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Hard coatings deposited by physical vapour deposition (PVD) are commonly used to improve the scratch resistance and hardness of objects made of softer materials such as steel, and they can also be used as decorative coatings since they exhibit a wide range of different colours. In this research, stainless steel tableware utensils were coated with multilayer Ti/TiCN thin films to give the tableware a wear-resistant decorative finish. A cathodic arc PVD system was used to deposit the coatings since it has the potential to produce very dense coatings with excellent adhesion and wear-resistance properties in relatively short deposition times. Several system parameters were varied between deposition cycles to create a large set of samples which included: changing the amount of flatware present inside of the chamber during deposition, changing the size of the flatware used, changing the mounting location of the flatware inside of the chamber, and changing the depletion level of the titanium cathode targets used to deposit titanium. It was found that changing these variables had an effect on the deposition rate of the coating and thus had an effect on the thickness of the titanium interlayer, which was found to be an important factor in achieving good adhesion of the TiCN layer. The optimal titanium interlayer thickness was found to be in the range of approximately 120 to 230 nm. / Thesis / Master of Applied Science (MASc)

Marine structures must withstand the corrosive effects of salt water in a way that is low cost, reliable, and environmentally friendly. Aluminum satisfies these conditions, and would be a good choice for a sacrificial anode to protect steel structures if it did not passivate. However, various elements can be added to aluminum to prevent this passivation. Currently, Al-Ga alloys are used commercially as sacrificial anodes but their performance is not consistent. In this research, Thermo-Calc software was used to simulate various aspects of the Al-Ga system in an attempt to understand and potentially correct this reliability issue. Simulations showed that gallium segregates to the grain boundaries during solidification and then diffuses back into the grains during cooling to room temperature. Simulations also suggest that faster cooling rates and larger grains cause the potential segregation of gallium at the grain boundaries to remain after cooling. A set of aluminum plus 0.1% weight percent gallium alloy plates were produced with varying cooling rates, along with a control set (cooled slowly in a sand mold). Some samples were later homogenized via annealing. Samples were subjected to a 168 hour long galvanostatic test to assess voltage response. The corrosion performance of samples was found to have both consistent and optimal voltage range when subjected to quick cooling rates followed by annealing. Testing samples at near freezing temperature seems to completely remove optimal corrosion behavior, suggesting that there are multiple causes for the voltage behavior. / Master of Science / Ships must withstand the corrosive effects of salt water in a way that is low cost, reliable, and environmentally friendly. Aluminum has properties which could allow a plate of it to rust instead of a ship it is attached to, thus protecting the ships from rusting. However, because aluminum usually does not rust, gallium can be added to aluminum to allow it to rust. Currently, aluminum-gallium alloys are used commercially to protect ships, but their performance is not consistent. In this research, various aspects of the aluminum-gallium system were simulated in an attempt to understand and potentially correct this reliability issue. Simulations showed that the gallium concentration may not be uniform in the alloy, and various conditions can cause the gallium concentration to be inconsistent. A set of aluminum-gallium alloy plates were cast in molds from liquid aluminum. Some of the plates were cooled quickly, and some cooled slowly. Some samples were later heated in an oven at high temperatures in an attempt to even out the gallium concentration. Samples were subjected to tests to observe corrosion behavior. The corrosion performance of samples was found to be best when subjected to quick cooling rates followed by the oven heating. Testing the samples in cold temperatures seemed to remove the desired corrosion behavior, suggesting that there are multiple reasons for the inconsistent corrosion behavior of aluminum gallium.

