A Differential Mobility Analyzer/Tandem Differential Mobility Analyzer (DMA/TDMA) was used to measure size distributions, hygroscopicity, and volatility during the May 2003 Aerosol Intensive Operational Period at the Central Facility of the Atmospheric Radiation Measurement Southern Great Plains site. Hygroscopic growth factor distributions for particles at eight dry diameters ranging from 0.012 µm to 0.600 µm were measured. These measurements, along with backtrajectory clustering, were used to infer aerosol composition and evolution. The hygroscopic growth of the smallest and largest particles analyzed was typically less than that of particles with dry diameters of about 0.100 µm. Condensation of secondary organic aerosol on nucleation mode particles may be responsible for the minimal growth observed at the smallest sizes. Growth factor distributions of the largest particles typically contained a non-hygroscopic mode believed to be composed of dust. A model was developed to characterize the hygroscopic properties of particles within a size distribution mode through analysis of the fixed-size hygroscopic growth measurements. This model was used to examine three cases in which the sampled aerosol evolved over a period of hours or days. Additionally, size and hygroscopicity information were combined to model the aerosol as a population of multi-component particles. With this model, the aerosol hygroscopic growth factor f(RH), relating the submicron scattering at high RH to that at low RH, is predicted. The f(RH) values predicted when the hygroscopic fraction of the aerosol is assumed to be metastable agree better with measurements than do those predicted under the assumption of crystalline aerosol. Agreement decreases at RH greater than 65%. This multi-component aerosol model is used to derive cloud condensation nuclei (CCN) spectra for comparison with spectra measured directly with two Desert Research Institute (DRI) CCN spectrometers. Among the 1490 pairs of DMA/TDMA-predicted and DRI-measured CCN concentrations at various critical supersaturations from 0.02-1.05%, the sample number-weighted mean R2 value is 0.74. CCN concentrations are slightly overpredicted at both the lowest (0.02-0.04%) and highest (0.80-1.05%) supersaturations measured. Overall, this multi-component aerosol model based on size distributions and size-resolved hygroscopicity yields reasonable predictions of the humidity-dependent optical properties and CCN spectra of the aerosol.

A Differential Mobility Analyzer/Tandem Differential Mobility Analyzer (DMA/TDMA) was used to measure size distributions, hygroscopicity, and volatility during the May 2003 Aerosol Intensive Operational Period at the Central Facility of the Atmospheric Radiation Measurement Southern Great Plains site. Hygroscopic growth factor distributions for particles at eight dry diameters ranging from 0.012 µm to 0.600 µm were measured. These measurements, along with backtrajectory clustering, were used to infer aerosol composition and evolution. The hygroscopic growth of the smallest and largest particles analyzed was typically less than that of particles with dry diameters of about 0.100 µm. Condensation of secondary organic aerosol on nucleation mode particles may be responsible for the minimal growth observed at the smallest sizes. Growth factor distributions of the largest particles typically contained a non-hygroscopic mode believed to be composed of dust. A model was developed to characterize the hygroscopic properties of particles within a size distribution mode through analysis of the fixed-size hygroscopic growth measurements. This model was used to examine three cases in which the sampled aerosol evolved over a period of hours or days. Additionally, size and hygroscopicity information were combined to model the aerosol as a population of multi-component particles. With this model, the aerosol hygroscopic growth factor f(RH), relating the submicron scattering at high RH to that at low RH, is predicted. The f(RH) values predicted when the hygroscopic fraction of the aerosol is assumed to be metastable agree better with measurements than do those predicted under the assumption of crystalline aerosol. Agreement decreases at RH greater than 65%. This multi-component aerosol model is used to derive cloud condensation nuclei (CCN) spectra for comparison with spectra measured directly with two Desert Research Institute (DRI) CCN spectrometers. Among the 1490 pairs of DMA/TDMA-predicted and DRI-measured CCN concentrations at various critical supersaturations from 0.02-1.05%, the sample number-weighted mean R2 value is 0.74. CCN concentrations are slightly overpredicted at both the lowest (0.02-0.04%) and highest (0.80-1.05%) supersaturations measured. Overall, this multi-component aerosol model based on size distributions and size-resolved hygroscopicity yields reasonable predictions of the humidity-dependent optical properties and CCN spectra of the aerosol.

