A corrosão provocada pelo biodiesel é um problema relevante associado à incompatibilidade do biodiesel com diversos materiais metálicos e poliméricos, sendo de suma importância quanto à durabilidade dos motores automotivos. O objetivo deste trabalho foi avaliar a corrosividade do biodiesel sobre os metais presentes no circuito de combustível dos motores que trabalham segundo o ciclo diesel aplicando técnicas gravimétricas e eletroquímicas. Todos os ensaios foram realizados em biodiesel puro obtido pela reação de transesterificação do óleo de soja refinado com etanol na presença de um catalisador alcalino. Foi avaliada a influência de dois métodos de purificação na corrosividade do biodiesel. A corrosividade do biodiesel e a degradação após contato com os íons metálicos foram avaliadas bem como em função da incidência de luz natural, temperatura e disponibilidade de oxigênio. Os resultados foram comparados com um biodiesel comercial fornecido pela Petrobrás. Ensaios de perda de massa segundo as normas ASTM G1 e ASTM G31 foram realizados para determinar a taxa de corrosão para cada metal nas diferentes condições de incidência de luz e temperatura. Na caracterização eletroquímica foi empregada a técnica de espectroscopia de impedância eletroquímica para avaliar o comportamento de corrosão dos metais em contato com o biodiesel puro, sem adição de eletrólito suporte. A qualidade do biodiesel e a degradação após contato com metais foram avaliadas pelas medidas do teor de água, teor de ácidos livres, viscosidade e estabilidade à oxidação a 110 °C. Além disso, foram empregadas na caracterização química do biodiesel a cromatografia gasosa associada à espectrometria de massas, a espectroscopia vibracional Raman e a fluorescência de Raios-X. Alguns produtos de corrosão foram caracterizados por difração de Raios-X. Os resultados dos testes de imersão segundo ASTM G1 mostraram que a perda de espessura é levemente maior quando há incidência de luz e estes valores diminuem significativamente quando o biodiesel é exposto à alta temperatura em atmosfera natural de oxigênio. A inibição da corrosão provocada em temperatura mais elevada quando o biodiesel é exposto em atmosfera natural de oxigênio deve-se à redução da solubilidade de oxigênio no biodiesel provocada pela temperatura mais elevada. Os resultados dos testes segundo a ASTM G31 indicaram que o borbulhamento de ar que favorece a reposição constante de oxigênio no meio, favorece o aumento da velocidade de corrosão, afetando principalmente os metais parcial ou totalmente imersos em biodiesel. Os testes de imersão realizados nas diferentes condições de luz, temperatura e oxigênio permitiram concluir que a corrosividade do biodiesel e a resistência à corrosão apresentada pelos metais dependem de um conjunto de variáveis os quais incluem a composição do biodiesel (matéria prima empregada na sua obtenção), grau de purificação do biodiesel somado ao efeito provocado pelo conjunto de fatores externos, tais como, incidência da luz, calor, presença de íons metálicos e oxigênio. Os ensaios eletroquímicos por espectroscopia de impedância eletroquímica permitiram usar uma célula de condutividade com eletrodos de platina como sensor da qualidade do biodiesel, mas os resultados com dois eletrodos iguais e com grande área não permitiram quantificar a corrosividade do biodiesel, apenas a qualidade do biodiesel. Os poucos resultados com microeletrodo de platina indicaram a possibilidade de uso dessa técnica para avaliar os fenômenos na interface metal/biodiesel. / Corrosion caused by biodiesel is a relevant issue regarding the problem of biodiesel compatibility with various metallic and polymeric materials, which is extremely important to assure durability of engines. The objective of this study was to evaluate the corrosiveness of the biodiesel on the metals commonly encountered in the automotive fuel system in diesel engine by gravimetric and electrochemical techniques. The influence of two purification methods was investigated. The biodiesel corrosiveness and degradations after the contact with metallic ions were also evaluated in relation to the influence of natural light incidence, temperature and oxygen availability. The results were compared with a commercial biodiesel supplied by Petrobras. Immersion tests according to ASTM G1 and ASTM G31 standards were performed to determine the corrosion rate for each metal at different conditions. The electrochemical characterization was performed by electrochemical impedance spectroscopy (EIS) to evaluate the metals corrosion behavior in contact with pure biodiesel, without addition of supporting electrolyte. The biodiesel quality and