Thermal Properties of Polysiloxane/Ag Nanocomposites with Different Network Structures and Distributions of Si-H Groups.

Polysiloxanes with silver nanoparticles (Ag NPs) have garnered attention for their distinctive physicochemical properties, which make them promising candidates for advanced material applications. This study presents a systematic investigation into the thermal properties and degradation mechanisms of polysiloxane/Ag nanocomposites, emphasising the innovative incorporation of Ag NPs directly into polysiloxane networks via in situ reduction of Ag⁺ ions by Si-H groups. Six polysiloxane matrices were synthesised by hydrosilylation of poly(methylhydrosiloxane) (PMHS) or poly(vinylsiloxane) (polymer V) with three cross-linking agents of varying molecular structures and functionality. Thermogravimetric analysis combined with mass spectrometry revealed that the introduction of Ag NPs alters the thermal properties of polysiloxane networks, primarily affecting the redistribution of Si bonds that occurs during the pyrolysis of these systems. Monitoring the pyrolysis process using FTIR spectroscopy allowed us to investigate the effect of the presence of Ag NPs on the degradation mechanism of the studied nanocomposites. The presence of the free-carbon phase and metallic silver phase in the Ag-containing silicon oxycarbide materials obtained was confirmed by Raman spectroscopy and XRD analyses, respectively. These findings demonstrate the possibility of fabricating Ag/SiOC materials with ceramic residues in the range of 43 to 84%. This work provides new insights into the thermal behaviour of polysiloxane/Ag nanocomposites and underscores their potential for high-performance applications in thermally demanding environments.