A obtenção de blendas condutoras a base de água, ainda é pouco explorada e apresenta uma interessante alternativa ao uso de compostos poluentes como os cromatos na proteção à corrosão metálica. Os polímeros condutores apresentam propriedades anti-corrosivas e podem ser processados em meio aquoso, eliminando o uso de solventes orgânicos altamente tóxicos e agressivos para o meio ambiente. O presente trabalho consiste no estudo da proteção da corrosão metálica por revestimento de filmes de blendas contendo Poli(anilina) (PANI). As blendas foram obtidas à partir da mistura de uma suspensão aquosa de PANI com uma dispersão aquosa de Poli(metil metacrilato). O uso de técnicas como potencial zeta, espalhamento de luz dinâmico, análise térmica e microscopia eletrônica de varredura permitiram a caracterização da mistura homogênea obtida. Medidas através do método da sonda de quatro pontas mostraram que as blendas apresentam condutividade mesmo com baixas quantidades de PANI e a técnica de espectroscopia Raman mostrou a presença da forma condutora deste polímero nos filmes das blendas. Técnicas como microscopia óptica, potencial a circuito aberto, voltametria linear e espectroscopia de impedância eletroquímica permitiram avaliar a proteção à corrosão de eletrodos metálicos de ferro, cobre e níquel recobertos com filmes das blendas de PANI em diferentes meios corrosivos. As blendas mostraram eficiência contra a corrosão e apresentam-se como um novo material não poluente para a proteção à corrosão metálica. / The development of water-based conducting blends has not yet been very much explored and it presents itself as an interesting alternative to the use of polluting compounds such as chromates in the protection of metals from corrosion. The conducting polymers present anti-corrosion properties and can be processed in aqueous medium, eliminating the use of organic solvents, which are highly toxic and threatening to the environment. This thesis is based on the study of protection from metallic corrosion using poly(aniline) (PANI) coating blends. The blends have been obtained by mixing a PANI aqueous suspension with a poly(methyl metacrylate) aqueous dispersion. Techniques such as zeta potential, dynamic light scattering, thermal analysis and scanning electronic microscopy allowed the characterization of the homogeneous mixture obtained. Measurements carried out by the four-point probe method showed that the blends present conductivity even despite low PANI quantities. In addition, the Raman spectroscopy technique showed the presence of the conducting form of this polymer on the blend films. Techniques such as optical microscopy, open-circuit potential, linear voltammetry and impedance spectroscopy allowed the evaluation of the corrosion protection of the iron, copper, and nickel metallic electrodes coated with PANI blend films in different corrosives mediums. The blends showed efficiency against corrosion and they are therefore a new environmentally friendly material for metallic corrosion protection.

Um método amplamente utilizado na proteção contra a corrosão de ligas de alumínio é a formação de camadas de conversão de cromo. Na busca de métodos \"ambientalmente amigáveis\" de proteção contra corrosão existe a possibilidade da utilização de polímeros condutores, como a polianilina (PAni), que pode atuar por efeito barreira, assim como pela absorção de cargas provenientes da solução e / ou camadas auto-organizadas (SAM, do inglês \"self assembled monolayers\"), onde a proteção pode ocorrer de forma indireta, quando a SAM atua como promotora de adesão para outros revestimentos ou de forma direta, quando a própria monocamada bloqueia o acesso de substâncias responsáveis pela corrosão, à superfície protegida. Neste trabalho é proposta a utilização de bi-camadas baseadas de propil-trimetóxi-silano (PTMS) + PAni e octadecil-trimetóxi-silano (ODTMS) + PAni para a proteção contra a corrosão das ligas de alumínio AA1050, AA2024 e AA7075. Para os ensaios de corrosão foram utilizadas as técnicas de potencial de circuito aberto, curvas de polarização potenciodinâmica e espectroscopia de impedância eletroquímica. Análise