Neste trabalho, realizamos um estudo da dependência da condutividade elétrica dc ( ), com a dopagem (tempo de exposição ao ácido clorídrico de (0 a 6 horas), temperatura (80 T 300K) e campo elétrico (E) em filmes auto-sustentáveis de polianilina. As amostras foram metalizadas com ouro em ambas as faces e as medidas realizadas utilizando-se o método de duas pontas. O pó utilizado nos filmes foi sintetizado quimicamente através da mistura da anilina com ácido clorídrico, a qual foi adicionada uma segunda solução de peroxidissulfato de amônio e que após desdopagem com hidróxido de amônio, obteve-se a base esmeraldina, esse produto foi dissolvido em N-Metil Pirrolidona possibilitando a obtenção dos filmes pelo método casting e posteriormente dopados por imersão em solução de ácido clorídrico em níveis desejados. Para um curto tempo de exposição ao ácido clorídico (menos de 30 minutos) observamos um rápido crescimento da condutividade com o aumento da dopagem. Para tempos mais longos a condutividade tende a saturação. Da análise da condutividade em função da temperatura obtivemos que ~ exp(T(-1/4)) consistente com o modelo de \"Saltos de Alcance Variável\" proposto por Mott. Nesse modelo a condução ocorre através do tunelamento assistido por fônons entre estados eletrônicos localizados. Se os estados são muito localizados um elétron só poderá saltar para o estado mais próximo, e assim a condutividade será proporcional ao fator de Boltzmann. Se a localização é menos intensa , um elétron pode saltar para sítios onde a energia de ativação é menor mas que estão situados mais distantes do que os primeiros vizinhos, ou seja, a condução ocorrerá por saltos com alcance variável. / In this work, we accomplished a study of the dependence of the dc electrical conductivity ( ), with the doping level (time of immersion of the film into the hydrochloric acid - 0 t 6 hours), temperature (80 T 300K) and electric field (E) in polyaniline thin films. The electric contacts to the samples were obtained using gold deposited in both faces and the measurements have been done using the method of two points. The powder used in the films was synthesized chemically through the mixture of the aniline with hydrochloric acid. A second solution of ammonium peroxidissulfate has been added to the mixture and after that the same has been treated with ammonium hydroxide. The emeraldine base so obtained has been dissolved in N-Methyl-2-pyrrolidinone to be used to produce the films by the method of casting. Later on the films have been doped by imersion with hydrochloric acid in wanted levels. For a short time of immersion into hydrochloric acid (less than 30 minutes) we observed a fast growth of the conductivity with the increase of the doping level. For longer times the conductivity tends to the saturation. Analyzing the conductivity as a function of temperature we obtained that ~ exp (T(-1/4)) consistent with the model of Variable Range Hopping proposed by Mott. In that model the conduction happens through the tunneling of carriers assisted by phonons between localized electronic states. If the localization is very strong, the carrier can only jump to the nearest state, and the conductivity will be proportional to the Boltzmann factor. If the location is less strong, a carrier can jump to sites for which the activation energy is smaller but which can reside further way. As a result we have conductivity with variable range hopping.

