A thermodynamic framework for the additive manufacturing of crystallizing polymers. Part I: A theory that accounts for phase change, shrinkage, warpage and residual stress

Abstract

A rigorous, comprehensive, and thermodynamically consistent theory has been developed for the fused deposition modelling (FDM) of semi-crystalline polymers. It is sufficiently general in that it can accommodate multiple phase transition mechanisms (crystallization, glass transition, and melting) during the heating and cooling cycles of the process encountered during FDM. The theory predicts the residual stresses and the resulting warpage in the polymer part due to the temperature-dependent, spatially varying specific volumes of each phase, precipitated by the inhomogeneous distribution of temperature. The theory treats the semi-crystalline polymer as a constrained mixture of multiple phases, where glass is assumed to be a new phase of the polymer. The statistically based Avrami kinetics for crystallization, modified for non-isothermal processes, is recovered as a particular case of our non-equilibrium thermodynamic analysis. Moreover, the theory predicts the temperature corresponding to the local free energy minima as the ideal glass transition temperature analogous to that of Franz and Parisi’s mean field theory with a statistical basis.