Zinc and its alloys are among the most widely utilised metallic coatings for the sacrificial protection of steel. Although excellent in this mode of protection, these coatings are often less durable when subjected to environments of combined wear and corrosion due to their intrinsic relative softness and ductility. A possible and fast growing way of improving the durability of these coating is by the codeposition of inert particles into the zinc and zinc-alloy matrix. The main aim of this research was therefore to improve the durability of zinc and zinc-nickel coatings by the incorporation of inert particles via electrolytic codeposition methods. The first five chapters of this thesis comprise literature review on the electrodeposition of zinc, its alloys and composite electrodeposition in general. A major part of which was dedicated to the review of various conventional methods and parameters such as current density, agitation, temperature, solution composition, bath additives and pH usually investigated in electrodeposition. The experimental work was principally based on DC electrodeposition and was aimed at understanding the deposition behaviour of zinc and zinc-nickel electrodeposition baths, conditions which influence them and solution compatibility to the introduction of silica particles. A systematic study on the deposition behaviour of both zinc/silica and zinc-nickel/silica composite baths was carried out with particular interest on the rate of particle incorporation and the influence of particles on zinc-nickel alloy deposition. The complimentary codeposition behaviour of the nickel and silica particles was observed. The influence of bath additives such as N,N Dimethyldodecylamine (NND) and sodium nitrate on the rate of silica incorporation was also studied. Both additives were found to improve the rate of particle incorporation for the zinc/silica. The morphologies and compositions of the coatings were analysed with the use of SEM and FEGSEM. Corrosion performance studies were carried out in a neutral salt spray chamber and linear polarisation resistance methods used to determine barrier corrosion properties of the coatings. Anodic polarisation studies were also carried out. The results show an improvement in the corrosion performance of these coatings with the addition of silica particles Reciprocating wear tests were used to determine the wear behaviour of the coatings in terms of weight loss. Improvement in wear resistance was not observed in the zinc/silica coatings probably due to the high content of silica in the coatings. Lower silica contents may be required for the desired improvements. However, there were obvious improvements in the wear behaviour of the zinc-nickel/silica coatings due to the presence of the silica particles.

Thesis (Ph. D.)--Virginia Polytechnic Institute and State University, 1992. / Vita. Abstract. Includes bibliographical references (leaf 140). Also available via the Internet.

Thesis (M.Sc.). / Written for the Division of Experimental Medicine. Title from title page of PDF (viewed 2009/06/30). Includes bibliographical references.

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.