Au cours de cette thèse, nous nous intéressons à deux applications nécessitant des sources laser impulsionnelles : l'imagerie active et l'usinage laser. L'imagerie active nécessite des sources laser efficaces émettant dans la gamme de sécurité oculaire (entre 1,5 µm et 1,7 µm) à des cadence de l'ordre du kilohertz et produisant des énergies par impulsion de plusieurs millijoules. Les sources efficaces émettant dans la gamme de sécurité oculaire utilisent l'ion erbium. Cependant la structure électronique complexe de l'ion erbium entraîne de nombreux effets parasites qui limitent fortement l'énergie accessible lors d'un fonctionnement à haute cadence. Pour diminuer l'influence de ces effets parasites nous avons utilisé le concept de fibres cristallines dans le cadre d'une collaboration entre le Laboratoire Charles Fabry et l'entreprise Fibercryst. La géométrie des fibres cristallines, combinant les propriétés des cristaux massifs et les avantages des fibres en verre nous a permis de dépasser les limites des sources actuelles. L'usinage de matériaux requière des sources laser impulsionnelles émettant dans le proche infrarouge (1 µm) et alliant forte énergie, forte puissance crête et forte puissance moyenne. Pour réaliser de telles sources, il est nécessaire d'utiliser des milieux à gain permettant de limiter les phénomènes thermiques et les effets induit par la puissance crête (effets non-linéaires). Pour cela nous avons utilisé à nouveau le concept de fibre cristalline, dopée cette fois ci par l'ion néodyme. Ces fibres cristallines ont été utilisées comme amplificateur de puissance pour amplifier des micro-lasers fonctionnant à haute cadence (de 1 à 100 kHz) et produisant des impulsions courtes (< 1 ns). / In this thesis we investigate two different pulsed laser sources for two specific applications : remote sensing and material processing. On the first part, remote sensing require efficient laser source emitting in the eye-safe range (1.5 – 1.7 µm) and producing several millijoules per pulse at a few kilohertz. Efficient eye-safe laser sources use erbium doped gain media. Nevertheless, the complex electronic structure of the erbium ion leads to several parasitic effects which limit the energy at high repetition rate. In order to minimize those effects we have used the concept of single crystal fibers developed in a close collaboration between the Laboratoire Charles Fabry and the company Fibercryst. The specific geometry of single crystal fibers, merging the advantages of bulk crystals and optical fibers, allows us to overcome limits of current laser sources. On the other part, material processing require near-infrared pulsed laser sources (1 µm) with high pulse energy, high average power and high peak power. In such laser sources, the amplifying medium must be design to avoid both thermal effects and non liner effects. For this purpose, we used neodymium doped single crystal fibers as power amplifier to enhance the performance of passively q-switched microlasers operating at high repetition rate (1 to 100 kHz) and emitting short pulses (< 1 ns).

No presente trabalho foram estudados os espectros de RPE de um radical nitróxido, 4-hidroxi-2,2,6,6-tetrametilpiperidina-l-oxil (TEMPOL, 11), introduzido como impureza em uma matriz diamagnética, 4-hidroxi-2,2,6,6-tetrametilpiperidina (I), de estrutura conhecida. O uso do radical deuterado, 4-hidroxi-2,2,6,6 -tetrametilpiperidina-d17-l-oxil (PD-TEMPOL, 111) mostrou um aumento considerável na resolução dos espectros para a maioria das orientações do campo magnético. A interação do grupo paramagnético N-O com os prótons vizinhos foram estudadas e os tensores superhiperfinos de dois prótons fortemente acoplados foram determinados. Um desses prótons forma ponte de hidrogênio com o grupo N-O e a distância estimada é 2,09ª&#176. Os autovalores do tensor são: -5,2; 5,4 e -5,1 gauss. O segundo próton está mais distanciado do radical e provavelmente não forma ponte com o radical. Os valores nas direções principais são: 2,0; -1,7;e -2,7 gauss. Com a finalidade de estudar o envolvimento dos prótons na relação eletrônica dos radicais foram estimados os tempos de relaxação T1 e T2 no intervalo de temperatura de -160 a 25&#176C através do método de saturação continua. Foram obtidos os valores em diversas orientações para os radicais protonado (II) e deuterado - (III) para compará-los. Os valores de T2 obtidos são praticamente constante no intervalo de temperatura onde foram medidos e sistematicamente são maiores para o radical deuterado. O tempo de relaxação spin-rede, T1 