Piezoresistivity in conductive polymer nanocomposites occurs because of the disturbance of particle networks in the polymer matrix. The piezoresistance effect becomes more prominent if the matrix material is compliant making these materials attractive for applications that require flexible force and displacement sensors such as e-textiles and biomechanical measurement devices. However, the exact mechanisms of piezoresistivity including the relationship between the matrix polymer, conductive particle, internal structure and the composite’s piezoresistance need to be better understood before it can be applied for such applications. The objective of this thesis is to report on the development of conductive polymer nanocomposites for use as flexible sensors and electrodes. Electrically conductive and piezoresistive nanocomposites were fabricated by a scalable melt compounding process. Particular attention was given to elucidating the role of matrix and filler materials, plastic deformation and porosity on the electrical conduction and piezoresistance. These effects were parametrically investigated through characterizing the morphology, electrical properties, rheological properties, and piezoresistivity of the polymer nanocomposites. The electrical and rheological behavior of the nanocomposites was modeled by the percolation-power law. Furthermore, a model was developed to describe the piezoresistance behavior during plastic deformation in relation to the stress and filler concentration.

Inherent safety is claimed for gas-cooled pebble bed reactors, such as the South African Pebble Bed Modular Reactor (PBMR), as a result of its design characteristics, materials used, fuel type and physics involved. Therefore, a proper understanding of the mechanisms of heat transfer, fluid flow and pressure drop through a packed bed of spheres is of utmost importance in the design of a high temperature Pebble Bed Reactor (PBR). In this study, correlations describing the effective thermal conductivity through packed pebble beds are examined. The effective thermal conductivity is a term defined as representative of the overall radial heat transfer through such a packed bed of spheres, and is a summation of various components of the overall heat transfer. This phenomenon is of importance because it forms an intricate part of the self-acting decay heat removal chain, which is directly related to the PBR safety case. In this study standard correlations generally employed by the thermal fluid design community for PBRs are investigated, giving particular attention to the applicability of the correlations when simulating the effective thermal conductivity in the near-wall region. Seven distinct components of heat transfer are examined namely: conduction through the solid, conduction through the contact area between spheres, conduction through the gas phase, radiation between solid surfaces, conduction between pebble and wall, conduction through the gas phase in the wall region, and radiation between the pebble and wall surface. The effective thermal conductivity models are typically a function of porosity in order to account for the pebble bed packing structure. However, it is demonstrated in this study that porosity alone is insufficient to quantify the porous structure in a randomly packed bed. A new Multi-sphere Unit Cell Model is therefore developed, which accounts more accurately for the porous structure, especially in the near-wall region. Conclusions on the applicability of the model are derived by comparing the simulation results with measurements obtained from various experimental test facilities. This includes the PBMRs High Temperature Test Unit (HTTU) situated on the campus of the North-West University in Potchefstroom in South Africa. The Multi-sphere Unit Cell Model proves to encapsulate the impact of the packing structure in a more fundamental way and can therefore serve as the basis for further refinement of models to simulate the effective thermal conductivity. / Thesis (PhD (Nuclear Engineering))--North-West University, Potchefstroom Campus, 2010

