Em 2012 foram gastos em torno de 80 bilhões de dólares com problemas relacionados à corrosão de materiais metálicos, entre eles custos diretos e indiretos em manutenções corretivas e preventivas. Esse elevado valor evidencia a importância de se trabalhar na proteção contra a corrosão. Há diversas maneiras de se mitigar os danos causados pelo fenômeno da corrosão em materiais metálicos, sendo uma delas o pré-tratamento dessas superfícies com camadas de conversão. O objetivo do presente trabalho é estudar o comportamento de um dos materiais mais utilizados na indústria automobilística, o aço galvannealed, depois de submetido a um pré-tratamento de superfície baseado na aplicação de um filme fino de sulfossilano seguido de pintura com tintas industriais. O desempenho do filme de silano foi comparado a um dos processos de pré-tratamento mais usuais do mercado brasileiro, que é a fosfatização. Após o desengraxe e limpeza do substrato com solução alcalina, o mesmo foi imerso por 15 minutos em uma solução de água e álcool (50/50 m/m) contendo 3% do silano bis-1,2-[trietoxisililpropil] tetrasulfeto (BTESPT), aditivada com 50 ppm de íons de Ce (IV). Depois de curar por 40 minutos a 150°C, obteve-se o filme de sulfossilano. Após o preparo dos corpos de prova com a aplicação do pré-tratamento, foi aplicada uma camada de revestimento orgânico tinta de fundo alquídica e tinta epóxi base água e o sistema secou ao ar por 15 dias. A avaliação desses sistemas teve como base testes eletroquímicos para avaliação de desempenho do filme e do revestimento orgânico, como as medidas de espectroscopia de impedância eletroquímica. Também foram feitos ensaios acelerados de corrosão com exposição dos corpos de prova recobertos em câmara de névoa salina (salt spray test) e imersão em água deionizada, além de medidas de aderência e flexibilidade dos revestimentos aplicados. Os resultados obtidos permitem afirmar que o filme de silano produzido a partir de BTESPT aditivado com íons de Ce (IV), aplicado sobre aço galvannealed, confere excelente proteção contra corrosão, mesmo quando comparado ao pré-tratamento mais comum de mercado a fosfatização tendo apresentado bom desempenho em todos os testes realizados, com destaque para os ensaios de impedância eletroquímica, exposição à névoa salina e imersão em água deionizada. / In 2012 around 80 billion dollars were spent with matters related to corrosion, including direct and indirect costs regarding corrective and preventive maintenance. The amount spent highlights the importance of working on the protection against corrosion. There are several ways to mitigate the damage caused by corrosion phenomenum in metals; one of them is the surface pretreatment with conversion layers. The objective of the present work is to study the behavior of galvannealed steel, one of the most used materials in automotive industry, after being pretreated with a thin layer of sulfursilane and coated with industrial paints. The performance of the silane film was compared to one of the most usual pretreatments in place, which is phosphatizing. After degreasing and cleaning the substrate with alkaline solution, the specimen was immersed for 15 minutes in a water/alcohol solution (50/50 w/w) containing 3% of bis-1,2-[triethoxysilylpropyl]tetrasulfide (BTESPT), dopped with 50 ppm of Ce (IV) ions. After curing for 40 minutes at 150ºC, the sulforsilane film was obtained. The organic coatings alkyd primer and waterborne epoxy coatings were applied over the silane and phosphate pretreatments and the systems dried for 15 days. Electrochemical impedance spectroscopy was used to evaluate the performance of the pretreatment layers combined with organic coatings. Accelerated corrosion tests, such as salt spray test and immersion in deionized water, were also performed, along with physical tests like adhesion and flexibility. Based on the results, it is possible to affirm that the silane thin film obtained from BTESPT dopped with Ce (IV) ions and applied over galvannealed steel offers excellent protection against corrosion, even if compared to the most common pretreatment currently in place phosphate conversion layer. It performed well in all tests carried out, especially the electrochemical impedance spectroscopy, salt spray test and immersion in deionized water.