de microscopia óptica e microscopia eletrônica de varredura (MEV) foram realizadas antes e após os ensaios de corrosão para verificar a eficiência de proteção contra corrosão dos revestimentos propostos. Adicionalmente foram realizados testes de névoa salina e aderência, além da caracterização das ligas por MEV e espectroscopia de energia dispersiva de raios X (EDX). Os resultados obtidos demonstram que os tratamentos utilizados resultaram em melhoras na resistência contra a corrosão na seguinte ordem: PTMS < ODTMS < PAni < PTMS + PAni < ODTMS + PAni, sendo que este último o que apresenta os melhores resultados como maiores deslocamentos do Ecorr para valores mais positivos, diminuição da icorr, menor número de pontos de corrosão após a realização das curvas de polarização, maiores valores de impedância total em todo o intervalo de frequência utilizado e maior resistência à exposição à névoa salina. / A method widely used in corrosion protection of aluminum alloys is the formation of conversion layers of chromium. In search of \"environmentally friendly\" corrosion protection methods there is the possibility of using conducting polymers such as polyaniline (PAni), which can act by barrier effect or absorbing charged particles from the solution and / or self-assembled monolayers (SAM), where protection may occur indirectly, when the SAM acts as a promoter of adhesion to other coatings, or directly, when the monolayer blocks the access of aggressive substances to the surface. This work proposes the use of bi-layers based on propyl-trimethoxy-silane (PTMS) + PAni and octadecyl-trimethoxy-silane (ODTMS) + PAni for corrosion protection of aluminum alloys AA1050, AA2024 and AA7075. For the corrosion tests were used different techniques such as: open circuit potential, potentiodynamic polarization curves and electrochemical impedance spectroscopy. Analysis of optical microscopy and scanning electron microscopy (SEM) were performed before and after the corrosion tests in order to verify the efficiency of the proposed coatings in corrosion protection. Additionally, tests of salt spray and adhesion were made, in addition to the characterization of the alloys by SEM and X-ray dispersive energy. The results show that the treatments resulted in improvements in corrosion resistance in the following order: PTMS < ODTMS < PAni < PTMs + PAni < ODTMS + PAni. The last one gives the best results such as larger shifts of the Ecorr to more positive values, decrease of the icorr, fewer corrosion points after the polarization curves, higher values of total impedance in the entire range of frequency used and more resistant to the exposure to salt spray.

This research is to synthesize polyaniline (PANI) thin film for polymer solar cells as a hole transport layer by using potentiostatic deposition of electrochemical method. In our previous studies, we have shown that the power conversion efficiencies of the solar cell device were improved for the slow polymerization rate. We choose the potentiostatic deposition method to improve the polymerization rate of PANI for the application in industry. In this study, we investigated optical transmittance, absorption spectrum, Highest Occupied Molecular Orbital (HOMO), surface roughness, and surface morphology of the PANI thin film by changing voltages and to discuss the factors on device efficiency. Then, we compared the device structures with hole transport layer PEDOT: PSS by spin-coating process. We found PANI thin films synthesized from different voltages, and the transmittance measurement results were similar. In addition, we found HOMO, surface roughness, and surface morphology of PANI thin film that varies with different voltages. The power conversion efficiencies of the device mainly were affected by the surface roughness and morphology of PANI thin film surface. Comparing to other parameters, PANI thin film polymerized at 0.8V owns the most appropriate surface roughness and surface morphology. The power conversion efficiency was up to 1.52% under AM 1.5G illumination based on ITO (150 nm) / PANI (75 nm) / P3HT: PCBM (100 nm) / Al (200 nm), and the device area of 0.16 cm2.

