Este trabalho de tese versa sobre o estudo espectroscópico da polianilina (PANI) formada em solução e nas cavidades de sólidos inorgânicos porosos e, também, sobre o monitoramento da interação entre a PANI e íons metálicos, através das técnicas espectroscópicas Raman ressonante, espectroscopia no infravermelho (IR), espectroscopia eletrônica no UV-VIS-NIR, ressonância paramagnética eletrônica (EPR) e absorção de raios X (XANES). Na síntese em solução, empregou-se o Cu(II) como agente oxidante em dois meios: (i) aquoso ácido e (ii) acetonitrila/água. As matrizes inorgânicas utilizadas foram a MCM-41, Cu(II)-MCM-41, Cu(II)-Montmorilonita e alfa-Zr(HOPO3)2.H2O. A espectroscopia Raman ressonante, utilizando diferentes radiações excitantes, demonstrou-se uma importante ferramenta no estudo dos diversos segmentos poliméricos nos diferentes ambientes químicos. Verificou-se a importância do meio reacional na natureza do polímero obtido. Usando Cu(II) em meio aquoso ácido, forma-se o de sal de esmeraldina enquanto em meio de acetonitrila/água, obteve-se um polímero contendo anéis fenazínicos e segmentos quinonadiimina e/ou fenilenodiamina. Os polímeros obtidos na sílica mesoporosa Cu(II)-MCM-41, na argila Cu(II)-MMT e no fosfato lamelar alfa-Zr(HPO4)2.H2O (alfa-ZrP) também apresentam novos segmentos provenientes de mecanismos de polimerização que diferem do usual acoplamento cabeça-cauda. Através da técnica \"layer-by-layer\" foi possível obter filmes de alfa-ZrP/PANI com a PANI na forma sal de esmeraldina e conformação estendida. Foi observado que complexação da esmeraldina base (EB) com Cu(II), Fe(III) e Zn(II) leva à formação de radicais cátions. O monitoramento do comportamento espectroscópico de soluções de EB e íons metálicos em solução de N-metil-pirrolidona demonstrou que as espécies presentes dependem da natureza dos íons metálicos, da proporção Metal/EB e das concentrações do polímero e do íon metálico. / This work presents the spectroscopic study of polyaniline (PANI) formed in solution and inside inorganic porous materials, and also the monitoring of the interaction of PANI and metallic ions through resonance Raman, infrared spectroscopy (IR), electronic UV-VIR-NIR spectroscopy, electronic paramagnetic resonance (EPR) and X-ray absorption near edge structure (XANES). In the polymerization of aniline in solution, Cu(II) ions were used as oxidizing in two different media: (i) acidic aqueous medium and (ii) acetonitrile/water. The inorganic hosts employed were MCM-41, Cu(II)-MCM-41, Cu(II)-Montmorillonite and alpha-Zr(HOPO3)2.H2O. Resonance Raman scattering by using exciting laser lines in a wide spectral range is an important technique for the structural investigation of the polymeric segments in different environments. It was verified the important role of the synthetic parameters in the structure of the polymeric material obtained. Using Cu(II) ions in acidic aqueous medium, emeraldine salt (ES) is formed while in acetonitrile/water medium it was observed a polymer having phenazine-like rings, quinonediimine and/or phenylenediamine segments. The obtained polymers into mesoporous silica Cu(II)-MCM-41, into Cu(II)-MMT clay and into the lamellar phosphate alpha-Zr(HPO4)2.H2O (alpha-ZrP) also present new segments resulted from distinct polymerization mechanisms from the usual head-to-tail coupling. Through the layer-by-layer technique it was possible to obtain alpha-ZrP/PANI films with PANI in the ES form and with extended conformation. It was observed that complexation of emeraldine base (EB) with Cu(II), Fe(III), and Zn(II) ions gives rise to radical cations formation. The monitoring of spectroscopic behavior of EB and metallic ions in NMP solution showed that the species present depend on the nature of metallic ion, on the Metal/EB ratio, and on the metallic ion and polymer concentrations.

