A Unified Thermo-Chemo-Mechanical Framework for Bulk and Frontal Polymerization: Coupled Kinetics and Front Stability

Abstract

Polymerization is a fundamental chemical process enabling large-scale production of material components across modern industries. By transforming a monomer mixture into a cross-linked polymer network, polymerization induces changes in temperature and material properties such as density and stiffness, which can generate residual stress and warping through coupled mechanisms that remain incompletely understood. Depending on processing conditions, polymerization may occur either in the bulk, sustained by continuous external energy input, or as a self-sustaining exothermic reaction front, commonly referred to as frontal polymerization. While frontal polymerization offers rapid and energy-efficient curing, its localized reaction zone produces sharp spatial gradients that amplify thermo-chemo-mechanical coupling effects. In this work, we develop a thermodynamically consistent framework that captures both bulk and frontal polymerization, incorporating stress-dependent reaction kinetics and the evolution of the stress-free configuration during curing. Using a narrow reaction-zone approximation in a uniaxial setting, we derive analytical predictions for propagation velocity, residual stress development, and stability. A perturbation analysis yields a stability criterion that generalizes the classical Zeldovich number by accounting for heat loss and mechanical loading, and enables construction of a phase diagram distinguishing stable, unstable, and quenched propagation regimes.