Doctor of Philosophy / Department of Grain Science and Industry / Xiuzhi Susan Sun / Soy protein is one of the most promising bio-degradable adhesives as an alternative to synthetic petroleum-based adhesives for wood composite industries. In this study, soy protein was modified to improve adhesion properties and water resistance, which could facilitate the industrialization of soy protein-based adhesives. Furthermore, we attempted to identify a reliable indicator to predict the adhesion properties of soy protein by establishing the correlation of physical and mechanical properties with adhesion properties of soy protein. One of the objectives in this work was to investigate if inorganic calcium silicate hydrate (CSH) hybrids could improve adhesion properties of soy protein-based adhesives. 3-aminopropyltriethoxysilane (APTES) was used as a crosslinking agent between organic soy protein and inorganic CSH phases. APTES helped to form a crosslinked interface between soy protein and CSH, which was confirmed by changes in thermal, rheological, spectroscopic, and morphological properties with aging effect. More entangled structure and reduction of water-sensitive functional groups could lead to improvements in adhesion strength compared to unmodified soy protein-based adhesives. The second objective was to identify reliable indicators to predict shear adhesion properties by building the correlation between physical properties and adhesion properties of enzymatically modified soy protein-based adhesives (ESP). ESP was prepared with three independent variables (X1: trypsin concentration, X2: incubation time, and X3: glutaraldehyde (GA) concentration as a crosslinker) using a response surface methodology (RSM) called a central composite design (CCD). The important physical properties of viscosity (Y1), tacky force (Y2), and water resistance (Y3) were measured and investigated their relationship with adhesion strength. Viscosity, tacky force and water resistance showed solid correlation with adhesion strength of ESP and they were used to predict adhesion performance of soy protein modification system in this work. In addition, we studied the correlation between film strength and adhesion strength of another soy protein system. Because cohesion among protein molecules plays an important role in film and bonding mechanisms, we assumed that the film strength may be a reliable indicator to predict the adhesion strength of soy protein. The mechanical properties of the film and adhesion properties of soy protein on cherry wood were measured in terms of different concentrations of plasticizer (poly (propylene glycol) bis (2-aminopropyl ether) (H2N–PPG–NH2)). The results found out the low correlation between film and adhesion strength of soy protein in the presence of the plasticizer. We believe this might be caused by different curing conditions for film and adhesive applications of soy protein. Curing conditions greatly affect the thermal and curing behavior as well as mechanical properties of final materials. Thus, similar or comparable curing conditions should be required to obtain the information on the relationship between film and adhesion strength of soy protein.

Master of Science / Department of Physics / Robert Szoszkiewicz / Nanoscale modifications of polymer surfaces by scratching them with sharp tips with curvature radii of tens of nanometers and at variable temperatures are expected to provide wealth of information characterizing wear response of these polymers. Such studies are important in the light of understanding the nanoscale behavior of matter for future applications in advanced polymer coatings. This thesis describes how Atomic Force Microscopy (AFM) and hot-tip AFM (HT-AFM) methods were used to characterize thermal and mechanical properties of a 30 nm thick film of poly(styrene-block-ethylene oxide), PS-b-PEO, and modify its lamellar surface patterns. Additionally, it is revealed how contact AFM and HT-AFM methods can efficiently characterize the wear response of two popular polymer surfaces, poly(methyl methacrylate), PMMA, and polystyrene, PS. The AFM and HT-AFM studies on PS-b-PEO copolymer were aimed at producing spatial alignment of respective PS and PEO parts. Instead, however, surface ripples were obtained. These measurements are explained using mode I crack propagation model and stick-and-slip behavior of an AFM tip. In addition, HT-AFM studies allowed extraction of several thermo-physical properties of a PS-b-PEO film at local volumes containing about 30 attograms of a polymer. These thermo-physical quantities are: PEO melting enthalpy of, 111 ± 88 J g[superscript]-1, PS-b-PEO local specific heat of 3.6 ± 2.7 J g[superscript]-1K[superscript]-1, and molecular free energy of Helmholtz of 10[superscript]-20 J nm[superscript]-2 for the PEO within PS-b-PEO. Utilizing a spiral scan pattern at constant angular speed and at various temperatures at the AFM tip-polymer interfaces, the wear response of PS and PMMA polymers was characterized. Cross-sections along the obtained spiral wear patterns provided plots of polymer corrugation as a function of scanning speed. From these studies it was found that the corrugation of the modified polymer surface decays exponentially with linear velocity of the scanning tip.

