ii ABSTRACT Percolation phenomena involving the electrical conductivity, dielectric constant, Hall coefficient, magnetoconductivity, relative magnetoresistivity, 1/ f noise and thermoelectric power are investigated in graphite (G) and hexagonal boron-nitride (BN) powder mixtures. Two kinds of systems are used in the experiments: highly compressed discs and parallelepipeds, cut from these discs, as well as 50%G-50%BN and 55%G-45%BN powder mixtures undergoing compression. The measured DC conductivities follow the power-laws 0"( <p, 0) ex: (<p-<Pc)t (<p > <Pc) and O"(<p, 0) ex: (<Pc-<Pti (<p < <Pc), and the low frequency (lOOHz & 1000Hz) dielectric constant varies as c( <p, W ~ 0) ex: (<Pc - <P )-S( <P < <Pc), where <Pc is the percolation threshold, t and s are the conductivity exponents, and s is the dielectric exponent. Near the percolation threshold and at high frequencies, the AC conductivity varies with frequency as 0"( <p, w) ex: WX and the AC dielectric constant varies as c( <p, w) ex: w-Y, where the exponents x and y satisfy the scaling relation x + y = 1. The crossover frequency We scales with DC conductivity as Wc ex: O"q( <p, 0) (<p > <Pc), while on the insulating side, Wc ~ 1, resulting in q ~O for the three G-BN systems. The loss tangent tan t5( <p, w) (<p < <Pc) is found to have a global minimum, in contrary to the results of computer simulations. The Hall constant could not be measured using existing instrumentation. The measured magnetoconductivity and relative magnetoresistivity follow the power-laws - 6. 0" ex: (<p - <Pc)3.08 and 6.R/ R ex: (<p - <Pc)O.28 respectively. These two exponents, iii 3.08 and 0.28, are not in agreement with theory. The 1/ f noise was measured for the conducting discs and parallelepipeds. The normalized 1/ f noise power varies as Sv I V2 ex RW with the exponents w = 1.47 and 1.72 for the disc and parallelepiped samples respectively. Furthermore, the normalized noise power near the percolation threshold is, for the first time, observed to vary inversely with the square-root of sample volume. Based on the Milgrom-Shtrikman-Bergman-Levy (MSBL) formula, thermoelectric power of a binary composite is shown to be a linear function of the WiedemanFranz ratio. A scaling scheme for the Wiedeman-Franz ratio for percolation systems is proposed, which yields power-law behavior for the thermoelectric power. The proposed power-laws for the thermoelectric power can be written as (Sm - Md ex (<p - <Pc)h 1 for <P > <Pc and as (Sm - /~1d ex (<Pc - <p)-h2 for <p < <Pc, where Sm is the thermoelectric power for the composites, Afl is a constant for a given percolation system, and hI and h2 are the two critical exponents. The experimental thermoelectric power data for the G-BN conducting parallelepipeds was fitted to the above powerlaw for <p > <Pc. A least squares fit yielded the exponent hI = -1.13 and parameter MI =9.511l V I I< respectively.

A utilização de solo natural misturado com bentonita empregado em camadas impermeáveis para retenção de contaminante é bastante comum em aterros sanitários. Neste trabalho, serão apresentados os resultados de ensaios com misturas de solo-bentonita nos teores de 3%, 5% e 7%, utilizando-se um solo arenoso proveniente da região de Pindorama (SP). Os ensaios de condutividade hidráulica para o solo-bentonita foram realizados em permeâmetros de parede flexível. Os resultados obtidos indicam que para os teores de 5% e 7% de bentonita a condutividade hidráulica apresenta-se com valores adequados para a construção de barreiras impermeáveis. A resistência ao cisalhamento do solo compactado puro e das misturas compactadas foi avaliada através de ensaios triaxiais do tipo consolidado não drenado (CU) e ensaios de compressão simples. A coesão efetiva e o ângulo de atrito efetivo do solo aumentou e diminuiu, respectivamente, com a adição de bentonita. Os ensaios de resistência à compressão simples para as misturas com 5% de bentonita atingiram valores aceitáveis para o emprego em camadas impermeabilizantes. / It is becoming very common the use of soil-bentonite mixtures for building sanitary landfill liners with the purpose of retaining pollutants. This work shows the results of hydraulic conductivity and shear strength tests performed with soil-bentonite mixtures with 3%, 5% and 7% bentonite content. The natural soil was gathered in the Pindorama area, which is located in the northeast of Sao Paulo state. The hydraulic conductivity tests were performed in a flexible wall permeameter. Test results show that mixtures with 5% and 7% bentonite content are suitable, in terms of hydraulic conductivity, for construction of sanitary landfill liners. The shear strength parameters of natural soil and mixtures have been assessed performing undrained triaxial compression tests and unconfined compression tests. The effective cohesion and the effective friction angle increased and decreased with the increase of the bentonite content, respectively. The unconfined compression test results have shown that mixtures with 5% bentonite content are suitable, in terms of shear strength, for construction of sanitary landfill liners.

