环氧树脂/氧化石墨纳米复合物的等温固化行为研究  被引量:9

ISOTHERMAL CURING BEHAVIORS OF EPOXY/GRAPHITE OXIDES NANOCOMPOSITES

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作  者:仇士龙[1] 王玉婷[1] 王成双[1] 袁钻如[2] 黄玉安[3] 谢鸿峰[1] 程镕时[1,4] 

机构地区:[1]南京大学化学化工学院教育部介观化学重点实验室高分子科学与工程系,南京210093 [2]南京大学现代分析中心,南京210093 [3]南京工程学院材料工程系,南京211167 [4]华南理工大学材料学院,广州510640

出  处:《高分子学报》2012年第1期25-32,共8页Acta Polymerica Sinica

基  金:中央高校基本科研业务费专项资金(项目号1106020514)资助项目

摘  要:用示差扫描分析仪(DSC)研究了氧化石墨(GO)对N,N,N',N'-四缩水甘油基-4,4'-二氨基二苯基甲烷环氧树脂(TGDDM)/4,4'-二氨基二苯基砜(DDS)体系的等温固化反应的影响,用X射线光电子能谱仪(XPS)和傅里叶变换红外光谱仪(FTIR)研究了GO上存在的官能团及其对TGDDM/DDS体系固化行为的影响,用热失重分析仪(TGA)研究了天然石墨和GO的热力学稳定性.XPS、FTIR和TGA结果表明,GO上存在的大量羟基、羧基、环氧基等官能团能够影响环氧树脂的固化行为.DSC研究发现,环氧树脂/氧化石墨纳米复合物的固化反应属于自催化类型,随着GO含量的增加,达到最大反应速率的时间不断减小,初始反应速率不断增大,这说明GO对环氧树脂的固化反应有促进作用.Kamal模型计算得到的结果表明,随着GO含量的增加自催化反应初期阶段表观活化能E1先减小再增大,而自催化反应结束后表观活化能E2略微减小.经Kamal模型扩散控制函数修正后,整个固化过程中拟合得到的结果与实验数据相当吻合.以上结果说明,少量的GO对TGDDM/DDS体系的固化反应起着催化作用.The cure kinetics of N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane (TGDDM) and 4,4'- diaminodiphenylsulphone (DDS) nanocomposites filled with graphite oxide (GO) was studied by isothermal differential scanning calorimetry (DSC). Furthermore, the functional groups on the surface of GO and their influence on the cure behaviors of TGDDM/DDS/GO nanocomposites were studied by X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared spectroscopy (FTIR), and the thermal stabilities of the neat graphite and GO were compared by thermalgravitimetric analysis (TGA). The XPS, FT-IR and TGA results showed that there were large numbers of polar functional groups such as hydroxyl, carboxyl and cyclic epoxide groups on the surface of GO,which effected the cure behaviors of TGDDM/DDS/GO nanocomposites. The experimental data of the isothermal DSC for both the neat TGDDM/DDS system and its GO nanocomposites showed an autocatalytic behavior. Furthermore,with the increase of GO contents,the time to the maximum cure rate decreased whereas the initial cure rate increased with the increase of GO contents, which indicated that GO catalyzed the cure reaction of epoxy. The apparent activation energy for the initial stage of the reaction (E1 ) of TGDDM/DDS/GO nanocomposites obtained by Kamal' s model decreased first and then increased with the increase of GO contents,while the apparent activation energy for the reaction after the initial autocatalytic stage (E2) slight decreased with the increase of GO contents. Good agreement between the experimental data and the autocatalytic model with the modified diffusion factor in the later stage of cure was found over the whole curing temperature range for all of the neat epoxy resin and its nanocomposites with GO. The results showed that the incorporation of GO accelerated the cure reaction of the TGDDM/DDS system at lower GO content due to the interaction between the functional groups on the surface of GO and the epoxy resin.

关 键 词:氧化石墨 环氧树脂 纳米复合物 固化动力学 

分 类 号:TB383.1[一般工业技术—材料科学与工程]

 

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