There are a number of “smart” coatings that can be applied to glass. These include self-cleaning coatings based on titanium dioxide, and low-E coatings based on fluorine-doped tin oxide. Products are often more desirable with colour options such as Pilkington Activ BlueTM. There are currently no alternatives to body tinting glass to achieve colour, which is a time-consuming and expensive procedure. The work in this project details a number of coloured coatings via the AACVD or combustion processing of metal nitrate/urea precursors.

No description available.

The electrochemical growth of metal-organic framework (MOF) coatings, utilising the anodic dissolution method, has been investigated as a means of preparing MOF coated electrodes for various electrochemical applications. A mechanistic understanding of the formation of the electrode coatings has been further developed. This understanding has been utilised to expand the scope of this technique; to allow for the electrochemical formation of Zn and Co zeoliticimidazolate framework (ZIF) coatings which was hitherto not believed to bepossible. Electrodes coated with Co and Zn ZIFs via this methodology were assessed for their capacitive behaviour and the Co ZIFs exhibited the highest, pure MOF areal capacitance values reported to date. This was attributed to the method of coating formation, which provides well adhered coatings of MOF particles integrated into the electrode surface providing a good electrical connection between the coating and the electrode. Incorporation of GO, via electrophoretic deposition during the coating growth, is shown to improve this capacitance still further. Thecorresponding Zn ZIFs exhibited resistances orders of magnitude higher than their Co analogues; modelling can explain this behaviour with the Co analogue of a given ZIF calculated to have a greater metal contribution to its LUMO leading to a more delocalised electronic structure. Electrodes coated with the Cu MOF HKUST-1 have enabled for the first time the use of MOFs as a template for the electrodeposition of anisotropic metal nanostructures. Such MOF encapsulated metal nanostructures are demonstrated to have applications in surface enhanced Raman spectroscopy (SERS). In addition the same MOF has been discovered to display a redox based hysteresis which allows for the rewritable storage of small amounts of electrically accessible data.

This work, within EPSRC LATEST2 (Light Alloys Towards Environmentally Sustainable Transport 2) Programme Grant, is focused on the development of environmentally-friendly corrosion inhibitors, nanocontainers loaded with inhibitors and epoxy coatings for corrosion protection of the aerospace alloy AA 2024-T3. More specifically, the electrochemical techniques of image assisted electrochemical noise, electrochemical impedance spectroscopy, split-cell technique and potentiodynamic polarization were used for the qualitative and quantitative evaluation and characterization of environmentally-friendly corrosion inhibitors on AA 2024-T3. Scanning electron microscopy observations complemented the electrochemical measurements. It was found that the organic inhibitor 2-mercaptobenzothiazole provides excellent corrosion inhibition properties to AA 2024-T3 in 3.5% sodium chloride solution. Among the tested nitrates, cerium nitrate provides the best inhibition performance. The concentration of the nitrate salt is critical in determining the corrosion protection. An excessive concentration of nitrate ions results in the dissolution of copper-containing oxides, increasing the corrosion rate. Different types of core-shell structured nanocontainers were synthesised with the methods of distillation precipitation polymerization, emulsion polymerization and sol-gel. The nanocontainers were characterized by scanning electron and transmission electron microscopy observations. The corrosion inhibitor 2-mercaptobenzothiazole was encapsulated into the nanocontainers. The encapsulation of 2-mercaptobenzothiazole was evaluated with energy dispersive X-ray analysis mapping micrographs from transmission electron microscopy measurements. Epoxy coatings with nanocontainers loaded with 2-mercaptobenzothiazole were applied on AA 2024-T3 for protection against corrosion. The corrosion protection properties of the coatings were evaluated with electrochemical impedance spectroscopy. The results indicated that epoxy coatings provide excellent barrier properties to AA 2024-T3 in the demanding environment of 3.5% sodium chloride solution with low frequency impedance values more than 1 GOhm cm2 for over 4000 hours of testing. Coatings containing nanocontainers loaded with 2-mercaptobenzothiazole tested with an artificial scribe revealed protection of the AA 2024-T3 substrate in the scribed area, decrease of the anodic delamination in the early hours and decrease number of cathodic dark areas after long immersion time. Overall, epoxy coatings with encapsulated inhibitors can be considered as a promising system for potential replacement of hexavalent chromium treatments on aerospace alloy AA 2024-T3.

