This thesis deals with temporary corrosion protection of stainless steel for the conditions of oversea sailing. At first the theoretical part describes types of the stainless steels focusing on their corrosion resistance and negatively or positively impacts affect of their resistance. There is also a proposal of methods of the temporary corrosion protection and testing its effectiveness. The recherché are summarized knowledge in testing resistance of stainless steels to pitting corrosion. The task of the study was to test the effectiveness of three different preservatives and comparing the quality of their temporary corrosion protection compared with unprotected chemically passivated stainless steels.

Turbulent fluid flow at high Reynolds numbers presents significant degradation risks to active-passive metals due to enhanced localized degradation phenomena. A multidisciplinary experiment was proposed to study the relationship between hydrodynamics in fully-developed pipe flow and both the growth and performance characteristics of passive films. Preliminary work was performed to set up (i) an environmental chamber for the experiment, (ii) design a custom wall shear stress sensor and constant temperature anemometer traverse system to monitor hydrodynamic conditions in-situ, (iii) monitor in-situ degradation through an array of ultrasonic thickness transducers, and (iv) acquire data and control the environment via a LabVIEW routine. A validation experiment was conducted on a 1220 mm long experimental section of 45.7 mm inner diameter AA2024-T3 tubing in simulated seawater. Extensive degradation was observed in-situ and confirmed with ex-situ techniques after sequential exposure to fully-developed turbulent flow at an expected wall shear stress of 10 Pa for 180ks (Reynolds number of 122,000) and then at 40 Pa for 630ks (Reynolds number of 262,000). No typical erosion-corrosion hydrological features were observed, however significant pitting and intergranular corrosion were observed with corrosion product caps covering 47% of the total ultrasonic transducers' measurement area. Passive film and pit growth were recorded via ultrasonic thickness measurements with an observed simultaneous decrease in dissolved oxygen content. The validation experiment successfully demonstrated the capability of the designed and constructed sensors for the proposed experiment. Numerous areas of suggested development and research were identified to ensure accuracy and improve interpretation of future experiments. / Master of Science

Pitting corrosion is a prevalent form of corrosive damage that can weaken, damage, and initiate failure in corrosion-resistant metallic materials. For instance, 304 stainless steel is commonly utilized in various structures (e.g., miter gates, heat exchangers, and storage tanks), but is prone to failure through pitting corrosion and stress corrosion cracking under mechanical loading, regardless of its high corrosion resistance. In this study, to better understand the pitting corrosion damage development, controlled corrosion experiments were conducted to generate pits on 304 stainless steel specimens with and without mechanical loading. The pit development over time was characterized using a high-resolution laser scanner. In addition, to achieve scalable and automatic assessment of pitting corrosion conditions, two convolutional neural network-based computer vision algorithms were adopted and implemented to evaluate the efficacy of networks to identify existence of pitting damage. One was a newly trained convolutional neural network (CNN) using MATLAB software, while the other one was a retrained version of GoogLeNet. Overall, the experimental results showed that time is the dependent variable in predicting pit depth. Meanwhile, loading conditions significantly influence pit morphology. Under compression loading, pits form with larger surface opening areas, while under tension loading, pits have smaller surface opening areas. Deep pits of smaller areas are dangerous for structural members, as they can lead to high stress concentrations and early stress corrosion cracking (SCC). Furthermore, while the training library was limited and consisted of low-resolution images, the retrained GoogLeNet CNN showed promising potential for identifying pitting corrosion based on the evaluation of its performance parameters, including the accuracy, loss, recall, precision, and F1-measure.

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Water chemistry and fluid velocity are factors that can perpetuate certain types of non-uniform pitting corrosion in copper tube, specifically in waters with high chlorine and a high pH. These two parameters can further act synergistically to alter pitting propensities in copper pipes subjected to this type of water. A preliminary short-term experiment considered pitting propensity in copper pipe as a function of water chemistry. This study used a water chemistry that had been documented to promote and sustain pitting in copper tube that further developed into fully penetrating pinhole leaks. Modifications to this base water chemistry found that dosing a chloramine disinfect (rather than free chlorine) or the addition of silica greatly reduced corrosion activity and pitting propensity on copper pipes. In another short-term experiment, copper pitting propensity was considered as a function of fluid velocity. A number of different fluid velocities were tested in several different pipe diameters using the same documented pitting water. Velocity was observed to significantly increase pitting propensity in all pipe diameters considered. At the highest fluid velocity tested (11.2 fps) a pinhole leak formed in ¼â tubing after only 2 months of testing. Larger pipe diameters were also found to increase the likelihood of forming deeper pits on the pipe surface at the same fluid velocity. Chlorine was a driving factor in corrosion for preliminary tests conducted using this pitting water. The reduction of chlorine to chloride is believed to be the primary cathodic reaction limiting the overall rate of corrosion in this type of water. As such, a subsequent study considered the relationship between the rate of chlorine reduction and corresponding corrosion activity. Chlorine reduction or demand rates were found to be good indicators for pitting propensity and corrosion activity for this particular type of water. All preceding work led to the development and design of a large scale, long-term, copper pitting study. A matrix of 21 unique conditions tested various water chemistries, flow conditions, corrosion inhibitors, and galvanic connections of copper pipes to other metallic plumbing materials. The severity of pitting corrosion was observed to be dramatically decreased by lower free chlorine residual concentrations, high alkalinity, and sufficient doses of copper corrosion inhibitors such as natural organic matter, silica, and orthophosphate. Pitting severity was consequently observed to increase at a low alkalinity, indicating that this parameter has a significant effect on corrosion reactions. Furthermore, the addition of aluminum solids to the base pitting water chemistry dramatically increased the formation of tubercle mounds on the inside of the copper pipes in contact with the waster. Aluminum solids have been observed to be a vital constituent for sustaining pit growth in this specific water at lower pHs, however, the role of this constituent at the high pH levels tested in this study was previously unknown. From simple visual observation, aluminum solids appear to increase the aggressiveness of this water even at higher pHs. / Master of Science

