Ce travail de thèse est consacré à la synthèse électrochimique de films minces d’hydroxydes doubles lamellaires (HDL) et à l’élaboration de biocapteurs enzymatiques à détection ampérométriques, utilisant ces films comme matrices d’immobilisation des enzymes. Des études préalables de synthèse de suspensions de HDLs à partir de la neutralisation de mélange de cations métalliques divalents et trivalents par la soude ont été effectuées. Les solides formés ont été caractérisés par spectroscopie FTIR et par diffraction des rayons X ; leurs compositions ont été déterminées par dosages chimiques et par ICP-OES. Les conditions permettant de former exclusivement un HDL ont été précisées pour plusieurs couples cations divalents / cations trivalents, en présence d’ions bicarbonate ou du complexant EDTA. Les suivis pHmétriques ont permis de définir les compositions d’électrolytes les plus adaptées pour les synthèses électrochimiques des films de HDLs. Des films minces d’Hydrotalcite ou de Pyroaurite ont été obtenus sur substrat conducteur (Pt, Au) par augmentation du pH local résultant de la réduction de l’oxygène dissous ou de l’eau. Les paramètres potentiel, courant et temps de réduction ont été étudiés. Des comportements électrochimiques linéaires de ces électrodes modifiées vis-à-vis de l’ion ferricyanure ou des produits de catalyse enzymatique, H2O2 et NADH, ont été mis en évidence. Deux types de biocapteurs, à glucose ou à lactate, ont été fabriqués par co-déposition électrochimique du film HDL et de l’enzyme, glucose oxydase ou lactate déshydrogénase. Leurs sensibilités ampérométriques pour leur substrat, glucose ou lactate, ont été étudiées en fonction de différents paramètres de préparation ou de fonctionnement. / This work is devoted to the electrochemical synthesis of layered double hydroxides (LDH) thin films and to the development of enzymatic biosensors with amperometric detection, using these films as immobilization matrices of enzymes. Preliminary studies of LDH suspensions synthesis by neutralization of mixed divalent and trivalent metallic cations with sodium hydroxide were performed. The powders were characterized by FTIR spectroscopy and X-ray diffraction, and their compositions were determined by chemical titration and ICP-OES. Conditions for the formation of pure LDH were specified for several couples of divalent / trivalent cations, in the presence of bicarbonate ions or EDTA. The pH titration curves allow the determination of the best suited electrolyte compositions for the electrodeposition of LDHs films. Hydrotalcite or Pyroaurite thin films were obtained on conductive substrates (Pt, Au) from the increase of local pH induced by dissolved oxygen or water electrochemical reduction. The following parameters were studied, potential, current and reduction time. The linear electrochemical behaviour of these LDH-modified electrodes was verified for the oxidation of ferricyanide ions or H2O2 and NADH, the products resulting from bio-catalysed reactions. Two types of biosensors, for glucose or lactate determination, were elaborated by electrochemical co-deposition of LDH film and enzyme, glucose oxidase or lactate dehydrogenase. Amperometric sensitivities for glucose or lactate were studied as a function of preparation and operation parameters.

<p>For patients suffering bradycardia, i.e., too slow heart rhythm, the common treatment is having a pacemaker implanted. The pacemaker system consists of the pacemaker and a pacing lead. The pacing lead is connected to the pacemaker and at the other end there is a stimulation electrode. The most common conductor material is a cobalt-based super alloy (MP35N^® or 35N LT^®), with the main constituents Ni, Co, Cr and Mo. The pacemaker electrode is often made of a substrate material with a rough surface coating. The substrate materials are predominantly platinum/iridium alloy and titanium. The material choice is of great importance for the performance and stability during long-term service. Excellent corrosion resistance is required to minimize elution of metal ions in the human body.</p><p>In this thesis, the electrochemical behaviour and corrosion resistance of the Co-based alloys and Ta (as electrode substrate), in a phosphate buffer saline (PBS) solution with and without addition of H₂O₂, was investigated by means of potentiodynamic polarization, cyclic voltammetry, electrochemical impedance spectroscopy and simulated pacemaker pulsing. The metal release from the Co-based alloy during the passivation treatment and exposure in the synthetic biological media was measured by using inductive coupled plasma - atomic emission spectroscopy (ICP-AES). Moreover, surface composition was analyzed by using x-ray photoelectron spectroscopy.</p><p>The results show that the chemical passivation of Co-based alloy 35N LT^® increased the corrosion resistance and reduced Co release significantly, even in more hostile environment, i.e. PBS with addition of H₂O₂. The increased corrosion resistance is due to the Cr enrichment in the surface layer. The reduced Co release is due to a preferential dissolution of Co from the surface oxide layer during the chemical passivation. The electrochemical investigation of uncoated and rough TiN coated Ta show that uncoated Ta is not suitable electrode material due to formation of a highly resistive surface oxide film. Whereas the rough TiN coated Ta exhibits desirable electrochemical performance for pacemaker electrodes. The addition of H₂O₂in the PBS has a large influence on the electrochemical behaviour of Ta, but the influence is small on the rough TiN coated Ta. </p>

