This work investigates fabrication methods of nickel oxide thin films and their use in organic electronics. Two fabrication techniques were studied: UV-ozone oxidation of pure nickel films and reactive RF magnetron sputtering. The former was used to produce Ni/Ni2O3 bi-layer anodes to use as a substitute for the de facto standard ITO anode. OLEDs fabricated using Ni/Ni2O3 bi-layer anodes exhibited comparable device performance to standard ITO devices. UV-ozone oxidation was also used to fabricate Ni2O3 buffer layers for OPVs. Solar cells fabricated using Ni2O3 coated ITO exhibited an enhanced power conversion efficiency of up to 90%. RF magnetron sputtering was used to produce NiOx buffer layers with tunable conductivity and optical transparency for OPVs. Solar cells fabricated using NiOx coated ITO exhibited an enhanced power conversion efficiency of up to 60%. Nickel oxide films have been characterized with various techniques: sheet resistance measurements, optical transmission, XPS, UPS, AFM, and TEM.

Master of Science / Department of Mechanical and Nuclear Engineering / Xiao J. Xin / Energy consumption due to dairy production constitutes 10% of all energy usage in the U.S. Food Industry. Improving energy efficiency in food refrigeration and freezing plays an important role in meeting the energy challenges of today. Freezing and hardening are important but energy-intensive steps in ice cream manufacturing. This thesis presents a series of models to address these issues. The first step taken to model energy consumption was to create a temperature-dependent ice cream material using empirical properties available in the literature. The homogeneous ice cream material is validated using finite element analysis (FEA) and previously published experimental findings. The validated model is then used to study the efficiency of various package configurations in the ice cream hardening process. The next step taken is to consider product quality by modeling the ice crystal size distribution (CSD) throughout the hardening process. This is achieved through the use of population balance equations (PBE). Crystal size and corresponding hardened ice cream coarseness can be predicted through the PBE model presented in this thesis. The crystallization results are validated through previous experimental study. After the hardening studies are presented, the topic of continuous freezing is discussed. The actual ice cream continuous freezing process is inherently complex, and therefore simplifying assumptions are utilized in this work. Simulation is achieved through combined computational fluid dynamics (CFD) and PBE modeling of a sucrose solution. By assuming constant fluid viscosity, a two-dimensional cross section is able to be employed by the model. The results from this thesis provide a practical advancement of previous ice cream simulations and lay the groundwork for future studies.

Master of Science / Department of Chemical Engineering / J. H. Edgar / Boron phosphide, BP, is a III-V compound semiconductor with a wide band gap of 2.0 eV that is potentially useful in solid state neutron detectors because of the large thermal neutron capture cross-section of the boron-10 isotope (3840 barns). In this study, cubic BP crystals were grown by crystallizing dissolved boron and phosphorus from a nickel solvent in a sealed (previously evacuated) quartz tube. The boron - nickel solution was located at one end of the tube and held at 1150°C. Phosphorus, initially at the opposite end of the tube at a temperature of 430°C, vaporized, filling the tube to a pressure of 1–5 atmospheres. The phosphorus then dissolved into solution, producing BP. Transparent red crystals up to 4 mm in the largest dimension with mostly hexagonal shape were obtained with a cooling rate of 3°C per hour. The crystal size decreased as the cooling rate increased, and also as growth time decreased. The characterization with x-ray diffraction (XRD) and Raman spectroscopy established that the BP produced through this method were highly crystalline. The lattice constant of the crystals was 4.534 Ǻ, as measured by x-ray diffraction. Intense, sharp Raman phonon peaks were located at 800 cm[superscript]-1 and 830 cm[superscript]-1, in agreement with the values reported in the literature. The FWHM for XRD and Raman spectra were 0.275° and 4 cm[superscript]-1 which are the narrowest ever reported and demonstrates the high quality of the produced crystals. Energy dispersive x-ray spectroscopy (EDS) and scanning electron microscope (SEM) also confirmed the synthesized crystals were cubic BP crystals, with a boron to phosphorus atomic ratio of 1:1. Defect selective etching of BP at 300ºC for two minutes with molten KOH/NaOH revealed triangular and striated etch pits with low densities of defects of ~4 x 10[superscript]7 cm[superscript]-2 and 9.2 x 10[superscript]7 cm[superscript]-2 respectively. The BP crystals were n-type, and an electron mobility of ~39.8 cm[superscript]2/V*s was measured. This is favorable for application in neutron detection. Scaling to larger sizes is the next step through gradient freezing and employing a larger crucible.

