The formation characteristics of organic-rich shales have proven to be affected by mineralogical composition, total organic content, water concentration, and bedding-plane orientation along with other parameters. However, it is not known with good accuracy what types of influence thermal maturation has on the immature organic matter on geomechanical properties of the formations. In order to quantify the behavior of the oil shale samples under thermal maturation, it is imperative to understand its elastic properties. Thus, it becomes vital to understand the shale’s elastic properties via geomechanical analysis of the selected core samples. In this experimental study, vertical core samples of Mahogany shale in Green River formation from the Anvil Points mine site were selected. These samples possess immature organic content consisting of Type-I kerogen. This study consists of an experimental investigation to comprehend if thermal maturation of immature organic matter has an impact on the geomechanical properties of shale formation. Hydrous pyrolysis experiments were conducted to represent the four different stages of petroleum formation: temperature ranges that represent the bitumen generation (300°C), bitumen generation and initial oil generation (330°C), oil generation (360°C) and the oil cracking to gas (390°C). The samples were tested in these four different temperature states were analyzed later for the changes in their geomechanical properties. The geomechanical properties are evaluated in terms of dynamic elastic properties and resistivity. Unfortunately, the pyrolyzed samples had sustained a heavy loss of their mechanical strength and integrity due to the expansion because of the samples undergoing thermal maturation resulting in their infringement. The weakening prevented us from analyzing the changes in static properties. However, investigation of the changes in dynamic elastic properties and resistivity was possible. The samples were evaluated for dynamic elastic properties before and after pyrolysis to note the variations that it had undergone during the process of thermal maturation that was artificially induced by hydrous pyrolysis. In this research study, we analyze the thermal maturation effects on the geomechanical properties of the oil shale plugs via the analysis of elastic properties and resistivity measurements. The post analysis of the thermally matured core plugs, we found a prominent decrease in the elastic properties such as the Young’s, bulk and shear modulus. We conclude that thermal maturation of organic-rich samples results in mechanical weakening of the sample. Correspondingly, resistivity data were a function of organic richness and temperature. An analytical comparison of the elastic properties of formations across the globe for a comprehensive evaluation of the differences amongst them is also carried out. The results of the study indicate that thermal maturation tends to decrease the mechanical integrity and strength of the rock. The generation of petroleum products due to the maturation of organic products results in pore volume expansion, which causes fracture development and most often the failure of the sample. The behavior of resistivity tends to be dependent on the amount of organic matter expelled during the thermal maturation as well as the amount of organic matter withheld in the core plug, which relatively makes them temperature dependent, as the organic matter expelled is a function of the temperature.

The development of ultrafast laser imaging and micromachining systems for use in integrated material modification and additive manufacturing setups is discussed. This thesis is organized into seven Chapters. The first chapter presents a brief overview and introduction of ultrafast lasers and the benefits of using them for linear and nonlinear microscopy and imaging as well as amplified laser material modification. Chapter two demonstrates the many capabilities of the amplified ultrafast laser machining system in the context of additive manufacturing (AM). The significant results here include the ability to process AM components by creating a surface finish to a certain specification, generating micro-cone structures on the surface for modifying wetting characteristics, and writing nanogratings onto the components for encoding numerical counterfeiting information. Chapter three shows the results of using the ultrafast laser micromachining in combination with spatial frequency modulated imaging (SPIFI) to produce enhanced resolution images in multiple linear and nonlinear modalities. Chapter four extends SPIFI to a previously unknown capability in which the imaging system is constructed in such a way as to acquire interferometric axial sensitivity. This is significant as it opens up the world of surface metrology and imaging the phase content of objects with enhanced resolution. The fifth chapter highlights an imaging system where SPIFI is used to gain enhanced resolution in multiple dimensions simultaneously. Chapter six provides a review of a focusing technique called simultaneous spatial and temporal focusing (SSTF) which can be utilized in a wide range of microscopy and micromachining applications and mitigates many problems ultrafast lasers have when interacting with materials and acquiring images. The final chapter provides general conclusions and an outlook to the future of using amplified ultrafast lasers to provide in-situ process monitoring for additive and subtractive manufacturing.

