Energy storage technologies are essential to overcome the temporal variability in renewable energy. The primary aim of this thesis is to develop reactor solutions to better analyze the potential of thermochemical energy storage (TCES) using non-stoichiometric metal oxides, for the multi-day energy storage application. A TCES system consists of a reduction reactor and an insulated MOx storage bin. The reduction reactor heats (to ~ 1100 °C) and partially reduces the MOx, thereby adding sensible and chemical energy (i.e., charging it) under reduced pO2 environments (~10 Pa). Inert gas removes the oxygen generated during reduction. The storage bin holds the hot and partially reduced MOx (typically particles) until it is used in an energy recovery device (i.e., discharge). Irrespective of the reactor heat source (here electrical), or the particle-inert gas flows (here countercurrent), the thermal reduction temperature and inert gas (here N2) flow minimize when the process approaches reversibility, i.e., operates near equilibrium. This study specifically focuses on developing a reduction reactor based on the theoretical considerations for approaching reversibility along the reaction path. The proposed Zigzag flow reactor (ZFR) is capable of thermally reducing CAM28 particles at temperatures ~ 1000 °C under an O2 partial pressure ~ 10 Pa. The associated analytical and numerical models analyze the reaction equilibrium under a real (discrete) reaction path and the mass transfer kinetic conditions necessary to approach equilibrium. The discrete equilibrium model minimizes the exergy destroyed in a practical reactor and identifies methods of maximizing the energy storage density () and the exergetic efficiency. The mass transfer model analyzes the O2 N2 concentration boundary layers to recommend sizing considerations to maximize the reactor power density. Two functional ZFR prototypes, the -ZFR and the -ZFR, establish the proof of concept and achieved a reduction extent, Δδ = 0.071 with CAM28 at T~950 °C and pO2 = 10 Pa, 7x higher than a previous attempt in the literature. The -ZFR consistently achieved  > 100 Wh/kg during >10 h. runtime and the -ZFR displayed an improved  = 130 Wh/kg during >5 h. operation with CAM28. A techno-economic model of a grid-scale ZFR with an associated storage bin analyzes the cost of scaling the ZFR for grid energy storage requirements. The scaled ZFR capital costs contribute < 1% to the levelized cost of thermochemical energy storage, which ranges from 5-20 ¢/kWh depending on the storage temperature and storage duration.

The relationships between the properties of materials and their microstructures have been a central topic in materials science. The microstructure-property mapping and numerical failure prediction are critical for integrated computational material engineering (ICME). However, the bottleneck of ICME is the lack of a clear understanding of the failure mechanism as well as an efficient computational framework. To resolve these issues, research is performed on developing novel physics-based and data-driven numerical methods to reveal the failure mechanism of materials in microstructure-sensitive applications. First, to explore the damage mechanism of microstructure-sensitive materials in general loading cases, a nonlocal lattice particle model (LPM) is adopted because of its intrinsic ability to handle the discontinuity. However, the original form of LPM is unsuitable for simulating nonlinear behavior involving tensor calculation. Therefore, a damage-augmented LPM (DLPM) is proposed by introducing the concept of interchangeability and bond/particle-based damage criteria. The proposed DLPM successfully handles the damage accumulation behavior in general material systems under static and fatigue loading cases. Then, the study is focused on developing an efficient physics-based data-driven computational framework. A data-driven model is proposed to improve the efficiency of a finite element analysis neural network (FEA-Net). The proposed model, i.e., MFEA-Net, aims to learn a more powerful smoother in a multigrid context. The learned smoothers have good generalization properties, and the resulted MFEA-Net has linear computational complexity. The framework has been applied to efficiently predict the thermal and elastic behavior of composites with various microstructural fields. Finally, the fatigue behavior of additively manufactured (AM) Ti64 alloy is analyzed both experimentally and numerically. The fatigue experiments show the fatigue life is related with the contour process parameters, which can result in different pore defects, surface roughness, and grain structures. The fractography and grain structures are closely observed using scanning electron microscope. The sample geometry and defect/crack morphology are characterized through micro computed tomography (CT). After processing the pixel-level CT data, the fatigue crack initiation and growth behavior are numerically simulated using MFEA-Net and DLPM. The experiments and simulation results provided valuable insights in fatigue mechanism of AM Ti64 alloy.