Doctor of Philosophy / Department of Chemistry / Viktor Chikan / Doping quantum dots to increase conductivity is a crucial step towards being able to fabricate a new generation of electronic devices built on the “bottom-up” platform that are smaller and more efficient than currently available. Indium, tin, and gallium have been used to dope CdSe in both the bulk and thin film regimes and introduce n-type electron donation to the conduction band. CdSe quantum dots have been successfully doped with indium, tin, and gallium using the Li4[Cd10Se4(SPh16)] single source precursor combined with metal chloride compounds. Doping CdSe quantum dots is shown to effect particle growth dynamics in the “heterogeneous growth regime.” Doping with indium, tin, and gallium introduce donor levels 280, 100, and 50 meV below the conduction band minimum, respectively. Thin films of indium and tin doped quantum dots show improved conductivity over films of undoped quantum dots. Transient Absorption spectroscopy indicates that indium doping introduces a new electron energy level in the conduction band that results in a 70 meV blue shift in the 1Se absorption bleach position. Novel characterization methods such as in-situ fluorescence growth monitoring, single quantum dot EDS acquisition, static and time-resolved temperature dependant fluorescence spectroscopy were developed in the course of this work as well. These results show that doping CdSe quantum dots with indium, tin, and gallium has not only been successful but has introduced new electronic properties to the quantum dots that make them superior to traditional CdSe quantum dots.

Doctor of Philosophy / Physics / Christopher M. Sorensen / We demonstrated that gram quantities of pristine graphene nanosheets (GNs) can be produced via detonation of a hydrocarbon. This one-step and catalyst-free method is eco-friendly and economical for the production of GNs. The hydrocarbons detonated were C₂H₂, C₂H₄, C₃H₈ and CH₄ in the presence of O₂. The carbon products obtained from the detonation were analyzed by XRD, TEM, XPS and Raman spectroscopy. Depending upon the ratio of O₂ to C₂H₂, the GNs of size up to ~ 250 nm, SSA up to ~ 200 m²/g and yield up to 70% with 2-3 layers' stack have been obtained so far. N₂O was determined as a good alternative to O₂ as an oxidizer to produce GNs by detonating C₂H₂ with it. A two-color pyrometer was designed and calibrated to measure the temperature of the detonation of hydrocarbons. The measured detonation temperatures were in between 2700 K and 4300 K. Along with the high detonation temperature, the composition of precursor hydrocarbon was observed to be crucial as well to determine its suitability to detonate with oxidizer to produce GNs. The hydrocarbons C₂H₂ and C₂H₄ were determined as the suitable precursors to produce GNs whereas detonation of C₃H₈ yields mere amorphous carbon soot and CH₄ gives no solid carbon while detonated with O₂. It has been proposed that the hydrocarbons with C/H≥0.5 are suitable for GNs production by detonation method. Highly oxidized graphene nanosheets (OGNs) were produced by solution-based oxidation of GNs prepared via a controlled detonation of acetylene at O₂/C₂H₂=0.8. The produced OGNs were about 250 nm in size and hydrophilic in nature. The C/O ratio was dramatically reduced from 49:1 in the pristine GNs to about 1:1 in OGNs, as determined by X-ray photoelectron spectroscopy. This C/O in OGNs is the least ever found in all oxidized graphitic materials that have been reported. Thus, the OGNs produced from the detonated GNs with such high degree of oxidation herein yields a novel and promising material for future applications.

