Effects of molecular mass and surface treatment on adsorbed poly(methyl methacrylate) on silica

The behavior of relatively monodisperse adsorbed poly(methyl methacrylate) (PMMA) samples, from 19 to 587 kDa on silica, was studied using modulated differential scanning calorimetry and FTIR. On untreated Cab-O-Sil silica, the glass transition temperatures (TgS) were higher (by around 30 degrees C), and the transitions were significantly broader (by a factor of 5-6) than those for the corresponding bulk samples. While the TgS for the bulk polymers showed the expected dependence on molecular mass, the polymers on untreated silica showed little dependence, i.e., at the same adsorbed amounts, the glass transitions were very similar. The FTIR spectra of the adsorbed PMMA (on untreated silica) showed the presence of at least two resonances, one for the bound (hydrogen bonded to surface silanols) and another for free carbonyls. Fitting of the spectra allowed the estimation of the bound fractions of carbonyls that were dependent on the adsorbed amount, but not molecular mass. On Cab-O-Sil treated with hexamethyldisilizane (HMDS), the adsorbed PMMA exhibited glass transition behavior with little molecular-mass dependence; the TgS for the different PMMA samples were very similar to those of the high-molecular mass bulk polymer, but with additional broadening of about a factor of 2. FTIR spectra for the PMMA samples on the treated silica did not show significant amounts of any of the hydrogen-bonded carbonyl groups. (C) 2008 Wiley Periodicals, Inc.