Inherent safety is claimed for gas-cooled pebble bed reactors, such as the South African Pebble Bed Modular Reactor (PBMR), as a result of its design characteristics, materials used, fuel type and physics involved. Therefore, a proper understanding of the mechanisms of heat transfer, fluid flow and pressure drop through a packed bed of spheres is of utmost importance in the design of a high temperature Pebble Bed Reactor (PBR). In this study, correlations describing the effective thermal conductivity through packed pebble beds are examined. The effective thermal conductivity is a term defined as representative of the overall radial heat transfer through such a packed bed of spheres, and is a summation of various components of the overall heat transfer. This phenomenon is of importance because it forms an intricate part of the self-acting decay heat removal chain, which is directly related to the PBR safety case. In this study standard correlations generally employed by the thermal fluid design community for PBRs are investigated, giving particular attention to the applicability of the correlations when simulating the effective thermal conductivity in the near-wall region. Seven distinct components of heat transfer are examined namely: conduction through the solid, conduction through the contact area between spheres, conduction through the gas phase, radiation between solid surfaces, conduction between pebble and wall, conduction through the gas phase in the wall region, and radiation between the pebble and wall surface. The effective thermal conductivity models are typically a function of porosity in order to account for the pebble bed packing structure. However, it is demonstrated in this study that porosity alone is insufficient to quantify the porous structure in a randomly packed bed. A new Multi-sphere Unit Cell Model is therefore developed, which accounts more accurately for the porous structure, especially in the near-wall region. Conclusions on the applicability of the model are derived by comparing the simulation results with measurements obtained from various experimental test facilities. This includes the PBMRs High Temperature Test Unit (HTTU) situated on the campus of the North-West University in Potchefstroom in South Africa. The Multi-sphere Unit Cell Model proves to encapsulate the impact of the packing structure in a more fundamental way and can therefore serve as the basis for further refinement of models to simulate the effective thermal conductivity. / Thesis (PhD (Nuclear Engineering))--North-West University, Potchefstroom Campus, 2010

Thermal conductivity measurements are made on a variety of systems in order to probe low energy quasiparticle excitations. In particular, thermal conductivity measurements were made on the iron based superconducting material LaFePO at temperatures from 60 mK to 1 K and in fields from 0 T to 5 T in order to shed light on the symmetry of the superconducting order parameter. A substantial non-zero electronic contribution to the thermal conductivity is observed and interpreted as sub-gap electronic quasiparticles which is clear evidence for a nodal gap symmetry. A high scattering rate and non-T3 temperature dependence of the conductivity is evidence against the d-wave scenario. However, the field dependence does seem to suggest that the anisotropic s+- picture is a likely candidate for the order parameter, although more theoretical work is required to confirm this. Thermal conductivity measurements were also made on the spin-ice system Ho2Ti2O7 between 50 mK and 1.4 K in applied magnetic fields from 0 T to 8 T in an attempt to observe the much debated magnetic monopole-like quasiparticles. An applied magnetic field of 8 T was applied along to [111] direction as to fully polarize the magnetic moments in order to extract the phonon contribution of the thermal conductivity. The low field thermal conductivity reveals evidence for an additional heat transfer mechanism that also scatters phonons which is magnetic in nature. This is taken to be evidence for the existence of monopole-like excitations out of the spin-ice ground state and is described by existing Debye-Huckel theory. Thermal transport was used in conjunction with charge conductivity to study the unconventional quantum critical point (QCP) in the heavy-Fermion superconductor beta-YbAlB4 at temperatures down to 60 mK and in fields up to 2 T. The results show that the Wiedemann-Franz law (WFL) is obeyed down to the lowest measured temperatures indicating that the Landau quasiparticles remain intact near the QCP. A small suppression of the Wiedemann-Franz ratio (L/L0 = kappa / sigma T L0) is seen at finite temperatures (T < 1 K) with minimal dependence on magnetic field. Comparing with other similar quantum critical systems, it becomes apparent that inelastic scattering events have little effect on the transport and are mainly field independent in beta-YbAlB4. An overview of the design for a new thermal conductivity mount is also presented. The design hinges around the idea of building the experiment mount into a small copper box rather than on an open frame. Not only does this provide mechanical stability for safe transportation, it also reduces the noise caused by electromagnetic interference (EMI) in the sample thermometers by more than a factor of ten over the old wire frame design.

