Intermolecular complexes between H₂O and atmospheric species HO, HO₂, H₂O₂, O₃, NO and NO₂ have been studied by ab initio molecular orbital methods. The studies have been performed to the MP2 theory level by using 4-31G, 6-31G, D95, 6-31G**, D95**, 6-311G**, 6-311+G**, 6-311++G**, 6-311+G(2d,lp) and 6-311+G(2d,2p) basis sets. The geometries were fully optimized. The vibrational frequencies were calculated. The Basis Set Superposition Error (BSSE) were estimated. Finally, the binding energies of the complexes were predicted with other thermochemical properties. The binding energies of H₂O•HO, H₂O•HO₂, H₂O•H₂O₂, H₂O•O₃, H₂O•NO and H₂O•NO₂ are estimated to be 5.7±0.6, 8.9±1.0, 7.3±1.3, 1.8±0.2, 1.17 (no BSSE correction) and 2.98 (no BSSE correction) Kcal/Mol, respectively. The Kcq for dimerization to yield H₂O•HO, H₂O•HF, H₂O•HO₂, H₂O•H₂O and H₂O•H₂O₂ are estimated to be 0.11, 2.8, 3.3, 0.067 and 0.11 atm¯¹, respectively. The H₂O•HO, H₂O•HF, H₂O•HO₂, H₂O•H₂O and H₂O•H₂O₂ are quite strongly bonded complexes, while H₂O•O₃, H₂O•NO and H₂O•NO₂ are only weakly bonded complexes. The Kcq changes with temperature are discussed, and their importance in atmospheric chemistry are addressed.

This study examined the effects of household fabric softeners on the thermal comfort and flammability of 100% cotton and 100% polyester fabrics after repeated laundering. Two fabric properties related to thermal comfort, water vapor transmission and air permeability, were examined. A 3 X 2 X 3 experimental design (i.e., 18 experimental cells) was developed to conduct the research. Three independent variables were selected: fabric softener treatments (i.e., rinse cycle softener, dryer sheet softener, no softener), fabric types (i.e., 100% cotton, 100% polyester), and number of laundering cycles (i.e., 1, 15, 25 cycles). Three dependent variables were tested: water vapor transmission, air permeability, and flammability. The test fabrics were purchased from Testfabrics, Inc. To examine the influence of the independent variables and their interactions on each dependent variable, two-way or three-way Analysis of Variance (ANOVA) tests were used to analyze the data. Results in this study showed that both the rinse cycle softener and the dryer sheet softener significantly decreased the water vapor transmission of test specimens to a similar degree. The rinse cycle softener decreased the air permeability of test specimens most and was followed by the dryer sheet softener. The rinse cycle softener increased the flammability of both cotton and polyester fabrics, but the dryer sheet softener had no significant effect on the flammability of both fabric types. Statistical analysis also indicated that the interactions were significant among the independent variables on water vapor transmission, air permeability, and flammability of the test specimens. For example, the rinse cycle softener significantly decreased the water vapor transmission and air permeability of cotton fabric but had no effect on polyester fabric. The dryer sheet softener also decreased the water vapor transmission of cotton fabric but had no effect on polyester fabric, and it had no effect on the air permeability of both cotton and polyester fabrics. In addition, the air permeability of cotton specimens treated with the rinse cycle softener continuously reduced after repeated laundering, but that of polyester fabrics treated with the rinse cycle softener only reduced after 15 laundering cycles and showed no continuous decrease when laundering cycles increased. When the influence of fabric softener treatments on flammability was examined, the results showed that the more the specimens were laundered with the rinse cycle softener, the greater the flammability of the test specimens. However, the dryer sheet softener did not have a significant effect on the flammability of the test fabrics even after repeated laundering. For the polyester fabric, all specimens treated with the dryer sheet softener or no softener passed the standard of children's sleepwear even after 25 laundering cycles, but those treated with the rinse cycle softener did not pass the standard. In conclusion, fabric softener treatment had a significant influence on the thermal comfort (i.e., water vapor transmission and air permeability) and flammability of 100% cotton and 100% polyester fabrics after repeated laundering cycles and the effects were significantly different among the three independent variables (i.e., fabric softener treatments, fabric types, and number of laundering cycles). The applications of these results were also discussed. / Master of Science

