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.

This investigation determined that severe corrosion of steel can occur in the submerged portions of reinforced concrete structures in marine environments. Field studies of decommissioned pilings from actual bridges revealed multiple instances of strong corrosion localization, showing appreciable local loss of steel cross-section. Quantitative understanding of the phenomenon and its causes was developed and articulated in the form of a predictive model. The predictive model output was consistent with both the corrosion rate estimates and the extent of corrosion localization observed in the field observations. The most likely explanation for the observed phenomena that emerged from the understanding and modeling is that cathodic reaction rates under oxygen diffusional limitation that are negligible in cases of uniform corrosion can nevertheless support substantial corrosion rates if the corrosion becomes localized. A dynamic evolution form of the model was created based on the proposition that much of the steel in the submerged concrete zone remained in the passive condition given cathodic prevention that resulted from favorable macrocell coupling with regions of the steel that had experienced corrosion first. The model output also matched observations from the field, supporting the plausibility of the proposed scenario. The modeling also projected that corrosion in the submerged zone could be virtually eliminated via the use of sacrificial anode cathodic protection; the rate of corrosion damage progression in the low elevation zone above water could also be significantly reduced. Continuation work should be conducted to define an alternative to the prevalent limit-state i.e., visible external cracks and spalls, for submerged reinforced concrete structures. Work should also be conducted to determine the possible structural consequences of this form of corrosion and to assess the technical feasibility and cost/benefit aspects of incorporating protective anodes in new pile construction.

En France, l‟ensemble des canalisations exploitées pour GDF Suez et Total représente un linéaire de 37 000 km de conduites enterrées en acier. Ces canalisations sont protégées de la corrosion externe par un double système de protection : un revêtement de type hydrocarboné ou polyéthylène et une protection cathodique (PC) par courant imposé. Les normes EN 12954 : 2001 et ISO 15589-1 : 2003 préconisent des valeurs seuils de potentiels de protection, dépendant de critères caractérisant le sol. Cependant, selon les spécificités locales du sol et de l‟environnement, ces valeurs indicatives peuvent s‟avérer insuffisantes ou excessives, voire non applicables. De plus, il est nécessaire de connaître la cinétique de corrosion résiduelle pour évaluer l‟efficacité du système de protection cathodique.Un travail de laboratoire a donc été initié par GDF SUEZ et TOTAL dans le but d‟améliorer le suivi de l‟application des critères de protection cathodique en (i) développant des outils et des méthodes pour estimer la corrosivité du sol par la mesure de paramètres physico-chimiques et électrochimiques et (ii) en identifiant les conditions « justes et nécessaires » pour garantir une vitesse de corrosion négligeable au cas par cas.Des coupons d‟acier ont été enfouis dans des « soil boxes » pendant 2,5 mois, avec ou sans PC. Les « soil boxes » étaient remplies avec différents sols prélevés lors de fouilles. L‟évolution en fonction du temps du système était suivi de façon hebdomadaire par la mesure du pH, de la conductivité du sol, du taux d‟humidité, du potentiel redox et du potentiel d‟abandon. Les vitesses de corrosion déduites des méthodes électrochimiques, i.e. la voltamétrie et la spectroscopie d‟impédance, ont été comparées avec les mesures de perte de masse.Les résultats montrent, d‟une part, que l‟analyse de la corrosivité du sol peut être réalisée avec la mesure de 3 paramètres prépondérants : résistivité, potentiel redox du sol et potentiel d‟abandon de l‟acier. Ces paramètres sont mesurables sur le terrain et permettent une bonne première estimation immédiate de la corrosivité du sol. D‟autre part l‟enregistrement de courbes de polarisation sur des coupons reliés à la canalisation, c‟est-à-dire sous PC, peut permettre de suivre l‟évolution des vitesses de corrosion résiduelle sous PC. / Buried gas transmission lines are protected against external corrosion by organic coatings. Cathodic protection (CP) is designed and operated with the aim to mitigate corrosion where coating is faulty. The EN 12954: 2001 standard specifies reference values of the protection potentials according to soil conditions. However some kind of soils, like silt and clay with high resistivity, are not considered by this standard. Moreover, it is necessary to estimate the residual dissolution rate of the structure under CP so as to quantify and optimize the efficiency of the CP system setup.A laboratory study has been initiated by GDF SUEZ and TOTAL with the general aim to improve guidance on cathodic protection criteria by (i) developing tools and methods to estimate soil corrosivity from electrochemical and physico-chemical parameters and (ii) identifying the “necessary and sufficient” conditions to guaranty a negligible corrosion rate on a case by case.Steel coupons were buried in soil boxes for 2.5 months, with or without CP. The soil boxes were filled with various soil media from the field. The evolution with time of the corrosion systems was followed by weekly measurements of physico-chemical and electrochemical parameters: pH, soil conductivity, humidity level, redox potential of soils and open circuit potential of steel coupons. The corrosion rates deduced from electrochemical methods, i.e. voltammetry and electrochemical impedance spectroscopy, were compared to weight loss measurements.Results show, on one hand, that soil corrosivity could be estimated by the measurements of 3 main parameters: soil resistivity, redox potential of soil and open circuit potential of steel. These parameters could be measured on the field and could immediately give a first good estimation of the soil corrosivity. On the second hand, a detailed analysis of the polarization curves led to an estimation of residual corrosion rates of coupons under CP. The decrease with time of this residual corrosion phenomenon could be followed and quantified. In the experimental conditions considered here, the efficiency of the CP could be demonstrated. Moreover, the methodology could allow adjusting the protection potential, if necessary.

