Fluorine‐Free Nonstick Heat‐Resistant Robust Coatings via Molecular/Nano Trans‐Dimensional Engineering

Nonstick coatings capable of withstanding extreme thermal conditions are critical for diverse applications, but it is extremely challenging to achieve the nonstick function and high-temperature durability simultaneously. To address this limitation, we propose a conceptually molecular/nano trans-dimensional engineering strategy to construct a nanoscale-architected polysiloxane coating via precisely controlled sol-gel hydrolysis of organosilane precursors. The coating matrix is uniquely composed of in situ generated ultrasmall nanoparticles (<10 nm), enabling a defect-minimized, densely crosslinked Si─O─Si network. These ultrasmall nanoparticles also serve dual roles as hard building blocks and thermally resistant nanocomponents to increase the stability of PDMS. Further, the high crosslink density can restrict polymer chain mobility, limiting PDMS degradation into low-molecular-weight cyclic siloxanes via back-biting cyclization. As a result, this coating delivers long-term thermal stability at 300°C, >98% visible light transmittance, ultra-high hardness (>9H pencil hardness), and intrinsic hydrophobicity (water contact angle >100°) without fluorinated compounds. This strategy establishes sustainable, highly comprehensive performance coatings, showing potential for applications where fluorine-free and thermally robust nonstick surfaces are desired.