Revisiting the Challenges in Fabricating Uniform Coatings with Polyfunctional Molecules on High Surface Energy Materials

Modifying the chemistry of a surface has been widely used to influence interfacial properties of a material or nature of interaction between two materials. This article provides an overview on the role of polyfunctional molecules, specifically silanes, in surface modification of polar surfaces (bearing soft nucleophiles). An emphasis on the mechanism of the reaction in the presence of adsorbed water, where the modifying reagents are hydrolysable, is discussed. To highlight the complexity of the reaction, modification of paper with trichlorosilanes is highlighted. Preparation of hydrophobic cellulosic paper, and structure–property relations under different treatment conditions is used to highlight that a monolayer is not always formed during the surface modification. Gel-formation via step-growth polymerization suggests that at the right monomer:adsorbed water ratio, a monolayer will not form but rather self-assembly driven particle formation will occur leading to a textured surface. The review highlights recent work indicating that the focus on monolayer formation, is at the very least, not always the case but gel formation, with concomitant self-assembly, might be the culprit in understanding challenges associated with the use of polyfunctional molecules in surface modification.