La polyaniline est un polymère conducteur intrinsèque aux potentialités indéniables dans le domaine de la micro-électronique. Elle allie la légèreté, le faible coût et la modularité des polymères avec les propriétés de conduction électrique des métaux. La mise à profit de ce mélange de propriétés à l’échelle industrielle nécessite une maitrise des procédés de mise en œuvre de la polyaniline, notamment sous forme de film polymère, domaine où il y a encore un manque de maitrise. Pour y remédier, il faudrait tout d’abord comprendre l’influence de chaque paramètre de mise en œuvre sur les propriétés de conduction du film de polyaniline. Pour cela, nous avons choisi une polyaniline plast-dopée commerciale à l’état de dispersion et avons fait une étude paramétrique sur l’effet du type de solvant utilisé pour la dispersion ainsi que celui de la température d’évaporation de celui-ci lors du dépôt du film. Deux types d’études ont été menés : la première porte sur les propriétés rhéologiques et diélectriques des dispersions de polyaniline et la seconde sur les propriétés structurales et de conduction des films. A travers la première étude, nous avons pu montré que lors du chauffage des dispersions de polyaniline, celles-ci subissaient une transition structurale liquide-liquide du second ordre dont les paramètres varient avec le type du solvant utilisé. A travers la seconde étude, nous avons aussi mis en évidence que les films déposés dans les domaines avoisinant la température transition de phase dans les mélanges liquides sont les moins conducteurs et les moins cristallisés. Selon le type de solvant choisi, deux mécanismes de conduction ont été trouvés : les sauts à portées variables tridimensionnel (VRH 3D), pour le cas de la série de films issus de la dispersion dans l’acide dichloroacétique et déplacement par effet tunnel induit par les fluctuations thermiques (FIT) pour la série de films issus de la dispersion dans le mélange acide dichloroacétique / acide formique. Il en ressort finalement que pour obtenir un film de polyaniline plast-dopée ayant la conductivité la plus élevée, il faut appliquer les conditions expérimentales qui permettent d’obtenir un degré de cristallinité élevé (298 K pour PANI/DCAA). / The purpose of this study is to perform polyaniline films with the highest conductivity. The effect of the solvent type and the casting temperature on the electrical properties of plastdoped polyaniline dispersions and films were investigated. For this purpose, rheological and dielectric investigations have been undertaken for dispersions of plast-doped polyaniline in two different solvents (dichloroacetic acid and formic acid / dichloroacetic acid mixture). Changes appearing above a certain temperature, 318K for PANI/DCAA and 313K for PANI/DCAA-FA, for both rheological dielectric and rheological parameters revealed the existence of a second order liquid-liquid structural transition occurring in the polyaniline organic dispersions. We also investigated the effect of the selected processing parameters on the film properties. We found that the DC conductivity mechanism is governed by Mott’s three-dimensional variable range hopping (3D VRH) model for PANI/DCAA films and by a fluctuation induced tunnelling model (FIT) for PANI/DCAA-FA films. Besides, the films cast at temperatures around the second order liquid-liquid structural transition temperature of polyaniline dispersions lead to the lowest conductivity and crystallinity, regardless of the solvent type used. A qualitative correlation was also found between the conductivity and the crystallinity of the polyaniline films. So, in order to obtain films with the highest electric conductivities, we have to apply experimental conditions leading to the highest crystallinity (298 K for PANI/DCAA).

