Melt rheology and structure of silicone resins

Rheological investigation and X-ray analysis of silicone resins have been performed to get a fundamental understanding of the relationship between melt rheology and structure. Rheological properties of the melts of silicone resins were characterized by dynamic shear measurements. Samples were a series of silicone resins having different side groups, such as methyl, phenyl, methylphenyl, and propylphenyl. A time-temperature superposition based on the WLF rule was successfully applicable. The free volume fraction at the glass transition temperature and the free volume expansion coefficient were estimated from the C-1 and C-2 values of the WLF-equation. The loss modulus G was found to be proportional to the angular frequency in a double-logarithmic plot over a wide frequency range. However, the storage modulus G ' exhibited a bending in a intermediate frequency region for all silicone resins. The shape of the G ' curve is unexpected from the results of gel permeation chromatography (GPC) and differential scanning calorimeter (DSC), which demonstrate that the silicone resins are amorphous polymers of relatively low molecular weight. To get more insight into the rheological properties of the silicone resins which indicate a heterogeneous structure, X-ray analysis was carried out. The X-ray measurement displayed two peaks, one broad peak around 4.5 Angstrom of d-spacing which corresponds to a random amorphous structure, and the other higher intensity peak from 8.5 Angstrom to 12 Angstrom. This peak strongly depends on the size of organic side groups. From the rheological characterization and the X-ray analysis, it can be concluded that the silicone resins consist of two components; one of them shows a random amorphous and the other a regular structure even in the molten stage.