Made available in DSpace on 2014-06-11T19:25:32Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-02-14Bitstream added on 2014-06-13T19:12:22Z : No. of bitstreams: 1 braunger_ml_me_rcla.pdf: 1994940 bytes, checksum: 93302556a6228fb6bcbdf01e53c83e00 (MD5) / Neste trabalho foi avaliada a condutividade elétrica de vidros com composição (mol%) 22Na2O·8CaO·65SiO2·5MO2, com M = Si, Ti, Ge, Zr, Sn e Ce, sem e com troca iônica Ag+↔Na+ em 350 ºC por 1 hora. Após a troca iônica, amostras também foram submetidas a tratamento térmico em 500 ºC durante 24 horas. As medidas elétricas foram realizadas com um analisador de impedâncias Solartron. Foram analisados gráficos de Z” vs. Z’ e de σ’ vs. f em função da temperatura com o objetivo de se determinar, de duas maneiras diferentes, as energias de ativação para a condutividade elétrica, Eσ. Os valores das resistências elétricas das amostras são obtidos a partir de gráficos Z” vs. Z’ quando Z” se anula para baixas frequências. Conhecendo-se o parâmetro geométrico da amostra, calcula-se a condutividade para corrente contínua, σdc. Através das curvas σ’ vs. f determina-se σdc quando f → 0. Gráficos de Ln σdc vs. T-1 possibilitaram determinar 0,724 < Eσ < 0,826 eV, valores que concordam com os encontrados na literatura. Após submetidas à troca iônica, as amostras apresentaram aumento da condutividade. Por outro lado, o tratamento térmico posterior diminui a condutividade da maioria das amostras, provavelmente, devido à formação de nanopartículas de prata metálica na matriz vítrea. Para verificar alterações da composição devido à troca iônica e ao tratamento térmico utilizamos a técnica de espectroscopia de energia dispersiva de raios-X, EDS, no volume e na superfície das amostras. Verificou-se que a Ag migra para o volume durante o tratamento térmico, tendendo a tornar constante a sua distribuição, dependendo do cátion tetravalente, M4+, presente na matriz vítrea. A espectroscopia de reflexão difusa no infravermelho, DRIFT, indicou alterações na estrutura da superfície das... / In this work, it has been evaluated the electrical conductivity of glasses with composition (mol%) 22Na2O·8CaO·65SiO2·5MO2, with M = Si, Ti, Ge, Zr, Sn and Ce, without and with ion exchange Ag+↔Na+ at 350 ºC for 1 hour. After the ion exchange, samples were also submitted to thermal treatment at 500 ºC for about 24 hours. Electrical measurements were carried out with a Solartron impedance analyzer. Z” vs. Z’ and σ’ vs. f plots were analyzed as a function of temperature in order to determine, by two distinct approaches, the activation energies for the electrical conductivity, Eσ. The values of the electrical resistances of the samples are obtained from Z” vs. Z’ plots when Z” nulls itself at low frequencies, and knowing the geometric parameter of the sample, the continuous current conductivity, σdc, can then be calculated. Through σ’ vs. f plots, one can determine σdc when f → 0. We were able to determine 0,724 < Eσ < 0,826 eV by Ln σdc vs. T-1 plots, and those values agree with the ones found in the literature. When submitted to ion exchange, the samples showed an increased conductivity. On the other hand, a subsequent thermal treatment diminishes the conductivity for most of the samples, probably due to the formation of metallic silver nanoparticles in the vitreous matrix. In order to check for compositional modifications due to the ion exchange and thermal treatment, we have employed the energy dispersive X-ray spectroscopy technique, EDS, in the bulk and surface of the samples. It has been observed that Ag migrates towards the bulk during the thermal treatment, tending to reach a constant distribution, depending on the tetravalent cation, M4+, in the vitreous matrix. The diffuse reflectance infrared Fourier transform, DRIFT, have pointed changes in the surface structure of the samples... (Complete abstract click electronic access below)

