It is essential to properly monitor in-situ soil compaction properties during most earthwork construction projects. Traditional in-situ soil compaction monitoring methods are often limited in their application. As a result, new methods are being developed to more accurately measure in-situ compaction parameters. Time domain reflectometry (TDR) is one such method. Relying on the propagation of an electromagnetic wave through the soil sample, TDR can be used to measure both in-situ moisture content as well as soil dry density. Although TDR is relatively new to the field of geotechnical engineering, it has previously been implemented in other fields with success. Researchers at Purdue University have made several advances to further incorporate the use of TDR technology into the field of geotechnical engineering and as a result an innovative TDR measurement system has been developed for compaction control monitoring. The method was standardized in the form of ASTM D 6780 in 2002. Further advancements led to an improved method referred to as the Purdue one-step TDR method. Research has indicated that the ASTM TDR method is sufficiently accurate for application in compaction monitoring applications. A comparison between the ASTM TDR method and traditional methods was carried out to evaluate the accuracy of the TDR method to traditional methods. To further expand the application of the TDR method, a correlation was developed between the TDR spike driving process with the in-situ CBR test. A comprehensive review of previous research was conducted to examine recent advancements leading to the improved Purdue one-step method. A study was also performed to evaluate the effect of variable pore fluid conductivity on the calibration of the Purdue one-step method.

Polymer composites formed from layered fillers with high surface volume ratio show enhanced reinforcement. Graphite oxide is a high modulus material that can be separated into thin layers with high surface area. The aim of this study is to prepare polymer layered graphite oxide composites using functionalised polyolefin to enhance compatibility with various forms of layered graphite oxide in varying concentration. Functionalised polyolefins reinforced with layered graphite oxides and expanded graphite oxides were prepared using solution blending and melt blending methods. Three different mixing methods with varying shear intensity were employed to prepare polymer layered graphite oxide composites. The crystalline structure, thermal and mechanical properties of the prepared polymer layered graphite oxide composites was studied. Oxidised graphite prepared from the Staudenmaier method and its exfoliated form were dispersed in poly(ethylene-co-methyl acrylate-co-acrylic acid) (EMAA) via solution blending to prepare EMAA layered composites. The thermal stability was determined using thermogravimetric analysis. The EMAA layered composites showed higher thermal stability in comparison with pure EMAA. The mechanical properties of these EMAA layered composites were determined through dynamic mechanical analysis. Shear modulus, yield stress and storage modulus of EMAA in the presence of graphite oxide fillers decreased. A solution blending method was used to prepare poly(propylene-grafted-maleic anhydride) layered expanded graphite oxide composites (PPMA-EGO). Two types of PPMA-EGO were prepared using different mixing methods - low and high shear were employed. The effects of preparative mixing methods on the PPMA-EGO properties were investigated. The mechanical properties of PPMA-EGO obtained from dynamic mechanical analysis indicated that EGO had a reinforcing effect on the elastic behaviour of PPMA-EGO. This is due to strong interfacial adhesion between PPMA and EGO as a result of hydrogen bonding. The elastic behaviour of PPMA-EGO was affected by the surface area of graphite flakes. Low sheared PPMA-EGO elastic behaviour was found to be higher compared with that of high sheared PPMA-EGO. A melt blending method was used to prepare PPMA-EGO with varying EGO concentration. The interconnected network structure of EGO in the PPMA-EGO was not observed as shown by its scanning electron microscopy images. Thermogravimetric analysis of PPMA-EGO indicates increased decomposition temperature of the PPMA matrix. Dynamic mechanical analysis showed enhanced storage modulus of PPMA-EGO. The maximum elastic modulus of PPMA-EGO was observed at 3 %wt of EGO. The electrical conductivity of PPMA-EGO was measured only for EGO concentrations above 2 %wt. The EGO concentration was found to be the most critical factor in the enhancement of the electrical conductivity of PPMA-EGO. Wide angle X-ray diffraction analysis of all polymer layered graphite oxide composites revealed no change in interlayer spacing of graphite layers, indicating the absence of EMAA intercalation in the graphite layers. The crystallisation temperature and crystallinity of all polymer layered graphite oxide composites were determined using differential scanning calorimetry. The results indicated that graphite oxide and expanded graphite oxides acted as nucleating agents in inducing the crystallisation of functionalised polyolefin in the layered composites. However, the degree of crystallinity of functionalised polyolefin decreased in the layered composites.