Convective cold pools are important modulators of the onset and evolution of deep convection in the tropics. Cold pools are generated by downdrafts and can outlive the storms they originate from to spark new convection. However, most of our understanding of cold pool mechanics comes from high-resolution simulations and a relatively small number of in situ observational studies. This thesis brings novel observational approaches together with climate model data to understand the behavior of cold pools on a global scale and how a mesoscale weather behavior can be accounted for in a climate-scale simulation. First, we leverage a dataset derived from the Advanced Scatterometer (ASCAT) satellite instrument by Garg et al. (2020) to quantify seasonal variations in cold pool activity and their relationship to deep convection across tropical ocean basins. The dataset identifies gradient features (GFs) in the surface wind field, which have been shown to serve as reliable proxies for the boundaries of atmospheric cold pools. We examine the relationship between GFs and climatologies of precipitation, column relative humidity (CRH), and bulk vertical wind shear. We also collocate GFs with precipitation and CRH. High GF frequency, precipitation, and CRH coincide in many regions of the tropics, consistent with our understanding of the physical connections between precipitation and cold pool generation. On the other hand, climatological bulk wind shear is often low in convective regions, and there is a weak inverse correlation between GF frequency and bulk wind shear, while our prior expectation might have been that shear promotes cold pool formation. Compared to GF frequency, GF size shows a weaker relationship with the convective environment, with some of the largest GFs occurring at lower CRH values for a given rainfall rate. In a few exceptional regions and seasons, such as the Indian Ocean in northern hemisphere summer, the region of greatest precipitation does not coincide with the region of greatest GF frequency. These cases also have very high seasonal mean CRH, suggesting that in these regions cold pool formation is suppressed by reduced evaporation of precipitation. Following that, we apply the GF data set to the task of evaluating the realism of the cold pool parameterization in the GISS E3 earth model originally designed by Del Genio et al. (2015). We compare the GF data set to model results from six versions of the GISS model with perturbed parameters. Cold pools generated by the model have significantly different geographic distribution to satellite-observed GFs, particularly in critical convective regions. They also appear to be much less common than GFs, though they have a broadly similar dependence on column water vapor (CWV), especially in terms of size. Finally, we seek to understand the mechanics of the model cold pool parameterization on its own. A subset of high-time resolution model versions is used to deconstruct the behavior of the model parameterization at the scale of individual time steps. Our aim is to see what level of physical realism is associated with the emergent trends seen in the climatological statistics. We find that the model generates cold pool temperature and moisture depressions of similar magnitude to cold pools measured from ships, but tend to dissipate too quickly. Model cold pools also appear to spark increased precipitation, as they are designed to do, but that precipitation appears to come from the stratiform model parameterization, not the moist convection one. Together, these results provide a first opportunity to empirically evaluate a model parameterization originally developed using theory.

Water vapour is the principle source of opacity at infrared wavelengths in the Earth’s atmosphere. In support of site testing for the European Extremely Large Telescope (E-ELT), we have used La Silla and Paranal as calibration sites to verify satellite measurements of precipitable water vapour (PWV). We reconstructed the PWV history over both sites by analysing thousands of archived high-resolution echelle calibration spectra and compared that to satellite estimates for the same period. Three PWV measurement campaigns were conducted over both sites using several independent measurement techniques. Radiosondes were launched to coincide with satellite measurements and provide a PWV reference standard allowing intercomparison between the various instruments and methods. This multi-faceted approach has resulted in a unique data set. Integral to this analysis is the internal consistency provided by using a common atmospheric model. / xvii, 206 leaves : ill. (some col.) ; 28 cm