Mammals secrete fluids from the sweat glands known as perspiration which helps in thermoregulation. However, sweat can interfere with vision, comfort, grip, and results in malodor due to bacterial action. To combat the aforementioned issues, antiperspirants are widely used personal hygiene products to stop the sweat by blocking the sweat glands. Typically, aluminum salts present in the antiperspirants dissolve in the sweat and create a temporary plug to cut the flow of sweat. However, there has been a long debate going on the safety concerns of aluminum-based antiperspirants. Although there is no concrete evidence to prove the carcinogenicity of aluminum, various studies have also shown that long exposure to aluminum can lead to breast cancer in women. Hence there is a potential need to find aluminum-free alternatives for antiperspirants. Consumers are also showing an increased demand for more natural cosmetic products. The current study presents a novel aluminum-free the hygroscopic gel which can potentially serve as an antiperspirant. A synthetic sweat duct has been developed to mimic the sweating behavior of humans and to test the synthesized gels. Hygroscopic materials readily absorb and/or adsorb water from a humid environment. The hygroscopic gel can cause long-range evaporation of water from the sweat leading tocrystallization of minerals which can ultimately clog the sweat duct and prevent sweating. / Master of Science / We secrete water-like fluid known as sweat which helps us cool down our body. Sweating is also common when we are in the situation of high stress, anxiety, or excitement as a reaction from the body. However, sweating can be disgusting when it results in bad odor or when our armpits look wet. It can also affect our grip, vision, and comfort. Hence we use antiperspirants to stop the sweat and get rid of various issues caused by sweat. These antiperspirants usually have aluminum salts which dissolve in sweat and makes a gel. This gel then clogs our sweat glands and we stop sweating. However, many scientists argue that the presence of aluminum salts in the body can lead to cancer. Although many scientists have also shown that the aluminum salts are completely safe, it is not completely clear. The yellow stains we see on the shirts near the sleeves are also due to these aluminum salts. These days, consumer is also very particular about the contents of the products being used and nobody wants to put any external chemicals inside the body. Here, we present a hydrogel, which is aluminum free and can serve as an alternative to aluminum-based antiperspirants. These hydrogels have a strong affinity to water and can even evaporate nearby water. Hence these hydrogels can be used to evaporate the water from the sweat and causing the salts present in the sweat to crystallize. These naturally present salts in the body can thereby cause the clogging of the sweat duct. Once clogged, it should stop sweating and keep us dry without worrying about safety concerns of aluminum salts.

