Le but de cette thèse est l’étude du système électrochimique or-cuivre en milieucyanure, la finalité étant la réalisation de microballons en or-cuivre de 800 μm de diamètre etd’épaisseur 20 à 40 μm. La composition, la microstructure ainsi que la rugosité doivent êtreparfaitement maîtrisées. La technique utilisée pour réaliser ce type d’objet est le dépôtélectrolytique en milieu cyanure.Dans un premier temps, l’influence des principaux paramètres d’élaboration(température de l’électrolyte, agitation, etc.) a été étudiée. Cette première étude a permis deréaliser des alliages d’or-cuivre de 5 μm d’épaisseur sur substrat plan de différentescompositions. En effet, il a été montré que la teneur en cuivre des dépôts augmente lorsque lepotentiel de réduction appliqué croît. Une augmentation du taux de cuivre modifie lesmécanismes de germination et de croissance des dépôts, ce qui a pour effet de diminuer lataille de grains et de modifier la microstructure. Ainsi, plus le dépôt est riche en cuivre, plus lataille de grains est faible et plus la structure est colonnaire, nodulaire voire dendritique.Des dépôts de 20 μm d’épaisseur ont ensuite été effectués sur substrat plan.Conformément à ce qui est décrit dans la littérature, ces dépôts se sont avérés très difficiles àréaliser en raison de l’apparition de nodules et de dendrites lorsque l’épaisseur augmente. Deplus, pour des épaisseurs supérieures à 10 μm, les dépôts sont alors constitués uniquementd’or, le cuivre n’étant plus réduit. Le changement de structure en cours de dépôt s’expliquepar l’inhibition de croissance engendrée par le cyanure libre. En effet, au cours de la réductionde l’aurocyanure et du cuprocyanure, du cyanure libre est libéré à la cathode. Ce cyanure libreinhibe la croissance latérale et promeut la croissance tridimensionnelle dite « instantanée »,provoquant l’apparition de nodules et de dendrites. Quant à l’appauvrissement en cuivre dudépôt, il s’explique également par la présence de cyanure libre à la cathode qui génère descomplexes cuprocyanure d’ordre 4. Les complexes d’ordre 4 possèdent une énergied’activation supérieure et un coefficient de diffusion plus élevé que les complexes d’ordre 3,d’où l’appauvrissement en cuivre du dépôt.Suite aux études électrochimiques, un modèle a été établi permettant d’expliquerl’influence du cyanure libre sur l’électrocristallisation des alliages d’or-cuivre. Ce modèle apermis de mettre en place des solutions visant à limiter l’inhibition électrochimique et ainsioptimiser les propriétés des alliages or-cuivre obtenus.L’une des solutions mises en place est l’application d’un champ ultrasonore pendant ledépôt. La cavitation générée par les ultrasons permet en effet d’évacuer le cyanure libre de lasurface de la cathode et d’optimiser le processus d’électrocristallisation. Ainsi, des dépôtsd’or-cuivre sur microballons ont été réalisés en présence d’ultrasons. Les analyses MEB etEDX de ces microballons montrent qu’il est possible d’obtenir des dépôts de 20 à 40 μmd’épaisseur de composition maitrisée. Les dépôts analysés ne présentent aucun gradient deconcentration dans l’épaisseur et il est ainsi possible de réaliser des alliages d’or-cuivrecontenant jusqu’à 45 %m de cuivre. Les dépôts réalisés présentent une structure lisse(80 ≤ Ra ≤ 230 nm) et compacte, et cela quelle que soit la concentration en cuivre. Quant à lamicrodureté de ces dépôts sur microballons, elle est fonction de la taille de grains (relation deHall-Petch) et donc de la concentration en cuivre du dépôt. / The aim of this PhD Thesis is to study the gold-copper cyanide electrochemicalsystem and finally to realize gold-copper microspheres with a diameter of 800 μm and athickness between 20 and 40 μm. The composition, the microstructure and the roughness ofthese shells must be perfectly controlled. To synthesise such a material, electrodepositionfrom a gold-copper alkaline cyanide bath has been chosen.Initially, the influence of the principal electrochemical parameters (temperature of theplating bath, stirring, etc.) was studied. This study showed that it is possible to realize5 μm thick gold-copper alloys with various compositions. Actually, it was shown that thecopper content of deposits varies with the applied potential. When increasing the coppercontent of coatings, the nucleation and growth mechanisms change. As a result, the grain sizeand the microhardness of the coatings are modified. An increase in the copper content reducesthe grain size witch increases the microhardness until a critical grain size of 6 nm. Thisincrease of copper content also