Elasticity and inelasticity of thermoplastic polyurethane elastomers: Sensitivity to chemical and physical structure

Cyclic tensile responses of fourteen polyurethane elastomers were studied, with respect to their chemical composition and physical structure. Hard segment, soft segment and chain extender were varied, while keeping the hard segment fraction at ca 40% and soft segment molar mass at 2000 g/mol. Hard segments were generated from 4,4′-methylene bis(phenyl di-isocyanate) (MDI), or 4,4′-dibenzyl di-isocyanate (DBDI). Physical structure was characterized by X-ray scattering (SAXS and WAXS), revealing significant variations in degree of phase separation and degree of crystallinity, especially in the DBDI-based polymers. Large differences were found in the mechanical responses during first loading to a given strain. Tensile modulus and work input increased significantly with degree of hard phase crystallinity, but were independent of degree of phase separation. First cycle hysteresis was found to increase with reduced phase separation and with replacement of MDI by DBDI. In second and subsequent load cycles, however, in which the Mullins effect was observed, a remarkable degree of uniformity of response was discovered. A unique linear relation was obtained between second cycle hysteresis and second cycle work input, for all strain levels, and for all materials except for two (with highest phase separation) which showed slightly lower second cycle hysteresis. The results can be explained in terms of pull-out of segments from the hard phase on the first cycle, to form a new series-coupled soft phase, whose constitutive response then appears almost independent of chemical and physical structure.