Estudos sobre a aplicação de revestimentos contendo polímeros condutores e nanopartículas metálicas sobre superfícies de ligas de alumínio têm sido avaliados como alternativa para a proteção contra a corrosão de superfícies metálicas. Revestimentos composto por uma bicamada contendo nanopartículas metálicas (AgCe) e polianilina (PAni) ambos na presença do ácido dodecilbenzenosulfônico (DBSA) foram aplicados em ligas de alumínio do tipo AA6063 e AA7075 por deposição de um filme casting, com a finalidade de aumentar a adesão e a capacidade de dispersão de carga do filme sobre a superfície das ligas. A camada de nanopartículas metálicas de AgCe aparece como opção para melhorar a morfologia e textura do revestimento de cério, assim como, minimizar processos corrosivos e por conseguinte, proporcionar maior utilidade destes materiais. Estas propriedades são esperadas para aumentar a capacidade do filme de PAni para proteger as superfícies metálicas contra a corrosão. Neste trabalho as amostras foram caracterizadas por difratometria de raios-X, espectroscopia na região do infravermelho, espectroscopia na região do ultravioleta visível, espectroscopia de fotoelétrons excitados por raios-X, microscopia de força atômica, microscopia eletrônica de varredura, espectroscopia de energia dispersiva e microscopia óptica, também foram realizados voltametria cíclica e ensaios de corrosão, como potencial de circuito aberto, polarização potenciodinâmica e espectroscopia de impedância eletroquímica. Na análise dos testes de corrosão, os valores para o potencial do circuito aberto das ligas de AA6063 e AA7075 são mais positivos para as amostras revestidas, ou seja, mais nobre, em relação às amostras não revestidas. Para os ensaios eletroquímicos de 3h de imersão em NaCl 3,5% os valores do potencial de corrosão (Ecorr) obtidos na polarização potenciodinâmica foram de -0,63 V para AA6063/AgCe/PAni e -0,61 V para AA7075/AgCe/PAni. Para os ensaios de corrosão com maiores tempos de imersão de 6, 30 e 60h que foram realizados somente para os revestimentos de PAni e n-AgCe/PAni por apresentaram Ecorr mais positivos e por indicarem aderência relativamente boa, também indicaram um melhor desempenho contra corrosão para o revestimento contendo as nanopartículas metálicas mesmo após o tempo máximo de imersão em NaCl 3,5%. Assim, a eficiência de proteção calculada revelou valores de 80% para a liga AA6063 e 91% para a liga AA7075, confirmando que o revestimento de n-AgCe/PAni promoveu a proteção contra corrosão em até 60h de imersão em ambiente salino. / Studies on the application of conductive polymers and films containing metallic nanoparticles on surfaces of aluminum alloys have been evaluated as an alternative for corrosion protection of metal surfaces. Coatings consisting by a bilayer of AgCe nanoparticles and polyaniline (PAni) both in the presence of dodecylbenzenesulfonic acid (DBSA) were applied to aluminum alloy type AA6063 and AA7075 by deposition of a casting film, in order to increase the adhesion and the charge dispersion capacity of the film on the alloys surfaces. The AgCe metallic nanoparticles layer appears as an option to improve the morphology and texture of the cerium coating, as well as to minimize corrosive processes and therefore provide greater utility of these materials. These properties are expected to increase the ability PAni films to protect the metallic surfaces against corrosion. In this work, samples were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, ultraviolet-visible spectroscopy, X-ray photoelectron spectrometry, atomic force microscopy, scanning electron microscopy, energy dispersive spectroscopy and optical microscopy and were also evaluated by corrosion tests as open circuit potential, potentiodynamic polarization, cyclic voltammetry and electrochemical impedance spectroscopy. In the analysis of corrosion tests, the values for the open circuit potential of AA6063 and AA7075 alloys were more positive for the coated samples, i.e. nobler relative to samples without coating. For the electrochemical tests of 3h of immersion in 3.5% NaCl, the values of corrosion potential (Ecorr) obtained in potentiodynamic polarization were -0.63 V for AA6063/AgCe/PAni and -0.61 V for AA7075/AgCe/PAni. For the corrosion tests with higher immersion times of 6, 30 and 60h, which were performed only for PAni and n-AgCe/PAni coatings because they presented more positive Ecorr and because of their relatively good adhesion, they also indicated a better performance against corrosion for the coating containing the metal nanoparticles even after the maximum immersion time in 3.5% NaCl. Thus, the calculated protection efficiency revealed values of 80% for the AA6063 alloy and 91% for the AA7075 alloy, confirming that the n-AgCe/PAni coating promoted corrosion protection in up to 60h immersion in the saline environment.

