Enhanced molybdate conversion coatings
thesisposted on 29.04.2013, 09:11 authored by Dane E. Walker
The replacement of chromate conversion coatings for zinc coated components has been necessitated by the materials finishing industries due to the inherent toxicity issues with Cr(VI) and the legislative enforcement of WEEE and ELV Directives by the European Union. Current replacements are based on non-chromate , Cr(III) systems, these may be perceived by some to be problematic as they still contain chromium . Molybdate based conversion coatings have long been viewed by many researchers to be a viable non-chromium alternative due to their low toxicity. An extensive literature review of the research carried out in the last 20 years was carried out, highlighting areas of interest for improving the corrosion resistance of the coatings studied. These were, primarily, the synergesis that exists with molybdate and phosphate compounds for corrosion resistance and the incorporation of nanoparticle silica into treatment solution. Also discovered was the importance of the acid used to adjust treatment solution pH, immersion time, oxidising agent additions and the incorporation of rare earth metal species. Silicate sealant layers were also highlighted as a post treatment. Molybdate-based coatings were formed on commercial electrodeposited acid zinc surfaces. Many treatment conditions were investigated, and initially performance analysed using DC Linear Polarisation Resistance (LPR) trials. Subsequently, the highest performing coatings were subjected to the more aggressive, industry standard, ASTM B 117 Neutral Salt Spray (NSS) corrosion test. The highest performing molybdate coatings were found to have an average LPR of ~ 9 000 Ω. cm2, in contrast to ~ 12 000 Ω. cm2 for the Cr(VI) based reference. NSS results were amongst the highest performing for molybdate based coatings documented, at 24 h until 5% white rust, however remained inferior to Cr(VI) coatings, which lasted 120 h. The highest performing coatings were characterised using FEG-SEM, Cryofracture EDXA and site specific AES. These techniques revealed that the enhanced molybdate coatings had a columnar structure that was around 300 nm thick, with pores that appeared to expose the substrate. AES showed this type of coating to have a mixed Mo, P and Zn oxide surface. Corrosion initiation was also studied; this can be thought of as an investigation to determine the point(s) of weakness or the mechanism that causes coating failure. Coatings were immersed in 5 % wt/ vol NaCl(aq) until they showed any surface change. Initial signs of corrosion were deemed to be any appearance of pitting or discolouration of the film, not a voluminous corrosion product. Untreated Zn, Cr(VI) and simple molybdate coatings were studied as well as enhanced molybdate coatings. There were clear differences in the way the coatings behaved at the onset of corrosion. Cr(VI) coatings delaminated, leaving an area of decreased Cr concentration. The enhanced molybdate coatings failed by the appearance of localised pores of ~ 70 µm in diameter. Substrate exposure was indisputably the reason for coating failure in chloride environments. In light of the work carried out in the present thesis the outlook for the use of molybdate as a potential replacement for chromate for the conversion coating of electrodeposited zinc surfaces is a positive one.