FundaÃÃo Cearense de Apoio ao Desenvolvimento Cientifico e TecnolÃgico / O grupo de materiais ferroelÃtricos com camada de bismuto (BLSFs) tem sido extensivamente estudados, devido à sua potencial utilizaÃÃo em memÃrias de acesso aleatÃrio (aplicaÃÃes FeRAMs). Estruturas perovskita em camadas de bismuto de SrBi2Nb2O9 (SBN) pertencem a famÃlia Aurivillius, que tÃm a fÃrmula geral (Bi2O2)2+(An-1BnO3n+1)2-, onde os sÃtios A sÃo ocupados por cÃtions maiores, enquanto que os cÃtions com elevada valÃncia estÃo localizados em sÃtios B e n à o nÃmero de camadas octaÃdricas entre as camadas de bismuto (Bi2O2)2+. A presenÃa de camadas de bismuto serve como amortecedor para suportar a fadiga da polarizaÃÃo e preservar a estabilidade do bismuto em ferroelÃtricos de camadas estruturadas. Neste trabalho, as propriedades estruturais e dielÃtricas de SrBi2Nb2O9 (SBN) em funÃÃo do nÃvel de adiÃÃo de Bi2O3 ou La2O3 em radiofrequÃncias (RF) e micro-ondas foram estudados. O SBN foi preparado utilizando o mÃtodo de reaÃÃo em estado sÃlido com a adiÃÃo de 3, 5, 10 e 15% de Bi2O3 ou La2O3. A Ãnica fase ortorrÃmbica foi formada apÃs a calcinaÃÃo a 900ÂC durante 2h. A anÃlise por difraÃÃo de Raios X (DRX), utilizando o refinamento de Rietveld confirmou a formaÃÃo de uma Ãnica fase com um composto de estrutura cristalina (a = 5.5129Ã, b = 5,5183à , c = 25,0819Ã; α = β = γ = 90Â). A microscopia eletrÃnica de varredura (MEV) do material mostrou morfologias globulares (quase esfÃrica) de grÃos em toda a superfÃcie das amostras. A temperatura de Curie encontrada para a amostra nÃo dopada foi de 400ÂC. Com adiÃÃes de Bi3+, a temperatura diminuiu e com adiÃÃes de La3+ a temperatura de Curie aumentou significativamente acima de 450ÂC. Nas mediÃÃes das propriedades dielÃtricas de SBN à temperatura ambiente, a 10 MHz, foi observado os maiores valores de permissividade para SBN5LaP (5% de La2O3), com valores de 116,71 e a mais baixa perda (0,0057) foi obtido por SBN15LaP (15% de La2O3). Na regiÃo de frequÃncia de micro-ondas, amostras adicionadas de Bi2O3 mostraram maior permissividade dielÃtrica que amostras adicionadas de La2O3, destacamos a SBN15BiG (15% Bi2O3) com a permissividade dielÃtrica mais elevada em 70,32 (3,4 GHz). Os valores de constante dielÃtrica estÃo compreendidos na faixa de 28-71 e as perdas dielÃtricas sÃo da ordem de 10-2. As amostras foram estudadas para possÃveis aplicaÃÃes em RF e componentes de micro-ondas. / The group of ferroelectric materials with bismuth layer (BLSFs) has been extensively studied due to their potential use in random access memories (FeRAMs applications). Layered structures of perovskite bismuth SrBi2Nb2O9 ( SBN ) belong to the Aurivillius family, which has the general formula (Bi2O2)2+(An-1BnO3n+1)2-, where the sites are occupied by the larger cations, whereas the cations with high valence are located in sites B and n is the number of octahedral layers between the layers of bismuth (Bi2O2)2+. The presence of the bismuth layer serves as a buffer to withstand fatigue and polarization preserving the stability of the bismuth layer structured ferroelectrics. In this work, the structural and dielectric properties of SrBi2Nb2O9 (SBN) based on the level of addition of Bi2O3 or La2O3 on radio frequencies (RF) and microwave were studied. The SBN was prepared using the method of solid state reaction with the addition of 3, 5, 10 and 15% of Bi2O3 and La2O3. A single orthorhombic phase was formed after calcination at 900 C for 2h. The analysis by X-ray diffraction (XRD) using the Rietveld refinement confirmed the formation of a single phase compound with a crystal structure (a = 5.5129Ã, b = 5.5183Ã, c = 25.0819Ã, α = β = γ = 90Â) . The scanning electron microscopy (SEM) showed the material (nearly round) globular grain morphologies across the surface of the samples. The Curie temperature found for the undoped sample was 400ÂC. With additions of Bi3+, and the decreased temperature and with additions of La3+ Curie temperature rose significantly above 450ÂC. In the measurement of the dielectric properties of SBN at room temperature to 10 MHz, the highest values for permittivity SBN5LaP (5% La2O3) were observed, with values of 116.71 and the lowest loss (0.0057) was obtained by SBN15LaP (15% La2O3). In the region of frequency microwave , added Bi2O3 samples showed higher dielectric permittivity that La2O3 samples added, highlight the SBN15BiG (15% Bi2O3) with higher dielectric permittivity in 70.32 (3.4GHz) . The values of dielectric constant are included in the range of 28-71 and the dielectric losses are of the order of 10-2. The samples were investigated for possible applications in RF and microwave components.

