Yes / This study aims to evaluate the impacts of using thermally enhanced concrete on the thermal performance of geoenergy structures and interaction between the thermo-active-structures and adjacent dry and partly saturated soils. Experiments using a fully instrumented testing rig were carried out on prototypes of energy pile and diaphragm wall made from normal concrete and thermally enhanced concrete by the addition of graphTHERM powder. Results illustrated that adding 36% of graphTHERM powder to the concrete by weight of cement was found to double the thermal conductivity of concrete and improve the stiffness by 15% without detrimental effects on the compressive strength. The heat transfer efficiency of energy pile and energy diaphragm wall made from thermally enhanced concrete was significantly improved by 50% and 66% respectively, in comparison with the efficiency of the same type of energy structure that was made from a typical normal concrete.

Soil-bentonite cutoff walls are commonly used to contain contaminants in the subsurface. A key property in determining the effectiveness of a cutoff wall is its hydraulic conductivity. There are important difficulties and uncertainties regarding the accuracy of commonly used methods of measuring the hydraulic conductivity of cutoff walls. When predicting contaminant transport through cutoff walls, common practice is to use the average hydraulic conductivity of the wall. There are some cases, however, such as circumferential cutoff walls with inward hydraulic gradients, where it is also important to consider the variability in hydraulic conductivity from point to point in the wall in contaminant transport studies. A pilot-scale facility was envisioned where subsurface barrier issues such as those mentioned above could be studied. In 1998, the Subsurface Barrier Test Facility (SBTF) was constructed. In this facility, pilot-scale subsurface barriers can be installed using real construction equipment and tested in a controlled environment. The effectiveness of various methods of measuring the hydraulic conductivity of cutoff walls was studied by building and testing three pilot-scale soil-bentonite cutoff walls at the SBTF. The following currently used test methods were evaluated: API tests on grab samples, lab tests on undisturbed samples, piezometer tests (slug tests), and piezocone soundings. The use of slug tests in cutoff walls was improved in this research in the areas of avoiding hydraulic fracture and accounting for the close proximity of the trench walls. The SBTF allows for measurement of the global, average hydraulic conductivity of an installed pilot-scale cutoff wall, which is a useful value to compare to the results of the above-mentioned tests. The two main factors differentiating the results of the different test methods used for the pilot-scale walls were remolding and sample size. Remolding of the API samples significantly reduced the hydraulic conductivity of these samples compared to the hydraulic conductivity measured in lab tests on undisturbed samples, which were of similar size. For the other tests, the degree and extent of remolding were less significant compared to in the API tests. For these tests, the scale of the measurement is believed to be the main factor differentiating the results. Hydraulic conductivity was found to increase as the sample volume increased, with the global measurement of the average hydraulic conductivity producing the highest value. The influence of variability in hydraulic conductivity on contaminant transport through cutoff walls was studied from a theoretical standpoint using the one-dimensional advection-diffusion equation. Charts were developed that can be used to estimate the flux through a cutoff wall based on knowledge of the average hydraulic conductivity of the wall and an estimate of the variability in hydraulic conductivity. Data sets of hydraulic conductivity from lab tests on soil-bentonite samples from four cutoff wall case histories were used to estimate typical values of variability. The contaminant transport analyses showed that the effect of variability may be significant when the hydraulic gradient opposes the concentration gradient, which is the case for a circumferential cutoff wall with an inward hydraulic gradient. The goal of a circumferential cutoff wall with an inward hydraulic gradient is to reduce the outward diffusive flux of contaminant by inducing an inward advective flux. The effect of variability in hydraulic conductivity is to reduce the effectiveness of this scheme. / Ph. D.