Les travaux réalisés dans le cadre de cette thèse ont porté sur la réalisation de polymères conducteurs de type polyaniline et de leurs composites associés à du graphène en vue d’une utilisation en tant que matériaux d’électrodes dans des dispositifs de stockage d’énergie de type supercondensateurs. Les travaux se sont tout d’abord orientés sur la synthèse de nouveaux liquides ioniques protiques (LIP) associant des cations pyrrolidinium (Pyrr+) et imidazolium (Imi+) avec des anions p-toluène sulfonate (PTS-), hydrogénosulfate (HSO4-) ou (+)-camphre-10-sulfonate (Cs-), et de l’étude de leur propriétés physico-chimiques (conductivité, viscosité) dans des mélanges binaires LIP/eau. Après avoir déterminé les formulations permettant d’atteindre les propriétés de transport optimales, les capacitances spécifiques de la Pani/HCl dans ces milieux LIP ont été déterminées et nous avons montré que les performances de dispositifs symétriques sont améliorées en capacitance, énergie et en puissance (400 F/g, 7 Wh.kg-1 et 4 kW.kg-1 pour les valeurs les plus élevées) par rapport à un milieu H2SO4 1M. Ces milieux LIP ont également été utilisés comme milieu de synthèse de la Pani. Nous avons ainsi montré que la nature des LIP, qui sont des milieux nanostructurants, pouvait modifier les propriétés électroniques, morphologiques et thermiques des Pani. Un optimum de conductivité électronique de la Pani (22 S/cm) a été atteint avec une synthèse réalisée dans le mélange binaire [Imi][HSO4]/eau 70/30 (pourcentage massique) générant une morphologie fibrillaire et une bonne cyclabilité (93% de rétention de capacitance sur 1000 cycles dans H2SO4 1M. Des valeurs de près de 400 F/g ont été obtenues dans le mélange [Pyrr][HSO4]/eau 41/59 optimisé. Dans le cas de la synthèse de la Pani réalisée dans [Pyrr][PTS]/eau, un gain en stabilité thermique (360°C) est obtenu grâce au dopage par l’anion PTS-. Finalement, une étude exploratoire sur la préparation de composites Pani/graphène et Pani/oxyde de graphène a été réalisée. Les synthèses des nanocomposites ont été effectuées dans les mélanges LIP/eau. L’optimisation de la composition du composite a été étudiée et indique que des rapports massiques de graphène ou oxyde de graphène d’environ 15% permettent d’atteindre des performances de stockage prometteuses et exaltées par rapport à celles obtenues pour des Pani sans graphène. / The work carried out during this PhD thesis is based on the preparation of conducting polymers such as polyaniline (Pani) and their composites associated with graphene for use as electrode materials for supercapacitors application. This work was first dedicated to the synthesis of new protic ionic liquids (PILs) combining pyrrolidinium (Pyrr+) or imidazolium (Imi+) cations with p-toluene sulfonate (PTS-), hydrogen sulfate (HSO4-) or (+)-camphor-10-sulfonate (Cs-) anion, and the study of their physico-chemicals properties (conductivity, viscosity) in binary mixtures PILs/water. After determining the formulations needed to achieve the optimum of transport properties, the specific capacitance of Pani/HCl in these PILs medium was determined, and we have shown that the performance of symmetrical devices are improved in capacitance, specific energy and specific power (400F/g, 7Wh/kg and 4kW/kg for the higher values) in comparison to those obtained in a H2SO4 1M medium. These PILs mediums were also used as a synthesis medium of Pani. We have shown that the nature of PILs, acting as soft template, could change the electronic, morphological and thermal properties of Pani. An optimum of electronic conductivity of Pani (22 S/cm) was obtained with a synthesis realized in the binary mixture [Imi][HSO4]/water 70/30 generating a fibrillar morphology and a good cyclability (93% capacitance retention over 1000 cycles in H2SO4 1M at 2 A/g). For Pani synthesis in [Pyrr][PTS]/water, a thermal stability gain (360 °C) is obtained thanks to a PTS- doped Pani. Finally, a preliminary study on the preparation of composite Pani/graphene and Pani/graphene oxide was performed. The syntheses of nanocomposites were realized in PILs/water mixtures. The optimization of the composition of the Pani nanocomposites was studied and it was found that a mass ratio of about 15% in weight of graphene or graphene oxide enables to obtain promising nanomaterials with higher electrochemical performances compared with pristine Pani.