é dependente da orientação para ambos os radicais. Em geral é obtida urna dependência linear de T1-1 versus T que foi explicada considerando um mecanismo de relaxação por tunelamento dos protons vizinhos entre dois poços de potenciais. Para o radical protonado é observada uma descontinuidade na curva de T1-1 versu T na região de -60&#176C; para o radical deuterado - isto é observado somente para algumas orientações. Este comporta mento poderia ser explicado como devido o congelamento da vibração das pontes de hidrogênio em torno desta temperatura. Um alagamento das linhas de RPE é observado para muitas orientações a partir de -100D&#176C que foi interpretado como devido o congelamento da rotação dos grupos metilas, do radical no caso (II) e da matriz no caso (I) / In the present work the ESR spectra of a nitroxide radical, 4-hydroxi-2,2,6,6-tetramethylpiperidine-l-oxyl (TANOL, lI), introduced as impurity in a diamagnetic host, 4-hydroxi-2, 2,6,6-tetramethylpiperidine (1), of know structure, has been investigated. The use of the deuterated radical, 4-hydroxi-2,2, 6,6-tetramethylpiperidine-d17-1-oxyl (PD-TANOL, 111) showed an improved resolution in the ESR spectra for most orientations of the magnetic field. The interactions of protons in the neighbourhood of the paramagnetic group N-O were studied and the superhyperfine tensors for the two strongly compled protons were determined one of these protons is hydrogen bonded to the N-O and the distance is estimated to be 2,09ª&#176. The superhyperfine tensor has principal values -5.2; +5.4; -5.1 gauss. The second proton is further away from the electron and probably is not hydrogen bonded. The principal values for this proton are 2.0; -1.7 and -2,7 gauss. In order to study the involvment of the protons in the electronic relaxation of the radicaIs, the relaxation times T1 and T2 were estimated in the temperature range -160&#176C 25&#176C for many orientations and comparing data for the protonated and deuterated radicaIs II and III, using the continuous wave saturation method. It is shown that the relaxation time T2 is practically constant in the temperature range studied and that it is sistematically greater for the deuterated radical implying narrower lines. The spin-lattice relaxation time TI is dependent upon the orientation of the magnetic field for both radicaIs. In general a linear temperature dependence of T1-1 versus T is obtained and a mechanism of tunelling of protons between close potential walls in used to explain this behavior. In the case of the protonated radical for many orientations of the magnetic field a break is observed in the T1-1 versus T curve around -60&#176C for the deuterated radical this is observed only for fewer orientations. This behaviour could be explained as due to the freezing of hydrogen bonds vibration near this temperature. For many orientations it is also observed that below -100&#176C a broadening of the ESR lines occurs which is probably re1ated to the freezing of the rotations of the methyl groups of the radical, in the case of II, and of the hast I in the case of radical III

Foram determinadas por meio de difração de raios x as estruturas de cinco compostos azaçúcares. Foram estudadas as interações envolvidas na formação das redes cristalinas em cada um dos compostos analisados. Foi encontrado que nos compostos azaçúcares estudados, as interações principais são as ligações de hidrogênio do tipo C-H···O e C-H···&pi;. Este comportamento foi verificado usando ferramentas como as superfícies de Hirshfeld e os gráficos de impressão digital. Realizou-se o estudo de docking molecular dos compostos azaçúcares com respeito à enzima purina nucleosídeo fosforilase (PNP). Foi determinado que estes compostos têm a capacidade de entrar no sitio ativo da PNP. O estudo das interações dos cinco azaçúcares com a PNP mostrou que estes compostos apresentam as mesmas interações presentes em inibidores da PNP já reportados. / Structures of five azasugars were determined by X-ray diffraction. Crystal network interactions were analyzed for each compound. The main interaction found for these azasugar compounds is hydrogen bond as C-H···O e C-H···&pi;. This behavior was verified by tools as Hirshfeld surface and 2D finger print plots. Molecular docking was performed for azasugar compounds in Purine Nucleoside phosphorylase (PNP). This study confirmed that these compounds are available to enter to the PNP active site. Interactions exploration showed the same interactions for the azasugars studied and for already known PNP inhibitors.