Nanotechnology has made it possible to create materials with unique properties. This development offers new opportunities and overcomes challenges for many thermal transport applications. Yet, it requires a more fundamental scientific understanding of nanoscale transport. This thesis emphasizes how simulation, mathematical, and numerical methods can lead to more grounded studies of nanoscale thermal transport for biological and physical applications. For instance, magnetic fluid hyperthermia (MFH), an emerging cancer treatment, is a noninvasive method to selectively destroy a tumor by heating a ferrofluid-impregnated malignant tissue with minimal damage to the surrounding healthy tissue. We model the problem by considering an idealized spherical tumor that is surrounded by healthy tissue. The dispersed magnetic nanoparticles in the tumor are excited by an AC magnetic field to generate heat. The temperature distribution during MFH is investigated through a bioheat transfer relation which indicates that the P\'eclet, Joule, and Fourier numbers are the more influential parameters that determine the heating during such a thermotherapy. Thus, we show that a fundamental parametric investigation of the heating of soft materials can provide pathways for optimal MFH design. Since ferrofluid materials themselves play a key role in heating, we examine six materials that are being considered as candidates for MFH use. These are simulated to investigate the heating of ferrofluid-loaded tumors. We show that iron-platinum, magnetite, and maghemite are viable MFH candidates since they are able to provide the desired heating of a tumor which will destroy it while keeping the surrounding healthy tissues at a relatively safe temperature. Recent advances in the synthesis and nanofabrication of electron devices have lead to diminishing feature sizes. This has in turn increased the power dissipation per unit area that is required to cool the devices, leading to a serious thermal management challenge. The phonon thermal conductivity is an important material property because of its role in thermal energy transport in semiconductors. A higher thermal conductivity material is capable of removing more heat since higher frequency phonons are able to travel through it. In this thesis, the effects of surface stress on the lattice thermal conductivity are presented for a silicon nanowire. Based on a continuum approach, a phonon dispersion relation is derived for a nanowire that is under surface stress and the phonon relaxation time is employed to subsequently determine its thermal conductivity. The surface stress is found to significantly influence the phonon dispersion and thus the Debye temperature. Consequently, the phonon thermal conductivity decreases with increasing surface stress. Different magnitudes of surface stress could arise from various material coatings and through different nanofabrication processes, effects of which are generally unclear and not considered. Our results show how such variations in surface stress can be gainfully used in phonon engineering and to manipulate the thermal conductivity of a nanomaterial. The thermal transport during thermoelectric cooling is also an important property since thermoelectric devices are compact, reliable, easy to control, use no refrigerants and require lower maintenance than do more traditional refrigeration devices. We focus on the Thomson effect that occurs when there is a current flow in the presence of a temperature gradient in the material, and investigate its influence on an intrinsic silicon nanowire cooler. The temperature dependence of the Thomson effect has a significant influence on the cooling temperature. We also consider thermal nonequilibrium between electrons and phonons over the carrier cooling length in the nanowire. The results show that a strong energy exchange between electrons and phonons lowers the cooling performance, suggesting useful strategies for thermoelectric device design. / Ph. D.

In this dissertation, novel approaches to PEMFC durability research are summarized. These efforts are significantly different from most other studies on durability in that rather than focusing on chemical degradation, more attention is given to the mechanical aspects of the PEMFC system. The tensile stress-strain behavior of Nafion® 117 (N117) and sulfonated poly(arylene ether sulfone) random copolymer (BPSH35) membranes is explored under ambient conditions, with respect to the effects of initial strain rate, counterion type, molecular weight and the presence of inorganic fillers. A three-dimensional "bundle-cluster" model is proposed to interpret the tensile observations, combining the concepts of elongated polymer aggregates, proton conduction channels as well as states of water. The rationale focuses on the polymer bundle rotation/interphase chain readjustment before yielding and polymer aggregates disentanglement/ reorientation after yielding. In addition, the influence of uniaxial loading on proton conductivity of N117 and BPSH35 membranes is investigated. When the membranes are stretched, their proton conductivities in the straining direction increase compared to the unstretched films, and then relax exponentially with time. The behavior is explained on the basis of the morphological variations of hydrophilic channels, accompanied by the rotation, orientation and disentanglement of the copolymer chains in the hydrophobic domains, as illustrated with the help of our bundle-cluster model. Finally, the long-term aging of hydrogen-air PEMFCs is examined with a cyclic current profile and under constant current conditions. The end-of-period diagnosis is performed for both MEAs at 100h aging intervals, including a series of cell polarization, impedance and electrochemical experiments. The results demonstrate that hydrogen crossover is the most significant result of degradation for the MEA under cyclic aging mode due to the formation of pinholes at approximately 500-600h, and mass transport limitations are the major degradation sources for constant current mode. A phenomenological mathematical model is set up to describe the PEMFC aging process under both cyclic and constant conditions. / Ph. D.

