Hydroxyl Influence on Adsorption and Lubrication of an Ultrathin Aqueous Triblock Copolymer Lubricant

This research aims to provide insights into the adsorption behaviors of two monomers of triblock copolymers (1,2-dimethoxyethane (1,2-DME) and 1,2-dimethoxypropane (1,2-DMP)) on a TiO₂ surface in aqueous solution. A multiscale theoretical framework by means of the density functional theory (DFT), ab initio molecular dynamics (AIMD), and classical molecular dynamics (MD) simulations is established. The DFT calculation confirms that these molecules adsorb more energetically on a hydroxylated surface than pure oxide. There is a difference in adsorption behaviors between 1,2-DMP and 1,2-DME molecules due to the covalent bonding between carbons and oxygen of the hydroxylated TiO₂ surface. The AIMD simulation reveals that the adsorption of both copolymers to the TiO₂ surface is hindered by the presence of water with 1,2-DME exhibiting a weaker adsorption than 1,2-DMP. The presence of 1,2-DME on the TiO₂ surface with water produced a smaller number of hydroxyl groups on the surface than 1,2-DMP. Moreover, the dissociative adsorption of water onto the rutile surface is the main cause for a chemical formation of terminating hydroxyl groups. The number of associated bonds is insignificant compared to the dissociated one since the dissociative adsorption is more favored than the associative one. MD simulation indicates that triblock copolymers adsorb stronger on the hydroxylated surface with a thinner adsorbed film thickness than that on the pure rutile. The presence of terminal hydroxyl groups on the rutile surface helps reducing the friction for aqueous 17R2 triblock copolymers, while it results in an increase of friction for normal copolymer L62.