Electrical double-layer formed at the interface between an electrode and an electrolyte has been a topic of innumerable studies. The electrical interface plays a crucial role in kinetics, mechanisms and applications in variety of electrochemical reactions. The electrical double-layer and electron-transfer reactions lead to many important applications of electrochemistry, which include energy storage devices, namely, batteries, fuel cells and supercapacitors. Electrochemical supercapacitors can withstand to higher power than batteries and deliver higher energy than the conventional electrostatic and electrolytic capacitors. A supercapacitor can be used as an auxiliary energy device along with a primary source such as a battery or a fuel cell for the purpose of power enhancement in short pulse applications. Among the various materials studied for electrochemical supercapacitors, carboneous materials, metal oxides and conducting polymers received attention. Among carboneous materials, various forms of carbon such as powders, woven cloths, felts, fibers, nanotubes etc., are frequently studied for electrochemical supercapacitors. Low cost, high porosity, higher surface area, high abundance and well established electrode fabrication technologies are the attractive features for using carboneous materials. However, specific capacitance (SC) of these materials is rather low. These electrodes store charge by electrostatic charge separation at the electrode/electrolyte interface. Electronically conducting polymers are interesting class of materials studied for supercapacitor application because of the following merits: high electronic conductivity, environmental friendliness, ease of preparation and fabrication, high stability, high capacitance and low cost. Polyaniline (PANI), polypyrrole and polythiophene are studied in this category. Transition metal oxides have attracted considerable attention as electrode materials for supercapacitors because of the following merits: variable oxidation state, good chemical and electrochemical stability, ease of preparation and handling. Hydrated RuO2 prepared by sol-gel process at low temperature has a specific capacitance as high as 720 F g-1 due to solid state pseudo faradaic reaction. However, high cost, low porosity and toxic nature limit commercialization of supercapacitors using this material. MnO2 is attractive as it is cheap, environmentally benign, its resources are abundant in nature and also it is widely used as a cathode material in batteries. An early study on capacitance behaviour of MnO2 was reported by Lee and Goodenough. Amorphous hydrous MnO2 synthesized by co-precipitation method exhibited rectangular cyclic voltammogram in various aqueous alkali salt solutions. A specific capacitance of 200 F g-1 was reported. Following this report, several reports appeared on capacitance characteristics of MnO2. According to the charge-storage mechanism reported, a specific capacitance of 1370 F g-1 is expected from MnO2. However, this value can be obtained in practice only when the mass of MnO2 is at the level of a few micrograms per cm2 area. At such a low thickness range, the utilization of the active material is high. As thin layers of MnO2 are uneconomical for practical capacitors, studies with a mass range of 0.4-0.5 mg cm-2 have been extensively reported. At this mass range, a maximum specific capacitance of about 240 F g-1 has been obtained. With an increase in mass per unit area, the specific capacitance of MnO2 decreases. The problem associated with low values of specific capacitance of thick layers of MnO2 is the following. The MnO2 deposits or coatings generally do not possess high porosity and the electrolyte cannot permeate into the coating. Only the outer layer of the electrode is exposed to the electrolyte. Consequently, the electrochemical utilization of the material decreases with an increase in thickness. Nevertheless, utilization of thick layers of the active materials is preferable for obtaining capacitance as high as possible in a given volume and area of the electrodes. Indeed, it would be ideal if specific capacitance of MnO2 is improved from its presently reported value of 240 F g-1 to a value equivalent to that of RuO2.xH2O, namely, 720 F g-1. In view of this, attempts are made to enhance specific capacitance of MnO2 by electrochemical deposition in presence of surfactants. Nanostructured MnO2 synthesized by inverse microemulsion route is also studied for electrochemical supercapacitors. The effect of crystallographic structure of MnO2 on the capacitance properties, studies on electrochemical deposition of MnO2 in acidic and neutral medium using electrochemical quartz crystal microbalance and capacitance characteristics of MnO2-polyaniline composites are also described in the thesis. Chapter 1 briefly discusses the importance of electrochemistry in energy storage and conversion, basics of electrochemical power sources, importance of MnO2, different synthetic procedures for MnO2 and its applications in energy storage and conversion in particular for electrochemical supercapacitors. Chapter 2 provides the experimental procedures and methodologies used for the studies reported in the thesis. In chapter 3, the effect of surface