An interdisciplinary study concerning the durability of adhesively elastomer/metal bonded joints in marine environments is reported. The generation of OH⁻ ions at the bondline due to an imposed cathodic current from an external source is suspected to be the predominant cause of failure. A surface analysis study was performed early in this research for the purpose of identifying the cause(s) of failure. Characterization of the rubber and the metal failure surfaces with XPS (X-ray Photoelectron Spectroscopy) showed similar composition on both sides and to that of the bulk degraded primer component of the adhesive. Saponification of the adhesive and the leaching of chlorine (forming HCI that attacks the oxide) are identified as two possible failure mechanisms. The locus of failure is believed to be very close to the . adhesive/oxide interface. The exposure of bulk adhesive free-standing films to different environments showed that the hydroxyl is detrimental in the environmental durability of these specimens judging by the percentage of net mass uptake. An alternate interfacial failure mechanism is also presented where the neutralization of the adhesion-promoting attachment sites (A.S.) at the interface leads to de-adhesion and whereby OH⁻ ions chemically break-up the -COOH-Fe bond forming a non-operative activated complex at the degraded crack tip. Debond, or loss of adhesion, can exist in two modes. Weakening denotes debond growth which takes place undetected to the naked eye, and is governed by a diffusion-control degradation process that gives a straight line when plotted against the square root of time. Delamination, on the other hand, is a "post weakening" process., Debond rates in this mode are influenced by the applied total strain energy release rate, G_T, and by the environment and can be described by an exponential function in G_T. The effect of shear stress on debond acceleration was determined to be minimal. While compressive stresses seem to be beneficial in slowing the ingression of the bulk hydroxyl into the bondline, no noticeable improvement was detected when an imposed current was used. The use of zinc phosphate-coated steel substrates is shown to improve bond durability significantly at low voltages. Similar trends are observed when silane (γ-aminopropyltrimethoxy) modified primer were used in bonding. Two approaches are used in order to model debonding: empirical and analytical. Statistical Analysis System (SAS) is used to fit the empirical model which draws heavily on the functional dependencies of debond rates on the accelerating parameters, i.e., temperature, stress, and applied voltage. An Arrhenius relationship is shown to model the effect of temperature very well. Also, voltage effect is correlated with the corresponding current densities which, in turn, were found to obey an exponential relationship with debond rates. SAS fits of the experimental data are shown to model the process accurately and could be utilized for life predictions. Integration of delamination rates in real time is a feasible method to predict durability as well. A generalized analytical model for debonding is also developed, and it draws on the similarities between this application and corrosion fatigue of metals. The model is based on the conservation of mass of the involved species and is composed of a system of partial equations and their associated boundary conditions. Furthermore, temperature and voltage-dependent diffusion coefficients and reaction rate constants were used. The resulting boundary value problem amounts to a diffusion-chemical reaction mechanism into which a mechano-chemical failure mechanism is incorporated. A simplified version of the full scale analytical model is solved numerically and some interesting conclusions concerning the failure criterion are drawn. The model also simulates the weakening and delamination behavior and allows for temperature and voltage treatment as well. Delay times are also predicted as a function of the applied voltage and temperature. A particularly important conclusion is that the "marching boundary" phenomena seems to account for most of the accelerating influence of applied G. / Ph. D.

Flexible plastic liners are sometimes installed into new and existing oil and gas pipelines to prevent corrosion of the pipe wall. A practical difficulty of this method is that the plastic liners are permeable to gases, which can collect and form an annular space between the liner and the pipe. If the operating pressure in the pipe decreases then the collected gas can cause the liner to collapse and block the pipe. One method for overcoming this problem is to insert vents at intervals along the liner to allow the gas to escape into the pipe during depressurisation. However, there is concern that this arrangement might lead to excessive corrosion beneath the vent where the pipe wall is exposed. The rate of corrosion is expected to be controlled by the vent size but this principle needs to be confirmed by experiment. The work described in this thesis is aimed at investigating this corrosion by experiment for a range of conditions typical of oil and gas production. A novel crevice corrosion cell was designed, consisting