Ibar Jean Pierre
Rheology Department, Polymat Institute, University of the Basque Country, 20018 Donostia-San Sebastian, Euskadi, Spain.
Polymers (Basel). 2025 Jan 19;17(2):239. doi: 10.3390/polym17020239.
This paper addresses the author's current understanding of the physics of interactions in polymers under a voltage field excitation. The effect of a voltage field coupled with temperature to induce space charges and dipolar activity in dielectric materials can be measured by very sensitive electrometers. The resulting characterization methods, thermally stimulated depolarization (TSD) and thermal-windowing deconvolution (TWD), provide a powerful way to study local and cooperative relaxations in the amorphous state of matter that are, arguably, essential to understanding the glass transition, molecular motions in the rubbery and molten states and even the processes leading to crystallization. Specifically, this paper describes and tries to explain 'interactive coupling' between molecular motions in polymers by their dielectric relaxation characteristics when polymeric samples have been submitted to thermally induced polarization by a voltage field followed by depolarization at a constant heating rate. Interactive coupling results from the modulation of the local interactions by the collective aspect of those interactions, a recursive process pursuant to the dynamics of the interplay between the free volume and the conformation of dual-conformers, two fundamental basic units of the macromolecules introduced by this author in the "dual-phase" model of interactions. This model reconsiders the fundamentals of the TSD and TWD results in a different way: the origin of the dipoles formation, induced or permanent dipoles; the origin of the Wagner space charges and the T transition; the origin of the T manifestation; the origin of the Debye elementary relaxations' compensation or parallelism in a relaxation map; and finally, the dual-phase origin of their super-compensations. In other words, this paper is an attempt to link the fundamentals of TSD and TWD activation and deactivation of dipoles that produce a current signal with the statistical parameters of the "dual-phase" model of interactions underlying the Grain-Field Statistics.
本文阐述了作者目前对聚合物在电压场激发下相互作用物理学的理解。电压场与温度耦合在介电材料中诱导空间电荷和偶极活性的效应可通过非常灵敏的静电计进行测量。由此产生的表征方法,即热刺激去极化(TSD)和热窗解卷积(TWD),为研究物质非晶态中的局部和协同弛豫提供了一种有力的方法,而这些弛豫对于理解玻璃化转变、橡胶态和熔融态中的分子运动乃至导致结晶的过程而言,可以说是至关重要的。具体而言,本文描述并试图解释聚合物中分子运动之间的“相互作用耦合”,该耦合基于聚合物样品在电压场作用下经历热诱导极化后以恒定加热速率去极化时的介电弛豫特性。相互作用耦合源于这些相互作用的集体层面所产生的局部相互作用调制,这是一个递归过程,遵循自由体积与双构象体构象之间相互作用的动力学,双构象体是作者在“双相”相互作用模型中引入的大分子的两个基本基本单元。该模型以不同方式重新审视了TSD和TWD结果的基本原理:偶极形成的起源,诱导偶极或永久偶极;瓦格纳空间电荷和T转变的起源;T表现的起源;弛豫图谱中德拜基本弛豫的补偿或平行性的起源;最后,它们超补偿的双相起源。换句话说,本文试图将产生电流信号的偶极的TSD和TWD激活与失活的基本原理与基于晶粒场统计的“双相”相互作用模型的统计参数联系起来。