Made available in DSpace on 2014-06-12T23:15:58Z (GMT). No. of bitstreams: 2 arquivo9147_1.pdf: 2986566 bytes, checksum: 8a61434d6a712fd656033948e266e3d3 (MD5) license.txt: 1748 bytes, checksum: 8a4605be74aa9ea9d79846c1fba20a33 (MD5) Previous issue date: 2007 / Polímeros Intrinsecamente Condutores (PICs) são macromoléculas orgânicas que exibem características de condutividade elétrica semelhantes aos metais. A polianilina (PANI) é conhecida como o PIC que apresenta, provavelmente, a melhor combinação de estabilidade, condutividade e baixo custo. Neste trabalho, sintetizou-se a PANI na forma nanoestruturada e foram confeccionados e caracterizados nanocompósitos poliméricos contendo PANI em matriz de polímero isolante, poli (metacrilato de metila) (PMMA) e biodegradável, poli (3-hidroxibutirato) (PHB). Dentre as aplicações potenciais destes compósitos, estão o desenvolvimento de novos materiais estáveis à radiação ionizante, aplicáveis como plásticos médicos e o desenvolvimento de novos materiais orgânicos condutores, mecanicamente estáveis, conhecidos como metais sintéticos para uso em micro-nanoeletrônica e biomedicina. Nanoestruturas fibrilares de polianilina dopada com HCl (PANF-HCl), sintetizadas pelo método de polimerização interfacial, foram dispersas em matriz de PMMA comercial, em 0,15%, em massa, e êndic quanto à ação radioestabilizante. Nesta concentração, as PANF-HCl apresentaram capacidade de estabilizar a matriz de PMMA comercial submetida à irradiação com raios gama em dose padrão de esterilização de 25kGy, de maneira a preservar 92% da massa molar viscosimétrica média (Mv) inicial do PMMA. Em amostras-controle irradiadas com a mesma dose, a retenção atingiu 42%. A produção de nanofibras de PANI foi também alcançada em sistemas monofásicos aquosos utilizando ácido (±)-canfor-10-sulfônico como dopante primário. Filmes compósitos de PMMA/PANI desdopada (PANI-EB) contendo 0,15% de PANI-EB, tanto em formato nanofibrilar quando granular, mostraram menores valores de &#945; (número de cisões por molécula original) que as amostras-controle, quando submetidos à irradiação com raios gama na dose de 25kGy. Particularmente, em compósitos contendo nanofibras, não houve alteração detectável de Mv após irradiação nesta dose (&#945; &#8776; 0). Na dose de 75kGy, os compósitos de PMMA/PANI-EB também sofreram menor degradação que as amostras-controle, mostrando que a PANI-EB é capaz de atuar como aditivo radioestabilizante em doses mais altas que a dose de esterilização. Quatro tipos de compósitos de PHB/nanofibras de PANI dopadas com HCl, em concentração entre 8 e 55% de PANI (em massa) foram preparados por polimerização da PANI in situ, em presença de emulsão de PHB. Estes compósitos apresentaram boa homogeneidade e características semicondutoras. Dados de FTIR e difração de raios X sugerem que os dois polímeros não interagem de maneira relevante nestes compósitos. A irradiação com raios gama, na dose de 25kGy, do compósito de PHB contendo 28% de PANI-HCl elevou sua condutividade de 4,5 x 10-2 para 1,1 S/m. Isto mostra a possibilidade de melhoramento das propriedades elétricas do material quando submetido à dose de esterilização. Estudos realizados pelo teste de Sturm mostraram que a irradiação com raios gama, nesta mesma dose, provocou a diminuição da biodegradabilidade do material compósito. Estes estudos também evidenciaram que os compósitos, irradiados ou nãoirradiados, se biodegradam mais rápido que o PHB durante o primeiro mês de testes. A partir deste período, a biodegradação do PHB se acelera, enquanto que a degradação do compósito praticamente deixa de ocorrer. A PANI-HCl não sofreu degradação apreciável num período de testes de 80 dias

No description available.

This thesis describes recent progress in electrochemical preparation of several conducting polymers. In particular, the synthesis and characterizations of pure polyaniline, pure polypyrrole, polyaniline/polypyrrole and polypyrrole/polyaniline copolymers and polyaniline-polypyrrole physical blends were studied. The focus has included firstly synthesis of these electrically conductive polymers. Secondly, thermal characteristics of electrochemically synthesized homopoly- mers, copolymers and their physical blends were investigated by thermal gravi- metric analysis (TGA), differential scanning calorimetry (DSC) and direct pyrol- ysis mass spectrometry (DIP-MS) techniques. In general, TGA analysis showed three-step thermal degradation. The first, at 100oC, was attributed to water, and unreacted monomers. The second weight losses observed at around 150 oC was because of evolution of water and/or acid. Finally, the removal of the dopant ion and low molecular weight species from the matrix were observed for pure PANI and pure PPy at 230 and 280 oC, respectively. PANI/PPy films and PPy/PANI films have decomposition temperatures at 272oC because of the loss of the dopant ion. It was also observed that pure PPy was thermally more resistant than pure PANI. Thirdly, thermal characteristics, and degradation products of electrochemi- cally prepared PANI/PPy and PPy/PANI films in solutions containing variable dopant (SO42&amp / #8722 / ) concentrations were analyzed and compared with pyrolysis mass spectrometry. Similar to TGA study, there were three main thermal degradation steps namely, evolution of low molecular weight species, dopant based products and degradation products of polymers. The dopant concentration was monitored to optimize the degradation behavior. Pyrolysis mass spectrometry data showed that the degree of degradation of the polymer already coated on the electrode enhanced as the dopant concentration used in synthesis increased.