This dissertation presents the synthesis and application of nanodiamond based materials for electrochemical biosensors. In this research work, nanodiamond particles have been used to prepare doped and undoped nanocrystalline diamond films, and conducting polymer composites for enhanced biosensing. The performance of the synthetized materials towards sensing applications was evaluated against glucose amperometric biosensing. Besides, cholesterol biosensing was attempted to prove the capabilities of the platform as a generic biosensing substrate. Biosensors have been proved to provide reliable detection and quantification of biological compounds. The detection of biological markers plays a key factor in the diagnosis of many diseases and, even more importantly, represents a major aspect in the survival rate for many patients. Among all of the biosensors types, electrochemical biosensors have demonstrated the best reliability to cost ratio. Amperometric biosensors, for example, have been used for decades as point of care sensing method to monitor different conditions such as glucose. Despite the amount the research presented, the sensitivity, selectivity, stability, low cost and robustness are always driving forces to develop new platforms for biosensor devices. In the first phase of this dissertation, we synthesized undoped and nitrogen doped nanocrystalline diamond films. The synthetic material was thoroughly studied using different material characterization techniques and taken through a chemical functionalization process. The functionalization process produced a hydrogen rich surface suitable for enzymatic attachment. Glucose oxidase was covalently attached to the functionalized surface to form the biosensing structure. The response of the biosensor was finally recorded following voltammetry and amperometric techniques under steady state and dynamic conditions. The experimental results demonstrated that conductivity induced by the doping process enhanced the sensitivity of the sensing structure with respect to the undoped substrate. Also, the functionalization procedure showed strong bonding to avoid enzyme leaching during the measurements. Later, in the second phase of this dissertation, the nanodiamond particles were used as filler for conducting polymer composites. The objective for developing these composite materials was to overcome the high resistivity observed for nanocrystalline films. The experimental results demonstrated that the inclusion of nanodiamond particles increased the sensitivity of the overall structure towards the quantification of glucose with respect to the nanocrystalline films and the bare polymer. Besides, the experiment showed a noticeable enhancement in the signal-to-noise ratio and the mechanical stability of the sensing platform due to the nanodiamond addition. The best structures from the previous experiments were further grafted with iron oxide nanoparticles to attempt signal amplification. Initial experiments with nanodiamond based composited showed similar current for low glucose concentrations for two different active electrochemical sensing areas. This observation indicates that more area is still available to transport signal and to enhance even further the sensing action. Oxidation of iron oxide nanoparticles after initial enzymatic decomposition of glucose has been proved to provide higher current for the same glucose concentration; thus, creating amplification effect for the signal. Finally, the toxicity of the nanomaterial synthesized during this dissertation was evaluated in mammalian cells. The advances in biosensing techniques indicate the potential application of amperometric platform for continuous implantable devices; hence, the toxicity of the materials becomes a key aspect of the platform design.