active agents, namely, sodium dodecyl sulphate (SDS) and Triton X-100 added to the electrolyte during electrodeposition of MnO2 on Ni substrate on capacitance properties is presented. Electrocrystallization studies show that MnO2 nucleates instantaneously under diffusion control and grows in three dimensions. The potentiodynamically prepared oxide provides higher specific capacitance than the potentiostatically and galvanostatically prepared oxides. Specific capacitance values of 310 and 355 F g-1 obtained for MnO2 electrodeposited in the presence of 100 mM SDS and 10 mM Triton X-100 are higher than the oxide electrodeposited in the absence of surfactants. Surfactant molecules adsorbed at the electrode/electrolyte interface alters structure of double-layer and kinetics of electrodeposition. Smaller particle size, greater porosity, higher specific surface area and higher efficiency of material utilization are the factors responsible for obtaining higher specific capacitance. Extended cycle-life studies indicate that the superior performance of MnO2 due to surfactants is present throughout the cycle-life tested. Chapter 4 pertains to electrochemical supercapacitor studies on nanostructured α-MnO2 synthesized by inverse microemulsion method and the effect of annealing. As synthesized nanoparticles of MnO2 was found to be in α-crystallographic structure with particles less than 50 nm size. Nanoparticles exhibited rectangular cyclic voltammograms between 0 and 1 V vs. SCE in aqueous 0.1 M Na2SO4 at sweep rates up to 100 mV s-1 due to the short diffusion path length. On annealing at different temperatures, a mixture of nanoparticles and nanorods with varying dimension is noticed. Specific capacitance of 297 F g-1 obtained during initial cycling decreases gradually on extended cycling. The capacitance loss is attributed to the increase in the resistance for intercalation/deintercalation of alkali cations into/from MnO2 lattice. MnO2 crystallizes into several crystallographic structures, namely, α-, β-, γ-, δ- and λ-structures. As these structures differ in the way MnO6 octahedra are interlinked, they possess tunnels or inter-layers with gaps of different magnitudes. Because capacitance properties are due to intercalation/deintercalation of protons or cations in MnO2, only some crystallographic structures, which possess sufficient gap to accommodate these ions, are expected to be useful for capacitance studies. The effect of crystal structure of MnO2 on its electrochemical capacitance properties is also included in chapter 4. Specific capacitance of MnO2 is found to depend strongly on the crystallographic structure, and it decreases in the following order: α ≅ δ > γ > λ > β. A specific capacitance value of 240 F g-1 is obtained for α-MnO2, whereas it is 9 F g-1 for β-MnO2. A wide (~ 4.6 Å) tunnel size and large surface area of α-MnO2 are ascribed as favorable factors for its high specific capacitance. A large interlayer separation (~7 Å) also facilitates insertion of cations in δ-MnO2 resulting in SC close to 236 F g-1. A narrow tunnel size (1.89 Å) does not allow intercalation of cations into β-MnO2. As a result, it provides very small SC. In Chapter 5, capacitance characteristics of PANI synthesized using (NH4)2S2O8, nanostructured MnO2 (α- and γ-form) and also PANI-MnO2 composites are presented. Morphology of PANI synthesized resembles the morphology of the MnO2 used as the oxidant. Electrochemical capacitance properties of PANI and composites are studied in a mixed electrolyte of 0.1 M HClO4 and 0.3 M NaClO4 between 0 and 0.75 V vs. SCE. Specific capacitance of 394 F g-1 is obtained for PANI synthesized using γ-MnO2. Chapter 6 describes the electrocatalytic behaviour of Mn3[Fe(CN)6]2 synthesized by ion-exchange reaction between MnSO4 and K3[Fe(CN)6] and the effect of annealing on its electrochemical capacitance properties. As prepared Mn3[Fe(CN)6]2 and also the sample heated at 100 oC exhibit redox couple in 0.1 M Na2SO4 electrolyte, corresponding to Fe(CN)64-/Fe(CN)63- present in the matrix. Mn3[Fe(CN)6]2 samples annealed at 150 oC and above decompose to oxides of manganese and iron, and hence exhibit capacitance characteristics in 0.1 M Na2SO4 electrolyte. A maximum specific capacitance of 129 F g-1 is obtained for Mn3[Fe(CN)6]2 annealed at 300 oC. Electrochemical quartz crystal microbalance (EQCM) investigations of kinetics of electrodeposition of MnO2 in acidic and neutral media, and capacitance behaviour are presented in chapter 7. Oxidation of Mn2+ to MnO2 is characterized by an anodic cyclic voltammetric peak both in acidic and neutral media. During the reverse sweep, however, reduction of MnO2 into Mn2+ occurs in two steps in the acidic medium and in a single step in the neutral medium. From EQCM data of mass variation during cycling, it is observed that the rate of electrodeposition of MnO2 is higher in the neutral medium than in the acidic medium. Specific capacitance of MnO2 deposited from the neutral medium is higher than that deposited from acidic medium owing to different crystallographic structures. Reversible insertion/deinsertion of hydrogen in to the layers of δ-MnO2 is observed in hydrogen evolution region. Details of the above studies are described in the thesis.