Anthropogenic disturbances can alter the abiotic composition of freshwater systems. These compositional changes can act as physiological stressors towards system inhabitants. However, little is known about how these altered abiotic factors influence stress hormones (corticosterone) in larval amphibians. Throughout the following chapters, I examined the effects of several abiotic factors on baseline and stress-induced corticosterone levels in the larvae of four amphibian species: Jefferson salamander (Ambystoma jeffersonianum), spotted salamander (A. maculatum), wood frog (Rana sylvatica), and grey treefrog (Hyla versicolor). Chapter II examined corticosterone level differences throughout development in A. jeffersonianum and R. sylvatica larvae under field, mesocosm, and laboratory venues. Baseline corticosterone levels in R. sylvatica increased near metamorphic climax in all venues, but not in A. jeffersonianum. Rather, baseline corticosterone levels differed with respect to venue throughout development in A. jeffersonianum. Chapter III examined corticosterone level differences among free-living A. jeffersonianum populations and possible abiotic factors underlying these hormone differences. Corticosterone levels significantly differed across populations. Increased baseline corticosterone levels significantly correlated to low pH. There was also a trend for increased baseline corticosterone levels to be positively correlated with chloride levels and negatively correlated with conductivity. Chapter IV examined the effects of laboratory manipulated pH on corticosterone levels in A. jeffersonianum, A. maculatum, R. sylvatica, and H. versicolor. There was a significant correlation between increased baseline corticosterone levels to low pH in all four species. Prey consumption (in both Ambystoma species) and survival (in A. jeffersonianum, A. maculatum, and R. sylvatica) were also negatively correlated to low pH. Chapter V examined the effects of increased conductivity on corticosterone levels in A. jeffersonianum, R. sylvatica, and H. versicolor. Increased conductivity exposure significantly correlated to increased baseline corticosterone levels in A. jeffersonianum and R. sylvatica. Prey consumption in A. jeffersonianum was also negatively correlated to increased conductivity. My dissertation shows that abiotic factors, such as pH and conductivity, can influence corticosterone levels in larval amphibians. These results suggest that corticosterone levels in larval amphibians may be a suitable biomarker reflective of altered freshwater habitat quality. However, my results also suggest that one should use a high degree of caution when using corticosterone levels in larval amphibians as a means to infer the health status of a population. / Ph. D.

All interfaces offer resistance to heat transport. As the size of a device or structure approaches nanometer lengthscales, the contribution of the interface thermal resistance often becomes comparable to the intrinsic thermal resistance offered by the device or structure itself. In many microelectronic devices, heat has to transfer across a metal-nonmetal interface, and a better understanding about the origins of this interface thermal conductance (inverse of the interface thermal resistance) is critical in improving the performance of these devices. In this dissertation, heat transport across different metal-nonmetal interfaces are investigated with the primary goal of gaining qualitative and quantitative insight into the heat transport mechanisms across such interfaces. A time-domain thermoreflectance (TDTR) system is used to measure the thermal properties at the nanoscale. TDTR is an optical pump-probe technique, and it is capable of measuring thermal conductivity, k, and interface thermal conductance, G, simultaneously. The first study examines k and G for amorphous and crystalline Zr47Cu31Al13Ni9 metallic alloys that are in contact with poly-crystalline Y2O3. The motivation