of an X100 carbon steel plate and a sheet of transparent Perspex, separated by a thin gasket. A small hole in the Perspex simulated a liner vent and allowed carbon dioxide to reach the steel surface. Tests were carried out in 3.5% NaCl solutions saturated with carbon dioxide at 1 bar partial pressure. Corrosion rates along the length of the annular space were measured using the Linear Polarisation Resistance (LPR) technique on pairs of insulated X100 electrodes set into the plate. The corrosion rates within the annular space have been shown to be small compared to those in the bulk solution and to diminish rapidly with distance from the vent. Mathematical modelling, based on the transport of carbon dioxide, is described to explain these findings and support the experimental work. The effectiveness of the LinerVentTM, installed over the vent, in a turbulence pipeline was demonstrated. The benefit of applying cathodic protection within the annular space was also demonstrated. The results are discussed in terms of the fundamental corrosion principles and their practical implications

The Center for Ocean Energy Technology at Florida Atlantic University is developing an ocean energy turbine system to investigate the feasibility of harnessing Florida's Gulf Stream current kinetic energy and transforming it into a usable form. The turbine system has components which are prone to marine corrosion given the materials they are made of and to the harsh environment they will be exposed to. This study assumes a two-part system composed of a coating system acting as a barrier and sacrificial anode cathodic protection which polarizes the metal structures to a potential value where corrosion is significantly reduced. Several configurations (varying in anode quantity, size and location) were considered in order to cathodically protect the structures with various coating qualities (poor, good and excellent). These cases were modeled and simulated via Boundary Element Method software and analyzed so as to assess the most appropriate design. / by Nicolas Gantiva. / Thesis (M.S.C.S.)--Florida Atlantic University, 2010. / Includes bibliography. / Electronic reproduction. Boca Raton, Fla., 2010. Mode of access: World Wide Web.

Dutos metálicos revestidos, enterrados e protegidos catodicamente, quando são instalados nas proximidades de linhas de transmissão e distribuição de energia elétrica, vêm apresentando problemas de corrosão, sendo esta atribuída às interferências de corrente alternada dispersas no solo. São muitos os critérios propostos na literatura para verificar se um duto está ou não sujeito a esse tipo de problema, mas tais critérios são contraditórios e ineficientes, uma vez que não levam em conta parâmetros termodinâmicos e não contemplam o acoplamento dos potenciais originados de corrente contínua com os potenciais oriundos de corrente alternada. O objetivo do presente trabalho foi estudar a corrosão causada por corrente alternada, selecionar um critério seguro de verificação da probabilidade de ocorrência dessa corrosão e desenvolver uma nova metodologia para a obtenção dos parâmetros necessários para a aplicação do critério proposto. Com base em uma ampla pesquisa bibliográfica, em resultados experimentais obtidos em laboratório e em campo, foi possível a seleção do seguinte mecanismo: a corrosão por corrente alternada é decorrente da oscilação do potencial da interface duto/solo que, dependendo do valor do pH nas suas vizinhanças, leva o sistema alternadamente ao domínio da corrosão e da imunidade ou alternadamente ao domínio da formação de óxidos (com e sem passivação) e da imunidade. Nessas condições, a corrosão do aço-carbono ocorre devido à irreversibilidade da reação Fe2+ + 2e- Fe, nos casos de alcalinização limitada, e à impossibilidade de formação de uma camada passiva protetora decorrente da flutuação de potencial entre o domínio de formação de óxidos e da imunidade, nos casos de alcalinização moderada. Como critério de verificação da ocorrência ou não de interferência de corrente alternada em dutos enterrados e catodicamente protegidos foi proposta, neste estudo, a obtenção da forma de onda do acoplamento entre os potencias originados de corrente contínua e os oriundos de corrente alternada sem a influência da queda ôhmica e a comparação do potencial de pico dessa forma de onda com o potencial estabelecido como limite aceitável do sistema de proteção catódica tradicional. Esta proposição foi feita com base na termodinâmica, o que garante que a previsão seja usada com mais segurança. Finalmente, foi desenvolvida uma sonda que, juntamente com uma instrumentação adequada, é capaz de fornecer a forma de onda do referido acoplamento em dutos enterrados e catodicamente protegidos, sem a interferência da queda ôhmica. / Corrosion problems have been observed in cathodically protected pipelines installed in the vicinity of high voltage power lines or electrical distribution systems. Many of these problems have been attributed to interferences coming from stray alternating currents. In the literature, there are many criteria proposed aiming at verifying the AC corrosion probability. However, such criteria are contradictory and ineffective since they do