Graduate Theses & Dissertations

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silicon sol-gel approach to the development of forensic blood substitutes
The research and development of synthetic blood substitutes is a reported need within the forensic community. This work contributes to the growing body of knowledge in bloodstain pattern analysis by offering a materials science approach to designing, producing and testing synthetic forensic blood substitutes. A key deliverable from this research is the creation of a robust silicon-based material using the solution-gelation technique that has been validated for controlled passive drip and spatter simulation. The work investigates the physical properties (viscosity, surface tension and density) of forensic blood substitute formulations and describes the similarity in the spreading dynamics of the optimized material to whole human blood. It then explores how blood and other fluids behave in impact simulation using high-speed video analysis and supports the use of the optimized material for spatter simulation. Finally, the work highlights the practical value of the material as an educational tool for both basic and advanced bloodstain experimentation and training. Author Keywords: bloodstain pattern analysis, forensic blood substitutes, high-speed video analysis, silicon solution-gelation chemistry, thin-film deposition, training and education
UV-Curable hybrid sol-gel materials
This thesis describes the synthesis, application and evaluation of a UV crosslinked 3-methacryloxypropyltrimethoxysilane-derived coating formulation. This is a two-component sol-gel system with 3-methacryloxypropyltrimethoxysilane (MaPTMS) and tetraethoxysilane (TEOS). Herein we show that if we change the co-solvent required for solubilizing MaPTMS from the more common methanol and ethanol to isopropanol we change the rate of hydrolysis from days or weeks to minutes. With the assistance of 2D 29Si-NMR we demonstrate that the system undergoes extensive condensation in twenty minutes. Using standard UV irradiation, the material can be extensively UV crosslinked with 70% of the methacryloxy functionality being consumed in 5 minutes upon irradiation in the presence of a photo-initiator. When this material is used to coat low carbon steel and immersed in an accelerated corrosion solution (dilute Harrison’s solution); this material affords low carbon steel 25 hours of protection when crosslinked and 17 hours of protection when uncrosslinked. The material was then used to encapsulate polyaniline (PANI), an intrinsic conductive polymer used in the corrosion protection of metal substrates. PANI has been encapsulated previously in sol-gel material, but due to the pH dependence of the solubility of PANI, it can not be encapsulated in more commonly chemically crosslinked sol-gel. As our system is UV crosslinked rather than chemically crosslinked, we were able to successfully demonstrate the inclusion of PANI into our coating system. Finally, this thesis includes a thorough computational investigation into the structure and band gap of PANI. Through the analysis of the band gap it was shown that the structure of the polymer commonly displayed in literature is not the correct structure of the polymer. Our results suggest that when PANI is made electrochemically, the oligomer contains two quinoid units next to one another instead of the more usually represented regularly alternating benzoid and quinoid units. The results also suggest that when PANI is made using the oxidant ammonium persulfate, the polymer most likely contains a Michael adduct structure somewhere in the polymer chain which dominates PANI’s electronic properties. Author Keywords: 3-Methacryloxypropyltrimethoxysilane, Computational Chemistry , Corrosion , Polyaniline, Tetraethoxysilane
TWO-DIMENSIONAL CONDUCTIVITY AT LaAlO3/SrTiO3 INTERFACES
Experiments have observed a two-dimensional electron gas at the interface of two insulating oxides: strontium titanate (SrTiO3) and lanthanum aluminate (LaAlO3). These interfaces exhibit metallic, superconducting, and magnetic behaviours, which are strongly affected by impurities. Motivated by experiments, we introduce a simple model in which impurities lie at the interface. We treat the LaAlO3 as an insulator and model the SrTiO3 film. By solving a set of self-consistent Hartree equations for the charge density, we obtain the band structure of the SrTiO3 film. We then study the relative contributions made by the occupied bands to the two-dimensional conductivity of the LaAlO3/SrTiO3 interface. We find that the fractional conductivity of each band depends on several parameters: the mass anisotropy, the filling, and the impurity potential. Author Keywords: conductivity, impurities, insulating oxides, Two-dimensional electron gases
Synthesis of Lipid Based Polyols from 1-butene Metathesized Palm Oil for Use in Polyurethane Foam Applications