Cemented Paste Backfill (CPB) is a relatively new backfilling technology for which a better understanding of binder hydration is required. This research uses electromagnetic (EM) wave-based techniques to non-destructively study a CPB consisting of tailings, sand, process water and binder (90% blast-furnace slag; 10% Portland cement). EM experiments were performed using a broadband network analyzer (20 MHz to 1.3 GHz) in the lab and capacitance probes (70 MHz) in the lab and field. Results showed that the EM properties are sensitive to curing time, operating frequency and specimen composition including binder content. The volumetric water content interpreted from dielectric permittivity varied little with curing. Temporal variations in electrical conductivity reflected the different stages of hydration. Laboratory results aided interpretation of field data and showed that a reduction in binder content from 4.5% to 2.2% delays setting of CPB from 0.5 days to over 2 days, which has important implications for mine design.

Cemented Paste Backfill (CPB) is a relatively new backfilling technology for which a better understanding of binder hydration is required. This research uses electromagnetic (EM) wave-based techniques to non-destructively study a CPB consisting of tailings, sand, process water and binder (90% blast-furnace slag; 10% Portland cement). EM experiments were performed using a broadband network analyzer (20 MHz to 1.3 GHz) in the lab and capacitance probes (70 MHz) in the lab and field. Results showed that the EM properties are sensitive to curing time, operating frequency and specimen composition including binder content. The volumetric water content interpreted from dielectric permittivity varied little with curing. Temporal variations in electrical conductivity reflected the different stages of hydration. Laboratory results aided interpretation of field data and showed that a reduction in binder content from 4.5% to 2.2% delays setting of CPB from 0.5 days to over 2 days, which has important implications for mine design.

Carbon nanotubes are made into films or bulks, their surface or junction morphology in the networks can be modified to obtain desired electrical transport properties by various surface modification methods. The methods include incorporation of organic molecules or inorganic nanoparticles, debundling of nanotubes by dispersing agents, and microwave irradiation. Because carbon nanotubes have unique carrier transport characteristics along a sheet of graphite in a cylindrical shape, the properties can be dramatically changed by the modification. This is ideal for developing high-performance materials for thermoelectric and photovoltaic energy conversion applications. In this research, decoration of various organic/inorganic nanomaterials on carbon nanotubes was employed to enhance their electrical conductivity, to improve thermoelectric power factor by modulating their electrical conductance and thermopower, or to obtain n-type converted carbon nanotube. The electrical conductivity of double-wall nanotubes (DWNTs) decorated with tetrafluoro-tetracyanoquinodimethane (F4TCNQ) was increased up to 5.9 × 10^5 S/m. The sheet resistances were measured to be 42 Ω/sq at 75% of transmittance for HNO3/SOCl2-treated DWNT films, making their electrical conductivities 200~300% better than those of the pristine DWNT films. A series of experiments at different ion concentrations and reaction time periods were systematically performed in order to find optimum nanomaterial formation conditions and corresponding electronic transport changes for better thermoelectric power factor. For example, the thermoelectric power factors were improved by ~180% with F4TCNQ on DWNTs, ~200% with Cu on SWNTs, and ~140% with Fe on single-walled nanotubes (SWNTs). Also SWNTs was converted from p-type to n-type with a large thermopower (58 μV/K) by using polyethyleneimine (PEI) without vacuum or controlled environment. This transport behavior is believed to be from charge interactions resulted from the difference between the work functions/reduction potentials of nanotubes and nanomaterials. In addition, different dispersing agents were utilized with DWNT and SWNTs to see a debundling effect in a film network. The highest electrical conductivity of ~1.72×10^6 S/m was obtained from DWNT film which was fabricated with a nanotube solution dispersed by chlorosulfonic acid. Debundling of nanotubes in the film network has been demonstrated to be a critical parameter in order to get such high electrical property. In the last experiment, Au nanoparticle decoration on carbon nanotube bundle was performed and a measurement of themophysical properties has done before and after modifying carbon nanotube surface. Carbon nanotube bundle, herein, was bridged on microdevice to enable the measurement work. This study demonstrates a first step toward a breakthrough in order to extract the potential of carbon nanotubes regarding electron transport properties.

