Synthesis and Behavior of the Polymer Covering on a Solid Surface. 3. Morphology and Mechanism of Formation of Grafted Polystyrene Layers on the Glass Surface

Abstract

Polystyrene films have been grafted by radical polymerization in situ on the surface of glass slides. The morphology of these films resulting from different grafting temperatures has been investigated by both the contact angle method and scanning probe microscopy with respect to the grafting time. At a grafting density regime where the theory proposes the existence of a homogeneous layer, the formation of island structures of grafted polymer with a size substantially higher than expected by the theory has been observed. Overshot polymer structures of large sizes are created. The amount of grafted polymer is substantially higher than that predicted from the conception of monolayer covering. The grafting layer becomes impermeable for water only at a high amount of grafted polymer, which corresponds to the multilayer structure of the coating. We suggested a mechanism for the grafting process that included at least three stages: (a) first, a brushlike polymer layer is formed; (b) subsequently, a second layer of ungrafted chains is created in the regime when excess chains are forced out from the first layer; (c) big polymer clusters, with an average size of 100−200 nm due to gel polymerization in the clusters, formed in the force out regime.