affects the microstructure: columnar, nodular even dendriticalstructures were observed.Then, 20 μm thick gold-copper coatings were realized using the same electrochemicalparameters. As expected, these coatings were very difficult to plate because of the instabilityof the electrocrystallization process resulting in the development of columnar and nodularstructures. Moreover, for thicknesses above 10 μm, all deposits are free from copper. Themicrostructure change of deposits can be explained by inhibition phenomena generated byfree cyanide. Actually, the reduction of gold-copper generates free cyanide at the cathodesurface which inhibits the electrocrystallization and promotes instantaneous nucleation. Thisproduction of free cyanide also modifies the electrolyte chemistry promoting the formation ofCu(CN)43- instead of Cu(CN)32-. Cu(CN)43- complexes have lower diffusion coefficients andhigher activation energy witch explains why copper content reduces when increasing thethickness of deposits.Then a model was established which explains the influence of free cyanide on thegold-copper electrocrystallization. This model permitted to develop solutions in order to limitthe inhibition phenomena and to optimize the electrocrystallization of gold-copper.One of the solutions developed is the application of an ultrasonic field. The cavitationgenerated by the ultrasonic field eliminates the free cyanide from the cathode surface andoptimize the electrocrystallization process. Gold-copper deposits on shells were then platedunder sonication. SEM and EDS results show that it is possible to make 20 to 40 μm thickcoatings with a controlled composition. All the coatings plated under sonication were smooth(80 ≤ Ra ≤ 230 nm) and compact for various copper contents. The microhardness of thesecoatings varies with grain size (Hall-Petch relation) which depends of copper content.

O presente trabalho trata da obtenção de ligas de NiFe de NiFeCo sob a forma de filmes finos e também no seu uso na tentativa em se construir um sensor magnético tipo fluxgate planar. A técnica de produção utilizada foi a eletrodeposição com regime galvanostático. A solução eletrolítica utilizada era constituída por sais de níquel e ferro e alguns aditivos. Para depositar os filmes de NiFe, o eletrodo auxiliar era constituído de níquel; enquanto que para depositar os filmes de NiFeCo, o eletrodo auxiliar era constituído de cobalto. Os filmes foram depositados em substratos de cobre utilizando densidades de corrente no intervalo de 4 até 28 mA/cm2, com tempos totais de 40 e 60 minutos. A caracterização morfológica foi realizada utilizando Microscopia Eletrônica de Varredura superficial e de seção lateral e para encontrarmos a composição dos elementos presentes na amostra, realizamos a Espectroscopia de Energia Dispersiva e Difração de Raios-X. Quanto à caracterização magnética foi utilizado o Magnetômetro de Amostra Vibrante e também magnetometria utilizando o Superconducting Quantum Interference Devices (este foi utilizado somente para os filmes de NiFeCo) como o elemento detector do equipamento. Os filmes de NiFe crescem com orientações cristalinas ao longo dos planos (110) e (200); as quantidades de níquel e ferro atingem valores constantes a partir da densidade de corrente de 15 mA/cm2 (embora sempre haja mais níquel que ferro); o ponto de menor coercividade magnética (58,4 A/m) também ocorre a partir dessa densidade de corrente, onde filmes com 1 ?m de espessura são conseguidos para um tempo total de 40 minutos. Nota-se uma assimetria para os campos aplicados perpendicular e paralelamente à superfície do filme. Os filmes de NiFeCo crescem com orientações ao longo dos planos (111) e (200). Embora sempre haja mais níquel (constante em 70%), as concentrações de Fe e Co se igualam apenas para uma densidade de corrente próxima de 15mA/cm2. Abaixo desse valor há mais ferro, e acima mais Co. A partir dessa densidade de corrente, novamente observa-se um mínimo no valor da coercividade magnética do material (81 A/m). A partir dessa densidade de corrente, tal grandeza teve seu valor mantido praticamente constante. Para essa densidade de corrente filmes de 6 ?m de espessura são obtidos para um tempo de 40 minutos. Uma menor assimetria magnética é observada comparada com o caso anterior. Por esses dados, acreditamos que o filmes de NiFeCo seja um melhor candidato para a confecção do sensor planar tipo fluxgate, e testes iniciais de sua fabricação também são apresentados. / This work presents the results about the fabrication and characterization of thin films of NiFe