Tunable wetting of nanoparticle-decorated polymer films

In this paper, amine-modified silica nanoparticles (NPs) with diameters (d) from 15 to 230 nm are covalently linked to poly(styrene-random-acrylic acid) (P(S-ran-AA)) films, and wettability is studied as a function of diameter and NP surface coverage. During attachment, films swell and exhibit long and short scale roughness, consisting of a ridged, honeycomb structure, approximately 1 mum wide and 45-50 nm deep, which encircles nanoscale features 10-15 nm high and approximately 50 nm apart. A maximum NP coverage of approximately 70% was achieved for d less than or nearly equal to the nanoscale roughness induced by surface swelling. For d several times greater than this nanoscale roughness, the maximum coverage was limited by interparticle repulsion and reached only approximately 30%. For NPs with diameters of 15-106 nm, the water contact angle increased from 75 degrees to 120 degrees as NP coverage increased from 0 to 70%. At low and high NP coverage, the Wenzel and Cassie models, respectively, accurately describe the data. However, at intermediate NP coverage, neither model is satisfactory. An increase in surface roughness alone cannot account for this discrepancy. Atomic force microscopy (AFM) studies show that the NPs partially embed into the swollen P(S-ran-AA) surface, suggesting that the amine-coated NPs are wet by the copolymer, exposing low surface energy styrene. These studies demonstrate that control over surface properties of coatings, such as wetting, can be achieved by selecting NP sizes that complement film roughness.