The interest in conjugated polymers has been two-fold. A rich variety of intriguing physical phenomena, combined with its immense technological implications in the area of molecular electronics, sensors etc. has inspired the researchers all over the globe. The work presented in this thesis is focussed on one of the most widely studied conjugated polymers, namely polyaniline (PANI), which is well known for its high conductivity and remarkable stability in the proton-doped form. The thesis is divided into two chapters and each chapter is further divided into several parts. In the first chapter, we take a look at some novel systems based on PANI that exhibit interesting electrical and optical properties. To begin with, we report the synthesis and characterization (Part I, Chapter 3) a new class of highly conducting polyaniline doped with electron deficient Lewis acids, namely the boron trihalides (BX3, X = F, Cl, and Br). We discuss the various attributes of this interesting class of materials that set it apart from the conventional proton-doped PANI systems. It is known that the conductivity in doped PANI is greatly influenced by the presence of structural disorder. Previous studies have associated the conductivity in doped PANI with the partial crystallinity that is achieved upon proton doping. At the same time, the amorphous regions that have a high degree of disorder were believed to suppress the metallic nature in these doped systems. In view of this "higher-crystallinity-higher-conductivity" picture, it is interesting to note that the BX3 doped PANI remain absolutely amorphous despite being more conducting than previously known samples. Through our investigation, we have been able to address some of the most important and long-standing questions pertaining to the nature of the charge carriers and the role of disorder in doped PANI. A detailed study of the transport properties in Part II, Chapter 3 helps us to understand the mechanism of charge transfer in these novel systems. With the help of our results, we establish that the present systems do not belong to the family of quasi one-dimensional conductors, in stark contrast to the conventional proton-doped samples. Instead, our systems are best described as granular metals, where the conduction mechanism is controlled by the size of the conducting grains and the nature of the grain boundaries. Through a comprehensive study of the magnetic properties based on d. c. magnetic susceptibility and EPR spectroscopy, we further establish that the intrinsic conductivity of these samples are much higher than the previously known systems. By studying the interaction of the mobile charge carriers and the localized spins in the systems, we have established that our samples are far less disordered, and therefore qualify as superior systems when compared to the more conventional proton-doped PANI. One of the serious disadvantages of the conventional protonated PANI lies in its thermal instability. On heating above 75 ±C in air, the polymer backbone undergoes an irreversible aerial oxidation that disrupts the extended conjugated structure. This is marked by a rapid drop in conductivity by a few orders of magnitude. BF3-doped PANI, which has the highest conductivity sample among the present series of samples, exhibits a remarkable thermal stability in air (Part III, Chapter 3). Upon heating, the conductivity initially increases and then reaches a saturation value. The polymer can be heated at temperatures as high as 225 ±C, without any signs of degradation. With the help of temperature dependent conductivity, XPS and FTIR spectroscopy we have tried to understand this unexpected phenomenon. In Part IV, Chapter 3, we report the synthesis and characterization of a novel class of functionalized PANI that exhibit an intense deep-blue photoluminescence. A de- tailed characterization based on absorption, photoluminescence, XPS, NMR and FTIR spectroscopy has been carried out to study the chemical state of this new class of light- emitting polymers. Further, we note that the synthetic procedure followed in this work can provide a very general route to the synthesis of diversely useful derivatives of PANI. In Chapter 4, we have investigated the microscopic origin of conductivity in doped PANI. Among the several factors that can influence the conductivity of doped polymers, one is the microstructural order. To understand this better, we carried out a detailed investigation, based on scanning tunneling microscopy (STM) and spectroscopy (STS) of undoped and doped PANI films (Part I, Chapter 4). We have shown for the ¯rst time that solution processed thin films of undoped PANI has an abundance of PANI anorods self organized over very large areas. Further, we observe that this ordered orphology is Preface vii very sensitive to the choice of dopants and the doping procedure. We have shown that the morphological order can greatly influence the electronic structure and therefore the properties of these systems. To understand the role of dopant-polymer interaction in controlling the conductivity of doped PANI, we carried out x-ray photoelectron spectroscopy (XPS) studies on a large number of partially and fully doped samples (Part II, Chapter 4). We find an interesting trend in the higher binding energy feature and the asymmetry of the N and C 1s spectra, which correlates directly with the respective conductivities of different samples. The analysis of these spectra brings out interesting facts about the chemical state and the electronic structure of these samples. In summary, we have reported new PANI based systems with improved electrical and interesting optical properties, and have studied various factors that influence the properties of these as well as some of conventional doped PANI systems.