This study compares four different methods to measure hydraulic conductivity (K) at two sites on the East Tennessee State University Valleybrook Campus. It compares the K values to each other, to the different K values between the two sites, and to United States Department of Agriculture (USDA) K values. Two field methods, Well Bail Test and Auger Hole Test, and two lab methods, Constant Head Permeameter Test and Grain Size Distribution Test (GSD), were performed on the clay rich Ultisol soils on an East Tennessee hillslope in the Valley and Ridge Physiographic Province. One site was located close to a monitoring well and the other on the floodplain of an existing stream. The Hazen, Alyamani & Sen, and Slichter methods were used to compute K from the GSD Test. The Alyamani & Sen, Slichter, and permeameter methods produced similar K values ranging from 9.52 x 10-6 to 1.25 x 10-3 cm/sec. These are similar to the USDA K values ranging from 9.17 x 10-4 to 2.82 x 10-4 cm/sec. The Hazen method overestimated K and ranged from 8.10 x 10-3 to 1.09 x 10-1 cm/sec. The Well Bail Test yielded a lower K value (ranging from 8.16 x 10-9 to 1.19 x 10-8 cm/sec) than the USDA values as expected for water flow in deeper soil horizons at a depth of 8.50 meters. Comparing these values helped to better understand the difference between various methods to compute the hydraulic conductivity.

Thermal textiles used in Personal Protective Equipment (PPE) are used to protect individuals from the hazards of thermal energy. An analytical model of the diffusion of thermal energy within the fabric was developed to simulate the transfer of thermal energy due to a hot liquid splash. Based on the model results, it was determined that that the use of an orthotropic material in which the thermal conductivities in the radial and axial directions are different can be used to decrease the amount of heat transferred through the fabric and thereby increase amount of protection in PPE. An orthotropic material particularly performs well under situations where splashes are small in size and short in time duration. The increased level of protection may be enough to prevent a second-degree burn as determined by the Stoll criterion for materials in which the radial thermal conductivity is much larger than the axial thermal conductivity. , However, situations with larger splashes over longer duration, the benefits are minimal and at best may reduce the amount of energy transferred over part of the splash site thereby minimizing potential size of burn areas. A semi empirical test method in which analytical results are matched to experimental results by iteratively changing the radial thermal conductivity was presented as a way to extract information about the extent that a fabric is orthotropic. Preliminary results as compared to numerical CFD experimentation show that with a calibrated model, the method has potential of giving good results. Further physical experimentation is recommended to further validate that this method could be of use in determining the extent that a fabric is orthotropic.

The emerging field of spintronics relies on the manipulation of electron spin in order to use it in spin-based electronics. Such a paradigm change has to tackle several challenges including finding materials with sufficiently long spin lifetimes and materials which are efficient in generating pure spin currents. This thesis predicts that two types of material families could be a solution to the aforementioned challenges: complex oxides and bismuth based materials. We derived a general approach for constructing an effective spin-orbit Hamiltonian which is applicable to all nonmagnetic materials. This formalism is useful for calculating spin-dependent properties near an arbitrary point in momentum space. We also verified this formalism through comparisons with other approaches for III-V semiconductors, and its general applicability is illustrated by deriving the spin-orbit interaction and predicting spin lifetimes for strained SrTiO3 and a two-dimensional electron gas in SrTiO3 (such as at the LaAIO3/SrTiO3 interface). Our results suggest robust spin coherence and spin transport properties in SrTiO3 related materials even at room temperature. In the second part of the study we calculated intrinsic spin Hall conductivities for bismuth-antimony Bi1-xSbx semimetals with strong spin-orbit couplings, from the Kubo formula and using Berry curvatures evaluated throughout the Brillouin zone from a tight-binding Hamiltonian. Nearly crossing bands with strong spin-orbit interaction generate giant spin Hall conductivities in these materials, ranging from 474 ((ћ/e)Ω-1cm-1) for bismuth to 96((ћ/e)Ω-1cm-1) for antimony; the value for bismuth is more than twice that of platinum. The large spin Hall conductivities persist for alloy compositions corresponding to a three-dimensional topological insulator state, such as Bi0.83Sb0.17. The spin Hall conductivity could be changed by a factor of 5 for doped Bi, or for Bi0.83Sb0.17, by changing the chemical potential by 0.5 eV, suggesting the potential for doping or voltage tuned spin Hall current. We have also calculated intrinsic spin Hall conductivities of Bi2Se3 and Bi2Te3 topological insulators from an effective tight-binding Hamiltonian including two nearest-neighbor interactions. We showed that both materials exhibit giant spin Hall conductivities calculated from the Kubo formula in linear response theory and the clean static limit. We conclude that bismuth-antimony alloys and bismuth chalcogenides are primary candidates for efficiently generating spin currents through the spin Hall effect.