The intensity of light produced from synchrotrons enables X-ray imaging down to the micron and submicron scale. This high degree of resolution is necessary to study metals in hydrated biological samples, where trace (metal) elements are found in the lowest concentration. Water within these aqueous samples will undergo radiolysis and produce various reactive oxygen species, which degrades the quality of information gathered from the sample during X-ray imaging. Studies have shown that the best way to counter the effects of radiolysis and preserve samples in their metabolic state during X-ray imaging is to keep them cryogenically frozen. We have developed affordable cryostats and novel protocol to not only improve cryo-imaging at current third-generation synchrotrons, but also enable cryo-imaging at existing synchrotrons that have limited accessibility. This dissertation will provide a detailed description of the tasks that were accomplished to contribute to the development cryo-imaging. The first task was the fabrication of a portable cryostage. The cryostage's discreet profile and unique design successfully enabled it to be effortlessly adapted into three beamlines across two different DOE facilities and facilitate multiple imaging modalities, i.e., correlative imaging. With the next task, we explored adding an ice frame about the stage to help reduce the accumulation of frost on the surface of a frozen sample that was explored. The addition of the ice frame significantly improved the imaging of frozen samples, nearly doubling the overall image clarity in comparison to when it was absent. The final task saw the application of a cryostream, in place of a cryostage, to provide a cooled convective flux across the sample for 2D and 3D visualization for cryo X-ray imaging. / Doctor of Philosophy / Synchrotrons are light producing particle accelerators that enable X-ray imaging down to the micron and submicron scale. This high degree of resolution is necessary to study metals in hydrated biological samples, where trace elements are found in low concentrations. The X-ray beam from the synchrotron will force any water within these aqueous samples to undergo radiation induced water decomposition, i.e., radiolysis, and produce hydroxyl radicals that will degrade the quality of information gathered from the sample during X-ray imaging. Early studies have shown that the best counter to the effects of radiolysis, while also preserving samples in their metabolic state during X-ray imaging, is to keep them cryogenically frozen. We have developed affordable cryostats and novel protocols to not only improve cryo-imaging at current third-generation synchrotrons, but also enable cryo-imaging at existing synchrotrons that have limited accessibility. This dissertation will describe, in detail, three tasks that were accomplished. The first task was to the fabrication of a portable cryostage. The cryostage unique design successfully enabled it to be used within different beamlines and for multiple imaging perspectives. With the next task, an ice frame to help reduce the accumulation of frost on the surface of a frozen sample being explored. The ice frame was shown to significantly improve the imaging of frozen samples. The final task saw the application of a cryostream, a jet stream of cold nitrogen gas, to enable an alternative approach for 2D and 3D visualization for cryo X-ray imaging.

Semiconductor wafer manufacturing facilities (fab) must maintain extremely clean air environments to minimize the number of wafers scrapped due to contamination which would result in reduced yields. The fab air is cleaned bypassing it through either HEPA or ULPA filters. A number of airborne fab contaminants may be hygroscopic causing them to exist as a solid or a liquid when in equilibrium with their environment's relative humidity. The effect of relative humidity on such contaminants is poorly documented whether they were to be captured in a filter or deposited on a wafer. The work presented here experimentally characterizes NaCl evolution within HEPA filters when exposed to humidity fluctuations and the effect of humidity on NH4Cl corrosiveness when deposited on cobalt coated wafers with a TiN layer. Successive deliquescence and efflorescence fluctuations were imposed on particles captured on a glass fiber HEPA filter. Scanning Electron Microscopy (SEM) and Environmental SEM (ESEM) studies of the filters showed that the NaCl, under humidity excursions, did not penetrate deep into the filter but deliquesced and effloresced near the top surface of the filter. Pressure drop measurements for filters containing NaCl particles showed differences in pressure drop associated with relative humidity changes. These pressure drop changes suggested some redistribution particle properties. When exposed to a relative humidity of 20%, the NH4Cl particles did not corrode the cobalt wafer beyond the location of the initial deposit. At 61% relative humidity, the surrounding areas of the particles were corroded with a solid artifact left at the original location. At 76% relative humidity the NH4Cl particles were observed to have deliquesced, which is below the expected deliquescence relative humidity. The corrosion of the cobalt wafer was most extensive when the NH4Cl particles had deliquesced. / text

Occupational asthma affects a variety of industry sectors, including agricultural and manufacturing. Currently, asthma pharmaceuticals are delivered via an inhaler and deposited in the respiratory system. The effectiveness of the medication depends partially on where the particle deposits in the lung. The specific aims of this research were to (1) develop a system to measure hygroscopic particle growth under different environmental conditions; (2) determine the accuracy of a hygroscopic growth model during the growth phase of salt particles; and (3) determine whether the large-diameter particles of an aerosol, those that will most likely deposit in the upper airways, can be separated from the smaller particles. Aim 1: A system was developed that satisfied the design criteria to measure particle growth within fractions of a second. The particles growth was measured every 0.03 seconds and had a relative humidity that only varied by a maximum of 1.3% over a 30 second trial. Aim 2: The next step in the research was to determine how well the model compares to reality in the initial growth phase. The model that included the initial growth rate as a saturated solution had a lower root mean square of error (RMSE) than the model that did not include a maximum saturation value. The maximum reduction in RMSE was 0.254. Aim 3: The analysis of a virtual impactor was conducted to see if aerosolized particles can be size separated at a cut point of 2.5 μm. The virtual impactor was designed to have small particles exit the device in one airflow and the large particles exit in a different airflow. Multiple trials were conducted however, there were only two trials that had any size separation between the two exiting flows. From these results, it was determined that large-diameter particles cannot be separated from smaller particles while remaining aerosolized. The cut-point was 2.3 μm, the small particles were split at 50% through both flows, and the flow that was supposed to contain 100% of all of the large particles only contained a maximum of 70%.