Fiber-reinforced polymer composites are an intriguing class of engineering materials that are increasingly exploited in the construction, aerospace, and energy sectors. Their high specific properties make them an ideal design choice where traditional engineering materials like metals are too heavy, or where unreinforced polymers are not stiff or strong enough. Furthermore, their anisotropic nature can be exploited for unique applications such as airfoils in aircraft wings or wind turbines. However, most structural composites use thermosetting polymers as their matrix, which presents several issues. Foremost is that thermosets cannot be easily recycled, so massive amounts of composite waste are landfilled at the end of a part’s service life. Secondly, thermoset subcomponents of a larger structure can only be joined using adhesives. Conversely, thermoplastic composites enable recycling after a part is retired from service and facilitate thermal joining of multi-part structures. Liquid infusible thermoplastic resins are beginning to emerge for use in vacuum-assisted resin transfer molding, which is the method of manufacture for wind turbine blades. While infusible thermosetting resins have been well characterized, basic characterization of rheological and kinetic behavior for thermoplastic resins is lacking. The present work provides important experimental development and data aimed at characterization of infusible thermoplastic resin systems. A novel thermoplastic biobased resin system is also developed, which has potential for commercial use.

Underground power cables serve a critical purpose in electric power applications and the electric grid. Many have experienced the frustration of a power outage resulting from a failed cable. This dissertation addresses underground electric power cable ampacity and provides analytical, experimental, and operational test results for underground cables. The motivation for this work stems from challenges facing the industry in determining cable ampacity due to the uncertainty in soil thermal resistivity and soil thermal stability. Analytical results compare multiple software models. Experimental results consist of radial temperature measurements of a buried cable at 3 heat rates for 5 to 21 days. Operational results include measurements of 1 kV DC combiner circuits installed at a 10 MW photovoltaic (PV) power plant. There are numerous methodologies for calculating ampacity that can result in substantial differences. Some of these differences stem from the concern of soil dry-out described as soil thermal stability. This dissertation proposes a method to address using a soil parameter called the Non-Drying Heat Rate. Experimental results indicate that soil around a cable dries based on the magnitude of heat flux and length of time but not directly proportional to the cable diameter as proposed in the Law of Times. A set of experiments was performed on a direct buried cable to compare with the Neher-McGrath method and commercially available software programs. The results show the Neher-McGrath calculations and CYMCAP software outputs overestimated the measured temperature with a mean error of 4% ± 10% for the 6 experiments performed. Soil drying was not predicted to occur based on the non-drying heat rate measurements, and the experimental results confirmed this. A PV power plant design was used as a case study concluding that the measurements for the DC combiner cables were significantly lower than the calculated temperatures. It illustrates the need for an industry accepted standard that provides a clear methodology for addressing soil thermal resistivity and soil thermal stability. This dissertation makes the following contributions: 1. Illustrates the need for an industry standard that addresses soil thermal stability 2. Proposes the non-drying heat rate method to address soil thermal stability 3. Indicates that the Neher-McGrath method is conservative by experimentation 4. Indicates no soil drying occurred during experimentation, as predicted by the non-drying heat rate method 5. Provides cable temperature measurements of an operational PV power plant