The rapid increase in thermoelectric (TE) materials R&D is a consequence of the growing need to increase energy efficiency and independence through waste heat recovery. TE materials enable the direct solid-state conversion of heat into electricity, with little maintenance, noise, or cost. In addition, these compact devices can be incorporated into existing technologies to increase the overall operating efficiency. High efficiency TE materials would enable the practical solid-state conversion of thermal to electrical energy. Optimizing the interdependent physical parameters to achieve acceptable efficiencies requires materials exhibiting a unique combination of properties. This research reports two methods of thermoelectric enhancement: lattice strain effects in silicon-germanium alloy type I clathrates and the nanostructured enhancement of lead chalcogenides. The synthesis and chemical, structural, and transport properties characterization of Ba8Ga16SixGe30-x type I clathrates with similar Ga-to-group IV element ratios but with increasing Si substitution (4 < x < 14) is reported. Substitution of Si within the Ga-Ge lattice framework of the type I clathrate Ba8Ga16Ge30 results in thermoelectric performance enhancement. The unique dependences of carrier concentration, electrical resistivity, Seebeck coefficient, and carrier effective mass on Si substitution level, may imply a modified band structure with Si substitution. These materials were then further optimized by adjusting the Ga-to-group IV element ratios. Recent progress in a number of higher efficiency TE materials can be attributed to nanoscale enhancement. Many of these materials demonstrate increased Seebeck coefficient and decreased thermal conductivity due to the phenomenological properties of nanometer length scales. To satisfy the demands of bulk industrial applications requires additional synthesis techniques to incorporate nanostructure directly within a bulk matrix. This research investigates, for the first time, dense dimensional nanocomposites prepared by densifying nanocrystals synthesized employing a solution-phase reaction. Furthermore, the carrier concentration of the PbTe nanocomposites can be adjusted by directly doping the nanocrystals, necessary for power factor optimization. These materials were fully characterized using a low temperature TE transport measurement system, and exhibit enhanced power factors when compared to bulk polycrystalline PbTe with similar carrier concentrations.

This study describes the development of a novel thin membrane exchange assembly (MEA) from a solid acid material, cesium hydrogen sulfate (CsHSO4), and from a composite anode electrocatalyst for electrolytic splitting of (100 %) H2S feed content gas operating at 135 kPa and 150 °C. A new class of anode electrocatalyst with the general composition, RuO2/CoS2, and an improved proton conductor, CsHSO4, have shown great stability and desired properties at typical operating conditions. This configuration demonstrated stable electrochemical operation for 24 h with a (100 %) H2S fuel stream at 423 K. This same system showed a maximum current density of (19 mA/cm²) at 900 mV. The performance of this new anode electrocatalyst when compared to that of Pt black investigated in a previous study showed an overall superiority in application. We have achieved a 30 % reduction in the overall system performance by fabricating a thin (200 µm) CsHSO4 electrolyte, which reduced the whole MEA thickness from 2.3 mm to 500 µm. The result of permeability measurements proved that this thin solid electrolyte is impermeable to H2S gas and physical integrity was preserved throughout the experimental period. Further resistance losses were compensated by using a high energy planetary milling system to enhance the ionic conductivity of CsHSO4. The difference in stability and electrochemical performance of these cells compared to that of Pt anode based systems is directly attributable to the anode materials developed in this project. Factorial experiments were used to characterize the effect of controllable process variables (electrolyte thickness, time, age of the electrolyte) on the cell current density and interfacial polarization resistances. As expected, cell current density and interfacial polarization resistances were a function of electrolyte thickness and age. Nevertheless, the effect of electrolyte thickness has a more prominent effect on the measured parameters. In addition, these experiments were used to identify regions of optimum system performance. Tafel plots were constructed to investigate the kinetic behavior of various anode based electrocatalysts. Exchange current densities, which are directly a measure of the electrochemical reaction, increased with RuO2/CoS2-based anodes. These experiments also suggested that high levels of feed utilization were possible using these materials. This was an impressive result considering the drastic improvement in electrochemical performance, current density, and sulfur tolerance compared to the other anode configurations.

