Doctor of Philosophy / Department of Chemistry / Kenneth J. Klabunde / For solar environmental remediation, a new generation of nanosized (< 10 nm) titanium dioxide photocatalysts codoped with metals and nonmetals, or metals only were prepared by the xero-gel and aero-gel methods. For silver or cobalt-based xero-gel titanium dioxide photocatalysts, photoactivities tests revealed that codoping of titanium dioxide with a metal (1% Ag or 2% Co) and nonmetals (carbon and sulfur) is necessary to achieve high-activities for acetaldehyde degradation under visible light (wavelength > 420 nm). It was concluded that high visible-light-activities for acetaldehyde degradation over codoped titanium dioxide were attributed to an interplay of anatase crystallinity, high-surface area, reduced band-gap (< 3.0 eV), uniform dispersion of doped metal ions, and suppressed recombination rate of photogenerated electron-hole pairs. Moreover, the nature and amount of codoped metals play a significant role in visible-light-induced photocatalysis. Metals (Al, Ga, and In) doped/codoped titanium dioxide photocatalysts were prepared by the aero-gel method. The photocatalytic studies showed that activities of metal doped/codoped photocatalysts under UV light (wavelength < 400 nm) were found to be dependent on pollutants. Indium demonstrated beneficial effects in both textural and photocatalytic properties. Gallium and indium codoped titanium dioxide photocatalysts displayed even better performance in the CO oxidation reaction under UV light. Notably, titanium dioxide codoped with Ga, In, and Pt, exhibited unique photoactivities for the CO oxidation under both UV and visible light irradiation, indicating that this system could have promise for the water-gas shift reaction for hydrogen production. Silver-based nanostructured titanium dioxide samples were developed for killing human pathogens (Escherichia coli cells and Bacillus subtilis spores). Biocidal tests revealed that silver, carbon, and sulfur codoped titanium dioxide nanoparticles (< 10 nm) possess very strong antimicrobial actions on both E. coli (logarithmic kill > 8) and B. subtilis spores (logarithmic kill > 5) for 30 minute exposures in dark conditions compared with Degussa P25. It was believed that the carbon and sulfur codoped titanium dioxide support and Ag species acted synergistically during deactivation of both E. coli and B. subtilis spores. Thus, titanium dioxide codoped with silver, carbon, sulfur can serve as a multifunctional generic biocide and a visible- light-active photocatalyst.

Master of Science / Department of Mechanical and Nuclear Engineering / William L. Dunn / A prototype system for detecting explosives at standoff distances, using a signature based radiation scanning approach, is being developed at Kansas State University. The prototype will incorporate both a machine x-ray source and a machine neutron source to generate signatures from unknown samples of material. These signatures can be compared to templates measured or calculated from known explosive samples using a figure-of-merit. The machine neutron source uses the fusion of deuterium and tritium to create 14.1 MeV neutrons. Due to its radioactivity, the tritium must be sealed within the system. A new method of controlling the gas pressure with the DT generator was developed using a Zr-V-Fe getter supplied by a commercial firm. The shielding and collimation of the 14.1 MeV neutron source is accomplished using layers of steel, high-density polyethylene and borated high-density polyethylene. This thesis describes the development of the gas control method for the sealed neutron source, design studies for the shielding and collimation of the neutron source and modifications made to the building in which the prototype is being housed.