behind this study is to determine the relative importance of energy coupling mechanisms such as electron-phonon or phonon-phonon coupling across the interface by changing the material structure (from amorphous to crystalline), but not the composition. From the TDTR measurements k=4.5 W m-1 K-1 for the amorphous metallic glass of Zr47Cu31Al13Ni9, and k=5.0 W m-1 K-1 for the crystalline Zr47Cu31Al13Ni9. TDTR also gives G=23 MW m-2 K-1 for the metallic glass/Y2O3 interface and G=26 MW m-2 K-1 for the interface between the crystalline Zr47Cu31Al13Ni9 and Y2O3. The thermal conductivity of the poly-crystalline Y2O3 layer is found to be k=5.0 W m-1 K-1. Despite the small difference between k and G for the two alloys, the results are repeatable and they indicate that the structure of the alloy plays a role in the electron-phonon coupling and interface conductance. The second experimental study examines the effect of nickel nanoparticle size on the thermal transport in multilayer nanocomposites. These nanocomposites consist of five alternating layers of nickel nanoparticles and yttria stabilized zirconia (YSZ) spacer layers that are grown with pulsed laser deposition. Using TDTR, thermal conductivities of k=1.8, 2.4, 2.3, and 3.0 W m-1 K-1 are found for nanocomposites with nickel nanoparticle diameters of 7, 21, 24, and 38 nm, respectively, and k=2.5 W m-1 K-1 for a single 80 nm thick layer of YSZ. The results indicate that the overall thermal conductivity of these nanocomposites is strongly influenced by the Ni nanoparticle size and the interface thermal conductance between the Ni particles and the YSZ matrix. An effective medium theory is used to estimate the lower limits for the interface thermal conductance between the nickel nanoparticles and the YSZ matrix (G>170 MW m-2 K-1), and the nickel nanoparticle thermal conductivity. / Ph. D.

This dissertation will outline solution processable materials and fabrication techniques to manufacture flexible electronic devices from them. Conductive ink formulations and inkjet printing of gold and silver on plastic substrates were examined. Line patterning and mask printing methods were also investigated as a means of selective metal deposition on various flexible substrate materials. These solution-based manufacturing methods provided deposition of silver, gold and copper with a controlled spatial resolution and a very high electrical conductivity. All of these procedures not only reduce fabrication cost but also eliminate the time-consuming production steps to make basic electronic circuit components. Solution processable semiconductor materials and their composite films were also studied in this research. Electrically conductive, ductile, thermally and mechanically stable composite films of polyaniline and sulfonated poly (arylene ether sulfone) were introduced. A simple chemical route was followed to prepare composite films. The electrical conductivity of the films was controlled by changing the weight percent of conductive filler. Temperature dependent DC conductivity studies showed that the Mott three dimensional hopping mechanism can be used to explain the conduction mechanism in composite films. A molecular interaction between polyaniline and sulfonated poly (arylene ether sulfone) has been proven by Fourier Transform Infrared Spectroscopy and thermogravimetric analysis. Inkjet printing and line patterning methods also have been used to fabricate polymer resistors and field effect transistors on flexible substrates from poly-3-4-ethyleneoxythiophene/poly-4-sytrensulfonate. Ethylene glycol treatment enhanced the conductivity of line patterned and inkjet printed polymer thin films about 900 and 350 times, respectively. Polymer field effect transistors showed the characteristics of traditional p-type transistors. Inkjet printing technology provided the transfer of semiconductor polymer on to flexible substrates including paper, with high resolution in just seconds. / Ph. D.

