Modeling of PEEK Crystallization Kinetics Under Transient Thermal Conditions

This study develops a kinetic model that captures poly-ether-ether-ketone (PEEK) crystallization over a temperature T window from glass transition (Tg) to melting (Tm) temperature, and across cooling rates from 5 to ~103 °C/min. The framework is a parallel dual-Nakamura formulation whose isokinetic parameters {kiT,ni,wiT} are obtained from a bi-level non-linear regression of isothermal crystallization tests conducted using a flash-differential scanning calorimeter (FSC). The weight wiT partitions the faster primary and slower secondary crystallization and is represented by a physics-based analytical function that captures its dome-shaped temperature dependence. A maximum isothermally achievable enthalpy function is introduced so that the model predicts enthalpy ΔH(t) natively under arbitrary thermal profiles. To extend this isothermal backbone to non-isothermal conditions, two explicit cooling-rate-dependent scalars are introduced, ωT˙ and χT˙, which shift wiT and limit attainable crystallinity at high cooling rates respectively. Finally, a rate-dependent induction time relation is added to adjust the onset of crystallization. Calibrating these rate functions against non-isothermal experiments, while keeping the isokinetic parameters fixed, yields a single isothermal–non-isothermal model that predicts ΔH(t) under arbitrary T(t) profiles. Model performance is validated using an interrupted FSC experiment with a multi-segment cooling program that mimics a local transient thermal history of PEEK during additive manufacturing. The sample is cooled through successive constant-rate segments with intermittent quench–remelt cycles to probe the accumulated crystallinity along the path. Without additional fitting, the model predicts the measured enthalpy evolution with R2 ≈ 0.95. The framework thus provides a practical route for predicting polymer crystallinity under processing-relevant thermal histories.