Doctor of Philosophy / Department of Grain Science and Industry / X. Susan Sun / Biobased polymers derived from renewable resources are increasingly important due to acute concerns about the environmental issues and limited petroleum resources. Poly(lactic acid) (PLA) is such a polymer that has shown great potential to produce biodegradable plastics. However, low glass transition temperature (Tg), low thermal stability, slow biodegradation rate, and high cost limit its broad applications. This dissertation seeks to overcome these limitations by reinforcing PLA with inorganic nanoparticles and low-cost agricultural residues. We first synthesized PLA nanocomposites by in situ melt polycondensation of L-lactic acid and surface-hydroxylized nanoparticles (MgO nanocrystals and TiO2 nanowires) and investigated the structure-property relationships. PLA grafted nanoparticles (PLA-g-MgO, PLA-g-TiO2) were isolated from the bulk nanocomposites via repeated dispersion/centrifugation processes. The covalent grafting of PLA chains onto nanoparticle surface was confirmed by Fourier transform infrared spectroscopy and thermalgravimetric analysis (TGA). Transmission electron microscopy and differential scanning calorimetry (DSC) results also sustained the presence of the third phase. Morphological images showed uniform dispersion of nanoparticles in the PLA matrix and demonstrated a strong interfacial interaction between them. Calculation based on TGA revealed that more than 42.5% PLA was successfully grafted into PLA-g-MgO and more than 30% was grafted into PLA-g-TiO2. Those grafted PLA chains exhibited significantly increased thermal stability. The Tg of PLA-g-TiO2 was improved by 7 °C compared with that of pure PLA. We also reinforced PLA with low-value agricultural residues, including wood flour (WF), soy flour (SF), and distillers dried grains with solubles (DDGS) by thermal blending. Tensile measurements and morphological images indicated that methylene diphenyl diisocyanate (MDI) was an effective coupling agent for PLA/WF and PLA/DDGS systems. MDI compatibilized PLA/WF and PLA/DDGS composites showed comparable tensile strength and elongation at break as pure PLA, with obviously increased Young’s modulus. Increased crystallinity was observed for PLA composites with SF and DDGS. Such PLA composites have similar or superior properties compared with pure PLA, especially at a lower cost and higher biodegradation rate than pure PLA. The results from this study are promising. These novel PLA thermoplastic composites with enhanced properties have potential for many applications, such as packaging materials, textiles, appliance components, autoparts, and medical implants.

Doctor of Philosophy / Department of Chemical Engineering / James H. Edgar / The sublimation recondensation crystal growth of aluminum nitride, titanium nitride, and yttrium nitride were explored experimentally and theoretically. Single crystals of these nitrides are potentially suitable as substrates for AlGaInN epitaxial layers, which are employed in ultraviolet optoelectronics including UV light-emitting diodes and laser diodes, and high power high frequency electronic device applications. A thermodynamic analysis was applied to the sublimation crystal growth of aluminum nitride to predict impurities transport (oxygen, carbon, and hydrogen) and to study the aspects of impurities incorporation for different growth conditions. A source purification procedure was established to minimize the impurity concentration and avoid degradation of the crystal’s properties. More than 98% of the oxygen, 99.9% of hydrogen and 90% of carbon originally in the source was removed. The AlN crystal growth process was explored in two ways: self-seeded growth with spontaneous nucleation directly on the crucible lid or foil, and seeded growth on SiC and AlN. The oxygen concentration was 2 ~ 4 x 1018cm-3, as measured by secondary ion mass spectroscopy in the crystals produced by self-seeded growth. Crystals grown from AlN seeds have visible grain size expansion. The initial AlN growth on SiC at a low temperature range (1400°C ~1600°C) was examined to understand the factors controlling nucleation. Crystals were obtained from c-plane on-axis and off-axis, Si-face and C-face, as well as m-plane SiC seeds. In all cases, crystal growth was fastest perpendicular to the c-axis. The growth rate dependence on temperature and pressure was determined for TiN and YN crystals, and their activation energies were 775.8±29.8kJ/mol and 467.1±21.7kJ/mol respectively. The orientation relationship of TiN (001) || W (001) with TiN [100] || W [110], a 45o angle between TiN [100] and W [100], was seen for TiN crystals deposited on both (001) textured tungsten and randomly orientated tungsten. Xray diffraction confirmed that the YN crystals were rock-salt structure, with a lattice constant of 4.88Å. Cubic yttria was detected in YN sample from the oxidation upon its exposed to air for limited time by XRD, while non-cubic yttria was detected in YN sample for exposures more than one hour by Raman spectra.

