Pu Yu

The Phase Stability of Cerium Species in Aqueous Systems

Cerium compounds have been identified as leading candidates to replace hexavalent chrome as conversion coatings on aluminum alloys to improve corrosion resistance. Cerium also shows promise for use as an inhibiting pigment in paint systems. The cerium conversion coatings can be deposited using either spontaneous or nonspontaneous electrolytic processes. In both cases the protective cerium oxide film forms by a precipitation mechanism that is very dependent on electrochemical potential and pH. The oxidation state and phase of the condensed cerium has been shown to be an important aspect of the corrosion protection properties provided by the film. Because of the strong influence of the solution chemistry and operating parameters on film performance, a basic knowledge of the system stability is essential. Toward this end, a revised E-pH diagram was developed for the Ce-H 2 O system. The Ce-H 2 O-HClO 4 system was chosen as an example system in which hydroxy ions are the only significant complexing species for the Ce ions. A stability diagram was constructed using more recent thermodynamic data on cerium species not available for the original diagram published in Pourbaixs atlas. Significant differences were noted between the previously published Ce-H 2 O diagram and the one presented here. Precipitation tests were carried out to verify the trends indicated in the new diagram. The importance of the updated E-pH diagram in understanding the formation processes of cerium conversion coatings are discussed.

Evaluation of Lead Anode Reactions in Acid Sulfate Electrolytes II. Manganese Reactions

Lead alloys containing calcium-tin, silver, or similar combinations are the primary insoluble anodes used for copper and zinc electrowinning. One potential concern with these anodes is the detrimental effect on cathode purity from incorporation of lead corrosion products. Other factors which are important to process economics are the reaction potential and overpotential required for oxygen evolution. In addition to the inherent overpotential, impurities in the electrolyte can have a significant polarization impact, such as the films that may form when manganese is present. In order to gain a better understanding of the fundamental behavior of various concentrations of manganese ions at lead anodes, the polarization behavior of lead calcium-tin and lead-silver alloys in sulfuric acid was evaluated. A common depolarizing agent, Co(II), was also used in some cases to determine possible interactions with manganese. The data show that manganese ions are active on the lead anodes and may precipitate manganese oxide in addition to electrochemical deposition. One possible precipitation mechanism seems to occur by the disproportionation of Mn(III). Co(II) lowers the electrode potential at given current densities which decreases Pb corrosion but favors MnO 2 formation.

SURFACE CHARACTERIZATION OF CERIUM BASED CONVERSION COATINGS

The goal of this research is to produce, characterize and evaluate coatings based on inorganic inhibitors which can serve as potential replacements for the chromated coatings currently used for corrosion protection in the aircraft industry. An inorganic cerium-based conversion coating has been developed and an invention disclosure has been made on the process. Panels survive over 336-hour salt fog testing at UMR and Boeing facilities which apparently meets the Mil Spec requirements for a conversion coating system. The cerium conversion coatings on aluminum7075 and 2024 panels were coated with a cathodic E-Coat. The panels that had been scribed, survived 2000 hours salt fog exposure.