A major challenge in the development of next generation electric and hybrid vehicle technology is the control and management of heat generation and operating temperatures. Vehicle performance, reliability and ultimately consumer market adoption are integrally dependent on successful battery thermal management designs. It will be shown that in the absence of active cooling, surface temperatures of operating lithium-ion batteries can reach as high as 50 °C, within 5 °C of the maximum safe operating temperature. Even in the presence of active cooling, surface temperatures greater than 45 °C are attainable. It is thus of paramount importance to electric vehicle and battery thermal management designers to quantify the effect of temperature and discharge rate on heat generation, energy output, and temperature response of operating lithium-ion batteries. This work presents a purely experimental thermal characterization of thermo-physical properties and operating behavior of a lithium-ion battery utilizing a promising electrode material, LiFePO4, in a prismatic pouch configuration. Crucial to thermal modeling is accurate thermo-physical property input. Thermal resistance measurements were made using specially constructed battery samples. The thru-plane thermal conductivity of LiFePO4 positive electrode and negative electrode materials was found to be 1.79 ± 0.18 W/m°C and 1.17 ± 0.12 W/m°C respectively. The emissivity of the outer pouch was evaluated to enable accurate IR temperature detection and found to be 0.86. Charge-discharge testing was performed to enable thermal management design solutions. Heat generated by the battery along with surface temperature and heat flux at distributed locations was measured using a purpose built apparatus containing cold plates supplied by a controlled cooling system. Heat flux measurements were consistently recorded at values approximately 400% higher at locations near the external tabs compared to measurements taken a relatively short distance down the battery surface. The highest heat flux recorded was 3112 W/m2 near the negative electrode during a 4C discharge at 5 °C operating temperature. Total heat generated during a 4C discharge nearly doubled when operating temperature was decreased from 35 °C to 5 °C, illustrating a strong dependence of heat generation mechanisms on temperature. Peak heat generation rates followed the same trend and the maximum rate of 90.7 W occurred near the end of 5 °C, 4C discharge rate operation. As a result, the maximum value of total heat generated was 41.34 kJ during the same discharge conditions. The effect of increasing discharge rate from 1C to 4C caused heat generation to double for all operating temperatures due to the increased ohmic heating. Heat generation was highest where the thermal gradient was largest. The largest gradient, near negative electrode current collector to external tab connection and was evaluated using IR thermography to be 0.632 °C/mm during 4C discharge with passive room temperature natural convection air cooling. Battery designs should utilize a greater connection thickness to minimize both electrical resistance and current density which both drive the dominant mode of heat generation, ohmic heating. Otherwise cooling solutions should be concentrated on this region to minimize the temperature gradient on the battery.

Self-propagating High-temperature Synthesis (SHS) is the synthesis of solid materials by a reaction wave propagating into the initial reactants, typically two metals, which can alloy exothermically. Typically, experiments are performed with the reactants in powder form, with relatively low density. Recent experiments by Bacciochini et al. revealed much larger flame speeds in densified powders near TMD (theoritical maximum density), obtained by the cold spray process. The present thesis investigates why the flame speed increases dramatically with an increase in density of the powders. The investigation rests on the analytical model formulated by Makino by controlling how the variables are affected by changes in density. Flame speed measurements were performed in mixtures of nickel (Ni) and aluminum (Al) at different initial densities. The density was varied by controlling the cold-pressing of the samples inside metallic channels and tubes. Experiments were also performed in ball-milled powders, in order to permit comparison with the experiments performed by Bacciochini in these mixtures at nearly maximum densities. The measurements revealed that the flame speed increases with the initial density, with a discontinuous transition occurring at approximately 60% theoretical maximum density (TMD). This transition also corresponds to the point where the powders deform plastically during the compaction process, suggesting that the intimate contact between the particles is responsible for the flame speed increase. The flame speed dependence on powder density is attributed to the changes in the heat conductivity of the pressed powders. At high densities, where the powders have plastically deformed, the continuous structure yields conductivities close to the idealized solid matrix. At these high densities, the conductivity was modeled using the Effective Medium Theory (EMT). Analytical predictions of the flame speed, using available thermo-chemical data for the Al-Ni system were found in good agreement with the present experiments at high densities. At low densities, since Al-Ni is a mixture of loose powders, the EMT model is no longer applicable. Thus, the thermal conductivity was experimentally measured and then was fitted using the semi-empirical model suggested by Aivazov. Using this data, Makino's model predicts the correct flame speed dependence observed experimentally. The present thesis has thus established that the dependence of flame speed on density is due mainly to the changes in the structure and thermal conductivity of the powders.