Water diffusion is widely believed to be a driving factor in the breakdown of corrosion protection by polymer coatings. However, in the epoxy-phenolic system examined, water absorption into more cured, electrically resistive coatings is shown to increase, contradicting the common perception that hydrophobic coatings yield improvements in corrosion protection. Water uptake into epoxy-phenolic coatings was estimated as a function of time using the dielectric and resistive properties of the coating measured using electrochemical impedance spectroscopy (EIS). Bulk water uptake through the coating surface and the localised nature of corrosive failure was then confirmed using localised electrochemical impedance (LEIS). This technique also allowed comparison of resistance for coatings with different curing degrees. The greater degree of water absorption into highly cured coatings was attributed to diffusion into the polymer free volume, which increases with prolonged crosslinking. Evidence for this mechanism was found in the decreasing density of epoxy-phenolic coatings as a function of cure time. The effect of coating volume was therefore evaluated with respect to the dry coating dielectric properties. Cathodic delamination of the epoxy-phenolic coatings was achieved on tinplated steel substrates, whereas this was not possible from tin-free steel (ECCS). The electrochemical behaviour of these two substrates was examined under the same NaCl concentration, their surfaces were analysed by XPS prior to immersion, and XRD after potentiostatic polarisations. The electrochemical behaviour of the bare substrates was found to be unchanged by heating to the coating cure temperature (within the accuracy of polarisation tests carried out). Nonetheless, the delamination rate of epoxy-phenolic coatings deposited on them was dependent on the coating crosslinking (cure time). The reason coating adhesion selectively failed on tinplate substrates is believed to be the lower concentration of hydroxides on its relatively flat surface, allowing less bonding to take place at the interface with the coating. The impact of the substrate on coating resistivity was further investigated by volume resistivity measurements in the presence and absence of a metallic substrate. The resistivity of free standing films was tested in permeation cells, and showed a direct correlation between the polymer resistivity and the resistivity of the solution in which it was immersed. In comparison, attached films remained highly resistive at all examined concentrations. To conclude, the results presented here demonstrate that water uptake is not as critical to the breakdown in the protection offered by epoxy-phenolics as bonding at the metal-polymer interface. These results suggest that the complex interaction between these two dissimilar materials determines the overall coating electrochemical behaviour.

