三氧化二铝对环氧树脂固化动力学及 热降解动力学的影响

采用热分析法研究了高含量Al₂O₃填料对环氧树脂（E51）/二氨基二苯甲烷（DDM）体系的固化表观活化能、热降解动力学和性能的影响.非等温差式扫描量热法（DSC）固化动力学研究表明，加入Al₂O₃体系的反应活化能由51.49 kJ/mol降低至48.12 kJ/mol；用n级非等温动力学法分析获得了固化反应的动力学参数.利用热重分析研究了环氧固化物体系的热降解动力学，用FWO方法计算固化物降解活化能结果表明，Al₂O₃粉体对E51/DDM体系初始分解活化能影响不大，当降解率达到30%时，Al₂O₃粉体对E51/DDM体系分解有明显的抑制作用.热重红外联用测试结果表明，甲烷、羰基化合物、胺和双酚A是E51/DDM热分解过程中的主要产物，Al₂O₃粉体能提高E51/DDM体系的热稳定性.动态热机械研究表明，Al₂O₃的加入增大了环氧树脂固化产物的储能模量.DSC测试结果表明，Al₂O₃加入后，体系的玻璃化转变温度由114.16℃提高到121.51℃.

Effects of Aluminum Oxide on Curing and Thermal Decomposition Kinetics of Epoxy Resin

The effects of high content Al₂O₃ particles on the apparent activation energy, thermal decomposition kinetics and properties of epoxy resin (E51)/4, 4'-Diaminodiphenylmet (DDM) system were investigated by a thermal analysis. The results on the curing kinetics of non-isothermal differential scanning calorimetry (DSC) showed that the addition of Al₂O₃ promoted the curing reaction. The activation energy of the E44/DDM system was reduced from 51.49 kJ/mol to 48.12 kJ/mol after 80%Al₂O₃ addition. In addition, the kinetic parameters of the curing reaction were obtained by the n order model. Thermo-gravimetric analyzer was used to study the thermal decomposition kinetics of the epoxy curing system. The FWO method was used to calculate the activation energy of the degradation. The results showed that the addition of Al₂O₃ powder had little effect on the initial decomposition activation energy of the 80%E51/DDM system. When the degradation rate reached 30%, the Al₂O₃ powder had obvious inhibitory effect on the decomposition of E51/DDM system. The results of TG-IR test showed that carbon oxides, methane, carbonyl compounds, amines and aromatic compounds are the main products in the process of E51/DDM thermal decomposition. Al₂O₃ powder can improve the thermal stability of the E51/DDM system. Dynamic mechanics showed that the addition of Al₂O₃ increased the modulus of storage of epoxy resin cured products. DSC results showed that the addition of Al₂O₃ powder increases the glass transition temperature from 114.16℃ to 121.51℃ of the system.