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Submitted by Luciana Ferreira (lucgeral@gmail.com) on 2015-10-20T12:28:15Z No. of bitstreams: 2 Dissertação - Leonardo Martins de Abreu - 2011.pdf: 1808129 bytes, checksum: 57f554d3a354cf1b50f5c6811cf545b5 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2015-10-20T12:32:59Z (GMT) No. of bitstreams: 2 Dissertação - Leonardo Martins de Abreu - 2011.pdf: 1808129 bytes, checksum: 57f554d3a354cf1b50f5c6811cf545b5 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Made available in DSpace on 2015-10-20T12:32:59Z (GMT). No. of bitstreams: 2 Dissertação - Leonardo Martins de Abreu - 2011.pdf: 1808129 bytes, checksum: 57f554d3a354cf1b50f5c6811cf545b5 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Previous issue date: 2015-08-02 / Using Hartree-Fock (HF) and the second-order Møller-Plesset perturbation theory (MP2) methods with the 6-31G(d) basis set, we have investigated the chain length dependence of the dipole moment, linear polarizability, first and second hyperpolarizabilities of fluorinated polyacetylene chains (PFHA). Such properties were calculated using converged geometries obtained at the HF/6-31G(d) e MP2/6-31G(d) levels theory. The converged geometric parameters were obtained from equilibrium geometry of the oligomer with 40 carbon atoms. Our results show that the dipole moment and the first hyperpolarizability grow initially and exhibit a saturation pattern with the size of chain. In opposition, the linear polarizability and second hyperpolarizability present an increase with increasing chain length. It is found that the effects of electron correlation have an important role on the equilibrium geometry and on the electric properties. For the first hyperpolarizability, in particular, the asymptotic value including the electron correlation effects is 17 times larger than the uncorrelated one. These calculations were performed using the GAUSSIAN03, GAUSSIAN09 and Finito.f programs. / Utilizando os métodos ab initio de Hartree-Fock (HF) e de Møller-Plesset em segunda ordem (MP2) com o conjunto de funções Base 6-31G(d), investigamos o comportamento do momento de dipolo, da polarizabilidade linear, da primeira e da segunda hiperpolarizabilidades para cadeias de poliacetileno fluoretadas. Tais propriedades foram calculadas usando geometrias convergidas nos níveis HF/6-31G(d) e MP2/6-31G(d), construídas a partir dos parâmetros geométricos convergidos da geometria de equilíbrio do oligômero com 40 átomos de carbono. Os resultados obtidos mostram que o momento de dipolo e a primeira hiperpolarizabilidade deste sistema crescem inicialmente e apresentam um regime de saturação com o crescimento da cadeia poliênica. Diferentemente, a polarizabilidade linear e a segunda hiperpolarizabilidade apresentam um comportamento crescente com o incremento de subunidades no sistema. É importante destacar que o efeito de correlação eletrônica tem um impacto importante sobre a geometria de equilíbrio e sobre as propriedades elétricas das cadeias de PFHA. Para a primeira hiperpolarizabilidade, em particular, o valor assintótico obtido incluindo o efeito de correlação eletrônica é, aproximadamente, 17 vezes o valor obtido sem estes efeitos. Todos os cálculos foram realizados utilizando os programas GAUSSIAN03, GAUSSIAN09 e Finito.f.

Estudou-se a polimerização do álcool furfurílico líquido na interface nonômero-catalisador delimitada pelo interior de um tubo de vidro capilar. A superfície do álcool furfurílico líquido contido em um tubo de vidro de diâmetro interno inferior a 5.4mm foi exposta aos vapores de ácido clorídrico concentrado, o catalisador. Observou-se a formação de uma película auto-organizada e colorida na interface que, sob a ação da gravidade, cai para o interior do tubo com velocidade constante. O espectro de absorção óptica identificou a formação de oligômeros com picos de absorção em 570nm, 650nm, 770nm e 930nm, sendo a de 650nm a mais de peso molecular dos oligômeros difere fortemente daqueles formados por catálise homogênea. A condutância dessas películas foi observada medindo-se a resistência elétrica de películas formadas sobre uma placa invertida de vidro plano / The polymerization of furfuryl alcohol in the interface alcohol-concentrated hydrochloric acid vapor was studied inside glass tubes whose internal diameter were smaller than 5.4mm. Shortly after exposition of furfuryl alcohol to the acid vapor an auto organized bluish pellicle is generated that under gravity falls inside the tube with constant velocity. The observed optical absorption spectrum peaks at 570nm, 650nm, 770nm and 930nm were attributed to oligomers with 3, 5, 7 and 9 mers, respectively. The optical absorption band at 650nm being the stronger. The oligomers molecular weight distribution so formed was found to strongly differ of the ones formed by homogeneous catalysis. The electrical conductivity of these pellicles, made of conjugated oligomers, were observed measuring the electrical resistance of pellicles specially made on the flat inverted glass plate

No description available.