This thesis explores the use of 1-butene cross metathesized palm oil (PMTAG) as a feedstock for preparation of polyols which can be used to prepare rigid and flexible polyurethane foams. PMTAG is advantageous over its precursor feedstock, palm oil, for synthesizing polyols, especially for the preparation of rigid foams, because of the reduction of dangling chain effects associated with the omega unsaturated fatty acids. 1-butene cross metathesis results in shortening of the unsaturated fatty acid moieties, with approximately half of the unsaturated fatty acids assuming terminal double bonds. It was shown that the associated terminal OH groups introduced through epoxidation and hydroxylation result in rigid foams with a compressive strength approximately 2.5 times higher than that of rigid foams from palm and soybean oil polyols. Up to 1.5 times improvement in the compressive strength value of the rigid foams from the PMTAG polyol was further obtained following dry and/or solvent assisted fractionation of PMTAG in order to reduce the dangling chain effects associated with the saturated components of the PMTAG. Flexible foams with excellent recovery was achieved from the polyols of PMTAG and the high olein fraction of PMTAG indicating that these bio-derived polyurethane foams may be suitable for flexible foam applications. PMTAG polyols with controlled OH values prepared via an optimized green solvent free synthetic strategy provided flexible foams with lower compressive strength and higher recovery; i.e., better flexible foam potential compared to the PMTAG derived foams with non-controlled OH values. Overall, this study has revealed that the dangling chain issues of vegetable oils can be addressed in part using appropriate chemical and physical modification techniques such as cross metathesis and fractionation, respectively. In fact, the rigidity and the compressive strength of the polyurethane foams were in very close agreement with the percentage of terminal hydroxyl and OH value of the polyol. The results obtained from the study can be used to convert PMTAG like materials into industrially valuable materials. Author Keywords: Compressive Strength, Cross Metathesis, Fractionation, Polyols, Polyurethane Foams, Vegetable Oils
Supercritical Water Chemistry
Supercritical water (SCW) exhibits unique properties that differentiates it from its low temperature behaviour. Hydrogen bonding is dramatically reduced, there is no phase boundary between liquid and gaseous states, heat capacity increases, and there is a drastic reduction of the dielectric constant. Efforts are underway for researchers to harness these properties in the applications of power generation and hazardous waste destruction. However, the extreme environment created by the high temperatures, pressures and oxidizing capabilities pose unique challenges in terms of corrosion not present in subcritical water systems. Molecular Dynamics (MD) simulations have been used to obtain mass transport, hydration numbers and the influence on water structure of molecular oxygen, chloride, ammonia and iron (II) cations in corrosion crevices in an iron (II) hydroxide passivation layer. Solvation regimes marking the transitions of solvation based versus charge meditated processes were explored by locating the percolation thresholds of both physically and hydrogen bonded water clusters. A SCW flow through reactor was used to study hydrogen evolution rates over metal oxide surfaces, metal release rates and the kinetics for the oxidation of hydrogen gas by oxygen in SCW. Insights into corrosion phenomena are provided from the MD results as well as the experimental determination of flow reactor water and hydrogen chemistry. Author Keywords: Flow Studies, Molecular Dynamics, Supercritical Water
Role of Dielectric Screening in SrTiO3-Based Interfaces
We build a theoretical model for exploring the electronic properties of the two-dimensional (2D) electron gas that forms at the interface between insulating SrTiO3 (STO) and a number of perovskite materials including LaTiO3, LaAlO3, and GdTiO3. The model treats conduction electrons within a tight-binding approximation, and the dielectric polarization via a Landau-Devonshire free energy that incorporates STO's strongly nonlinear, nonlocal, field-, and temperature-dependent dielectric response. We consider three models for the dielectric polarization at the interface: an ideal-interface model in which the interface has the same permittivity as the bulk, a dielectric dead-layer model in which the interface has permittivity lower that the bulk, and an interfacial-strain model in which the strain effects are included. The ideal-interface model band structure comprises a mix of quantum 2D states that are tightly bound to the interface, and quasi-three-dimensional (3D) states that extend hundreds of unit cells into the STO substrate. We find that there is a substantial shift of electrons away from the interface into the 3D tails as temperature is lowered from 300 K to 10 K. We speculate that the quasi-3D tails form the low- density high-mobility component of the interfacial electron gas that is widely inferred from magnetoresistance measurements. Multiple experiments have observed a sharp Lifshitz transition in the band structure of STO interfaces as a function of applied gate voltage. To understand this transition, we first propose a dielectric dead-layer model. It successfully predicts the Lifshitz transition at a critical charge density close to the measured one, but does not give a complete description for the transition. Second, we use an interfacial-strain model in which we consider the electrostrictive and flexoelectric coupling between the strain and polarization. This coupling generates a thin polarized layer whose direction reverses at a critical density. The transition occurs concomitantly with the polarization reversal. In addition, we find that the model captures the two main features of the transition: the transition from one occupied band to multiple occupied bands, and the abrupt change in the slope of lowest energy band with doping. Author Keywords:
