Swelling measurement of polymers in high pressure carbon dioxide using a spectroscopic reflectometer

Abstract

We developed an in situ thickness monitor using a spectroscopic reflectometer to measure the swelling behaviors of polymer thin films in carbon dioxide up to 30MPa. Because the change in thickness was measured under high-pressure CO2, the measurement was performed through a sapphire window with a relatively high refractive index. We found that the window effect on the reflectivity can be successfully eliminated. To confirm the accuracy of the analysis, we measured the swelling behaviors of four polymers (poly(methyl methacrylate) (PMMA), polystyrene (PS), poly(n-butyl methacrylate) (PBMA), and poly(dimethylsiloxane) (PDMS)), and compared the swelling measurements with reported data. The swelling ratios of the polymers were in reasonable agreement with literature data. Notably, anomalous swelling was observed for PBMA and PDMS, although anomalous swelling has been observed in films much thinner than those of our samples, probably due to the low glass transition temperatures and high swelling ratios of PBMA and PDMS.