Direct carbon fuel cell (DCFC) is a high temperature fuel cell (around 700 "C) that produces electrical energy from the direct conversion of the chemical energy of carbon. DCFC has a higher achievable efficiency of 80% compared to other fuel cells and the corresponding CO2 emission is very low compared to conventional coal-burning power plants. Moreover, a DCFC can use diversified fuel resources even waste material, which is advantageous compared to other types of fuel cells which are limited to specific fuels. DCFCs are still under development due to a number of fundamental and technological challenges such as the efficiency of carbon fuels and the effect of impurities on the performance and lifetime of the DCFC. These are key factors for the development and commercialization of these devices. In this study, three biochars obtained from the pyrolysis of poultry litters (PL) collected from Tunisian and US farmers, were characterized to see whether they can be potential anode fuels for DCFC or not. PL biochars have low fixed carbon contents (19-35 wt%) and high ash contents (32.5-63 wt%). These ashes contain around 40 wt% catalytic oxides for carbon oxidation reaction, however, these oxides have very low electrical conductivities, which resulted in the very low (negligible) electrical conductivity of the PL biochars (7.7x10-9-70.56x10-9 S/cm) at room temperature. Moreover, the high ash contents resulted in low surface areas (3.34-4.2 m"/g). These findings disqualified PL biochar from being a potential anode fuel for DCFCs. Chemical demineralization in the sequence HF/HCl followed by carbonization at 950" C of the PL biochars will result in higher fixed carbon content, higher surface area, and higher electrical conductivities. Moreover, the treated PL biochars would contain a potential catalyst (Calcium in the form of CaF2) for carbon oxidation. All these criteria would qualify the treated PL biochars to be potential fuels for DCFC. / Master of Science

Prior studies have demonstrated Appalachian coal mining often causes elevated specific conductance (SC) in streams, and others have examined SC effects on benthic macroinvertebrate communities using point-in-time SC measurements. However, both SC and benthic macroinvertebrate communities exhibit temporal variation. Twelve Appalachian headwater streams with minimally impacted physical habitat and reference-quality physicochemical conditions (except elevated SC) were sampled ten to fourteen times each for benthic macroinvertebrates between June 2011 and November 2012. In situ loggers recorded SC at 15-minute intervals. Streams were classified by mean SC Level (Reference 17-142 S/cm, Medium 262-648 S/cm, and High 756-1,535 S/cm). Benthic macroinvertebrate community structure was quantified by the Virginia Stream Condition Index and other metrics. Structural metric differences among SC Levels and month of sampling were explored. Reference-SC streams exhibited significantly higher scores on most metrics, supporting previous findings that SC may act as a biotic stressor, even in streams lacking limitations from degradation of physical habitat or other physicochemical conditions. Temporal variation was greatest in Medium-SC streams, which had the most metrics exhibiting significant differences among months and the greatest range of monthly means for six metrics. Metrics involving % Plecoptera and/or % Trichoptera were not sensitive to elevated SC, as Leuctridae and Hydropsychidae exhibited increased abundance in streams with elevated SC. Best scores for benthic macroinvertebrate community metrics differed based on selected metric, SC Level, and month. Consequently, timing of sampling is important, particularly in streams with elevated SC because community metric scores may be impacted by dominant taxa life history patterns. / Master of Science

