Analysis of Permeation and Diffusion Coefficients to Infer Aging Attributes in Polymers Subjected to Supercritical...

There is a need to understand the permeation flux behavior of polymers exposed to high-pressure and -temperature fluids continuously for long time intervals. This study investigates evidence of structural alterations in polymer specimens as indicators of material aging through the monitoring of transport coefficients at pressure steps from 10 barg to 400 barg and temperatures ranging between 30 °C and 90 °C. The continuous flow permeation methodology is a well-established technique described in the literature for applications from membrane separation processes to polymeric pressure barriers used for complex fluid containment in the oil and gas industry. In this study, a novel methodology has been used that allows the permeating flux of supercritical CO₂ and H₂ gas through raised-temperature polyethylene and polyvinylidene fluoride films at varying elevated temperatures and pressures to be determined, over timescales of several months using gas chromatography. During these long-term measurements, changes in the test conditions, principally in temperature and stepwise increases in differential gas pressure, were made in order to determine the activation energy for permeation along with the transport coefficients of permeation, diffusion, and sorption. At no time was the polymer film allowed to outgas during the temperature or pressure alterations. The permeation experiments are complemented by differential scanning calorimetry tests to track changes in polymer crystallinity before and after exposure of the specimen to plasticizing gases, which revealed the extent of structural alterations inflicted on the specimen due to high temperature and pressure loads. It is seen that specimens that were exposed to starting high pressures aged more than those that had gradual increases in feed pressure. Furthermore, the relationship between transport coefficients and fractional free volume in the polymer upon exposure to high pressure and temperature conditions is explored. Lastly, the benefit of using fugacity in place of feed pressure for the calculation of the permeability coefficient is discussed. This study contributes to the understanding of the effect of prolonged exposure of the polymeric specimens to CO₂ and H₂ gas under stepwise pressure and temperature loading on their flux behaviors and crystallinity, and to candidate polyethylene-based specimens for oil field deployment.