The development of emerging high-tech technologies comes with a growing demand for composite materials with outstanding mechanical properties and wear resistance. Herein, we fabricated organic-inorganic self-stratifying gradient coatings based on silicon density by chemically bonding octa- and mono-amino polyhedral oligomeric silsesquioxane (POSS) onto the polyimide (PI) resin. The microstructure and chemical characteristics of POSS-PI-based composite coatings were investigated. The enhancements to the mechanical properties and wear resistance of the PI-based composites due to the gradient structure were also investigated. As expected, the addition of POSS significantly increased the composites’ thermal stability and mechanical properties. In particular, the tensile strength and nano-indentation hardness of the 4 wt.% POSS-PI composites were enhanced by 28.6% and 68.4%, respectively. Furthermore, compared with that of pure PI, the wear rate of the POSS-PI self-stratifying coatings decreased by 78.9%, which was due to the enhanced cross-linking density and gradient structure that resulted from the self-stratifying of POSS.

The irradiation of atomic oxygen (AO) severely restricts the application of polymeric lubricating coatings in low Earth orbit (LEO). Herein, octa- and mono-amino polyhedral oligomeric silsesquioxanes (POSSs) were chemically bonded onto polyimide/molybdenum disulfide (PI/MoS₂) composite coatings with a gradient structure based on Si density. The gradient coatings presented better wear resistance under different loads; notably, the wear rate decreased by 83.5%. Additionally, the effects of AO exposure on the surface morphologies, chemical structure, and tribological properties of the gradient coatings were investigated in detail. The results indicated that the mass loss and wear rates under AO irradiation decreased significantly, which can be attributed to the passivated network-like SiO₂ layer that covered the coating surface after AO irradiation. As a result, the addition of POSS significantly improved the tribological properties and AO resistance.

In low Earth orbit (LEO), special environments such as atomic oxygen (AO), alternating high and low temperatures, and high vacuum can seriously affect the reliability and service lifetime of moving parts of space equipment. Therefore, there is an increasingly urgent demand for long-life, high-performance lubricating protective coatings with the rapid evolution of astronautical technology. In this study, polyimide (PI) was modified by polyhedral oligomeric silsesquioxane (POSS) with different numbers of functional groups to fabricate PI-based self-stratifying gradient composite lubricating coatings. The coating exhibited significantly enhanced AO resistance, and its vacuum tribological properties under alternating high and low temperature conditions were investigated. Results show that the mass loss of the gradient coating under AO exposure was significantly reduced by 78%, and the tribological properties of the coating under high and low temperature alternating conditions were significantly different. The friction coefficient was more stable and was smaller than that at high temperatures, and the wear rates of the POSS-modified coating also decreased by 77.5% and 50% for both high and low temperatures compared with that of the PI/PTFE coating.