Transparent and Hard Zirconia-Based Hybrid Coatings with Excellent Dynamic/Thermoresponsive Oleophobicity, Thermal Durability, and Hydrolytic Stability

Smooth, transparent, and extremely hard zirconia (ZrO2)-based inorganic-organic hybrid films showing excellent dynamic oleophobicity, thermal durability, and hydrolytic stability were successfully prepared through a simple combination of zirconium tetrapropoxide (Zr(O(CH2)2CH3)4) with stearic acids. In this study, we have particularly focused on the effects of stearic acid molecular architecture (linear-stearic acid (LSA) and branched-stearic acid (BSA)) on surface physical/chemical properties. Although, in each case, the resulting hybrid (Zr:LSA and Zr:BSA) films achieved by a simple spin-coating method were highly smooth and transparent, the final surface properties were markedly dependent on their molecular architectures. Thanks to the thermal stability of BSA, our Zr:BSA hybrid films displayed a greatly improved thermal effective range (maximum of 200 °C), while for Zr:LSA hybrid films, serious thermal damage to surface dewetting behavior was observed at less than 150 °C. The hardness of the Zr:BSA hybrid films were markedly increased by curing at 200 °C for 1 h (from 1.95 GPa to 3.03 GPa), while maintaining their dynamic dewettability toward n-hexadecane, when compared with Zr:LSA hybrid films (0.95-1.19 GPa). Small volume n-hexadecane droplets (5 μL) were easily set in motion, sliding across and off our best Zr:BSA hybrid film surfaces at low substrate tilt angles (<10°) without pinning. Moreover, they also showed thermoresponsive dynamic dewetting behavior, reasonable resistance to hydrolysis in an aqueous environment, and antifingerprint properties.