Low temperature preparation and fuel cell properties of rare earth doped barium cerate solid electrolytes

The solid electrolytes, BaCe(0.8)Ln(0.2)O(2.9) (Ln: Gd, Sm, Eu), were prepared by the sol-gel method. XRD indicated that a pure orthorhombic phase was formed at 900 degrees C. The synthesis temperature by the sol-gel method was about 600 degrees C: lower than the high temperature solid phase reaction method. The electrical conductivity and impedance spectra were measured and the conduction mechanism was studied. The grain-boundary resistance of the solid electrolyte could be reduced or eliminated by the sol-gel method. The conductivity of BaCe0.8Gd0.2O2.9 is 7.87 x 10(-2) S.cm(-1) at 800 degrees C. The open-circuit voltage of hydrogen-oxygen fuel cell using BaCe0.8Gd0.2O2.9 as electrolyte was near to 1 V and its maximum power density was 30 mW.cm(-2).

Electrochemical promotion of a metal catalyst supported on a mixed-ionic conductor

It has been found that the catalytic activity and selectivity of a metal film deposited on a solid electrolyte could be enhanced dramatically and in a reversible way by applying an electrical current or potential between the metal catalyst and the counter electrode (also deposited on the electrolyte). This phenomenon is know as NEMCA [S. Bebelis, C.G. Vayenas, Journal of Catalysis, 118 (1989) 125-146.] or electrochemical promotion (EP) [J. Prichard, Nature, 343 (1990) 592.] of catalysis. Yttria-doped barium zirconate, BaZr_0.9Y_0.1O_{3 - α} (BZY), a known proton conductor, has been used in this study. It has been reported that proton conducting perovskites can, under the appropriate conditions, act also as oxide ion conductors. In mixed conducting systems the mechanism of conduction depends upon the gas atmosphere that to which the material is exposed. Therefore, the use of a mixed ionic (oxide ion and proton) conducting membrane as a support for a platinum catalyst may facilitate the tuning of the promotional behaviour of the catalyst by allowing the control of the conduction mechanism of the electrolyte. The conductivity of BZY under different atmospheres was measured and the presence of oxide ion conduction under the appropriate conditions was confirmed. Moreover, kinetic experiments on ethylene oxidation corroborated the findings from the conductivity measurements showing that the use of a mixed ionic conductor allows for the tuning of the reaction rate. © 2006 Elsevier B.V. All rights reserved.

Electro-Optical Properties of Metal Phthalocyanines and Naphthalocyanines

The thesis deals with the preparation of chemical, optical, thermal and electrical characterization of five compounds, namely metal free naphthalocyanine, vanadyl napthalocyanine, zinc naphlocyanine, europium dinaphthalocyanine, and europium diphthalocyanine in the pristine and iodine-doped forms. Two important technological properties of these compounds have been investigated. The electrical properties are important in applications sensors and semiconductor lasers. Opto-thermal properties assume significance for optical imaging and data recording. The electrical properties were investigated by dc and ac techniques. This work has revealed some novel information on the conduction mechanism in five macrocyclic compounds and their iodine-doped forms. Also useful data on the thermal diffusivity of the target compounds have been obtained by optical techniques.

Studies on Electrical and Thermal Properties of Certain Selected Photonic Materials

The present thesis is centered around the study of electrical and thermal properties of certain selected photonic materials.We have studied the electrical conduction mechanism in various phases of certain selected photonic materials and those associated with different phase transitions occurring in them. A phase transition leaves its own impressions on the key parameters like electrical conductivity and dielectric constant. However, the activation energy calculation reveals the dominant factor responsible for conduction process.PA measurements of thermal diffusivity in certain other important photonic materials are included in the remaining part of the research work presented in this thesis. PA technique is a promising tool for studying thermal diffusivities of solid samples in any form. Because of its crucial role and common occurrence in heat flow problems, the thermal diffusivity determination is often necessary and knowledge of thermal diffusivity can intum be used to calculate the thermal conductivity. Especially,knowledge of the thermal diffusivity of semiconductors is important due to its relation to the power dissipation problem in microelectronic and optoelectronic devices which limits their performances. More than that, the thermal properties, especially those of thin films are of growing interest in microelectronics and microsystems because of the heat removal problem involved in highly integrated devices. The prescribed chapter of the present theis demonstrates how direct measurement of thermal diffusivity can be carried out in thin films of interest in a simple and elegant manner using PA techniques. Although results of only representative measurements viz; thermal diffusivity values in Indium, Aluminium, Silver and CdS thin films are given here, evaluation of this quantity for any photonic and / electronic material can be carried out using this technique in a very simple and straight forward manner.