This document describes the design and deployment of a first generation water vapor density sensing unit, the HumiSense. This device is based on an open, air-filled capacitor which is part of a resonant circuit. The frequency of the resonant circuit mixed with a fixed frequency oscillator is the basis of the method to generate a signal that is associated to the change in water vapor density within the open capacitor with time. The physical testing results were inconclusive given that there were many unresolved artifacts in the data. Several suggestions for improving the device for future device generations were provided. / Graduation date: 2013

This Doctoral thesis is focused on optimizing the design of modern wooden structures. Because this theme is very comprehensive, the work analyzes the distribution of moisture through the building envelope in detail. In the introduction are summarizes the knowledge of the physical processes in the constructions, there are also the properties of wood as a material and basic information about system of timber structures. The next section describes used methodology and experimental measurements realized on an experimental timber house EXDR1. There is specified the principle of measurement based on the SWOT analysis, the use measuring devices or possible solutions in the field of numerical modeling too. Main results and conclusions of the dissertation for technical practice including possibilities of further research are summarized in the final section.

The present work focuses on the sources and transport of water vapor to the La Plata Basin (LPB), and the role of groundwater dynamics on the simulation of hydrometeorological conditions over the basin. In the first part of the study an extension to the Dynamic Recycling Model (DRM) is developed to estimate the water vapor transported to the LPB from different regions in South America and the nearby oceans, and the corresponding contribution to precipitation over the LPB. It is found that more than 23% of the precipitation over the LPB is from local origin, while nearly 20% originates from evapotranspiration from the southern Amazon. Most of the moisture comes from terrestrial sources, with the South American continent contributing more than 62% of the moisture for precipitation over the LPB. The Amazonian contribution increases during the positive phase of El Niño and the negative phase of the Antarctic Oscillation. In the second part of the study the effect of a groundwater scheme on the simulation of terrestrial water storage, soil moisture and evapotranspiration (ET) over the LPB is investigated. It is found that the groundwater scheme improves the simulation of fluctuations in the terrestrial water storage over parts of the southern Amazon. There is also an increase in the soil moisture in the root zone over those regions where the water table is closer to the surface, including parts of the western and southern Amazon, and of the central and southern LPB. ET increases in the central and southern LPB, where it is water limited. Over parts of the southeastern Amazon the effects of the groundwater scheme are only observed at higher resolution, when the convergence of lateral groundwater flow in local topographical depressions is resolved by the model. Finally, the effects of the groundwater scheme on near surface conditions and precipitation are explored. It is found that the increase in ET induced by the groundwater scheme over parts of the LPB induces an increase in near surface specific humidity, accompanied by a decrease in near surface temperature. During the dry season, downstream of the regions where ET increases, there is also a slight increase in precipitation, over a region where the model has a dry bias compared with observations. During the early rainy season, there is also an increase in the local convective available potential energy. Over the southern LPB, groundwater induces an increase in ET and precipitation of 13 and 10%, respectively. Over the LPB, the groundwater scheme tends to improve the warm and dry biases of the model. It is suggested that a more realistic simulation of the water table depth could further increase the simulated precipitation during the early rainy season.

