| Abstract: | Incremental vapor sorption and desorption runs have been carried out with o-dichlorobenzene (ODCB) a strongly swelling solvent, in 2, 6, and 10 mil polyether polyurethane films. Two-stage sorption behavior occurs at intermediate and higher concentrations but is generally absent in the desorption runs. Analysis of the two-stage curves, using the Berens-Hopfenberg model of independent Fickian diffusion and first-order relaxation processes, leads to apparent diffusion coefficients which increase with thickness and show a pronounced maximum with concentration, whereas the relaxation rate constant decreases with concentration. Correction for the pressure drift during the runs, due to the low vapor pressure of ODCB, reduces the thickness dependence. The negative concentration dependence of the relaxation rate constant is related to the distribution of microdomain stabilities. Calculated values of the self-diffusion coefficient show that the maximum in the apparent diffusion constant with concentration can be accounted for largely, but not entirely, by the thermodynamic contributions. It is proposed that the additional factor is relaxation-controlled swelling which arises from the strong coupling between the matrix and hard-segment responses. |
