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This research developed a CrN/NbN coating with promising properties for tribological applications where corrosion plays a big role. Building on this knowledge base a novel approach to the surface treatment was selected, in which multiple layers, each chosen for a specific purpose, were optimised to combine the best properties of each. In this approach a careful consideration of macro- and microstructure of each layer is required in order to extract the good properties of each layer while eliminating the negative ones. It was shown in the work that, if such consideration is neglected, a catastrophic failure may follow. For example poor adhesion may cause a total failure of the coating. As the number of layers and interfaces increase a good understanding on the structure and the properties of each layer becomes very important as the number of parameters and possible combinations increase many times. In this whole work the intention was to take a very practical approach to the coating. The objective was to combine different approaches, such as duplex treatments and multi layering and investigate the specific interactions that are not otherwise apparent. The results of this work show that such an approach is viable and should lead to excellent results as long as the wear mechanisms of the coating are understood and the coating is correctly engineered for the application.

PVD hard ceramic coatings grown via the combined cathodic arc/unbalance magnetron deposition process were studied using Raman microscopy. Characteristic spectra from binary, multicomponent, multilayered and superlattice coatings were acquired to gain knowledge of the solid-state physics associated with Raman scattering from polycrystalline PVD coatings and to compile a comprehensive spectral database. Defect-induced first order scattering mechanisms were observed which gave rise to two pronounced groups of bands related to the acoustical (150-300cm[-1]) and optical (400-750cm[-1]) parts of the phonon spectrum. Evidence was gathered to support the theory that the optic modes were mainly due to the vibrations of the lighter elements and the acoustic modes due to the vibrations of the heavier elements within the lattice. A study into the deformation and disordering on the Raman spectral bands of PVD coatings was performed. TiAIN and TiZrN coatings were intentionally damaged via scratching methods. These scratches were then analysed by Raman mapping, both across and along, and a detailed spectral interpretation performed. Band broadening occurred which was related to "phonon relaxation mechanisms" as a direct result of the breaking up of coating grains resulting in a larger proportion of grain boundaries per-unit-volume. A direct correlation of the amount of damage with band width was observed. Band shifts were also found to occur which were due to the stresses caused by the scratching process. These shifts were found to be the largest at the edges of scratches. The Raman mapping of "droplets", a defect inherent to PVD deposition processes, found that higher compressive stresses and large amounts of disorder occurred for coating growth onto droplets. Strategies designed to evaluate the ability of Raman microscopy to monitor the extent of real wear on cutting tools were evaluated. The removal of a coating layer and subsequent detection of a base layer proved successful. This was then expanded to real wear situations in which tools were monitored after 3,6,12,64,120 and 130 minutes-in-cut. A PCA chemometrics model able to distinguish between component layers and oxides was developed. Raman microscopy was found to provide structural and compositional information on oxide scales formed on the surfaces of heat-treated coatings. Wear debris, generated as a consequence of sliding wear tests on various coatings, was also found to be primarily oxide products. The comparison of the oxide types within the debris to those formed on the surface of the same coating statically oxidised, facilitated a contact temperature during sliding to be estimated. Raman microscopy, owing to the piezo-spectroscopic effect, is sensitive to stress levels. The application of Raman microscopy for the determination of residual compressive stresses within PVD coatings was evaluated. TiAlN/VN superlattice coatings with engineered stresses ranging -3 to -11.3 GPa were deposited onto SS and HSS substrates. Subsequent Raman measurements found a correlation coefficient of 0.996 between Raman band position and stress (determined via XRD methods). In addition, there was also a similar correlation coefficient observed between hardness and Raman shift (cm-1). The application of mechanical stresses on a TiAlCrN coating via a stress rig was investigated and tensile and compressive shifts were observed.

Niobium is well known for its excellent corrosion resistance based on the formation of a stable passive oxide layer, which protects the metal against corrosion in most aqueous media and makes it an interesting candidate for corrosion resistant coating applications. However, deposition of Nb films is restricted to few technologies and difficulties arise from the toxic nature of the electrolytes employed in electrodeposition of Nb, the high reactivity of the metal with residual gases in vacuum plasma spraying and its high melting point (Tm = 2500 0C) in PVD deposition. The present thesis describes the development of corrosion resistant Nb coatings on stainless steel and brass substrates by the combined steered arc/unbalanced magnetron sputtering technique. Evaluation of the corrosion behaviour is performed by potentiodynamic polarisation measurements in 3% NaCl. It is shown that corrosion resistant Nb coatings, with passivation characteristics similar to that of bulk Nb, can be produced on stainless steel substrates by unbalanced magnetron sputtering at a low deposition temperature (T = 250 0C) under reduced ion bombardment. However, the ion etching pre-treatment of the substrate prior to deposition has a significant influence on the corrosion resistance of the coating/substrate system. The employed polarisation measurements reveal that a fully passive and protective behaviour could only be achieved if Nb ions from the cathodic arc source are chosen as the etching species. In contrast, coatings deposited after Cr ion etching from the arc source and inert Ar ion etching, utilising a glow discharge, exhibit localised breakdown and pitting of the substrate. Cross sectional TEM imaging and STEM-EDX analyses reveal that bombardment of the stainless steel substrate by the multiply charged Nb ions generates a compositionally intermixed, very fine crystalline or "amorphised" interface layer, with a thickness of ~3-8nm, depending on the Nb ion energy. It is proposed that this layer acts as an additional barrier against corrosion due to (i) the structural homogeneity achieved by amorphisation and (ii) chemical stabilisation due to the introduction of Nb in the near surface region. The energy of the bombarding Nb ions, i.e. the substrate bias voltage during the etching stage, was found to further influence the corrosion resistance. Best results are achieved with "medium" bias voltages in the range of -600V to -800V, which is believed to be due to an optimum combination of structural and chemical protection mechanisms. The fully passive corrosion behaviour could not be observed in the case of brass substrates. However, the PVD coating systems on brass and on stainless steel are superior, in the employed polarisation measurements, to commercially produced, electroplated Cr, Ni and Ni/Cr coatings on the same substrate materials. Other coating properties investigated in the present study include microstructure, hardness, crystallographic orientation and residual film stresses.