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One interesting approach is the development of conductive polymer composite fibers for innovative textile applications such as in sensors, actuators and electrostatic discharge. In this study, conductive polymer composite fibers were prepared using several different blends containing conductive components: a conjugated polymer (polyaniline-complex) and/or carbon nanotubes. Different factors such as processing parameters, the morphology of the initial blends and the final fibers, fiber draw ratio and material selection were studied separately to characterize their effects on the fiber properties. In binary blends of PP/polyaniline-complex, the processing conditions, the matrix viscosity and the fiber draw ratio had substantial effects on the electrical conductivity of the fibers and linearity of resistance-voltage dependence. These factors were associated with each other to create conductive pathways through maintaining an appropriate balance of fibril formation and breakage along the fiber. The blend morphology was defined as the initial size of the dispersed conductive phase (polyaniline-phase), which depended on the melt blending conditions as well as the PP matrix viscosity. Depending on the initial droplet phase size, an optimum draw ratio was necessary to obtain maximum conductivity by promoting fibril formation (sufficient stress) and preventing fibril breakage (no excess stress) to create continuous pathways of conductive phase. Ternary blend fibers of PP/PA6/polyaniline-complex illustrated at least three-phase morphology with matrix/core-shell dispersed phase style. When ternary fibers were compared to binary fibers, the former could combine better mechanical and electrical properties only at a specific draw ratio; this showed that draw ratio was a more determinant factor for the ternary fibers, as both conductivity and tensile strength depended on the formation of fibrils from the core-shell droplets of the PA6/polyaniline-complex through the polypropylene matrix. The achieved maximum conductivity so far was in the range of 10 S/cm to 10 S/cm, which for different samples were observed at different fiber draw ratios depending on the mixing conditions, the matrix viscosity or whether the fiber was a binary or ternary blend. To improve the properties, PP/polyaniline-complex blends were filled with CNTs. The CNTs and the polyaniline-complex both had an increasing effect on the crystallization temperature and the thermal stability of PP. Furthermore, the maximum conductivity was observed in samples containing both CNTs and polyaniline-complex rather than the PP with either one of the fillers. Although increasing the content of CNTs improved the conductivity in PP/CNT fibers, the ease of melt spinning, diameter uniformity and mechanical properties of fibers were adversely affected. Diameter variation of PP/CNT as-spun fibers was shown to be an indication of hidden melt-drawings that had occurred during the fiber extrusion; this could lead to variations in morphology such as increases in the insulating microcracks and the distance between the conductive agglomerates in the drawn parts of the fiber. Variations in morphology result in variations in the electrical conductivity; consequently, the conductivity of such inhomogeneous fiber is no longer its physical property, as this varies with varying size. / Thesis to be defended in public on Friday, May 20, 2011 at 10.00 at KC-salen, Kemigården 4, Göteborg, for the degree of Doctor of Philosophy.

Darbo tikslas - ištirti askorbo rūgšties elektrocheminės oksidacijos ant elektrodų, modifikuotų polianilinu ir poli(N-metilanilinu), dėsningumus, siekiant sukurti jautrius askorbatui jutiklius. Ištirta įvairių faktorių įtaka anilino ir N-metilanilino elektrocheminei polimerizacijai bei gautų PANI ir PNMA sluoksnių savybėms. Atlikti palyginamieji modifikuotų elektrodų tyrimai skirtingo pH tirpaluose ir parodyta, kad PNMA lyginant su polianilinu pasižymi geresniu aktyvumu silpnai rūgščiuose ir neutraliuose tirpaluose. Ištirtas modifikuotų elektrodų amperometrinio atsako į askorbatą pobūdis, ir pasiūlytas autokatalizinis askorbato elektrooksidacijos mechanizmas ant PANI modifikuoto elektrodo. Panaudojus PANI ir PNMA modifikuotus elektrodus, sukurti amperometrinių askorbato jutiklių prototipai ir atlikti jų palyginamieji tyrimai. / The main purpose of this work - to investigate patterns of electrochemical oxidation of ascorbic acid on polyaniline and poly(N-methylaniline) modified electrodes, in order to develop ascorbate-sensitive sensors. A detailed study of various factors affecting the aniline and N-methylaniline electrochemical polymerization and the resulting properties of PANI and PNMA layers was carried out for this purpose. Comparative study of modified electrodes in solutions of different acidity was performed and it was shown that PNMA had a better redox activity in slightly acidic and neutral solutions compared to polyaniline. The nature of amperometric response of modified electrodes to ascorbate was investigated and autocatalytic mechanism of ascorbate electrooxidation on PANI modified electrode was suggested. Using PANI and PNMA modified electrodes, prototypes of amperometric ascorbate sensors have been developed and their comparative studies were carried out.

