Aminosilane layers on the plasma activated thermoplastics: influence of solvent on its structure and morphology

The chemistry and the structure of aminosilane layer on the plasma activated thermoplastic substrates, e.g., polycarbonate (PC), polystyrene (PS), poly(methyl methacrylate) (PMMA), and cyclic olefin co-polymer (COC) were investigated at the molecular level. The nature of the surface functional groups of the silane layers prepared by solution phase deposition in aqueous and anhydrous solvents were studied using various techniques including ellipsometry, goniometry, atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and attenuated total reflectance infrared spectroscopy (ATR-IR). The XPS analyses revealed the presence of various oxygen functionalities on the plasma activated thermoplastics. Considerable differences were observed for the structure of aminosilane depending on the solvent used for the reaction. Deposition from aqueous solution resulted in relatively flat and smooth surfaces with consistent thickness compared to the anhydrous solution deposition. In the former case, 33% of the total nitrogen accounted for protonated amine and 16% for the free amino groups. In the latter, only 6% accounted for the protonated amine. The point of zero charge (pzc), on the aminosilane modified PC was found to be around 7, indicated that the surface is positively charged below pH 7 and negatively charged above pH 7. The surface analysis data suggested that various interactions are possible between the plasma activated thermoplastic surface and the aminosilane. In general, they are bound to the surface through covalent bond formation between the oxygen functionalities on the thermoplastic surface and the amino or the silanol groups of the aminosilane.