For patients suffering bradycardia, i.e., too slow heart rhythm, the common treatment is having a pacemaker implanted. The pacemaker system consists of the pacemaker and a pacing lead. The pacing lead is connected to the pacemaker and at the other end there is a stimulation electrode. The most common conductor material is a cobalt-based super alloy (MP35N® or 35N LT®), with the main constituents Ni, Co, Cr and Mo. The pacemaker electrode is often made of a substrate material with a rough surface coating. The substrate materials are predominantly platinum/iridium alloy and titanium. The material choice is of great importance for the performance and stability during long-term service. Excellent corrosion resistance is required to minimize elution of metal ions in the human body. In this thesis, the electrochemical behaviour and corrosion resistance of the Co-based alloys and Ta (as electrode substrate), in a phosphate buffer saline (PBS) solution with and without addition of H2O2, was investigated by means of potentiodynamic polarization, cyclic voltammetry, electrochemical impedance spectroscopy and simulated pacemaker pulsing. The metal release from the Co-based alloy during the passivation treatment and exposure in the synthetic biological media was measured by using inductive coupled plasma - atomic emission spectroscopy (ICP-AES). Moreover, surface composition was analyzed by using x-ray photoelectron spectroscopy. The results show that the chemical passivation of Co-based alloy 35N LT® increased the corrosion resistance and reduced Co release significantly, even in more hostile environment, i.e. PBS with addition of H2O2. The increased corrosion resistance is due to the Cr enrichment in the surface layer. The reduced Co release is due to a preferential dissolution of Co from the surface oxide layer during the chemical passivation. The electrochemical investigation of uncoated and rough TiN coated Ta show that uncoated Ta is not suitable electrode material due to formation of a highly resistive surface oxide film. Whereas the rough TiN coated Ta exhibits desirable electrochemical performance for pacemaker electrodes. The addition of H2O2 in the PBS has a large influence on the electrochemical behaviour of Ta, but the influence is small on the rough TiN coated Ta. / QC 20101122

Resumo: Os polímeros condutores a Base de Tiofeno-Schiff despontam como materiais alternativos para obtenção de eletrodos modificados com potencial aplicação em sensores químicos devido as excelentes propriedades condutoras e quelantes conferidas pelo poli-tiofeno e pelas Bases de Schiff, respectivamente. Neste trabalho, o complexo Tiofeno-Salen foi sintetizado e caracterizado por UV8Vis e FTIR, em seguida, monômeros complexos metálicos-tiofeno-Schiff foram sintetizados com a complexação de cátions metálicos de transição como Ni2+, Cu2+, VO2+, Fe3+, Ru3+ e Ce4+ e novamente caracterizados por UV8Vis e FTIR para comprovar a formação dos monômeros complexos metálicos-tiofeno-Schiff. Filmes poliméricos desses complexos metálicos foram obtidos pela técnica de eletropolimerização anódica e foram caracterizados eletroquimicamente por voltametria cíclica em solução aquosa. Verificou-se a influência de diversas variáveis experimentais tais como solvente, eletrólito de suporte, intervalo de varredura de potenciais, velocidade de varredura de potenciais, concentração do monômero e número de ciclos durante a etapa de eletropolimerização. Os substratos condutores utilizados na etapa de eletropolimerização foram o eletrodo de platina e o eletrodo de carbono vítreo, demonstrando a influência do substrato condutor na etapa de eletropolimerização e verificou-se que o eletrodo de platina apresentou maior eficiência de transferência eletrônica quando comparado ao eletrodo de carbono vítreo devido a natureza amorfa do carbono vítreo para esses filmes poliméricos estudados. Os eletrodos de platina modificados com esses filmes poliméricos foram também utilizados no estudo das suas propriedades eletroquímicas para a detecção de analitos de interesse analítico como L-dopa, ditionito, piridoxina, sulfito, nitrito, L-tiroxina e ácido gálico. / Abstract: Conducting polymers of the Thiophene-Schiff Bases emerge as alternative materials to obtain modified electrodes with potential applications in chemical sensors due to the excellent conductive chelating properties conferred by the poly-thiophene and the Schiff Bases, respectively. In this work, the complex Thiophene-Salen was synthesized and characterized by UV-Vis and FTIR, then monomers complex metals8thiophene8Schiff were synthesized with the complexation of cations of transition metals such as Ni2+, Cu2+, VO2+, Fe3+, Ru3+ and Ce4+ and again characterized by UV-Vis and FTIR to confirm the formation of monomer-metal complexes