Thesis (M.S.)--Michigan State University. Dept. of Electrical and Computer Engineering, 2008. / Title from PDF t.p. (viewed on Aug. 7, 2009) Includes bibliographical references (p. 58-59). Also issued in print.

Thesis (M.S.)--Montana State University--Bozeman, 2005. / Typescript. Chairperson, Graduate Committee: Vic A. Cundy. Includes bibliographical references (leaf 80).

Two failure modes related to water management in Proton Exchange Membrane fuel cells (dehydration and flooding) were investigated using electrochemical impedance spectroscopy as a diagnosis tool. It was hypothesised that each failure mode corresponds to changes in the overall stack impedance that are observable in different frequency ranges. This hypothesis was corroborated experimentally. The experimental implementation required new testing hardware and techniques. A four-cell stack capable of delivering individually conditioned reactants to each cell was designed, built, tested, and characterised under a variety of operating conditions. This stack is the first reported prototype of its type. The stack was used to perform galvanostatic, impedance measurements in situ. The measurements were made at three different temperatures (62, 70 and 80°C), covering the current density range 0.1 to 1.0 A cm−2 , and the frequency range 0.1 to 4 × 105 Hz. The recorded data represent the first reported set of measurements covering these ranges. The failure modes were simulated on individual cells within the stack. The effects on individual cell and stack impedance were studied by measuring the changes in stack and cell impedances under flooding or dehydration conditions. Dehydration effects were measurable over a wide frequency range (0.5 to 105 Hz). In contrast, flooding effects were measurable in a narrower frequency range (0.5 to 102 Hz). Using these results, separate or concurrent impedance measurements in these frequency ranges (or narrow bands thereof) can be used to discern and identify the two failure modes quasi-instantaneously. Such detection was not possible with pre-existing, do techniques. The measured spectra were modelled by a simple equivalent circuit whose time constants corresponded to ideal (RC) and distributed (Warburg) components. The model was robust enough to fit all the measured spectra (for single cells and the stack), under normal and simulated-failure conditions. Approximate membrane conductivities were calculated using this model. The calculations yielded a range from 0.04 to 0.065 S cm−1 (under normal humidification), and conductivities that deviated from these nominal range under flooding or dehydrating conditions. The highest conductivity value (was ∼0.10 S cm−1) was measured under flooding conditions at j = 0.4 A cm−2. The lowest conductivity (∼0.02 S cm−1) corresponded to a dehydrated cell at j = 0.1 A cm−2. These values fall within the ranges of published data for modern proton exchange membranes. The phenomenological and numerical results reported in this work represent the first demonstration of these techniques on a PEMFC stack under real operating conditions. They are also the basis of ongoing research, development, and intellectual property protection. / Graduate