A well-insulated dark conventional rooftop can be hotter than any other urban surface, including pavements. Since rooftops cover around 20 – 25% of most urban areas, their role in the urban heat island effect is significant. In general, buildings exchange heat with the surroundings in three ways: heat release from the cooling/heating system, air exchange associated with exfiltration and relief air, and heat transfer between the building envelope and surroundings. Several recent studies show that the building envelope generates more heat release into the environment than any other building component.Current advancements in material science have enabled the development of materials and coatings with very high solar reflectance and thermal emissivity, and that can alter their radiative properties based on surface temperature. This dissertation is an effort to quantify the impact of recent developments in such technologies on urban air. The current study addresses three specific unresolved topics: 1) the relative importance of rooftop solar reflectance and thermal emissivity, 2) the role of rooftop radiative properties in different climates, and 3) the impact of temperature-adaptive exterior materials/coatings on building energy savings and urban cooling. The findings from this study show that the use of rooftop materials with solar reflectance above 0.9 maintain the surface temperature below ambient air temperature most of the time, even when the materials have conventional thermal emissivity (0.9). This research has demonstrated that for hot cities, rooftops with high solar reflectance and thermal emittance maximize building energy savings and always cool the surrounding air. For moderate climate regions, high solar reflectance and low thermal emittance result in the greatest building energy cost savings. This combination of radiative properties cools the air during the daytime and warms it at night. Finally, this research found that temperature-adaptive materials could play a significant role in reducing utility costs for poorly insulated buildings, but that they heat the surrounding air in the winter, irrespective of the rooftop insulation. Through the detailed analysis of building façade radiative properties, this dissertation offers climate-specific design guidance that can be used to simultaneously optimize energy costs while minimizing adverse warming of the surrounding environment.

The objective of this dissertation is to study the optical and radiative properties of inhomogeneous metallic structures. In the ongoing search for new materials with tunable optical characteristics, porous metals and nanowires provides an extensive design space to engineer its optical response based on the morphology-dependent phenomena.This dissertation firstly discusses the use of aluminum nanopillar array on a quartz substrate as spectrally selective optical filter with narrowband transmission for thermophotovoltaic systems. The narrow-band transmission enhancement is attributed to the magnetic polariton resonance between neighboring aluminum nanopillars. Tuning of the resonance wavelengths for selective filters was achieved by changing the nanopillar geometry. It concludes by showing improved efficiency of Gallium-Antimonide thermophotovoltaic system by coupling the designed filter with the cell. Next, isotropic nanoporous gold films are investigated for applications in energy conversion and three-dimensional laser printing. The fabricated nanoporous gold samples are characterized by scanning electron microscopy, and the spectral hemispherical reflectance is measured with an integrating sphere. The effective isotropic optical constants of nanoporous gold with varying pore volume fraction are modeled using the Bruggeman effective medium theory. Nanoporous gold are metastable and to understand its temperature dependent optical properties, a lab-scale fiber-based optical spectrometer setup is developed to characterize the in-situ specular reflectance of nanoporous gold thin films at temperatures ranging from 25 to 500 oC. The in-situ and the ex-situ measurements suggest that the ii specular, diffuse, and hemispherical reflectance varies as a function of temperature due to the morphology (ligament diameter) change observed. The dissertation continues with modeling and measurements of the radiative properties of porous powders. The study shows the enhanced absorption by mixing porous copper to copper powder. This is important from the viewpoint of scalability to get end products such as sheets and tubes with the requirement of high absorptance that can be produced through three-dimensional printing. Finally, the dissertation concludes with recommendations on the methods to fabricate the suggested optical filters to improve thermophotovoltaic system efficiencies. The results presented in this dissertation will facilitate not only the manufacturing of materials but also the promising applications in solar thermal energy and optical systems.