The double-sensor conductivity probe is one of the most commonly used techniques for obtaining local time-averaged parameters in two-phase flows. The uncertainty of this measurement technique has not been well understood in the past as it involves many different steps and influential factors in a typical measurement. This dissertation aims to address this gap by performing a systematic and comprehensive study on the measurement uncertainty of the probe. Three types of uncertainties are analyzed: that of measurands, of the model input parameters, and of the mathematical models. A Monte Carlo uncertainty evaluation framework closely simulating the actual measuring process is developed to link various uncertainty sources to the time-averaged two-phase flow quantities outputted by the probe. Based on the Monte Carlo uncertainty evaluation framework, an iteration method is developed to infer the true values of the quantities that are being measured. A better understanding of the uncertainty of the double-sensor conductivity probe is obtained. Multiple advanced techniques, such as high speed optical imaging and fast X-ray densitometry, recently become mature and easily accessible. To further improve the accuracy of local two-phase flow measurement, a method is developed to integrate these techniques with the double-sensor conductivity probe by considering the measuring principles and unique advantages of each technique. It has been demonstrated that after processing and synergizing the data from different techniques using the current integration method, the final results show improved accuracy for void fraction, gas velocity and superficial gas velocity, compared to the original probe measurements. High-resolution two-phase flow data is essential for the further development of various two-phase flow models and validation of two-phase CFD codes. Therefore, a comprehensive high-accuracy database of two-phase flows is acquired. The gas-phase information is obtained by the integration method developed in this dissertation, and the recently developed Particle Image Velocimetry and Planar Laser Induced Fluorescence (PIV-PLIF) technique is utilized to measure liquid-phase velocity and turbulence characteristics. Flow characteristics of bubbly flow, slug flow and churn-turbulent flow are investigated. The 1-D drift-flux model is re-evaluated by the newly obtained dataset. The distribution parameter model has been optimized based on a new void-profile classification method proposed in this study. The optimized drift-flux model has significant improvements in predicting both gas velocity and void fraction. / Doctor of Philosophy / The double-sensor conductivity probe is one widely used technique for measuring local time-averaged parameters in two-phase flows. Although a number of studies have been carried out in the past, a good understanding of the uncertainty of this technique is still lacking. This paper aims to address this gap by performing a systematic and comprehensive study on the measurement uncertainty of the probe. Three types of uncertainties are analyzed: that of measurands, of the model input parameters, and of the mathematical models. A better understanding of the uncertainty of the double-sensor conductivity probe has been obtained. Considering the unique measuring principles and advantages of multiple advanced techniques, a method is developed to integrate these techniques with the double-sensor conductivity probe to further improve the accuracy of local two-phase flow measurement. It has been demonstrated that the integration method significantly improves the accuracy of probe measurements. Realizing the needs of high-resolution two-phase flow data to the further development of various two-phase flow models and validation of two-phase CFD codes, a comprehensive database of two-phase flows is acquired. The gas-phase and liquid-phase information are acquired by the new integration method and the recently developed Particle Image Velocimetry and Planar Laser Induced Fluorescence (PIV-PLIF) technique, respectively. The classical 1-D drift-flux model is re-evaluated by the newly obtained dataset. The distribution parameter model has been optimized, resulting in significant improvements in predicting both gas velocity and void fraction.

One goal of this research was to characterize shoot tissue-level responses in loblolly pine to soil moisture limitation in combination with fertilization as well as to more severe soil moisture limitation. We found that neither fertilization alone, nor fertilization in combination with soil moisture limitation resulted in changes to shoot tissue water relations parameters classically characterized in drought response studies. More severe water limitation was necessary to elicit responses, and those responses had not been fully described previously. The more severe water limitation resulted in increased capacitance beyond turgor loss, increased relative water content at turgor loss, a more negative turgor loss point, an increased bulk modulus of elasticity, more negative osmotic potential at 100% relative water content, and an increased apoplastic water fraction. As there were indications of reduced water use and moisture stress in the absence of shoot level responses under less severe drought, such parameters are insufficient alone to characterize moisture stress in fertilized and in less severely water limited loblolly trees. Additionally, we sought a morphological or physiological explanation for the reduced transpiration and increased water use efficiency reported for fertilized trees in the Virginia Piedmont. Our characterizations of the responses of root distribution and hydraulics to limited soil moisture here complement existing research, which demonstrated changes to root distribution and hydraulics in response to fertilization. The responses we discovered in fertilized trees that accompanied reduced transpiration and increased water use efficiency