Ce travail est consacré à la recherche de nouveaux matériaux sans plomb à structure pérovskite, de formules (A⁺,Bi³⁺)BO₃ et (A⁺,Bi³+)(B,B’)O₃ où A⁺ = {Li⁺, Na⁺, K⁺, Rb⁺}. Le but visé est le remplacement des pérovskites à base de plomb actuellement utilisées dans les dispositifs électroniques. La possibilité de substitution du plomb par un pseudo-ion (A⁺,Bi³⁺) a été étudiée pour (i) les pérovskites simples PbTiO₃ et PbZrO₃ et (ii) les pérovskites complexes Pb(Mg⅟₃Nb⅔)O₃ et Pb(Zn⅟₃Nb⅔)O₃.La synthèse de la composition (Li⅟₂Bi⅟₂)TiO₃ (LBT) a conduit à un composé pyrochlore de type Bi₂Ti₂O₇. Les autres compositions ont permis d'obtenir les pérovskites (Na⅟₂Bi⅟₂)ZrO₃ (NBZ), (K⅟₂Bi⅟₂)ZrO₃ (KBZ), (Na⅟₂Bi⅟₂)(Mg⅓Nb⅔)O₃ (NBMN), (K⅟₂Bi⅟₂)(Mg⅟₃Nb⅔)O₃ (KBMN) et (K⅟₂Bi⅟₂)(Zn⅟₃Nb⅔)O₃ (KBZN). Un important travail de synthèse a été effectué, en utilisant plusieurs voies et différents précurseurs, afin d'essayer d'éliminer les phases secondaires qui accompagnent généralement ces pérovskites.Les structures cristallines ont été étudiées par diffraction de neutrons à l'aide de la méthode de Rietveld. Celles-ci ont été déterminées pour LBT, NBZ, KBZ et KBMN. Les propriétés électriques de ces matériaux ont également été étudiées. Aucun d'entre eux n'est ferroélectrique. KBZ est électrostrictif. Enfin, NBZ, NBMN et KBMN montrent d'intéressantes propriétés de relaxeurs. / The present work focused on the research of new lead-free perovskite materials with the formula (A⁺,Bi³⁺)BO₃ and(A⁺,Bi³+)(B,B’)O₃ with A⁺ = {Li⁺, Na⁺, K⁺, Rb⁺}. The aim of this study is to find potential candidates to replace the lead-based perovskite used in the electronic devices nowadays. The possibility to substitute the lead ion par a couple (A⁺,Bi³⁺) has been examined for (i) the simple perovskites PbTiO₃ and PbZrO₃ and (ii) the complex perovskites Pb(Mg⅟₃Nb⅔)O₃ and Pb(Zn⅟₃Nb⅔)O₃.The synthesis of the composition (Li⅟₂Bi⅟₂)TiO₃ (LBT) has led to a pyrochlore Bi₂Ti₂O₇-like compound. The other compositions have conducted to the perovskites compounds (Na⅟₂Bi⅟₂)ZrO₃ (NBZ), (K⅟₂Bi⅟₂)ZrO₃ (KBZ), (Na⅟₂Bi⅟₂)(Mg⅓Nb⅔)O₃ (NBMN),(K⅟₂Bi⅟₂)(Mg⅟₃Nb⅔)O₃ (KBMN) and (K⅟₂Bi⅟₂)(Zn⅟₃Nb⅔)O₃ (KBZN). A lot of work has been carried out for the syntheses, using different precursor or process, in order to suppress the secondary phases which are often obtained with these perovskites. The crystalline structures have been studied by neutron diffraction, using the Rietveld method. These have been determined for the LBT, NBZ, KBZ and KBMN compounds. The electrical properties of these materials have also been studied. None of them is ferroelectric. KBZ is électrostrictif. Finally, NBZ, NBMN and KBMN present some interesting relaxor properties.

Impedance spectroscopy (IS) is a powerful and sophisticated tool to characterize intrinsic electrical properties of any materials and its interface, measuring the electric and transport properties of the materials, investigating the mechanism of electrochemical reaction etc. The fundamental principle of IS is the measurement of the impedance (equivalent to resistance in DC analysis) of the system under investigation over a wide frequency range. The IS study provides quantitative information about the conductance, the dielectric coefficient, the static properties of the interfaces like contact resistance, and its dynamic change due to adsorption or charge transfer phenomenon. Commercial Impedance analyzers that are available today are bulky and cannot be carried or deployed at remote locations for monitoring so easily, also such systems are expensive. Though IS concept is not new, standard Impedance analyzers are interfaced to the computer and require detailed analysis of the data by experts. Advancement in data conversion and signal processing is opening up opportunities for handheld smart devices. Hence it is felt that there is a need to develop a versatile low cost, portable (handheld) impedance analyzer instrument which can be used to characterize non linear materials like semiconductors, biological objects, and electrochemical samples. The instrument should be capable accepting test parameters using a touch screen based keypad and display test results on a Graphical LCD for quick analysis. Hence a standalone handheld instrument is designed to work independently without any PC control. The designed instrument consists of Digital Direct Synthesis (DDS) signal generator, a constant current source, Analog to digital convertor, Microcontroller to control frequency sweep parameters and acquire data, TFT Graphics LCD for displaying various plots, touch screen user interface to input sweep parameters and data storage section for offline analysis of obtained data. The instrument is designed to work on a battery or a regulated power supply. The instrument has options to display Nyquist plot, capacitance versus frequency plot, real and imaginary value of impedance versus frequency plot etc. Experimental investigations are conducted using this instrument on few passive components like resistor, inductor, capacitor and combinations. The instrument is also used to monitor the performance of polyimide based capacitive humidity sensor and its characteristics like sensitivity, linearity, repeatability and hysteresis. The measurement accuracy of the impedance varies from 0.7% to 4.67% depending on the impedance range. Bio impedance measurements are carried out on biological samples like Banana and the measured values are compared with the standard LCR meter. The bio impedance measurements are repeatable and comparable with the standard LCR meter readings and it is found to be within ±1% accuracy at the calibrated frequency. The instrument is also validated using industry standard Gauge R & R procedure to understand the repeatability and reproducibility of the instrument. The instrument exhibited good Repeatability and Reproducibility in current mode excitation than voltage mode excitation and Gauge R & R is 55% with P/T ratio is less than 2.5%.

