The impact of the incorporation of graphene nanoplatelets (GN) on the properties of hydroxyl-terminated poly(dimethylsiloxane) (PDMS) matrices was investigated. The composites were prepared by solution mixing, using tetrahydrofuran (THF) as a solvent. Brookfield viscosimetry, implemented during the vulcanization process, revealed that GN increases the viscosity of the system, compared to pristine PDMS, proportionally to its concentration. X-ray diffraction patterns suggested an efficient dispersion of GN in the polysiloxane matrix. The D and G bands ratio (ID/IG) calculation, based on RAMAN spectra of GN/PDMS specimens, revealed more defects in graphene nanoplatelets when incorporated in the PDMS matrix. By differential scanning calorimetry (DSC), a marginal increase in crystallization, glass transition and melting temperatures of PDMS in GN/PDMS composites was observed. Improvement of the thermal stability of LMW PDMS composites, especially for higher GN concentrations (3 and 5 phr), was noticed by thermogravimetric analysis (TGA). Additionally, GN enhanced the tensile strength of composites, up to 73% for the 3 phr GN/LMW PDMS composite. A significant increase in the elongation at break was recorded, whereas no effect on the modulus of elasticity was recorded. The decrease in toluene-swelling, for the LMW PDMS matrix composites, was attributed to the increase in the tortuosity path because of the efficient dispersion of GN. A decrease in oxygen permeability of 55–65% and 44–58% was measured in membranes made of PDMS composites containing 0.5 phr and 1 phr GN, respectively. Dielectric relaxation spectroscopy (DRS) measurements recorded a significant increase in the conductivity of the higher graphene content composites.
