Nesta dissertação de mestrado se monitorou in situ e ex situ a corrosão de corpos de prova de cobre metálico por ressonância magnética nuclear no domínio do tempo (RMN-DT). A reação ocorreu em solução aquosa de HCl 1 mol L-1 fornecendo íons de cobre Cu2+ como produtos da corrosão. A corrosão foi monitorada com um espectrômetro RMN de bancada, através da correlação entre os tempos de relaxação transversal (T2) adquiridos por meio da sequência de pulso CPMG e a concentração de Cu2+ na solução. As reações foram estudadas usando como corpos de prova placas e cilindros de cobre, na presença e ausência de campo magnético e na presença e ausência de potencial elétrico aplicado. Esses experimentos foram realizados para estudar o efeito das forças magnéticas que podem afetar as reações. Os experimentos de RMN-DT-eletroquímica (RMN-DT-EQ) foram executados usando o corpo de prova em formato de placa de cobre como eletrodo de trabalho, fio espiral de platina como contra eletrodo e um eletrodo de referência de Ag/AgCl (KCl 3 mol L-1). Os experimentos sem potencial aplicado foram realizados usando-se somente os corpos de prova de cobre na solução de HCl. Os resultados mostraram que o campo magnético não alterou o efeito da corrosão quando se aplicou um potencial de 1V. No entanto a reação foi inibida na corrosão sem potencial elétrico aplicado. Esses resultados levaram a hipótese de que, na reação com potencial aplicado, a força de Lorentz foi minimizada pelas forças de gradiente de campo magnético e força de gradiente da concentração de espécies paramagnética. No caso da corrosão sem potencial elétrico aplicado, a hipótese para a inibição da corrosão foi que as forças de gradiente mantiveram os íons de cobre na interface corpo de prova/solução, o que dificultou a reação. O efeito do campo magnético sobre a superfície do cilindro de cobre ao final do processo de corrosão também foram analisados pelas técnicas de microscopia eletrônica de varredura e microscopia de força atômica enquanto que a solução resultante do processo de corrosão teve os valores da concentração de íons Cu2+ quantificados pelas espectroscopias de absorção no ultravioleta e visível e de absorção atômica com chama. / In this Masters dissertation the corrosion of metallic copper samples was monitored in situ and ex situ by time domain nuclear magnetic resonance (TD-NMR). The reaction was performed in an aqueous solution containing HCl (1 mol L-1), where Cu2+ ions were the corrosion products. A benchtop NMR spectrometer was used to monitor the reaction through the correlation between the transverse relaxation times (T2), acquired with the CPMG pulse sequence, and the concentration of Cu2+ in the solution. The reactions were studied using copper plaques and cylinders in the presence and absence of a magnetic field and in the presence and absence of an applied potential. These experiments were performed to study the effect of the magnetic forces which affect reactions with and without an applied potential. The coupling experiments between TD-NMR and electrochemistry (EC-NMR) were performed using a copper plaque as a working electrode, a platinum wire in a spiral shape as a counter electrode and a Ag/AgCl KCl 3 mol L-1 reference electrode. Experiments in which no potential was applied were performed by inserting the copper sample in an HCl aqueous solution. Results showed that the magnetic field didn’t alter the corrosion process when a 1V potential was applied but it did inhibit the corrosion of copper when no potential was applied. These results lead to the hypothesis that, in the reaction with an applied potential, the Lorentz force was minimized by the forces created by the magnetic field and the concentration gradient of the paramagnetic species (Cu2+). In the case of corrosion experiments without an applied potential a possibility is that the forces created by the concentration gradient force copper ions to stay on the interface copper/solution, which hinders the reaction. The effect of the magnetic field on the surface of the copper cylinder at the end of the corrosion process was also analysed by scanning electron microscopy and atomic force microscopy while the concentration of Cu2+ in the solution was measured by UV-vis spectroscopy and flame atomic absorption spectrometry.

