤维复合材料力学性能研究[J].玻璃钢/复合材料,2018(5):27-33.Yu Qianqian,Chen Gang,Zheng Zhicai,et al.Study of mechanical properties of acidification grapheme modified epoxy resin and its carbon fiber composite[J].Fiber Reinforced Plastics/Composites,2018(5):27-33.
[15]韩潇,肇研,孙健明,等.氧化石墨烯/炭纤维/环氧树脂基复合材料的制备及其层间剪切性能[J].新型炭材料,2017,32(1):48-55.Han Xiao,Zhao Yan,Sun Jianming,et al.Effect of graphene oxide addition on the interlaminar shear property of carbon fiberreinforced epoxy composites[J].New Carbon Materials,2017,32(1):48-55.
[16]秦文贞.纳米粒子修饰碳纤维及其复合材料性能研究[J].上海:东华大学,2016.Qin Wenzhen.Study on the nano-particles modified carbon fiber and the propertie of carbon fiber composites[J].Shanghai:Donghua University,2016.