Ball-Milling Enhanced UV Protection Performance of Ca2Fe-Sulisobenzone Layered Double Hydroxide Organic Clay.

Using a co-precipitation technique, the anionic form of sulisobenzone (benzophenone-4) sunscreen ingredient was incorporated into the interlayer space of CaFe-hydrocalumite for the first time. Using detailed post-synthetic millings of the photoprotective nanocomposite obtained, we aimed to study the mechanochemical effects on complex, hybridized layered double hydroxides (LDHs). Various physicochemical properties of the ground and the intact LDHs were compared by powder X-ray diffractometry, N2 adsorption-desorption, UV-Vis diffuse reflectance, infrared and Raman spectroscopy, scanning electron microscopy and thermogravimetric measurements. The data showed significant structural and morphological deformations, surface and textural changes and multifarious thermal behavior. The most interesting development was the change in the optical properties of organic LDHs; the milling significantly improved the UV light blocking ability, especially around 320 nm. Spectroscopic results verified that this could be explained by a modification in interaction between the LDH layers and the sulisobenzone anions, through modulated π-π conjugation and light absorption of benzene rings. In addition to the vibrating mill often used in the laboratory, the photoprotection reinforcement can also be induced by the drum mill grinding system commonly applied in industry.