This work focused on the study of three independent projects involving perovskite oxide materials and their applications as solid oxide fuel cell (SOFC) anodes and electrochemical oxygen sensors. The underlying theme is the versatility and tune-ability of the perovskite structure. Reactivity and conductivity (ionic as well as electronic) are modified to optimize performance in a specific application. The effect of Ce doping on the structure and the conductivity of BaFeO3 perovskite materials is investigated and the resulting materials are applied as oxygen sensors. The new perovskite family, Ba1-xCexFeO3-δ (x=0, 0.01, 0.03, and 0.05), was prepared via a sol-gel method. Powder XRD indicates a hexagonal structure for BaFeO3 with a change to a cubic perovskite upon Cerium doping at the A site. The solubility limit of Ce at the A site was experimentally determined to be between 5-7 mol %. Bulk, electronic and ionic conductivities of BaFeO3-δ and Ba0.95Ce0.05FeO3-δ were measured in air at temperatures up to 1000˚C. Cerium doping increases the conductivity throughout the entire temperature range with a more pronounced effect at higher temperatures. At 800˚C the conductivity of Ba0.95Ce.05FeO3-δ reaches 3.3 S/cm. Pellets of Ba0.95Ce.05FeO3-δ were tested as gas sensors at 500 and 700˚C and show a linear, reproducible response to O2. Promising perovskite anodes have been tested in high sulfur fuel feeds. A series of perovskite solid oxide fuel cell (SOFC) anode materials: Sm0.95Ce0.05FeO3-δ, Sm0.95Ce0.05Fe0.97Ni0.03O3-δ and Sm0.95Ce0.05Fe0.97Co0.03O3-δ have been tested for sulfur tolerance at 500°C. The introduction of the extreme 5% H2S enhances the performance of these anodes, verified by EIS and CA experiments. Post mortem analyses indicate that the performance XII enhancement arises from the partial sulfidation of the anode, leading to the formation of FeS2, Sm3S4 and S on the perovskite surface. Testing in lower concentrations of sulfur, more common in sour fuels, 0.5% H2S, also enhances the performance of these materials. The SCF-Co anode shows promising stability and an increase in exchange current density, io, from 13.72 to 127.02 mA/cm2 when switching from H2 to 0.5% H2S/99.5% H2 fuel composition. Recovery tests performed on the SCF-Co anode conclude that the open cell voltage (OCV) and power density of these cells recover within 4 hours of H2S removal. We conclude that the formation of metal sulfide species is only partially reversible, yielding an anode material with an overall lower Rct upon switching back to pure H2. Combining their performance in sulfur containing fuels with their previously reported coke tolerance makes these perovskites especially attractive as low temperature SOFC anodes in sour fuels. A new perovskite family Ba1-xYxMoO3 (x=0-0.05) has been investigated in regards to electrical conductivity and performance as IT-SOFC anode materials for the oxidation of H2. Refinement of p-XRD spectra as well as SEM imaging conclude that the solubility limit of Y doping at the A site is 5 mol%, beyond which Y2O3 segregation occurs. The undoped BaMoO3 sample has a colossal room temperature conductivity of 2500 S/cm in dry H2. All materials maintain metallic conductivity in the temperature range of 25-1000°C with resistance increasing with Y doping. The Ba1-xYxMoO3 (x=0, 0.05) materials exhibit good performance as SOFC anode materials between 500-800°C, with Rct values at 500°C in dry H2 of 3.15 and 6.33 ohm*cm2 respectively. The catalytic performance of these perovskite anodes is directly related to electronic conductivity, as concluded from composite anode performance.