Master of Science / Department of Mechanical and Nuclear Engineering / Kevin Lease / Carbon fiber reinforced composites (CFRP’s) are a mainstay in many industries, including the aerospace industry. When composite components are damaged on an aircraft, they are typically repaired with a composite patch that is placed over the damaged material and cured into the existing composite material. This curing process involves knowledge of the curing time necessary to sufficiently cure the patch. The inexact nature of curing composites on aircraft causes a significant waste of time and material when patches are unnecessarily redone. Knowing how differences in cure cycle affect the strength of the final material could reduce this waste. That is the focus of this research. In this research, the interfacial shear strength (IFSS) of carbon fiber/epoxy composites was investigated to determine how changes in cure cycle affect the overall material strength. IFSS is a measure of the strength of the bond between the two materials. To measure this, the microbond method was used. In this method, a drop of epoxy is applied to a single carbon fiber. The specimen is cured and the droplet is sheared from the fiber. The force required to debond the droplet is recorded and the data is analyzed. The IFSS of AS4/Epon828, T650/Epon828, and T650/Cycom 5320-1 composites were evaluated. For the former two material systems, a cure cycle with two steps was chosen based on research from others and then was systematically varied. The final cure time was changed to determine how that parameter affected the IFSS. It was found that as the final cure time increased, so did the IFSS and level of cure achieved by the composite to a point. Once the composite reached its fully cured state, increasing the final cure time did not noticeably increase the IFSS. For the latter material system (T650/Cycom 5320-1), the two cure cycles recommended by the manufacturer were tested. These had different initial cure steps and identical final cure steps. Although both cure cycles caused high IFSS, the cycle with the higher initial temperature, but shorter initial cure time achieved a higher level of cure than that with a longer time, but shorter temperature.

Master of Science / Department of Chemistry / Jun Li / With the increasing consumption of energy and the depletion of fossil fuels, finding an alternative energy source is critical. Solar energy is one of the most promising energy sources and solar cells are the devices that convert solar radiation into electricity. Currently, the most widely used solar cell is based on p-n junction formed with crystalline silicon materials. While showing high efficiency, the high fabrication cost limits its broad applications. Dye sensitized solar cell (DSSC) is a promising low-cost alternative to the Si solar cell, but its efficiency is much lower. Improvements in materials and interfaces are needed to increase the DSSC efficiency while maintain the low cost. In this thesis, three projects were investigated to optimize the DSSC efficiency and reduce the cost. The first project is to optimize the TiO[subscript]2 barrier layers on Fluorine-doped Tin Dioxide (FTO) surface. Two preparation methods, i.e. TiCl[subscript]4 solution treatment and thermal oxidation of sputtered Ti metal films, were employed and systematically studied in order to minimize electron-hole recombination and electron backflow during photovoltaic processes of DSSCs. TiCl[subscript]4 solution treatment method was found to create a porous TiO[subscript]2 barrier layer. Ti sputtering method created a very compact TiO[subscript]2 blocking layer. Two methods showed different characteristics and may be used for different DSSC studies. The second project is to reduce the DSSC cost while maintaining the efficiency by replacing the expensive Pt counter electrode with a novel vertically aligned carbon nanofiber (VACNF) electrode. A large specific electrode surface area (~125 cm[superscript]2 over 1 cm[superscript]2 geometric area) was obtained by using VACNFs. The relatively high surface area, good electric conductivity and the large numbers of active graphitic edges existed in cone-like microstructure of VACNFs were employed to improve redox reaction rate of I[subscript]3[superscript]-/I[superscript]- mediators in the electrolyte. Faster electron transfer and good catalytic activities were obtained with such counter electrodes. The third project is to develop a metal organic chemical vapor deposition (MOCVD) method to coat TiO[subscript]2 shells on VACNF arrays as potential photoanodes in the DSSC system in order to improve the electron transfer. Fabrication processes were demonstrated and preliminary materials were characterized with scanning electron microscopy and transmission electron microscopy. MOCVD at 300 mTorr vapor pressure at 550° C for 120 min was found to be the optimal condition.

