含能功能化氧化石墨烯的制备、热分解行为及其对AP热分解的催化作用

为了提高氧化石墨烯(GO)对高氯酸铵(AP)热分解反应的催化活性,以GO和2,4,6-三硝基苯胺(TNA)为原料,N,N-二甲基甲酰胺、三乙胺为溶剂和酸束缚剂,合成一种新型含能功能化氧化石墨烯(EFGO);采用HRTEM、FT-IR、Raman和XPS表征了EFGO结构;采用TG-DTG和DSC分析了EFGO的热分解行为及EFGO对AP热分解反应的催化作用。结果表明,TNA通过共价键修饰至GO片层表面,其中,TNA分子中的—NH2与GO片层表面的C—O—C发生开环反应,生成C—NH键;EFGO热稳定性高,在143.8~770.0℃范围内发生了非常缓慢的失重过程,最大失重率发生在约172.1℃,整个过程失重21.2%;EFGO质量分数分别为2.5%、5%和10%时,可使AP在高温阶段的分解峰温分别降低25.6、48.0和113.1℃,表观分解放热量分别增加371、1499和2693J/g;表明EFGO对AP热分解反应的催化活性相对于GO得到显著提高,将其作为非金属含能催化剂应用于AP基固体推进剂具有潜在的应用前景。

Preparation and Thermal Decomposition Behavior of Energetic Functionalized Graphene Oxide and Its Catalytic Effect on the Thermal Decomposition of AP

In order to improve the catalytic activity of graphene oxide(GO)on the thermal decomposition of ammonium perchlorate(AP),a novel energetic functionalized graphene oxide(EFGO)was prepared by GO and 2,4,6-trinitroaniline(TNA)as raw materials,N,N-dimethylformamide and triethylamine as the solvent and acid binding agent.Its structure was characterized by HRTEM,Raman,FT-IR and XPS.The thermal decomposition behavior of EFGO and its catalytic effect on the thermal decomposition of AP were analyzed and investieated by TG-DTG and DSC.The results showed that TNA was grafted to the surface of the GO sheet by covalent bond.The—NH2 in the TNA molecule reacted with the epoxy group on the surface of the GO sheet to form a C—NH bond.EFGO had high thermal stability,and a very slow mass loss process occurred in the range of 143.8-770.0℃.The maximum mass loss rate occurred at about 172.1℃and the whole mass loss was 21.2%.When the contents of EFGO in AP mixtures were 2.5%,5%and 10%respectively,the exothermic peak temperatures of AP in the high temperature decomposition stage decrease by 25.6,48.0 and 113.1℃,the overall heat of AP increase by 371,1499 and 2693J/g,respectively.It indicated that EFGO has a better catalytic effect on the thermal decomposition of AP compared to GO,and it has a potential application as a metal free energetic catalyst in the AP-based solid propellants.