The research provides data of pH and conductivity, some anions (e. g. fluoride, chloride, bromide, nitrate, phosphate and sulphate), monovalent cations (e. g sodium, ammonium and potassium), divalent cations (e. g calcium and magnesium) heavy metals (e. g. iron, copper, zinc, nickel, cobalt, cadmium and manganese) and organic compounds – from water samples of rivers of Brunei Darussalam, namely, Brunei River, Belait River, Tutong River and Temburong River. The higher values of certain parameters with respect to the acceptable standard limits for river water indicate the pollution in river water samples of the study area, make the waters unsuitable for various applications and do pose a human health hazard. The pH levels in Brunei Darussalam is quite reassuring and mostly safe. Although there are some stretches of rivers that show slightly lower levels of pH, there is no cause for any alarm as these waterways are not sources of drinking water. As for anions and cations, the only anion of significant levels detected in Brunei Rivers is chloride whereas only monovalent cation detected in significant levels, is sodium. The concentrations of chloride and sodium ions are below the standard concentrations. Brunei Rivers are still free from chloride and sodium pollution. For heavy metals, only iron is detected in Brunei Rivers. Brunei being a oil based country experiments were done to identify levels of a numbers of significant toxic organic compounds, including, toluene and benzene which have been detected in the waters of the oil mining district of Belait District but are within normal limits. The use of a photolytic cell system to achieve the photodegradation of benzene, toluene, ethylenediaminetetra-acetic acid (EDTA) and the surfactant – hexadecyltrimethyl-ammonium bromide (C19H42NBr) is reported. The system has been optimised by investigating the effects of the addition of hydrogen peroxide (H202) as an oxidant and the addition of titanium dioxide (TiO2) as a catalyst. The results show that the photolytic system can be used to achieve >99% degradation of organic contaminants. The research also includes a final chapter on management system which covers water protection, pollution control and solid waste management in Brunei. In addition to investigating various factors of the solid waste management in Brunei, the researcher has also exposed some of the weaknesses that need immediate addressing. Various measures have been suggested to make Brunei's water more efficient. Moreover, ways of preserving the high quality of Brunei's water figures in this chapter.

Cast Al-Si and Al-Si-Mg alloys containing up to 12.6 wt. pct. silicon and 1.0 wt. pct. magnesium were prepared. The changes in electrical conductivity/resistivity of these alloys due to strontium additions have been investigated and explained in terms of variations in microstructure. The conductivity behaviour of strontium-containing and strontium-free alloys was found to exhibit marked differences, depending on the silicon and magnesium contents and the rate of solidification. The electrical conductivity of single phase alloys containing less than 1.60 wt. pct. Si decreased with increasing silicon and magnesium levels. However, strontium had no effect on the conductivity of these solid solution alloys since it does not dissolve appreciably in the aluminum matrix or change the solid solubility of silicon and magnesium in aluminum. Silicon precipitation processes in the supersaturated solid solution alloys of Al-Si and Al-Si-Sr have been examined using the Johnson-Mehl-Avrami equation and found to be isokinetic. Strontium, however, retarded the growth rate of silicon precipitates. Strontium did not affect the kinetics of G.P. zone formation in Al-Si-Mg alloys but it suppressed the formation of stable Mg$ sb2$Si precipitates during subsequent aging at 175$ sp circ$C. Unlike the single phase alloys, two phase Al-Si and Al-Si-Sr alloys, in the range of 2.0 to 12.6 wt. pct. Si, exhibited different electrical conductivity behaviour. The strontium-containing alloys showed a higher conductivity than alloys with no strontium, and this conductivity difference increased as the silicon and magnesium contents were increased and the solidification rate was decreased. It has been demonstrated this difference is due to changes in the silicon morphology. Electron scattering at the interface between the aluminum matrix and the eutectic silicon phase contributes significantly more to the resistivity of unmodified alloys than that of modified alloys. In addition, the resistivity of

From measurements of thermal and electrical conductivities of 64 ocean sediment samples obtained from piston cores taken off the Oregon Coast, and from 37 water-saturated sandstone samples analyzed by Zierfuss and Van der Vliet (1956), as well as 51 thermal conductivities and water contents of ocean sediments analyzed by Ratcliffe (1960), this research shows that a useful relationship can be obtained giving thermal conductivity when electrical conductivity is known. Analysis of the data was made using theoretical concepts which have been known for many years to relate thermal and electrical conductivity to porosity. The results of this research may make possible a convenient determination of in situ thermal conductivity that would give the average conductivity in materials containing large variations in conductivity. / Graduation date: 1966