Climate change is expected to lead to more intense and severe rainfall events in the future, significantly increasing the risk of urban flooding. This change, characterized by spatial and temporal shifts in precipitation patterns, presents a challenge to the capacity of existing urban drainage systems, which may lead to higher runoff volumes than they were initially designed to handle. Relying solely on enlarging stormwater infrastructure to tackle this issue could be expensive and may transfer the flooding risk downstream, rather than effectively resolving it. Furthermore, climate change may also lead to prolonged dry spells, potentially resulting in soil compaction and diminished soil infiltration rates. Given these considerations, it is essential to ensure urban drainage systems are both adaptable and space-efficient, with an enhanced capacity to manage the heightened rainfall caused by climate change.   As awareness of the hydrological and environmental impacts of urbanization on catchments grows, there has been a paradigm shift toward adopting green infrastructure solutions. These approaches diverge from traditional 'end-of-pipe' strategies, emphasizing more holistic and sustainable methods. The overall aim of this thesis is to investigate the implications of climatic conditions and geographic location on the retention and detention capacity of three types of infiltration-based facilities: a biofilter cell, a green roof, and a grass swale. A rainfall-runoff model of a biofilter cell and a green roof, combined with swale irrigation experiments, was used to evaluate the capacity of these facilities to reduce runoff volumes and attenuate peak flows. The analysis was conducted in four urban areas representing oceanic (Cfc), humid continental (Dfb), and subarctic (Dfc) climatic zones. The assessment also includes the effect of temporal and spatial variation of saturated hydraulic conductivities (ksat). Swale irrigation experiments were conducted to evaluate the effect of outflow controls on swale retention and detention capacities, under high soil moisture conditions.   Results for biofilter cells and green roofs showed that retention capacities were influenced by the combined effect of antecedent wetness, the extent of winter periods, and the frequency and intensity of rainfall events. Conversely, green roofs were found to have a higher sensitivity to initial soil conditions and antecedent dry weather periods, which was observed through a spread distribution of runoff volume reductions. Grass swales exhibited a large spatial distribution of hydraulic conductivity (ksat) values, with lower values at the swale bottom and higher values at the slope on the right side. Results from a full-scale infiltration test showed that overall, grass swale infiltration capacities are representative of the measured ksat values at the swale bottom. Finally, the presence of outflow controls was observed to enhance the retention and detention capacities of grass swales, even under high levels of soil moisture content. This increase in swale hydrological functionality was influenced by swale outflow controls, leading to greater utilization of the grass swale surface area. Differences between swales with outflow controls and those without were noted due to the effect of the additional storage capacity provided by an outlet control weir. Conversely, it was shown that swales without outflow controls experienced limited retention under high soil moisture content, restricted by the finite capacity of surface depression storage.

The use of electrospun polystyrene (PS) fibers to create continuous long range ordered multi-scale porous structures in titanium diboride (TiB2) is investigated in this work. The introduction of electrospun PS fibers as a sacrificial filler into a colloidal suspension of TiB2 allows for easy control over the pore size, porosity, and long range ordering of the porous structures of the sintered ceramic. Green bodies were formed by vacuum infiltrating an electrospun-fiber-filled mold with the colloidal TiB2 suspension. The size, volume, distribution, and dispersion of the pores were optimized by carefully selecting the sacrificial polymer, the fiber diameter, the solvent, and the solid content of TiB2. The green bodies were partially sintered at 2000 C in argon to form a multiscale porous structure via the removal of the PS fibers. Aligned continuous cylindrical pores were derived from the PS fibers in a range of ~5 - 20 μm and random porosity was revealed between the ceramic particles with the size of ~0.3 - 1 μm. TiB2 near-net-shaped parts with the multi-scale porosities (~50 to 70%) were successfully cast and sintered. The multi-scale porous structure produced from electrospun fibers was characterized both thermally and mechanically, at room temperature. The conductivity ranged from 12-31 W m^(-1) K^(-1) at room temperature and the compressive strength ranged from 2-30 MPa at room temperature. Analytical thermal and mechanical models were employed to understand and verify he processing-structure-properties relationship. Finally, a method was devised for estimating the effective thermal conductivity of candidate materials for UHTC applications at relevant temperatures using a finite difference model and a controlled sample environment. This low-cost processing technique facilitates the production of thermally and mechanically anisotropic structures into near-net shape parts, for extreme environment applications, such as ultra high temperature insulation and active cooling components. / MS / Society is on the cusp of hypersonic flight which will revolutionize defense, space and transport technologies. Hypersonic flight is associated with conditions like that of atmospheric re-entry, high heat and force or specific locations of a space craft. The realization of hypersonic flight relies on innovative materials to survive the harsh conditions for repeated flight. We have created a new material with tiny holes that can help prevent heat flow from the harsh atmosphere from damaging the hypersonic craft. Thesis tiny holes are made from placing a polymer fiber in an advanced ceramic (which withstand high temperatures) and removing the fiber to leave holes. The tiny hole’s effect on strength and heat flow have been studied, to understand how the tiny holes can be made better. It is difficult to test materials in the harsh atmosphere associated with hypersonic flight, so a program has been written to estimate thermal properties of candidate materials for hypersonic flight.