Under normal conditions, cathodically protected mild steel in seawater is protected by a precipitated film of calcium carbonate and magnesium hydroxide, the so-called calcareous film. This study has attempted to investigate the dynamics of calcareous deposit formation during cathodic protection and the composition of calcareous deposits formed under different applied current densities, and also the role played by the initial current density in forming a good quality calcareous deposit. In addition, an under protection situation can occur where current demand values are under estimated, or where structures are approaching the end of their design lives. In these conditions, a calcareous film might well occur but complete protection is probably not possible. These situations have also been studied. At low insufficient current densities where steel corrosion is still occurring, a clear correlation exists between the iron containing corrosion product and the overlaying magnesium hydroxide layer. Such effects have also been investigated using pH titration analysis, where the effect of co-precipitation of the iron and magnesium oxides/hydroxides has been shown. At higher current densities a layered precipitate has been shown to occur consisting of an inner magnesium containing layer and an outer calcium containing layer. At obvious overprotection current densities, the mechanical stresses involved in hydrogen evolution are assumed to give rise to film cracking. To augment and compliment the study on calcareous calcium/magnesium films formed during cathodic protection, a calcium-magnesium containing pigment has also been investigated in aqueous solutions at open circuit as a possible corrosion inhibitor. Another study looked at the same inhibitor in conjunction with a sacrificial zinc anode. Very effective inhibition has been shown with the film containing not only magnesium, calcium and phosphorous but also zinc. In all the investigations electrochemical methods have been used together with various surface analytical techniques.

