The separation of oxidation-reduction reactions into individual half-cells with a resulting "mixed potential" is well known as a dissolution mechanism for metals; however, the mechanism by which non-conducting crystals lose ions to the solution has been studied only slightly.

Fundação de Amparo a Pesquisa do Estado de Minas Gerais / Surface texturing can be used to improve the tribological performance of mechanical contacts, in particular in the case of lubricated systems. The purpose of this work is to improve an alternative method for surface texturing based on electrochemical machining. Electrochemical dissolution combines high speed, good reproducibility and high cost-benefit ratio, which are important factors when an industrial application of surface texturing is pursued. Since the area to be textured is not required to be masked, the technique is optimized, without the need of a pre or post treatment of each surface. Another nonconventional machining technique, Electrical Discharge Machining (EDM), was used to drill microholes in the cover of the tool that will be used in the microtexturing operations. The pattern of microholes in the tool is copied onto the workpiece through the action of electrochemical dissolution. The improvement of the electrochemical texturing technique was achieved with the design of an electronic circuit with a data acquisition system and of an electrochemical cell and with the specification of the electrolyte pumping system, which improved the surface finish of the textured workpiece, as well as with the development of tools that made possible the confection of different microtexture patterns. In the electrochemical cell, the tool material was AISI 230 ferritic stainless steel and the workpiece material was carbon steel AISI 1010o. Sodium Chloride was chosen as the electrolyte tool makes the electrical contact between the electrodes. During the electrochemical texturing tests, the effect of important parameters such as the gap between electrodes, the applied voltage and the total texturing time were evaluated, and the best values found were a gap of 100 mm, a voltage between 30V and 40V and a texturing time between 20s and 60s. Different texturing patterns were obtained with good results, including dots, trace-dots and chevrons. A tribological test showed a reduction in friction and wear of a textured surface lubricated with MoS2, when compared with a smooth surface. / A texturização superficial pode ser utilizada para melhorar o desempenho tribológico de contatos mecânicos, em particular em regimes lubrificados. O presente trabalho tem o objetivo de aprimorar uma metodologia alternativa para a texturização de superfícies baseada em princípios de usinagem eletroquímica. A dissolução eletroquímica alia rapidez, reprodutibilidade e elevado custo-benefício, que são extremamente importantes quando se visa a aplicação da microtexturização em escala industrial. O não mascaramento da área a ser texturizada otimiza a técnica, dispensando um tratamento prévio e posterior de cada superfície. Uma técnica também não convencional de usinagem, a eletroerosão, foi utilizada para a microfuração da tampa da ferramenta a ser usada na microtexturização. O padrão de microfuração da ferramenta é copiado à peça pela ação da dissolução eletroquímica. O aprimoramento da técnica de texturização eletroquímica foi acompanhado pelo projeto de um circuito eletrônico com sistema de aquisição de dados, de uma célula eletroquímica e pelo dimensionamento de um sistema para bombeamento e fluxo de eletrólito, que permitiram uma melhora no acabamento superficial das peças microtexturizadas, além do desenvolvimento de ferramentas que viabilizaram a confecção de diferentes padrões de microtexturização. Na célula de texturização eletroquímica, o material da ferramenta foi o aço inoxidável ferrítico AISI 430 e o da peça foi o aço carbono 1010. O eletrólito escolhido para promover o contato elétrico entre os eletrodos foi o NaCl. Durante a texturização eletroquímica foram avaliados parâmetros importantes como o distanciamento entre eletrodos, a tensão aplicada e o tempo total de texturização, sendo que os melhores resultados foram obtidos para um distanciamento de 100 mm, uma tensão de 30 a 40 V e um tempo de texturização entre 20 e 60 s. Foram texturizados ainda padrões com formatos de ponto, traço-ponto e V , obtendo-se bons resultados. Um teste tribológico mostrou uma redução do atrito e uma diminuição do desgaste de uma superfície texturizada lubrificada com MoS2, quando comparada com uma superfície lisa. / Mestre em Engenharia Mecânica