The use of graphene and conductive polyaniline nanomaterials in the field of electrochemistry is increasing due to their excellent conductivity, rapid electron transfer and high specific surface area. However, these properties are strongly dependent on the preparation processes. To accelerate the development of advanced electrochemical sensors for the simultaneous detection of trace amounts of heavy metal ions, two facile and green methods are proposed to improve their performance in this thesis. The first one was dedicated to make graphene-carbon nanotube hybrid nanocomposites. The introduction of carbon nanotubes not only greatly enhances the conductivity of graphene but also suppresses, to some degree, the aggregation between graphene nanosheets. Another method proposed in this thesis work was to synthesize a phytic acid doped polyaniline nanofiber based nanocomposite. The synergistic contribution from polyaniline nanofibers and phytic acid enhances the accumulation efficiency and the charge transfer rate of metal ions during the differential pulse anodic stripping voltammetry analysis. The above-mentioned nanocomposite modified electrodes were all successfully applied to real samples for the simultaneous detection of Cd2+ and Pb2+ with good recovery rates. Meanwhile, corrosion protection is another important branch in the field of electrochemistry. In this direction, an active alkyd-polyaniline composite coating with self-healing functionality was prepared. The polyaniline used in this thesis was doped with p-toluene sulfonic acid, which was employed to increase the conductivity of polyaniline, and 1 wt.% of as-prepared polyaniline nanoparticles were found to offer an effective conductive network for anticorrosion. Finally, the reasons that such low loading levels of nanomaterials can result in significantly reinforced properties in nanocomposites were studied with combined atomic force microscopy (AFM) techniques. The results demonstrated that the interphase for a 40-nm-sized silica particle could extend to 55–70 nm in poly(ethyl methacrylate) (PEMA) and poly(isobutyl methacrylate) (PiBMA) polymer matrix, and the interphase exhibited a gradient distribution in surface nanomechanical properties. / <p>QC 20170315</p>

Thèse numérisée par la Direction des bibliothèques de l'Université de Montréal.

Foram realizadas análises por espectros absorção, fluorescência e excitação para anilina e orto-toluidina em água, com e sem a adição de HCl. Os resultados indicam que as propriedades do meio dependem das concentrações de amina e de HCl, sendo observado principalmente pelos espectros de excitação de fluorescência. Espectros de 1H RMN parecem indicar um efeito de agregação destas moléculas pelas mudanças observadas na forma e na posição dos sinais dos prótons. Foi realizada a síntese de polianilina e de poli-o-toluidina, sendo o acompanhamento efetuado por espectroscopia ultravioleta-visível e pela técnica de perfil de potencial, indicando similaridades entre os dois métodos. As sínteses de polianilina e de poli-o-toluidina também foram realizadas via fotoquímica, sendo os produtos de reação caracterizados por espectroscopia ultravioleta visível e por infravermelho. / The aim this work was to study aniline and orto-toluidine in aqueous solution with or without HCl addition. The analyses were realized by absorption and fluorescence spectrum. The results show that the proprieties are relation on amines and chloridric acid concentrations, especially it was observed by fluorescence excitation spectrum. Changes in protons sign position and in the form can be indicating an effect of aggregation with these molecules though 1H RMN spectrum. UV-Vis spectroscopy and open circuit potential measurements were used for monitor the synthesis of polyaniline and the poly-o-toluidine. Theses methods show similar results. Also, the synthesis of polyaniline and the poly-o-toluidine were realized by photochemistry via, which the reaction products were characterized by UV-Vis spectroscopy and FTIR.