Orientador: Francisco das Chagas Marques / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-14T14:37:10Z (GMT). No. of bitstreams: 1 OliveiraJunior_MyrianoHenriquesde_D.pdf: 13534676 bytes, checksum: 4da81eaf9a2b22721528c9804801a446 (MD5) Previous issue date: 2009 / Resumo: Neste trabalho desenvolvemos um sistema de deposição de filmes finos pela técnica de arco catódico filtrado (FCVA- Filtered Cathodic Vacuum Arc), que possibilita o desenvolvimento de ligas metálicas e, sobretudo, a deposição de filmes de carbono amorfo altamente tetraédrico. Utilizando este sistema desenvolvemos filmes de carbono amorfo (a-C) com elevada dureza (estimado em cerca de 50 a 60GPa) e alta concentração de ligações sp3 C-C em função da polarização do substrato. Estudamos as propriedades ópticas, mecânicas (stress e dureza), estruturais (Raman e RBS) e a estabilidade térmica (efusão de gases) destes filmes em função da energia de deposição. Também desenvolvemos e caracterizamos filmes de carbono crescidos por FCVA assistido por um feixe de íons secundário de Ar e Kr com diferentes energias, onde analisamos os efeitos da energia deste feixe sobre as propriedades físicas do material resultante. Além das estruturas de carbono intrínseco realizamos um estudo sobre filmes de carbono amorfo hidrogenado depositados por PECVD (plasma enhanced chemical vapor deposition) com diferentes tensões de bias (de 60 à 550V) e atmosferas mistas de CH4/Kr, onde variamos a pressão parcial deste gás nobre entre 0 e 50%. Estudamos a influência deste gás nobre sobre as propriedades estruturais do material assim como a forma como os átomos deste elemento se distribuem dentro da rede amorfa. Esta última análise foi baseada em estudos conduzidos a partir da absorção de raios-x na borda K do átomo de criptônio, onde verificamos a aglomeração destes átomos na forma de estruturas solidas. Também investigamos os processos de transformações estruturais ocorridas em estruturas a-C:H e ta-C com a temperatura baseadas na efusão de gases. Para este estudo construímos um sistema que funciona em ultra-alto vácuo, com temperatura controlada variando de ambiente até cerca de 1000 graus. Os estudos sobre as propriedades estruturais foram baseados, sobretudo, em medidas de espectroscopia de espalhamento Raman com radiação de excitação na região do visível e do ultravioleta, o que possibilita a obtenção de informações mais detalhadas sobre a forma como os átomos sp2 e sp3 distribuem-se no material. Por fim, exploramos o potencial de aplicação de três tipos de carbono amorfo; tipo polimérico (PLC), tipo diamante (DLC) e tetraédrico (ta-C) como monocamadas antirefletoras para células solares de silício cristalino e comparamos com o desempenho obtido com camadas fabricadas com materiais usualmente empregados na indústria para tal aplicação. Os resultados mostraram que filmes de carbono amorfo podem ser utilizados como camada anti-refletora. Os filmes de carbono tipo polimérico apresentaram resultados muito semelhantes aos obtidos com camadas convencionais de dióxido de estanho / Abstract: In this work we designed, manufactured and characterized a Filtered Cathodic Vacuum Arc (FCVA) deposition system. This technique is usually applied in the preparation of metallic alloys and highly sp3 - hybridized amorphous carbon thin films. By using this system we prepared a series of amorphous carbon films (a-C) with high hardness (up to ~60GPa) and high concentration of sp3 C-C bonds varying the deposition energy of the C+ ions. Mechanical (hardness and intrinsic stress) and structural (Raman, RBS and gas effusion) were investigated. Another series of a-C was developed by FCVA, but using an assisted beam of Ar or Kr as a function of the ion energy. The main purpose of this work is to understand of the effects of the bombardment of an energetic ion beam on the physical properties of the films. Another study performed on hydrogenated amorphous carbon films (a-C:H) were carried out on samples deposited by plasma enhanced chemical vapor deposition (PECVD). The films were prepared with different self-bias, varying from 60 up to 550V, and different mixed atmospheres of methane and krypton gases, varying the partial pressure of krypton from 0 to 50%. Films prepared at low bias are polymeric-like (PLC), while films prepared at high bias are diamond-like (DLC). We had performed investigations on the influence of this noble gas on the structural properties of the a-C:H films and how the Kr atoms are arranged within the amorphous matrix. The distribution of Kr atoms was studied mainly by x-ray absorption on the krypton absorption K-edge. Due to the absence of EXAFS oscillations the spectra were interpreted using the XANES region, which gave us evidences of clustering of Kr atoms. The processes involved in the a-C:H nd ta-C structural transformations during the thermal annealing were analyzed by means of thermal gas effusion measurements (using a quadrupole spectrometer) in a system developed in our laboratory. Raman scattering spectroscopy measurements were carried out with excitation radiation in the visible and ultraviolet ranges. This choice is justified due to the more detailed information obtained by multiwavelength Raman spectroscopy on the distribution of sp2and sp3sites within the amorphous carbon matrix. Finally, we had evaluated the possibility of the application of three types of amorphous carbon structures, the diamond-like and polymeric-like carbon, and the ta-C as antireflective coating on crystalline silicon solar cells. We observed that all amorphous carbon structures (DLC, PLC and ta-C) increase the short-circuit current of the solar cells. In the case of PLC films, the result is comparable to that obtained with conventional antireflective coating such as tin dioxide (SnO2) / Doutorado / Física da Matéria Condensada / Doutor em Ciências

Content of this diploma thesis is project of the digital control design for a thyristor source with GSM communication. Designed for corrosion protection. The work contain design of the whole device from the initial proposals of the electro diagrams up to finished product. It describes the events that arise in corrosion, explains the principle of operating a thyristor as a power switch. It also describes the creation and structure of a simple menu using the STM32 microprocessor. It explains the principle of controlling a source. Next, it deals with controlled rectifiers using a thyristor.

