Hierarchical Adsorption of Network-Forming Associative Polymers

In this paper, we discuss the hierarchical adsorption of micelles formed from network-forming, telechelic, associative polymers at an air-water interface. We propose an interfacial mechanism that involves three distinct steps: (i) adsorption of the micellar coronas at the interface, (ii) unfolding of the micelles to anchor the hydrophobic tails at the interface, and (iii) formation of a secondary adsorption layer by bridging between the primary layer and micelles in the bulk. While the first, transport-limited process is relatively fast, the latter processes are surprisingly slow; it may take up to 10(6) s for the adsorption to complete.