Water transport properties of thermoplastic polyurethane films

Two linear segmented polyurethanes, based on poly(oxyethylene) (POE) as a soft segment and 4,4′‐diphenylmethane diisocyanate and 1,4‐butanediol as hard segments and differing in their soft segment length, have been studied from a water vapor transport point of view. For both polyurethanes, the water sorption is governed by a Fickian process, and the thermoplastic polyurethane with the longer POE segments displays the higher water diffusion rate. The water sorption isotherms are Brunauer Emmet Teller (BET) type III for both thermoplastic polyurethanes, and the water uptakes are directly related to the polymer POE content. The Flory–Huggins theory cannot correctly describe the sorption isotherms. More sophisticated approaches (Koningsveld–Kleinjtens or Guggenheim‐Anderson‐de Boer (GAB) models) are needed to fit the experimental water uptakes. The positive deviation from Henry's law and the decrease in the apparent diffusion coefficient observed at a high activity have been particularly studied. In this activity range, an isotherm analysis based on the cluster integral of Zimm and Lundberg suggests some clustering phenomenon, which seems consistent with the diffusion coefficient variation. In agreement with the sorption results, the water permeability coefficients are small at low activities, and they increase greatly with the relative pressure of water. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 473–492, 2004