Doctor of Philosophy / Department of Physics / Hongxing Jiang / The optical and structural properties of Er-doped GaN/InGaN materials and devices synthesized by metal organic chemical vapor deposition (MOCVD) were investigated. Er-doped GaN via MOCVD emits a strong photoluminescence (PL) emission at 1.54 um using both above and below-bandgap excitation. In contrast to other growth methods, MOCVD-grown Er-doped GaN epilayers exhibit virtually no visible emission lines. A small thermal quenching effect, with only a 20% decrease in the integrated intensity of the 1.54 um PL emission, occurred between 10 and 300 K. The dominant bandedge emission of Er-doped GaN at 3.23 eV was observed at room temperature, which is red-shifted by 0.19 eV from the bandedge emission of undoped GaN. An activation energy of 191 meV was obtained from the thermal quenching of the integrated intensity of the 1.54 um emission line. It was observed that surface morphology and 1.54 um PL emission intensity was strongly dependent upon the Er/NH3 flow rate ratio and the growth temperature. XRD measurements showed that the crystalline ordering of the (002) plane was relatively unperturbed for the changing growth environment. Least-squares fitting of 1.54 um PL measurements from Er-doped GaN of different growth temperatures was utilized to determine a formation energy of 1.82 ± 0.1 eV for the Er-emitting centers. The crystalline quality and surface morphology of Er-doped InGaN (5% In fraction) was nearly identical to that of Er-doped GaN, yet the PL intensity of the 1.54 um emission from Er-doped InGaN (5% In fraction) was 16 x smaller than that of Er-doped GaN. The drop in PL intensity is attributed to the much lower growth temperature in conjunction with the high formation energy of the Er- emitting centers. Er-doped InGaN grown at fixed growth temperature with different growth pressures, NH3 flow rates, and Ga flow rates was also investigated, and showed that increased In fractions also resulted in a smaller 1.54 um PL intensity. Er-doped InGaN p-i-n diodes were synthesized and tested. The electroluminescence (EL) spectra under forward bias shows strong Er based emission in the infrared and visible region. The different emission lines from EL spectra in contrast to PL spectra implies different excitation methods for the Er based emission in the p-i-n diode than in the PL excited epilayer.

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.

The mechanisms of thermal transport in defect-free silicon nanostructures are examined using a combination of lattice dynamics (LD) calculations and the Boltzmann transport equation (BTE). To begin, the thermal conductivity reduction in thin films is examined using a hierarchical method that first predicts phonon transport properties using LD calculations, and then solves the phonon BTE using the lattice Boltzmann method. This approach, which considers all of the phonons in the first Brillouin-zone, is used to assess the suitability of common assumptions used to reduce the computational effort. Specifically, we assess the validity of: (i) neglecting the contributions of optical modes, (ii) the isotropic approximation, (iii) assuming an averaged bulk mean-free path (i.e., the Gray approximation), and (iv) using the Matthiessen rule to combine the effect of different scattering mechanisms. Because the frequency-dependent contributions to thermal conductivity change as the film thickness is reduced, assumptions that are valid for bulk are not necessarily valid for thin films. Using knowledge gained from this study, an analytical model for the length-dependence of thin film thermal conductivity is presented and compared to the predictions of the LD-based calculations. The model contains no fitting parameters and only requires the bulk lattice constant, bulk thermal conductivity, and an acoustic phonon speed as inputs. By including the mode-dependence of the phonon lifetimes resulting from phonon-phonon and phonon-boundary scattering, the model predictions capture the approach to the bulk thermal conductivity better than predictions made using Gray models based on a single lifetime. Both the model and the LD-based method are used to assess a procedure commonly used to extract bulk thermal conductivities from length-dependent molecular dynamics simulation data. Because the mode-dependence of thermal conductivity is not included in the derivation of this extrapolation procedure, using it can result in significant error. Finally, phonon transport across a silicon/vacuum-gap/silicon structure is modelled using lattice dynamics and Landauer theory. The phonons transmit thermal energy across the vacuum gap via atomic interactions between the leads. Because the incident phonons do not encounter a classically impenetrable potential barrier, this mechanism is not a tunneling phenomenon. The heat flux due to phonon transport can be 4 orders of magnitude larger than that due to photon transport predicted from near-field radiation theory.

This thesis describe methods to improve the interfacial stability of an interpenetrating phase composite (IPC) polyvinylurethanecarbonate), and to increase the hydrophobicity of the polymer phase. The current IPCs introduce covalent bonding between the phases via silanizing agents to enhance the interfacial stability. Incorporation of the silanizing agents was also intended to reduce the IPC’s sensitivity to interfacial hydration, thereby enhancing the IPC’s resistance to degradation during aging. Lysine diisocyanate was used to increase the hydrophobic character in the polyvinylurethanecarbonate resin. The polymer resins were infiltrated into porous CPP blocks with 25 volume% interconnected porosity and polymerized to produce the IPCs. After mechanical testing following a aging study it was found that the silanizing agents contributed to stability of the mechanical properties under aqueous conditions. It was concluded that the mechanical properties and stability were comparable to available biodegradable composites, as well as being biocompatible to a preosteoblast model cell line.