Μελέτη της αλληλεπίδρασης μεταξύ προσροφημένων πολυμερικών στρωμάτων

Abstract

Flexible polymer chains end-tethered to a surface in good solvent tend to extend away from the surface due to excluded volume interactions. At sufficiently high grafting densities the chains become elongated normal to the surface, this extension being opposed by an elastic restoring force of entropic origin to form a layer of stretched chains referred to as a “polymer brush”. These systems have been studied extensively in recent years by numerous experimental techniques and theoretical methods. In the present investigation we have studied asymmetric star-shaped polymers whereby the different arms are either non-adsorbing PS chains or short PB chains terminating in a zwitterionic end-group known to adsorb strongly on surfaces such as mica or quartz. In this manner, it is possible on the one hand to form brushes with a single PS chain, but multiple zwitterionic stickers, and on the other to study the reverse case of multiple non-adsorbing arms attached to a surface via a single zwitterions. We have used the surface force balance technique to determine the interaction between such brush-layers formed on mica and neutron scattering to determine the absorbed amount and interanchor distance. Interactions between polymer brushes formed by highly asymmetric star-like polymers with a long PS arm and one, two or three short PB arms each terminating in a zwitterionic end-group were studied in order to explore the effect of the sticking energy on the brush structure. Polystyrene stars with two and three tails bearing a single end group were also studied to investigate how the height of the adsorbed layer and the grafting density are affected. Our measurements show no significant differences between PS with 1, 2 and 3 end groups. This may be due to kinetic reasons since additional polymer chains are hindered from attaching to a brush-bearing surface. The behavior of two PS chains with one end-group ((PS)2-PB-X) seems not to differ appreciably from that of PS-PB-X copolymer. On the other hand three PS chains with one end-group ((PS)3-PB-X) appeared to form layers with smaller brush height and greater interanchoring distance, relative to PS-PB-X layers. We can attribute this to the extra stretching that the three-chain architecture imposes on the adsorbed brush. In the present investigation we have also studied weak polyelectrolytes. Polyelectrolytes (charged polymer chains) remain among the least understood materials despite their importance in biology (proteins, DNA) and materials science. Their behavior and characteristics are not yet fully understood because of complicated correlations due to their charged nature that gives rise to long-range interactions. The counterplay of their properties as polymers and electrolytes with counterions around polyelectrolyte chains imposes additional difficulties on explaining their behavior. The association of counterions around polyelectrolytes and the pH of the solution are two parameters than can affect the properties of such systems. Especially weak polyelectrolytes (like poly-acrylic acid) are even sensitive to pH changes because of the alterable degree of dissociation. We measured forces between two charged polymer layers of Poly (isoprene-acrylic acid) diblock copolymers adsorbed on mica surfaces. Poly (isoprene-acrylic acid) diblock copolymers can be adsorbed from one end (poly-isoprene) which is sorter than the poly-(acrylic acid) part. The properties of the polymer layer at various salt concentrations and different pH of the solutions were measured by Surface Forces Apparatus. Information about the height of the polymer layer, and the adsorbed amount were extrapolated. The extracted results were compared with theoretical predictions showing well fit.