Effect of time and thermo-mechanical couplings on polymers

TL;DR

This paper investigates how thermo-mechanical couplings influence the behavior of polymers, challenging traditional views by analyzing dissipative effects and proposing a thermodynamic framework for understanding time-temperature equivalence.

Contribution

It introduces a thermodynamic approach to analyze coupling effects in polymers, extending the understanding of time-temperature superposition beyond viscous effects.

Findings

Coupling effects significantly influence polymer behavior.

Dissipative effects are small but impactful.

Proposes a thermodynamic model for polymer deformation.

Abstract

Analysis of the thermo-mechanical behaviour of polymers has been and still is the subject of many rheological studies both experimentally and theoretically. For small deformations, the modelling framework retained by rheologists is often of linear visco-elasticity, which led to the definition of complex modules and used to identify the glass transition temperature as the so called rule of time-temperature superposition. In this context, the effects of time are almost unanimously associated with viscous effects. It has also been observed that the dissipative effects associated with viscous effects are often very small compared to the coupling of sources indicating a high sensitivity of polymeric materials to temperature variations. This work is mainly focused on establishing the exact role of coupling effects, which also induce the effect of time. Using traditional experimental methods of visco-analysis (DMTA) and via an energy analysis of the behaviour, the goal of the thesis is to try to restate the time-temperature equivalence rule under the Thermodynamics of Irreversible Processes, taking into account the dissipative effects and coupling induced process deformation.