Master’s thesis deals with the problems of the inner surface finish design for the CASTOR container. In the theoretical part are analyzed properties of metallic surfaces with their defects and various options of surface finishes for increased protection. The practical part of the thesis is focused on the design of appropriate technologies for specific requirements of the surface finish for the CASTOR container, creating test samples and their evaluation.

The design of efficient and stable solar selective coatings for Concentrating Solar Power (CSP) central receivers requires a comprehensive knowledge about the incorporated materials. In this work solar selective coatings were grown by filtered cathodic vacuum arc (FCVA) deposition. The complete stacks consist of an infrared reflection layer, an absorber layer of C:ZrC nanocomposites and an antireflection layer. The Carbon-transition metal nanocomposites were studied as absorber materials because they show appropriate optical properties, i.e. high absorption in the solar region and low thermal emittance. Furthermore metal carbides are thermally and mechanically stabile in air at high temperatures. In order to optimize the absorber layer, the metal content was controlled by adjusting the pulse ratio between the two arc sources. The elemental composition of the absorber layers was determined by Ion Beam Analysis. X-Ray diffraction (XRD) measurements show the formation of metal carbides when the metal content is high enough. The optical properties of the deposited coatings were characterized by spectroscopic ellipsometry (SE). The reflectance spectra of the complete selective coating were simulated with the optical software CODE. Bruggeman effective medium approximation (EMA) was employed to average the dielectric functions of the two components which compose the nanocomposite in the absorber layer. Good agreement was found between simulated and measured reflectance spectra of the solar selective multilayer.

The optimisation of the specular reflectance of solar collectors is a key parameter to increase the global yield of concentrated solar power (CSP) plants. In this work, the influence of filtered cathodic vacuum arc deposition parameters, particularly working pressure and deposition time, on the specular and diffuse reflectance of aluminium thin films, was studied. Changes in specular reflectance, measured by ultraviolet–visible and near-infrared spectroscopy (UV-vis-NIR) spectrophotometry, were directly correlated with thin film elemental concentration depth profiles, obtained by Rutherford backscattering spectrometry (RBS), and surface and cross-sectional morphologies as measured by scanning electron microscopy (SEM) and profilometry. Finally, atomic force microscopy (AFM) provided information on the roughness and growth mechanism of the films. The two contributions to the total reflectance of the films, namely diffuse and specular reflectance, were found to be deeply influenced by deposition conditions. It was proven that working pressure and deposition time directly determine the predominant factor. Specular reflectance varied from 12 to 99.8% of the total reflectance for films grown at the same working pressure of 0.1 Pa and with different deposition times. This transformation could not be attributed to an oxidation of the films as stated by RBS, but was correlated with a progressive modification of the roughness, surface, and bulk morphology of the samples over the deposition time. Hence, the evolution in the final optical properties of the films is driven by different growth mechanisms and the resulting microstructures. In addition to the originally addressed CSP applications the potential of the developed aluminium films for other application rather than CSP, such as, for example, reference material for spectroscopic diffuse reflectance measurements, is also discussed.

Cyclopropyl-containing substrates have been frequently utilized as "probes" for the detection of SET pathways in organic and biorganic systems. These reactions are based on the cyclorpropylcarbinyl → homoallyl rearrangement, which is fast and essentially irreversible. The implicit assumption in such studies is that if a "radical" species is produced, it will undergo ring opening. We have found that there are two important factors to consider in the design of SET probes: 1) ring strain, the thermodynamic driving force for the rearrangement, and 2) resonance energy, which may help or hinder rearrangement, depending on the specific system. Delocalization of spin and charge were found to be important factors pertaining to substituent effects on the rates of radical anion rearrangements. Previous studies from our lab have centered on highly conjugated phenyl cyclopropyl ketones. This work considers a series of compounds varying in their conjugative components from a highly conjugated spiro[2.5]octa-4,7-dien-6-one and derivatives to simple aliphatic ketones. Utilizing cyclic, linear sweep voltammetry, and preparative electrolysis techniques, it was discovered that all substrates yielded ring opened products with rates and selectivities that will prove useful and informative in the design of mechanistic probes based on the cyclorpropylcarbinyl → homoallyl rearrangement. Rates of homogeneous electron transfer from a series of hydrocarbon mediators to substrates were measured using homogeneous catalysis techniques. Standard reduction potentials and reorganization energies of substrates were derived using Marcus theory. Conjugative interactions with the cyclopropyl group are discussed. / Ph. D.