Several recent projects in building science have examined the hygric performance of building materials. Most building materials adsorb from and desorb water vapour to their environments. This phenomenon could be used to help control relative humidity fluctuations in buildings, experienced during periods of moisture production such as cooking, washing or bathing. They could also be used to reduce the need for mechanical ventilation and air conditioning to remove excess moisture. To understand how a building material responds to transient changes in relative humidity, testing is required.<p> This thesis outlines the testing performed on gypsum board, a common wall and ceiling finishing material used inside buildings. The effect of paint coatings on the gypsum boards and heat and mass transfer coefficients of the air passing over the gypsum bed was tested. The data produced from these experiments was used to validate several numerical models through an International Energy Agency/Energy Conservation in Buildings and Community Systems (IEA/ECBCS), Annex 41: Whole Building Heat, Air and Moisture Response. The validated models are important for simulating the process of adsorption and desorption in building materials to predict failure in the building envelope and expected indoor air conditions.<p> A sensitivity analysis is also presented which examines the effects of the sorption isotherm and vapour permeability of the gypsum and paints as well as the heat and mass transfer coefficients the boards are exposed to. The sensitivity range used was determined from the tests performed on the gypsum boards and paints which were also performed during the work of Annex 41.<p> The results of this thesis produced a high quality data which can also be used to validate future numerical models. All information required for validation of future models is available such as dimensions of test section, test conditions, material properties and the experimental data.<p> The results show that when designing for passive humidity control in buildings using gypsum boards, the most influential factor is the type of coating or paint applied to the surface. The sensitivity analysis showed that material properties such as vapour permeability and the sorption isotherms, for the expected temperature range, should be well known for increased accuracy of the simulation. The material properties were determined from inter-laboratory testing at 14 different institutions to achieve confident values.<p> The effect of increasing the heat and mass transfer coefficients, over the range of coefficients studied in this thesis, showed negligible differences in the results. The simulated results had very good agreement between the models and were mostly within experimental uncertainty of the measurements.

Several recent projects in building science have examined the hygric performance of building materials. Most building materials adsorb from and desorb water vapour to their environments. This phenomenon could be used to help control relative humidity fluctuations in buildings, experienced during periods of moisture production such as cooking, washing or bathing. They could also be used to reduce the need for mechanical ventilation and air conditioning to remove excess moisture. To understand how a building material responds to transient changes in relative humidity, testing is required.<p> This thesis outlines the testing performed on gypsum board, a common wall and ceiling finishing material used inside buildings. The effect of paint coatings on the gypsum boards and heat and mass transfer coefficients of the air passing over the gypsum bed was tested. The data produced from these experiments was used to validate several numerical models through an International Energy Agency/Energy Conservation in Buildings and Community Systems (IEA/ECBCS), Annex 41: Whole Building Heat, Air and Moisture Response. The validated models are important for simulating the process of adsorption and desorption in building materials to predict failure in the building envelope and expected indoor air conditions.<p> A sensitivity analysis is also presented which examines the effects of the sorption isotherm and vapour permeability of the gypsum and paints as well as the heat and mass transfer coefficients the boards are exposed to. The sensitivity range used was determined from the tests performed on the gypsum boards and paints which were also performed during the work of Annex 41.<p> The results of this thesis produced a high quality data which can also be used to validate future numerical models. All information required for validation of future models is available such as dimensions of test section, test conditions, material properties and the experimental data.<p> The results show that when designing for passive humidity control in buildings using gypsum boards, the most influential factor is the type of coating or paint applied to the surface. The sensitivity analysis showed that material properties such as vapour permeability and the sorption isotherms, for the expected temperature range, should be well known for increased accuracy of the simulation. The material properties were determined from inter-laboratory testing at 14 different institutions to achieve confident values.<p> The effect of increasing the heat and mass transfer coefficients, over the range of coefficients studied in this thesis, showed negligible differences in the results. The simulated results had very good agreement between the models and were mostly within experimental uncertainty of the measurements.