not take into account thermodynamic parameters and do not include the coupling of potential coming from direct current and the potential due to stray alternating current. The aim of this work was to study pipeline corrosion induced by stray alternating current, to select a safe criterion for the probability of this corrosion and to develop a new methodology for obtaining the required parameters for the application of the selected criterion. A broad literature review and the results obtained from a series of tests and analyses have allowed choosing the following mechanism: AC corrosion is a result of the fluctuation of the pipe/soil potential which, depending on the pH of the soil near the pipe, takes the system alternatively to the corrosion and to the immunity domains or alternatively to the oxide formation (with or without passivation) and to the immunity domains. Under these conditions, the corrosion of carbon steel occurs due to the irreversibility of the reaction Fe2+ + 2e- Fe reaction in cases of limited alkalinization and due to the impossibility of forming a protective passive layer caused by the potential fluctuation between the oxide formation and the immunity domains in cases of moderate alkalinization. In this study, a method to obtain the waveform of the AC+DC potential, without the ohmic drop, was proposed. The comparison of the peak potential of the AC + DC waveform with the potential value established as an acceptable threshold for traditional cathodic protection systems was used as a criterion for AC corrosion assessment. This criterion is proposed based on thermodynamic principles which ensure that the prediction is reliable. Finally, a probe was developed. This probe, along with a proper instrumentation, is able to provide the desired waveform for a safe application of the proposed criterion.

Devido à relevância de filmes finos, as técnicas que são utilizadas para produzi-los e também para caracteriza-los tem se tornado importante. Neste contexto, foram analisados filmes finos de até 100 nm, de duas ligas metálicas (cromel e alumel), obtidos a partir da deposição por plasma de Arco Catódico Filtrado em Vácuo (Filtered Cathodic Vacuum Arc - FCVA). O objetivo deste projeto foi avaliar a similaridade em composição elementar entre os materiais utilizados para deposição, que operam como cátodos, e os filmes finos depositados, a partir de medições obtidas pela técnica de microanálise quantitativa Energy Dispersive Spectroscopy (EDS). Para comparação entre resultados e apreciação de compatibilidade, foi realizada avaliação estatística considerando o Teste t, no qual a estatística do teste é dada pela Distribuição t de Student, adotando nível de significância de 5%. Os valores obtidos por EDS Quantitativo para os cátodos foram de (em wt%) (90,3 ± 0,5)% de Ni e (9,72 ± 0,19)% de Cr para o cromel e (95,1 ± 0,8)% de Ni, (2,02 ± 0,14)% de Mn, (1,65 ± 0,04)% de Si e (1,15 ± 0,05)% de Al para o alumel. Já para os filmes finos, foram de (90,2 ± 0,5)% de Ni e (9,8 ± 0,5)% de Cr para o cromel e (95,2 ± 0,4)% de Ni, (2,8 ± 0,4)% de Mn, (0,77 ± 0,17)% de Si e (1,08 ± 0,09)% de Al para o Alumel, ambos apresentando compatibilidade com as medidas por Rutherford Backscattering Spectrometry (RBS) - técnica comumente utilizada para este tipo de espécime. Verificou-se que a composição elementar do filme fino de cromel não apresentou diferença significativa com o cátodo da mesma liga. Entretanto, para o filme fino de alumel, houve evidências de diferença significativa com relação ao cátodo, apontada pelo elemento silício. / Due the relevance of thin films, the techniques used to produce and also to characterize them has become important. In this context, it was analyzed thin films up to 100 nm of two alloys (Chromel and Alumel) obtained by plasma deposition using Filtered Cathodic Vacuum Arc (FCVA). The objective of this project was to evaluate the similarity in elemental concentration of the materials used for deposition, which act as cathodes, and the deposited thin films, through measurements obtained by quantitative microanalysis technique Energy Dispersive Spectroscopy (EDS). In order to compare results and compatibility assessment was performed statistical analysis considering the t-test in which the test statistic is given by the Student\'s t - distribution, adopting a significance level of 5%. The values obtained by Quantitative EDS for the cathodes were (in wt%) (90.3 ± 0.5)% of Ni and (9.72 ± 0.19)% of Cr for the Chromel and (95.1 ± 0.8)% of Ni, (2.02 ± 0.14)% of Mn, (1.65 ± 0.04)% of Si and (1.15 ± 0.05)% of Al for the Alumel. As for the thin films, they were (90.2 ± 0.5)% of Ni and (9.8 ± 0.5)% of Cr for the Chromel and (95.2 ± 0.4)% of Ni, (2.8 ± 0.4)% of Mn, (0.77 ± 0.17)% of Si and (1.08 ± 0.09)% for Al Alumel, both featuring compatibility with the measures by Rutherford Backscattering Spectrometry (RBS) - technique commonly used for this type of specimen. It was verified that the elemental concentration of the thin film of Chromel presented no significant difference with the cathode of the same alloy. However, for the Alumel thin film, there was evidence of a significant difference with respect to the cathode, appointed by element Silicon.