Siloxane, a common contaminant present in biogas, is known for adverse effects on cogeneration prime movers. In this work, the solid oxide fuel cell (SOFC) nickel-yttria stabilized zirconia (Ni-YSZ) anode degradation due to poisoning by siloxane was investigated. For this purpose, experiments with different fuels, different deposition substrate materials, different structure of contamination siloxane (cyclic and linear) and entire failure process are conducted in this study. The electrochemical and material characterization methods, such as Electrochemical Impedance Spectroscopy (EIS), Scanning Electron Microscope- Wavelength Dispersive Spectrometers (SEM-WDS), X-ray Photoelectron Spectroscopy (XPS), X-ray Diffraction (XRD), and Raman spectroscopy, were applied to investigate the anode degradation behavior. The electrochemical characterization results show that the SOFCs performance degradation caused by siloxane contamination is irreversible under bio-syngas condition. An equivalent circuit model (ECM) is developed based on electrochemical characterization results. Based on the Distribution of Relaxation Time (DRT) method, the detailed microstructure parameter changes are evaluated corresponding to the ECM results. The results contradict the previously proposed siloxane degradation mechanism as the experimental results show that water can inhibit anode deactivation. For anode materials, Ni is considered a major factor in siloxane deposition reactions in Ni-YSZ anode. Based on the results of XPS, XRD and WDS analysis, an initial layer of carbon deposition develops and is considered a critical process for the siloxane deposition reaction. Based on the experimental results in this study and previous studies about siloxane deposition on metal oxides, the proposed siloxane deposition process occurs in stages consisting of the siloxane adsorption, initial carbon deposition, siloxane polymerization and amorphous silicon dioxide deposition.

Radiation heat transfer can surpass blackbody limit when distance between the hot emitter and cold receiver is less than the characteristic wavelength of electromagnetic radiation. The enhanced radiation heat transfer achieved is also called near-field radiation heat transfer. Several theoretical and experimental studies have demonstrated enhancement in near-field radiation heat transfer for isotropic materials such as silicon carbide (SiC), undoped and doped Si. The enhancement achieved however is narrow-banded. Significant improvement in radiation heat transfer is necessary to satisfy some of the energy demands. So, there is a growing interest to use hyperbolic materials because of its enhancement due to propagating modes. The main objective of the current thesis project is to investigate the control of hyperbolic bands using boron nitride nanotubes (nanostructure of hexagonal boron nitride) for near-field radiative heat transfer. Optical properties of boron nitride nanotubes are calculated using Maxwell-Garnet’s effective medium theory and its corresponding hyperbolic bands are identified. It is observed that the boron nitride nanotubes have only one hyperbolic band located at higher frequencies. Preliminary comparisons of the near-field radiative heat flux calculations with literature are performed using a more general 4×4 transfer matrix method. Due to its high computational time, anisotropic thin film optics is used to calculate near-field radiative heat transfer. Factors contributing to enhancement is investigated. In the end, Spectral allocation ratio, the ratio of heat flux contributed from higher frequencies to the heat flux contributed from lower frequencies is calculated to assess the contribution of each hyperbolic band to total heat flux.

The space industry is rapidly expanding, and components are getting increasinglysmaller leading to the prominence of cubesats. Cubesats are satellites from about coffee mug size to cereal box size. The challenges of shortened timeline and smaller budgets for smaller spacecraft are also their biggest advantages. This benefits educational missions and industry missions a like but can burden teams to be smaller or have less experience. Thermal analysis of cubesats is no exception to these burdens which is why this thesis has been written to provide a guide for conducting the thermal analysis of a cubesat using the Deployable Optical Receiver Aperture (DORA) mission as an example. Background on cubesats and their role in the space industry will be examined. The theoretical side of heat transfer necessary for conducting a thermal analysis will be explored. The DORA thermal analysis will then be conducted by constructing a thermal model in Thermal Desktop software from the ground up. Insight to assumptions for model construction to move accurately yet quickly will be detailed. Lastly, this fast and quick method will be compared to a standard finite element mesh model to show quality results can be achieved in significantly less time.