Tendo em conta os constantes problemas que apresentasse com os processos de corrosão, o presente trabalho de pesquisa tem como foco principal a alteração nas propriedades de superfície das ligas de alumínio empregadas nas aeronaves, AA2024 e AA7075, utilizando mono e bicamadas baseadas de octadecil-trimetóxi-silano (ODTMS) + poli(anilina-co-3-aminobenzoico/PAni3ABA) a fim de encontrar melhores condições para a redução da corrosão puntiformes. Posteriormente, avalia-se as características protetoras dos filmes através de testes de corrosão, como potencial de circuito aberto, curvas de polarização anódica e espectroscopia de impedância eletroquímica visando a caracterização do comportamento eletroquímico das amostras. Também foram realizadas análises de microscopia óptica para verificar a eficiência de proteção contra a corrosão dos revestimentos propostos antes e após os ensaios de corrosão. Os resultados obtidos demonstram que as camadas utilizadas melhoram a resistência contra a corrosão na seguinte ordem: PAni3ABA > ODTMS + PAni3ABA > ODTMS, sendo a primeira a que apresentou os melhores resultados como maiores deslocamentos do Ecorr para valores mais positivos, diminuição da icorr e menor número de pontos de corrosão após a realização das curvas de polarização. Além de testes de aderência para os filmes também foram efetuadas caracterizações das ligas por MEV. / Taking into account the constant problems that presents with corrosion processes, this research work has focused primarily on the change in surface properties of aluminum alloys used in aircraft, AA2024 and AA7075, with mono and bilayers using as a base octadecyl trimethoxy silane (ODTMS) + poly (aniline-co-3-aminobenzoic / PAni3ABA) to find optimum conditions for reducing corrosion punctiform. Later, it evaluates the protective features of the films through corrosion tests such as open circuit potential, anodic polarization curves and electrochemical impedance spectroscopy in order to characterize the electrochemical behavior of the samples. They were also carried out optical microscopy analysis to verify the efficiency of protection against corrosion of the coatings proposed before and after corrosion testing. The results obtained show that the layers used improve corrosion resistance in the following order: PAni3ABA> ODTMS + PAni3ABA> ODTMS, the first being the one that presented the best results as larger shifts towards more positive values, reduced and fewer corrosion points after performing the polarization curves. In addition to compliance tests for the films were also made characterizations of alloys by SEM.

Neste trabalho, serão apresentados o comportamento eletroquímico e espectro-eletroquímico dos polímeros condutores poli(sulfeto de fenileno fenilenamina) (PPSA) e poli(anilina) (PANI) no líquido iônico bis(trifluorometanosulfonil)imideto de 1-butil-2,3-dimetilimidazólio (BMMITFSI). Os experimentos eletroquímicos em BMMITFSI mostram que o PPSA apresenta dois processos redox reversíveis sem sinais de perda de eletroatividade e mostram também a obtenção da PANI pela polimerização eletroquímica da anilina com os dois processos redox típicos das transformações em leucoesmeraldina &#8596; esmeraldina &#8596; pernigranilina, sem a necessidade de adição de ácidos e sem nenhum sinal de degradação em potenciais elevados. Os experimentos de UV-Vis e Raman Ressonante evidenciaram a estabilização das estruturas oxidadas formadas em líquido iônico tornando este fato a principal razão para o comportamento reversível dos processos redox de ambos os polímeros. Os experimentos de resistência in situ da PANI, demonstraram que a pernigranilina obtida em potenciais elevados é mantida na forma condutora. Estes fenômenos observados em ambos os polímeros indicam que a alta atmosfera iônica do BMMITFSI, estaria estabilizando as estruturas mais oxidadas (dicátions) em potenciais elevados, o que evita a degradação e perda de eletroatividade do PPSA e permite a condutividade da PANI na forma pernigranilina sal. / In this work, the electrochemical and spectroelectrochemical behavior of Poly(phenylenesulfide phenyleneamine) (PPSA) and polyaniline (PANI) conducting polymers in a room temperature ionic liquids, 1-butyl-2-3-dimethylimidazolium bis(trifluorometanessulfonil)imide (BMMITFSI) is presented. Electrochemical experiments of a PPSA in BMMITFSI show two reversible redox processes without loss of electroactivity. Aniline polymerization to obtain PANI films with typically two redox processes due to leucoemeraldine &#8596; esmeraldine &#8596; pernigraniline transformations was also carried out in the absence of acids, and even cycling till high positive potentials, no degradation signals were observed. UV-Vis and Resonance Raman studies show the stabilization of dications in BMMITFSI as the main reason to the reversible redox behavior observed on both conducting polymers and the in-situ resistance measurements corroborated the stabilization of pernigraniline salt at high oxidation potentials in the conducting form of PANI. These results obtained in room temperature ionic liquid shows that the high ionic medium given by the BMMITFSI would shield the positive charges, which would stabilize the dication species at high potentials, avoiding the degradation and loss of electroaticity of PPSA and allowing charge transport on pernigraniline salt.

