【作者】 丁娟；

【导师】 黄英；

【作者基本信息】 西北工业大学 ， 材料学， 2016， 博士

【摘要】 近些年来,碳纳米材料一直是材料科学领域的研究热点,其中,石墨烯的发现引起了研究者的极大兴趣。石墨烯由于具有优异的性能使其应用于吸波、锂电池、太阳能电池、聚合物基复合材料、催化剂和传感器等各个方面。在众多的研究方向中,石墨烯填充聚合物基复合材料是一个重要的方向,但是,由于石墨烯的尺寸效应,容易发生团聚,使得石墨烯在聚合物基体中难以均匀分散,在很大程度上影响了聚合物基复合材料的性能。因此,对石墨烯材料进行改性就成为了研究重点。本文旨在研究一种硅烷偶联剂KH-560改性的石墨烯及石墨烯-氧化锌微米球二元复合材料,以热固性树脂为聚合物基体,采用溶液混合的方法对树脂基体进行填充,制得的石墨烯/聚合物基复合材料具有优异的机械性能、介电性能和热稳定性能。本论文的主要研究内容及研究成果如下:1.研究了功能化石墨烯/氰酸酯（FGNs/CE）复合材料的制备及其性能。分析了硅烷偶联剂改性石墨烯的结构和元素组成、FGNs/CE复合材料的机械性能和热稳定性能。研究发现,在整个固化过程中,FGNs/CE纳米复合材料的固化温度随着功能化石墨烯（FGNs）含量的增加而降低,FGNs起催化作用,其中,FGNs/CE预聚体的最高放热峰（Tmax）,外延终止温度（Tc）和结晶度比纯氰酸酯树脂的有所降低。当FGNs含量为3 wt.%时,FGNs/CE纳米复合材料的机械性能提高到最佳。同时,FGNs的加入有效提高了FGNs/CE纳米复合材料的热稳定性。2.研究了功能化石墨烯（FGNs）填充氰酸酯/环氧树脂基体的制备方法和综合性能,分别讨论了石墨烯的含量对功能化石墨烯/氰酸酯/环氧树脂（FGNs/CE/EP）复合材料的性能的影响。研究发现,当FGNs含量为2.0 wt.%时,FGNs/CE/EP纳米复合材料的弯曲强度和冲击强度最佳,且分别为170.8 MPa和15.5 kJ/m²,FGNs/CE/EP纳米复合材料的介电性能和热性能均得到提高。同时,探讨了不同环氧树脂含量对FGONs/CE/EP纳米复合材料的综合性能的影响,发现环氧树脂的引入提高了FGONs/CE/EP纳米复合材料的机械性能,其中,冲击强度和弯曲强度分别为纯氰酸酯树脂的1.41倍和1.72倍。当环氧树脂含量为40 wt.%时,FGONs/CE/EP纳米复合材料的储能模量最小,和纯氰酸酯树脂相比,FGONs/CE/EP纳米复合材料的Tg和热稳定性降低。3.分别研究了功能化氧化石墨烯/氰酸酯/双马来酰亚胺（FGONs/CE/BMI）和石墨烯-氧化锌/氰酸酯/双马来酰亚胺（RGO-ZnO/CE/BMI）复合材料的制备方法和性能,讨论了石墨烯-氧化锌（RGO-ZnO）复合物的物相组成、结构、形貌及氰酸酯基复合材料的机械性能和热稳定性,发现功能化氧化石墨烯（FGONs）的引入提高了FGONs/CE/BMI纳米复合材料的机械性能,当FGONs含量为1.0 wt.%时,FGONs/CE/BMI纳米复合材料的弯曲强度和冲击强度达到最佳值,分别为110MPa和10.98 kJ·m^-2。和纯CE树脂相比较,FGONs/CE/BMI纳米复合材料的介电性能更低。随着FGONs含量的增加,FGONs/CE/BMI纳米复合材料的热稳定性较好。对RGO-ZnO/CE/BMI复合材料的研究发现,当RGO-ZnO含量为1 wt.%时,RGO-ZnO/CE/BMI复合材料的弯曲和冲击性能均最佳,为110 MPa和10.9kJ/m²,但高含量的RGO-ZnO在RGO-ZnO/CE/BMI复合材料中容易发生聚集。和CE/BMI共聚物相比,RGO-ZnO/CE/BMI复合材料的热稳定性较好。4.研究了超高体积含量的碳纳米管（MWCNTs）、石墨烯（GNs）和氮化硼（hBN）粒子填充氰酸酯树脂基体的导热、导电性能和热性能。分别制备了氰酸酯/碳纳米管（CE/MWCNTs）、氰酸酯/石墨烯（CE/GNs）、氰酸酯/碳纳米管/石墨烯（CE/MWCNTs/GNs）、氰酸酯/氮化硼（hBN/CE）和氰酸酯/石墨烯/氮化硼（CE/GNs/hBN）复合材料。研究发现,MWCNTs和GNs、GNs和hBN的协同作用对CE/MWCNTs/GNs和GNs/hBN/CE复合材料的导热性能比单独的MWCNTs、GNs和hBN填充氰酸酯树脂的导热效果好。以GNs/CE复合材料为例,由于石墨烯具有较高的导电性和耐热性能,GNs/CE复合材料具有优异的导电性能和热稳定性能。5.采用预浸料工艺制备了超高FGNs体积含量的FGNs/CE/CF复合材料,研究了FGNs/CE/CF复合材料的导热、导电性能、机械性能和热性能。随着FGNs体积含量的增加,FGNs/CE/CF复合材料的弯曲强度和层间剪切强度（ILSS）呈现先升后降的趋势,FGNs/CE/CF复合材料的导热性能达到了5.10 W/m K,FGNs和CE/CF复合材料之间的复合效应提高了FGNs/CE/CF复合材料在0°方向的导电性能。更多还原