A solid oxide fuel cell (SOFC) is an energy conversion device that has the potential to efficiently generate electricity in an environmentally-friendly manner. In general, a SOFC operates between 750&deg;C and 1000&deg;C utilizing hydrogen or hydrocarbons as fuel and air as an oxidant. The three major components comprising a fuel cell are the electrolyte, the cathode, and the anode. At present, the state-of-the-art SOFC is made from a dense yttria-stabilized zirconia (YSZ) electrolyte, a porous lanthanum manganite cathode, and a porous nickel/YSZ composite anode. With the advent of the anode-supported SOFC and the increased interest in using a wider range of fuels, such as those containing sulphur, knowledge of the anode properties is becoming more important. <br /> The properties of the current anodes are limited due to the narrow range of nickel loadings imposed by the minimum nickel content for electrical conductivity and the maximum allowable nickel loading to avoid thermal mismatch with the YSZ electrolyte. In addition, there is little research presented in the literature regarding the use of nickel metal as a starting anode material, rather than the traditional nickel oxide powder, and how porosity may affect the anode properties. <br /> The purpose of this investigation is to determine the influence nickel morphology and porosity distribution have on the processing and properties of tape cast Ni/YSZ composites. Specifically, the sintering characteristics, electrical conductivity, and thermal expansion behaviour of tape cast composites created from YSZ, nickel, nickel oxide (NiO), nickel coated graphite (NiGr), and/or graphite (Gr) powders are investigated. In addition to samples made from 100% YSZ, 100% Ni, and 100% NiO powders, five composite types were created for this investigation: NiO/YSZ, NiO&Gr/YSZ, Ni/YSZ, NiGr/YSZ, and Ni&Gr/YSZ each with nickel loadings varying between 4 vol% Ni of total solids and 77 vol% Ni of total solids. Another set of composites with a fixed nickel loading of 27 vol% Ni and 47 vol% Ni of total solids and varying graphite loadings were also created. <br /> During the burnout stage, the composites made from nickel oxide powder shrink slightly while the composites made from nickel metal expand due to nickel oxidation. Graphite additions below 20 vol% of the green volume do not alter the dimensional changes of the composites during burnout, but graphite loadings greater than 25 vol% of the green volume cause significant expansion in the thickness of the composites. <br /> After sintering, the amount of volumetric sintering shrinkage decreases with higher nickel loadings and is greater for the composites made with nickel oxide compared to the composites made from nickel metal. The porosity generated in the composites containing graphite is slightly higher than the volume of graphite added to the composite and is much greater than the porosity contained in the graphite-free composites. <br /> Dimensional changes of the porous Ni/YSZ and NiO/YSZ composites during both burnout and sintering were analysed based on concepts of constrained sintering of composite powder mixtures. In some cases constrained sintering was evident, while in others, a more simple rule of mixtures behaviour for shrinkage as a function of YSZ content was observed. <br /> When nickel oxide is reduced to nickel metal during the reduction stage there is essentially no change in the composite volume for the composites containing YSZ because the YSZ prevents the composites from shrinking. After reduction the additional porosity generated in the composites is equivalent to the change in volume due to the reduction of nickel oxide to nickel metal. <br /> When measuring the electrical conductivity, each composite type demonstrated classic percolation behaviour. The NiGr/YSZ composites had the lowest percolation threshold, followed by the Ni/YSZ and NiO/YSZ composites. When graphite was added with a nickel coating, the added porosity did not disrupt the nickel percolation network and allowed the nickel to occupy a larger effective volume compared to a composite made with similar sized solid nickel particles. When graphite was added to the composites, the electrical conductivity was reduced and the percolation threshold increased. <br /> Generally, the coefficient of thermal expansion (CTE) for Ni/YSZ composites are expected to follow the rule of mixtures prediction since the elastic properties for nickel and YSZ are similar. However when porosity is distributed unevenly between the YSZ and nickel phases, the CTE prediction will deviate from the rule of mixtures. When cornstarch was added to the NiGr/YSZ composites, the CTE increased as the amount of porosity in the YSZ phase increased. The CTE of the NiGr/YSZ composites followed the rule of mixtures indicating that the porosity was evenly distributed between the nickel and YSZ phases. For the other composite types, the measured CTE was higher than the rule of mixtures prediction suggesting that more porosity was contained within the YSZ phase.