degradation after contact with metals were evaluated by assessing water content, viscosity and oxidation stability at 110 °C. In addition, the vibrational Raman spectroscopy and X-ray fluorescence were also performed. Some of the corrosion products were characterized by X-ray diffraction. The results of ASTM G1 tests showed that the thickness loss for metals determined at room temperature is slightly higher when there is light incidence and these values significantly decrease for the highest temperature at low availability of oxygen. The main conclusion is that the significant reduction in corrosion rate when the biodiesel is exposed to high temperature (heat) in a natural atmosphere of oxygen (ASTM G1) should be assigned to the impressive decrease of oxygen solubility caused by high temperature. The results of ASTM G31 tests indicated that air bubbling along with higher temperature affects mostly partial or totally immersed samples. The increase of corrosion rate evidenced by the weight loss measurements according to ASTM G31 for different metals is attributed to the effect of high concentration of dissolved oxygen. The immersion tests showed that biodiesel corrosiviness as well as corrosion resistance presented by metals depends on a set of variables including composition (dependent on feedstock), biodiesel purity summed to external factors like incidence of light, heat, oxygen and presence of metallic ions. The degradation of biodiesel is strongly affected by heat, light and presence of metallic ions as evidenced by the increase in water content and viscosity as reduction in induction period and Raman peaks intensity decrease for assigned double bonds. The electrochemical characterization by EIS allowed finding that a classical conductivity cell can be used as an interesting quality of sensor for biodiesel quality, but the results with two similar electrodes and big exposed area could not evaluate the biodiesel corrosiveness. The potenciostatic tests performed for copper and carbon steel indicated that it is possible to evaluate both metals corrosion behavior in biodiesel and this is promising technique for this purpose and needs deeper investigation. The few results with a platinum microelectrode have indicated the possibility of using the technique to assess the metal/biodiesel interface phenomena.

A corrosão provocada pelo biodiesel é um problema relevante associado à incompatibilidade do biodiesel com diversos materiais metálicos e poliméricos, sendo de suma importância quanto à durabilidade dos motores automotivos. O objetivo deste trabalho foi avaliar a corrosividade do biodiesel sobre os metais presentes no circuito de combustível dos motores que trabalham segundo o ciclo diesel aplicando técnicas gravimétricas e eletroquímicas. Todos os ensaios foram realizados em biodiesel puro obtido pela reação de transesterificação do óleo de soja refinado com etanol na presença de um catalisador alcalino. Foi avaliada a influência de dois métodos de purificação na corrosividade do biodiesel. A corrosividade do biodiesel e a degradação após contato com os íons metálicos foram avaliadas bem como em função da incidência de luz natural, temperatura e disponibilidade de oxigênio. Os resultados foram comparados com um biodiesel comercial fornecido pela Petrobrás. Ensaios de perda de massa segundo as normas ASTM G1 e ASTM G31 foram realizados para determinar a taxa de corrosão para cada metal nas diferentes condições de incidência de luz e temperatura. Na caracterização eletroquímica foi empregada a técnica de espectroscopia de impedância eletroquímica para avaliar o comportamento de corrosão dos metais em contato com o biodiesel puro, sem adição de eletrólito suporte. A qualidade do biodiesel e a degradação após contato com metais foram avaliadas pelas medidas do teor de água, teor de ácidos livres, viscosidade e estabilidade à oxidação a 110 °C. Além disso, foram empregadas na caracterização química do biodiesel a cromatografia gasosa associada à espectrometria de massas, a espectroscopia vibracional Raman e a fluorescência de Raios-X. Alguns produtos de corrosão foram caracterizados por difração de Raios-X. Os resultados dos testes de imersão segundo ASTM G1 mostraram que a perda de espessura é levemente maior quando há incidência de luz e estes valores diminuem significativamente quando o biodiesel é exposto à alta temperatura em atmosfera natural de oxigênio. A inibição da corrosão provocada em temperatura mais elevada quando o biodiesel é exposto em atmosfera natural de oxigênio deve-se à redução da solubilidade de oxigênio no biodiesel provocada pela temperatura mais elevada. Os resultados dos testes