with thiophene-Schiff. Polymer films of these complexes were obtained by anodic electropolymerization technique and were characterized electrochemically by cyclic voltammetry in aqueous solution. There was the influence of different experimental variables such as solvent, supporting electrolyte, potential scan range, potential scan rate, monomer concentration and number of cycles during the electropolymerization. The conductive substrates used in the electropolymerization were platinum electrode and a glassy carbon electrode, demonstrating the influence of the conductive substrate in the electropolymerization and was found that the platinum electrode showed a higher electron transfer efficiency when compared to the carbon electrode vitreous due to amorphous nature of glassy carbon for these polymer films studied. The platinum modified electrodes with these polymer films were also used to study their electrochemical properties for the detection of analytes of analytical interest as L-dopa, dithionite, pyridoxine, sulphite, nitrite, L-thyroxine and gallic acid presented higher apllication as chemical sensors for these analytes. / Orientador: Marcos Fernando de Souza Teixeira / Coorientador: Luiz Humberto Marcolino Junior / Banca: Lúcio Angnes / Banca: Homero Marques Gomes / Mestre

Made available in DSpace on 2014-06-11T19:29:06Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-11-28Bitstream added on 2014-06-13T20:48:16Z : No. of bitstreams: 1 pereira_par_me_sjrp.pdf: 2491155 bytes, checksum: 9deb7dfefe2de27d42938548e5d1567a (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Os polímeros condutores a Base de Tiofeno-Schiff despontam como materiais alternativos para obtenção de eletrodos modificados com potencial aplicação em sensores químicos devido as excelentes propriedades condutoras e quelantes conferidas pelo poli-tiofeno e pelas Bases de Schiff, respectivamente. Neste trabalho, o complexo Tiofeno-Salen foi sintetizado e caracterizado por UV8Vis e FTIR, em seguida, monômeros complexos metálicos-tiofeno-Schiff foram sintetizados com a complexação de cátions metálicos de transição como Ni2+, Cu2+, VO2+, Fe3+, Ru3+ e Ce4+ e novamente caracterizados por UV8Vis e FTIR para comprovar a formação dos monômeros complexos metálicos-tiofeno-Schiff. Filmes poliméricos desses complexos metálicos foram obtidos pela técnica de eletropolimerização anódica e foram caracterizados eletroquimicamente por voltametria cíclica em solução aquosa. Verificou-se a influência de diversas variáveis experimentais tais como solvente, eletrólito de suporte, intervalo de varredura de potenciais, velocidade de varredura de potenciais, concentração do monômero e número de ciclos durante a etapa de eletropolimerização. Os substratos condutores utilizados na etapa de eletropolimerização foram o eletrodo de platina e o eletrodo de carbono vítreo, demonstrando a influência do substrato condutor na etapa de eletropolimerização e verificou-se que o eletrodo de platina apresentou maior eficiência de transferência eletrônica quando comparado ao eletrodo de carbono vítreo devido a natureza amorfa do carbono vítreo para esses filmes poliméricos estudados. Os eletrodos de platina modificados com esses filmes poliméricos foram também utilizados no estudo das suas propriedades eletroquímicas para a detecção de analitos de interesse analítico como L-dopa, ditionito, piridoxina, sulfito, nitrito, L-tiroxina e ácido gálico. / Conducting polymers of the Thiophene-Schiff Bases emerge as alternative materials to obtain modified electrodes with potential applications in chemical sensors due to the excellent conductive chelating properties conferred by the poly-thiophene and the Schiff Bases, respectively. In this work, the complex Thiophene-Salen was synthesized and characterized by UV-Vis and FTIR, then monomers complex metals8thiophene8Schiff were synthesized with the complexation of cations of transition metals such as Ni2+, Cu2+, VO2+, Fe3+, Ru3+ and Ce4+ and again characterized by UV-Vis and FTIR to confirm the formation of monomer-metal complexes with thiophene-Schiff. Polymer films of these complexes were obtained by anodic electropolymerization technique and were characterized electrochemically by cyclic voltammetry in aqueous solution. There was the influence of different experimental variables such as solvent, supporting electrolyte, potential scan range, potential scan rate, monomer concentration and number of cycles during the electropolymerization. The conductive substrates used in the electropolymerization were platinum electrode and a glassy carbon electrode, demonstrating the influence of the conductive substrate in the electropolymerization and was found that the platinum electrode showed a higher electron transfer efficiency when compared to the carbon electrode vitreous due to amorphous nature of glassy carbon for these polymer films studied. The platinum modified electrodes with these polymer films were also used to study their electrochemical properties for the detection of analytes of analytical interest as L-dopa, dithionite, pyridoxine, sulphite, nitrite, L-thyroxine and gallic acid presented higher apllication as chemical sensors for these analytes.