L'oxyde d'aluminium anodique poreux (AAO) est formé par anodisationde l'aluminium dans une solution électrolytique acide, sous une tensionconstante et de la température de l'électrolyte. Des techniques spectroscopiquespareilles que la spectroscopie infrarouge FT (ATR-FTIR), diffraction des rayonsX (XRD), spectroscopie Raman, la microscopie à force atomique (AFM) etmicroscopie électronique à balayage (MEB) utilisés pour caractériser la matrice.L'oxydation anodique d'acides L-aminés et des mélanges de monomèrescomprenant 0,1 M aniline et des acides L-aminés dans le milieu aqueux acide deplatine et électrode lisses électrodes Pt modifié (Pt / AAO) est étudié.L'oxydation des acides L-aminés et les électropolymérisation de l'aniline 0,1 Mavec des acides L-aminés tels que la L-alanine, la L-sérine, la L-méthionine,acide L-aspartique, la L-lysine, et phénylalanine en acide le milieu a étéeffectuée par voltammetric cyclique électrochimique couplée à microbalance àcristal de quartz (EQCM). La concentration des acides aminés, le pH del'électrolyte et les effets de balayage de numéros de voltamétrie cyclique ont étéexaminées. L'analyse spectroscopique comme réflectance totale atténuée FTspectroscopie infrarouge (ATR-FTIR), UV-visible, la spectroscopiephotoélectronique à rayons X (XPS), la spectroscopie Raman, et la diffractiondes rayons X (XRD) sont utilisés pour caractériser les couches minces obtenues.Microscopie électronique à balayage (MEB) utilisé pour étudier la morphologiede surface mince de films. La solubilité pour les polymères sont étudiées. Laprésence de liaisons peptidiques est clairement mise en évidence. DFTmodélisation de poly-L-acides aminés volet sur Pt (001) couplée à des mesuresspectroscopiques sont en faveur de L-amino-acides électropolymérisation enacides poly-L-aminés d'une manière irréversible.Les électrosynthèses de poly-L-amino acides, la polyaniline et depolymères ont été utilisées en tant que récepteur de protons à l'état solide pHcapteur solide. / Anodic aluminum oxide porous (AAO) is formed by the anodization ofaluminum in acidic electrolytic solution under at constant voltage and electrolytetemperature. Spectroscopic techniques such as FT infrared spectroscopy (ATRFTIR),X-ray diffraction (XRD), Raman spectroscopy, atomic force microscopy(AFM) and scanning electron microscopy (SEM) used to characterize thetemplate.The anodic oxidation of L-amino acids and monomer mixtures comprising0.1 M aniline and some L-amino acids in acidic aqueous medium on platinumsmooth electrodes and modified Pt electrode (Pt/AAO) is studied. The oxidationof L-amino acids and in presence of aniline 0.1 M with L-amino acids such as Lalanine,L-serine, L-methionine, L-aspartic acid, L-lysine, and L- phenylalaninein acidic media was carried out by cyclic voltammetry coupled withelectrochemical quartz crystal microbalance (EQCM). The Amino acidconcentration, pH of the electrolyte and the scan number effects on cyclicvoltammetry were examined. Spectroscopic analysis such as attenuated totalreflectance FT infrared spectroscopy (ATR-FTIR), UV-Visible, X-rayphotoelectron spectroscopy (XPS), Raman spectroscopy, and X-ray diffraction(XRD) are used to characterize the resulting thin film coatings. Scanningelectron microscopy (SEM) used to study the morphology of thin films surfaceas well as the solubility are studied. The presence of peptide bonds is clearlyhighlighted. DFT modelization of poly-L-amino acids strand on Pt(001) coupledto spectroscopic measurements are in favor of L-amino acidselectropolymerization into poly-L-amino acids in an irreversible way.The electrosynthesis of poly-L-amino acids, polyaniline and polymerswere used as proton receptor for solid state pH solid sensor.

Ce travail porte dans un premier temps sur l’optimisation du matériau constituant la couche d’injection des trous dans les diodes électroluminescentes organiques (OLEDs) et les cellules solaires organiques (OPVCs). Les Polyanilines (PANIs) utilisées dans ce travail sont dispersées dans différents solvants organiques ou dans l'eau. L’effet de l’épaisseur, de la morphologie et de la conductivité des films de PANI sur l’efficacité des cellules solaires a été étudié. Les résultats montrent que la conductivité et l’épaisseur des films de PANI affectent énormément l’efficacité des dispositifs OLEDs ou OPVCs. Le dopant et le solvant utilisés dans la synthèse de la dispersion de PANI jouent aussi un rôle important. Dans un second temps, différentes PANIs ainsi que des latex de PEDOT et des nanotubes de carbone ont été utilisés seuls en tant qu'électrode dans le but d'accéder à des dispositifs "tout polymère". L’influence du pH, de la conductivité, du travail de sortie, la nature du dopant et du solvant sur les propriétés de l’injection de charge ont été analysés. / The optimization of hole injection materials in organic light emitting diodes (OLEDs) and organic photovoltaic cells (OPVCs) is reported. Water and organic solvent-based PANIs were used. We have studied the influence of the thickness, the morphology and the conductivity of PANI films in (OPVCs) performances. The results show that the conductivity and the thickness of the PANI film greatly affect (OLED) and (OPVCs) effectiveness. The dopant and the solvent used in the synthesis of PANI dispersion also play an important role. PANI and PEDOT dispersions as well as carbon nanotube were also used as electrodes without ITO. The effect of pH, conductivity, the work function, the nature of the dopant and the solvent in the injection property were analyzed.