A controlled column experiment was conducted to investigate the geophysical response of gasoline spills into the partially saturated sand column. The column was 0.61 diameter (ID) and 2 m high cylindrical polyvinyl chloride, which was packed with the Borden sand to a height of 1.95 m, flushed with CO2, saturated, and drained to a height of 0.73 m. The monitoring techniques used for this experiment was DC resistivity and time domain reflectometry (TDR) methods. The column was equipped with resistivity electrodes and TDR probes, which were placed on the column wall vertically with 3 cm intervals, on opposite sides, two monitoring wells, an injection well, a manometer, an outlet/inlet system, and a vent. A total amount of 5 liters of standard API 91-01 gasoline was added to the system in steps of 1, 2, and 2 liters to examine the geophysical response to different amounts of gasoline. Measurements were taken before and after each injection and also during subsequent fluctuation of the water table. Both monitoring techniques were able to record even the minor changes in the trend of conductivity and permittivity profiles due to the addition of the small amount of gasoline during the first spill. The conductivity and permittivity profiles obtained before lowering the water level below the original level and those obtained after the water level reached to the original level do not match, which is an indication of entrapped gasoline inside the pores. Two core samples was taken from the sand symmetrically after each water table fluctuation and analyzed for total petroleum hydrocarbon (TPH) analysis and the results were compared to the conductivity and permittivity results. The conductivity profile obtained using DC resistivity method was compared to that of obtained using TDR method. The profiles match in the saturated zone where all of the pores are connected with water and therefore electrolytic conduction is predominant. In the unsaturated zone, where there is low pore water connectivity, TDR measured conductivity values are higher than those measured using the resistivity method. Water saturation values were calculated using conductivity and permittivity values before and after each injection. Different values of saturation exponent (n) were tested for Archie’s law until an appropriate value was found which gave the best water saturation from conductivity data for clean Borden sand. Then, the water saturation obtained from permittivity values using Topp’s equations for different materials were compared to that of obtained from conductivity values using Archie’s equation. Topp’s equation for 30 µm glass beads provided the best match. Furthermore, other equations developed by other researchers were examined to obtain water saturation profiles from the permittivity values; all of them overestimate the water saturation for Borden sand. The water saturation profiles after the gasoline spills obtained using both Archie’s law and Topp’s equation do not match, perhaps because both equations were developed for three-phase (water-solid-air) systems.