Le développement de la plaque bipolaire - PB -métallique nécessite une amélioration des propriétés du matériau qui la constitue. L'utilisation de l'acier implique une meilleure compréhension du film passif - FP. En effet, le cahier des charges de la PB demande une bonne conduction électronique ainsi qu'une longue durée de vie. L'amélioration de ces paramètres passe par une meilleure corrélation et compréhension entre les propriétés semi-conductrices et la résistance à la corrosion. La difficulté liée à l'étude de la passivation réside dans les nombreux phénomènes modifiant le comportement du film passif. De nombreux modèles présentés dans la littérature peuvent être utilisés pour caractériser la passivation. L'un des principaux, le Modèle de Défauts Ponctuels de D. D. Macdonald (Point Defect Model - PDM), décrit le FP à partir d'une série de réactions électrochimiques se déroulant à l'interface métal/oxyde et à l'interface oxyde/électrolyte. La réactivité est limitée par le transport de matière à travers l'oxyde. Après une étude bibliographique, ce phénomène semble être un paramètre discriminant dans le choix des modèles. Une méthode de sélection permettant une utilisation de chacun de ces modèles en fonction de leurs spécificités est proposée. Ainsi, cette méthode est basée sur la corrélation entre la mesure du transport de matière à partir des équations du PDM et l'analyse des Spectres d'Impédance Electrochimique (SIE). Le PDM caractérisant le transport de matière indépendamment de la SIE, il devient possible de déterminer le bien-fondé de la prise en compte de celui-ci dans les mesures de spectroscopie d'impédance électrochimique. L'évolution de la densité du porteur de charge majoritaire avec le potentiel de formation de l'oxyde permet d'accéder au coefficient de transport à partir des équations du PDM. Connaissant l'épaisseur de l'oxyde par des mesures XPS, la constante de temps et la fréquence caractéristique peuvent être déterminées. Sur la base de ces deux valeurs, un modèle descriptif d'analyse des spectres est sélectionné en évitant le sur-paramétrage. Cette méthode est appliquée d’abord à un matériau modèle, le chrome pur exposé à un milieu acide (pH 2), à différentes températures (30°C et 80°C). Elle valide la nécessité de la prise en compte du transport de matière à 80°C ainsi que la présence d'une surface composée d'une couche d'oxyde interne et d'une couche d'hydroxyde externe. Dans un second temps, cette méthode est utilisée sur un matériau industriel, un acier de type AISI 316L, à différents pH (1,2 et 3) et à différentes températures (30°C et 80°C). Elle a permis de décrire l'oxyde en surface comme une jonction p-n prenant en compte une couche riche en chrome interne avec un gradient de concentration de fer. Cette méthode a permis de caractériser de manière approfondie l'acier de type AISI 316L. Bien que ne concernant que le substrat, cette étape est déterminante dans l'amélioration des performances des PB métalliques. / Developments in metallic bipolar plate, to apply more widely fuel cells, require an improved of the constitutive material. The use of stainless steel calls for a good understanding of the passive film. The required specifications are for good electrical conductivity and a long life-time. Those two parameters correspond to a correlation between the semiconductive properties and the good corrosion behavior. Nevertheless, the main problems of the passivity lie on the multiplicity of the phenomena that alter the passive film behavior. Numerous models described in the literature can be used to characterize the passivation. The Point Defect Model (PDM) describes the passivation through electrochemical reactions at the metal / oxide and at the oxide / electrolyte interfaces. The reactivity is limited by mass transport through the oxide. From the literature, those phenomena seems to be a discriminating parameter in the choice of a model. The selective method proposed allows us to use each model taking into account their specifics. This methodology is based on the correlation between the mass transport characterization, thanks to the PDM, and the analysis of the Electrochemical Impedance Spectroscopy (EIS). The PDM determines the transport coefficient apart from EIS measurements, so to validate the consideration of the mass transport during the analysis of the electrochemical impedance spectra. The evolution of the main charge carrier density as a function of the oxide formation potential allows us to calculate the transport coefficient from PDM equations. Thanks to the thickness of the oxide (determined by X-ray Photoelectron Spectroscopy), the time constant of the mass transport is determined. Based on this value, a descriptive model is used to analyze the EIS data, avoiding overparametrization. This method is applied first on a model material, pure chromium exposed to acidic solution (pH 2) at several temperatures (30°C and 80°C). It shows that the mass transport has to be taken into account at 80°C and the EIS model considers an inner chromium oxide layer and an outer chromium hydroxide. Secondly, the method is used to characterize an industrial material, AISI 316L stainless steel, at several pH (1, 2 and 3) and at several temperatures (30°C and 80°C). In this case, the oxide is describe as a p-n semiconductor junction with an chromium rich inner layer and an outer iron rich layer. The present methodology permits to deeply characterize the AISI 316L stainless steel. Even if this study concerns the substrate, this step is decisive to improve the performances of the metallic bipolar plates