This dissertation describes the use of measured aerosol size distributions and size-resolved hygroscopic growth to examine the physical and chemical properties of several particle classes. The primary objective of this work was to investigate the optical and cloud forming properties of a range of ambient aerosol types measured in a number of different locations. The tool used for most of these analyses is a differential mobility analyzer / tandem differential mobility analyzer (DMA / TDMA) system developed in our research group. To collect the data described in two of the chapters of this dissertation, an aircraft-based version of the DMA / TDMA was deployed to Japan and California. The data described in two other chapters were conveniently collected during a period when the aerosol of interest came to us. The unique aspect of this analysis is the use of these data to isolate the size distributions of distinct aerosol types in order to quantify their optical and cloud forming properties. I used collected data during the Asian Aerosol Characterization Experiment (ACE-Asia) to examine the composition and homogeneity of a complex aerosol generated in the deserts and urban regions of China and other Asian countries. An aircraft-based TDMA was used for the first time during this campaign to examine the size-resolved hygroscopic properties of the aerosol. The Asian Dust Above Monterey (ADAM-2003) study was designed both to evaluate the degree to which models can predict the long-range transport of Asian dust, and to examine the physical and optical properties of that aged dust upon reaching the California coast. Aerosol size distributions and hygroscopic growth were measured in College Station, Texas to investigate the cloud nucleating and optical properties of a biomass burning aerosol generated from fires on the Yucatan Peninsula. Measured aerosol size distributions and size-resolved hygroscopicity and volatility were used to infer critical supersaturation distributions of the distinct particle types that were observed during this period. The predicted cloud condensation nuclei concentrations were used in a cloud model to determine the impact of the different aerosol types on the expected cloud droplet concentration. RH-dependent aerosol extinction coefficients were also calculated.

This thesis develops and evaluates a method to simulate energy consumption and water production for a novel sorption dehumidication pro-cess. The system consists of a chamber comprising a hygroscopic materialand a heating device. The process consists of an adsorption phase anda regeneration phase. For both the regeneration phase and the adsorp-tion phase the model considers the heat distribution by thermal diusionand convection and the water transport by diusion and convection. Forthe regeneration phase the radiation is also considered since the radia-tive power increases with temperature to the power of four. Further, amodel for the condensation process is implemented and a model for thecondensation is suggested. To model the properties of the hygroscopicmaterials, the adsorption curves for SiO2 and AlO2 are investigated. Themodel were evaluated by comparing the simulated values with experimen-tal measurements.The results from the the simulation of the regeneration phase showsa good agreement with experimental data for the power and the energyconsumption even though the simulated values are a bit underestimated,about 10%. The water production is simulated to be about 25% higherthan the measured values. This discrepancy could be explained by aleakage of water vapour that was found in the experimental set up, whichis not considered in the model. This could also explain the underestimatedenergy consumption since the condensation energy in the system is toogreat. To improve the accuracy for the model the water leakage wouldneed to be implemented. The overestimation of water seemed to be thesame for the measurements from the same apparatus.For the adsorption phase a developed model, from an article for ad-sorption in silica, was implemented and tuned for the specic system. Thesimulations are in good agreement with the measurements but could betested further for more certainty.