Bipolar electrochemistry is an interesting concept for high throughput screening techniques due to the ability to induce gradients in a range of materials and their properties, such as composition, particle size, or dopant levels, among many others. One of the key advantages of the method is the ability to test, create or modify materials without the need for a direct electrical connection. In this thesis, the viability of this method has been explored for a range of possible applications, such as metal recycling, nanoparticle modification and corrosion analysis. In the initial part of the work a process to electrodeposit gradients in metal composition was evaluated, with a view to applying the technique to the extraction and recycling of metals from fly ash. Compositional gradients in the metals under study could be readily obtained from controlled reference solutions, although the spatial resolution of the metals was not sufficient to perform separation. Only copper could be easily deposited from the fly ash solution. Bipolar electrodeposition was also successfully used to modify the particle size across substrates decorated with gold nanoparticles. The approach was demonstrated both for surfaces possessing either a uniform particle density or a gradient in particle density. In the latter case samples with simultaneous, orthogonal gradients in both particle size and density were obtained. A combination of the bipolar approach with rapid image analysis was also evaluated as a method for corrosion screening, using quantitative analysis of gradients in pitting corrosion damage on stainless steels in HCl as a model system. The factors affecting gradient formation and the initiation of corrosion were thoroughly investigated by the use of a scanning droplet cell (SDC) technique and hard x-ray photoelectron spectroscopy (HAXPES). The ability to screen arrays of different materials for corrosion properties was also investigated, and demonstrated for stainless steel and Ti-Al alloys with pre-formed compositional gradients. The technique shows much promise for further studies and for high throughput corrosion screening applications.

Visando-se determinar as temperaturas mais adequadas de nitretação e carbonitretação por plasma dos aços inoxidáveis austenítico AISI 316L, ferrítico AISI 409 e super duplex ASTM A890 Gr 5A e suas influências nas resistências ao desgaste e à corrosão, amostras desses aços foram tratadas a 400, 450 e 500°C, e submetidas a ensaios micrográficos, de raios X, ensaios microabrasivos e de corrosão. Todas as temperaturas de tratamentos utilizadas nos vários aços estudados produziram camadas com grande regularidade, que tiveram suas espessuras e durezas aumentadas com o aumento da temperatura de tratamento. Em todos os casos, ocorreu um grande aumento nas resistências ao desgaste microabrasivo das amostras nitretadas ou carbonitretadas, em comparação com o substrato, comprovando a efetividade da fase \"S\", produzida nas temperaturas mais baixas, no aumento das durezas e resistências ao desgaste. No caso das amostras tratadas em temperaturas mais elevadas, o nitreto de cromo foi o responsável principal pelo aumento dessa resistência. Verificou-se por meio dos resultados das curvas de polarização anódicas das camadas nitretadas e carbonitretadas a 400°C que, para os três tipos de aços em estudo, tais camadas apresentaram comportamentos semelhantes e superiores aos dos substratos, devido a formação de austenita ou ferrita expandidas. No caso das temperaturas de tratamentos de 450 e 500°C, as amostras carbonitretadas apresentaram desempenho superior ao das nitretadas e, próximos aos dos substratos, não tendo ocorrido degradação dessa propriedade. Os tratamentos de nitretação e carbonitretação por plasma, realizados nas temperaturas adequadas definidas no presente trabalho para os principais tipos de aços inoxidáveis, produziram camadas com elevadas durezas e resistências ao desgaste, sem perdas nas características de corrosão, que inclusive melhoraram em alguns casos, permitem a ampliação do uso dos aços inoxidáveis para situações que requeiram aquelas propriedades. / Aiming to determine the most appropriate temperatures of plasma and carbonitriding of the AISI 316L austenitic stainless steel, AISI 409 stainless steel and ASTM A890 Gr5A super duplex steel and their influence corrosion and wear resistances of those steel samples, they were treated 450 and 500°C, and submitted to micrography analyses, X-ray diffraction, abrasive wear and corrosion tests. All treatment temperatures used in the several studied steels produced layers with great regularity, which increased their thickness and hardness with the increase of the treatment temperature. In all the cases, a great increase occurred in the micro-abrasivive resistance of the nitrided and carbonitrided samples, in comparison with the substrate, proving the effectiveness of the \"S\" phase, produced in the temperatures, in the increase of the hardness and wear resistances. In the the samples treated at higher temperatures, the chromium nitride was the responsible one for the increase in the wear resistance. It was verified through the results of the potenciodinâmicos corrosion the nitrided and carbonitrided layers at 400°C, that for the three types of stee study, such layers presented similar and superior behaviors to that of the substrate, due to austenite or expanded ferrite formation. In the case of the treatment temperatures of 450 and 500°C, the carbonitrided samples presented s performance to the nitrided one and similar performance to the substrates s without the occurrence of any degradation of that property. The plasma nitriding and plasma carbonitriding treatments, carried out in the temperatures defined in the present work, for the principal types of stainless to produce layers with high hardness and wear resistances, without losses corrosion characteristics, which even got better in some cases, allow to expand the use of the stainless steels in situations where those properties are required.