Doctor of Philosophy / Department of Civil Engineering / Mustaque Hossain / The engineers from the Kansas Department of Transportation (KDOT) often have to decide whether or not to accept non-conforming Superpave mixtures during construction. The first part of this study focused on estimating lives of deficient Superpave pavements incorporating nonconforming Superpave mixtures. These criteria were based on the Hamburg Wheel-Tracking Device (HWTD) test results and analysis. The second part of this study focused on developing accelerated mix testing models to considerably reduce test duration. To accomplish the first objective, nine fine-graded Superpave mixes of 12.5-mm nominal maximum aggregate size (NMAS) with asphalt grade PG 64-22 from six administrative districts of KDOT were selected. Specimens were prepared at three different target air void levels @ N[subscript]design gyrations and four target simulated in-place density levels with the Superpave gyratory compactor. Average number of wheel passes to 20-mm rut depth, creep slope, stripping slope, and stripping inflection point in HWTD tests were recorded and then used in the statistical analysis. Results showed that, in general, higher simulated in-place density up to a certain limit of 91% to 93%, results in a higher number of wheel passes until 20-mm rut depth in HWTD tests. A Superpave mixture with very low air voids @ N[subscript]design (2%) level performed very poorly in the HWTD test. HWTD tests were also performed on six 12.5-mm NMAS mixtures with air voids @ N[subscript]design of 4% for six projects, simulated in-place density of 93%, two temperature levels and five load levels with binder grades of PG 64-22, PG 64-28, and PG 70-22. Field cores of 150-mm in diameter from three projects in three KDOT districts with 12.5-mm NMAS and asphalt grade of PG 64-22 were also obtained and tested in HWTD for model evaluation. HWTD test results indicated as expected. Statistical analysis was performed and accelerated mix testing models were developed to determine the effect of increased temperature and load on the duration of the HWTD test. Good consistency between predicted and observed test results was obtained when higher temperature and standard load level were used. Test duration of the HWTD can thus be reduced to two hours or less using accelerated mix testing (statistical) models.

Doctor of Philosophy / Department of Civil Engineering / Mustaque Hossain / A Superpave asphalt mixture with 4.75-mm nominal maximum aggregate size (NMAS) is a promising, low-cost pavement preservation treatment for agencies such as the Kansas Department of Transportation (KDOT). The objective of this research study is to develop an optimized 4.75-mm NMAS Superpave mixture in Kansas. In addition, the study evaluated the residual tack coat application rate for the 4.75-mm NMAS mix overlay. Two, hot-in-place recycling (HIPR) projects in Kansas, on US-160 and K-25, were overlaid with a 15- to 19-mm thick layer of 4.75-mm NMAS Superpave mixture in 2007. The field tack coat application rate was measured during construction. Cores were collected from each test section for Hamburg wheel tracking device (HWTD) and laboratory bond tests performed after construction and after one year in service. Test results showed no significant effect of the tack coat application rate on the rutting performance of rehabilitated pavements. The number of wheel passes to rutting failure observed during the HWTD test was dependent on the aggregate source as well as on in-place density of the cores. Laboratory pull-off tests showed that most cores were fully bonded at the interface of the 4.75-mm NMAS overlay and the HIPR layer, regardless of the tack application rate. The failure mode during pull-off tests at the HMA interface was highly dependent on the aggregate source and mix design of the existing layer material. This study also confirmed that overlay construction with a high tack coat application rate may result in bond failure at the HMA interface. Twelve different 4.75-mm NMAS mix designs were developed using materials from the aforementioned but two binder grades and three different percentages of natural (river) sand. Laboratory performance tests were conducted to assess mixture performance. Results show that rutting and moisture damage potential in the laboratory depend on aggregate type irrespective of binder grade. Anti-stripping agent affects moisture sensitivity test results. Fatigue performance is significantly influenced by river sand content and binder grade. Finally, an optimized 4.75-mm NMAS mixture design was developed and verified based on statistical analysis of performance data.

