The response to climate change must include decisive and collaborative solutions that minimize global CO₂ emissions and enable a shift to low-carbon energy (renewable electricity) and CO₂-derived chemicals and fuels. A major challenge of minimizing fossil fuel use is producing critical chemicals and fuels for heavy industry and transportation in novel ways. These traditionally fossil-derived products can be derived from CO₂ that is captured from point sources or the atmosphere. Reactive CO₂ capture is an emerging area of research that focuses on developing materials and processes for CO₂ capture and in situ conversion to valuable chemicals or fuels. By combining these two steps, costly and energy-intensive steps of conventional integrated capture and conversion schemes are eliminated, including sorbent regeneration, CO₂ purification, pressurization, and transportation. These operations typically drive up the cost of capture and conversion processes, making them less economically attractive. The dual function material (DFM) is an Al₂O₃-supported, nano-dispersed catalyst and sorbent combination that demonstrates both capture and catalytic conversion properties, making reactive capture possible. Feasibility of the 1% Ru, 10% “Na₂O”/Al₂O₃ DFM for CO₂ direct air capture (DAC) and in situ catalytic methanation (DACM) has been demonstrated in previous work. Recent work has prioritized advanced laboratory testing and laboratory aging of this DFM under a variety of simulated ambient capture climates to assess the advantages and limitations of the material. A monolith was used as a structured support for the DFM to minimize reactor pressure drop, a particularly relevant challenge for DAC applications where large volumes of air must be processed to separate the small volume of CO₂ (~ 400 ppm). Findings from DFM monolith studies (1% Ru, 10% “Na₂O”/Al₂O₃//monolith) were shared with an engineering partner to support scale up efforts. Laboratory-simulated DACM cycles consisted of DAC performed at various real-world simulated ambient conditions followed by catalytic methanation, where the DFM was heated to 300°C in 15% H₂/N₂. Simulated DAC included O2 and humidity, and a surprising finding showed significant enhancement of CO₂ adsorption due to humidity in the capture feed. The maximum CO₂ capture capacity of the DFM monolith was measured to be 4.4 wt% (based on the weight of DFM material) at 25°C with 2 mol% H₂O in the DAC feed. Aging studies revealed consistent CO₂ capture and CH₄ production after over 450 hours of cyclic DACM testing that included simulated ambient conditions. No signs of deactivation of either the “Na₂O” sorbent or Ru catalyst were observed. The light-off temperature (indicative of kinetic control) observed for catalytic methanation was constant between fresh and aged cycles. These findings verified the qualifications of the 1% Ru, 10% “Na₂O”/Al₂O₃//monolith for the DACM application and supported further advanced bench and pilot plant testing by our engineering collaborator. Additional parametric studies were conducted to evaluate the effects of varying humidity during DAC and revealed that a higher H₂O concentration in the DAC feed correlates with greater CO₂ captured and converted with no evidence of competitive adsorption between CO₂ and H₂O. Additionally, it was found that temperature changes within ambient range (0 – 40°C) played little role in varying CO₂ captured under dry conditions, whereas moisture was found to be a major driver of capture capacity. Furthermore, stable performance at a reference condition was always achieved after excursions to varying ambient conditions. DACM tests revealed 30 – 40% of captured CO₂ desorbs during the temperature swing step, which was attributed mainly to the slow heating rate and low H₂ content (15%) required for safe laboratory operation. Unreacted CO₂ was eliminated by shortening the DAC step and engaging partial capture capacity of the DFM. This mode of cycling is more representative of that which would be carried out at scale, as shorter adsorption durations capitalize on the fastest adsorption kinetics exhibited by a capture material. Consistent with reported literature, findings suggest that CO₂ is preferentially adsorbed to stronger capture sites at the onset of DAC that are better able to retain CO₂ during heat up. Though the DFM is not fully utilized, these partial capacity cycles demonstrated higher conversions to CH₄ and a more efficient use of the material that will require less downstream purification at scale.