【Abstract】 Carbon nanomaterials have been a hot research in materials science,the discovery of graphene caused an interests of researchers.Graphene is widely used in microwave absorption,lithium battery,solar cells,polymer composites,catalyst and sensor,et al.,due to its excellent physical and chemical performance.Graphene filled in polymers is an important direction in numerous research fields.However,graphene is hard to disperse evenly in polymer and is prone to reunite due to the size effect of graphene,which affects the performance of polymer composites.Therefore,the graphene material modification has become a hot research focus.The purpose of this paper is to prepare a kind of silane coupling agent(KH-560)to modify graphene and synthesis a graphene-zinc oxide micro-sphere binary composites.With cyanate ester resin as a polymer matrix and the functional graphene and the graphene-zinc oxide micro-sphere compound filled in the matrix via a solution blending method,the mechanical properties,dielectric properties and thermal stability properties of functionalized graphene/cyanate resin composites are investigated.Based on the topic,the main research contents and research results of this paper are as follows:1.In this thesis the preparation procedure of functionalized graphene/cyanate ester(FGNs/CE)composite was prepared and the integrated properties of the FGNs/CE composite were investigated.The structure and elements composition of silane coupling agent modified graphene and the mechanical properties,thermal stability properties of the FGNs/CE composite were analysed.It showed that the cured temperature of FGNs/CE composite decreased with the increase of functionalized graphene(FGNs)content in the whole curing process due to the FGNs as a catalyst in the FGNs/CE composite.Compared to the virgin cyanate ester resin,the Tmax,Tc and crystallinity of the FGNs/CE composite were decreased.When the content of FGNs was 3 wt.%,the mechanical properties of the FGNs/CE composite achieved the best and the thermal stability of the FGNs/CE composite increased as well.2.The preparation and comprehensive properties of functionalized graphene(FGNs)and functionalized graphene oxide(FGONs)filled in cyanate ester/epoxy copolymer matrix were investigated.The content of FGNs on the effect on the integrated properties of functionalized graphene/cyanate ester/epoxy(FGNs/CE/EP)composites was analysised.When the content of FGNs was 2.0 wt.%,the flexural and impact strength of FGNs/CE/EP composites achieved the best,were 170.8 MPa and 15.5kJ/m~2,respectively,the dielectric and thermal properties of FGNs/CE/EP composites were improved.We also discussed different content of epoxy resin on the effect of functionalized graphene oxide/cyanate ester/epoxy FGONs/CE/EP composites,founding that the mechanical properties of FGONs/CE/EP composites enhanced by introducing epoxy resin,the impact and flexural strength were 1.41 times and 1.72times compared to the virgin cyanate ester resin,respectively.When the content of epoxy resin was 40 wt.%,the storage modulus of FGONs/CE/EP composites was minimum.Compared to the virgin CE resin,the glass transition temperature(Tg)and thermal stability of FGONs/CE/EP composites were decreased.3.The preparation and comprehensive properties of functionalized graphene oxide/cyanate ester/bismaleimide(FGONs/CE/BMI)composites and graphene-zinc oxide/cyanate ester/bismaleimide(RGO-ZnO/CE/BMI)composites were studied.We analysed the structure and phase composition of graphene-zinc oxide(RGO-ZnO)compound and morphology,mechanical properties and thermal stability of FGONs/CE/BMI and RGO-ZnO/CE/BMI composites,founding that the introduction of FGONs improved the mechanical properties of FGONs/CE/BMI composites,when the content of FGONs was 1.0 wt.%,the flexural and impact strengths of FGONs/CE/BMI composite reached 110 MPa and 10.98 kJ/m~2,respectively.Compared to the pure CE resin,the dielectric properties of FGONs/CE/BMI composite were low.The thermal stability of FGONs/CE/BMI composite was good with the content of FGONs increased.When the content of RGO-ZnO was 1.0 wt.%,the flexural and impact strengths of RGO-Zn O/CE/BMI composite reached the optimum values,which were 110 MPa and 10.98 kJ/m~2,respectively.However,high content of RGO-ZnO compound was easy to aggregate in RGO-Zn O/CE/BMI composite.Compared to CE/BMI copolymer,the thermal stability of RGO-ZnO/CE/BMI composite was good.4.High volume content of multiwalled carbon nanotube(MWCNTs),functionalized graphene(GNs)and boron nitride(hBN)particles filled in cyanate ester resin matrix were prepared,the thermal conductivity,electrical conductivity and thermal properties of CE/MWCNTs、CE/GNs、CE/MWCNTs/GNs、hBN/CE and GNs/hBN/CE were investigated.It showed that the thermal conductivity of synergy effect of MWCNTs and GNs、GNs and hBN on CE/MWCNTs/GNs and GNs/hBN/CE composites were good than the thermal conductivity of single MWCNTs,GNs and hBN filling in cyanate ester resin.As GNs/CE for example,GNs/CE composite has excellent electrical conductivity and thermal stability due to excellent electrical conductivity and heat resistant of GNs.5.High FGNs volume content of FGNs/CE/CF composites was prepared with a presoak method and the thermal conductivity,electrical conductivity,mechanical and thermal properties of FGNs/CE/CF composites were investigated.The flexural strength and interlaminar shear strength(ILSS)rose in the first stage,and then decreased with the volume content of FGNs increased.The thermal conductivity of FGNs/CE/CF composite was 5.10 W/m K,the electrical conductivity of FGNs/CE/CF composite in 0°direction improved due to the composition effect between FGNs and CE/CF composites.更多还原