Master of Science / Department of Mechanical and Nuclear Engineering / Steven J. Eckels / Christopher M. Sorensen / Large specific surface areas and high concentrations of reactive edge and defect sites make NanoActive™ metal oxide powders ideal chemical adsorbents. These powders are dispersed in aerosol form to remediate toxic wastes and neutralize chemical and biological warfare agents. In the destructive adsorption of toxic chemicals, effective application requires particles be as small as possible, thus, maximizing surface area and number of edge and defect sites. Other applications, e.g. smoke clearing, require particles be large so they will settle in a timely manner. Ideally, particle size control could be engineered into powder dispersion devices. The purpose of this study was to explore particle cohesion and aerodynamic deaggregation mechanisms to enhance the design of powder dispersion devices. An aerosol generator and four experimental nozzles were designed to explore the most commonly referenced deaggregation mechanisms: particle acceleration, particles in shear and turbulent flows, and particle impaction. The powders were then dispersed through the nozzles with increasing flow rates. A small angle light scattering device was used to make in situ particle size measurements. The nozzle designed for impaction deaggregated the NanoActive™ MgO particles to a lesser degree than the other three nozzles, which deaggregated the particles to a similar degree. Flows in three of the four nozzles were simulated in a commercial computational fluid dynamics package. Theoretical particle and aggregate stresses from the literature were calculated using simulated data. These calculations suggest particle acceleration causes internal stresses roughly three orders of magnitude larger than shear and turbulent flows. These calculations, coupled with experimental data, lead to the conclusion that acceleration was the most significant cause of particle deaggregation in these experiments. Experimental data also identified the dependence of deaggregation on primary particle size and agglomerate structure. NanoActive™ powders with smaller primary particles exhibited higher resistance to deaggregation. Small primary particle size was thought to increase the magnitude of van der Waals interactions. These interactions were modeled and compared to theoretical deaggregation stresses previously mentioned. In conclusion, deaggregation is possible. However, the ideas of particle size control and a universal dispersion device seem elusive considering the material dependent nature of deaggregation.

Doctor of Philosophy / Department of Chemical Engineering / Larry E. Erickson / Over the past decade, nanomaterials have been the subject of enormous interest. Their defining characteristic is a very small size in the range of 1-100 nm. Due to their nanometer size, nanomaterials are known to have unique mechanical, thermal, biological, optical and chemical properties, together with the potential for wide-ranging industrial applications. Here, we synthesized nanocrystalline metal oxides through the sol-gel process and used these materials as desulfurization adsorbents and photocatalysts. Deep desulfurization of fuels has received more and more attention worldwide, not only because of health and environmental consideration but also due to the need for producing ultra-low-sulfur fuels, which can only be achieved under severe operating conditions at high cost using hydrodesulfurization (HDS). Consequently, development of new and affordable deep desulfurization processes to satisfy the decreasing limit of sulfur content in fuels is a big challenge. Sol-gel derived Cu/Al[subscript]2O[subscript]3 and Zn/Al[subscript]2O[subscript]3 adsorbents have been demonstrated to be effective in the removal of thiophene from a model solution. Results showed that Cu[superscript]+ was the active site and thermal treatment under vacuum was critical for Zn/Al[subscript]2O[subscript]3 since a defective, less crystalline spinel led to stronger interaction between zinc ions and thiophene molecules in the adsorption process. The kinetic study suggested that most of the adsorption occurred in the first 30 min, and adsorption equilibrium was attained after 1.5 h. Both adsorbents showed good regenerative property. TiO2 is considered the most promising photocatalyst due to its high efficiency, chemical stability, non-toxicity, and low cost for degradation and complete mineralization of organic pollutants. However, the use of TiO[subscript]2 is impaired because it requires ultraviolet (UV) activation ([Lambda]<387 nm). The shift of optical response of TiO[subscript]2 from the UV to the visible light region would have a profound positive effect on the efficient use of solar energy in photocatalytic reactions. We shifted the optical response of TiO[subscript]2 and improved the photocatalytic efficiency through size modification and transition metal ion and nonmetal atom doping. Experimental results showed that C and V co-doped TiO[subscript]2 catalysts had much higher activity than commercial P25 TiO[subscript]2 towards the degradation of acetaldehyde under visible light irradiation. For the first time, we reported that activities were comparable in the dark and under visible light irradiation for co-doped TiO[subscript]2 with 2.0 wt% V. C and N co-doped TiO[subscript]2 exhibited higher activity for the degradation of methylene blue than pure TiO[subscript]2 under visible light and UV irradiation. Possible mechanisms were discussed based on the experimental results.