Investigations on the electrical and structural properties of polyaniline doped with camphor sulphonic acid

Polyaniline is chemically synthesised and doped with camphor sulphonic acid. FTIR studies carried out on these samples indicate that the aromatic rings are retained after polymerisation. The percentage of crystallinity for polyaniline doped with camphor sulphonic acid has been estimated from the X-ray diffraction studies and is around 56% with respect to polyaniline emeraldine base. The change in dielectric permittivity with respect to temperature and frequency is explained on the basis of interfacial polarisation. AC conductivity is evaluated from the observed dielectric permittivity. The values of AC and DC conductivity and activation energy are calculated. The activation energy values suggested that the hopping conduction is the prominent conduction mechanism in this system.

Structural and electrical studies on tetrameric cobalt phthalocyanine and polyaniline composites

Polyaniline and oligomeric cobalt phthalocyanine are blended in different proportions by chemical methods. These blends are characterised by spectroscopic methods and dielectric measurements. Dielectric studies on the conducting polymer blends are carried out in the frequency range of 100 kHz to 5MHz from room temperature (300 K) to 373 K. Dielectric permittivity and dielectric loss of these blends are explained on the basis of interfacial polarisation. From the dielectric permittivity studies, ac conductivity of the samples were calculated and the results are correlated. In order to understand the exact conduction mechanism of the samples, dc electrical conductivity of the blends is carried out in the temperature range of 70–300 K. By applying Mott’s theory, it is found that the conducting polymer composites obey a 3D variable range hopping mechanism. The values of Mott’s temperature (T0), density of states at the Fermi energy (N(EF)), range of hopping (R) and hopping energy (W) for the composites are calculated and presented

Dielectric and Conductivity Studies on Cobalt Phthalocyanine Tetramers

Electrically conductive organic and metalloorganic polymers are of great interest and they have applications in electronic, optical, photonic, photoelectric, electrochemical, and dielectric devices. Tetrameric cobalt phthalocyanine was prepared by conventional chemical method. The dielectric permittivity of the tetrameric cobalt phthalocyanine sample was evaluated from the observed capacitance values in the frequency range 100 KHz to 5 MHz and in the temperature range of 300 to 383°K. It is found that the system obeys the Maxwell Wagner relaxation of space charge phenomenon. Further, from the permittivity studies AC conductivity was evaluated. The values of AC conductivity and DC conductivity were compared. Activation energy was calculated. To understand the conduction mechanism Mott’s variable range hopping model was applied to the system. The T 1/4 behavior of the DC conductivity along with the values of Mott’s Temperature (T0), density of states at the Fermi energy N (EF), and range of hopping R and hopping energy W indicate that the transport of charge carriers are by three-dimensional variable range hopping

Characterization of anodic silicon oxide films grown in room temperature ionic liquids

The electroformation of silicon oxide was performed in two room temperature ionic liquids (RTIL), 1-butyl-3-methyl-imidazolium bis(trifluoromethane sulfonyl) imide (BMITFSI) and N-n-butyl-N-methylpiperidinium bis(trifluoromethane sulfonyl) imide (BMPTFSI). This phenomenon was studied by electrochemical techniques and it was observed that the oxide growth follows a high-field mechanism. X-ray Photoelectron Spectroscopy experiments have shown that a non-stoichiometric oxide film was formed, related to the low water content present in both RTILs (< 30 ppm). The roughness values obtained by using AFM technique of the silicon surface after etching with HF was 1.5 nm (RMS). The electrochemical impedance spectroscopy at low frequencies range was interpreted as a resistance in parallel with a CPE element, the capacitance obtained was associated with the dielectric nature of the oxide formed and the resistance was interpreted considering the chemical dissolution of the oxide by the presence of the TFSI anion. The CPE element was associated with the surface roughness and the very thin oxide film obtained. (C) 2007 Elsevier Ltd. All rights reserved.