Replacing organic liquid electrolytes with nonflammable solid electrolytes can improve safety, offer higher volumetric and gravimetric energy densities, and lower the cost of lithium-ion batteries. However, today’s all-solid-state batteries suffer from low Li-ion conductivity in the electrolyte, slow Li-ion transport across the electrolyte/electrode interface, and slow solid-state Li-ion diffusion within the electrode. Defect chemistry is critical to understanding ionic conductivity and predicting the charge transport through heterogeneous solid interfaces. The goal of this dissertation is to analyze and improve solid state materials for energy storage applications by understanding their defect structure and transport properties. I have investigated defect chemistry of cubic Li7La3Zr2O12 (c-LLZO), one of the most promising candidate solid electrolytes for all-solid-state lithium batteries. By combining conductivity measurements with defect modeling, I constructed a defect diagram of c-LLZO featuring the intrinsic formation of lithium vacancy-hole pairs. The findings provided insights into tailoring single-phase mixed lithium-ion/electron conducting materials for emerging ionic devices, i.e., composite cathodes requiring both fast electronic and ionic paths in solid-state batteries. I suggested that oxygen vacancies could increase the Li-ion conductivity by reducing the amount of electron holes bound with lithium vacancies. Using a simpler but also attractive solid electrolyte Li2ZrO3 (LZO) as an example, I significantly improved Li-ion conductivity by creating extra oxygen vacancies via cation doping. In particular, Fe-doped LZO shows the highest Li-ion conductivity reported for the family of LZO compounds, reaching 3.3 mS/cm at 300 °C. This study brought attentions to the long-neglected oxygen vacancy defects in lithium-ion conductors and revealed their critical role in promoting Li-ion transport. More importantly, it established a novel defect engineering strategy for designing Li-oxide based solid electrolytes for all-solid-state batteries. I surface-modified LiNi0.6Co0.2Mn0.2O2 cathode material with a LZO coating prepared under dry air and oxygen, and systematically investigated the effect of coating atmosphere on their transport properties and electrochemical behaviors. The LZO coating prepared in oxygen is largely amorphous. It not only provided surface protection against the electrolyte corrosion but also enabled faster lithium-ion transport. Additionally, oxygen atmosphere facilitated Zr diffusion from the surface coating to the bulk of LiNi0.6Co0.2Mn0.2O2, which stabilized the crystal structure and enhanced lithium ion diffusion. Consequently, LiNi0.6Co0.2Mn0.2O2 cathodes coated with Li2ZrO3 in oxygen achieved a significant improvement in high-voltage cycling stability and high-rate performance.

Groundwater in the Kentucky Appalachian region is constrained by physiography and lithology. Lithostratigraphy, groundwater flow, and chemistry were delineated in the alluvial aquifer along the Cumberland River at H.L. Disney Training Center. To assess groundwater-river interactions and water quality, 11 monitoring wells were installed and sampled quarterly, plus the river and an existing bedrock well. Analytical results were evaluated for temporal and spatial trends. Collected soil cores were analyzed for bulk chemistry and grain size. Solute speciation and saturation indices were calculated and hydraulic conductivity estimated from grain-size analyses. Pumping and slug tests were performed to estimate hydraulic conductivity and hydraulic head was monitored using logging transducers for river stage comparison. Site lithology consists of loamy soils underlain by silty clay, transitioning downward to clayey-fine sands on friable sandstone/shale. Alluvium becomes finer-grained and has lower hydraulic conductivities with proximity to the river (10-9–10-2 cm/s). Meteoric recharge drives local groundwater flow from ridges toward rivers. Hydraulic head fluctuates with stage and temporary gradient reversals occur. Groundwater does not appear to be impacted by current land use. Wells have elevated iron and manganese concentrations; post-treatment, the alluvial aquifer may provide sufficient quality and rates of water to support onsite military activities.

The effective radiative conductivity of fibrous material is an important part of the evaluation of the thermal performance of fibrous insulators. To better evaluate this material property, a three-dimensional direct simulation model which calculates the effective radiative conductivity of fibrous material is proposed. Two different geometries are used in this analysis. The simplified model assumes that the fibers are in a cylindrical shape and does not require identically-sized fibers or a symmetric configuration. Using a geometry with properties resembling those of a fibrous insulator, a numerical calculation of the geometric configuration factor is carried out. The results show the dependency of thermal conductivity on temperature as well as the orientation of the fibers. The calculated conductivity values are also used in the continuum heat equation, and the results are compared to the ones obtained using the direct simulation approach, showing a good agreement. In continue, the simulated model is replaced by a realistic geometry obtained from X-ray micro-tomography. To study the radiative heat transfer mechanism of fibrous carbon, three-dimensional direct simulation modeling is performed. A polygonal mesh computed from tomography is used to study the effect of pore geometry on the overall radiative heat transfer performance of fibrous insulators. An robust procedure is presented for numerical calculation of the geometric configuration factor to study energy-exchange processes among small surface areas of the polygonal mesh. The methodology presented here can be applied to obtain accurate values of the effective conductivity, thereby increasing the fidelity in heat transfer analysis.