As estruturas cristalinas dos complexos Ln(ClO4)3.6[PONH2(C6H5)2] onde Ln=Eu, La, Cu[NH2(CH3)2CCO2]2, NiBr2.4[AsO(C6H5)3].8H2O (verde) e NiBr2.4[AsO(C6H5)3].1,5(CH3C6H5).H2O (alaranjado) bem como do ligante PONH2(C6H5)2 foram determinadas por difração de raios-X. Os complexos envolvendo íons lantanídeos refinaram a fatores R finais de R(Eu)=0,125, e R(La)=0,133 e foram encontradas a seguintes características principais: a) o sistema cristalino é cúbico; b) a coordenação do cátion é feita por seis átomos de oxigênio dos ligantes em configuração octaédrica (Eu) e antiprismática trigonal (La) com as terras raras em posições de alta simetria (23 para Eu e 3 para La); c) o restante das estruturas apresentam diferentes graus de desordem. À luz da sua configuração geométrica, a presença de uma forte banda 5Do-7F2 no espectro de fluorescência do complexo de Eu, proibida por considerações de simetria, é explicada como decorrente de acoplamentos vibrônicos. O desdobramento da linha &#965;P=0 do espectro de infravermelho do coplxo de La é atribuído à presença de grupos P=0 não equivalentemente ligados a terra rara devido à desordem desta. O composto envolvendo o íon Cu(II) (fator R final 0,053) cristaliza no sistema monoclínico com os complexos se empacotando em camadas paralelas ao plano cristalino (100) com redes de pontes de H intracamada e com francas interações entre camadas consecutivas, o que explica o comportamento magnético quasi-bidimensional observado nestes cristais. O complexo de Ni(II) de coloração verde (fator R final 0,039) apresenta o íon metálico sobre um centro de simetria coordenado por seis moléculas de água numa conformação octaédrica distorcida, as quais estão ligadas aos grupos tfaso[AsO(C6H5)3] e íons brometo por fatores pontes de H. No complexo de coloração alaranjada (fator R final 0,087) o cátion está pentacoordenado com os quatro oxigênios dos ligantes tfaso formando a base de uma pirâmide quadrangular e um ânion Br- ocupando a quinta posição. Como uma conseqüência da resolução e refinamento da estrutura do complexo de Eu, a estrutura cristalina do ligante PONH2(C6H5) puro foi também determinada e refinada a um fator R de 0,033. / The crystal structure of the complexes Ln(ClO4)3.6[PONH2(C6H5)2] where Ln=Eu, La, Cu[NH2(CH3)2CCO2]2, NiBr2.4[AsO(C6H5)3].8H2O (green), NiBr2.4[AsO(C6H5)3.1,5(CH3C6H5).H2O (orange) and of the ligand PONH2(C6H5)2 have been determined by X-ray diffraction. The complexes involving lanthanide ions refined to final R factors of R(Eu)=0.125 and R(La)=0.133 and the following main features were found: a) the crystal system is cubic; b) the cation is coordinated to six ligand oxygens in octahedral earths on position of high symmetry (23 for Eu and 3 for La); c) the rest of the structures shows different degrees of disorder. In the light of the geometrical configuration, the occurrence of a strong band 5Do-7F2 in the fluorescence spectrum of the Eu complex, forbidden on symmetry grounds, is interpreted as a consequence of vibronic coupling. A splitting of the infrared &#965;P=0 band in the La complex is attributed to the presence of P=0 goups non-equivalently bonded to the rare earth due to the disorder of this atom. The compound involving the Cu(II) ion (final R factor of 0.053) crystallizes in the monoclinic system with the complexes packed in layers parallel to the (100) crystal plane, with intralayer nets of H bonds and weak interactions between consecutive layers, which explains the quasi two-dimensional magnetic behavior observed in these crystals. In the green Ni(II) complex (final R=0.039), the metallic ion is sited on a center of symmetry and is octahedrally coordinated to six water molecules which are hydrogen bonded to the tfaso[AsO(C6H5)3] groups and the bromide ions. In the orange complex (final R=0.087) the cation is pentacoordinated with the four oxygens of the tpas ligands forming the basis of a quadrangular pyramid and one Br- anion in the fifth position. As a by product in the solution and refinement of the Eu complex structure, the crystal structure of the pure ligand PONH2(C6H5) was also determined and refined to a R-factor of 0.033.

