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Kissinger Method in Kinetics of Materials: Things to Beware and Be Aware of

机译:材料动力学中的基辛格方法:要当心和当心的事物

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摘要

The Kissinger method is an overwhelmingly popular way of estimating the activation energy of thermally stimulated processes studied by differential scanning calorimetry (DSC), differential thermal analysis (DTA), and derivative thermogravimetry (DTG). The simplicity of its use is offset considerably by the number of problems that result from underlying assumptions. The assumption of a first-order reaction introduces a certain evaluation error that may become very large when applying temperature programs other than linear heating. The assumption of heating is embedded in the final equation that makes the method inapplicable to any data obtained on cooling. The method yields a single activation energy in agreement with the assumption of single-step kinetics that creates a problem with the majority of applications. This is illustrated by applying the Kissinger method to some chemical reactions, crystallization, glass transition, and melting. In the cases when the isoconversional activation energy varies significantly, the Kissinger plots tend to be almost perfectly linear that means the method fails to detect the inherent complexity of the processes. It is stressed that the Kissinger method is never the best choice when one is looking for insights into the processes kinetics. Comparably simple isoconversional methods offer an insightful alternative.
机译:Kissinger方法是一种非常普遍的估算热刺激过程的活化能的方法,该方法通过差示扫描量热法(DSC),差示热分析(DTA)和导数热重分析(DTG)研究。其使用的简单性被基本假设导致的许多问题所抵消。一阶反应的假设引入了一定的评估误差,当应用线性加热以外的温度程序时,该误差可能会变得非常大。加热的假设被嵌入到最终方程中,该方程使该方法不适用于冷却获得的任何数据。该方法产生的单活化能与单步动力学的假设相吻合,这会给大多数应用带来问题。这可以通过将Kissinger方法应用于某些化学反应,结晶,玻璃化转变和熔化来说明。在等转化活化能显着变化的情况下,基辛格图趋于几乎完全线性,这意味着该方法无法检测过程的内在复杂性。需要强调的是,当人们正在寻找有关过程动力学的见解时,基辛格方法永远不是最佳选择。相对简单的等转换方法提供了有见地的替代方法。

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