Des études expérimentales et théoriques du mécanisme d'électrodéposition de différents revêtements à base de cobalt : le cobalt métallique, les alliages binaires Co-Ni, Co-Cu et l'alliage ternaire Co-Ni-Cu sont menés.Les propriétés de ces films dépendent fortement des paramètres expérimentaux tels que le pH de l'électrolyte, la nature du substrat, etc.. Un champ magnétique jusqu'à 12T est superposé parallèlement à la surface de l'électrode de travail. La convection forcée induite dans l'électrolyte modifie les conditions hydrodynamiques et par conséquent, influe sur la structure et la morphologie des films obtenus. Par ailleurs, la cinétique des processus et la croissance des cristaux sont améliorées dans des conditions magnéto électrochimique. Les microstructures obtenues suite au procédé électrochimique en présence d'un champ magnétique sont caractérisées par différentes propriétés magnétiques trouvant un intérêt potentiel en tant que matériaux magnétiques doux et / ou dur. Dans le cadre du projet ANR COMAGNET, les matériaux subissent ensuite un traitement thermique en présence d'un champ magnétique, des phénomènes de recristallisation et interdiffusion sont mis en évidence induisant des modifications des propriétés magnétiques.Enfin, des calculs de l'énergie d'adsorption de l'atome d'hydrogène et de l'ion H+ sur différentes faces cristallographiques du cobalt sont menés par modélisation DFT (Théorie de la Fonctionnelle de la Densité). Ces résultats, mis en relation avec l'étude expérimentale, montrent le lien entre la formation de certaines structures cristallographiques et l'évolution simultanée de l'hydrogène à la surface de l'électrode pendant l'électrolyse. / The present work is focused on the experimental and theoretical studies of the electrodeposition mechanism of Co-based films, including single Co, binary Co-Ni, Co-Cu and ternary Co-Ni-Cu alloy films. The modeling and structure-properties relationship by a multi-scale approach is investigated.The preliminary study involves determination and optimization of the electrodeposition parameters in order to obtain nanocrystalline films with satisfied surface quality and promising magnetic properties. It is shown that the electrolytic pH, to-be-deposited type of substrate and deposition time are of high importance in the fabrication of nanoscale materials. Among them, the electrolytic pH is the one, which has the greatest effect on the structure formation. The film growth as well as its quality can be strongly affected by a superimposition of an external magnetic field. The electrodeposition process was carried out under parallel to the electrode surface magnetic fields with magnets strength up to 12T. The results reveal that the induced forced convection in the electrolyte changes the hydrodynamic conditions and thus, affects the structure and morphology of the obtained films. Furthermore, the process kinetics and crystal growth are enhanced under magnetic electrodeposition conditions.Microstructure formed by the electrochemical processing is characterized by some significant magnetic properties, which may result in soft and/or hard magnetic materials, depending on their application approach. Additionally, the microstructure of films has been improved by the magnetic annealing treatment. Thus, the recrystallization and interdiffusion phenomena are observed, and modification of the magnetic properties is induced.Considering the electrodeposition process carried out in aqueous solutions the secondary process, which is the hydrogen evolution reaction (HER), needs to be taken into account. The theoretical study based on the tools of quantum mechanics (QM) and density functional theory (DFT) is used to determine the adsorption energies of hydrogen. In this work, the calculation results are related with the experimental study and may explain the structure formation assisted by the simultaneous evolution of hydrogen at the electrode surface.

Nesta dissertação de mestrado se monitorou in situ e ex situ a corrosão de corpos de prova de cobre metálico por ressonância magnética nuclear no domínio do tempo (RMN-DT). A reação ocorreu em solução aquosa de HCl 1 mol L-1 fornecendo íons de cobre Cu2+ como produtos da corrosão. A corrosão foi monitorada com um espectrômetro RMN de bancada, através da correlação entre os tempos de relaxação transversal (T2) adquiridos por meio da sequência de pulso CPMG e a concentração de Cu2+ na solução. As reações foram estudadas usando como corpos de prova placas e cilindros de cobre, na presença e ausência de campo magnético e na presença e ausência de potencial elétrico aplicado. Esses experimentos foram realizados para estudar o efeito das forças magnéticas que podem afetar as reações. Os experimentos de RMN-DT-eletroquímica (RMN-DT-EQ) foram executados usando o corpo de prova em formato de placa de cobre como eletrodo de trabalho, fio espiral de platina como contra eletrodo e um eletrodo de referência de Ag/AgCl (KCl 3 mol L-1). Os experimentos sem potencial aplicado foram realizados usando-se somente os corpos de prova de cobre na solução de HCl. Os resultados mostraram que o campo magnético não alterou o efeito da corrosão quando se aplicou um potencial de 1V. No entanto a reação foi inibida na corrosão sem potencial elétrico aplicado. Esses resultados levaram a hipótese de que, na reação com potencial aplicado, a força de Lorentz foi minimizada pelas forças de gradiente de campo magnético e força de gradiente da concentração de espécies paramagnética. No caso da corrosão sem potencial elétrico aplicado, a hipótese para a inibição da corrosão foi que as forças de gradiente mantiveram os íons de cobre na interface corpo de prova/solução, o que dificultou a reação. O efeito do campo magnético sobre a superfície do cilindro de cobre ao final do processo de corrosão também foram analisados pelas técnicas de microscopia eletrônica de varredura e microscopia de força atômica enquanto que a solução resultante do processo de corrosão teve os valores da concentração de íons Cu2+ quantificados pelas espectroscopias de absorção no ultravioleta e visível e de absorção atômica com chama. / In this Masters dissertation the corrosion of metallic copper samples was monitored in situ and ex situ by time domain nuclear magnetic resonance (TD-NMR). The reaction was performed in an aqueous solution containing HCl (1 mol L-1), where Cu2+ ions were the corrosion products. A benchtop NMR spectrometer was used to monitor the reaction through the correlation between the transverse relaxation times (T2), acquired with the CPMG pulse sequence, and the concentration of Cu2+ in the solution. The reactions were studied using copper plaques and cylinders in the presence and absence of a magnetic field and in the presence and absence of an applied potential. These experiments were performed to study the effect of the magnetic forces which affect reactions with and without an applied potential. The coupling experiments between TD-NMR and electrochemistry (EC-NMR) were performed using a copper plaque as a working electrode, a platinum wire in a spiral shape as a counter electrode and a Ag/AgCl KCl 3 mol L-1 reference electrode. Experiments in which no potential was applied were performed by inserting the copper sample in an HCl aqueous solution. Results showed that the magnetic field didn’t alter the corrosion process when a 1V potential was applied but it did inhibit the corrosion of copper when no potential was applied. These results lead to the hypothesis that, in the reaction with an applied potential, the Lorentz force was minimized by the forces created by the magnetic field and the concentration gradient of the paramagnetic species (Cu2+). In the case of corrosion experiments without an applied potential a possibility is that the forces created by the concentration gradient force copper ions to stay on the interface copper/solution, which hinders the reaction. The effect of the magnetic field on the surface of the copper cylinder at the end of the corrosion process was also analysed by scanning electron microscopy and atomic force microscopy while the concentration of Cu2+ in the solution was measured by UV-vis spectroscopy and flame atomic absorption spectrometry.

