Annealing-induced morphological changes in segmented elastomers

Thermal analysis has been used to study annealing-induced ordering in segmented elastomers. Twelve segmented elastomers were studied each having approximately 50% by wt hard segment content. Seven general classes of materials were examined including polyether and polyester polyurethanes, polyether polyurethane-urea, and polyether-polyester. Materials were slow cooled (-10°C min^-1) from the melt to an annealing temperature (-10°, 20°, 60°, 90° or 120°C) where they were annealed (16, 12, 8, 6 or 4 days, respectively). Annealing was followed by slow cooling (-10°C min^-1) to -120°C after which a d.s.c. experiment was run. In general, annealing resulted in an endothermic peak at a temperature 20°-50°C above that of the temperature of annealing. This phenomenon was observed in both semicrystalline and amorphous materials. The closer the annealing endotherm was to a crystalline endotherm without exceeding it in temperature, the larger its size. Annealing endotherms resulted from hard or soft segment ordering. Only one annealing endotherm was observed for a given annealing history, even though in some materials hard and soft segments could exhibit annealing-induced morphological changes. Hard segment homopolymers were studied yielding results similar to the block polymers containing shorter sequences of the same material. This suggests that annealing-induced ordering is an intradomain phenomenon not associated with the interphase between domains, or necessarily dependent on the chain architecture of segmented elastomers.