Compounds in the series La1-xTiO3 have been prepared in the powder and single crystalline forms. The structures of these compounds were studied with x-ray, neutron, and electron diffraction techniques. In all cases, a distortion from the ideal perovskite structure was found. Throughout the series, transitions occur in structural, magnetic, and electrical properties. The structure of La.67TiO3 was found to be of a distorted perovskite type arising from distortions in the titanium octahedra as a result of an ordering of the lanthanum positions and A-site cation vacancies. Although this phase has been reported many times, the crystal structure has not been determined. The La.67TiO3 and La.70TiO3 phases have the same structure and were assigned to the Pmmn space group. At La75.TiO3, a Ti3+ concentration of 2 8%, the symmetry of the structure changes from Pmmn to Imma, and distortion of the perovskite structure is caused by octahedral tilting within the lattice. A further structural transition occurs at a Ti3+ concentration of 64%, La8gTiO3, where the symmetry changes from Imma to Pnma. Again distortions from the ideal perovskite structure are caused by octahedral tilts within the system. Transitions were also observed in electrical and magnetic properties. These transitions occur at the same Ti3+ concentrations as the transitions observed in the structural properties, which suggests a correlation between properties based on Ti3+ concentration. The occurrence of A-site cation vacancies within the lattice is directly related to the Ti3+ concentrations within the individual materials. Changes in the Ti3+ concentration affect the size of the unit cell as well as the electrical and magnetic properties which range from insulators at low Ti3+ concentrations to metals at high Ti3+ concentrations. / Thesis / Master of Science (MSc)

This thesis addresses two hypotheses: 1) ooplasmic ion activity is regulated during water uptake by locust eggs, and, 2) activities of Ca⁺⁺ and H⁺ are maintained at levels appropriate for their use as signals for developmental processes, including activation, in insect eggs. Hypothesis 1 is based on the perturbing effect of large changes in intracellular Na and/or K activity on enzyme function in eukaryotic cells. Hypothesis 2 is based on the ionic hypothesis of activation developed from studies of eggs of marine invertebrates. Electrical potential difference across egg membranes (PD_egg), and ooplasmic activities of Na⁺, K⁺, Cl⁻, Ca⁺⁺ and H⁺ were measured with double-barrelled ion-selective microelectrodes. Locust eggs maintained a measurable potential difference across egg membranes throughout development. Input resistance (Rᵢₙ) decreased by approximately 5-fold in eggs after fertilization suggesting that the chorion is not the major barrier to ion movements into and out from the egg. Chilling and anoxia decreased the contribution of a metabolic component to PD_egg. The effects of hypercapnia on PD_egg and ooplasmic pH suggest that the metabolic component may be a H⁺-pump. Chloride diffusion contributes to PD_egg in eggs after fertilization; contributions of other ions were relatively small. Potential differences measured in internally perfused locust eggs after osmotic lysis of the serosal epithelium indicated that the chloride-dependent component of PD_egg is developed across the chorion and/or serosal cuticle. In vivo values of PD_egg are probably less negative than values measured in control saline because chloride content of ground water is low. Ooplasmic sodium and potassium activities remained at typically intracellular levels during water uptake, possibly due to release from internal stores. Chloride activities were typical of extracellular fluids and were not regulated during water uptake. Measurements of pH and pea in locust eggs are consistent with the increases in these parameters predicted by the ionic hypothesis of activation. calcium activity in the ooplasm of unfertilized locust eggs (pCa 6.4 -4.9) appeared to be at a level appropriate for the use of calcium as a signal or second messenger. Calcium activity increased 100fold within 1 day of fertilization, and 1000-fold by day 3. Calcium entry from external sources at fertilization and release from internal stores later in development may contribute to the progressive increase in ooplasmic Ca⁺⁺ activity. The ooplasm likely alkalinizes after oviposition as ambient pCo₂ declines. Available data suggest a metabolically-dependent proton pump may control ooplasmic pH in locust eggs, in contrast to the Na⁺/H⁺ exchanger implicated in alkalinization of marine invertebrate eggs. / Thesis / Master of Science (MS)

The object of the thesis is to obtain the apparent- resistivity curves and induced-polarization (IP) effects that are utilized in geophysical exploration. Two different earth geometries, the thin horizontal conductive layer and vertical dike, were studied. The solution for both cases is identical. First, quasi- static electrical conditions were assumed, so that the problem could be solved using potential fields. The exact solution to the problem was obtained by using the Bessel integral formulation. Also, the image method was employed to find the potential fields. We noticed that the image -type series converges best when the dike or layer was thick (ratio of thickness to electrode spacing, b/a, is large) and the reflection coefficient was not near ±1. Otherwise, it is preferable to employ the thin conductive sheet model. The next step was to determine the dilution and distortion factors which are relevant to the induced polarization response. Finally, numerical results were obtained using a Fortran computer program. These calculations were compared with some results taken from the literature and good agreement is seen.

No description available.