Redox cycles with reducible perovskite oxides of the form ABO$_3$ can provide thermochemical energy storage (TCES) with higher energy density and storage temperatures than molten-salt systems for large-scale energy storage in concentrating solar power (CSP). Perovskites from earth abundant cations are desirable for cost-effective solutions, but such materials must demonstrate appropriate thermodynamics for high specific TCES and favorable kinetics for heat-driven reduction and exothermic re-oxidation. This dissertation explores the thermodynamics and kinetics of doped CaMnO$_{3-\delta}$ particles for TCES redox cycles where particles are heated and reduced in N$_2$ ($P_{\text{O2}} \approx 10^{-4}$ bar) to high temperatures (700 to $1000^{\circ}$C) in a solid-particle solar receiver. Chemical and sensible energy stored in the reduced perovskite particles is released as needed to a supercritical CO$_2$ power cycle via re-oxidation and cooling of the material. Thermodynamics of Ca$_{1-x}$Sr$_x$MnO$_{3-\delta}$ ($x=0.05$ and $0.1$) and CaCr$_y$Mn$_{1-y}$O$_{3-\delta}$ ($y=0.05$ and $0.1$) are characterized through thermogravimetric analysis and calorimetry. Results indicate Ca$_{1-x}$Sr$_x$MnO$_{3-\delta}$ compositions can store over 200 kJ kg$^{-1}$ more specific energy storage compared to inert particulate TES media for $T \ge 900^\circ$C; the specific energy storage potential of Ca$_{0.9}$Sr$_{0.1}$MnO$_{3-\delta}$ at $T=900^\circ$C and $P_\text{O2}=10^{-4}$ bar is 706 kJ kg$^{-1}$. Challenges are expected achieving these high values of energy storage in a transport-limited receiver with low residence time for CSP. Redox kinetics are explored in a packed bed reactor with rapid heating capabilities. Results in isothermal tests show that oxidation is significantly faster than reduction. Modeling of packed bed experiments indicate that reduction at $T \ge 800^\circ$C is limited by build-up of oxygen in the gas phase and equilibrium thermodynamics between the solid and gas phases. Long-term redox cycling tests, which simulate a nominal TCES cycle, demonstrate excellent chemical stability for all materials. A standard deviation of 1.9\% on the extent of reduction over 1000 cycles was observed for Ca$_{0.9}$Sr$_{0.1}$MnO$_{3-\delta}$. Modeling efforts of the packed bed experiments allow for characterization of redox kinetics, to be implemented in computational models for system component design. One of the most promising compositions, Ca$_{0.9}$Sr$_{0.1}$MnO$_{3-\delta}$, is implemented in a 1-D receiver model to explore designs and operating conditions for perovskite-based energy storage systems.

Due to growing awareness of environmental impacts and the economic volatility of petroleum, there has been a drastic increase in research towards biomass-derived, sustainable alternatives to petroleum-based processes and products. Notably, commodity chemicals for production of commercial products are exclusively manufactured using feedstocks derived from crude oil refining and currently account for over one third of the worldwide industrial energy demand. As the market demand for petrochemicals are only forecasted to grow, development and advancement of renewable chemical processes is timely. Lignocellulosic biomass presents as a promising alternative source for these aromatic monomers due to the diverse structure and inherently high oxygen content within its components: lignin, cellulose, and hemicellulose. However, significant research is needed in order to realize the use of lignocellulosic biomass as a platform for such chemical products and to push these renewable chemical processes toward industrial and commercial relevance. This work focuses on the catalytic conversions of cis,cis-muconic acid (cis,cis-2,4-hexadienedioic acid), a polyunsaturated C6 dicarboxylic acid that can be microbiologically produced from lignocellulosic biomass streams. The state of catalysis for Diels-Alder reactions involved in upgrading schemes of muconic acid and other biomass-derived products to drop-in and functional alternative commodity monomers is reviewed and evaluated, followed by concentrated studies into the iodine-catalyzed isomerization of cis,cis¬-dimethyl muconate to the Diels-Alder active isomer, trans,trans-dimethyl muconate. Finally, an investigation into the use of atomic layer deposition to enhance the leaching resistance and thermal stability of supported platinum group metal catalysts during condensed phase hydrogenation of muconic acid to adipic acid is presented.

Polymer coating is the most suitable route to protect the metallic surfaces, and it has many purposes including anti-static coating, electromagnetic shielding, anti-reflective and anti-corrosion properties. The long term performance of the metallic surface can be achieved by polymer coatings. The discovery of nanoparticles introduced a new class of materials having higher surface area, high-performance polymer nano-composites appear attainable. For polymer anti-corrosion coatings, in addition to the inherited barrier effect provided by pure polymer films, the film blocking properties can be improved using plate-like nano-fillers. Incorporating fillers, such as graphene nano-platelets, has proven effective as anti-corrosion coating. These coatings usually improve the barrier, mechanical, electrical, optical, rheological, adhesion properties, and resistance against the environmental degradation; However, polymer coatings loaded with graphene displayed long-term enhanced corrosion after erupting the barrier due to inherited electrical conductivity and higher position in the galvanic series. Herein, we exfoliated the hexagonal boron nitride (h-BN) from micro particles into nano-sheets and incorporated it as fillers at different concentration in polymer coatings to enhance the barrier properties. For comparison, graphene nano-platelets were also used. Transmission electron micrographs confirmed the exfoliation of hexagonal boron nitride (h-BN). For exfoliation, we selected two different particles size i.e., 0.07 µm and 5.0 µm. The barrier properties of the coatings were determined in 3.5 % NaCl during different times of immersion, via different electrochemical techniques such as open circuit potential, electrochemical impedance spectroscopy and potentiodynamic. The coatings containing exfoliated h-BN (5.0 µm) particles exhibited improved resistance for longer periods of immersion compared to graphene nano-platelets. The improved corrosion properties can be attributed to the high aspect ratio, plate-like shape and electrically insulated nature of the exfoliated (h-BN) nano-sheets. Specifically, the thesis will be composed of the following steps: 1) preparation of exfoliated hexagonal boron nitride (h-BN) from different particles and synthesis of anti-corrosion coating by dispersion of fillers in polymer matrix via solvent blending, 2) electrochemical techniques for the determination of anticorrosion properties and 3) characterization of exfoliated nano-sheets and nanocomposites.

