Vyazovkin Sergey
Department of Chemistry, University of Alabama at Birmingham, 901 S. 14th Street, Birmingham, AL, 35294, USA.
Macromol Rapid Commun. 2017 Feb;38(3). doi: 10.1002/marc.201600615. Epub 2016 Dec 23.
This article surveys the decade of progress accomplished in the application of isoconversional methods to thermally stimulated processes in polymers. The processes of interest include: crystallization and melting of polymers, gelation of polymer solutions and gel melting, denaturation (unfolding) of proteins, glass transition, polymerization and crosslinking (curing), and thermal and thermo-oxidative degradation. Special attention is paid to the kinetics of polymeric nanomaterials. The article discusses basic principles for understanding the variations in the activation energy and emphasizes the possibility of using models for linking such variations to the parameters of individual kinetic steps. It is stressed that many kinetic effects are not linked to a change in the activation energy alone and may arise from changes in the preexponential factor and reaction model. Also noted is that some isoconversional methods are inapplicable to processes taking place on cooling and cannot be used to study such processes as the melt crystallization.
本文综述了在将等转化率方法应用于聚合物热刺激过程方面所取得的十年进展。所关注的过程包括：聚合物的结晶和熔融、聚合物溶液的凝胶化和凝胶熔融、蛋白质的变性（解折叠）、玻璃化转变、聚合和交联（固化）以及热降解和热氧化降解。特别关注了聚合物纳米材料的动力学。本文讨论了理解活化能变化的基本原理，并强调了使用模型将此类变化与各个动力学步骤的参数联系起来的可能性。文中强调，许多动力学效应并非仅与活化能的变化相关，还可能源于指前因子和反应模型的变化。还指出，一些等转化率方法不适用于冷却过程中发生的过程，不能用于研究诸如熔体结晶等过程。