Today we face the formidable challenge of meeting the fuel needs of a growing population while minimizing the adverse impacts on our environment. Thus, we search for technologies that can provide us with renewable fuels while mitigating the emission of global pollutants. To this end, use of non-thermal plasma processes can offer novel methods for efficiently and effectively converting carbon dioxide and water vapor into synthesis gas for the production of renewable fuels. Particularly, non-thermal plasma technologies offer distinct advantages over conventional methods including lower operating temperatures, reduced need for catalysts and potentially lower manufacturing and operation costs. The non-thermal plasma reactors have been studied for ozone generation, material synthesis, decontamination, thruster for microsatellites, and biomedical applications. This dissertation focuses on producing synthesis gas using a non-thermal, microhollow cathode discharge (MHCD) plasma reactor. The prototype MHCD reactor consisted of a mica plate as a dielectric layer that was in between two aluminum electrodes with a through hole. First, electrical characterization of the reactor was performed in the self-pulsing regime, and the reactor was modeled with an equivalent circuit which consisted of a constant capacitance and a variable, negative differential resistance. The values of the resistor and capacitors were recovered from experimental data, and the introduced circuit model was validated with independent experiments. Experimental data showed that increasing the applied voltage increased the current, self-pulsing frequency and average power consumption of the reactor, while it decreased the peak voltage. Subsequently, carbon dioxide and water vapor balanced with argon as the carrier gas were fed through the hole, and parametric experiments were conducted to investigate the effects of applied voltage (from 2.5 to 4.5 kV), flow rate (from 10 to 800 mL/min), CO₂ mole fraction in influent (from 9.95% to 99.5%), dielectric thickness (from 150 to 450 [mu]m) and discharge hole diameter (from 200 to 515 [mu]m) on the composition of the products, electrical-to-chemical energy conversion efficiency, and CO₂-to-CO conversion yield. Within the investigated parameter ranges, the maximum H2/CO ratio was about 0.14 when H2O and CO₂ were dissociated in different reactors. Additionally, at an applied voltage of 4.5 kV, the maximum yields were about 28.4% for H2 at a residence time of 128 [mu]s and 17.3% for CO at a residence time of 354 [mu]s. Increasing residence time increased the conversion yield, but decreased the energy conversion efficiency. The maximum energy conversion efficiency of about 18.5% was achieved for 99.5% pure CO₂ at a residence time of 6 [mu]s and an applied voltage of 4.5 kV. At the same applied voltage, the maximum efficiency was about 14.8% for saturated CO₂ at a residence time of 12.8 [mu]s. The future work should focus on optimizing the conversion yield and efficiency as well as analyzing the temporal and spatial changes in the gas composition in the plasma reactor. / text

Master of Science / Department of Civil Engineering / Robert J. Peterman / Epoxy polymer overlays have been used for decades on existing bridge decks to protect the deck and extend its service life. The polymer overlay’s ability to seal a bridge deck is now being specified for new construction. Questions exist about the amount of drying time needed to achieve an acceptable concrete moisture content to ensure an adequate bond to the polymer overlay. Current Kansas Department of Transportation (KDOT) specifications for new bridge decks call a 14 day wet curing period followed by 21 days of drying (Kansas DOT, 2007) If not enough drying is provided, the moisture within the concrete can form water vapor pressure at the overlay interface and induce delamination. If too much drying time is provided projects are delayed, which can increase the total project cost or even delay overlay placement until the next spring. A testing procedure was developed to simulate a bridge deck in order to test the concrete moisture content and bonding strength of the overlay. Concrete slabs were cast to test typical concrete and curing conditions for a new bridge deck. Three concrete mixtures were tested to see what effect the water –cement ratio and the addition of fly ash might have on the overlay bond strength. Wet curing occurred at 3 different temperatures (40°F, 73°F, and 100°F) to see if temperature played a part in the bond strength as well. The concrete was then allowed to dry for 3, 7, 14, or 21 days. Five epoxy-polymer overlay systems that had been preapproved by KDOT were each used in conjunction with the previously mentioned concrete and curing conditions. After, the slabs were setup to perform pull-off tests to test the tensile rupture strength. The concrete slabs with the different epoxy overlays were heated to 122-125°F to replicate summer bridge deck temperatures. Half of the pull-off tests were performed when the slabs were heated and half were performed once the slabs had cooled back down to 73°±5°F. Results from the pull-off tests as well as results from a moisture meter taken on the concrete prior to the overlay placement were compared and analyzed. Testing conditions were compared with each other to see which had a larger effect on the epoxy polymer overlay’s bond strength.