<p>Major efforts have been spent during recent years in worldwide attempts to achieve an electronic paper technology; the common name for novel flexible displays utilizing substrates such as paper, plastics or thin metal sheets. Various kinds of technology are available that potentially will be used for an electronic paper, which differs from each other mainly with respect to the choice of active materials, substrates and manufacturing techniques. There are many applications for electronic paper technology, ranging from high-resolution displays used in electronic books to updateable large-area billboards. The latter suggests a novel electronic display function that could extend the utilization of cellulose-based paper, which is one of the most common materials ever produced by mankind, by using the paper as a thin and flexible carrier. The requirement for fast update speed in such large area applications would probably be a bit more relaxed compared to traditional display technologies, while low-power consumption and bi-stability are among the factors that should be further emphasized, together with the utilization of well-established printing techniques to enable low-cost manufacturing of the displays. The choice of active materials is therefore crucial in order to reach these objectives in reality and this paves the way for printable conjugated polymers with electrochromic properties. Chemical synthesis of these materials during the last decades has resulted in a vast variety of electrochromic polymers with custom-tailored functionality covering a broad range of optical absorption and electrical conductivities.</p><p>This thesis review the studies done on the electrochemical switching of poly(3,4-ethylenedioxythiophene) (PEDOT). For this material both the electrical conductivity and the optical absorption is controlled by the oxidation state. Active matrix addressed displays that are printed on flexible substrates have been obtained by arranging electrochemical smart pixels, based on the combination of electrochemical transistors and electrochromic display cells, into cross-point matrices. The resulting polymer-based active-matrix displays are operated at low voltages and the same active material can be used in electrochemical transistors and conducting lines and in electrochromic display cells employing the electronic and the opto-electonic properties of the material, respectively. In addition to this, a switchable optical polarizer is briefly discussed. This is a device utilizing electrochromism of stretch-aligned polyaniline (PANI). The combination of two identical devices in a vertical architecture, orthogonally oriented with respect to each other, results in a filter in which the orientation of the polarized optical absorption is governed by the voltage polarity applied to the device.</p> / Report code: LiU-TEK-LIC- 2006:18

La spectroscopie électrochimique d'impédance (SEI) renseigne sur les mécanismes à l'interface électrode-électrolyte, mais ne peut pas identifier la nature des espèces adsorbées à la surface de l'électrode. La spectroscopie Raman est une technique puissante pour la recherche structurale ; elle peut fournir les informations requises au niveau moléculaire, qui sont absentes des mesures de SEI. Le but de ce travail a été de mettre au point la méthode de couplage dynamique de ces deux techniques. Cette nouvelle méthode -La spectro-électrochimie Raman-Impédance- a ensuite été appliquée à l'étude d'un film de polymère conducteur. Le principe de la méthode consiste à analyser le spectre émis par l'interface, et à convertir l'intensité des bandes choisies en une tension électrique. Plusieurs fonctions de transfert ΔV/ΔI, ΔRaman/ΔV, Δ Raman/ΔI ; sont enregistrées simultanément. Les premiers résultats de cette méthode appliquée à l'étude d'un film mince de polyaniline prouvent que l'équilibre acido-basique à l'intérieur du polymère doit être pris en considération sur la base d'un mécanisme cinétique impliquant deux réactions rédox et une réaction chimique.

Electroactive polymers (EAP) are an emerging branch of smart materials that possess the capability to change shape in the presence of an electric field. Opportunities for the advancement of knowledge were identified in the branch of EAP consisting of inherently electrically conductive polymers. This dissertation explores methods by which the unique properties of composite materials having conductive polymers as a constituent may be exploited. Chapter 3 describes the blending of polyaniline with conventional thermoplastics. Processing these polyblends into foams yielded a porous conductive material. The effect of blend composition and processing parameters on the resulting porous morphology and electrical conductivity was investigated. These findings represent the first systematic study of porous conductive polymer blends. In Chapter 4, multilayer electroactive polymer actuators consisting of polypyrrole films electropolymerized on a passive polymer membrane core were harnessed as actuators. The membrane is vital in the transport of ionic species and largely dictates the stiffness of the layered configuration. The impact of the mechanical properties of the membrane on the actuation response of polypyrrole-based trilayer bending actuators was investigated. Candidate materials with distinct morphologies were identified and their mechanical properties were evaluated. These results indicated that polyvinylidene difluoride membranes were superior to the other candidates. An electrochemical synthesis procedure was proposed, and the design of a novel polymerization vessel was reported. These facilities were utilized to prepare actuators under a variety of synthesis conditions to investigate the impact of conductive polymer morphology on the electromechanical response. Characterization techniques were implemented to quantitatively assess physical and electrochemical properties of the layered composite. Chapter 5 proposes a new unified multiphysics model that captures the electroactive actuation response inherent to conductive polymer trilayer actuators. The main contribution of this investigation was the proposal and development of a new hybrid model that unifies concepts from charge transport and electrochemomechanical models. The output of the proposed model was compared with published data and shown to be accurate to within 10%. Finally, Chapter 6 demonstrated the application of these materials for use as precision mirror positioners in adaptive optical systems.