Este trabalho apresenta o desenvolvimento e a aplicação de um método alternativo para determinação de manganês em amostras de cimento e clínquer por voltametria de redissolução catódica por onda quadrada empregando eletrodos de ouro. Após estudos exploratórios acerca do comportamento eletroquímico do manganês no eletrólito suporte H3BO3 0,20 mol L-1 / KCl 0,10 mol L-1 com pH 6,5 e a otimização dos parâmetros operacionais para a voltametria de onda quadrada, foram obtidos excelentes resultados na determinação de manganês nas amostras analisadas. Destacam-se a ótima linearidade, verificada em duas faixas distintas de concentração, e os baixos limites de detecção e quantificação obtidos (3,1 x 10-8 mol L-1 e 9,8 x 10-8 mol L-1, respectivamente), além da concordância entre os resultados obtidos pela técnica eletroanalítica quando comparados aos resultados fornecidos pela espectrometria de absorção atômica de chama (FAAS). Para o tratamento das amostras foi avaliada a eficiência da extração ácida assistida por ultrassom. Foram avaliados ácidos minerais individualmente (HCl, H2SO4 e HClO4 em diferentes concentrações), em mistura ou ainda associados a H2O2. Os melhores resultados foram obtidos utilizando uma solução de HCl 3 mol L-1, que extraiu quantitativamente o manganês nas amostras analisadas. Os resultados obtidos foram concordantes com a metodologia padrão utilizada para a abertura da amostra e posterior análise por espectrometria de absorção atômica de chama, que emprega o aquecimento em chapa e a mesma solução extratora. / This work describes the development and application of a new alternative method for determination of manganese in cement and clinker samples by square wave cathodic stripping voltammetry using gold electrodes. After exploratory studies on the electrochemical behavior of manganese in H3BO3 0.20 mol L-1 / KCl 0.10 mol L-1 supporting electrolyte at pH 6.5 and the optimization of operating parameters for the square wave voltammetry, excellent results were obtained for determination of manganese in the samples analyzed. Most notable are the excellent linearity, verified in two distinct concentration bands and the low limits of detection and quantification obtained (3,1 x 10-8 mol L-1 e 9,8 x 10-8 mol L-1, respectively), in addiction to the concordance between the obtained results by the electroanalytical technique when compared to the provided by the flame atomic absorption spectrometry. For samples treatment were tested the efficiency of the ultrasound-assisted extraction. Were evaluated individually mineral acids (HCl, H2SO4 and HClO4 at different concentrations) in a mixture or associated with H2O2. the best results were obtained using a 3 mol L-1 HCl solution, which extracted manganese quantitatively from the analysed samples, in comparison to the standard method for extraction, targeting a later atomic absorption flame spectrometry analysis, which uses the plate heating and the same extracting solution. The obtained results for the analysed samples agrees with the cement and clinker samples of the used literature

Alumínio Pulverizado Termicamente (TSA) é amplamente utilizado em instalações offshore como revestimento de ânodo de sacrifício em tubulações de aço carbono. O transporte e a instalação desses componentes podem levar a pequenos danos no revestimento, o que pode expor a superfície do aço à água do mar. Sabe-se que o depósito calcário é formado na superfície do aço polarizado catodicamente. Assim, esta pesquisa avaliou o TSA aplicado por sistema de pulverização de arco duplo (TWAS) no aço ao carbono S355J2 + N quando ocorrem danos (holidays) para estudar a formação de depósitos calcários no aço e adquirir dados sobre o desempenho do