SynopsisThe sorption and transport of several gases in poly(pheny1ene oxide) were measured at 35"C, and the results have been analyzed in terms of the dual sorption/mobility models which have been successfully employed for this purpose for other glassy polymers. Both the extent of sorption and rate of permeation of gases are quite large for poly(pheny1ene oxide) compared to other glassy polymers with rigid chain backbones. It is shown that the high extent of sorption is owing to the high glass transition temperature of this polymer, but this is not a significant factor in its high permeability to gases. The latter stems from large diffusion coefficients. It is shown that the capacity of the Langmuir mode of sorption inherent to glassy polymers is related to the value of the glass transition temperature in a general way for a wide variety of polymers. Observations about the diffusion coefficients for numerous gas-polymer pairs are discussed.
SynopsisThe coagulation of viscom polymer solutions by diffusional interchange with a liquid bath is the key step to fiber formation by wet-spinning. Model experiments were performed on gelled solutions of an acrylic polymer in dimethylacetamide, to determine the mass-transfer rates of solvent and nonsolvent (water) during coagulation, the rate of movement of a boundary associated with coagulation, and the final equilibrium between the coagulated phase and the bath. Each is given as a function of bath composition and temperature. The data are analyzed by means of various diffusion models, one of them giving quite good agreement. The data and the models are used in conjunction with each other for the elucidation of the mechanism of the processes involved in coagulation.
A “dual sorption” model has been proposed by Michaels, Vieth, et al. to explain extensive equilibrium sorption data for several gases in some glassy polymers. To explain data on sorption kinetics, it was further postulated that one of the sorption modes immobilizes the gas molecules. Stated mathematically, this model leads to a modified form of Fick's second law. Both normal and desorption time lags for diffusion have been computed here for this model of diffusion in glassy polymers. The computed time lags are shown to be dependent on the boundary concentrations used in permeation. Experimental measurement of these time lags would be a sensitive and critical test to ascertain the validity of this theory.
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