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聚乙交酯非等温结晶行为研究
(华东理工大学上海市多相结构材料化学工程重点实验室)
Nonisothermal Crystallization Behavior of Biodegradable Polyglycolide
(Shanghai Key Laboratory of Multiphase Materials Chemical Engineering,East China University of Science and Technology)
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投稿时间:2018-07-13    修订日期:2018-09-10
中文摘要: 利用差示量热扫描热分析仪(DSC)测得了不同降温速率下聚乙交酯的非等温结晶的温度-热焓曲线。分别通过Ozawa法、Jeziorny法和莫志深法对聚乙交酯的非等温结晶机理进行了分析。Ozawa法结果表明:在给定的温度范围内,Ozawa法并不适用于描述聚乙交酯的非等温结晶行为;Jeziorny法结果表明:不同降温速率下聚乙交酯结晶过程的Avrami指数n值接近4,聚乙交酯非等温结晶为均相成核、晶粒三维增长的过程;莫志深法结果表明:Avrami指数与Ozawa指数的比值a基本无变化,动力学参数f(T)的值随降温速率增加逐渐增大,即在更快的降温速率下,聚乙交酯结晶更充分,可获得更高的结晶度。通过Kissinger方程计算得到聚乙交酯结晶扩散活化能为-66.9 kJ/mol。
Abstract:The nonisothermal crystallization temperature-enthalpy curves of polyglycolide (PGA) were obtained by Differential Scanning Calorimeter (DSC) at different cooling rate ranged from 2.5 ℃/min to 20 ℃/min. The relation of relative crystallinity of PGA and crystallization time at different cooling rate were also obtained as S shape curves, which showed that crystallization rate increased with the increase of cooling rate. Compared with Ozawa method, the Jeziorny method and Mo’s method were both successfully applied to describe the nonisothermal crystallization behavior of PGA, respectively. The results of Jeziorny method showed that the Avrami exponent (n) at different cooling rate ranged from 3.72 to 3.96, which was apparently close to 4, indicating that the nonisothermal crystallization of PGA was a process of homogeneous nucleation with three-dimensional growth. The results of Mo’s method showed that the specific value of Avrami exponent and Ozawa exponent “a” kept invariant regardless of the change of cooling rate. The kinetic parameter “f(T)” increased gradually with the increasing of cooling rate, revealing higher degree of crystallinity can be obtained at higher cooling rate. The value of activation energy of crystallization of PGA, calculated by Kissinger equation for the linear relationship between ln(φ/Tp2) and 1/Tp, was ,-66.9 kJ/mol.
文章编号:20180713001     中图分类号:TQ317.9    文献标志码:
基金项目:十三五国家重点研发计划(2016YFB0302701),国家自然科学基金(21676083),上海市启明星计划项目(16QB140130),中央高校基本科研业务费专项资金(22221817014)和111项目(B08021)。
引用本文:
喻祖圣,郑翔睿,奚桢浩,赵玲.聚乙交酯非等温结晶行为研究[J].功能高分子学报,DOI:10.14133/j.cnki.1008-9357.20180713001.
Yu Zu-sheng,Zheng Xiang-rui,Xi Zhen-hao,Zhao Ling.Nonisothermal Crystallization Behavior of Biodegradable Polyglycolide[J].Journal of Functional Polymers,DOI:10.14133/j.cnki.1008-9357.20180713001.