Adsorption kinetics of amphiphilic diblock copolymers: from kinetically frozen colloids to macrosurfactants

We investigated the spontaneous adsorption properties of charged amphiphilic diblock copolymers on hydrophobic surfaces and explained the transition of behavior from depleting frozen colloids (that do not adsorb at all) to fast adsorbing macrosurfactants when the hydrophobicity of the nonsoluble block is reduced. Three copolymer families have been used with the same hydrophilic block poly(acrylic acid), a weak acid whose ionization alpha can be varied by changing the pH. The hydrophobic blocks polystyrene, PS, poly(n-butyl acrylate), PBA, and poly(diethylene glycol ethyl ether acrylate), PDEGA, have interfacial tensions with water gammacore/solvent, respectively, of 32, 20, and 3 mN/m. We were mainly interested in the regime of high ionization alpha > 0.3, where PAA chains have no affinity for hydrophobic surfaces, and we verified experimentally that micelles do not adsorb directly. With the three copolymer families we show that the adsorption kinetics at an early stage is driven by the self-assembly properties in bulk solution: adsorption is hampered for PS-b-PAA (physically/kinetically frozen micelles in solution), controlled by unimer extraction for PBA-b-PAA (nonequilibrium micelles in solution with very low CMC < 10-4 wt %), and controlled by unimer diffusion and electrostatic repulsion for PDEGA-b-PAA (micelles at equilibrium in solution with high CMC is approximately 1-5 wt %). This explains the power law dependences of adsorption with concentration as C-1 for PBA-b-PAA and C-2 for PDEGA-b-PAA. It is finally the interfacial tension with water of the nonsoluble block and not its glass transition that is the main control of bulk solution self-assembly and consequently of the adsorption kinetics properties of amphiphilic diblocks. We also proved by preparative GPC that the fraction of non-self-assembling diblock chains, which exists in all highly hydrophobic amphiphilic diblock systems, plays a negligible role in the adsorption properties. Finally, we investigated the intrinsic thermodynamic affinity between amphiphilic diblocks and hydrophobic surfaces. We show quantitatively that this affinity depends dominantly on the interfacial energies between the hydrophobic block, the surface, and water: diblocks with strongly hydrophobic nonsoluble blocks (PS, PBA) have a low affinity for weakly hydrophobic surfaces, and oppositely, diblocks with weakly hydrophobic nonsoluble block (PDEGA) have a universal affinity for hydrophobic surfaces (like small-molecule surfactants but for different physical reasons). Finally, we showed via surface rheology that when adsorption occurs anchoring is strong and irreversible for very hydrophobic diblocks (PBA-b-PAA) and weaker and (partially) reversible for less hydrophobic diblocks (PDEGA-b-PAA).