Effect of interfaces on the crystallization behavior of PDMS

The reversible thermal behavior of a non-entangled semicrystalline polymer, poly(dimethylsiloxane), PDMS, was investigated in the presence of sub-micron particles. Filled polymer systems of this type are characterized by a large surface-to-volume ratio but lack the external confinement that is typical for a thin film geometry. Differential-scanning calorimetry (DSC) measurements indicate that the presence of the nanometric solid additives enhances the crystallization rate as compared to native PDMS melts. Different types of additives and surface interactions resulted in a similar effect, suggesting that the origin of the enhanced crystallinity is non-specific. The effect is attributed to entropic interactions in the boundary layer.