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Orientador: Ervino Carlos Ziemath / Banca: Lygia Christina de Moura Walmsley / Banca: Ana Candida Martins Rodrigues / Resumo: Neste trabalho foi avaliada a condutividade elétrica de vidros com composição (mol%) 22Na2O·8CaO·65SiO2·5MO2, com M = Si, Ti, Ge, Zr, Sn e Ce, sem e com troca iônica Ag+↔Na+ em 350 ºC por 1 hora. Após a troca iônica, amostras também foram submetidas a tratamento térmico em 500 ºC durante 24 horas. As medidas elétricas foram realizadas com um analisador de impedâncias Solartron. Foram analisados gráficos de Z" vs. Z' e de σ' vs. f em função da temperatura com o objetivo de se determinar, de duas maneiras diferentes, as energias de ativação para a condutividade elétrica, Eσ. Os valores das resistências elétricas das amostras são obtidos a partir de gráficos Z" vs. Z' quando Z" se anula para baixas frequências. Conhecendo-se o parâmetro geométrico da amostra, calcula-se a condutividade para corrente contínua, σdc. Através das curvas σ' vs. f determina-se σdc quando f → 0. Gráficos de Ln σdc vs. T-1 possibilitaram determinar 0,724 < Eσ < 0,826 eV, valores que concordam com os encontrados na literatura. Após submetidas à troca iônica, as amostras apresentaram aumento da condutividade. Por outro lado, o tratamento térmico posterior diminui a condutividade da maioria das amostras, provavelmente, devido à formação de nanopartículas de prata metálica na matriz vítrea. Para verificar alterações da composição devido à troca iônica e ao tratamento térmico utilizamos a técnica de espectroscopia de energia dispersiva de raios-X, EDS, no volume e na superfície das amostras. Verificou-se que a Ag migra para o volume durante o tratamento térmico, tendendo a tornar constante a sua distribuição, dependendo do cátion tetravalente, M4+, presente na matriz vítrea. A espectroscopia de reflexão difusa no infravermelho, DRIFT, indicou alterações na estrutura da superfície das... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: In this work, it has been evaluated the electrical conductivity of glasses with composition (mol%) 22Na2O·8CaO·65SiO2·5MO2, with M = Si, Ti, Ge, Zr, Sn and Ce, without and with ion exchange Ag+↔Na+ at 350 ºC for 1 hour. After the ion exchange, samples were also submitted to thermal treatment at 500 ºC for about 24 hours. Electrical measurements were carried out with a Solartron impedance analyzer. Z" vs. Z' and σ' vs. f plots were analyzed as a function of temperature in order to determine, by two distinct approaches, the activation energies for the electrical conductivity, Eσ. The values of the electrical resistances of the samples are obtained from Z" vs. Z' plots when Z" nulls itself at low frequencies, and knowing the geometric parameter of the sample, the continuous current conductivity, σdc, can then be calculated. Through σ' vs. f plots, one can determine σdc when f → 0. We were able to determine 0,724 < Eσ < 0,826 eV by Ln σdc vs. T-1 plots, and those values agree with the ones found in the literature. When submitted to ion exchange, the samples showed an increased conductivity. On the other hand, a subsequent thermal treatment diminishes the conductivity for most of the samples, probably due to the formation of metallic silver nanoparticles in the vitreous matrix. In order to check for compositional modifications due to the ion exchange and thermal treatment, we have employed the energy dispersive X-ray spectroscopy technique, EDS, in the bulk and surface of the samples. It has been observed that Ag migrates towards the bulk during the thermal treatment, tending to reach a constant distribution, depending on the tetravalent cation, M4+, in the vitreous matrix. The diffuse reflectance infrared Fourier transform, DRIFT, have pointed changes in the surface structure of the samples... (Complete abstract click electronic access below) / Mestre

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Esta dissertação apresenta a caracterização e o preparo de filmes a partir de amido de mandioca nativo e modificado industrialmente (amido acetilado e amido oxidado - acetilado), através da plastificação com glicerol , sorbitol ou etileno glicol. Estes filmes foram preparados adicionando-se um sal (perclorato de lítio) com o propósito de serem utilizados como eletrólitos sólidos poliméricos (ESP), os quais apresentam grande potencial de aplicação em dispositivos eletrocrômicos, sensores e baterias, por isso os ESPs devem ser: transparentes, apresentar boa aderência e maleabilidade além de boa condutividade iônica. As modificações conferidas ao amido foram estudadas empregando-se técnicas caracterização por espectroscopia no infravermelho, RMN e análise elementar. A distribuição de massa molecular das amostras de amido nativo e dos amidos modificados também foi estudada através da técnica de cromatografia de permeação em gel (GPC). Os filmes foram preparados utilizando-se diferentes proporções de plastificante e de sal e em seguida com intuito de efetuar as caracterizações físico-químicas estas amostras foram submetidas à análises de espectroscopia de impedância eletroquímica, difração de Raios-X, Microscopia Eletrônica de Varredura (MEV), análises espectrofotométricas de UV-visível, além das análises térmicas (TG e DSC). / This dissertation presents the preparation and characterization of films obtained from native and industrially modified (acetilate and oxidate-acetilate), cassava starches, through the plasticization with glycerol, sorbitol or ethylene glycol. These films are prepared adding a salt (lithium perchlorate) so that they can be used as solid polymeric electrolytes (ESP), which present great application potential in electrochromic devices, sensors and batteries, therefore the films obtained must be transparent, present good adherence and flexibility besides good ionic conductivity. The modifications of the starch were studied using techniques of characterization by infrared espectroscopy, RMN and elementary analysis. The distribution of the molecular mass of the samples of native and modified starches was also studied by means of gel permeation chromatography (GPC). The films were prepared using different proportions of plasticizers and salt. For the physical-chemical characterization of the samples, they were subjected to analyses of electrochemical impedance spectroscopy, X-Ray diffraction, Scanning Electronic Microscopy (SEM), Uv-visible spectroscopy, besides thermal analyses (TG and DSC).

