Revealed architectures of adsorbed polymer chains at solid-polymer melt interfaces

We report the chain conformations of polymer molecules accommodated at the solid-polymer melt interfaces in equilibrium. Polystyrene "Guiselin" brushes (adsorbed layers) with different molecular weights were prepared on Si substrates and characterized by using x-ray and neutron reflectivity. The results are intriguing to show that the adsorbed layers are composed of the two different nanoarchitectures: flattened chains that constitute the inner higher density region of the adsorbed layers and loosely adsorbed polymer chains that form the outer bulklike density region. In addition, we found that the lone flattened chains, which are uncovered by the additional prolonged solvent leaching (∼120 days), are reversibly densified with increasing temperature up to 150 °C. By generalizing the chain conformations of bulks, we postulate that the change in probabilities of the local chain conformations (i.e., trans and gauche states) of polymer molecules is the origin of this densification process.