O desenvolvimento de novos revestimentos ou métodos de proteção considerados ambientalmente amigáveis é extremamente importante para a substituição das eficientes camadas de conversão do cromo, as quais são amplamente utilizadas para proteção anticorrosiva do alumínio e suas ligas. Entre as alternativas relatadas na literatura, podemos destacar a aplicação de filmes de polianilina (PAni) e o uso de camadas de conversão de cério. Neste trabalho é proposta a utilização de revestimentos do tipo bicamadas formada pela combinação de: 1) duas camadas de polianilina ou 2) camadas de conversão de cério (depositadas pelo método electroless ou catodicamente) e filmes de PAni para proteção contra a corrosão das ligas de alumínio AA7075-T6 e AA8006-F em meio aquoso contendo íons cloreto. Nos ensaios de corrosão foram utilizados o monitoramento do potencial de circuito aberto e a polarização potenciodinâmica em meio de NaCl 0,6 mol L-1. A superfície das ligas com e sem os recobrimentos foram analisadas por microscopia óptica e microscopia eletrônica de varredura. Também foi realizado o teste de aderência dos filmes de PAni presentes nas bicamadas sobre as ligas estudadas. O revestimento bicamada composto por uma camada de filme de PAni quimicamente depositada e um filme casting de PAni apresenta excelente aderência sobre as ligas AA7075-T6 e AA8006-F e combina a proteção oferecida pelos filmes casting com a boa aderência dos filmes de PAni depositados quimicamente. O uso da bicamada de cerato electroless e PAni apresenta propriedades anticorrosivas inferiores quando comparadas ao filme de PAni aplicado diretamente sobre o substrato metálico, entretanto, o uso de cerato electroless melhora a aderência dos filmes casting de PAni sobre as ligas estudas. O uso de bicamadas formadas por cerato depositado catodicamente e PAni sobre a liga AA8006-F apresenta valores de potencial de corrosão e potencial de pite inferiores ao do filme casting de PAni aplicado diretamente sobre o substrato metálico, enquanto que para a liga AA7075-T6 foram obtidas melhores propriedades anticorrosivas quando utilizada uma camada de cerato espessa (obtida utilizando uma solução de cério contendo 8 ou 25 &micro;L mL-1 de H2O2). / The development of new coatings or protection methods considered environmentally friendly is extremely important to replace the efficient conversion layers of chromium, which are widely used for corrosion protection of aluminum and its alloys. Among the alternative methods reported in the literature, it can be highlighted the application of polyaniline (PAni) films and the use of cerium conversion layers. This work proposes the use of bi-layers based on: 1) two layers of polyanilines or 2) combination cerium conversion layers (deposited by electroless or cathodic electrodeposition) and PAni films for corrosion protection of AA7075-T6 and AA8006-F alloys in aqueous solutions containing chloride ions. Open circuit potential and potentiodynamic polarization curves were used for the corrosion tests, which were performed in 0.6 mol L-1 NaCl solution. The surface of the alloys with and without the coatings were characterized by optical microscopy and scanning electronic microscopy. It was also performed the adhesion test of the PAni films present in the bi-layers on the studied alloys. The bi-layers formed by a layer of PAni chemically deposited and a layer of PAni film exhibited excellent adhesion to the AA7075-T6 and AA8006-F alloys and combined the protection offered by the cast film of PAni with the good adhesion of PAni chemically deposited. The use of a bi-layer formed by cerium oxides (deposited by electroless) with PAni film as coating presented lower anticorrosive properties compared to the PAni films applied directly on the substrate, however, the use of the cerium layer improves the adhesion of the PAni films on the alloys. The use of bi-layers formed by electrodeposited cerium oxides and PAni films on AA8006-F showed corrosion potential and pitting potential lower when compared with the PAni film directly applied on the substrate, whereas for AA7075-T6, the best anticorrosive properties was obtained using a thick cerium layer (cerium solution containing 8 or 25 &micro;L mL-1 of H2O2).