No description available.

Organic coatings are widely used to lower the corrosion rate of metallic structures. However, penetration of water, oxygen and corrosive ions through pores present in the coating results in corrosion initiation and propagation once these species reach the metal substrate. Considering the need for systems that offer active protection with self-healing functionality, composite coatings containing polyaniline (PANI) conducting polymer are proposed in this study. In the first phase of my work, PANI was synthesized by various methods and characterized. The rapid mixing synthesis method was chosen for the rest of this study, providing PANI with high electrical conductivity, molecular structure of emeraldine salt, and morphology of spherical nanoparticles. PANIs doped with phosphoric and methane sulfonic acid revealed hydrophilic nature, and I showed that by incorporating a long-chain alkylphosphonic acid a hydrophobic PANI could be prepared. The second phase of my project was dedicated to making homogenous dispersions of PANI in a UV-curable resin based on polyester acrylate (PEA). Interfacial energy studies revealed the highest affinity of PEA to PANI doped with phosphoric acid (PANI-PA), and no attractive or long-range repulsive forces were measured between the PANI-PA surfaces in PEA.This is ideal for making conductive composites as, along withno aggregation tendency, the PANI-PA particles might come close enough to form an electrically connected network. Highly stable PEA/PANI-PA dispersions were prepared by pretreatment of PANI-PA in acetone followed by mixing in PEA in small portions under pearl-milling. The third phase of my project dealt with kinetics of the free radical polymerization that was utilized to cure the PEA/PANI-PA mixture. UV-vis absorption studies suggested a maximum allowed PANI-PA content of around 4 wt.% in order not to affect the UV curing behavior in the UV-C region. Real-time FTIR spectroscopy studies, using a laboratory UV source, revealed longer initial retardation of the photocuring and lower rates of crosslinking reactions for dispersions containing PANI-PA of higher than 3 wt.%. The presence of PANI-PA also made the formulations more sensitive to changes in UV light intensity and oxygen inhibition during UV curing. Nevertheless, curing of the dispersions with high PANI-PA content, of up to 10 wt.%, was demonstrated to be possible at either low UV light intensities provided the oxygen replenishment into the system was prevented, or by increasing the UV light intensity to very high levels. In the last phase of my project, the PEA and PEA/PANI-PA coatings, cured under high intensity UV lamps, were characterized. SEM analysis showed small PANI-PA particles to be closely packed within the matrix, and the electrical conductivity of the composite films was measured to be in the range of semiconductors. This suggested the presence of a connected network of PANI-PA, as confirmed by investigations of mechanical and electrical variations at the nanoscale by PeakForce TUNA AFM. The data revealed the presence of a PEA-rich layer at the composite-air interface, and a much higher population of the conductive network within the polymer matrix. High current signal was correlated with a high elastic modulus, consistent with the level measured for PANI-PA, and current-voltage studies on the conductive network showed non-Ohmic characteristics. Finally, the long-term protective property of the coatings was characterized by OCP and impedance measurements. Short-term barrier-type corrosion protection provided by the insulating PEA coating was turned into a long-term and active protection by addition of as little as 1 wt.% PANI-PA. A large and stable ennoblement was induced by the coatings containing PANI-PA of up to 3 wt.%. Higher content of PANI-PA led to poorer protection, probably due to the hydrophilicity of PANI-PA facilitating water transport in the coating and the presence of potentially weaker spots in the film. An iron oxide layer was found to fully cover the metal surface beneath the coatings containing PANI-PA after final failure observed by electrochemical testing. / <p>QC 20141103</p>