TSA sob altas temperaturas. A aplicação de diferentes condições também foi considerada: presença de selantes; liga do revestimento (99,5% de Al e Al-5% de Mg) e condições enterradas/não enterradas. Dois tipos de experimentos foram realizados: i) testes em potencial livre sob temperaturas constantes (30, 60 e 90°C) e diferentes tamanhos de holidays (expondo 5, 10 e 20% da superfície do aço) e ii) testes sob gradient térmico onde óleo a ~125°C foi adicionado em uma torre polimérica e água externa a ~10°C ficou em contato com a superfície das amostras (tanto potencial livre como polarização de -950 mVAg/AgCl foram aplicados). Análises incluíram inspeção visual, microscópio eletrônico de varredura e difração de Raio-X. A partir dos testes em temperaturas constante, o TSA atingiu um bom potencial de proteção (-800 a -900 mVAg/AgCl) e pouca diferença nos resultados devido à diferença na composição doTSA e no tamanho do holiday foi observada. As taxas de corrosão foram mantidas entre 0,02 e 0,01 mm/ano. No ensaio sob gradiente térmico e potencial livre, a perda de revestimento e as taxas de corrosão foram de 0,4 a 0,002 mm/ano. Além disso, o potencial alcançado foi de uma faixa menor do que a obtida anteriormente (-745 a -835 mVAg/AgCl). No entanto, quando o TSA foi combinado com proteção catódica externa e gradiente térmico, a espessura do TSA foi satisfatório e as taxas de corrosão obtidas foram inferiores a 0,076 mm/ano. O depósito calcário formado no holiday protegeu o aço contra a corrosão e seu mecanismo de crescimento baseado nesta pesquisa foi construído. / Thermally Sprayed Aluminium (TSA) is widely used in offshore facilities as sacrificial anode coating for carbon-steel risers and pipelines. Transportation and installation of those components can lead to small damages in the coating, which can expose the steel surface to the seawater. It is known that calcareous deposit is formed on the cathodically polarised steel surface. Thus, this research evaluated the TSA applied by twin wire arc spray system (TWAS) on S355J2+N carbon-steel when damage (holidays) is present in order to study the calcareous deposit formation on steel and acquire data regarding the TSA performance at high temperatures. Application of different conditions was also considered: presence of sealing; coating alloy (99.5%Al and Al-5%Mg) and buried/unburied conditions. Generally, two types of experiment were conducted – i) tests at free potential at steady temperatures (30, 60 and 90°C) and different holiday sizes (exposing 5, 10 and 20% of the steel surface) and ii) tests under thermal gradient where oil at ~125°C was added in polymeric tower and external water at ~10°C was in contact with the samples surface (both free potential and polarisation of -950 mVAg/AgCl were applied). Methodology of analyses included visual inspection, scanning electron microscope and X-ray Diffraction. From the tests at steady temperatures, the TSA reached a very good protective potential (-800 to -900 mVAg/AgCl) and little difference in results due to difference in TSA composition and holiday size was observed. Corrosion rates were kept between 0.02 and 0.01 mm/year. From the thermal gradient test under free potential, the coating loss and corrosion rates were 0.4 to 0.002 mm/year. Also, the potential achieved was in a lower range than previously obtained (-745 to -835 mVAg/AgCl). However, when TSA was combined with external cathodic protection and thermal gradient, the thickness of the TSA was satisfactory and corrosion rates obtained were below 0.076 mm/year. The calcareous deposit formed within the holiday protected the steel substrate against corrosion and its growth mechanism based in this research was built.