Despite the poor understanding of charge transfer in conducting polymers, conducting-polymer-based devices have achieved considerable commercial success. This success is based largely on the reproducibility of the measurable properties. It is the purpose of this study to further clarify charge transfer characteristics of conducting polymers under varying conditions. We studied a conducting polymer called polyaniline. Polyaniline was available in its doped conducting form called emeraldine salt and in its undoped form called emeraldine base. Three types of polyaniline were studies, electrosynthesized (doped by HCI), chemically synthesized (doped by HCI) and commercial polyaniline obtained from Adlrich Company and doped by camphor sulfonic acid. Initially we investigated whether charge transfer was ionic or electronic by observing the change in resistance with time for a fixed applied current. It was concluded that condition in this material is electronic. Electrical measurements were obtained using the four-point probe and the Montgomery methods. The samples investigated were in pellet and film forms. We investigated charge transfer over the temperature regime 30-450 K by applying the following methods: scanning electron microscopy to investigate the surfaces of pellet and film samples, Fourier transform infrared spectroscopy and Raman spectroscopy to investigate the effect of annealing on the molecular structure of the polymer and thermal analysis to investigate the loss of substances from the polymer as a result of the annealing process. The conductivity of the material was also analyzed over the entire temperature regime. The following were observed: • Conductivity in polyaniline is governed my monomer units. • The decrease in conductivity with increase annealing temperature is related to moisture loss, loss of dopant ions and polymer degradation. • The variable range hopping model in three dimensions, satisfactorily describes charge transfer mechanism in polyaniline. • Conductivity in polyaniline is temperature activated. • Conductivity varies with position on the sample surface. • The effect of pellet pressing pressure to conductivity is negligible. • Current-voltage characteristics for polyaniline exhibit non-ohmic behavior at high current values, (>0.2 mA for T <80 K), applied between the current probes of a four-point probe measuring instrument. / Dissertation (MSc (Physics))--University of Pretoria, 2006. / Physics / unrestricted

Submitted by GUILHERME DOGNANI null (gdognani@bol.com.br) on 2016-02-18T16:52:20Z No. of bitstreams: 1 Dognani, G_Dissertação.pdf: 3231196 bytes, checksum: c5c016c95556862b76a9859f8b519f60 (MD5) / Approved for entry into archive by Juliano Benedito Ferreira (julianoferreira@reitoria.unesp.br) on 2016-02-19T17:27:35Z (GMT) No. of bitstreams: 1 dognani_g_me_bauru.pdf: 3231196 bytes, checksum: c5c016c95556862b76a9859f8b519f60 (MD5) / Made available in DSpace on 2016-02-19T17:27:35Z (GMT). No. of bitstreams: 1 dognani_g_me_bauru.pdf: 3231196 bytes, checksum: c5c016c95556862b76a9859f8b519f60 (MD5) Previous issue date: 2016-01-22 / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / A técnica de eletrofiação tem sido utilizada na obtenção de fibras com diversos materiais poliméricos. Neste trabalho, foram desenvolvidos, de maneira inédita, materiais eletrofiados a partir de borracha natural e polianilina. Por esta técnica, foram obtidas mantas eletrofiadas com fibras de diâmetro menor que 1 µm. Para o desenvolvimento destas mantas eletrofiadas tornou-se necessário primeiramente realizar um amplo estudo sobre os parâmetros de processo, o qual constou em variar o fluxo de vazão da solução polimérica de 0,1, 0,25, 0,5 mL/h, a tensão aplicada ao processo de 10, 12,5, 15 kV e a rotação do coletor rotativo onde as fibras foram depositadas em 30, 40, 50 rpm. Após o estudo dos parâmetros de eletrofiação, foi selecionada uma série com os melhores parâmetros, que proporcionou a obtenção de mantas de borracha natural denominadas BN. Estas mantas foram posteriormente recobertas com polianilina pelo método de polimerização in situ, obtendo mantas de BN/PAni dopada e BN/PAni desdopada. Para fins de comparação foram também produzidas membranas densas pelo método casting, que foram caracterizadas quanto suas propriedades elétricas, onde mostrou bons resultados, se comportando como material ôhmico alcançando a condutividade na ordem de 10-6 S/m para BN/PAni dopada, enquadrado assim entre os materiais semicondutores. Além das propriedades elétricas foram também investigadas as propriedades térmicas, espectroscópicas e morfológicas dos materiais estudados. Os resultados deste trabalho mostraram que é possível eletrofiar a borracha natural formando fibras de diâmetro que alcançaram valores mínimos de até 0,92 μm. / The electrospinning technique has been used to obtain fibers with various polymer materials. In this work were developed in an unprecedented fibers electrospun from natural rubber and polyaniline. For this technique, fibers mats were obtained with fiber diameter of less than 1 micrometers. For the development of these electrospun mats became necessary to first perform an extensive study on the process parameters, which consisted in varying the flow of polymer solution at 0.1, 0.25, 0.5 ml/h, the voltage applied to the process 10, 12.5, 15 kV and rotation of the collector where the fibers were deposited on 30, 40, 50 rpm. After studying the electrospinning parameters, it selected a series with the best parameters, which provided obtaining natural rubber mats called NR. These mats were covered with polyaniline by in situ polymerization method, getting NR/PAni doped and NR/PAni undoped mats. For purposes of comparison were also produced membranes by casting method, which were characterized as its electrical properties, which showed good results, behaving as ohmic materials reaching the conductivity on the order of 10-6 S/m for NR/PAni doped, entering among the semiconductor materials. In addition to the electrical properties were also investigated the thermal, spectroscopic and morphological materials properties. These results showed that it is possible produced natural rubber fibers electrospun forming diameter fibers that have reached minimum values of up to 0.92 micrometers. / FAPESP: 2013/18692-6