Das Ziel der vorliegenden Arbeit ist die bessere Verarbeitung von Polyanilin (PANI), da dies bisher ein großer Nachteil unter leitfähigen Polymeren war. Dazu wird ein sperriges Tensid und Dotand, Dodecylbenzensulfonsäure (DBSA) verwendet. Zur Synthese der PANI kommen zwei verschiedene Methoden zur Anwendung, die in dieser Dissertation in zwei Kapiteln beschrieben werden. Im ersten Teil wurden in einem kleinen Reaktionsvolumen (250 mL) PANI-DBSA-Suspensionen synthetisiert, wobei mit einem binären Gemisch aus 2-Propanol und Wasser als Lösungsmittel gearbeitet wird um die Löslichkeit zu unterstützen. Die micellenunterstützte Synthese produziert grüne Dispersionen, welche nach länger als einem Jahr noch keine sichtbare Ausscheidung zeigen. Eine detaillierte spectroelektrochemische Untersuchung der PANI-DBSA-Nanokolloide wurde durchgeführt und gibt eine bessere Erklärung der Charge-Transfer-Prozesse zwischen PANI-Kolloiden und Elektrodenoberfläche. In einem alkalischen Medium ist das UV-Vis-Spektrum von der Beweglichkeit der Anionen und von einem elektrokinetischen Phänomen abhängig. Um den „metal-to-insulator”-Übergang zwischen PANI-Kolloiden, welcher durch pH-Wert-Änderung des Mediums geschehen kann, zu zeigen, wurden UV-Vis- und pre-resonanz-Raman-Spektroskopie verwendet. Im zweiten Teil der Dissertation wird zur Polymerisation von Anilin sowie seinen Copolymeren mit o-Toluidin eine neue Technik der Polymerisation beschrieben, welche durch inverse Emulsion erfolgt. Diese benutzt Benzoylperoxid, ein ungewöhnlicheres organisches Oxidationsmittel. Die erhaltenen PANI sind in gebräuchlichen organischen Lösungsmitteln, wie in Chloroform, vollständig löslich. Mit einer klar-transparenten, grünen Lösung von PANI können metallische Oberflächen oder Glas leicht tropfenbeschichtet werden. Zyklische Voltammetrie und spektroelektrochemische Verfahren kamen zum Einsatz, um die Elektroaktivität, das UV-Vis-Verhalten und die „metal-to-insulator”-Übergänge der chemisch synthetisierten PANI als Funktion des verwendeten Elektrodenpotentials zu untersuchen. Die elektrische Leitfähigkeit der Materialien ist relativ hoch (R = 10 ). SEM-Untersuchungen zeigen, dass die Menge des zugesetzten DBSA die Morphologie des Polymers stark beeinflusst. Aus in situ UV-Vis-spektroskopischen Messungen lässt sich eine gute elektrochromische Reversibilität des Polymers erkennen. DBSA kann Poly(o-toluidin) (POT) effektiv dotieren, auch wenn von der Methylgruppe eine sterische Hinderung ausgeht. Die spektroskopischen Untersuchungen, wie UV-Vis, FT-IR, Raman-Spektroskopie und zyklische Voltammetrie, zeigen deutlich, dass wirkliche Copolymere gebildet werden und die Möglichkeit von Kompositen nicht in Betracht kommt. Das entstandene Poly(anilin-co-o-toluidin) (PAT) ist in schwach polaren Lösungsmitteln wie Chloroform löslich. Wie erwartet, sind die elektrischen Leitfähigkeiten der Copolymere viel kleiner als die Leitfähigkeit von PANI-DBSA.

Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2016-05-03T12:36:50Z No. of bitstreams: 1 Tese de Luiz Henrique Silva.pdf: 6975356 bytes, checksum: 6f89c76c6cbc6a200ec6763f7d465b69 (MD5) / Approved for entry into archive by Ana Hilda Fonseca (anahilda@ufba.br) on 2016-05-12T13:37:14Z (GMT) No. of bitstreams: 1 Tese de Luiz Henrique Silva.pdf: 6975356 bytes, checksum: 6f89c76c6cbc6a200ec6763f7d465b69 (MD5) / Made available in DSpace on 2016-05-12T13:37:14Z (GMT). No. of bitstreams: 1 Tese de Luiz Henrique Silva.pdf: 6975356 bytes, checksum: 6f89c76c6cbc6a200ec6763f7d465b69 (MD5) / CAPES / Nas ultimas décadas tem sido crescente o interesse pelo estudo do comportamento de materiais em escala nanométrica. Esse interesse ocorre devido a alguns materiais apresentarem novas propriedades físico-químicas tais como óticas, magnéticas, de transporte, catalíticas, etc quando são produzidos nessa escala de tamanho. Assim, o presente trabalho foi baseado no estudo físico-químico de materiais a partir da interação de nanopartículas de ouro (Au0) com óxido de vanádio com estruturas unidimensionais, sintetizados por reações de troca e utilizando a rota sonoquímica. Na reação de troca foi escolhida como referência uma solução de NaCl, onde se constatou, pelas análises de DRX, FTIR, MEV, MET e XPS, uma substituição das moléculas de dodecilamina (CH3(CH2)10CH2NH2), presentes na região entre as camadas dos nanotubos de óxido de vanádio (NTs-VOx), por íons Na+. Enquanto que as análises por UV/Vis, DRX, MEV, MET, EDS e XPS comprovaram a formação de um material unidimensional na forma nanotubular contendo nanopartículas Au0 estabilizada em dendrímeros (NT-VOx-DEN-(Au0)), onde as nanopartículas Au0 apresentaram diâmetros homogêneos de aproximadamente 3,0 nm e monodispersas na superfície dos nanotubos. Por fim as análises por DRX, FTIR, MEV, MET e XPS dos materiais utilizando a rota sonoquímica, indicaram a formação de nanofios de óxido de vanádio NFs-VOx contendo nanopatículas Au0, sintetizadas “in situ”. Estas nanopartículas possuem tamanho médio de 9,0 nm e encontram-se agrupadas na forma de aglomerados ou “ilhas” sobre a superfície dos nanofios. / In the last decades it has been growing interest in the study of the behavior of materials at the nanometer scale. This interest is due to some materials present new properties such as optical, magnetic, transport, catalytic, etc when are produced on this scale of size. Thus, this work was based on the physical chemistry study materials from the interaction of gold nanoparticles with one-dimensional vanadium oxide, synthesized by exchange reactions and using the sonochemical route. For the exchange reaction was selected as reference NaCl solution, where it was found, from the analysis by XRD, FTIR, SEM, TEM and XPS, a substitution of dodecylamine molecules (CH3(CH2)10CH2NH2) in the region between the layers of vanadium oxide nanotube (NTs-VOx) by Na+ ions. While the analysis by UV / Vis, XRD, SEM and TEM and EDS XPS confirmed the formation of a one-dimensional on the form nanotubular material containing gold nanoparticles encapsulated in dendrimers (NTs-VOx-DEN-(Au0)) where, the gold nanoparticles presented homogeneous diameter of approximately 3.0 nm and monodispersed on the surface of nanotube. Finally the analysis by XRD, FTIR, SEM, TEM and XPS materials obtained from the sonochemical route, indicated the formation of vanadium oxide VOx nanowires NFS- containing gold nanopatículas, synthesized "in situ".