Целью работы является высокотемпературный синтез ультрадисперсной кислородо-дефицитной керамики оксида алюминия и исследование люминесцентных свойств полученных керамик при импульсном возбуждении пучком электронов. В результате высокотемпературного синтеза исследуемого объекта получена ультрадисперсная керамика оксида алюминия. Показано, что интенсивный синтез в восстановительной среде приводит к изменению массы и геометрических параметров вследствие термического травления образцов. Исследована пористость синтезируемых образцов и построены диаграммы распределения частиц по размерам. Обнаружен рост интенсивности катодолюминесценции F-центров керамик, синтезированных в восстановительной среде в присутствие углерода, с увеличением температуры и длительности изотермического нагрева. Полученные керамики являются перспективными для их применения в дозиметрии ионизирующих излучений и радиотехнике. Проведен анализ экологических рисков и соблюдения правил безопасности жизнедеятельности при экспериментальных исследованиях. / The goal of current paper is to synthesize an ultrafine oxygen-deficient aluminum oxide ceramic by high-temperature technique and to study its luminescent properties by pulsed cathodoluminescence (PCL). Ultra dispersive aluminum oxide ceramics were obtained after high-temperature synthesis. It was shown that an intensive synthesis in a reducing atmosphere causes mass and geometric parameters changes due to samples thermal etching. The porosity of synthesized samples and constructed particle size distribution diagram were investigated. The growth of ceramics samples F-centers cathodoluminescence intensity due to temperature increase and duration of isothermal heating were observed. Ones were synthesized in reducing ambient with carbon presence Obtained ceramics samples are promising material for application in dosimetry of ionizing radiation and radio engineering. Analysis of environmental risks and health and safety regulations in experimental environment was carried out.

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Mn oxides have high redox potentials and are known to be very reactive, rendering many contaminants susceptible to degradation via oxidation. Although Mn oxides typically occur as mixtures with other metal oxides (e.g., Fe, Al, and Si oxides) and natural organic matter (NOM) in soils and aquatic environments, most studies to date have studied the reactivity of Mn oxides as a single oxide system. This study, for the first time, examined the effect of representative metal oxides (Al2O3, SiO2, TiO2, and Fe oxides) and NOM or NOM-model compounds (Aldrich humic acid (AHA), Leonardite humic acid (LHA), pyromellitic acid (PA) and alginate) on the oxidative reactivity of MnO2, as quantified by the oxidation kinetics of triclosan (a widely used phenolic antibacterial agent) as a probe compound. The study also examined the effect of soluble metal ions released from the oxide surfaces on MnO2 reactivity. In binary oxide mixtures, Al2O3 decreased the reactivity of MnO2 as a result of both heteroaggregation and complexation of soluble Al ions with MnO2. At pH 5, the surface charge of MnO2 is negative while that of Al2O3 is positive resulting in intensive heteroaggregation between the two oxides. Up to 3.15 mM of soluble Al ions were detected in the supernatant of 10 g/L of Al2O3 at pH 5.0 whereas the soluble Al concentration was 0.76 mM in the mixed Al2O3 + MnO2 system at the same pH. The lower amount of soluble Al in the latter system is the result of Al ion adsorption by MnO2. The experiments with the addition of 0.001 to 0.1 mM Al3+ to MnO2 suspension indicated the triclosan oxidation rate constant decreased from 0.24 to 0.03 h-1 due to surface complexation. Fe oxides which are also negatively charged at pH 5 inhibited the reactivity of MnO2 through heteroaggregation. The concentration of soluble Fe(III) ions ( 4 mg-TOC/L or [alginate/PA] > 10 mg/L, a lower extent of heteroaggregation was also observed due to the negatively charged surfaces for all oxides. Similar effects on aggregation and MnO2 reactivity as discussed above were observed for ternary MnO2‒Al2O3‒NOM systems. HAs, particularly at high concentrations (2.0 to 12.5 mg-C/L), alleviated the effect of soluble Al ions on MnO2 reactivity as a result of the formation of soluble Al-HA complexes. Alginate and PA, however, did not form soluble complexes with Al ions so they did not affect the effect of Al ions on MnO2 reactivity. Despite the above observations, the amount of Al ions dissolved in MnO2+Al2O3+NOM mixtures was too low, as a result of NOMs adsorption on the surface to passivate oxide dissolution, to have a major impact on MnO2 reactivity. In conclusion, this study provided, for the first time, a systematical understanding of the redox activity of MnO2 in complex model systems. With this new knowledge, the gap between single oxide systems and complex environmental systems is much narrower so that it is possible to have a more accurate prediction of the fate of contaminants in the environment. / Civil Engineering