Neste trabalho foram estudadas diferentes modificações superficiais do titânio (Ti) como método de preparação de superfícies de eletrodos para baterias de íons lítio (Li+) Inicialmente, as modificações foram produzidas pelas micro-indentações, com posterior corrosão eletroquímica por pites em soluções de brometo. As superfícies polidas, tratadas termicamente e modificadas através de micro-indentações foram avaliadas em diferentes parâmetros, tais como o potencial aplicado, concentração dos íons agressivos no eletrólito, temperatura, tempo dos testes e principalmente, sobre o impacto das deformações causadas pela força indentações para localização de orifícios produzidos por pites. Filmes porosos de titânia (TiO2) crescidos sobre o Ti puro, foram produzidos por anodização a plasma (anodização por centelhamento ou sparking) em 1M H3PO4 e em 1M Na2SO4 e por anodização nanotubular em 1M H3PO4 + 1M NaOH + 0,4 %(peso) HF. Os resultados mostraram, em óxidos tipo “esponja” formados na anodização a plasma em 1M H3PO4 e 1M Na2SO4, a incorporação de elementos do eletrólito contendo, respectivamente, P e S, numa relação de P/O > S/O e em óxidos nanotulares, a predominante incorporação de elemento de F. Posteriormente, as superfícies corroídas por pites e as superfícies de óxidos crescidos por anodização a plasma foram convertidas por sulfetação em diferentes materiais micro e nanoestruturados compostos por sulfetos e oxisulfetos de titânio, ajustando-se as condições de processo. O desenvolvimento proposto mostrou que é possível modificar a composição química do óxido formado por anodização a plasma para nanocristais de TiS2, nanofitas de TiS3 e TiOxSy, sem danificar a morfologia original dos nanoporos de TiO2. Os compostos formados podem ser usados como eletrodos nanoarquiteturados tridimensionais (3D) para microbaterias de íons lítio (Li+) com alta densidade de potência. A síntese desses compostos é realmente promissora, porque eles têm a capacidade de inserir mais íons lítio do que TiO2 puro, resultando em uma melhoria na capacidade das microbaterias. / In this study, different surface modifications of titanium (Ti) were studied as a method of surface preparation of electrodes for ion lithium batteries (Li+). Initially, the modifications were produced by micro-indentation with subsequent electrochemical pitting corrosion in solutions of bromide. The polished surfaces, heat treated and modified through micro indentations were evaluated for different values of parameters, such as applied potential, concentration of aggressive ions in the electrolyte, temperature, polarization time, and mainly intensity of the deformation caused by indentations for localizing holes produced by pitting. It was expected the adjust of location of these parameter settings promotes nucleation of pits, according to the pattern of indentations and growth of pitting depth for increased surface area. Porous films of titania (TiO2) were produced on pure Ti by plasma anodization (or sparking) in 1M H3PO4 and 1M Na2SO4. Nanotubes were synthesized by porous anodization in 1M NaOH + 1M H3PO4 + 0.4 (wt%) HF. The results showed oxide "sponge" like formed by plasma anodization, incorporating elements of the electrolyte containing respectively, P and S in a ratio P/O> S/O and, in nanotubular oxides, with predominant incorporation of F. Subsequently, the pitted surfaces and the surfaces of oxides grown by plasma anodization were converted by sulfidation into different micro and nanostructured materials consisting of titanium sulfide and oxisulfides by adjusting the process conditions. The proposed development has shown that it is possible to modify the chemical composition of the oxide formed by plasma anodizing to nanocrystals of TiS2 and nanobelts of TiS3 and TiOxSy without damaging the original morphology of the nanoporous TiO2. The formed compounds can be used as three-dimensional (3D) nanoarchitectured electrodes for ion lithium batteries (Li+) with high power density. The synthesis of these compounds is promising due to a higher ability to intercalate more ions lithium than pure TiO2, resulting in an improvement in the capacity of microbatteries.