The free volume in dried and H2O-loaded biopolymers studied by positron lifetime measurements.

We present experiments on glucose-gelatin compounds using positron annihilation lifetime spectroscopy (PALS) in order to study the behavior of the free volume dependent on H2O loading, drying, and uniaxial pressure. A semiempirical quantum mechanical model was applied in order to correlate the lifetime of orthopositronium in nanoscaled voids to the void size. This allowed us to determine the absolute value of the mean void radius in the biopolymer samples. In addition, the variation of the total free volume of the differently treated samples is quantified and illustrated by a log-normal distribution function. Most interesting results have been obtained after saturation loading with H2O that leads to the formation of voids with a mean size of 84.3(1.9) Å(3) and to an increase of the total free volume by a factor of 2.5. This observation in the swelled sample is explained by the entropy elastic regime well above the glass transition temperature that greatly facilitates the formation of free volume. Differential scanning calorimetry (DSC) measurements were performed in order to determine the glass transition temperature and to support the interpretation of the results obtained by PALS.