Richard H. Blunk

Silica nanoparticle layer-by-layer assembly on gold.

Layer-by-layer (LBL) assembly of silica nanoparticles is investigated as a means of controlling the surface wetting properties of gold electroplated onto 316 L stainless-steel substrates while maintaining a low electrical surface contact resistance. The strong polyelectrolyte acrylamide/beta-methacryl-oxyethyl-trimethyl-ammonium copolymer is used as the cationic binder. The impact of silica nanoparticle zeta (zeta) potential for a range of -37.1 to 5.9 mV in the thickness, wettability, and contact resistance of the final LBL-assembled coatings is presented. The zeta potential is varied by altering both the pH and alcohol (ethanol) content of the silica suspensions and polymer suspension, consistent with the predictions of the Debye-Huckel equation. Nanoparticle adsorption is found to occur rapidly, with surface coverage equilibration obtained after only 1 min and uptake that is nearly linear with respect to the number of bilayers deposited. An increase in the absolute value of the (negative) zeta potential in the silica suspension is found to increase the bilayer thickness to an average value as high as 82% of the individual nanoparticle diameter for the smaller nanoparticles investigated, suggesting that nearly complete surface coverage may be achieved after the application of only a single nanoparticle-polymer bilayer (a coating thickness as low as 15.6 nm) and that nanoparticle adsorption is enhanced by electrostatic attraction between substrate and adsorbate. Counterintuitively, a more porous bilayer structure is observed if the zeta potential of the previously deposited nanoparticles is increased while the substrate is immersed in the cationic copolymer suspension, suggesting that copolymer adsorption in inhibited by substrate-solvent interactions. Wetting measurements demonstrate that silica LBL assembly results in a substantial reduction in contact angle from 84 degrees on the bare substrate surface to as low as 15 degrees after the application of a single bilayer and 7 degrees after the application of eight bilayers. A monotonic increase in coating contact resistance is observed with an increase in the thickness with a characteristic volumetric electrical through-plane resistivity of as low as 1.63 kOmega.cm obtained from contact resistance measurement.

Surface-tension-driven flows of coatings: Bondline readout formation

Bondline readout (BLRO) is a coating defect frequently observed on adhesively bonded, polymeric automotive body panels. This paper addresses ridging BLRO in clearcoats, not optical and mechanical BLRO, which are characterized by metalflake orientation (dark/light effects) in basecoats and by distortion in substrates, respectively. Ridging BLRO is due to film thickness differences and results from Marangoni-type, surface-tension-driven flows. In this study, the effects of several parameters on BLRO are investigated experimentally. These parameters include initial film thickness, heating rate, viscosity, solvent-to-resin surface-tension ratio, and solvent volatility. The experiments clearly demonstrate three modes of BLRO flow—formation, flow-out, and reformation—that result from competing surface-tension-gradient forces (temperature- versus concentration-induced). Experimental results are used to validate a proposed BLRO mechanism and, in subsequent work, a BLRO-predicting numerical code.

Competing effects of silanol surface concentration and solvent dielectric constant on electrostatic layer-by-layer assembly of silica nanoparticles on gold

Two types of silica nanoparticles having differing concentrations of ionizable surface groups are used to investigate the interplay between nanoparticle surface charge and solvent dielectric constant in nanostructure development during layer-by-layer assembly with a cationic polyacrylamide. Zeta (zeta) potential measurements are used to determine the extent of silanol dissociation with pH. For 19-nm-diameter X-Tec 3408 silica nanoparticles from Nano-X GmbH (NanoX), complete dissociation yields a zeta-potential value of about -44mV and occurs between pH 5 and 6 in 50% ethanol-in-water mixture by volume. By contrast, 65-nm-diameter polishing silica from Electron Microscopy Supply (EMS) has a zeta potential that does not equilibrate even up to pH 7 with a value of -59mV under otherwise similar solution conditions. The more negative zeta potential at a given pH is found to substantially reduce nanoparticle adsorption. This behavior is opposite that observed when the dielectric constant of the suspension is decreased, independent of particle size. Nanoparticle surface chemical heterogeneity is discussed as a plausible explanation for such seriously discrepant behavior and the effects on multilayer electrical contact resistance for proton-exchange membrane (PEM) fuel-cell coating applications are presented.