Memory Effects in the Quiescent Crystallization of Polyamide 12: Self-Seeding, Post-Condensation, Disentangling, and Self-Nucleation beyond the Equilibrium Melting Temperature

Abstract

This paper addresses the role of memory effects from earlier thermal protocols on the non-isothermal crystallization behavior of polyamide 12 (PA12). It turns out that memory effects can induce differences in crystallization temperatures as large as 30 °C when cooled from the melt at 10 °C/min. DSC experiments reveal that memory effects in PA12 result from (1) self-nucleation by the action of crystalline residues (self-seeding), (2) chemical post-condensation, and (3) polymer chain disentangling and re-entangling. Self-nucleation and disentangling facilitate crystallization, while melt post-condensation and re-entangling hamper it. It was demonstrated that repeated crystallization stimulates disentangling and that re-entangling in the liquid state proceeds more rapidly the higher the temperature. Effects due to solid-state post-condensation are very intriguing and particularly relevant to laser sintering based additive manufacturing. It was observed that solid-state post-condensation at 175 °C for 1 h negatively affects crystallization in a subsequent heating/cooling cycle but that solid-state annealing at 175 °C for 20 h leads to an enhanced crystal perfection and chain rearrangements whose non-crystalline self-nucleating remnants in the melt at 240 °C need more than 1 h to relax and no longer stimulate crystallization during cooling. Importantly, 240 °C is higher than the equilibrium melting temperature of PA12.