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Polyelectrolyte adsorption to surfaces is widely employed in water treatment and mining. However, little is known of the relative interaction strengths between surfaces and polymer. This fundamental property is assumed to be dominated by electrostatics, i.e. attractive interactions between opposite charges, which are set by the overall ionic strength (“salt concentration”) of the solution, and charge densities of the surface and the polymer. A common, counterintuitive, finding is a range of salt concentration over which the amount of adsorbed polyelectrolyte increases as electrostatic interactions are tempered by the addition of salt. After an adsorption maximum, higher salt concentrations then produce the expected gradual desorption of polyelectrolyte. In this work, the salt response of the adsorption of the same narrow molecular weight distribution polycation, poly(N-methyl-4-vinyl pyridinium), PM4VP, to a variety of surfaces was explored. Oxide powders for adsorption included Al2O3, SiO2, Fe2O3, Fe3O4, TiO2, ZnO and CuO. Planar surfaces included silicon wafer, mica, calcium carbonate and CaF2 single crystals. The PM4VP was radiolabeled with 14C so that sensitive, sub-monolayer amounts could be detected. The position of the peak maximum, or the lack of a peak, in response to added salt was used to rank the electrostatic component of the interaction. The importance of charge regulation, a shift in the surface pKa in response to solution species, was highlighted as a mechanism for adsorption on the “wrong” side of the isoelectric point, and also as a factor contributing to the difficulty of reaching the totally desorbed state even at the highest salt concentrations. 

Coatings that prevent or decrease fouling are sought for many applications, including those that inhibit the attachment of organisms in aquatic environments. To date, antifouling coatings have mostly followed design criteria assembled over decades: surfaces should be well/strongly hydrated, possess low net charge and maintain a hydrophilic character when exposed to the location of use. Thus, polymers based on ethylene glycol or zwitterionic repeat units have been shown to be highly effective. Unfortunately, hydrated materials can be quite soft, limiting their use in some environments. In a major paradigm shift, this work describes glassy antifouling films made from certain complexes of positive and negative polyelectrolytes. The dense network of electrostatic interactions yields tough materials below the glass transition temperature, Tg, in normal use, while the highly ionic character of these polyelectrolyte complexes ensures strong hydration. The close proximity of equal numbers of opposite charges within these complexes mimics zwitterionic structures. Films, assembled layer-by-layer from aqueous solutions, contained sulfonated poly(ether ether ketone), SPEEK, a rigid polyelectrolyte which binds strongly to a selection of quaternary ammonium polycations. Layer-by-layer buildup of SPEEK and polycations was linear, indicating strong complexes between polyelectrolytes. Calorimetry also showed complex formation was exothermic. Surfaces coated with these films in the 100 nm thickness range completely resisted adhesion of the common flagellate green algae, Chlamydomonas reinhardtii which were removed from surfaces at the minimum applied flow rate of 0.8 cm s-1. The total surface charge density of adsorbed cations, determined with a sensitive radioisotopic label, was very low, around 10% of a monolayer, which minimized adsorption driven by counterion release from the surface. The viscoelastic properties of the complexes, which were stable even in concentrated salt solutions, were explored using rheology of bulk samples. When fully hydrated, their Tgs were observed to be above 75 oC.