Mechanically Robust Atomic Oxygen‐Resistant Coatings Capable of Autonomously Healing Damage in Low Earth Orbit Space Environment

: Polymeric materials used in spacecraft require to be protected with an atomic oxygen (AO)-resistant layer because AO can degrade these polymers when spacecraft serves in low earth orbit (LEO) environment. However, mechanical damage on AO-resistant coatings can expose the underlying polymers to AO erosion, shortening their service life. In this study, the fabrication of durable AO-resistant coatings that are capable of autonomously healing mechanical damage under LEO environment is presented. The self-healing AO-resistant coatings are comprised of 2-ureido-4[1H]-pyrimidinone (UPy)-functionalized polyhedral oligomeric silsesquioxane (POSS) (denoted as UPy-POSS) that forms hydrogen-bonded three-dimensional supramolecular polymers. The UPy-POSS supramolecular polymers can be conveniently deposited on polyimides by a hot pressing process. The UPy-POSS polymeric coatings are mechanically robust, thermally stable, and transparent and have a strong adhesion toward polyimides to endure repeated bending/unbending treatments and thermal cycling. The UPy-POSS polymeric coatings exhibit excellent AO attack resistance because of the formation of epidermal SiO2 layer after AO exposure. Due to the reversibility of the quadruple hydrogen bonds between UPy motifs, the UPy-POSS polymeric coatings can rapidly heal mechanical damage such as cracks at 80 °C or under LEO environment to restore their original AO-resistant function.