and NiFeCo alloys. The attempts to construct the planar fluxgate are also presented. Galvanostatic electrodeposition using an electrolytic solution containing Ni and Fe was used: NiSO4 (0,7 mol/l); NiCl2 (0,02 mol/l); FeSO4 (0,03 mol/l); H3BO3 (0,4 mol/l) and C7H5O3NS.2H2O (0,016 mol/l). The auxiliary electrode was made on Ni for the NiFe films, while another one made on Co was used for the NiFeCo films. Films were deposited on copper substrates using current densities form 4 up to 28 mA/cm2, and total deposition time of 40 and 60 minutes. Structural characterization was performed using Scanning Electron Microscopy (surface and cross-section); Energy Dispersive Spectroscopy, and Xray Diffraction. Magnetic characterization was performed using two methods: the Vibrating Sample Magnetometry and magnetometry using a SQUID (Superconducting Quantum Interference Devices) sensor. NiFe films grow with crystalline planes oriented along the (110) e (200) directions; the amount of each material reach constant values for current densities above 15 mA/cm2 (even though there is always more Ni). The point of minimum magnetic coercivity (58,4 A/m) also occurs for this current density, where films 1 ?m-thick are obtained for a total deposition time of 40 minutes. An asymmetry is observed for magnetic fields applied parallel and perpendicular to the surface of the films. NiFeCo films grow with crystalline planes oriented along the (111) and (200) directions; the amount of Ni remains constant (about 70%) for the whole current density range. The amount of Fe decreases with increasing current density, while the amout of Co shows the opposite behavior. They have equal values for current densities of about 15mA/cm2, where the minimum coercivity of 81A/m is achieved. For higher current densities the coercivity remains constant. For the current density of 15mA/cm2, 6 ?m-thick films are obtained for a total deposition time of 40 minutes. The magnetic asymmetry is smaller than for the case of the NiFe films. According to the obtained data, we believe that NiFeCo is a better candidate for the fabrication of planar magnetic fluxgate sensors. Initial tests for the fabrication of a prototype are also presented.

Submitted by Erika Demachki (erikademachki@gmail.com) on 2017-03-14T18:52:47Z No. of bitstreams: 2 Dissertação - Elter Gouveia Gama - 2016.pdf: 9144026 bytes, checksum: d1fc24837019fb8951a0853874963512 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2017-03-20T12:24:25Z (GMT) No. of bitstreams: 2 Dissertação - Elter Gouveia Gama - 2016.pdf: 9144026 bytes, checksum: d1fc24837019fb8951a0853874963512 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2017-03-20T12:24:25Z (GMT). No. of bitstreams: 2 Dissertação - Elter Gouveia Gama - 2016.pdf: 9144026 bytes, checksum: d1fc24837019fb8951a0853874963512 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2016-06-21 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The present paper concern to the electrochemical characterization of the gold electrodeposition process into a carbon paste (CP) to produce graphite powder covered by gold. This electrode also was used to study the voltammetric features of dopamine oxidation. The voltammetric study of gold electrodeposition process indicated that for MCPE-oily, the reduction of AuCl4 - occurs from potentials more negative than ~+0.60 V (peak at ~+0.35 V) and gold oxidation from potential more positive than ~+0.40 V (peak at +0.65 V). For MCPE-aqueous, without and with glycerol, the reduction of AuCl4 - occurred from potentials more negative than ~+0.73 V (peak at ~0.40 V) and the gold oxidation from more positive potentials than ~ +0.25 V (peak at +0.57 V). These processes were dependents on the gold ion concentration into the CP. It was also verified that the Au(III) reduction probably occurred throughout of the MCP volume, but not homogeneously. It was verified that the reduction process takes place preferably in the MCP interface/aqueous NaCl solution and decreased toward the interior of the PC. In addition, it was observed that the process of gold electrodeposition on the MCPE behaves as a quasi-reversible system, thereby indicating that the system has a strong dependence on the mass transport (diffusion and migration) and electron transfer. In addition, it was found that the cathodic peak currents for MCPE-aqueous were higher than the MCPE-oily, indicating that the reduction kinetics in aqueous medium is highest, probably due to the increase in the mass transport rate in aqueous solution. Studies using factorial design with the