Soilless substrates, such as peat, pine bark, and coir, are widely used as growing media in containerized crops for their favorable characteristics, including low bulk density, balanced air exchange and water retention, disease resistance, and low pH and salinity. However, improper irrigation of these media can have negative outcomes such as root asphyxia, pathogen development, and reduced plant growth. Understanding pore size distributions, water dynamics, and gas diffusivity of these substrates is essential to promote plant growth. The effects of different particle sizes of soilless media on processes such as infiltration, hydraulic conductivity, and gas diffusivity are also not well understood. The characterization of these effects is important for the overall improvement of container crop production. This thesis presents three studies that aimed to characterize the physical and hydraulic properties of pine bark substrates, both unamended and amended with peat or coir. The first study looked at three substrate types: unamended, unscreened pine bark, peat-amended pine bark, and coir amended pine bark. Three methods were employed to quantify pore distributions: non-equilibrium infiltration measurements, equilibrium water retention characterization, and scanning electron microscopy. We characterized pore distributions during wetting and drainage for the three substrates. Coir-amended bark had the largest water-conducting porosity, highest hydraulic conductivity, and most water retention. Unamended pine bark had the highest microporosity, and the addition of peat and coir lowered macroporosity, with peat having the greater effect. The total porosity inferred from the infiltration method was significantly smaller than that inferred from drainage experiments due to assumptions related to pore shape. The second study focused on defining hydraulic conductivity and water retention for pine bark substrates of five different particle sizes, <1 mm, 1-2 mm, 2-4 mm, 4-6 mm, and an unscreened fraction. We utilized the same methods from the first study. The resulting data showed that the smallest particle sizes (i.e., <1 mm and 1-2 mm) had the highest hydraulic conductivity and greatest water retention. The three larger sizes had lower hydraulic conductivity and poor water retention, including the unscreened fraction, which more closely followed the results of the 2-4 mm size. The final study examined gas diffusivity of the five pine bark particle sizes at different moisture levels: 60% moisture content (initial conditions), saturated at the bottom of the sample, near-saturated at the sample bottom, and drained from saturation to container capacity. We used a one-chamber gas diffusion setup to find gas diffusion coefficients (Ds). The results displayed an inverse relationship between Ds values and substrate water content. In addition, the larger particle sizes were less sensitive to changes in water content due to their well-draining large pores. Proper balance of aeration and water retention is necessary for the success of soilless growing media. Overall, the smaller particle size fractions had the best water retention and hydraulic conductivity rates while the larger fractions had the largest Ds coefficients. This work contributes valuable knowledge on the physical and hydraulic properties of different size fractions of pine bark substrates, which can assist nursery growers in optimizing water usage for sustainable container crop production. / Master of Science / Since the 1950's soilless substrates have been an important resource for growing a variety of fruits, vegetables, flowers, and ornamental plants. Soilless growing media have become more popular choices for containerized plant production compared to natural soils due to improved air exchange, increased disease resistance, and more plants per acre. They are also favored because they help conserve resources, reduce agricultural waste, and minimize transportation requirements as compared to traditional cropping methods. The most popular types of soilless media include peat, coir, compost, and pine bark. In the U.S., pine bark is the main substrate used, as it is renewable and widely available. Growers still face many issues when using containerized crop production. For example, pine bark is susceptible to water runoff which can cause environmental problems and increase costs from this loss of water and fertilizer. Further characterizing of water and gas dynamics in of pine bark growing media is important for conserving water and fertilizer resources while optimizing plant growth in this container cropping industry. Pore characteristics, aeration, and water movement are key factors of substrates to be described to solve these challenges. This project aimed to apply soil physics strategies to soilless media, focusing on describing pore sizes, water movement, water holding capacity, and air movement in pine bark substrates. We utilized three methods throughout this study. For the first method, we took infiltration measurements to examine how water moved into the media, while the second utilized controlled drainage experiments to observe how water moved out of the media. The final method was characterizing gas movement through the substrates at different water contents and particle sizes. The results found showed that the smaller particle sizes and pine bark mixed with peat and coir had increased ability to retain water and allow water movement as compared to the larger particle sizes and unamended pine bark. In contrast, the larger particles had less water retention but improved gas movement. These results could be applied by stacking different particle sizes or mixes over one another could optimize water retention in the top of the container and drainage and gas movement in the bottom of the container. Overall, the application of this work is to create best management practices for growers to be able to balance water retention and gas movement in order to optimize plant growth.