Estudou-se neste trabalho a preparação de LiLa(WO4)2:TR3+ (LLW:TR) nas formas de fibras monocristalinas (micro-pulling-down) e de microcristais pó cerâmico (método dos precursores poliméricos). No que se refere às fibras: a taxa de puxamento no crescimento de LiLa(1-x)Eux(WO4)2 para 0&le;x&le;1 é influenciada pela diferença de raio iônico do Li e das TR; a estrutura tetragonal da scheelita descreve as composições 0&le;x&le;1; a incorporação do Eu gera distorções na estrutura sem reduzir a simetria local do íon; uma queda de luminescência para x>0,20 é observada; e as estruturas para 0&le;x&le;1 foram modeladas através de simulação atomística com bastante precisão. No que se refere aos microcristais: o efeito do controle de pH na preparação de LLW:Nd 1,0 mol% foi avaliado; obteve-se aglomerados de morfologia irregular e com tamanhos médios entre 22-48 &mu;m, cujo aumento é maior em função da temperatura do que do tempo de calcinação. No que se refere à construção experimental do diagrama de fases do sistema xLi2W2O7-(1-x)La2W2O9: confirmou-se que o LLW (formado numa região de homogeneidade de 0,48&le;x&le;0,55) se decompõe peritéticamente a 1000°C; a dopagem por TR influencia sua fusão; dados do crescimento, de DTA e de DRX de fibras de LLW, crescidas com composições baseadas neste diagrama, corroboram o mesmo. O processo de obtenção de fibras foi otimizado, com um excesso mínimo de 1,5 mol% de Li2W2O7. / In this work, the preparation and characterization of LiLa(WO4)2:RE3+ (LLW:RE) microcrystals as single crystal fibers (micro-pulling-down technique) and as powder (polymerizable complex method) was studied. Concerning the fibers: the pulling rate for LiLa(1-x)Eux(WO4)2 (0&le;x&le;1) is influenced by the difference between the constituents ionic radii; the tetragonal scheelite-like structure describes all compositions; the Eu incorporation distorts the LLW lattice without reducing the dopant local symmetry; a luminescence quenching for x>0.20 was observed; and the structure modelling for 0&le;x&le;1 by atomistic simulation was carried out with good precision. Concerning the powder microcrystals: the pH control effect on the preparation of Nd:LLW 1,0 mol% was evaluated; they presented irregular morphology and agglomerates with average sizes of 22-48 &mu;m with higher increase for the calcination temperature than for the time. Concerning the experimental construction of the phase diagram of the system xLi2W2O7-(1-x)La2W2O9: it was confirmed that the LLW (formed in the a homogeneity region of 0.48&le;x&le;0.55) decomposes peritectically at 1000°C; RE-doping influences the LLW melting; growth, DTA and XRD data of LLW fibers (grown from the compositions based on this diagram) confirmed it. The process of fiber obtaining was optimized with a minimum excess of 1.5 mol% of Li2W2O7.