Cerâmicas de zircônia estabilizada com ítria são utilizadas na forma densa como eletrólito e na forma porosa como ânodo em células a combustível de óxido sólido. Neste trabalho cerâmicas porosas de zircônia estabilizada com 8 mol% de ítria foram preparadas por meio da adição de diferentes teores de KI, NaCl e grafite como aditivo sacrificial. A remoção térmica do aditivo foi avaliada por meio de análises termogravimétrica, térmica diferencial e dilatométrica. As amostras foram preparadas por meio de mistura, compactação e sinterização a 1400 ºC/2 h. As amostras foram caracterizadas por difração de raios X(DRX) e análise topográfica em microscópio de varredura por sonda e microscópio eletrônico de varredura de superfícies polidas e atacadas para avaliação da distribuição do teor de poros e tamanho médio de grãos. O teor do aditivo residual foi avaliado por fluorescência de raios X (FRX). O comportamento elétrico foi analisado por espectroscopia de impedância (EI) na faixa de frequências 5 Hz-10 MHz entre 300 ºC e 450 ºC. Os resultados de FRX mostram que não há resíduo do aditivo após sinterização. A análise de DRX indica que todas as amostras têm fase única, cúbica tipo fluorita. Os diagramas de impedância mostram que há aumento i) das resistividades elétricas intergranular e intragranular, evidenciando a formação de poros em ambas as regiões, ii) do ângulo de descentralização do semicírculo a baixas frequências, devido ao aumento do grau de heterogeneidade pela presença de poros, e iii) do produto do fator de bloqueio R pelo fator de frequência f, consequência do aumento do teor de poros. Esses resultados estão em concordância com os resultados das análises de microscopia de varredura por sonda e de microscopia eletrônica de varredura. / Dense and porous yttria-stabilized zirconia ceramics are used as electrolytes and anodes, respectively, in solid oxide fuel cells. Porous ZrO2: 8 mol% Y2O3 (8YSZ) were prepared by using NaCl, KI and graphite as sacrificial additives. The thermal removal of the additives was evaluated by thermogravimetry, differential thermal analysis and dilatometry. The samples were prepared by thoroughly mixing 8YSZ to the additives, pressing and sintering at 1400 ºC/2 h. The samples were characterized by X-ray diffraction (XRD) and by observation of polished and etched surfaces in scanning probe microscope (SPM) and scanning electron microscope (FEG-SEM) to evaluate pore content. The evaluation of the NaCl and KI content was carried out by X-ray fluorescence (XRF) analysis. The electrical behavior was analyzed by impedance spectroscopy (IS) in the 5 Hz-10 MHz frequency range from 300 ºC to 450 ºC. The XRF results show no remaining KI or NaCl in the sintered samples. The XRD patterns show all samples are single cubic fluorite phase. The IS plots show that there is an increase i) of the intergranular and the intragranular electrical resistivity, an indication of bulk and grain boundary pore formation, ii) of the decentralization angle of the grain boundary semicircle in the impedance plots due to increasing heterogeneity of the samples, and iii) of the product of the blocking factor R to the frequency factor f, as a consequence of the increase in pore content. These results are in agreement with the SPM and SEM observations.

Electrochemical impedance spectroscopy (EIS) is a technique consisting of the application of a small perturbing current or voltage to an electrochemical system and measuring the response of the system. The response of the system can be described through the notion of impedance, Z, which is defined as the transfer function between the voltage and the current signal. By describing the impedance, one can gain insight into the interpretation of EIS experiments for the measurement of fundamental physical properties (eg diffusion coefficients). The impedance responses of electrochemical systems have been described in the past as an arrangement of ideal equivalent-circuit elements. Simple lumped-parameter circuits and more complex finite-transmission-line circuits have been used in the past, but the disadvantage of this approach is the difficulty in interpreting the equivalent-circuit parameters in terms of fundamental properties. It is then interesting to determine impedance by describing mathematically the fundamental physical processes that govern the response of the system. By describing and predicting analytically the impedance response induced by the perturbing current signal, one can: (i) gain considerable insight into the electrochemical process of interest, (ii) make explicit use of the modeling approach to address operational issues such as process design optimization, monitoring, diagnostics and control, and (iii) offer an interpretation to carefully designed EIS experiments for the measurement of fundamental physical properties such as diffusion coefficients or surface of active catalyst.

