Made available in DSpace on 2014-10-09T12:36:50Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:56:00Z (GMT). No. of bitstreams: 1 04366.pdf: 5734662 bytes, checksum: 226af9141e1984ce9dff1230b5f437ed (MD5) / Tese (Doutoramento) / IPEN/T / University of Manchester, England

No description available.

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.

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Reactive Plasma Spraying (RPS) with a hydrocarbon gas has been studied as a method to improve the mechanical properties of a commercially available 80:20 nickel-chromium alloy, and subsequently as a method to reduce the oxygen content of sprayed MCrAlY coatings. A conventional d.c. plasma torch has been modified by attaching a conical graphite tube (reactor) onto the end of the gun. The powder is then sprayed through the reactor with injected reactive hydrocarbon gas. The reactor shrouds the plasma flame from the external atmosphere and contains the desirable inner atmosphere necessary for RPS. When spraying using a reactor and reactive gas the plasma environment is changed significantly. Work has been carried out to establish the effect various spray parameters have on the final coating such that new parameters can be selected which maximise the coatings quality and performance Reactively sprayed 80: 20 Ni/Cr coatings have been produced with an in- stiu carbide reinforcing phase, leading to greatly improved wear properties compared with conventionally sprayed coatings. Reactively sprayed MCrAlY coatings have been deposited with an order of magnitude reduction in oxide levels, leading to considerably fewer line defects such as oxide stringers and delarninations. An attempt has been made with the aid of computational fluid dynamics software, to model phenomenon occurring inside the reactor section as a method to appraise reactor design and suggest further design improvements.

Made available in DSpace on 2014-10-09T12:36:50Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:56:00Z (GMT). No. of bitstreams: 1 04366.pdf: 5734662 bytes, checksum: 226af9141e1984ce9dff1230b5f437ed (MD5) / Tese (Doutoramento) / IPEN/T / University of Manchester, England

New methods in the fabrication of top coat and bond coat have been introduced to improve the efficiency and performance of advanced thermal barrier coatings (TBCs).i. Top coat. Thick yttria-stabilized-zirconia (YSZ) coatings (300-400 μm) have been fabricated by using electrophoretic deposition (EPD) method. The EPD coatings have more favorable microstructures with uniformly distributed porosity and stronger bonding, in comparison with conventional air-plasma spray (APS) coatings. ii. Bond coat. Pt-diffused single γ’-phase bond coat has been fabricated by applying selective etching prior to the electroplating of Pt on CMSX-4 single crystal superalloys. The concern on the compromised scale adhesion caused by the depletion of Pt is effectively avoided, as Pt remains stable in a coherent γ’-phase layer after long-term diffusion and oxidation. Considerable cost of Pt could also be reduced. Commercial TBCs, comprising an electron beam physical vapour deposition (EBPVD) top coat, a Pt-enriched intermetallic bond coat and a CMSX-4 single crystal superalloy, have also been investigated focusing on the failures that typically occurred at the scale/alloy interface. Advanced characterization techniques have been used to study the chemical factors (Al, Pt, S, Hf, etc.) that determine the durability of TBCs. Mechanisms have been discussed that control the TBCs behaviours of diffusion, oxidation, and adhesion. i. Diffusion. A depletion of Pt near the scale/alloy interface inevitably occurs at high temperatures, which significantly weakens the scale adhesion. Mechanisms controlling the diffusion of Pt in Ni-based single crystal superalloys at high temperatures have been investigated focusing on the evolution of phase, microstructure, and composition. It was found that Pt has negative chemical interactions with Al, Ti and Ta, all of which could stabilize Pt in β- and γ’-phases, and therefore avoid the depletion of Pt. ii. Oxidation. Selective oxidation behaviour of Ni-based superalloys has been studied by using thermodynamic calculations, which is mainly affected by alloy compositions, oxygen partial pressures and temperatures. It was found that the formation of a protective α-Al2O3 scale is more favoured under lower oxygen partial pressures and higher temperatures. The additions of Al and Pt in Ni-based superalloys could also promote the formation of Al2O3 and the exclusion of NiO and spinel. The additions of reactive elements (RE), however, are less effective and may even cause severe internal oxidations due to a competitive oxidation between Al and RE.iii. Adhesion. Sulphur effect in TBCs mainly refers to a segregation of sulphur at the scale/alloy interface, which significantly deteriorates the scale adhesion to alloys. High resolution secondary ion mass spectrometry (Nano-SIMS) was employed to trace sulphur in commercial TBCs. The undesired “sulphur effect” on scale adhesion was suggested to be caused by the formation of residual sulphides beneath the scale with weaker ionic bonding to alloy cations, rather than a segregation of sulphur atoms. Possible solutions have been suggested to alleviate the sulphur effect in TBCs.

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Surface modifications of bone-interfacing biomedical devices can increase their longevity by promoting bond formation and new bone growth, while reducing the toxic effects of corrosion and wear particles. Coatings which contain biocompatible polymers, bioceramics, drugs, and functional molecules are one route to achieve this. Here, a biomimetic approach is developed for the fabrication of poly(ethyl methacrylate) (PEMA) coatings. For the first time it is shown that PEMA can be solubilized in non-toxic solvents by naturally occurring bile acids. Their unique chemical structure and amphiphilicity allows for efficient solubilization of polymer macromolecules. Advancements in colloidal sciences enable a facile deposition method termed “dip coating” to be utilized. The feasibility of highly concentrated solutions of high molecular mass PEMA was a key factor for film deposition by dip coating. Singular layers or multilayered PEMA films could be deposited. Heat-treated PEMA films provided corrosion protection to stainless steels. This inexpensive and simple technique can be up scaled to larger manufacturing levels, leading to mass production and clinical development of novel coatings for biomedical applications. Additional challenges in the fabrication of composite coatings by dip coating were successfully addressed using bile acids. To produce high quality composite coatings by dip coating, a stable suspension is required. Particle aggregation leads to uneven coatings, poor adhesion, and weakened mechanical properties. It was shown that bile acids could act as dispersing agents to mediate this. PEMA coatings containing inorganic materials hydroxyapatite, silica, titania, and diamond were fabricated. The inorganic component of the films could be increased to 50 wt.%. Model drugs tetracycline and ibuprofen were used for the creation of drug-loaded PEMA coatings. Lastly, composite coatings containing functional molecules including heparin and nanocellulose were created. Overall, these coatings provide corrosion resistance to metallic orthopedic implants, while enhancing potential biocompatibility of the device. The biomimetic approach developed in this investigation was motivated by the role of bile acids and bile salts as solubilizers of cholesterol and other molecules within the digestive system of mammals. A solubilization mechanism has been proposed. This work paves the way for the fabrication of future composite coatings containing other high molecular mass polymers, inorganic nanomaterials, and functional materials or drugs. / Thesis / Master of Applied Science (MASc) / Biomedical devices have various properties they must possess to perform their function within the body without harming the patient. Coatings applied to these devices can mitigate the body’s response by reducing corrosion, preventing wear, and promoting bond formation. This increases the lifespan of the device and prevents invasive revision surgeries. Advances in materials engineering and colloidal sciences can help achieve these goals. Materials selection for novel coatings can be inspired by the composition of real bone - consisting of a polymer matrix with embedded inorganic nanomaterials. Additionally, manufacturing techniques that avoid high temperatures are desirable. Therefore, advances in colloidal sciences which enable coatings to be fabricated by a simple and inexpensive method known as dip coating is of paramount importance. This work used natural biosurfactants bile acids to aid in fabrication of coatings for biomedical devices using advanced polymer poly(ethyl methacrylate) and functional inorganic materials.

No description available.