oily and aqueous MCPE indicated that the factors: HAuCl4 concentration in the PC, deposition charge and the additive presence affected the performance of the MCPEs in ferrocyanide solution. Micrographs obtained by scanning electron microscopy (SEM) for oily and aqueous MCPE indicated that the gold electrodeposit occurred on some graphite flakes with an homogeneous layer of gold. The TEM images of the graphite powder with gold electrodeposit for MCPE-oily showed gold particles with dimensions of 52.1 nm to 281.5 nm distributed evenly over the graphite flake. X-ray diffraction analisys indicated that the gold electrodeposit was polycrystalline. The dopamine (DA) oxidation was dependenting on the electrodeposition parameters and DA solution composition. The analytical curve for the DA oxidation in NaCl/NaS2O5 did not provide adequate linearity, being influenced by the DA/NaS2O5 ratio and acidity solution. / O presente trabalho trata da caracterização eletroquímica do processo de eletrodeposição de ouro dentro de uma pasta de carbono (PC) para produzir pó de grafite recoberto com ouro. Este eletrodo também foi utilizado para estudar o perfil voltamétrico da oxidação de dopamina. O estudo voltamétrico do processo de eletrodeposição indicou que para o EPCM-oleoso a redução de AuCl4 - ocorre a partir de potenciais mais catódicos que ~+0,60 V (pico em +0,35 V), e a oxidação de ouro a partir de potenciais mais anódicos que ~+0,40 V(pico em +0,65 V). Para o EPCM-aquoso sem e com glicerol a redução de AuCl4 - ocorreu a partir de potenciais mais negativos que ~+0,73 V (pico em ~0,40 V) e oxidação de ouro ocorre a partir de potenciais mais positivos que ~+0,25 V (pico em +0,57 V). Estes processos foram dependentes da concentração de íons ouro na PC. Verificouse também, que a redução do Au3+ provavelmente ocorre em todo o volume da PCM, porém não homogeneamente. Quanto a extensão da eletrodeposição, observou-se que o para os EPCMs oleosos e aquosos o processo de redução ocorre preferencialmente na interface PCM/solução aquosa de NaCl e diminuiu em direção ao interior da PC. Ademais foi observado que o processo de eletrodeposição de ouro no EPCM comporta-se como um sistema quase-reversível, indicando com isso que o sistema tem uma forte dependência do transporte de massa (migração e difusão) e transferência de elétrons. Ademais, observou-se que as correntes de pico catódico para os EPCMs aquoso foram maiores do que os EPCMs oleoso, indicando que a cinética de redução em meio aquoso é maior possivelmente devido a maior velocidade no transporte de massa no meio aquoso. Estudo por planejamento fatorial realizado com EPCM oleoso e aquoso indicou que os fatores (concentração de HAuCl4 na PC, carga de deposição e presença de aditivo) afetaram a performance dos EPCMs em solução de ferrocianeto. Micrografias obtidas por microscopia eletrônica de varredura (MEV) para o EPCM oleoso e aquoso indicaram que a eletrodeposição de ouro ocorreu sobre algumas placas de grafite com uma camada homogênea de ouro. As imagens de MET do pó de grafite com ouro eletrodepositado para o EPCM oleoso mostraram partículas de ouro com dimensões de 52,1 nm a 281,5 nm, distribuídas sobre as placas de grafite. Análise por difração de raios X, indicou que houve eletrodeposição de ouro policristalino no pó de grafite. A oxidação de dopamina foi dependente dos parâmetros de eletrodeposição e da composição da solução de DA. A curva analítica para a oxidação DA em NaCl/Na2S2O5 não apresentou linearidade adequada, sendo influenciada pela razão DA/ Na2S2O5 e acidez da solução.

A eletrodeposição de gálio sobre cobre em meios de KOH 5,0 molL-1 e NaOH 5,0 molL-1 contendo 5,0 mmolL-1 de íons galato foi estudada na presença de surfatantes com cadeia de doze átomos de carbono. Foram estudados três surfatantes aniônicos - o dodecil sulfato de sódio (SDS), o dodecil benzeno sulfonato de sódio (SDBS) e o laurato de potássio (LK) - e um surfatante catiônico - o cloreto de dodecil amônio (DAC), em concentrações acima da c.m.c. Os estudos foram feitos sobre eletrodo de disco rotativo de cobre a 1000 rpm, empregando soluções alcalinas desaeradas e à temperatura de 25 ºC. Foram utilizadas como técnicas eletroquímicas a voltametria linear e a cronoamperometria. A análise da superfície, após a eletrodeposição, foi feita por microscopia eletrônica de varredura (MEV) e espectroscopia por dispersão de energia (EDS). Todos os anfifílicos estudados afetam a velocidade dos processos simultâneos de redução Ga(III)/Ga e H2O/H2. A ação inibidora ou catalítica, depende do potencial aplicado