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Title: A study of hexavalent and trivalent chromium conversion coatings on zinc surfaces
Authors: Chapaneri, Roshan
Keywords: Chromium conversion coatings (CCC)
Surface analysis
Hexavalent chromium
Trivalent chromium
Electroplated zinc
Zinc whiskers
Issue Date: 2010
Publisher: © Roshan Chapaneri
Abstract: 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.
Description: A Doctoral Thesis. Submitted in partial fulfilment of the requirements for the award of Doctor of Philosophy of Loughborough University.
URI: https://dspace.lboro.ac.uk/2134/6690
Appears in Collections:PhD Theses (Materials)

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