There is a need to estimate the amount of gas hydrates occurring in the subsurface to establish the potential of natural gas hydrates as, for example, gas resource, geo-hazards, or climate change factors. Controlled laboratory measurements of the seismic properties of pure hydrate and hydrate-bearing sediment are critical to calibrate seismic and more importantly well-logging methods used to estimate gas hydrate accumulations. In general, the presence of hydrates is accompanied by an increase in acoustic velocity and attenuation. The stiffening effect of hydrate formation in unconsolidated sediment strongly depends on hydrate habit: hydrate formation along the grain surfaces increases velocities already at low (Sh ~ 3%) hydrate saturation, whereas hydrate located in the pore space will increase velocity only at high (Sh > 20%) hydrate saturation. I measured ultrasonic P- and S-wave velocity and attenuation in pure tetrahydrofuran (THF) hydrate and THF hydrate-bearing sediment as functions of pressure and temperature. In addition, I measured complex electrical conductivity in a methane hydrate-bearing sandstone during multiple cycles of hydrate formation and dissociation. These combined measurements allow us to understand the effect of hydrate growth on geophysical properties, interactions between sediment – water – hydrate and hydrate – water interfaces, and provide a better understanding of why an increase in hydrate saturation in sediment is accompanied by an increase in wave attenuation in well log data. The ultrasonic measurements show that presence of liquid water between hydrate grains increases attenuation in pure THF hydrates and sand-clay mixtures with varying hydrate saturation (0, 40, 60, and 80%). The observations suggest that trapped water within the hydrate causes the heightened attenuation. A comparison with laboratory data obtained using methane as a hydrate former verifies that acoustic properties of THF hydrate-bearing sediments are comparable to the methane hydrate-bearing sediments found in nature, demonstrating that THF hydrate is an appropriate proxy for methane hydrate. After an increase in pressure from 435 to 2175psi, the loss-diagram shows that samples with various hydrate saturation (0, 40, 60, and 80%) converge to the same linear behavior; as the hydrate saturations increase, the Ki - µi ratios decrease, implying a change in loss mechanisms. These findings help make a better prediction on the effects of hydrate saturation in the subsurface on the sediment properties and can be used to interpret field seismic observations. Similar to acoustic attenuation, electrical conductivity is sensitive to the existence and amount of free water. Hydrate formation results in a thin hydrate layer along the grains. The conductivity data suggest that small layers of unreacted free water are present between the thin layer of hydrate and the sediment grains. This is very important because residual water has a significant effect on wave attenuation. Hydrate formation consumes pure H2O which, during the onset of hydrate formation, results in an increase of temperature due to the exothermic reaction. This is observed as a sudden increase in electrical conductivity. Further cooling results in the observed decrease in conductivity. The reverse effect is detected during hydrate dissociation. Combined, these two processes could be used to monitor the hydrate formation or dissociation front in the subsurface.