Dans un contexte général de réduction de la pollution atmosphérique, l’industrie automobile cherche à augmenter le rendement des moteurs thermiques pour en limiter la consommation et les émissions. Pour satisfaire cet objectif, les températures de combustion sont en constante augmentation, ce qui entraîne une augmentation de la sollicitation thermique de la face d’échappement de ces moteurs. Ces pièces n’étant pas refroidies, elles sont exposées à des températures toujours plus élevées, ce qui nécessite une durabilité à haute température accrue des matériaux. Cette thèse a pour objectif d’évaluer la durabilité des pièces de fonderie de la face échappement telles que les collecteurs, corps de turbine ou turbo collecteurs réalisées en fonte GSSiMo+ et en acier inoxydable moulé 1.4826Nb à des températures supérieures à leur température maximale actuelle d’utilisation. Une première étape a porté sur l’effet de la vapeur d’eau sur l’oxydation de la surface pendant des traitements thermiques continus et cycliques et sur l’évolution associée de la microstructure. La seconde étape a porté sur l’effet de ces traitements thermiques sur les propriétés mécaniques à température ambiante. Enfin, un montage de fatigue thermomécanique par dilatation différentielle entre un support en carbure de silicium et une éprouvette métallique en V a été conçu pour être utilisé sur un banc d’oxydation cyclique sous atmosphère contrôlée afin d’étudier les mécanismes de fissuration et d’endommagement en fatigue thermomécanique ainsi que l’effet de l’environnement sur l’initiation de fissures dans ces conditions. L’augmentation de la température maximale des cycles thermiques appliqués de 700 à 800°C pour la fonte GS SiMo+ et de 850 à 950°C pour l’acier 1.4826Nb a pour principale conséquence une accélération de la perte de section par oxydation et une diminution des propriétés mécaniques du fait de l’évolution de la microstructure. Cette perte de section paroxydation est fortement accélérée en présence de vapeur d’eau. Les essais préliminaires réalisés avec le montage de fatigue thermomécanique ont permis de valider son dimensionnement et de mettre en avant les cycles thermomécaniques pour lesquels l’initiation et la propagation de fissures étaient les plus rapides sur des cycles 300-800°C pour la fonte et 300-950°C pour l’acier.Une plus ample campagne d’essai reste à réaliser pour évaluer les mécanismes de fissuration et l’effet de l’environnement en fonction de la température maximale / Due to tightening environmental standards, the automotive industry is constantly trying to improvethe efficiency of the internal combustion engines in order to increase their fuel economy andreduce their carbon emissions. The main way to meet this goal on a turbocharged engine is toincrease the combustion temperature. This leads to increasing exhaust gas temperature andincreasing thermal loads on exhaust manifolds and turbine housings. These components beinguncooled, their maximum temperature is increasing and require better durability at hightemperature. The main objective of this thesis is to evaluate the durability of SiMo spheroidalgraphite iron (SGI) and 1.4826Nb cast stainless steel (CSS) at higher temperature than the actualmaximum operating temperature in order to evaluate their use on engines with higher power. Thefirst part of the study focuses on the effect of water vapor on high temperature oxidation duringcontinuous and cyclic heat treatments and on the underlying microstructure evolution. The secondpart focuses on the effect of these heat treatments on the tensile properties at room temperature.At last, a thermomechanical fatigue test setup has been designed to study the effect ofenvironment on crack initiation during thermomechanical fatigue (TMF). This setup uses thedifference in thermal expansion between silicon carbide and metallic materials to generatemechanical strain and stress in a V-shaped specimen during thermal cycling in a controlledatmosphere cyclic oxidation test bench. Increasing maximum temperature during thermal cyclingfrom 700 to 800°C for SiMo SGI and from 850 to 950°C for 1.4826Nb CSS leads to acceleratedwall thickness loss due to increased oxidation and to a drop in mechanical properties duemicrostructure evolution. The wall thickness loss is further accelerated in humid atmosphere.Preliminary tests performed with the TMF setup demonstrated the design is valid and enabled toidentify the thermomechanical loads leading to faster crack initiation and propagation for 300-800°C thermal cycling of SiMo SGI and 300-950°C thermal cycling of 1.4826Nb CSS. More testsare necessary to identify the crack initiation mechanisms according to the maximum temperatureof the thermal cycle and the atmosphere