nÃo hà / O desenvolvimento de revestimentos metÃlicos cada vez mais resistentes à corrosÃo e ao desgaste mecÃnico tem originado inÃmeros estudos na Ãrea de eletrodeposiÃÃo. Com intuito de se obter ligas metÃlicas com boas propriedades mecÃnicas, associadas a uma elevada resistÃncia à corrosÃo, à que os revestimentos de Zn-Mn tÃm sido bastante abordados nos Ãltimos anos, tendo em vista que estes oferecem melhores caracterÃsticas anticorrosivas quando comparados com revestimentos de zinco metÃlico, usualmente utilizados na indÃstria convencional. Neste trabalho, objetivou-se a obtenÃÃo e caracterizaÃÃo das ligas de Zn-Mn eletrodepositadas sobre eletrodos de platina e cobre metÃlico a partir de soluÃÃes a base de sais de sulfato dos metais em questÃo. Estudou-se a liga de Zn-Mn com utilizaÃÃo de voltametria cÃclica e linear, como tambÃm de cronoamperometria, onde nesta etapa todas as amostras foram obtidas em banho sem agitaÃÃo, à temperatura ambiente, 25ÂC, em diferentes densidades de corrente. Analisou-se tambÃm a estrutura fÃsica e morfolÃgica das ligas obtidas com uso de tÃcnicas como Microscopia EletrÃnica de Varredura (MEV) e Energia Dispersiva de Raios-X (EDX), variando-se parÃmetros como: densidade de corrente aplicada, pH da soluÃÃo eletrolÃtica, temperatura de deposiÃÃo e concentraÃÃo dos reagentes presentes no eletrÃlito. Para anÃlise da estrutura quÃmica das espÃcies formadas na liga em questÃo, utilizou-se a tÃcnica de DifraÃÃo de Raios-X (DRX) nas amostras obtidas em eletrodo de cobre. A partir dos resultados obtidos por meio das anÃlises voltamÃtricas, pÃde-se determinar os potenciais de reduÃÃo e oxidaÃÃo para a liga Zn-Mn onde estes ocorreram isoladamente para o zinco e para o manganÃs. Para as anÃlises de MEV e EDX observou-se que o manganÃs na liga apresenta-se na forma de oxido e o zinco na forma de metal isolado. Para as anÃlises de DRX, pÃde-se determinar as fases em que as espÃcies de Zn-Mn apresentam-se na liga, assim como tambÃm espÃcies de zinco e manganÃs isoladas. Os melhores resultados foram obtidos quando se aplicou uma densidade de corrente de 10 mA.cm-2, pH 6,0, temperatura ambiente e proporÃÃo de 1:1 entre o zinco e o manganÃs no eletrÃlito. / The development of alloys that are resistant to corrosion and good wear resistance led to several studies on the electrodeposition field. With the intention of carry out alloys with good mechanic properties, associated to a high corrosion resistance, Zn-Mn alloys have been frequently studied in the last years, once they offer better anticorrosive characteristics when compared to metallic zinc films, usually used in the conventional industry. This work aimed obtain and characterize Zn-Mn alloy electrodeposited on platinum electrode and metallic cooper from solutions composed by sulfate salts from the metals previously mentioned. Zn-Mn alloys were studied by using of cyclic and linear voltammetry, and also chronoamperommetry, in which all samples were obtained in bath without agitation, room temperature, 25 C, on different current densities. The physical and morphological structure of the alloys that have been obtained were analyzed by using technique such as scanning electronic microscopy (SEM) and X-ray dispersive energy (XDE), varying parameters such as: current density applied, pH, deposition temperature and reagents concentration in the bath. In order to analyze the chemical structure of the species formed on the alloy mentioned, a x-ray diffraction (XRD) technique was used with the samples obtained in cooper electrode. From the results obtained through voltammetric analyses, it is possible to determine the potential of reduction and oxidation of Zn-Mn alloy, which occurred separately to zinc and manganese. It was possible to observe that the manganese in the alloy appears as the oxide and the zinc as an isolated metal. Through XRD analysis, it was possible to determine the phases in which the Zn-Mn species appears in the alloy, and also isolated zinc and manganese. The best results were obtained when was applied 10mA.cm-2 current density; pH 6,0; room temperature and 1:1 proportion of zinc and manganese in the electrolytic bath.

Surfaces submerged in marine environments rapidly get colonized by marine organisms, a process known as biofouling. Fouling costs maritime industries billions of dollars annually. The most common methods of combating marine biofouling are toxin containing antifouling coatings which often have detrimental non-target environmental effects. These effects and proposed bans on harmful substances in antifouling coatings, mandates development of more environmentally friendly antifouling technologies. Of these, foul-release coatings, which minimize attachment and adhesion of fouling organisms (rather than killing them) are promising alternatives. Here I explored the utility of petroleum waxes as novel antifouling/foul-release coatings. I first investigated the responses of propagules (larvae or spores) of six common fouling organisms to wax coatings in the laboratory. A wide variation in the response of these different organisms, and in the different types of response (settlement, adhesion, etc.) by the same organism, was observed, but the most inhibitory coatings were those made from microcrystalline wax and silicone oil. However, in field trials in Sydney Harbour, paraffin waxes had the strongest antifouling performance, with activity up to one year (the trial duration). These waxes also had strong foul-release effects, with fouling that did attach mostly removed by a low pressure water jet. Composition of fouling communities on paraffin waxes differed significantly from other waxes or controls, with little or no hard fouling organisms (barnacles, bivalves) on paraffin. The mechanisms of antifouling and foul-release actions of paraffin waxes appear to be due to changes in surface properties. The surfaces of the paraffin waxes changed noticeably after 4 - 8 weeks immersion in the sea or in seawater aquaria. Antibiotic treatments showed that this change in surface appearance was due to biological (microbial) activity. Bacteria appear to remove the amorphous phase from the surface of the paraffin waxes, revealing an underlying crystalline phase, which is less affected by bacterial action. I suggest that these crystals form a microstructured ?bed of nails? of crystals of varying shapes and sizes which inhibit settlement and reduce adhesion strength of those organisms which do settle.