that differed from responses to reduced soil moisture alone were primarily large decreases to shallow root presence. We found this to be readily quantified using measures of root length density. Decreases to whole-tree hydraulic conductivity were also shown to occur with fertilization and were shown not to occur in shoot tissue, suggesting limitation via rhizosphere or root xylem conductance. Our results support the supposition that fertilization narrows hydraulic safety margins and potentially predisposes loblolly trees to moisture stress, particularly prolonged, severe water limitation following fertilization. Finally, we tested the validity of throughfall exclusion for simulating reduced rainfall using a greenhouse 'split-pot' study, which applied spatially fixed heterogeneous soil moisture to young, well-watered loblolly pines. The 'split-pot' experiments demonstrated that spatially fixed soil moisture heterogeneity does not confound drought effects; needle area specific transpiration was not decreased, nor was water use efficiency increased. This supports the validity of inferences taken from drought simulation experiments with loblolly pine where throughfall exclusion troughs reduce soil moisture content in a consistent, spatially heterogeneous manner. / Doctor of Philosophy / We investigated various effects of soil moisture limitation alone, and in combination with common fertilization practices in loblolly pine production. Responses at the shoot and needle level to different levels of soil moisture limitation produced new findings concerning how tissues respond to more severe water limitation. A 30% decrease in throughfall precipitation alone, or in combination with fertilization did not elicit drought related shoot tissue responses despite the presence of other indications of moisture stress and reduced water use. We also sought to explain why fertilized trees experiencing water limitation had environmental sensitivities that were different from unfertilized tree receiving ambient rainfall amounts or from trees only experiencing water limitation without fertilization. We found that changes to shallow root presence, especially root length density, accompanied the different patterns of environmental sensitivity and water use. Also, the water conducting ability of roots changed unevenly in soil with uneven moisture levels. The ability of roots to resist loss of conductivity to water did not change unevenly in the same way. We did another set of experiments to determine if using impervious troughs to catch rain is a valid approach to reducing soil moisture for the purpose of testing how loblolly responds to water limitation. These throughfall exclusion troughs create uneven soil moisture reduction, which can have effects on plant water use that are separate from water limitation alone. We found that in well-watered young trees, uneven soil moisture alone did not produce responses that could be confused with the effects of water limitation. This finding indirectly validates the use of throughfall exclusion troughs to simulate reduced rainfall.

Buffer transfer of cells is a critical process in many biomedical applications such as dielectrophoresis experiments, optical trapping, and flow cytometry. Existing methods for buffer transfer of cells are time consuming, require skilled technicians and involve expensive equipment such as centrifuge and bio safety hoods. Furthermore, even a minute error in transferring the cells can easily result in cell lysis and decrease in viability. In this work, a lab-on-a-chip device is proposed that uses a textit{passive microfluidic approach} to effectively transfer cells from a growth medium to a desired buffer for downstream cDEP analysis. This eliminates the need for any external fields, expensive equipment, and significantly reduces manual efforts. Computational studies were carried out to analyze the impact of device geometry, channel configuration, and flowrate on the effectiveness of buffer transfer. The proposed device was evaluated through a parametric sweep and the device configurations were identified that induce low values of fluid shear stress, support high throughput, and maintains minimal diffusion. Finally, a method for fabricating the device in the laboratory using PDMS was illustrated. The outcome of this study helps further the development of highly effective microfluidic devices capable of performing buffer transfer of multiple cell lines. / Master of Science / Prior to performing biomedical experiments, cells often need to be transferred from the chemical solution in which they are grown to a different buffer that is customized for the analysis technique. This process is called buffer transfer and it is a critical process that needs to be performed before running many cell experiments. The way in which buffer transfer is carried out in most labs is time consuming, requiring skilled technicians and expensive machines. Moreover, even a small error while performing buffer transfer can easily cause the cells to die and reduce the cell count available for performing experiments. In this work, we propose an easy-to-use device that can perform the buffer exchange process without the need for expensive technologies or skilled technicians. The device achieves this exchange by leveraging fluid flow the channel to filter the cells out of the growth medium and transferring the cells to the desired chemical solution while washing the unwanted chemical solution away. We used CAD modeling and computational analysis to develop the device. The performance of the device was enhanced through a parametric analysis such that the device induces low shear stress, supports high flow through the channels and limits the mixing between the growth medium and the buffer. Finally, we have also illustrated a method for building the device in the laboratory. The results of this research work would help in furthering current efforts in the buffer transfer of cells.