Beaucoup de recherches sont menées sur les polymères organométalliques et en particulier dans le but d'obtenir des bons matériaux utilisables dans les dispositifs photovoltaïques. Ce mémoire rapporte les derniers avancements de notre groupe de recherche dans ce secteur. Premièrement, la synthèse et la caractérisation de polymères organométalliques conjugués du type (-espaceur-C[xi]C-PtL[indice inférieur 2]-C[xi]C-)[indice inférieur n] avec comme espaceur des quinones diimine para-bis(diphényle) tetrasubstitués (C[indice inférieur 6]H[indice inférieur 4]-N=C[indice inférieur 6]X[indice inférieur 4]=N-C[indice inférieur 6]H[indice inférieur 4] où X = H, F, Cl) et comme ligand L= P(n-Bu)[indice inférieur 3] ont été réalisées. Les espaceurs, les composés modèles, et les polymères ont été caractérisés par RMN [indice supérieur 1]H, [indice supérieur 31]P, UV-vis, IR, ATG, cristallographie, analyse élémentaire et par voltampérométrie cyclique. Les espaceurs et les polymères diamines (C[indice inférieur 6]H[indice inférieur 4]-NH-C[indice inférieur 6]X[indice inférieur 4]-NH-C[indice inférieur 6]H[indice inférieur 4]) ont également été synthétisés et caractérisés afin de comparer le comportement d'un polymère conjugué (quinone diimine) avec un polymère non conjugué (quinone diamine). Les polymères platine-diamine montrent des spectres d'absorption où la bande de plus basse énergie provient d'une transition de type [pi]-[pi]* tandis que les polymères quinone diimines montrent des bandes électroniques provenant de transitions électroniques de type transferts de charge (avec le centre platine comme donneur et quinone diimine comme accepteur). Une analyse de l'influence de l'effet électro-attracteur des différents substituants sur les spectres d'absorption ainsi que les propriétés électrochimiques ont été effectuées pour étudier les mécanismes de transfert de charge du platine vers les espaceurs diimines. Des résultats préliminaires encourageant de conversion d'énergie solaire en énergie électrique, grâce à des cellules de Grätzel, ont été obtenus pour certains de ces composés. Deuxièmement, un nouveau type de polymère organométallique bio-inspiré à base de quinone-diimines et de porphyrines a été synthétisé et caractérisé par RMN [indice supérieur 1]H, UV-vis, IR, ATG, cristallographie, spectroscopie de luminescence et mesures de paramètres photophysiques, et analyse élémentaire. Ces polymères montrent des spectres d'absorptions où la bande de plus basse énergie provient de transitions électroniques du type transfert de charge partant de la métallo-porphyrine vers la quinone diimine (C[indice inférieur 6]H[indice inférieur 4]-N=C[indice inférieur 6]X[indice inférieur 4]=N-C[indice inférieur 6]H[indice inférieur 4] où X = F, Me). Ces absorptions sont extrêmement déplacées vers les grandes longueurs d'onde (> 800 nm) et affichent des coefficients d'extinction molaires très grands (30 000 M[indice supérieur -1] .cm[indice supérieur -1]). Ces composés affichent des très grands rendements quantiques pour des polymères à base de porphyrines. Ces excellentes propriétés font de ces composés une nouvelle classe intéressante de polymères utilisables pour des applications photoniques.

It is ideal to theoretically predict the activity of a catalyst. It has been recognized that not only the type of metal, but also its atomic size plays an important role in catalysis. In the past, atomic clusters have been created by sputtering from a sacrificial metal plate and then using a mass selector to choose cluster sizes from 1-233 atoms of gold. This approach has practical limitations. In this thesis, I describe a procedure by which atomic clusters of gold containing 1-8 atoms are deposited in polyaniline as an isolation matrix. My atomic deposition follows a cyclic pathway. Atomic clusters of palladium and atomic alloys of gold and palladium are also deposited in polyaniline using the same process. It is to show that this method will also work for other metals. These composite materials are characterized, and the catalytic activity for alcohol oxidation is evaluated. This thesis is divided into seven chapters. The first chapter discusses the chemistry of polyaniline for using gold and palladium as catalysts. The technique developed to deposit the atomic clusters is discussed in the second chapter. This technique deposits one atom of metal per imine site on polyaniline, per cycle. The cycle is repeated n-times until a cluster of specified size, Mn, and composition has been synthesized. It is known that polyaniline plays an important role in stabilization of the formed clusters which prevents their aggregation. The optimization of this technique is the topic of the third chapter along with the description of how these composite films are produced. To end this chapter, the composite films are characterized by cyclic voltammetry, Kelvin probe, and X-ray photoelectron spectroscopy. In chapters 4 and 5, the catalytic activity of the polyaniline/gold composites for the oxidation of alcohols in alkaline media using cyclic voltammetry is evaluated. In chapter 4, the correlation of the electrochemical activity