<p dir="ltr">This Thesis is divided into four parts. Its main themes are the thermal transport characteristics of Surface Phonon-Polaritons (SPhPs) and Surface Plasmon Polaritons (SPPs).</p><p dir="ltr">Chapter 1 introduces the main problem at issue in this Thesis: the decline in thermal conductivity with decreasing thicknesses in electronic devices and the feasibility of optimizing polar semiconductors and metals to produce polaritons that augment heat dissipation at these length scales.</p><p dir="ltr">Chapter 2 discusses Surface Phonon-Polariton (SPhP)-mediated thermal conductivity, or radiation conduction, in polar semiconductors. It considers the propagation of SPhPs in the case of two semi-infinite planes consisting of air and a polar semiconductor with a dielectric function described by its transverse- and longitudinal-optical (TOLO) phonon energies. It characterizes twenty different polar semiconductors in terms of radiation conduction via SPhPs and proposes a Figure of Merit (FoM) that describes the effectiveness of polariton conductance using easily-measured TO and LO phonon energies and linewidths.</p><p dir="ltr">Chapter 3 considers the propagation of SPPs in the case of two semi-infinite planes consisting of air and a metal with a dielectric function described by the Lorentz-Drude (LD) model. This chapter characterizes the effectiveness of eleven different metals as radiation conductors via SPPs and relates polariton conductance to electrical resistivity. It proposes a FoM analogous to the Wiedemann-Franz law that relates the effectiveness of polariton conductance and thermal conductance to the material’s electron scattering or linewidth.</p><p dir="ltr">Chapter 4 chapter compares the relative effectiveness of SPhP- and SPP-mediated radiation conduction. It describes why SPPs demonstrate far higher polariton conductance values than SPhPs by highlighting the underlying mechanisms at work in both—that is, available modes of energy transmission and their respective mean free path lengths.</p>

Currently, ASHRAE has determined the zone method and modified zone method are appropriate calculation methods for materials with a high difference in conductivity, such as cold-formed steel (CFS) walls. Because there is currently no standard U-Factor calculation method for CFS walls, designers and code officials alike tend to resort to the zone method. However, the zone method is restricted to larger span assemblies because the zone factor coefficient is 2.0. This tends to overestimate the amount of surface area influenced by CFS. The modified zone method is restricted to C-shaped stud, clear wall assemblies with framing factors between 9 and 15%. The objective of the research is to narrow the gap of knowledge by re-examining the modified zone method in order to more accurately determine R-Values and U-Factors for CFS wall assemblies with whole wall framing factor percentages of 22% and above.

