超声振动对快速固化环氧树脂体系固化动力学特性的影响

Influence of ultrasonic vibration on curing kinetics of rapid curing epoxy resin system

  • 摘要: 通过非等温差示扫描量热法,结合黏度测试和傅里叶红外光谱分析,研究了不同超声波振动条件下环氧树脂体系的固化特性。基于Flynn-Wall-Ozawa/FWO、Kissinger-Akahira-Sunose/KAS和Boswell积分型动力学模型,计算了不同超声波振动下环氧树脂体系的活化能。结合Malek最大概然函数法,得到了超声振动下树脂体系的固化反应动力学方程,并与实测固化度对比进行了验证。研究表明,超声振动振幅越大,树脂体系黏度降低越明显,较小的超声波振幅振动下树脂体系活化能增大,而振幅增大后活化能有明显的降低。固化物的红外光谱分析表明,随着超声振幅的增大,羟基吸收峰减弱,表明超声效应加速了胺基加成反应或者羟基醚化反应。超声振动条件下的树脂固化反应模型符合自催化模型形式,但超声振动并不能改变树脂体系的固化反应机制。以上研究结果对设计和优化碳纤维增强树脂复合材料超声振动辅助树脂传递模塑成型(RTM)工艺具有一定的指导意义。

     

    Abstract: Using the non-isothermal differential scanning calorimetry method, the viscosity test and Fourier infrared spectrum scanning technique, the curing characteristics of epoxy resin system under ultrasonic vibration with different amplitudes were studied. Based on Flynn-Wall-Ozawa/FWO, Kissinger-Akahira-Sunose/KAS and Boswell integral kinetic models, the activation energy of resin system under various ultrasonic vibration conditions was calculated. Combined with the Malek most probable function method, the curing reaction kinetic equation of resin system under ultrasonic vibration was obtained, which was verified by experimentally recorded curing degree. Results show that the greater the ultrasonic vibration amplitude, the more obvious the reduction of viscosity of the epoxy resin system. The activation energy of resin system increases under ultrasonic vibration with smaller amplitude, and the activation energy decreases significantly when the amplitude increases. The infrared spectrum test of cured product shows that with the increase of the ultrasonic amplitude, the hydroxyl absorption peak drops, which probably due to the fact that the ultrasonic effect accelerates the amine group addition reaction or the hydroxyl etherification reaction. The resin curing reaction model under ultrasonic vibration is in agreement with the form of autocatalytic model, which shows that ultrasonic effect cannot change curing reaction mechanism of epoxy resin system. The above research results have certain guiding significance for the design and optimization of ultrasonic vibration assisted resin transfer molding (RTM) technique for manufacturing carbon fiber reinforced polymer composites.

     

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