for the oxidation of n-PrOH with the odd-even pattern from the calculated HOMO-LUMO gap energies for the same size clusters is shown. It is shown that the infrared spectrum of polyaniline with different sizes of atomic gold clusters also follows the odd-even pattern. Chapter 5 expands on the discussion of the catalytic oxidation of alcohols. The oxidation of methanol, ethanol, propanol, and butanol is surveyed. The peak currents are again dominated by the odd-even pattern. In chapter 6, the versatility of the atomic deposition cycle is shown by depositing atomic palladium clusters. The peak currents for the oxidation of n-PrOH by these palladium composite films again follows the predicted pattern of the calculated HOMO-LUMO gap energies for atomic palladium clusters. This chapter also explores bimetallic atomic clusters of gold and palladium. The results indicate that the catalytic activity depends on the orientation of the cluster in the polyaniline matrix. Chapter 7 discusses the oxidation of methanol, ethanol, and isopropanol on AunPd1 bimetallic atomic clusters. The addition of palladium in the cluster increases the peak current densities for the oxidation of both alcohols except for the most stable of the atomic gold clusters, while it inactivated the electrodes for isopropanol. The possible future work for this project is discussed in chapter 8. Overall, this thesis has developed a novel and unique technique for depositing atomic metal clusters into a polyaniline matrix. The technique is versatile enough to deposit atomic metal clusters other than gold, as shown by creating atomic palladium clusters and atomic bimetallic clusters of gold and palladium. This is extremely useful, since this single technique can produce many different types of atomic catalysts. The composite materials have been shown to be catalytically active for the oxidation of alcohols in alkaline media. This indicates a significant improvement to conserve precious metals while still retaining a high catalytic activity.

Cette thèse est divisée en trois parties. La première traite la synthèse de la polyaniline (PANI), un polymère conducteur de trou, utilisé dans plusieurs applications. En variant les quantités du monomère et de l'oxydant tout en fixant leur rapport molaire à 1:1,25, et en ajoutant de l'oxyde de magnésium, des aiguilles et des nouvelles structures semblables aux échinides sont formées. Le mécanisme de formation des structures unidimensionnelles est expliqué à l'aide de la théorie des multicouches. La deuxième partie est consacrée à la fabrication des monocouches photovoltaïques à faible coût en se basant sur le principe de fonctionnement des cellules à pigment photosensible (en anglais DSSC, Dye-Sensitized Solar Cell). En 1991, Grätzel a réintroduit l'effet photo-électrochimique en développant la première DSSC, une des cellules solaire troisième génération, formée d'un film de TiO2 (photo-anode) pigmenté à l'aide d'un colorant et d'un électrolyte qui sert à régénérer le pigment oxydé. Malgré leur faible coût, les DSSCs font face à de nombreux problèmes tels que le coût élevé du pigment, la fuite de l'électrolyte, la sublimation du couple I-/I3- à travers I2, etc. Afin de résoudre ces problèmes, des monocouches photovoltaïques ont été développées. Des composites formés de PANI et TiO2 sont la base de ces dispositifs nouvelle génération. La polymérisation in-situ de l'aniline en présence des nanoparticules de TiO2 conduit à une forte interaction entre la PANI et les particules de TiO2 où une structure " core (TiO2)/shell (PANI) " existe dans le composite. Dans le dispositif photovoltaïque basé sur le composite PANI-TiO2, PANI est considérée comme pigment à la photo-anode et comme poly-électrolyte plus profondément dans le composite. En plus, des textiles fabriqués utilisant ces composites photo-génèrent une tension de 0,6 V et un courant de 1 A/m2 lorsque l'éthanol est injecté dans le dispositif. Une nouvelle architecture a été développée qui sert à améliorer la performance de la cellule et en même temps stocker l'énergie pour des utilisations ultérieures. La dernière partie est consacrée à la fabrication des DSSCs basées sur les pigments naturels. L'anthocyane, un pigment naturel halochromique responsable de la couleur rouge dans les plantes, a été extrait du chou rouge et utilisé pour pigmenter les films de TiO2. Cette propriété se traduit par la fabrication des DSSCs de différentes couleurs et comportement photovoltaïque. Avec un pH égal à 0, une Vco et une Jcc de 520 mV et 185 μA/cm2 sont respectivement obtenues prouvant la possibilité d'utiliser le chou rouge comme source de pigment à très faible coût des DSSCs.