The research presented here investigates the effects of laser trimming on the state of stress in alumina Al₂O₃ hybrid microelectronics substrates. Evaluation of stress was performed using x-ray diffraction residual stress analysis and dynamic strain measurements using strain gages before and after laser trimming. X-ray diffraction measurements were carried out in both the longitudinal and transverse directions on the front and back sides of the substrates. The dynamic strain measurements were performed in situ with strain gages attached to the bottom of the substrates while the substrates were trimmed with a 400 watt YAG laser. The substrates were characterized using optical microscopy, scanning electron microscopy / energy dispersive x-ray analysis (SEM/EDAX), electron probe microanalysis (EPMA) and electron spectroscopy for chemical analysis (ESCA). The results from these characterization steps gave results for fractography (optical), surface and bulk composition (SEM/EDAX), chemical composition (ESCA) and phase analysis (EPMA). Results show that laser trimming produces stress gradients which are generally tensile in nature and could have deleterious effects on the mechanical integrity of the substrates if used in hybrid microelectronic applications. Furthermore the stress distribution across the substrates was found to be uniformly distributed showing no peak stresses near the heat affected zone (HAZ) boundary. Phase analysis determined that the substrates contained a magnesium aluminum spinel phase (MgAl₂O₄) and that the glass and pore phases are randomly distributed in the substrates. This could have some overall effect on the state of residual stress in the substrates after they have been laser trimmed. / Master of Science

The research focus was to determine diffusion mechanisms responsible for densification behavior of SHS produced Al2O3/TiB2 Ceramic Matrix Composites (CMCs). Previous research has shown SHS produced Al₂O₃/TiB₂ composites exhibited unique microstructural properties that contributed to high strength, fracture toughness, and hardness properties. Pressureless densification of SHS produced Al₂O₃/TiB₂ composites would provide a cost savings because the equipment for pressureless densification is less expensive and less complicated than equipment required for densification with pressure. Models for sintering of CMCs and calculation of Sintering Time Constants (STC) were used to predict the densification behavior of the SHS produced Al2O3/TiB2 composite. The Levin, Dirnfeld, Shwam equation was used to determine the Rate Controlling Diffusion Mechanism (RCDM) and activation energy for sintering. X-Ray Diffraction (XRD) analysis of the as-milled reaction product powder revealed the presence of an aluminum borate (Al₁₈B₄O₃₃) as a third phase, as well as, in pressureless heat treated samples. Based on experimental results and analysis, it seemed possible the Al₁₈B₄O₃₃ compound may have formed by reaction of Al₂O₃ with TiB2 along their interfaces. Aluminum borates have been observed to form Al₁₈B₄O₃₃ (s) + B₂O₃ (l) at temperatures above 1000°C. The RCDM for densification of SHS produced Al₂O₃/TiB₂ was found to be liquid phase diffusion with volume diffusion also likely being active during densification. In addition, Al₁₈B₄O₃₃ seemed to be the preferred compound formed during oxidation. Further research should be performed to control formation of Al₁₈B₄O₃₃; as well as, on the oxidation behavior of the SHS produced Al2O3/TiB2. / Master of Science

