Enthalpy relaxation of polyamide 11 of different morphology far below the glass transition temperature

Abstract

Polyamide 11 (PA 11) samples of different supermolecular structure, including the crystal-free glass and semi-crystalline PA 11 of largely different semi-crystalline morphology, were prepared by fast scanning chip calorimetry (FSC). These samples were then annealed at different temperatures well below the glass transition temperature Tg. The main purpose of the low-temperature annealing experiments was the calorimetric detection of mobility of chain segments at temperatures as low as -40 °C (≈Tg - 80 K) where still excellent impact resistance is predicted. It was found that annealing PA 11 at such low temperature, regardless the thermal history and supermolecular structure including crystallinity as well as crystal shape and size, permits distinct enthalpy relaxation at rather short time scale with the structural changes reverting on subsequent heating as detected with pronounced sub-Tg-enthalpy-recovery peaks. The main glass transition, associated to large-amplitude segmental mobility, as well as relaxations at temperatures only slightly below Tg are even more distinctly sensitive to the crystal morphology. In contrast to spherulitically grown lamellar crystals, presence of high-specific-surface area nanometer-sized ordered domains causes a shift of the glass transition temperature of the amorphous phase to higher temperature, proving stronger coupling of ordered and amorphous phases than in case of lamellae. In addition, the increased coupling of the crystalline and amorphous phases slows down the cooperative rearrangements on annealing the glass slightly below Tg. The performed study contributes to further understanding of the spectrum of structural relaxations in PA 11 including the effect of presence of crystals. Enthalpy relaxation and consequently the reduction of entropy at temperatures slightly below Tg strongly depends on the semi-crystalline morphology, while an only minor effect is seen on low-temperature annealing at Tg - 80 K, possibly indicating different molecular mechanisms for the processes occurring in both temperature ranges. The low-temperature process even seems proceeding in the crystalline fraction of the material.