A study of hexavalent and trivalent chromium conversion coatings on zinc surfaces

Physical, chemical and corrosion properties of a hexavalent chromium conversion coating (CCC) and that of a commercial third generation trivalent chromium system; Tripass LT1500, on zinc electrodeposited steel has been studied. Moreover, the role of additives has been studied to elucidate film formation and corrosion resistance mechanisms. Micro-cracking and self-repair corrosion protection behaviour commonly associated with hexavalent CCCs has also been investigated. Scanning Electron Microscopy (SEM) studies showed that for both hexavalent and trivalent CCCs were in general, flat with a spherical-like structure and in the case of the former microcracked beyond 122 nm conversion coating thickness. In general, the micro-crack pattern observed e.g. a dense crack network, depended upon the underlying zinc substrate morphology. The study has also demonstrated the effect of SEM imaging and prior specimen preparation conditions on hexavalent CCC micro-cracking and blistering. X-ray Photoelectron Spectroscopy (XPS), Auger Electron Spectroscopy (AES) and Infrared (IR) data has indicated that the hexavalent CCC film formation appears to be a electrochemical / sol-gel mechanism given the lack of zinc content at surface and subsurface regions within the conversion coating, presence of H2O and in particular the contribution of Cr(OH)3 as opposed to Cr2O3. An alternative film formation mechanism may exist for trivalent CCC given a higher proportion of zinc at surface and sub-surface regions, IR data analysis indicating that chromium is possibly deposited from a chromium (III) complex ion such as [CrC2O4(H2O)4] + , moreover as Cr(OH)3 and Cr2O3 compounds as indicated by XPS data analysis. The role of cobalt nitrate during film formation is unclear given that cobalt was not detected within the trivalent CCC from XPS and AES data. Electrochemical LPR measurements, polarisation curves and XPS data has shown in general, self-repair corrosion protection properties for hexavalent CCC to be lacking. Instead, it is proposed that the corrosion protection behaviour for hexavalent and trivalent CCC to be barrier. Polarisation curves and LPR data showed that the corrosion resistance performance for trivalent CCC was higher than hexavalent CCC, in general. LPR data showed that the omission of cobalt nitrate and increased addition of sodium molybdate content within the Tripass LT1500 treatment solution formulation was found to overall decrease corrosion resistance within the trivalent CCC. In addition, silica based topcoat and black trivalent CCCs was also investigated and characterised using AES, SEM and LPR. Zinc whiskers was also observed from zinc electrodeposits following exposure to thermal treatment (150°C for 1 h). Elemental analysis and grain pattern investigations failed to help determine the cause of zinc whisker initiation. Zinc whiskers was seen to protrude out of hexavalent and trivalent CCCs, with the latter requiring a longer thermal exposure time

Effect of heat treatment on zinc whisker growth from electrodeposited coatings

The effects of simple heat treatments on electrodeposited zinc coatings formed on mild steel substrates were examined. It was found that over a temperature range of 50-200°C for 1 and 24 h periods zinc whisker growth was evident. The additional effects of electrodeposited coating thickness and subsequent chromium-based passivation processes were also examined in terms of their effect on whisker growth. Individual whisker morphologies were investigated utilising a field emission gun scanning electron microscopy (FEGSEM) and focused ion beam field emission gun scanning electron microscopy (FIB-FEGSEM)

An X-ray photoelectron spectroscopy investigation of chromium conversion coatings and chromium compounds

Hexavalent and trivalent chromium based conversion coatings on zinc electrodeposited steel have been investigated using X-ray photoelectron spectroscopy (XPS) with the aim of elucidating their film chemistry. Furthermore, a monochromatic Al Kα X-ray source was utilised and the spectra produced evaluated using curve fitting software to elucidate oxidation state information. In addition, a number of chromium compounds were investigated and used to complement the curve fitting analysis for the conversion coatings. High resolution Cr2p spectra from chromium compounds exhibited multiplet splitting for Cr2O3. Additional satellite emissions can also be observed for Cr2O3 and Cr(OH)3. Curve fitting of hexavalent chromium conversion coating (CCC) 2p3/2 spectra contained both Cr(VI) and Cr(III) species with the content of the former slightly higher when the X-ray beam take-off angle (TOA) was reduced to determine more surface specific information. The Cr(III) content was determined to be mainly composed of Cr(OH)3 with some Cr2O3. In comparison, trivalent CCCs were largely composed of Cr2O3 as opposed to Cr(OH)3. Survey scans of both coatings revealed that the trivalent CCCs had a higher relative zinc content