The dissolution profile of orally delivered drugs can be controlled through the use of osmotically controlled drug delivery devices. The most commonly used device is the osmotic tablet, which is essentially a tablet core that is coated with a rate-limiting semipermeable membrane. The feasibility of applying a coating onto a tablet using dense gas techniques was studied. Two different coating materials, polymethymethacrylate (PMMA, Mw = 120,000 g/mol) and cellulose acetate (CA, 39.8 wt% acetyl content) were applied onto an 8 mm osmotic tablet core using the Gas Anti-solvent (GAS) process. For PMMA, the pressurisation rate, coating temperature and volumetric expansion of up to 250% had minimal effect on the coating quality. The concentration, solvent type and the use of polyethylene glycol (Mw = 200 g/mol) had a more pronounced effect on the coating. The coating process was optimised to apply a smooth and uniform coating with a 50 ??m thickness. For CA, the pressurisation rate and the coating temperature had little effect on the coating that was applied. The process was more sensitive to a change in the concentration of the solution and the volumetric expansion that was used. It was found that the concentration could not be increased too much without affecting the coating quality. A CA coating was applied onto a PMMA-coated tablet using the optimised conditions. The thickness in the tablet coating increased by 10 ??m. Dissolution tests of the uncoated and coated tablets were carried out. The CA coatings were found to be insufficient in limiting the rate of water entering the tablet and performed similarly to an uncoated tablet core. The PMMA coatings were found to limit the rate of delivery of the model drug. However, variations in the PMMA coatings resulted in an inconsistent delivery profile across batches. The tablets coated with both PMMA and CA had a delivery rate in between that of uncoated and PMMA-coated tablets, indicating that the application of the second coating had compromised the initial PMMA coating.

There is an every increasing need to develop more durable and higher performing coatings for use in a range of products including tools, devices and bio-implants. Nano-structured coatings either in the form of a nanocomposite or a multilayer is of considerable interest since they often exhibit outstanding properties. The objective of this thesis was to use advanced plasma synthesis methods to produce novel nano-structured coatings with enhanced properties. Coatings consisting of combinations of aluminum (Al), aluminum nitride (AlN) and amorphous carbon (a-C) were investigated. Cathodic vacuum arc deposition and unbalanced magnetron sputtering were used to prepare the coatings. By varying the deposition conditions such as substrate bias and temperature, coatings with a variety of microstructures were formed. A comprehensive range of analytical methods have been employed to investigate the stoichiometry and microstructure of the coatings. These include Transmission Electron Microscopy (TEM), Scanning Transmission Electron Microscopy (STEM), Electron Energy Loss Spectroscopy, Auger Electron Spectroscopy, X-ray diffraction and Raman spectroscopy. In addition to the investigation of microstructure, the physical properties of the coatings were measured. Residual stress has been recognized as an important property in the study of thin film coatings since it can greatly affect the quality of the coatings. For this reason, residual stress has been extensively studied here. Hardness measurements were performed using a nano indentation system, which is sensitive to the mechanical properties of thin films. This thesis undertook the most comprehensive investigation of the Al/AlN multilayer system. A major finding was the identification of the conditions under which layers or nanocomposite form in this system. A model was developed based on energetics and diffusion limited aggregation that is consistent with the experimental data. Multilayers of a-C and Al were also found to form nanocomposites. No hardness enhancement as a function of layer thickness or feature size was observed in either the Al/AlN or a-C/a-C systems. It was found that the most important factor which determines hardness is the intrinsic stress, with films of high compressive stress exhibiting the highest hardness. Nano-structured multilayers of alternating high and low density a-C were investigated. For a-C multilayers prepared using two levels of DC bias, evidence of ion beam induced damage was observed at the interfaces of both the low and high density layers. In addition, the structure of the high density (ta-C, known as tetrahedral amorphous carbon) layers was found to be largely unchanged by annealing. These results extend our understanding of how a-C form from energetic ion beams and confirms the thermal stability of ta-C in a multilayer. This thesis also presented the first attempt to synthesis a-C multilayered films with a continuously varying DC bias in sinusoidal pattern. The resulting films were shown to have a structurally graded interface between layers and verified that ion energy and stress are the most important factors which determine the structure of a-C films.