Student Number : 0009815Y - PhD thesis - School of Physics - Faculty of Science / Determining the properties of composites and how these relate to those of the components and the microstructure is extremely useful as it enables the understanding of existing materials and the design of new materials with a variety of applications. However, the link between the ac conductivity data and the microstructure and composition of the composite is not a simple one. Simulations of binary composites are presented which show that from relatively simple component properties arise complex composite properties. Accurate identi¯cation of the components of composites, using characteristic frequencies, is demonstrated for simulated and actual experimental data. The Maxwell-Wagner and Brick Layer Models, which are often applied beyond the range of their original derivation, are found to consistently ¯t the data of yttria-stabilized zirconia ceramics measured at various tempera- tures. The results from ¯tting single crystal and polycrystalline sample data indicate that accurate modeling of the properties of the polycrystalline sam- ples requires more theoretical work on the conduction mechanisms in single crystals and the grains of the ceramics. Data from a polyester-resin/silicon system is found to be best ¯tted us- ing the Single Exponent Phenomenological Percolation Equation (SEPPE) with experimentally measured component properties as input. The percola- tion threshold obtained suggests a system where the insulator tends coat the conductor. The results show that, with the actual component properties as input, the SEPPE can be used to qualitatively and semi-quantitatively model and ¯t composite ac conductivity data. Analysis of the ac conductivity of liquid-phase-sintered silicon carbide ce- ramics showed that for this system, the features often observed in the imped- ance spectra are all due to a multi-component grain bondary/binder phase and not the SiC grains. This multi-component grain boundary phase can be ¯tted accurately to the Brick Layer Model, indicating a microstructure where an insulating component coats a more conducting component.

A micro-electrophysiological analysis system (-EPAS) using various microfabrication techniques for single cell study was developed. Conventional microfabrication techniques combined with plastic and polymer microfabrication techniques have been used to realize the system. The system is capable of performing patch clamp recording and whole cell electrical impedance spectroscopy (EIS) on a single cell. Methodologies for single cell manipulation were developed. The ion channel activities of primary cultured bovine chromaffin cells were measured in both the patch clamping mode and the whole cell EIS mode. Membrane capacitance of the chromaffin cell was calculated from these measurements. Increases in the capacitances were observed when certain ion channels were blocked using toxins. The dielectric properties of human breast cancer cell lines from different pathological stages were measured and compared to a normal human breast cell line in the whole cell EIS mode. The measured properties were correlated to the pathological stages of the breast cancer cell lines. Decreases in the membrane capacitances were observed for the more pathologically progressed cancer cell lines.

Photovoltaic (PV) conversion of solar energy appears to be one of the most promising ways of meeting the increasing future energy demand. In space, photovoltaic power source is the only alternative. The demand for higher power has necessitated the use of high speed switching charge controller and power conditioner. To design an efficient and reliable switching charge controller, the static (I-V) and dynamic (AC) characteristics of a solar cell need to be understood. The AC parameters of a solar cell can be measured either by Frequency Domain technique or by Time Domain technique. In frequency domain technique, a small signal is applied about the operating point and the AC parameters are measured. Hence, in the frequency domain technique the steady state values of AC parameters at a particular operating condition are measured. In time domain technique, a transient measurement is made where the cell voltage varies from short-circuit to open circuit or vice versa. Hence, this technique gives only the time constant of a solar cell. The impedance spectroscopy is a frequency domain technique widely used in electro chemistry to study battery characteristics. In the present investigation, the impedance spectroscopy is proposed for measuring the AC parameters of solar cells. An experimental set-up has been developed to measure the solar cell AC parameters. The AC parameters of Silicon (BSR and BSFR) solar cells and GaAs/Ge solar cells are measured using impedance spectroscopy (IS). The cell capacitance, the parallel resistance and the series resistance are measured and compared. GaAs/Ge solar cell has shown only transition Capacitance throughout its operating range while silicon (BSR and BSFR) solar cells exhibited both transition and diffusion capacitances. Theoretical and experimental values of the cell parallel resistance are compared and are in good agreement. While the diode factor in silicon solar cell varies from 2 to 1, where as in GaAs/Ge solar cell it varies from 4 to 2 to 1. Measurements conducted using open circuit voltage buildup (time domain technique) on silicon BSR solar cell shows that the collected data can be used for the restricted purpose of measuring cell transient response. The dime domain technique could not estimate the solar cell. It may be noted that the impedance spectroscopy assumes piece-wise linearity of the solar cell characteristics, lending itself for easy measurement and modeling. This assumption is valid as the signal amplitude is less than thermal voltage (VT). Since, the parameters are measured under steady state, the values are more stable and accurate. An attempt has also been made to correlate the measured AC parameters with the requirements of switching charge controllers. These correlations can be used to design the switching controllers for device rating, circuit stability and other aspects.