e da natureza do surfatante. Os surfatantes aniônicos inibem a reação H2O/H2 a baixas sobretensões catódicas. Em tais condições se admite que haja um número menor de moléculas de água adsorvidas por estarem os sítios do metal parcialmente ocupados pelas moléculas do anfifílico. A elevadas sobretensões catódicas a reação H2O/H2 é catalisada por estes anfifílicos, admitindo-se, nestas condições, que eles favoreçam a liberação do gás hidrogênio da superfície. O DAC, surfactante catiônico, inibe a reação H2O/H2 em toda a faixa de sobretensões catódicas estudada. Atribui-se a sua adsorção a uma interação eletrostática anfifílico-eletrodo, gerando um efeito inibidor maior à medida que o potencial se torna mais negativo. O SDBS inibe a eletrodeposição do gálio, mas confere ao depósito aspecto mais brilhante, a valores de potencial em que catalisa a reação H2O/H2. Soluções recém preparadas de SDS na presença de dodecanol (produto da hidrólise do anfifílico nestes meios), eleva os rendimentos de eletrodeposição do gálio de 12% para 18% a -1 ,35V (vs Hg/HgO). Neste mesmo potencial o DAC eleva os rendimentos do processo de forma comparável, embora iniba o mesmo na região de potencial em que a reação H2O/H2 é significativa. O LK inibe a eletrodeposição do gálio em todos os potenciais estudados, o que se atribui à formação de complexos com o íon Ga(III). Os ensaios por MEV e EDS confirmaram os rendimentos maiores de gálio na presença da mistura SDS-DOH. O depósito de gálio obtido a -1,55V (vs Hg/HgO) se dá sobre toda a superfície do cobre. A análise química radial mostrou que tanto na ausência de surfatantes quanto na presença da mistura SDS+DOH, a distribuição do gálio na superfície do disco de cobre, ainda que mostre decréscimo na bordas do eletrodo, é praticamente constante na maior parte da superfície. / Gallium electrodeposition on copper in 5.0 molL-1 KOH and 5.0 molL-1 NaOH solutions containing 5.0 mmolL-1 gallate ions, has been studied in the presence of twelve carbon atoms surfactants. Three anionic surfactants have been studied - sodium dodecyl sulfate (SDS), sodium dodecyl benzenosulfonate (SDBS) and potassium laurate (LK), and one cationic surfactant - dodecyl ammonium chloride (DAC) at concentrations above the c.m.c. The experiments have been made using rotating disk copper electrode (rotation frequency equal to 1000 rpm), using deaerated alkaline solutions at 25 ºC. Electrochemical techniques as linear voltammetry and chronoamperometry were used. Surface analysis after electrodeposition was made using scanning electron microscopy (SEM) and energy dispersion spectroscopy (EDS). All of the amphiphilics studied change the rate of the simultaneous cathodic Ga(III)/Ga and H2O/H2 processes. The inhibitive or catalytic reation depends on both the applied potencial and surfactant nature. Anionic surfactants inhibit the H2O/H2 reaction at lower overvoltages. It can be admitted under these conditions a lower number of adsorved water molecules due to the simultaneous adsorption of amphiphilic molecules. At higher cathodic overvoltages the H2O/H2 reaction is catalised by these surfactants. It can be admitted under these conditions that these molecules remove the hydrogen molecules from the electrode surface. DAC, a cationic surfactant, inhibits the reaction H2O/H2 on the entire range of cathodic overvoltages studied. Its adsorption can be attributed to the electrostatic interaction amphiphilic-electrode and in consequence, the inhibitive effect increases as the potencial attains more negative values. SDBS inhibits the gallium electrodeposition but the deposit is brighter with added SDBS. Recently prepared SDS solutions inhibits Ga(III)/Ga reaction. The presence of dodecanol (SDS hydrolise product in these media) increases the gallium electrodeposition yield from 12% to 18% at -1,35V/(Hg/HgO). At this same potencial DAC increases the yield of the process, similarly, but it inhibits the same reaction on the potencial range where the H2O/H2 reaction is significative. LK inhibits the gallium electrodeposition process on the entire range of potencials studied. This result can be attribuited to laurate gallium complex formation. SEM and EDS analyses have confirmed the best electrodeposition performance in the presence of SDS+DOH. The gallium deposits obtained at -1,55V/(Hg/HgO) spread on the entire copper surface. The radial chemical analysis has shown that either in the absence either in the presence of SDS+DOH mix gallium distribution is practically constant and uniform, except on the edge of the copper disk electrode.