A solid oxide fuel cell (SOFC) is an energy conversion device that has the potential to efficiently generate electricity in an environmentally-friendly manner. In general, a SOFC operates between 750&deg;C and 1000&deg;C utilizing hydrogen or hydrocarbons as fuel and air as an oxidant. The three major components comprising a fuel cell are the electrolyte, the cathode, and the anode. At present, the state-of-the-art SOFC is made from a dense yttria-stabilized zirconia (YSZ) electrolyte, a porous lanthanum manganite cathode, and a porous nickel/YSZ composite anode. With the advent of the anode-supported SOFC and the increased interest in using a wider range of fuels, such as those containing sulphur, knowledge of the anode properties is becoming more important. <br /> The properties of the current anodes are limited due to the narrow range of nickel loadings imposed by the minimum nickel content for electrical conductivity and the maximum allowable nickel loading to avoid thermal mismatch with the YSZ electrolyte. In addition, there is little research presented in the literature regarding the use of nickel metal as a starting anode material, rather than the traditional nickel oxide powder, and how porosity may affect the anode properties. <br /> The purpose of this investigation is to determine the influence nickel morphology and porosity distribution have on the processing and properties of tape cast Ni/YSZ composites. Specifically, the sintering characteristics, electrical conductivity, and thermal expansion behaviour of tape cast composites created from YSZ, nickel, nickel oxide (NiO), nickel coated graphite (NiGr), and/or graphite (Gr) powders are investigated. In addition to samples made from 100% YSZ, 100% Ni, and 100% NiO powders, five composite types were created for this investigation: NiO/YSZ, NiO&Gr/YSZ, Ni/YSZ, NiGr/YSZ, and Ni&Gr/YSZ each with nickel loadings varying between 4 vol% Ni of total solids and 77 vol% Ni of total solids. Another set of composites with a fixed nickel loading of 27 vol% Ni and 47 vol% Ni of total solids and varying graphite loadings were also created. <br /> During the burnout stage, the composites made from nickel oxide powder shrink slightly while the composites made from nickel metal expand due to nickel oxidation. Graphite additions below 20 vol% of the green volume do not alter the dimensional changes of the composites during burnout, but graphite loadings greater than 25 vol% of the green volume cause significant expansion in the thickness of the composites. <br /> After sintering, the amount of volumetric sintering shrinkage decreases with higher nickel loadings and is greater for the composites made with nickel oxide compared to the composites made from nickel metal. The porosity generated in the composites containing graphite is slightly higher than the volume of graphite added to the composite and is much greater than the porosity contained in the graphite-free composites. <br /> Dimensional changes of the porous Ni/YSZ and NiO/YSZ composites during both burnout and sintering were analysed based on concepts of constrained sintering of composite powder mixtures. In some cases constrained sintering was evident, while in others, a more simple rule of mixtures behaviour for shrinkage as a function of YSZ content was observed. <br /> When nickel oxide is reduced to nickel metal during the reduction stage there is essentially no change in the composite volume for the composites containing YSZ because the YSZ prevents the composites from shrinking. After reduction the additional porosity generated in the composites is equivalent to the change in volume due to the reduction of nickel oxide to nickel metal. <br /> When measuring the electrical conductivity, each composite type demonstrated classic percolation behaviour. The NiGr/YSZ composites had the lowest percolation threshold, followed by the Ni/YSZ and NiO/YSZ composites. When graphite was added with a nickel coating, the added porosity did not disrupt the nickel percolation network and allowed the nickel to occupy a larger effective volume compared to a composite made with similar sized solid nickel particles. When graphite was added to the composites, the electrical conductivity was reduced and the percolation threshold increased. <br /> Generally, the coefficient of thermal expansion (CTE) for Ni/YSZ composites are expected to follow the rule of mixtures prediction since the elastic properties for nickel and YSZ are similar. However when porosity is distributed unevenly between the YSZ and nickel phases, the CTE prediction will deviate from the rule of mixtures. When cornstarch was added to the NiGr/YSZ composites, the CTE increased as the amount of porosity in the YSZ phase increased. The CTE of the NiGr/YSZ composites followed the rule of mixtures indicating that the porosity was evenly distributed between the nickel and YSZ phases. For the other composite types, the measured CTE was higher than the rule of mixtures prediction suggesting that more porosity was contained within the YSZ phase.

