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The effect of incorporation of clay nanoparticles on the vulcanization reaction of silanol-terminated polysiloxane was studied. Three different types of commercial clays were investigated as reinforcement, namely: Cloisite 20 A (organically modified with nonpolar aliphatic chains), Cloisite 30B (modified with aliphatic chains containing hydroxyl-end groups) and Nanofil 116, an unmodified montmorillonite as a reference. Nanoclays were found to increase the rate of curing, assessed by viscosity measurements, in all the examined systems and the acceleration rate is proportional to the content of the additive. Moreover, an increase of the area of peaks corresponding to the formation of Si[BOND]O[BOND]Si bonds (900–1200 cm−1) was recorded by FTIR spectroscopy for pure and reinforced poly(dimethylsiloxane) (PDMS). Temperature modulated differential scanning calorimetry was also used for accurately monitoring the curing reaction of organoclay/PDMS hybrids, through the heat capacity and the enthalpy of cold crystallization measurements. For pure PDMS low reaction rate was observed during the first 200 min, followed by fast acceleration. A linear increase of the reaction rate as a function of time was observed for the organoclay/PDMS hybrids. POLYM. ENG. SCI., 55:957–965, 2015. © 2014 Society of Plastics Engineers