L'objectif du travail de recherche mené concerne l'élaboration des nouveaux matériaux d'électrodes modifiés pour des applications dans le domaine des biocapteurs. Le travail a été subdivisé en trois parties portant sur le greffage du sel de diazonium pour application immunocapteur, l'électroadressage des d'anticorps et l'électrodépôt d'un espaceur pour application aptacapteur. Dans la première partie de ce travail, nous nous sommes consacrés d'abord à l'électrogreffage du nitrobenzène diazonium sur la surface d'or pour le développement de capteurs immunologiques destinés à la détection de la bactérie Staphylococcus aureus. Une limite de détection de 10 UFC/mL a été atteinte. Dans la deuxième partie, la détection de l'ochratoxine A est présentée, basée sur l'électroadressage covalent de l'anticorps modifié par la fonction diazonium sur des électrodes de Diamant Dopé Bore (BDD). Une limite de détection de 0.007ng/mL a été obtenue et l'immunocapteur a été testé sur des échantillons réels. Enfin, on a développé un aptacapteur basé sur le greffage d'un espaceur (PEG) sur la surface des microcellules BDD pour la quantification de la biotoxine OTA. Une limite de détection de 0,01ng/L a été obtenue et application à un échantillon réel (le riz) a été démontrée. Les résultats obtenus, basés sur des méthodes électrochimiques de détection (variation de l'impédance ou du courant d'une sonde redox) sont encourageantes en termes de sensibilité, limite de détection, reproductibilité et spécificité / The objective of the research work was to the development of modified electrode materials for biosensor application. The work was devided into three parts: electrografting of diazonium salt for immunosensor application, electroadressing of antibodies and electrodeposition of PEG spacer for aptasensor application. In the first part of this work, the modification of gold surfaces with nitrobenzene diazonium cation was investigated in order to develop an immunosensors for the detection of Staphylococcus aureus. A detection limit of 10 CFU/mL has been obtained. The second part was focused on the electrically addressable deposition of diazonium functionalized antibodies on boron-doped diamond (BDD) microcells for the detection of OTA. A detection limit of 0.007ng/mL has been obtained and the immunosensor was tested on real samples. Finally, we developed an amperometric aptasensor based on electrochemical grafting of a PEG-COOH spacer on a BDD microcell for the detection of OTA biotoxin. A detection limit of 0.01 ng/L has been obtained and application to a real sample (rice) has been demonstrated. The amperometric and impedimetric techniques used in this work lead to promising results in terms of sensitivity, specificity and reproductibility

Les travaux présentés dans ce mémoire ont pour but de mieux comprendre l’électrodéposition de revêtements nanocomposites et d’approfondir leur caractérisation. Le système étudié est un revêtement de zinc renforcé par des nanoparticules de cérine. Les dépôts de zinc sont élaborés par électrodéposition en courant continu et pulsé dans un bain ammonium chlorure dans lequel sont introduites des nanoparticules de cérine commerciales de 50 nm de diamètre. A l’issue d’une phase d’optimisation, des conditions de bain particulières caractérisées par un pH basique et l’utilisation d’un surfactant anionique ont ainsi été sélectionnées afin de s’assurer d’une suffisante stabilité de la suspension. L’influence des nanoparticules sur les mécanismes et rendements d’électrodéposition est étudiée. Une caractérisation précise des revêtements élaborés en courant continu a été développée au moyen de diverses techniques (MEB-EDS, DRX, SIMS, SDL, MET). Cette approche multi-disciplinaire a pour but d’évaluer l’incorporation de cérine dans le composite et localiser celle-ci dans l’épaisseur, approche originale et novatrice dans le domaine des revêtements composites à matrice zinc. Les nanoparticules influencent les propriétés des revêtements, avec une augmentation de dureté jusqu’à quarante pourcents. L’impact sur le comportement à la corrosion est mineur mais une amélioration en immersion longue durée est observée. Dans le but d’augmenter plus drastiquement l’incorporation et donc les propriétés, une modification de la morphologie du zinc parait indispensable. Dans cette optique, une démarche d’élaboration en courants pulsés a été conduite avec des résultats limités du fait de la forte influence des particules sur les mécanismes de germination/croissance en pulsés. L’utilisation d’un élément d’alliage tel le nickel est une perspective encourageante pour obtenir des revêtements composites aux propriétés optimisées. / The work presented within this thesis aims to better understand the electrodeposition of nanocomposite coatings and to improve their characterization. The system studied is a zinc coating reinforced by nanoparticles of ceria (50 nm in size). Zinc coatings are produced by DC and PC electroplating from an ammonium chloride bath in which the commercial ceria nanoparticles were introduced. Following an optimization stage, specific bath conditions with a alcaline pH and the use of an anionic surfactant have been selected to ensure sufficient stability of the suspension. The influence of nanoparticles on the mechanisms and plating efficiency is studied. A deep characterization of coatings was performed using various techniques (SEM-EDS, XRD, SIMS, GDOES, TEM). This plural approach aims to assess the dispersion of ceria in the composite surface and bulk, which leads to an original and innovative approach in the field of zinc matrix composite coatings. Nanoparticles influence the properties of coatings, increasing hardness up to forty percent. The impact on the corrosion behavior is minor but a slight improvement in long-term immersion is observed. In order to increase more drastically the incorporation of ceria and therefore properties of the resulting coating, change in the morphology of the zinc seems essential. In this context, an approach developed towards pulsed currents was conducted with limited results because of the strong influence of particles on the mechanisms of germination / growth. The use of an alloying element such as nickel is a promising prospect for composite coatings with optimal properties.