A controlled column experiment was conducted to investigate the geophysical response of gasoline spills into the partially saturated sand column. The column was 0.61 diameter (ID) and 2 m high cylindrical polyvinyl chloride, which was packed with the Borden sand to a height of 1.95 m, flushed with CO2, saturated, and drained to a height of 0.73 m. The monitoring techniques used for this experiment was DC resistivity and time domain reflectometry (TDR) methods. The column was equipped with resistivity electrodes and TDR probes, which were placed on the column wall vertically with 3 cm intervals, on opposite sides, two monitoring wells, an injection well, a manometer, an outlet/inlet system, and a vent. A total amount of 5 liters of standard API 91-01 gasoline was added to the system in steps of 1, 2, and 2 liters to examine the geophysical response to different amounts of gasoline. Measurements were taken before and after each injection and also during subsequent fluctuation of the water table. Both monitoring techniques were able to record even the minor changes in the trend of conductivity and permittivity profiles due to the addition of the small amount of gasoline during the first spill. The conductivity and permittivity profiles obtained before lowering the water level below the original level and those obtained after the water level reached to the original level do not match, which is an indication of entrapped gasoline inside the pores. Two core samples was taken from the sand symmetrically after each water table fluctuation and analyzed for total petroleum hydrocarbon (TPH) analysis and the results were compared to the conductivity and permittivity results. The conductivity profile obtained using DC resistivity method was compared to that of obtained using TDR method. The profiles match in the saturated zone where all of the pores are connected with water and therefore electrolytic conduction is predominant. In the unsaturated zone, where there is low pore water connectivity, TDR measured conductivity values are higher than those measured using the resistivity method. Water saturation values were calculated using conductivity and permittivity values before and after each injection. Different values of saturation exponent (n) were tested for Archie’s law until an appropriate value was found which gave the best water saturation from conductivity data for clean Borden sand. Then, the water saturation obtained from permittivity values using Topp’s equations for different materials were compared to that of obtained from conductivity values using Archie’s equation. Topp’s equation for 30 µm glass beads provided the best match. Furthermore, other equations developed by other researchers were examined to obtain water saturation profiles from the permittivity values; all of them overestimate the water saturation for Borden sand. The water saturation profiles after the gasoline spills obtained using both Archie’s law and Topp’s equation do not match, perhaps because both equations were developed for three-phase (water-solid-air) systems.

Polymer electrolyte membrane fuel cells (PEMFCs) have the potential to play a major role as energy generators for transportation and portable applications. One of the current barriers to their commercialization is the cost of the components and manufacturing, specifically the bipolar plates. One approach to preparing PEMFCs for commercialization is to develop new bipolar plate materials, related to mass production of fuel cells. Thermoplastic/carbon filler composites with low filler loading have a major advantage in that they can be produced by a conventional low-cost injection molding technique. In addition, the materials used are inexpensive, easy to shape, and lightweight. An optimal bipolar plate must possess high surface and bulk electronic conductivity, sufficient mechanical integrity, low permeability, and corrosion resistance. However, it is difficult to achieve high electrical conductivity from a low-cost thermoplastic composite with low conductive filler loading. Concerns over electrical conductivity improvement and the injection processability of composites have brought forth the idea of producing a polypropylene/three-carbon-filler composite for bipolar plate application. The thesis addresses the development of synergistic effects of filler combinations, investigating composite conductive materials and using composite bipolar plate testing in PEMFCs. One significant effect of conductive network formation is the synergetic effects of different carbon filler sizes, shapes, and multiple filler ratios on the electrical conductivity of bipolar plate materials. A polypropylene resin combined with low-cost conductive fillers (graphite, conductive carbon black, and carbon fibers with 55 wt% of filler loading) compose the main composite for all investigations in this research. Numerous composite formulations, based on single-, two-, and three-filler systems, have been created to investigate the characteristics and synergistic effects of multiple fillers on composite conductivity. Electrical conductivity measurements corresponding to PEMFC performance and processing characteristics were investigated. Experimental work also involved other ex-situ testing for the physical requirements of commercial bipolar plates. All combinations of fillers were found to have a significant synergistic effect that increased the composite electrical conductivity. Carbon black was found to have the highest influence on the increase of electrical conductivity compared to the other fillers. The use of conjugated conducting polymers such as polypyrrole (PPy) to help the composite blends gain desirable conductivities was also studied. Electrical conductivity was significantly improved conductivity by enriching the conducting paths on the interfaces between fillers and the PP matrix with PPy. The conductive network was found to have a linkage of carbon fibers following the respective size distributions of fibers. The combination of Fortafil and Asbury carbon fiber mixture ameliorated the structure of conductive paths, especially in the through-plane direction. However, using small fibers such as carbon nanofibers did not significantly improve in electrical conductivity. The useful characteristics of an individual filler and filler supportive functions were combined to create a novel formula that significantly improved electrical conductivity. Other properties, such as mechanical and rheological ones, demonstrate the potential to use the composites in bipolar plate applications. This research contributes a direction for further improvement of marketable thermoplastic bipolar plate composite materials.