An amperometric glucose biosensor was fabricated using electospun polyaniline fibers. Polyaniline was reacted with camphorsulfonic acid to produce a salt, which was then dissolved in chloroform containing polystyrene. Using this solution, fibers were formed and collected by electrospinning. Glucose oxidase was immobilized onto these fibers using an electrostatic layer-by-layer adsorption technique. In this method, poly(diallyldimethylammonium chloride) was used as the counter ion source. The level of adsorption was examined and evidence of layer-by-layer adsorption was obtained using a quartz crystal microbalance technique. A biosensor was fabricated from these fibers as a working electrode, and used to measure the glucose concentration accurately.

Polyaniline (PAn) is an important conjugated conducting polymer because of its good environmental stability. However, the conductive form of polyanilune is difficult to processed because it is insoluble in common organic solvent. This property limits its processibility and application. In the study, we developed a feasible route for preparing polyaniline/surfactant core-shell latex to solve the insoluble problem. The polyaniline latex was made by emulsion polymerization of aniline monomer, using ionic polymer (poly(4-vinylpyridine)-methanesulfonic acid; P4VP(MSA)) as the surfactant and dopant. And then, the nano-size and core-shell morphologies of polyaniline latex was studied by Transmission electron microscopy (TEM) technique. The best conductivity of polyaniline film is approach to 10-2 S/cm.

This dissertation describes a new electrochemical synthesis of novel composite materials based on montmorillonite (MMT) clay and intrinsically conducting polyaniline (PANI). PANI was successfully incorporated into MMT galleries to form PANI−MMT nanocomposites. Electropolymerization of anilinium ions which are intercalated inside the clay layers have been carried out at a constant applied potential. The synthetic conditions have been optimized taking into account the effect of concentration of aniline, magnetic stirring and potential cycling. The resulting organic-inorganic hybrid material, PANI-MMT has been characterized by various physicochemical techniques. Results of elemental analysis show that nanocomposite contains only 10 % of conducting PANI. Formation of PANI inside the clay tactoid has been confirmed by the expansion of inter layer distance of MMT as revealed by X-ray diffraction studies. Relatively lower interlayer expansion for PANI-MMT than that of anilinium-MMT indicates the higher stereoregularity in PANI-MMT which has strong influence on electrical properties of nanocomposites. Infrared spectroscopy studies reveal the presence of physicochemical interaction, probably hydrogen bonding, between clay and polyaniline. Cyclic voltammetry studies indicate that presence of electroinactive clay does not influence the electrochemical activity of PANI. Electrochromic behaviour of PANI-MMT nanocomposites have been studied using in situ UV-Vis spectroscopy which reveals that electrochromism of PANI in the composite material has been retained. One of the main technological applications of conducting polymers, particularly PANI, is in the area of corrosion protection of active metals. PANI-MMT nanocomposites synthesized using the present method and a chemically synthesized PANI which is soluble in organic solvents have been used to protect C45 steel surface against corrosion. Corrosion studies have been performed using electrochemical impedance measurements(EIM)and anodic polarization studies. Electrochemical impedance data has been analyzed using a suitable equivalent circuit. Corrosion protection of steel offered by both PANI-MMT and organically soluble PANI is evident form the increase in the value of charge transfer resistance of the coated steel surfaces. Time dependent EIM measurements reveal that charge transfer resistance gradually decreases with time, however, the values are much higher than that of uncoated surfaces. Two capacitive loops, one at higher and another at lower frequencies, observed in the Nyquist plots have been assigned to the electrical properties of coating material (in the present case, PANI-MMT or soluble PANI) and electrochemical process at the interface, respectively. An anodic shift in the corrosion potential, a decrease in the corrosion rate and a significant increase in the polarization resistance indicate a significant anti-corrosion performance of both PANI-MMT nanocomposite and organically soluble PANI deposited on the protected steel surface. / Diese Dissertation beschreibt