The purpose of this study was to investigate the supported catalyst of the type CuO-Al₂O₃ which has been described by Lockwood and Frazer (13). This type of catalyst is unique in that it has a high activity at low temperatures, is suitable for use at high temperatures and has been reported to be truly catalytic in the oxidation of carbon monoxide. Lockwood and Frazer (15) have described the preparation of a catalyst of this type. Their description of the method of preparation and of the quantities of materials used is rather inadequate for an exact duplication of the catalyst which they prepared and studied. The method of procedure used in the study of this catalyst has been to vary both the composition and heat treatment of the catalysts and to observe the subsequent change in catalytic activity. 1. Increasing the copper oxide content of the copper oxide-aluminum catalysts increases the activity of the catalysts at least over the composition range studied. 2. Increasing the temperature to which the copper oxide-aluminum oxide catalysts are heated increases the activity. 3. The temperatures required for the catalysts to exhibit 100% activity are all above 270°C. 4. It was found impossible to reproduce the copper oxide-aluminum catalyst which was prepared by Lockwood and Frazer. 5. A catalyst prepared from pure copper oxide was more active than any of the catalysts which were studied. / M.S.

The unprecedented ability of plasmonic metal nano-structures to concentrate light into deep-subwavelength volumes has propelled their use in a vast array of nanophotonics technologies and research endeavors. They are used in sensing, super-resolution imaging, SPP lithography, SPP assisted absorption, SPP-based antennas, light manipulation, etc. To take full advantage of the attractive capabilities of CMOS compatible low-cost plasmonic structures based on Al and Cu, nanolaminate coatings are investigated to improve their long-term stability in corrosive physiological environments. The structures are fabricated using phase-shifting PDMS masks, e-beam deposition, RIE, Atomic Layer Deposition and Rapid Thermal Annealing. An alternate approach using Nanosphere Lithography (NSL) was also investigated. Films were examined using ellipsometry, atomic force microscopy and transmission measurements. Accelerated in-situ tests of Hafnium Oxide/Aluminum Oxide nanolaminate shells in a mildly pH environment with temperatures akin to physiological environments emulated using PBS show greatly enhanced endurance, with stable structures that last for more than one year. / Master of Science / When light (electromagnetic radiation) interacts with the free (conduction) electrons of a metallic nanostructure it leads to a coupling resulting in collective excitations (oscillations) that lead to strong enhancements of the local electromagnetic fields surrounding the nanoparticles, this phenomenon is called Localized Surface Plasmon Resonance (LSPR) and plasmonics are structures that are capable of exhibiting this phenomenon. The condition for LSPR to occur is that the dimension scale of the structure is less than the wavelength of the electromagnetic radiation interacting with it. This implies that the structure has to be in nanoscale dimensions. LSPR based plasmonic structures are compact, sensitive and can be integrated with electronic devices and can be used in various applications like implantable biological sensors (blood pH sensing, diabetics sensing, etc.), devices that integrate several laboratory testing functionalities on a single chip, studies to determine the dynamics of chemical reactions, increasing the efficiency of solar power generation, etc. LSPR is exhibited by metallic nano-particles like gold, silver, copper and aluminum. Metals like copper corrode at a rapid rate in water at room temperature and hence nano scale structures made from them that can exhibit LSPR cannot be used in higher temperature ionic environments without a protective coating. High density, uniform coatings with less defect density can be deposited using Atomic layer deposition (ALD). In this research Atomic Layer Deposited Aluminum Oxide and Hafnium Oxide nanolaminate structures are explored to increase the long-term stability of plasmonic structures in physiological solutions. In-situ tests are carried out in a Phosphate-buffered Saline (PBS) solution with a pH value of 7.2 (simulating physiological conditions) at a temperature of 37℃ (physiological temperature) and 85.1℃ (accelerated testing). The results demonstrate that the dielectric nano coatings investigated in this project can increase the stability of the plasmonic structures in the corrosive physiological environment from a few days to more than one year.

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