| Abstract: | Segmented polyurethanes (PU) with crystalline soft segments were prepared with different crystalline polyols as soft segments. Morphology and microstructure of the PUs were investigated using Differential Scanning Calorimetry (DSC), Wide‐angle X‐ray Diffraction (WAXD), and Positron Annihilation Lifetime Spectra (PALS). Water vapor transport properties of the PU membranes were measured in the temperature range of crystal melting of their soft segments. Dependence of free volume of the PUs on temperature and the relationship between the free volume and water vapor permeability of the PU membranes were investigated. The results show that the mean free volume size and fractional free volume increase more rapidly in the temperature range of crystal melting than in other temperature intervals. In the specified temperature range, water vapor permeability of the polyester based PU membranes increases significantly, caused by the steep increase in free volume, due to crystal melting of the soft segments. Water vapor permeability of the polyester based PUs exhibits approximately direct correlation with the fractional free volume within the temperature range of crystal melting. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1865–1872, 2005 |