Submitted by Irene Nascimento (irene.kessia@ufpe.br) on 2016-10-18T18:14:55Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Tese_Final2016_VersaoDigital.pdf: 7557339 bytes, checksum: a22206b5f13175a64f4d1634bc9f3fc4 (MD5) / Made available in DSpace on 2016-10-18T18:14:55Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Tese_Final2016_VersaoDigital.pdf: 7557339 bytes, checksum: a22206b5f13175a64f4d1634bc9f3fc4 (MD5) Previous issue date: 2016-06-08 / O presente trabalho trata da obtenção de tinta utilizando dois pigmentos em dois vernizes diferentes (Epóxi–Ep e Poliuretana–PU) e dos testes de eficiência dessas tintas para prevenção da corrosão em aços. Um pigmento a base de Polianilina (Pani) na presença do ácido dodecilbenzeno sulfônico (ADBS) e o outro a base do compósito Pani-Fe3O4. A Pani sintetizada quimicamente foi secada a vácuo e caracterizada pelas técnicas de espectroscopia de Infravermelho e de UV/Vis. As placas de aço carbono SAE 1006 com e sem revestimentos foram submetidas a ensaio cíclico de corrosão em uma câmara de névoa salina (CNS). O monitoramento da corrosão foi feito por análises de fotografia e microscopia óptica. A interação camada-substrato foi investigada por meio da espectroscopia de impedância eletroquímica (EIE) e a superfície dos revestimentos por Espectroscopia Raman. No geral, os resultados indicaram que a Pani-ADBS teve maior desempenho no verniz Ep do que no verniz PU, enquanto o pigmento Pani-Fe3O4 apresentou maior desempenho no verniz PU. Existe evidência de que a Pani-ADBS adicionada ao Ep, na concentração de 0,1%, resulta em melhor proteção do aço ao final do ensaio de 30 dias. O indicativo pode ser visto pela maior resistência (3,95 x 109 ·cm2) e menor capacitância (7,14 x 10-11 F·cm-2). Discussão similar também pode ser feita com o revestimento PU, uma vez que ele apresentou maior resistência da camada (9,81 x 108 ·cm2) e menor capacitância (8,06 x 10-11 F·cm-2). Essa evidência também foi observada pelos resultados de potencial de circuito aberto (Eca). O espalhamento Raman detectou indícios de degradação química dos revestimentos Ep e PU. Baseado nos resultados obtidos neste trabalho é razoável a utilização do modelo ácido-base para explicar o mecanismo de proteção do aço pelos pigmentos Pani-ADBS e Pani-Fe3O4. O mecanismo de proteção do aço ainda carece de mais estudos, entretanto os resultados de potencial de circuito aberto e impedância eletroquímica sugerem que o mecanismo de proteção pode ser explicado por barreira física e em termos de compatibilidade entre o pigmento e a matriz polimérica. / This work describes the production of paints using two pigments in two different polymer matrices (epoxy-Ep and polyurethane-PU) and tests efficiency of these formulations in the prevention of corrosion in steel. A Polyaniline (Pani) based pigment in the presence of a functionalized protonic acid, known as dodecylbenzene sulfonic acid (DBSA) and the other based on Pani-Fe3O4 composite. The chemically synthesized Pani powder was vacuum-dried and characterized by infrared spectroscopy and UV/Vis. The paints were applied to metallic carbon steel SAE 1006 plates. The plates were subjected to cyclic corrosion essay to test the performance of the coatings against corrosion. The film-substrate interaction was investigated by electrochemical impedance spectroscopy (EIS). Raman spectroscopy was used for chemical analysis of surface coatings. It was observed that the Pani-DBSA had its most pronounced effect on the epoxy varnish than in the polyurethane varnish. While the pigment Pani-Fe3O4 showed better performance in the polyurethane varnish. There is evidence that PANI-DBSA added to the Ep at a concentration of 0.1% results in better protection of steel at the end of the 30 day test. This indication can be seen by the increased resistance (3.95 x 109 ·cm2) and a lower capacitance (7.14 x 10-11 F·cm-2). Similar discussion can also be done with the PU coating, as it showed the highest resistance (9.81 x 108 ·cm2) and a lower capacitance (8.06 x 10-11 F·cm-2). These results were confirmed by open circuit the potential (Eoc). The Raman scattering detected chemical evidence of Ep and PU coatings degradation. According to the results obtained in this study, it is reasonable to use the acid-base model to explain the steel protective mechanism by Pani-DBSA and Pani-Fe3O4 pigments. The steel protection mechanism still needs more studies; however, the results of open circuit potential and electrochemical impedance suggest that the protection mechanism can be explained by a physical barrier and in terms of polarity between pigment and matrix.