Two bio-based insulating oils (BHOs) with average carbon chain lengths of approximately 18 and 22 were investigated as short- and long-chain BHOs. By constructing an oil-paper composite insulation system, the generation law of characteristic gases in the two systems was studied by partial discharge experiments. Based on the ReaxFF reaction molecular dynamics simulation under electrothermal coupling stress, the cracking path, cracking rate, evolution of oxygen-containing small molecules, and generation path of characteristic gases of cellulose polymer were revealed. Both systems produced H₂, CH₄, C₂H₂, C₂H₄, C₂H₆, CO, and CO₂, with CO₂ dominant and C₂H₆ least abundant. The short-chain BHO generated markedly higher amounts of H₂, CO, C₂H₂, and C₂H₄ than the long-chain BHO; after 15 min, its H₂ and CO concentrations were about 3.4- and 2.1-times those in the long-chain system, respectively. ReaxFF simulations showed that cellulose degradation in the short-chain BHO followed stepwise chain scission and continuous decarbonylation, favoring CO and unsaturated gas precursors. In contrast, cellulose chains disappeared faster in the long-chain BHO, producing more oxygen-containing organic fragments and C₁-C₅ oxygenated molecules and a higher small-molecule conversion ratio. Characteristic gas pathway analysis revealed that all seven gases could be generated from cellulose pyrolysis intermediates, and different oil environments primarily influenced gas generation behavior by altering the evolution pathways of these intermediates. These findings, at the molecular scale, elucidate the impact of BHO environments on the degradation mechanism of cellulose polymers, providing a theoretical basis for the condition assessment and design of environmentally friendly oil-paper insulation systems.

Silicone rubber is an important external insulating material for composite bushings, composite insulators, and other power equipment. During long-term service, it is inevitably exposed to coupled environmental and electrical stresses, such as elevated temperature, moisture ingress, strong electric fields, and partial discharge, which may lead to hydrophobicity loss, surface chalking, crack propagation, and particle shedding. To reveal the microscopic degradation mechanism of silicone rubber under complex operating conditions, a molecular model of methyl vinyl silicone rubber was constructed using Materials Studio. A stable silicone rubber molecular structure was obtained through crosslinking, geometry optimization, and ensemble relaxation. Subsequently, a reactive molecular dynamics simulation system under coupled temperature–humidity–electric field conditions was established using LAMMPS and the ReaxFF reactive force field. Different temperature gradients, electric field intensities, and aging–recovery stages were designed to investigate the degradation behavior of silicone rubber. The evolution of the maximum carbon content, maximum silicon content, carbon-containing decomposition products, and typical small-molecule products, including H₂, H₂O, CH₄, C₂H₂, C₂H₄, and C₂H₆, was statistically analyzed. In addition, atomic trajectory tracking was performed to clarify the processes of methyl group detachment, Si-O bond cleavage, water molecule participation, and molecular chain reconstruction. The results show that high temperature mainly promotes methyl group detachment from side chains and fracture of the siloxane main chain, while a strong electric field accelerates the decomposition process and induces the transformation of long siloxane chains into shorter chains. Water molecules can react with broken siloxane chains to form hydroxyl-containing structures, making the structural degradation partially irreversible. The degradation process of silicone rubber under coupled temperature–humidity–electric field stress can be summarized as side-chain detachment, main-chain scission, water-assisted reactions, free-radical recombination, and local molecular aggregation. This study provides a molecular-level theoretical basis for aging mechanism analysis, condition assessment, and lifetime prediction of composite external insulating materials.