Les alliages Mg-Ca sont des alliages biocompatibles et biodégradables largement utilisés pour des applications biomédicales comme prothèses bio-résorbables. Ils sont très utilisés car leurs taux de corrosion et de dégradation dans l'organisme peuvent être contrôlés par le taux de calcium et par l'influence du milieu d'implantation. Ces solutions ont inspirées le Groupe SEB qui cherche à mettre au point un procédé fiable de minéralisation d'une eau par dissolution d'alliages Mg-Ca. L'objectif de ce travail de thèse est double, à savoir, la conception des alliages Mg-Ca pour ce procédé, en choisissant les techniques de production adaptées et les paramètres d'élaborations optimisés, puis, la mise en œuvre d'un processus de dissolution assisté par un courant et la maîtrise des paramètres de dissolution. Le magnésium et le calcium étant des métaux très réactifs au contact de l'atmosphère, l'élaboration d'alliages Mg-Ca se fait sous atmosphère neutre. Il est possible d'obtenir une microstructure stable avec des teneurs en calcium comprises entre 0% et 33% atomique, lorsque le calcium et le magnésium forment l'intermétallique Mg2Ca. Lors du refroidissement du mélange métallique à fusion, il se forme une microstructure d'équilibre constituée de dendrites (de Mg si 0 at.% < Ca < 10 at.% et de Mg2Ca si 10 at.% < Ca < 33 at.%) et d'un agrégat eutectique lamellaire composé de Mg et de Mg2Ca. La dissolution anodique d'alliages Mg-Ca s'effectue par l'application d'une différence de potentiel entre une électrode constituée de l'alliage à dissoudre et une contre électrode constituée d'un métal plus noble. Il a été mis en évidence que les relargages d'ions Mg2+ et Ca2+ en solution peuvent être augmentés en diminuant la chute ohmique entre les électrodes (distance minimale, tension appliquée maximale) et en augmentant la réactivité du processus (alliages riches en calcium, conductivité et minéralité de la solution, durée de dissolution et surfaces exposées importantes). Cependant, les forts relargages d'ions Mg2+ et Ca2+, qui alcalinisent fortement la solution, favorisent la formation de précipités limitant la dissolution tels que le tartre, les oxydes et hydroxydes de magnésium et de calcium. Plusieurs solutions pour réguler le pH de la solution et optimiser les relargages de cations Mg2+ et Ca2+ ont été envisagées. / The Mg-Ca alloys are biocompatible and biodegradable alloys widely used for biomedical applications such as bioresorbable implants because of their corrosion rate and degradation behaviour into human body. These solutions have inspired the SEB Group to develop a new process for the mineralization of water by dissolving Mg-Ca alloys. The objective of this thesis is to design new Mg-Ca alloys choosing the appropriate production techniques and optimizing elaborations settings and then, to work on the dissolution process assisted by a current controling of dissolution parameters. Magnesium and calcium being very reactive metal in contact with the atmosphere, the development Mg-Ca alloys was done in a neutral atmosphere. It is possible to obtain a stable microstructure with calcium contents between 0% and 33 atomic% through the intermetallic form Mg2Ca. It's possible to obtain equilibrium microstructures consisting of dendrites (Mg if 0 at.% <Ca <10 at.% And Mg2Ca if 10 at.% <Ca <33 at.%) and a lamellar eutectic aggregate made from Mg and Mg2Ca. Anodic dissolution of Mg-Ca alloys is made by applying a potential between one electrode made from the Mg-Ca alloy and a counter electrode made from a more noble metal. It has been demonstrated that the releases of Mg2+ and Ca2+ in solution may be controlled throught the decrease of the resistance drop between the electrodes (minimum distance, maximum applied voltage) and the increase of the process reactivity (rich alloys calcium, mineral and conductivity of the solution, dissolving time and significant exposed surfaces). However, strong releases of Mg2+ and Ca2+, which strongly alkalize the solution, promote the formation of precipitates limiting dissolution rate such as scale, oxides and hydroxides formation. Several solutions to regulate the pH of the solution and optimize the releases of cation Mg2+ and Ca2+ were considered.