eine neue elektrochemische Synthese neuartiger Compositmaterialien basierend auf dem Tonmineral Montmorillonite (MMT) und intrinsisch leitfähigem Polyanilin (PANI). Die Elektropolymerisation von Aniliniumionen, welche in die Tonmineralschichten eingebaut sind, wurde bei einem konstanten Potenzial durchgeführt. Das resultierende organisch-anorganische Hybridmaterial PANI-MMT wurde mit verschiedenen physikochemischen Methoden charakterisiert. Die Ergebnisse der Elementaranalyse zeigen, dass nur 10 % des Nanocompositmaterials aus leitfähigem PANI bestehen. Die Vergrößerung des Zwischenschichtabstandes von MMT, die bei Röntgendiffraktometrieuntersuchungen beobachtet wurde, lässt auf die Bildung von PANI innerhalb der Tonmineral-Taktoide schließen. IR-spektroskopische Untersuchungen deuten auf das Vorhandensein von Wechselwirkungen physikochemischer Art, wahrscheinlich Wasserstoffbindungen zwischen dem Tonmineral und Polyanilin, hin. Untersuchungen mit zyklischer Voltammetrie zeigten, dass die Anwesenheit von elektroinaktivem Tonmineral die elektrochemische Aktivität von PANI nicht beeinflusst. Das elektrochrome Verhalten von PANI-MMT Nanocompositen wurde mit UV-Vis-Spektroskopie untersucht, wobei sich herausstellte, dass das elektrochrome Verhalten vom PANI im Compositmaterial erhalten bleibt. Eines der technologischen Hauptanwendungsgebiete von leitfähigen Polymeren, insbesondere von PANI, ist der Korrosionsschutz von aktiven Metallen. PANI-MMT Nanocomposite die mit der angegebenen Methode (elektrochemisch) synthetisiert wurden und chemisch synthetisiertes in organischen Medien lösliches PANI wurden zum Korrosionsschutz von C45 Stahl eingesetzt. Die Korrosionsuntersuchungen wurden mit Hilfe von elektrochemischen Impedanzmessungen (EIM) und anodischen Polarisationsuntersuchungen durchgeführt. Der von PANI-MMT und von in organischen Medien löslichem PANI gebotene Korrosionsschutz ist wahrscheinlich auf die Zunahme des Ladungsdurchtritts widerstandes der beschichteten Stahloberfläche zurückzuführen. Die anodische Verschiebung des Korrosionspotenzials, eine Verringerung der Korrosions-geschwindigkeit und eine deutliche Zunahme des Polarisationswiderstandes sind eindeutige Hinweise für das Antikorrosionsvermögen von PANI-MMT und auch von in organischen Medien löslichem PANI, welche auf der zu schützenden Stahloberfläche abgeschieden wurden.

Over the past few years, the need for a clean and renewable fuel has sharply risen. This is due to increasing fossil fuel costs and the desire to limit or eliminate harmful by-products which are created during the burning of these fuels. Hydrogen is the most abundant element in the universe and can be used in either fuel cells or traditional internal combustion engines to produce energy with no harmful emissions. One of the main obstacles facing the implementation of a hydrogen economy is its storage. Classical methods of storage involve either high and unsafe pressures or liquid storage involving a large amount of energy. Two alternative hydrogen storage methods are investigated - physisorption, which is the weak chemical bonding to a material, as well as chemisorption, which is a strong chemical bond of hydrogen to a host material. Polyaniline, a conducting polymer, is investigated in both its bulk form as well as in nanostructured forms, more precisely nanofibers and nanospheres, to store hydrogen via physisorption. It is found the bulk form of polyaniline can store only approximately 0.5wt.% hydrogen, which is far short of the 6wt.% required for practical applications. Nanofibers and nanospheres, however, have been developed, which can store between 4wt.% and 10wt.% of hydrogen at room temperature with varying kinetics. A new complex metal hydride comprised of LiBH4, LiNH2 and MgH2 has been developed to store hydrogen via chemisorption. While the parent compounds require high temperatures and suffer of slow kinetics for hydrogen sorption, the work performed as part of this dissertation shows that optimized processing conditions reduce the hydrogen release temperature from 250°C to approximately 150°C, while the addition of nano sized materials has been found to increase the kinetics of hydrogen sorption as well as further decrease the hydrogen release temperature, making this one of the first viable hydrogen storage materials available. This is the first time that nanostructured polyaniline has been investigated for its hydrogen performance. Additionally, the thorough investigation of the effects of nano sized additives and processing parameter optimization of the multinary hydride are first reported in this dissertation.