CRITICAL INVESTIGATION OF METHODS FOR KINETIC-ANALYSIS OF THERMOANALYTICAL DATA
CRITICAL INVESTIGATION OF METHODS FOR KINETIC-ANALYSIS OF THERMOANALYTICAL DATA
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DOI：
10.1007/bf01912021
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发表时间：
1975-01-01
期刊：
影响因子：
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通讯作者：
OZAWA, T
中科院分区：
文献类型：
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作者：
OZAWA, T
本文应用Freeman和卡罗尔（Ⅰ）、Coats和Redfern（Ⅱ）、Sharp和温特沃斯（Ⅲ）以及本文作者（Ⅳ）的方法，计算了五个理论热分析数据，这些数据是在不同的升温速率下按假定的动力学参数计算的。这是一个一级反应，一个二级反应，聚合物主链中的两种随机断裂情况，以及两个平行竞争一级反应的系统。虽然方法I，II和III不能适用于后三种情况下，当一个不适用于这些情况下，近直线关系观察和虚假的不真实的动力学参数得到。对于聚合物主链无规断裂的两种情况，作者的方法给出了正确的动力学参数。对于最后一种情况，表观活化能随着转化率的增加而增加，这意味着即使是方法IV也不能应用。文中还讨论了产生这些结果的原因和避免产生虚假结果的方法。
The methods of Freeman and Carroll (I), Coats and Redfern (II), Sharp and Wentworth (III) and the present author (IV) are applied to five theoretical thermoanalytical data calculated for assumed kinetic parameters at various heating rates. These are a first-order reaction, a second-order reaction, two cases of random scission in main chains of polymers, and a system of two parallel competitive first-order reactions. Although methods I, II and III cannot be applied to the latter three cases, when one does apply them to these cases, nearly straight relations are observed and false unreal kinetic parameters are obtained. For the two cases of random scission in the main chains of polymers, the author's method gives correct kinetic parameters. For the last case, the increase of the apparent activation energy with increasing conversion implies that even method IV cannot be applied. The reason for these results and methods for avoiding false unreal results are discussed.