Superior Hard but Quickly Reversible Si–O–Si Network Enables Scalable Fabrication of Transparent, Self-Healing, Robust, and Programmable Multifunctional Nanocomposite Coatings

A coating with programmable multifunctionality based on application requirements is desirable. However, it is still a challenge to prepare a hard and flexible coating with a quick self-healing ability. Here, a hard but reversible Si–O–Si network enabled by aminopropyl-functionalized poly­(silsesquioxane) and triethylamine (TEA) was developed. On the basis of this Si–O–Si network, basic coatings with excellent transparency, hardness, flexibility, and quick self-healing properties can be prepared by filling soft polymeric micelles into hard poly­(silsesquioxane) networks. The highly cross-linked continuous network endows the coating with a hardness (H = 0.83 GPa) higher than those of most polymers (H < 0.3 GPa), while the uniformly dispersed micelles decrease the Young’s modulus (E = 5.89 GPa) to a value as low as that of common plastics, resulting in excellent hardness and flexibility, with an H/E of 14.1% and an elastic recovery rate (W_e) of 86.3%. Scratches (∼50 μm) on the coating can be healed within 4 min. The hybrid composition of poly­(silsesquioxane) networks also shows great advantages in integration with other functional components to realize programmable multifunctionality without diminishing the basic properties. This nanocomposite design provides a route toward the preparation of materials with excellent comprehensive functions without trade-offs between these properties.