In dieser Arbeit wurde die Ausgangsverbindung der eisenbasierten Supraleiter, LaFeAsO, durch die Synthese und Charakterisierung von poly- und einkristallinen Proben untersucht. Supraleitung kann in den eisenbasierten Supraleitern durch Elektronen- oder Lochdotierung hervorgerufen werden. Die Substitution von Eisen durch Mangan, formal eine Lochdotierung, hat hingegen einen destruktiven Effekt auf die Supraleitung. Dieser ist bei optimal fluordotiertem LaFeAs(O,F) um Größenordnungen stärker ausgeprägt als bei Nd- oder Sm-FeAs(O,F). Indem Lanthan partiell durch das kleinere Yttrium substituiert wurde, konnte gezeigt werden, dass diese unterschiedlich starke Mangantoleranz durch die Unterschiede im Seltenerdmetall-Ionenradius bedingt ist. Weiterhin finden sich Anzeichen, dass die Unterdrückung der Supraleitung durch Mangan mit Elektronenlokalisierung korreliert ist. Das Fehlen von großen dreidimensionalen Einkristallen der SEFeAsO-Verbindungsklasse stellt ein großes Hindernis in der Erforschung der elektronischen Eigenschaften der eisenbasierten Supraleiter dar. Im Rahmen dieser Arbeit konnte gezeigt werden, dass das Verfahren der Festkörper-Einkristallzüchtung ein geeignetes Mittel darstellt, um große, facettierte SEFeAsO-Einkristalle mit ausgeprägtem Wachstum in c-Richtung zu erhalten. Mit diesem neu entwickelten Einkristallzüchtungsverfahren konnte ein aktualisiertes Phasendiagramm von La(Fe,Co)AsO erstellt werden. Die Substitution von Eisen durch Cobalt entspricht einer Elektronendotierung und führt zu Supraleitung mit einer maximalen Sprungtemperatur von 12 K. Die Ausgangsverbindung LaFeAsO zeigt bei etwa 156 K einen strukturellen Phasenübergang von einer tetragonalen zu einer orthorhombischen Struktur, weiterhin tritt unterhalb von etwa 138 K eine Spindichtewelle auf. In Einklang mit dem bekannten Phasendiagramm werden mit Cobaltdotierung die beiden Übergänge unterdrückt, mit höheren Cobaltkonzentrationen kommt es zu Supraleitung. Anders als beim bekannten Phasendiagramm kann eine deutliche Aufspaltung zwischen magnetischem und strukturellen Übergang bei kleinen Cobaltkonzentrationen beobachtet werden. Außerdem findet sich eine Region der Koexistenz zwischen Supraleitung und Spindichtewelle. Bisher konnte ein solcher Zustand im SE(Fe,Co)AsO-System nicht beobachtet werden.

Une large investigation sur l’influence de plusieurs défauts métallurgiques sur les processus de diffusion et de piégeage de l’hydrogène a été conduite sur le nickel. Ce travail a été réalisé selon deux orientations scientifiques. Une première approche a consisté à évaluer l’impact des défauts intrinsèques et plus particulièrement les joints de grains et les dislocations géométriquement nécessaires sur les modes de transport et de ségrégation de l’hydrogène. Le couplage de caractérisations microstructurales avec les essais de perméation électrochimiques et de thermo-désorption a permis d’établir que les joints de grains présentant une structure ordonnée appelés « spéciaux » représentent des zones privilégiées à la ségrégation de l’hydrogène. Une seconde catégorie de joints de grains dits « généraux » ou « random » présentant un excès de volume important constituent des promoteurs à la diffusion de l’hydrogène. Ces derniers sont la principale source des phénomènes de courts-circuits de diffusion relatés dans les matériaux cubiques à faces centrées. La seconde approche de cette étude a consisté en l’étude de l’interaction de l’hydrogène avec les hétérogénéités de déformation plastique. Les essais de perméation électrochimique réalisés sur des microstructures obtenues par déformation ont montré qu’en traction monotone, les cellules équiaxes et les murs de dislocations représentent des pièges pour l’hydrogène. Celles-ci ralentissent son transport. Ce dernier est essentiellement assuré par le mécanisme de diffusion interstitielle. Par ailleurs, pour la microstructure de déformation résultant de l’essai en fatigue, une accélération de la diffusivité de l’hydrogène a été enregistrée ce qui suggère qu’un phénomène comparable au court-circuit de diffusion intervient dans le transport de l’hydrogène. Concernant les deux approches, les résultats obtenus suggèrent une contribution de l’hydrogène dans la formation de lacunes. / A thorough investigation on the influence of several metallurgical defects on the hydrogen diffusion and trapping was conducted