Electrical and thermal conductivities of the yttria-stabilised zirconia/alumina (YSZ/Al2O3) composites and the yttria-zirconia-ceria (YSZ-CeO2) solid solutions are studied in this thesis. The electrical conductivity of the YSZ/Al2O3 composites decreases with an increase in the volume fraction of Al2O3 and exhibits typical percolation behaviour. The electrical conductivity of the YSZ/Al2O3 interface is higher than that of the YSZ grain boundary, but lower than that of the YSZ grains. The thermal conductivity of the YSZ/Al2O3 composites increases with an increase in the Al2O3 volume fraction, and it can be fitted well to the Maxwell theoretical model, which indicates the absence of obvious interfacial thermal resistances in the composites. The low interfacial thermal resistance of the YSZ/Al2O3 interface is due to the 'clean' and coherent nature of the YSZ/Al2O3 interface, along with the small difference between the elastic properties of YSZ and Al2O3. The electrical conductivity of the [(ZrO2)1-x(CeO2)x]0.92(Y2O3)0.08 (0 ≤ x ≤ 1) solid solutions has a 'V-shape' variation as a function of the mole ratio of CeO2 (x). In the ZrO2-rich region (x < 0.5), CeO2 doping increases the concentration of defect associates which limits the mobility of the oxygen vacancies; in the CeO2-rich region (x > 0.5), the increase of x increases the lattice parameter, which enlarges the free channel for oxygen vacancy migration. A comparison of the YSZ-CeO2 solid solutions with the YSZ-HfO2 series indicates the ionic radius of the tetravalent dopant determines the composition dependence of the ionic conductivity of the solid solutions.The thermal conductivity of the [(ZrO2)1-x(CeO2)x]0.92(Y2O3)0.08 (0 ≤ x ≤ 1) solid solutions also has a 'V-shape' variation as a function of the mole ratio of CeO2 (x), which indicates an incorporation of Zr4+ and Ce4+ can effectively decrease the thermal conductivity of the end members YSZ and yttria-doped ceria (YDC). In the ZrO2-rich region (0 ≤ x ≤ 0.5), the thermal conductivity is almost temperature independent; in the CeO2-rich region (0.5 ≤ x ≤ 1), it decreases obviously with increasing temperature. By calculating the phonon scattering coefficients, it is concluded that the composition dependence of the thermal conductivity in the ternary solid solutions is dominated by the mass difference between Zr and Ce at the cation sites, whereas the temperature dependence is determined by the order/disorder of oxygen vacancies at the anion sites.

京都大学 / 新制・課程博士 / 博士(理学) / 甲第23458号 / 理博第4752号 / 新制||理||1681(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 北川 宏, 教授 吉村 一良, 教授 竹腰 清乃理 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

No description available.

No / Traditionally materials with the fluorite and perovskite structures have dominated the research in the area of oxide ion/proton conducting solid electrolytes. In such cases, the key defects are oxide ion vacancies, and conduction proceeds via a simple vacancy hopping mechanism. In recent years, there has been growing interest in alternative structure types, many of which contain tetrahedral moieties. For these new systems, an understanding of the accommodation of defects and the nature of the conduction mechanism is important for the optimisation of their conductivities, as well as to help target related structures that may display high oxide ion/proton conduction. Computer modelling studies on a range of systems containing tetrahedral moieties are presented, including apatite-type La9.33+xGe6O26+3x/2, cuspidine-type La4Ga2-xTixO9+x/2 and La1-xBa1+xGaO4-x/2. The type of anion defect (vacancy or interstitial), their location and the factors affecting their incorporation are discussed. In addition, modelling data to help to understand their conduction mechanisms are presented, showing novel aspects including the important role of the tetrahedral moieties in the conduction processes.

No / Traditionally materials with the fluorite and perovskite structures have dominated the research in the area of oxide ion/proton conducting solid electrolytes. In such cases, the key defects are oxide ion vacancies, and conduction proceeds via a simple vacancy hopping mechanism. In recent years, there has been growing interest in alternative structure types, many of which contain tetrahedral moieties. For these new systems, an understanding of the accommodation of defects and the nature of the conduction mechanism is important for the optimisation of their conductivities, as well as to help target related structures that may display high oxide ion/proton conduction. Computer modelling studies on a range of systems containing tetrahedral moieties are presented, including apatite-type La9.33+xGe6O26+3x/2, cuspidine-type La4Ga2¿xTixO9+x/2 and La1¿xBa1+xGaO4¿x/2. The type of anion defect (vacancy or interstitial), their location and the factors affecting their incorporation are discussed. In addition, modelling data to help to understand their conduction mechanisms are presented, showing novel aspects including the important role of the tetrahedral moieties in the conduction processes