skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Mechanisms of gas permeation through polymer membranes. Progress report, April 30, 1980-March 31, 1981

Technical Report ·
OSTI ID:6206921

The objective of this study is to assess the validity of a free-volume model of gas permeation through nonporous polymer membranes. This model provides a formalism for the prediction of permeability coefficients for pure gaseous penetrants and their mixtures as a function of both pressure and temperature. Three characteristic free-volume parameters, designated A/sub d/, B/sub d/, and ..gamma.., are required for this purpose. The three parameters were determined for CH/sub 4/ in polyethylene from diffusivity and solubility measurements with polymer rods between 5 and 35/sup 0/C, and at pressures of up to 40 atm. Permeability coefficients for CH/sub 4/ estimated from the free-volume model by means of these parameters were found to be in satisfactory agreement with experimental values obtained from independent permeability measurements with thin polyethylene membranes. A new and more rigorous method of estimating permeability coefficients for gas mixtures from the free-volume model has been developed. Permeability coefficients were calculated by this method for the components of equimolar C/sub 2/H/sub 4/-C/sub 3/H/sub 8/, CO/sub 2/-C/sub 2/H/sub 4/, and CO/sub 2/-C/sub 3/H/sub 8/ mixtures and of a 74.9% CO/sub 2/-25.1% C/sub 2/H/sub 4/ mixture. Satisfactory overall agreement was found between these coefficients and values obtained experimentally between 20 and 50/sup 0/C and at pressures of up to 28 atm. Simple linear correlations have been found for the free-volume parameters A/sub d/, B/sub d/, and ..gamma.. as a function of certain basic physicochemical properties of penetrants and penetrant-polymer systems. These correlations can be determined with only a few measurements with a given polymer, and are useful for estimating values of A/sub d/, B/sub d/, and ..gamma.. for other penetrants in the same polymer. The free-volume model has bee modified and extended to describe gas permeation through both rubbery and glassy polymer membranes. The extended model should be applicable to porous as well as nonporous membranes.

Research Organization:
Syracuse Univ., NY (USA). Dept. of Chemical Engineering and Materials Science
DOE Contract Number:
AS02-78ER05015
OSTI ID:
6206921
Report Number(s):
DOE/ER/05015-1; ON: DE81025637
Country of Publication:
United States
Language:
English