on nickel. This work was conducted towards two scientific orientations. A first approach was to assess the impact of intrinsic defects, especially grain boundaries and geometrically necessary dislocations on the hydrogen transport and segregation mechanisms. Combining microstructural characterizations with electrochemical permeation tests and thermal desorption spectroscopy, it has established that the grain boundaries with ordered structure called "special grain boundaries" are preferential areas for hydrogen segregation. On the other hand, a second category of grain boundaries called "general" or "random" with high free volume and disordered structure are promoters for hydrogen diffusion, and they represent the main sources of the phenomena short-circuit diffusion reported in the face-centered cubic materials. The second approach of this work consisted in the study of the interaction of hydrogen with the plastic deformation heterogeneities. The electrochemical permeation tests performed on microstructures obtained by deformation showed that for the traction monotonous, the equiaxed cells and walls of dislocations are the potential traps for hydrogen and they slow its transport, this latter is mainly provided by the interstitial diffusion mechanism. In addition, for fatigue microstructure, rapid diffusivity of hydrogen was recorded, and suggesting that a phenomenon similar to short-circuit diffusion is involved in the transport of hydrogen. On two approaches, the results suggest a contribution of hydrogen in the formation of vacancies

Estudou-se neste trabalho a preparação de LiLa(WO4)2:TR3+ (LLW:TR) nas formas de fibras monocristalinas (micro-pulling-down) e de microcristais pó cerâmico (método dos precursores poliméricos). No que se refere às fibras: a taxa de puxamento no crescimento de LiLa(1-x)Eux(WO4)2 para 0&le;x&le;1 é influenciada pela diferença de raio iônico do Li e das TR; a estrutura tetragonal da scheelita descreve as composições 0&le;x&le;1; a incorporação do Eu gera distorções na estrutura sem reduzir a simetria local do íon; uma queda de luminescência para x>0,20 é observada; e as estruturas para 0&le;x&le;1 foram modeladas através de simulação atomística com bastante precisão. No que se refere aos microcristais: o efeito do controle de pH na preparação de LLW:Nd 1,0 mol% foi avaliado; obteve-se aglomerados de morfologia irregular e com tamanhos médios entre 22-48 &mu;m, cujo aumento é maior em função da temperatura do que do tempo de calcinação. No que se refere à construção experimental do diagrama de fases do sistema xLi2W2O7-(1-x)La2W2O9: confirmou-se que o LLW (formado numa região de homogeneidade de 0,48&le;x&le;0,55) se decompõe peritéticamente a 1000°C; a dopagem por TR influencia sua fusão; dados do crescimento, de DTA e de DRX de fibras de LLW, crescidas com composições baseadas neste diagrama, corroboram o mesmo. O processo de obtenção de fibras foi otimizado, com um excesso mínimo de 1,5 mol% de Li2W2O7. / In this work, the preparation and characterization of LiLa(WO4)2:RE3+ (LLW:RE) microcrystals as single crystal fibers (micro-pulling-down technique) and as powder (polymerizable complex method) was studied. Concerning the fibers: the pulling rate for LiLa(1-x)Eux(WO4)2 (0&le;x&le;1) is influenced by the difference between the constituents ionic radii; the tetragonal scheelite-like structure describes all compositions; the Eu incorporation distorts the LLW lattice without reducing the dopant local symmetry; a luminescence quenching for x>0.20 was observed; and the structure modelling for 0&le;x&le;1 by atomistic simulation was carried out with good precision. Concerning the powder microcrystals: the pH control effect on the preparation of Nd:LLW 1,0 mol% was evaluated; they presented irregular morphology and agglomerates with average sizes of 22-48 &mu;m with higher increase for the calcination temperature than for the time. Concerning the experimental construction of the phase diagram of the system xLi2W2O7-(1-x)La2W2O9: it was confirmed that the LLW (formed in the a homogeneity region of 0.48&le;x&le;0.55) decomposes peritectically at 1000°C; RE-doping influences the LLW melting; growth, DTA and XRD data of LLW fibers (grown from the compositions based on this diagram) confirmed it. The process of fiber obtaining was optimized with a minimum excess of 1.5 mol% of Li2W2O7.

