Recentemente foi demonstrado que a técnica de ressonância magnética nuclear no domínio do tempo (RMN-DT) é uma importante ferramenta analítica que é passível de ser acoplada com a eletroquímica (EQ-RMN). No entanto, como foi demonstrado nesse presente trabalho, a técnica de RMN não é passiva, ou seja, ela atua sobre as reações eletroquímicas aumentando a velocidade das reações realizadas in situ quando essas são limitadas por transporte de massas e/ou transferência de cargas. Essa alteração da taxa de reação é ocasionada por um fenômeno conhecido por magnetoeletrólise, que tem como principal resultante a força de Lorentz, que é o produto vetorial entre o campo magnético e o fluxo de íons gerado durante a eletrólise. O efeito do campo magnético sobre diferentes sistemas eletroquímicos foi comprovado na presença de campo magnético de equipamentos de RMN de baixa e alta resolução. Além do foco dado para a magnetoeletrólise durante o acoplamento EQ-RMN, novas células eletroquímicas foram miniaturizadas para a utilização com a RMN a partir de um método simples, rápido e robusto. Também foram feitas medições de velocimetria utilizando a técnica de imagem por spin eco com as quais foi possível visualizar e quantificar o efeito do campo magnético atuando sobre a reação de eletrodeposição de cobre realizada in situ. Esse trabalho foi o primeiro a utilizar o campo magnético do espectrômetro de RMN para estudar a magnetoeletrólise. Além disso, esse trabalho de doutorado foi o primeiro a utilizar um espectrômetro de RMN de bancada de alta resolução para o acoplamento com a eletroquímica. / Recently it was demonstrated that time domain Magnetic Nuclear Resonance (TD-NMR) is an important analytical technique which can be coupled to electrochemistry (EC-NMR). However, it was demonstrated in this work that NMR is not a passive technique, in other words it affects the electrochemical reactions performed in situ by increasing the reaction rate of mass transport and/or charge transfer limited reactions. This change in the reaction rate is caused by a phenomenon known as magnetoeletrolysis, it has as main resultant the Lorentz force, which is the vectorial product between the magnetic field vector and the ion flow produced during the electrolysis. The magnetic field effect on different electrochemical systems has been shown in the presence of magnetic fields of low and high resolution NMR spectrometers. In addition to the focus given to magnetoelectrolysis during the EC-NMR coupling, novel electrochemical cells were miniaturized for coupling with NMR by using a simple, rapid and robust method. Velocimetry measurements were also made using the spin-echo imaging technique with which it was possible to visualize and quantify the effect of the magnetic field acting on the in situ copper electrodeposition reaction. This work was the first to use the magnetic field of the NMR spectrometer to study magnetoelectrolysis. In addition, this doctoral thesis was the first to use a bench-top high resolution NMR spectrometer for coupling with electrochemistry.

Recentemente foi demonstrado que a técnica de ressonância magnética nuclear no domínio do tempo (RMN-DT) é uma importante ferramenta analítica que é passível de ser acoplada com a eletroquímica (EQ-RMN). No entanto, como foi demonstrado nesse presente trabalho, a técnica de RMN não é passiva, ou seja, ela atua sobre as reações eletroquímicas aumentando a velocidade das reações realizadas in situ quando essas são limitadas por transporte de massas e/ou transferência de cargas. Essa alteração da taxa de reação é ocasionada por um fenômeno conhecido por magnetoeletrólise, que tem como principal resultante a força de Lorentz, que é o produto vetorial entre o campo magnético e o fluxo de íons gerado durante a eletrólise. O efeito do campo magnético sobre diferentes sistemas eletroquímicos foi comprovado na presença de campo magnético de equipamentos de RMN de baixa e alta resolução. Além do foco dado para a magnetoeletrólise durante o acoplamento EQ-RMN, novas células eletroquímicas foram miniaturizadas para a utilização com a RMN a partir de um método simples, rápido e robusto. Também foram feitas medições de velocimetria utilizando a técnica de imagem por spin eco com as quais foi possível visualizar e quantificar o efeito do campo magnético atuando sobre a reação de eletrodeposição de cobre realizada in situ. Esse trabalho foi o primeiro a utilizar o campo magnético do espectrômetro de RMN para estudar a magnetoeletrólise. Além disso, esse trabalho de doutorado foi o primeiro a utilizar um espectrômetro de RMN de bancada de alta resolução para o acoplamento com a eletroquímica. / Recently it was demonstrated that time domain Magnetic Nuclear Resonance (TD-NMR) is an important analytical technique which can be coupled to electrochemistry (EC-NMR). However, it was demonstrated in this work that NMR is not a passive technique, in other words it affects the electrochemical reactions performed in situ by increasing the reaction rate of mass transport and/or charge transfer limited reactions. This change in the reaction rate is caused by a phenomenon known as magnetoeletrolysis, it has as main resultant the Lorentz force, which is the vectorial product between the magnetic field vector and the ion flow produced during the electrolysis. The magnetic field effect on different electrochemical systems has been shown in the presence of magnetic fields of low and high resolution NMR spectrometers. In addition to the focus given to magnetoelectrolysis during the EC-NMR coupling, novel electrochemical cells were miniaturized for coupling with NMR by using a simple, rapid and robust method. Velocimetry measurements were also made using the spin-echo imaging technique with which it was possible to visualize and quantify the effect of the magnetic field acting on the in situ copper electrodeposition reaction. This work was the first to use the magnetic field of the NMR spectrometer to study magnetoelectrolysis. In addition, this doctoral thesis was the first to use a bench-top high resolution NMR spectrometer for coupling with electrochemistry.

