Dependance of Poly(acrylic acid) Interfacial Adhesion on the Nanostructure of Electrodeposited ZnO Films

Understanding the impact of the intricate morphology and surface chemistry of ZnO nanorod arrays on their interactions with polyelectrolyte polymers is crucial for the development of nascent ZnO-based adhesion-promoting materials. AFM-based single molecule force spectroscopy was applied for the analysis of the adsorption of poly(acrylic acid) (PAA) on zinc oxide (ZnO) film covered stainless steel substrates in aqueous electrolytes at pH 7. Based on the electrodeposition process, the morphology of zinc oxide films could be varied ranging from platelet-like crystals to nanorods. This approach allowed for the morphology dependent analysis of macromolecular adsorption processes on complex ZnO nanostructures which have diverse applications in the field of adhesion-promoting thin films. The surface chemical composition, as determined by X- ray photoelectron spectroscopy, could be correlated to the AFM-based desorption studies. Only equilibrium desorption events (plateaus), centered at 42 pN, were observed on mirror polished, preconditioned stainless steel. However, for platelet-like ZnO films, the poly(acrylic acid) desorption showed a mixture of rupture events (mean rupture forces of about 350 pN) and equilibrium desorption, while ZnO nanorod structures showed solely rupture events with mean rupture forces of about 1300 pN. These results indicate that simultaneous multiple ruptures of carboxylate-zinc bonds occur due to the macromolecular coordination of poly(acrylic acid) to the ZnO nanorods. The analysis of the interfacial adhesion processes is further supported by the dwell time dependence of desorption processes.