This thesis documents research done in the development and the exploration of feasibility for a high-throughput method to measure local thermal properties. The present capabilities in the measurement of local thermophysical properties such as thermal conductivity, thermal diffusivity, and Kapitza resistance are very inefficient and impractical to fully understand and characterize heat transport through certain materials and features. This work follows up on past work in local thermal property measurement via the spatial domain thermoreflectance (SDTR) method, and explores the possibility of parallelizing the process. The parallelized SDTR (P-SDTR) method involves using laser projector sources to periodically heat and measure the changes of reflectivity of a sample surface at multiple locations simultaneously. These measurements are made possible by the development of a lock-in camera that can measure the characteristics of modulated light using lock-in amplification at several spots across an area with an advanced camera sensor. This method allows for the measurement of local thermal properties across features such as grain boundaries, or directional properties in anisotropic materials. An experimental setup is developed to determine at which heating and probing parameters a thermoreflectance signal can be measured. A finite element model is also made to simulate the P-SDTR process, and validate that the assumptions made in SDTR can be made in P-SDTR measurements. It is shown that at an appropriate separation of heating/measurement locations, the solutions from the simulation approach that of a single measurement spot. An initial device design is proposed and tested. Future work in the development of the P-SDTR device is also laid out.

In this study, the effects of electrode microstructure and electrolyte parameters on intermediate temperature solid oxide fuel cell (ITSOFC) performance were investigated using a one-dimensional SOFC model from the Pacific Northwest National Laboratory (PNNL). After a brief review of the fundamental SOFC operating processes and a literature review incorporating more advanced SOFC topics, such as electrode microstructure modeling and mixed ionic and electronic (MIEC) composite cathodes, it was determined from the PNNL benchmark results that the dominating ITSOFC losses were caused from the activation and Ohmic overpotentials. The activation overpotential was investigated through the exchange current density term, which is dependent on the cathode activation energy, the cathode porosity, and the pore size and grain size at the cathode triple phase boundary (TPB). The cathode pore size, grain size, and porosity were not integrated in the PNNL model, therefore, an analytical solution for exchange current density from Deng and Petric (2005) was utilized to optimize their effects on performance. The Ohmic loss was determined to be entirely dependent on the electrolyte ionic conductivity, and an optimal value for this conductivity was determined. Simultaneous optimization of the above parametric evaluations led to a 388 % increase in performance from the PNNL benchmark case at 600 °C. Although this was deemed successful for this project, future research should be focused on numerically quantifying and modeling the electrode microstructure in two and·three-dimensions for more accurate results, as the electrode microstructure may be highly multi-dimensional in nature.

Structurally precision graphene nanoribbons (GNRs) are promising candidates for next-generation nanoelectronics due to their intriguing and tunable electronic structures. GNRs with hybrid edge structures often confer them unique geometries associated with exotic physicochemical properties. Herein, a novel type of cove-edged GNRs with periodic short zigzag-edge segments is demonstrated. The bandgap of this GNR family can be tuned using an interplay between the length of the zigzag segments and the distance of two adjacent cove units along the opposite edges, which can be converted from semiconducting to nearly metallic. A family member with periodic cove-zigzag edges based on N = 6 zigzag-edged GNR, namely 6-CZGNR-(2,1), is successfully synthesized in solution through the Scholl reaction of a unique snakelike polymer precursor (10) that is achieved by the Yamamoto coupling of a structurally flexible S-shaped phenanthrene-based monomer (1). The efficiency of cyclodehydrogenation of polymer 10 toward 6-CZGNR-(2,1) is validated by FT-IR, Raman, and UV–vis spectroscopies, as well as by the study of two representative model compounds (2 and 3). Remarkably, the resultant 6-CZGNR-(2,1) exhibits an extended and broad absorption in the near-infrared region with a record narrow optical bandgap of 0.99 eV among the reported solution-synthesized GNRs. Moreover, 6-CZGNR-(2,1) exhibits a high macroscopic carrier mobility of ∼20 cm2 V–1 s–1 determined by terahertz spectroscopy, primarily due to the intrinsically small effective mass (m*e = m*h = 0.17 m0), rendering this GNR a promising candidate for nanoelectronics.