SiC is a hard man-made material and has emerged as an excellent material for a wide range of applications which are exposed to extreme conditions such as high temperatures and harsh chemical environments. These applications range from SiC being used as an abrasive, to a refractory material, to a semiconductor material for high power and high frequency electronic devices. The properties of the material for each application is different, with the semiconductor grade material for electronic devices being the most refined. SiC, with its excellent thermal properties and high resistance to harsh chemical environments, lends itself to being an ideal support for catalyst systems. Various characterisation & analysis techniques such as Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy (EDS), X-ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR) and Gas Chromatography (GC) are used in this thesis to investigate the suitability of single crystal SiC for high temperature catalytic systems. Low temperature oxidation of methane was used to investigate the catalytic activity of: Porous and standard 4H-SiC with and without Pd Porous and Standard 6H-SiC with and without Pd. Nanocrystalline Beta-SiC powder with and without Pd. Part of the samples were impregnated with Pd using Palladium Nitrate (Pd (NO3)2) which is a common precursor for Pd. Activation treatments which were investigated were oxidation and reduction. Oxidation was generally better in activating the catalyst, as was expected, since the PdO phase is known to be more active in oxidising methane. A mixed set of Pd and PdO were observed by SEM and EDS which were the main characterisation techniques used to analyze the structure of the catalysts before and after the reaction. The Beta-SiC showed by far the best activity which could be attributed to the micro-crystalline powder format in which it was used, where as all other catalysts studied here were derived from crushed wafer pieces. Type II porous 4H-SiC was another of the samples which registered impressive results, vis-à-vis catalytic activity.

Le contenu de ce rapport vise à résumer l'ensemble des activités de recherche que j'ai menées durant ces dernières 10 années ainsi que les perspectives et les projets pour les années à venir. Le dossier se scinde en plusieurs parties. La première partie de mon rapport expose mes travaux scientifiques effectués. Leur contenu s'intègre dans le cadre de l'électronique de spin et repose essentiellement sur l'étude du magnétisme et du transport polarisé en spin dans des systèmes de jonctions tunnel magnétiques. Ce travail m'a amené à élaborer des systèmes type jonctions tunnel magnétiques et à étudier la corrélation entre leurs propriétés magnétiques et leurs propriétés de transport polarisé en spin à des échelles macroscopiques et microscopiques. Les travaux sur les JTMs epitaxiees ont démontré qu'une physique au-delà du modèle des électrons libres gouverne le transport électronique dans les systèmes cristallins. La mise en évidence directe de la corrélation entre la structure électronique et chimique de l'interface métal oxyde et le transport tunnel polarisé en spin montre un fort potentiel pour le contrôle des caractéristiques magnéto-électriques de dispositifs spintroniques. Les études actuelles sur les effets de cohérence électronique dans des structures epitaxiees à multiples barrières tunnel et le contrôle de propriétés magnétiques par des courants de spin hors-équilibre ouvrent la voie vers une nouvelle physique et de nouvelles applications. D'une part, la complexité des mécanismes de transport dans les systèmes épitaxies a généré un important investissement personnel dans les techniques de calcul de structure électronique ab-initio ainsi que dans la création des outils de modélisation des propriétés magnétiques et de transport tunnel. D'autre part, du point de vue expérimental, l'ensemble des techniques que j'ai utilise regroupe l' épitaxie par jets moléculaires et la pulvérisation cathodique en ce qui concerne l' élaboration des échantillons, ainsi que des méthodes de caractérisation in situ (diffraction d' électrons RHEED, spectroscopie Auger) ou ex-situ (AFM pour la structure, MFM pour le micro magnétisme, VSM et e et Kerr pour le magnétisme macroscopique, et des diverses techniques de mesure électriques sous champ pour le magneto-transport). Une deuxième partie du rapport résume des résultats récents obtenus sur des systèmes tunnel complexes. Une autre partie du rapport résumé mes objectifs et projets de recherche pour les années à venir. Ils consistent a poursuivre les études de magnétisme et transport polarise en spin dans des hétéro-structures complexes de faible dimensionnalité avec un accent tout particulier vers le développement d'un axe théorique orienté vers la modélisation du transport électronique par des techniques type ab-initio. Dans un rapport annexe , je présente mon Curriculum Vitae, ma production scientifique, et un résumé des activités que j'ai effectuées dans l'enseignement, l'administration de la recherche, la participation a des contrats et des responsabilités collectives.