Ces travaux de thèse portent sur l’influence de l’état métallurgique sur les propriétés mécaniques et physico-chimiques des alliages électrodéposés nanostructurés de Ni-W pour lesquels la gamme de taille de grains peut être élargie à l’échelle nanométrique grâce à l’ajout de tungstène. Les alliages sont obtenus par électrodéposition en régime continu ou pulsé, à partir d’un bain citrate/ammonium. Une approche multi-échelle associant différentes techniques d’analyse (MEB, EBSD, MET, DRX, EDS, µFluo-X, SIMS et extraction à chaud) permet la caractérisation fine des paramètres métallurgiques. Nos résultats montrent que l’augmentation de la teneur en tungstène engendre un affinement de la taille de grains qui s’accompagne d’une évolution de la morphologie, de la texture cristallographique et de la contamination par les éléments légers (O, H, N, C). Afin de séparer l’influence des différents paramètres métallurgiques sur les propriétés, une démarche originale a été proposée, notamment en utilisant des recuits thermiques sous atmosphère contrôlée comme un moyen de faire varier la microstructure sans modifier la teneur en W et en prenant en compte l’influence de l’état de surface. En plus de l’effet classique de la taille de grains sur l’augmentation de la microdureté, la loi de Hall et Petch dépend fortement des solutés interstitiels et substitutionnels. En milieux acides et alcalins désaérés, le tungstène joue un rôle majeur aussi bien dans le domaine cathodique que dans le domaine anodique. Les autres paramètres métallurgiques comme la taille de grains interviennent plutôt au deuxième ordre. / The aim of this study is to understand the influence of the metallurgical state on the mechanical and anti-corrosion properties of electrodeposited nanostructured Ni-W alloys, in which the grain size can be extended towards nanometric scale by the tungsten addition. Citrate-ammonium baths were used to obtain the alloys by applying direct and pulse currents. A combination of several microstructural techniques at different scales (SEM, EBSD, TEM and XRD) has permitted the characterization of the morphology, the grain size, the crystallographic texture and the nature of grain boundaries. Concentrations of alloying element and contaminants were determined using several techniques such as EDX, GDOES, SIMS, µ-XRF and hot extraction analysis. The obtained results show that tungsten incorporation leads to grain refinement but also to other microstructural changes (morphology or crystallographic texture) and to different levels of contamination. In order to separate the influence of the different metallurgical parameters on the mechanical and corrosion properties, an innovative process was proposed using annealing treatments under controlled atmosphere to vary the microstructure without modifying the tungsten concentration. In addition to the influence of the grain size on the hardness evolution in alloys, the Hall-Petch relationship is also strongly dependent on the incorporation of light elements and tungsten. The study of the polarization curves in acidic and alkaline deaerated solutions revealed that the tungsten addition plays an important role on the electrochemical reactivity in both anodic and cathodic domains and that the other metallurgical parameters such as grain size intervene only at second order.

Cette thèse visait à développer des techniques de croissance électrochimiques d'oxydes pour obtenir des semi-conducteurs de type p utilisables comme photocathodes dans les cellules solaires à colorant (p-DSSC). Dans la littérature, la méthode d'électrodépôt n'a pas été explorée pour l'application p-DSSC. Les conditions de synthèse de films de NiO avec une épaisseur contrôlée ont été définies. Des couches de NiO ont été obtenues par électrodépôt en milieu aqueux, en milieu éthanol, en milieu diméthylsulfoxide DMSO et en milieu mixte DMSO/eau. Ces couches ont été caractérisées par DRX, spectroscopie Raman, MEB, mesures optiques, etc¿ puis testées comme photocathode dans des p-DSSC. L'électrodépôt de l'oxyde cuivreux Cu2O en milieu aqueux a été également étudié. Les rendements de conversion photovoltaïques des dispositifs ont été déterminés. Une nanostructuration des couches d'oxyde de nickel et d'oxyde cuivreux a aussi été réalisée en utilisant comme agent structurant des sphères de polystyrène fonctionnalisées par des groupements carboxyls. Enfin, nous avons exploré l'électrodépôt de la delafossite de cuivre CuFeO2 en milieu DMSO. / The objective of this thesis was the electrochemical deposition (ECD) of p-type semiconductors forthe fabrication of p-Dye Sensitized Solar Cells (p-DSSCs). The electrodeposition method remained unexploredfor the p-DSSC applications. The best conditions for ECD of nickel oxide layers with a controlled thickness havebeen defined. Nickel oxide has been deposited in water medium, in ethanol, in dimethyl sulfoxide (DMSO)medium and in a mixture of DMSO/water solvent. The layers have been characterized by XRD, Ramanspectroscopy, SEM, optical measurements… then have been tested as a photocathode in p-DSSCs. The cuprousoxide (Cu2O) electrodeposition in an aqueous bath has also been investigated. The photovoltaic efficiency of thevarious prepared layers has been evaluated in p-DSSCs. We have also prepared inverse opal organized structureswith a perfectly defined macropore organization and size using a macrosphere polystyrene template. Finally, wehave explored the ECD of a copper delafossite CuFeO2 in DMSO medium.

