非晶聚合物构型熵的温度关系

Temperature dependence of configurational entropy in amorphous polymer

基于无序非晶材料“关联重排区域”的构型熵理论,运用构型熵与热容量差的关系式、弛豫时间与活化势垒的基本公式,及聚合物量热学的实验结果和热容量差与温度的基本关系,研究了4种情况下构型熵、介电弛豫指数和关联重排区域大小的温度变化关系.研究结论表明:聚合物的构型熵随温度的上升均增大,并由同一物质非晶态的热容量与晶态的热容量之差决定,其变化限制在热容量差为恒定及与温度成倒数的范围之内.

By means of the calorimetric experimental results and the temperature dependence of heat capacity differences, four kinds of temperature dependences of configurational entropy, dielectric relaxation index and cooperatively rearranging region are studied, on the basis of configurational entropy theory on cooperatively rearranging region in disordered amorphous materials by the methods of the relationship between configurational entropy and heat capacity difference, and the equation of relaxation time with activated energy barri- ers. The investigated results express that configurational entropy will increase with increasing temperature and is determined by the heat capacity difference, which is restricted within the constant value and a value inverse with temperature.