segundo a ASTM G31 indicaram que o borbulhamento de ar que favorece a reposição constante de oxigênio no meio, favorece o aumento da velocidade de corrosão, afetando principalmente os metais parcial ou totalmente imersos em biodiesel. Os testes de imersão realizados nas diferentes condições de luz, temperatura e oxigênio permitiram concluir que a corrosividade do biodiesel e a resistência à corrosão apresentada pelos metais dependem de um conjunto de variáveis os quais incluem a composição do biodiesel (matéria prima empregada na sua obtenção), grau de purificação do biodiesel somado ao efeito provocado pelo conjunto de fatores externos, tais como, incidência da luz, calor, presença de íons metálicos e oxigênio. Os ensaios eletroquímicos por espectroscopia de impedância eletroquímica permitiram usar uma célula de condutividade com eletrodos de platina como sensor da qualidade do biodiesel, mas os resultados com dois eletrodos iguais e com grande área não permitiram quantificar a corrosividade do biodiesel, apenas a qualidade do biodiesel. Os poucos resultados com microeletrodo de platina indicaram a possibilidade de uso dessa técnica para avaliar os fenômenos na interface metal/biodiesel. / Corrosion caused by biodiesel is a relevant issue regarding the problem of biodiesel compatibility with various metallic and polymeric materials, which is extremely important to assure durability of engines. The objective of this study was to evaluate the corrosiveness of the biodiesel on the metals commonly encountered in the automotive fuel system in diesel engine by gravimetric and electrochemical techniques. The influence of two purification methods was investigated. The biodiesel corrosiveness and degradations after the contact with metallic ions were also evaluated in relation to the influence of natural light incidence, temperature and oxygen availability. The results were compared with a commercial biodiesel supplied by Petrobras. Immersion tests according to ASTM G1 and ASTM G31 standards were performed to determine the corrosion rate for each metal at different conditions. The electrochemical characterization was performed by electrochemical impedance spectroscopy (EIS) to evaluate the metals corrosion behavior in contact with pure biodiesel, without addition of supporting electrolyte. The biodiesel quality and degradation after contact with metals were evaluated by assessing water content, viscosity and oxidation stability at 110 °C. In addition, the vibrational Raman spectroscopy and X-ray fluorescence were also performed. Some of the corrosion products were characterized by X-ray diffraction. The results of ASTM G1 tests showed that the thickness loss for metals determined at room temperature is slightly higher when there is light incidence and these values significantly decrease for the highest temperature at low availability of oxygen. The main conclusion is that the significant reduction in corrosion rate when the biodiesel is exposed to high temperature (heat) in a natural atmosphere of oxygen (ASTM G1) should be assigned to the impressive decrease of oxygen solubility caused by high temperature. The results of ASTM G31 tests indicated that air bubbling along with higher temperature affects mostly partial or totally immersed samples. The increase of corrosion rate evidenced by the weight loss measurements according to ASTM G31 for different metals is attributed to the effect of high concentration of dissolved oxygen. The immersion tests showed that biodiesel corrosiviness as well as corrosion resistance presented by metals depends on a set of variables including composition (dependent on feedstock), biodiesel purity summed to external factors like incidence of light, heat, oxygen and presence of metallic ions. The degradation of biodiesel is strongly affected by heat, light and presence of metallic ions as evidenced by the increase in water content and viscosity as reduction in induction period and Raman peaks intensity decrease for assigned double bonds. The electrochemical characterization by EIS allowed finding that a classical conductivity cell can be used as an interesting quality of sensor for biodiesel quality, but the results with two similar electrodes and big exposed area could not evaluate the biodiesel corrosiveness. The potenciostatic tests performed for copper and carbon steel indicated that it is possible to evaluate both metals corrosion behavior in biodiesel and this is promising technique for this purpose and needs deeper investigation. The few results with a platinum microelectrode have indicated the possibility of using the technique to assess the metal/biodiesel interface phenomena.