As energy demands continuously increase, oil and gas fields delve into ultra-deep water, which leads to severe operating conditions in terms of pressure, temperature, and water salinity. These conditions pose significant flow assurance challenges, especially gas hydrate formation and scale deposition. Reliable prediction of hydrate phase equilibrium at extreme conditions, in terms of high salinity and high pressure, is necessary for development and operations in ultra-deep water oil and gas production. However, according to the literature review, no open literature studies exist for the hydrate phase equilibria in brine systems above 69 MPa (10,000 psia) due to the challenges associated with experimental designs, safety issues and pitting corrosion problems. As a result, current hydrate prediction tools commonly used are not fully benchmarked and become unreliable at the extreme conditions of very high pressure and high salinity. In this study, experimental data on methane hydrate phase equilibria containing electrolytes, sodium chloride (NaCl), potassium chloride (KCl), and ammonium chloride (NH4Cl) were measured for concentrations up to about 10 wt% at pressure below 10.3 MPa through both isochoric and differential scanning calorimetry (DSC) method with stepwise heating. The results from both methods show good agreement with each other, which proves the accuracy and reliability of experimental methods and measurements. Moreover, the effect of the cation in the electrolyte on the hydrate inhibition strength is identied through the measurements, showing that hydrate inhibition strength by the sodium cation was slightly stronger than that of potassium and ammonium cations due to smaller ionic size for Na+. With validating the reliability of both methods used for measurement of hydrate phase equilibria and identifying the limitation of DSC method in salt concentration, a unique system capable to operate up to 207 MPa has been designed and set up considering safety issues and corrosion problems to measure hydrate dissociation conditions with isochoric method. Due to no data in open literature, the measurements of both structure I and structure II hydrate in single and mixed salts, including NaCl, KCl, CaCl2, MgCl2 and CaBr2, as well as mixed organic inhibitor and salts, such as MEG and CaBr2, become valuable for benchmarking existing prediction tools and improving prediction methods. In addition, the increased stability of methane hydrate at high pressure is discovered through the measurement of methane hydrate phase equilibria with fresh water. It is explained and understood by studying the effect of pressure on macroscopic and microscopic properties of water, methane gas and hydrate through both thermodynamic calculations and molecular simulations. As the interplay of hydrates and salt precipitation is fundamentally important due to the possible co-precipitation of two solids, both phase behavior and kinetics for gas hydrates formation/dissociation are studied by the developed experimental system. The measurements of both three phase (liquid – hydrates – gas) and four-phase (liquid – hydrates – solid salts – gas) equilibria with under-saturated and over-saturated NaCl and KCl solutions, separately, elucidates that the equilibrium boundary moves to lower temperature and higher pressure as the salt concentration increased up to the limit of saturation in the solution, and was unchanged from the conditions at saturation with four phases (liquid – hydrates – solid solids – gas) in equilibrium. Moreover, observed unusual inflection points in the pressure trace as a factor of time for the kinetic experiments, demonstrating that (i) hydrates can still form even with salt precipitated and (ii) the formation of hydrates and salt precipitation are competing effects. Finally, to bridge the gap between the measured data and its applicability, a simple but robust correlation (Hu-Lee-Sum correlation) has been developed to capture the hydrate suppression temperature at a given pressure, for not only high salinity brines, but also systems with mixed thermodynamic hydrate inhibitors (THIs). Due to its inherent property of generality and simplicity, it is a useful tool for the flow assurance engineer to accurately estimate hydrate dissociation temperature at given conditions with the average absolute deviation smaller than 2.0 K. Therefore, this comprehensive study, including measurements and prediction of hydrate phase equilibria, as well as kinetic experiments of hydrate growth rate, at extreme conditions, in terms of high pressure, high salinity and mixture of inhibitors, plays an important role on ultra-deepwater oil and gas production which go beyond hydrate management in pipe flow, such as, setting depth of surface-controlled subsurface safety valve (SCSSV) and identification of effective risk mitigation.

No existing research provides an integrated analysis of the key parameters that contribute to long-runout landslides in the Western United States. This study begins the task by assembling a dataset of geological, topographical, and hydrological parameters for landslides from eight study areas. Six measures of mobility were analyzed and two (landslide height drop to runout length ratio, H/L and landslide runout length, L) were selected for further use. Analysis of the correlations of the measured parameters with H/L and L was performed to quantify how well they predict these two mobility measures. The initial slope angle was found to match H/L for small landslides that did not experience a break in slope. Landslides in concave topography, landslides on previously moved material, and landslides in confined topography were found to possess lower H/L values, indicating higher mobility. Finally, landslides occurring on previously moved material and landslides in confined topography were found to possess larger values of L.