Results of a study of the micromorphology and current efficiency of zinc electrodeposited from flowing, acidic chloride solutions are reported. The effects of six variables were examined: flow rate, current density, zinc and hydrogen ion concentration, concentrations of nickel, iron and cadmium impurity ions, and the nature of the substrate. The development of micromorphology was studied in-situ by means of videomicrography and ex-situ by means of scanning electron microscopy. This investigation focused on the formation of grooved deposits, which are found under a wide range of deposition conditions. The major conclusions of this study are: the most important variable determining whether grooved deposits form is the interfacial concentration; large protrusions orient themselves parallel to the flow direction with the orientation starting upstream and progressing downstream; large protrusions become ridges due to growth of the highest current density portions of the electrode under mass transport control. The current efficiency was measured using EDTA titration and weight measurements. The fraction of the current taken by zinc deposition increased with zinc concentration, ranging up to 100%, and decreased with pH. The efficiency of zinc deposition was affected by the flow rate and the substrate employed. Impurities lowered the current efficiency.

A micropatterned electrode was prepared for the study of electrocrystallization. Using microphotolithography, in conjunction with evaporation and pulse electrodeposition of thin films, a set of artificially roughened electrodes with hemispherical surface features five microns in diameter was developed. Voltammetric studies were conducted to determine the best electrode material. Gold, platinum, and various carbon surfaces were evaluated for zinc nucleation density and hydrogen overpotential. Surface homogeneity was examined by both light and scanning electron microscopy. Gold was determined to possess the best combination of material properties: chemical inertness, low melting point, and a high work function allowing underpotential deposition of zinc which reduces the rate of hydrogen evolution. Stripping coulometry was employed to determine zinc limiting currents, and evaluate effective diffusion coefficients in concentrated zinc chloride solutions. Although the method worked well for dilute zinc chloride and copper sulfate solutions, it failed at higher current densities; the emergence of surface roughness obscured actual limiting current plateaus.