Spin interactions play a key role in the function of molecular materials from naturally occurring biological complexes to synthetic materials for light-harvesting and light-emission. This thesis investigates the spin interactions of spin-1 triplet excitons formed by singlet fission. Singlet fission produces two triplet excitons from one light-induced singlet state and holds promise to enable solar energy generation beyond traditional efficiency limits. As the lifetime of triplet pairs depends sensitively on their spin degree of freedom, in this thesis we deploy spin-sensitive techniques to understand the interactions and evolution of triplet pairs. After introducing the relevant theoretical and experimental background underlying singlet fission and the role of spin, we describe the first observation of strongly exchange coupled, high-spin triplet-pair states ($S=2$) in a solid-state organic semiconductor and show that the singlet fission process allows for the formation of long-lived, strongly coupled spin-two states. We then describe the development and use of photoluminescence-detected avoided level-crossings in applied magnetic fields to quantify the strength of exchange coupling and identify specific optical signatures of exchange-coupled triplet pairs. Using high magnetic fields ($\leq\mbox{60 T}$) we isolate and measure the exchange coupling and optical signatures of multiple distinct triplet pairs in the same material. Finally, we probe the mechanisms of formation and decay of spin polarization from triplet pair states using pulsed spin resonance. The measured dynamics are consistent with polarization driven by fluctuations in exchange coupling between pairs and spin-orbit mediated decay of triplet excitons to the ground state. The combined measurements of the spin parameters and polarization dynamics of triplet pairs from ns to ms timescales provides a quantitative picture of the spin states generated by singlet fission.

This thesis investigates how magnetographic data may be used to study the longterm behaviour of the magnetic field distribution across the surface of the sun.

In this thesis the following problems are studied: 1-Relativistic self-focusing and channelling of intense laser pulses have been studied in underdense plasma using 2D PIC simulations, for different laser powers and plasma densities. Analytical solutions for the stationary evacuated channels have been recovered in PIC simulations. It is shown that otherwise stable channels can accelerate electrons due to surface waves on the walls of the channels. Relativistic filaments with finite electron density are unstable to transverse modulations which lead in the nonlinear stage to the break-up of laser pulses into independent filaments. 2-Although 3D simulations are limited, they are more realistic. Azimuthal stability of the laser pulses in interaction with underdense plasma can only be studied in 3D geometry. Relativistic self-focusing and channelling of intense laser pulses have been studied in underdense plasma using 3D PIC simulations, for different laser powers and plasma densities. Analytical solutions for the stationary evacuated channels and ring structure have been recovered in PIC simulations. The stability of ring structure due to azimuthal perturbations has been studied both in theory and in simulations. The gain length of such instability is smaller at higher densities $(>0.1n_{cr})$. It is shown that the azimuthal perturbation can break up the azimuthal symmetry of the laser pulse. 3-Working with circularly polarized laser pulses, gave us a motivation to study Inverse Faraday Effect in interaction of circularly polarized laser pulses with plasma. Axial magnetic field generation by intense circularly polarized laser beams in underdense plasmas has been studied with 3D particle-in-cell (PIC) simulations and by means of theoretical analysis. The source of azimuthal nonlinear currents and of the axial magnetic field depends on the transverse inhomogeneities of the electron density and laser intensity. The fields reach maximum strength of several tens of MG for laser pulses undergoing relativistic self-focusing and channelling in moderately relativistic regime. 4-Electron wakefield acceleration was studied in support of the experiment which was carried on using 7 TW laser beam at Canadian Advanced Laser Light source facility. 2D simulations were performed to study this problem. The energy the electrons gained in the process was peaked at 20-30 Mev close to the experimental results.

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This study uses the PIC (particle-in-cell) method to simulate unsteady three-dimensional behavior in argon plasma under low pressure , low density between two plates. Plasma has been widely used in materials processing, film manufacturing, nuclear fusion , light source , etc. It is therefore important to study Plasma behavior . This model ignores secondary electron emission , recombination between ions and electrons and assumes a uniform distribution of the neutrals having velocity of a Maxwellian distribution. The lower plate in subject to a biased voltage and magnetic field. The result show the effects of a biased voltage in density and velocity of the ion and electron with the low plate.