Windows are one of the most significant locations of heat transfer through a building envelope. In warm climates, it is important that heat gain through windows is minimized. Heat transfer through a window glazing occurs by all major forms of heat transfer (convection, conduction, and radiation). Convection and conduction effects can be limited by manipulating the thermal properties of a window’s construction. However, radiation heat transfer into a building will always occur if a window glazing is visibly transparent. In an effort to reduce heat gain through the building envelope, a window glazing can be designed with spectrally selective properties. These spectrally selective glazings would possess high reflectivity in the near-infrared (NIR) regime (to prevent solar heat gain) and high emissivity in the atmospheric window, 8-13μm (to take advantage of the radiative sky cooling effect). The objective of this thesis is to provide a comprehensive study of the thermal performance of a visibly transparent, high-emissivity glass window. This research proposes a window constructed by coating soda lime glass in a dual layer consisting of Indium Tin Oxide (ITO) and Polyvinyl Fluoride (PVF) film. The optical properties of this experimental glazing were measured and demonstrated high reflectivity in the NIR regime and high emissivity in the atmospheric window. Outdoor field tests were performed to experimentally evaluate the glazing’s thermal performance. The thermal performance was assessed by utilizing an experimental setup intended to mimic a building with a skylight. The proposed glazing experimentally demonstrated reduced indoor air temperatures compared to bare glass, ITO coated glass, and PVF coated glass. A theoretical heat transfer model was developed to validate the experimental results. The results of the theoretical and experimental models showed good agreement. On average, the theoretical model demonstrated 0.44% percent error during the daytime and 0.52% percent error during the nighttime when compared to the experimentally measured temperature values.

The thermal conductivity of cadmium sulfide (CdS) colloidal nanocrystals (NCs) and magic-sized clusters (MSCs) have been investigated in this work. It is well documented in the literature that the thermal conductivity of colloidal nanocrystal assemblies decreases as diameter decreases. However, the extrapolation of this size dependence does not apply to magic-sized clusters. Magic-sized clusters have an anomalously high thermal conductivity relative to the extrapolated size-dependence trend line for the colloidal nanocrystals. This anomalously high thermal conductivity could probably result from the monodispersity of magic-sized clusters. To support this conjecture, a method of deliberately eliminating the monodispersity of MSCs by mixing them with colloidal nanocrystals was performed. Experiment results showed that mixtures of nanocrystals and MSCs have a lower thermal conductivity that falls approximately on the extrapolated trendline for colloidal nanocrystal thermal conductivity as a function of size.

Vanadium-dioxide-based devices show great switchability in their optical properties due to its dramatic thermochromic phase transition from insulator to metal, but generally have concerns due to its relatively high transition temperature at 68 °C. Doping the vanadium dioxide with tungsten has been shown to reduce its transition temperature at the cost lower optical property differences between its insulating and metallic phases. A recipe is developed through parametric experimentation to fabricate tungsten-doped vanadium dioxide consisting of a novel dual target co-sputtering deposition, a furnace oxidation process, and a post-oxidation annealing process. The transmittance spectra of the resulting films are measured via Fourier-transform infrared spectroscopy at different temperatures to confirm the lowered transition temperature and analyze their thermal-optical hysteresis behavior through the transition temperature range. Afterwards, the optical properties of undoped sputtered vanadium films are modeled and effective medium theory is used to explain the effect of tungsten dopants on the observed transmittance decrease of doped vanadium dioxide. The optical modeling is used to predict the performance of tungsten-doped vanadium dioxide devices, in particular a Fabry-Perot infrared emitter and a nanophotonic infrared transmission filter. Both devices show great promise in their optical properties despite a slight performance decrease from the tungsten doping. These results serve to illustrate the excellent performance of the co-sputtered tungsten-doped vanadium dioxide films.