Finite-volume methods have been used for modeling of fluidflows involved in forced convection electrochemical coating androtating spray painting systems. Electrodeposition on a singlecircular cylinder under forced convection for Reynolds numbers10 and 200 was simulated. Comparisons with earlier numericaland theoretical results are presented and it is shown that theunsteady wake that appears for Reynolds numbers greater than 50affects the mass transfer from the surface of the cylinder onlyin an average sense. This result is compared with a heattransfer case, where unsteadiness is much more manifest. Theeffect of application of circulation movement around thecylinder surface was considered, showing that the use ofoptimal values for circulation can create a recirculation zonearound the cylinder and result in a remarkable improvement ofthe deposit uniformity. The magnetoelectrolysis researchdiscipline is presented with focus on magnetic fields uses onmass transfer processes. A classification of the governingdimensionless parameters that control the phenomena isproposed. Application of magnetoelectrolysis on electroplatingprocesses is done for the first time. It is found that the useof an alternating magnetically induced force around thecylinder can result in interesting improvement of quality andproductivity. Application of numerical methods is also studiedin another field of the surface finishing industry, thepainting atomizers. A critical situation of "reverse flow" isanalyzed. Different parameters of this phenomenon are studiedand suggestions for atomizers design are given and tested. <b>Keywords:</b>mass transfer, electrochemical coating, iontransport, forced convection, diffusion, magnetoelectrolysis,electrolyte, limiting current, numerical simulation,finite-volume methods, paint atomization, Coanda effect.

Untersuchung konvektiver Transportprozesse innerhalb einer auf der Lorentz-Kraft basierenden Strömung während der elektrolytischen Abscheidung.

<p>Finite-volume methods have been used for modeling of fluidflows involved in forced convection electrochemical coating androtating spray painting systems. Electrodeposition on a singlecircular cylinder under forced convection for Reynolds numbers10 and 200 was simulated. Comparisons with earlier numericaland theoretical results are presented and it is shown that theunsteady wake that appears for Reynolds numbers greater than 50affects the mass transfer from the surface of the cylinder onlyin an average sense. This result is compared with a heattransfer case, where unsteadiness is much more manifest. Theeffect of application of circulation movement around thecylinder surface was considered, showing that the use ofoptimal values for circulation can create a recirculation zonearound the cylinder and result in a remarkable improvement ofthe deposit uniformity. The magnetoelectrolysis researchdiscipline is presented with focus on magnetic fields uses onmass transfer processes. A classification of the governingdimensionless parameters that control the phenomena isproposed. Application of magnetoelectrolysis on electroplatingprocesses is done for the first time. It is found that the useof an alternating magnetically induced force around thecylinder can result in interesting improvement of quality andproductivity. Application of numerical methods is also studiedin another field of the surface finishing industry, thepainting atomizers. A critical situation of "reverse flow" isanalyzed. Different parameters of this phenomenon are studiedand suggestions for atomizers design are given and tested.</p><p><b>Keywords:</b>mass transfer, electrochemical coating, iontransport, forced convection, diffusion, magnetoelectrolysis,electrolyte, limiting current, numerical simulation,finite-volume methods, paint atomization, Coanda effect.</p>

Untersuchung konvektiver Transportprozesse innerhalb einer auf der Lorentz-Kraft basierenden Strömung während der elektrolytischen Abscheidung.