Role of Branching on the Structure of Polymer Brushes Formed from Comb Copolymers

The distinguishing feature of a polymer brush at equilibrium is the stretched configuration of the chains that results from tethering the polymer chains by one end at the solid-fluid interface. The stretched configuration of the chains and the crowded nature of the interfacial layer is the origin of many of the useful properties of polymer brushes: these layers resist compression and aggregation, effectively dissipate shear stresses, and respond reversibly to changes in their solution environment.

Understanding the Grafting of Telechelic Polymers on a Solid Substrate to Form Loops

Recent experimental and theoretical studies have demonstrated that relative to singly tethered chains, the presence of polymer loops at interfaces significantly improves interfacial properties such as adhesion, friction, and wettability. In the present study, a simple system was studied to examine the formation of polymeric loops on a solid surface, where the grafting of carboxylic acid terminated telechelic polystyrene from the melt to an epoxy functionalized silicon is chosen. The impact of telechelic molecular weight, grafting temperature, and surface functionality on the telechelic attachment process is studied. It was found that grafting of the telechelic to the surface at both ends to form loops is the primary product of this grafting process. Moreover, examination of the kinetics of the grafting process indicates that it is reaction controlled. Fluorescence tagging of the dangling ends of singly bound chains provides a mechanism to monitor their time evolution during grafting, and these results indicate that the grafting process is accurately described by recent Monte Carlo simulation work. The results also provide a method to control the extent of loop formation at interfaces and therefore provide an opportunity to further understand the role of the loops in the interfacial properties in multicomponent polymer systems.