Comportamento elétrico a alta temperatura de termistor cerâmico alfa-Fe2O3 com coeficiente de temperatura negativo

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Dielectric spectroscopy and thermally stimulated discharge current in PEEK film

A permissividade complexa de filmes de poli(eter-eter-cetona) (PEEK) foram investigados num grande intervalo de frequência. Não foram observados picos de relaxação no intervalo de frequência de 1,0 Hz a 10(5) Hz, mas no intervalo de baixa frequência (10-4 Hz) há uma evidência de pico, o qual também pode ser observado com medidas de corrente de despolarização termo-estimulada (TSDC). Este pico está relacionado com a transição vítrea do polímero. A energia de ativação relacionada a esta relaxação dipolar foi obtida e ovalor é Ea = 0,44 eV, que é similar à energia de ativação de muitos polímeros sintéticos. As cargas espaciais se mostraram importantes no mecanismo de condução como evidenciado nas medidas da corrente de despolarização.

Effect of the sintering conditions on the electrical properties of Nd(3+) modified PLZT ceramics

The effect of the sintering method on the microstructural and electrical properties of (Pb(0.89)Nd(0.02)La(0.09))(Zr(0.65)Ti(0.35))O(3) (PNLZT) ceramics was studied by impedance spectroscopy. Structural and microstructural analyses were performed using x-ray and scanning electron microscopy techniques. Two different sintering routes were employed: the conventional and the hot-pressing sintering methods. The impedance analysis provided a convincing evidence for the existence of both grain (g) and grain boundary (gb) contributions to the conduction process. An equivalent circuit for the impedance behaviour has been proposed and discussed. The variation in the sintering method produces significant changes in the grain and grain boundary conductivities. For the grain effect, the main conduction mechanism has been associated with oxygen vacancy migration. Otherwise, for grain boundary conductivity the impedance behaviour has been discussed in terms of the brick-layer and the constriction resistance models (BLM and CRM, respectively).

Schottky emission in nanoscopically crystallized Ce-doped SnO2 thin films deposited by sol-gel-dip-coating

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Thickness dependence of leakage current in BaBi2Ta2O9 thin films

BaBi2Ta2O9 thin films having a layered structure were fabricated by metalorganic solution deposition technique. The films exhibited good structural, dielectric, and insulating properties. The room temperature resistivity was found to be in the range of 10(12)-10(14) Omega cm up to 4 V corresponding to a field of 200 kV/cm across the capacitor for films annealed in the temperature range of 500-700 degrees C. The current-voltage (I-V) characteristics as a function of thickness for films annealed at 700 degrees C for 1 h, indicated bulk limited conduction and the log(I) vs V-1/2 characteristics suggested a space-charge-limited conduction mechanism. The capacitance-voltage measurements on films in a metal-insulator-semiconductor configuration indicated good Si/BaBi2Ta2O9 interface characteristics and a SiO2 thickness of similar to 5 nm was measured and calculated. (C) 1999 American Institute of Physics. [S0003-6951(99)00830-X].

Effect of Ta2O5 doping on the electrical properties of 0.99SnO(2)center dot 0.01CoO ceramic

The effect of Ta2O5 doping in 0.99SnO(2). 0.01CoO on the microstructure and electrical properties of this ceramic were analyzed in this study. The grain size was found to decrease from 6.87 mu m to 5.68 mu m when the Ta2O5 concentration increased from 0.050 to 0.075 mol%. DC electrical characterization showed a dramatic increase in the current loss and decrease in the non-linear coefficient with the increase of the Ta2O5 concentration. The conduction mechanism is by thermionic emission and the potential barriers are of Schottky type, separated by a thin film. (C) 2000 Kluwer Academic Publishers.