Master of Science / Department of Civil Engineering / Kyle A. Riding / Air void clustering around coarse aggregate in concrete has been identified as a potential source of low strengths in concrete mixes by several Departments of Transportation around the country. Research was carried out to (1) develop a quantitative measure of air void clustering around aggregates, (2) investigate whether air void clustering can be reproduced in a laboratory environment, (3) determine if air void clustering can blamed for lower compressive strengths in concrete mixes, (4) and identify potential factors that may cause clustering. Five types of coarse aggregate and five different air entraining agents were included in the laboratory study to see if aggregate type or chemical composition of air entraining agent directly relates to air void clustering. A total of 65 mixes were made, implementing the frequently used technique of retempering that has been previously associated with air void clustering around aggregates. Compressive strength specimens as well as samples for hardened void analysis were made. Compressive strength at 7 and 28 days was determined and the automated hardened void analysis (including a new method of clustering evaluation) was performed on all samples. It was found that it is possible to reproduce air void clustering in laboratory conditions. However, the results have shown that retempering does not always cause air void clustering. It was also observed that air void clustering is not responsible for a decrease in compressive strength of retempered concrete as neither aggregate type nor chemical composition of air entraining agent had a significant impact on severity of void clustering around coarse aggregate particles. It was also found that the total air content and an inhomogeneous microstructure and not air void clustering were responsible for lower strengths.

Doctor of Philosophy / Department of Mechanical and Nuclear Engineering / Douglas S. McGregor / Strengthening the crystal lattice of lanthanide halides, which are brittle, anisotropic, ionic crystals may increase the availability and ruggedness of these scintillators for room-temperature γ-ray spectroscopy applications. Eight dopants for CeBr[subscript]3, including CaBr[subscript]2, SrBr[subscript]2, BaBr[subscript]2, ZrBr[subscript]4, HfBr[subscript]4, ZnBr[subscript]2, CdBr[subscript]2, and PbBr[subscript]2, were explored at two different doping levels, 500ppm and 1000ppm, in an effort to identify potential aliovalent strengthening agents which do not adversely affect scintillation performance. All dopants and doping levels exhibited improved ingot yields over the undoped case, indicating an improvement in the ease of crystal growth. Scintillation performance was gauged using four key metrics. Scintillation emission spectra or, rather, radioluminescence spectra were recorded using x-ray irradiation. Total light yield was estimated through pulse height comparison with bismuth germanate (BGO) scintillators. Scintillation kinetics were checked by measuring single interaction pulses directly output by a fast response PMT. Finally, light yield proportionality was measured using a Compton coincidence system. Samples from each ingot were harvested to benchmark their performance with the four metrics. Of the eight dopants explored, only BaBr[subscript]2 and PbBr[subscript]2 clearly altered scintillation spectral emission characteristics significantly. The remaining dopants, CaBr[subscript]2, SrBr[subscript]2, ZrBr[subscript]4, HfBr[subscript]4, CdBr[subscript]2 and ZnBr[subscript]2, altered scintillation performance to a lesser degree. No dopant appeared to affect light yield proportionality, nor did any drastically alter the light decay characteristics of CeBr[subscript]3. HfBr[subscript]4 and ZnBr[subscript]2-doped CeBr[subscript]3 exhibited the highest light yields, significantly higher than the undoped CeBr[subscript]3 samples tested. Finally, aliovalent doping appeared to greatly improve CeBr[subscript]3 ingot yields, regardless of the dopant, thus it is a promising method for improving crystal strength while not deleteriously affecting scintillation performance. HfBr[subscript]4 and ZnBr[subscript]2 both demonstrated high performance without any noticeable negative side-effects and are prime candidates for future study.