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.

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.

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.

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.

Studies on nuclear technology have been ongoing since nuclear power became uniquely important to meet climate change goals while phasing out fossil fuels. Research on the fluoride salt cooled high temperature reactor (FHR), which is funded by the United States Department of Energy (DOE), has developed smoothly with the ultimate goal of a 2030 deployment. One challenge presented by FHR is that the primary coolant salt can acquire contamination from fuel failure and moisture leaking into the system. If contamination happens, it will result in a low concentration of fission products, fuel, transuranic materials and oxide impurities in the coolant. These impurities will then affect the properties of the molten salt in the long term and need to be removed without introducing new impurities. Most of the research conducted recently has focused on impurity separation in chloride molten salts. More research urgently needs to be conducted to study the impurity separation method for the fluoride molten salts. In this study, the La₂O₃-LiF-NaF-KF (La₂O₃-FLiNaK) system is used to demonstrate impurity separation in molten fluoride salt. Since lanthanum oxide needs to be dissolved in the fluoride molten salt and studies in this field are still not complete, the solubility of lanthanum oxide in FLiNaK have been measured at different temperatures to obtain the temperature-dependent solubility and understand the corresponding dissolution mechanisms first. In the solubility related experiments, Inductively Coupled Plasma Mass Spectrometry (ICP-MS) is utilized to analyze the concentration of lanthanum ions in the molten FLiNaK salt, while X-ray powder diffraction (XRD) was applied to determine the phase patterns of molten salt. Second, electrochemical experiments with tungsten and graphite as working electrodes were conducted individually to demonstrate the separation of the dissolved oxide from the salt. When the tungsten working electrode was applied, the lanthanum ions were reduced to lanthanum metal at the tungsten cathode, while the fluorine ions reacted with the tungsten anode to form tungsten fluoride. In the experiments, the production of tungsten fluoride could lead to increasing current in the cell, even overload. Moreover, theoretically, tungsten fluoride WF4 is soluble in the fluoride salt thus introducing new impurities. All these issues make tungsten not the best choice when applied to the separation of oxygen ions. Therefore, another common working electrode graphite is used. It not only has all the advantages of tungsten, but also has good performance on separation of oxygen ions. When the graphite electrode was applied, the lanthanum ions were separated in the form of lanthanum carbide (LaC₂), while the oxygen ions can be removed in the form of carbon dioxide (CO₂) or carbon monoxide (CO). In addition, only graphite was consumed during the whole separation process, which is why the graphite anode electrode is called the “sacrificial electrode”. Third, First Principle Molecular Dynamics (FPMD) simulations with Vienne Ab initio Simulation Package (VASP) was conducted to study the properties of the fluoride molten salt. In this study, the structure information and enthalpy of formation were obtained. Generally, the simulation process can be divided into four steps: (1) the simulation systems are prepared by packing ions randomly via Packmol package in the simulation cell; (2) an equilibrium calculation is performed to pre-equilibrate the systems; (3) FPMD simulations in an NVT ensemble are implemented in VASP; (4) based on the FPMD simulations results, the first peak radius and the first-shell coordination number were evaluated with partial radial distribution function (PRDF) analysis to determine the statistics of molten salt structure information, while the transport properties, e.g., the self-diffusion coefficient was calculated according to the function of mean square displacement (MSD) of time generated by the Einstein-Smoluchowshi equation. The viscosity and ionic conductivity were obtained by combining the self-distribution coefficient with the Einstein-Stokes formula and Nernst-Einstein equation. / Master of Science / With the fast development of modern society and economy, more and more energy is urgently needed to meet the growth of industry. Since the traditional energy, such as nature gas, coal, has limited storage and not sustainable, nuclear energy has attracted much attention in the past few decades. Although lots of study has been conducted by thousands of researchers which has attributed to application of nuclear power, there are still some concerns in this field, among which, impurities removal is the most difficult part. Fluoride salt cooled high temperature reactor (FHR) is one of the most promising Gen IV reactor types. As the name indicates, molten salt is the coolant to serve as the heat exchanger intermedium. In addition, it’s inevitable that fission products, i.e. lanthanum, moisture, would leak into the coolant pipe, thus affect the molten salt properties, even degrade reactor performance, therefore, those impurities must be removed without introducing new impurities. In this study, the La₂O₃-LiF-NaF-KF (La₂O₃-FLiNaK) system is used to demonstrate impurity separation into molten fluoride salt. First, solubility of lanthanum oxide in FLiNaK has been measured at different temperatures to understand its dissolution mechanisms. Then, electrochemical experiments with tungsten and graphite as working electrodes were conducted individually to demonstrate the separation of the dissolved oxide from the salt. It has been concluded that tungsten performed well to separate La3+, while failed in the separation of O2-. However, graphite working electrode has succeeded in the removal of La³⁺ and O²⁻. Finally, molecular dynamic simulation with first principle was also conducted to further understand the local structure and heat of formation in the molten FLiNaK and La₂O₃-FLiNaK salt.

[pt] A corrosão é a patologia mais recorrente no concreto armado, responsável por custos elevados na recuperação das estruturas afetadas. Além dos custos diretos como os materiais utilizados na recuperação, a mão de obra especializada, substituição de peças ou equipamentos afetados, existem os custos indiretos como a paralização da utilização da estrutura, mobilização de moradores em caso de edificações residenciais, perda de produção em caso de edificação industriais, entre outros. Encontrar e apresentar meios para o combate e a prevenção da corrosão é de extrema importância. A proteção catódica tem se apresentado nas últimas décadas como uma forma eficaz de combate a corrosão, não só paralisando o processo corrosivo totalmente, mas também prevenindo o surgimento de novos pontos. Seu uso vem sendo aplicado cada vez mais em estruturas de concreto armado, como pontes, cais, edifícios industriais e residenciais e túneis. Diversos materiais vêm sendo testados e aprovados, possibilitando a flexibilização e a adaptação do melhor sistema para cada estrutura. Relatos de casos com uso da proteção catódica tem mostrado a sua eficácia mesmo depois de anos de instalação. Essa dissertação apresenta a proteção catódica, seus sistemas de uso, casos em que foi instalada, um experimento com proteção catódica por corrente impressa para a restauração de uma ferramenta de aço, além de um modelo computacional desenvolvido para o dimensionamento de anodos galvânicos para estruturas de concreto armado. / [en] Corrosion is the most recurrent pathology in reinforced concrete, responsible for high costs in the recovery of affected structures. In addition to direct costs such as materials used in the recovery, specialized labor, replacement of affected parts or equipment, there are indirect costs such as the interruption of use of the structure, mobilization of residents in case of residential buildings, loss of production in case of industrial buildings, among others. Finding and introducing means to combat and prevent corrosion is extremely important. Cathodic protection has been presented in the last decades as an effective way to combat the corrosion, as it not only paralyzes the corrosive process completely, but also preventing the combat to new points. Its use has been increasingly applied in structures such as bridges, industrial and residential buildings, and tunnels. Various materials have been tested and approved, adaptation system for flexibility and adaptation to better each structure. Case reports with the use of cathodic protection have had attention even after years of installation. This dissertation presents cathodic protection, its systems of use, cases in which it was installed, an experiment with cathodic protection by impressed current for the restoration of a steel tool, as well as a computational model developed for the design of galvanic anodes for reinforced concrete structures.