Diffusion of short chain alcohols from amorphous maltose-water mixtures above and below their glass transition temperature

The apparent diffusion coefficient for short chain alcohols in undercooled maltose-water mixtures close to the calorimetric glass transition temperature, Tg, was measured by following desorption using headspace gas chromatography. The plasticising effect of the alcohols on Tg was characterised using differential scanning calorimetry. The initial appearance of alcohol in the headspace showed a linear dependence on the square root of time, allowing it to be modelled as a Fickian diffusive process. The diffusion coefficient decreased with increasing molecular size of alcohol and proximity to Tg. Close to the glass transition the variation of diffusion coefficient with temperature and composition does not follow that of viscosity and, for ethanol, divergence was observed at Tg/T> 0.88.