First-principles insights into atomic oxygen diffusion inside polyhedral oligomeric silsesquioxane cages

Atomic oxygen erosion is a significant threat to exterior spacecraft polymers. Polyhedral oligomeric silsesquioxane (POSS) is a potential kind of material in resisting AO diffusion erosion, but lack of mechanism studies for application supports. In this research, we used the first-principles calculations to investigate the mechanism based on two types of nominally hydrated POSS named T8 (Si8O12H8) and T10 (Si10O15H10). According to the results, we found that the minimum energy path (MEP) of AO diffusing inside POSS is the adjacent-edge-path rather than the center-path. We also found the energy barriers that hinder the diffusion motion of AO inside POSS are originated from the structural distortion of POSS, which are negatively correlated to Si-O bond length and positively correlated to structural compactness. Thus, compacter POSS structures with shorter Si-O bond length are expected to give better AO diffusion resistance properties.