Cette thèse s'inscrit dans le cadre d'une collaboration avec EADS Innovation Works et AIRBUS. L'objectif des travaux est d'identifier les modes d'endommagements possibles d'éléments de structure métalliques d'aéronefs développés en service et d'en comprendre les mécanismes et les effets sur les propriétés des matériaux afin de contribuer au développement d'une méthode de contrôle non destructif innovante. Le matériau sélectionné est un alliage d'aluminium 2024-T351, l'un des matériaux constitutifs de la voilure et du fuselage d'avions civils. Les modes d'endommagement étudiés sont la corrosion et le vieillissement microstructural. La première partie de ces travaux est consacrée à l'analyse de l'influence des conditions d'exposition au milieu corrosif sur le développement de la corrosion intergranulaire et à l'identification des mécanismes de dégradation associés et de leurs cinétiques. Des conditions d'exposition originales alternant des phases d'immersion et d'émersion à différentes températures ont été explorées dans la mesure où elles semblent particulièrement représentatives des conditions d'exposition réelles. Les mécanismes proposés pour comprendre l'endommagement observé dans certaines de ces conditions d'exposition au milieu corrosif, impliquent un phénomène apparenté à de la fragilisation par l'hydrogène, phénomène qui n'est, à l'heure actuelle, pas encore reconnu pour les alliages d'aluminium de la série 2xxx. L'influence de l'hydrogène sur les propriétés physico-chimiques et mécaniques du matériau est donc étudiée dans la seconde partie de ces travaux. Enfin, l'influence d'un vieillissement microstructural sur les propriétés de l'alliage ainsi que les couplages possibles entre vieillissement microstructural et phénomènes de corrosion sont abordés dans une dernière partie. L'ensemble des résultats obtenus permet de révéler des pistes pour développer une méthode CND innovante permettant la caractérisation physique in-situ du niveau d'endommagement à l'échelle locale d'éléments de structures en alliages d'aluminium. / In the framework of a collaborative program research with EADS Innovation Works and AIRBUS, this work aims to identify the possible sources of in service damage of pieces of aircraft structure and the impact of these degradations on the mechanical properties of the materials. The results obtained allow describing the mechanisms involved and their kinetics, in order to contribute to the development of an innovative non destructive method. The material selected is the aluminum alloy 2024-T351, one of the constitutive materials for skin and wings of civil aircraft. For this study, the corrosion and the microstructural evolutions have been selected among the possible causes of degradation identified. The first part of this study is dedicated to the analysis of the influence of exposure conditions to the aggressive media on the development of intergranular corrosion and to the identification of the corrosion mechanisms involved and theirs kinetics. Original exposure conditions, alternating immersion steps in corrosive media and emersion steps in air at different temperatures, have been used insofar as these conditions have been estimated as representative of real exposure conditions. For some exposure conditions, the proposed mechanism to explain the damage observed implies a phenomenon related to hydrogen embrittlement which is, at the moment, not well recognized for aluminum alloys of the 2xxx series. The influence of hydrogen on the mechanical and physicochemical properties of the 2024 is so treated in the second part of this study. Finally, the impact of microstructural ageing as well as its possible coupling with corrosion is discussed in the last part. The whole results obtained allow the identification of leads to develop an innovative non destructive method allowing the physical characterization of local damage of aluminum alloys used to build civil aircrafts.

This master’s thesis is focused on corrosion resistance of nickel-phosphorus coatings on magnesium alloy AZ91. In the theoretical part is summarized current knowledge about magnesium alloys and electroless deposition of Ni-P coatings including ongoing reactions. Theoretical part also lists all substances contained in the nickel bath and their specific use there. In the second half of theoretical part are discussed corrosion and immersion tests. Theoretical part is ended by review aimed towards the research in areas of immersion tests. Experimental part describes individual steps of pretreatment on magnesium alloy and then deposition of the Ni-P coating. Composition and morphology of deposited Ni-P coating and magnesium alloy were studied using energy dispersive spectroscopy. Experiment part also contains list of experiments trying to figure out ideal thickness of low-phosphorus coating which is able to protect magnesium alloy from corrosion. Master’s thesis is ended with the list of immersion tests and results which outcomes from them.

The submitted work is aimed at the unconventional fluoride conversation coating preparation on the AZ31, AZ61, ZE10 and ZE41 magnesium alloys by their immersion in Na[BF4] molten salt. The influence of the preparation parameters (such as temperature and time) on the quality of the fluoride conversion coating is investigated. Methods of light and scanning electron microscopy were used for the evaluation of morphology, chemical composition and thickness of the coating. Short and long-term corrosion tests were executed to analyze the corrosion performance in simulated body fluid solution at 37 ± 2 °C with and without the fluoride conversion coating. The short-term behavior was evaluated by potentiodynamic tests, namely by the linear polarization. Long-term performance was assessed by electrochemical impedance spectroscopy or immersion tests. The coating preparation parameters influence on the character of the formed fluoride conversion coating was defined based on the obtained results. The next part of the thesis deals with the description of the possible mechanism of formation and kinetics of growth of the unconventional fluoride conversion coating on the selected AZ61 magnesium alloy. In this part, further detailed analyses were carried out to investigate the microstructure and chemical composition of the fluoride conversion coating using focused ion beam, transmission electron microscopy and X-ray photoelectron spectroscopy.