Le mécanisme élémentaire de l'électrodépôt de films de MnO2 fût étudié sur des électrodes de Pt massif dans des électrolytes aqueux. Il se révèle être une réaction multi-étapes sensible au pH et à la force ionique. La chronoampérométrie couplée à des électrolytes neutres peu concentrés favorise l'électrodépôt de films stables de MnO2. Le FTO est un meilleur substrat que l'ITO parce qu'il présente une activité électrochimique plus élevée et favorise la stabilité mécanique de films électrodéposés de MnO2. De plus, le potentiel d'électrodépôt influence à la fois la structure et la morphologie des films de MnO2. Les films amorphes de MnO2 obtenus à potentiel élevé possèdent une activité électrocatalytique et une stabilité plus élevées que la birnessite. Un traitement thermique peut améliorer amplement leur activité électrocatalytique et leur stabilité mécanique. Une transition de phase des films de MnO2 apparaît à 500 °C. Leur morphologie change de façon dramatique après chauffage au-delà de cette température. Les échantillons chauffés à 500 °C ont la meilleure activité électrocatalytique pour l'OER. Les cations Na+, K+, Ca2+ and Mg2+ sont insérés en petites quantités dans la structure des films de MnO2 au cours de la démarche d'électrodépôt, mais ils influencent néanmoins la structure et la morphologie des films. Finalement, les films de birnessite ou amorphes apparaissent comme des candidats prometteurs en tant que catalyseurs pour la dissociation photoélectrochimique de la dissociation de l'eau, puisqu'ils génèrent des photocourants considérables sous lumière solaire. Pour cela, des films de MnO2 épais, amorphes et recuits à 500 °C produisent les meilleures performances. / The basic electrodeposition mechanism of MnO2 films was studied first on bulk Pt electrodes in various aqueous electrolytes. It was revealed that MnO2 electrodeposition is a multi-step reaction that is sensitive to pH and ionic strength. Chronoamperometry coupled to low concentration neutral aqueous solutions favors the electrodeposition of stable MnO2 films. FTO was found to be a better substrate than ITO, because it has a higher electrochemical activity and could enhance the mechanical stability of electrodeposited MnO2 films. Moreover, the potential used for electrodeposition has great influence on both the structure and the morphology of MnO2 films. Amorphous MnO2 films obtained at high potential possess higher electrocatalytic activity and stability than the birnessite-type MnO2 variety. The heat treatment can greatly enhance the electrocatalytic activity and mechanical stability. A phase transition of MnO2 films appears at 500 °C. The morphology changes dramatically after heating above this temperature. Samples heated at 500 °C are found to have the best electrocatalytic activity towards OER. Na+, K+, Ca2+ and Mg2+ cations were found to be inserted in small amounts into the structure of MnO2 films during the electrodeposition procedure but they influence the structure and morphology of the films. Finally, birnessite type and amorphous MnO2 films appear to be promising candidates as catalysts for photoelectrochemical water splitting, as they are able to generate considerable photocurrents under solar light illumination. In this purpose, thick and amorphous films with 500 °C heat treatment are supposed to produce the best performances.

The control of interfacial microstructural stability is of utmost importance to the reliability of liquid solder interconnects in high temperature electronic assemblies. This is primarily due to excessive intermetallic compounds (IMCs) that can form and continuously grow during high temperature operation, which practically renders conventional barrier metallisations inadequate. In this study, electrically conducting, NbOx containing Ni coatings were developed using electrodeposition. Their suitability as a solder diffusion barrier layer was assessed in terms of the electrical conductivity and barrier property. The present work explores a novel electrochemical route to produce Ni-NbOx composite coatings of good uniformity, compactness and purity, from non-aqueous glycol-based electrolytes consisting of NiCl2 and NbCl5 as metal precursors. The effects of cathodic current density and NaBH4 concentrations on the surface morphology, composition and thickness of the coatings were examined. A combined study of Scanning Transmission Electron Microscopy (STEM) and Electrochemical Quartz Crystal Microbalance (EQCM) was conducted to understand the fundamental aspects of this novel electrodeposition process. The composite coatings generally exhibited good electrical conductivity. The reaction behaviour between a liquid 52In-48Sn solder and Ni-NbOx, with Nb contents up to 6 at.%, were studied at 200°C. The results indicate that, Ni-NbOx with sufficient layer thickness and higher Nb content, offered longer service lifetime. Nb enrichment was generally observed at or close to the reaction front after high temperature storage, which suggests evident effectiveness of the enhanced diffusion barrier characteristics.