CO2 sorption and diffusion in polymethyl methacrylate–clay nanocomposites

This study reports the glass transition temperature (T_g), and sorption and diffusion of subcritical CO₂ gas in polymethyl methacrylate (PMMA) nanocomposites containing organically modified smectite clay, Cloisite 20A (C20A). A range of methods for preparing the PMMA‐clay nanocomposites was investigated and a solution coprecipitation method was selected as the most appropriate. Using this method, PMMA nanocomposite containing 2, 4, 6, and 10 wt% nanoclay loadings were prepared. Wide‐angle X‐ray diffraction (XRD) analysis and scanning electron microscopy (SEM) indicated that the 2 wt% nanocomposite materials had a well‐dispersed intercalated clay structure. The T_g for PMMA‐C20A nanocomposites, as measured by differential scanning calorimetry (DSC), was found to be independent of the clay loading. CO₂ solubility studies from 0 to 65°C and pressures up to 5.5 MPa using an in situ gravimetric technique were performed on compression‐molded films. The organoclay was found to have no effect on the solubility of CO₂ in PMMA, and therefore the solubility of CO₂ in the nanocomposite can be determined from the solubility of CO₂ in the matrix polymer alone. Diffusion coefficients were determined using the appropriate transport models for these test conditions and the diffusion coefficients for CO₂ in PMMA‐C20A composites were found to increase with organoclay loading. It is believed that the processing path taken to prepare the nanocomposites may have resulted in the agglomeration of the C20A organoclay, thereby preventing the polymer chains from fully wetting and intercalating a large number of clay particles. These agglomerations are responsible for the formation of large‐scale holes within the glassy nanocomposite, which behave as low resistance pathways for gas transport within the PMMA matrix. POLYM. ENG. SCI., 45:904–914, 2005. © 2005 Society of Plastics Engineers