Real-space renormalization group approach to the Anderson model
Many of the most interesting electronic behaviours currently being studied are associated with strong correlations. In addition, many of these materials are disordered either intrinsically or due to doping. Solving interacting systems exactly is extremely computationally expensive, and approximate techniques developed for strongly correlated systems are not easily adapted to include disorder. As a non-interacting disordered model, it makes sense to consider the Anderson model as a first step in developing an approximate method of solution to the interacting and disordered Anderson-Hubbard model. Our renormalization group (RG) approach is modeled on that proposed by Johri and Bhatt [23]. We found an error in their work which we have corrected in our procedure. After testing the execution of the RG, we benchmarked the density of states and inverse participation ratio results against exact diagonalization. Our approach is significantly faster than exact diagonalization and is most accurate in the limit of strong disorder. Author Keywords: disorder, localization, real-space renormalization, strong correlations
Phosphoric Acid Chemically Activated Waste Wood
Activated Carbon (AC) is commonly produced by gasification, but there has been increasing interest in chemical activation due to its lower activation temperatures and higher yields. Phosphoric acid, in particular, succeeds in both these areas. Phosphoric acid activated carbon (PAC) can be environmentally sustainable, and economically favourable, when the phosphoric acid used in the activation is recycled. This thesis describes the digestion and activation of waste wood using phosphoric acid, as well as methods used to recover phosphoric acid, functionalize the produced activated carbon with iron salts and then test their efficacy on the adsorption of target analytes, selenite and selenate. In order to achieve an efficient phosphoric acid based chemical activation, further understanding of the activation process is needed. A two-step phosphoric acid activation process with waste wood feed stock was examined. The filtrate washes of the crude product and the surface composition of the produced PAC were characterized using X-ray Photoelectron Spectroscopy (XPS), Fourier Transform-Infrared spectroscopy (FT-IR), Ion Chromatography (IC), and 31P Nuclear Magnetic Resonance (NMR). XPS of the unwashed PAC contained 13.3 atomic percent phosphorous, as phosphoric acid, while the washed sample contained 1.4 atomic percent phosphorous as PO43-, and P2O74-. Using 31P NMR, phosphoric acid was identified as the primary phosphorous species in the acidic 0.1 M HCl washings, with pyrophosphates also appearing in the second 0.1 M NaOH neutralizing wash, and finally a weak signal from phosphates with an alkyl component also appearing in the DI wash. IC showed high concentrations of phosphoric acid in the 0.1 M HCl wash with progressively lower concentrations in both the NaOH and DI washes. Total phosphoric acid recovery was 96.7 % for waste wood activated with 25 % phosphoric acid, which is higher than previous literature findings for phosphoric acid activation. The surface areas of the PAC were in the 1500-1900 m2g-1 range. Both pre and post activation impregnation of iron salts resulted in iron uptake. Pre-activation resulted in only iron(III) speciation while post-activation impregnation of iron(II)chloride did result in iron(II) forming on the PAC surface. The pre-activated impregnated PAC showed little to no adsorption of selenite and selenate. The post-activation impregnated iron(II)chloride removed up to 12.45 ± 0.025 mg selenium per g Iron-PAC. Competitive ions such as sulfate and nitrate had little effect on selenium adsorption. Phosphate concentration did affect the uptake. At 250 ppm approximately 75 % of adsorption capacity of both the selenate and the selenite solutions was lost, although selenium was still preferentially adsorbed. Peak adsorption occurred between a pH of 4 and 11, with a complete loss of adsorption at a pH of 13. Author Keywords: Activated Carbon, doping, Iron, phosphoric acid, selenium
Novel Functional Materials From Renewable Lipids
Vegetable oils represent an ideal and renewable feedstock for the synthesis of a variety of functional materials. However, without financial incentive or unique applications motivating a switch, commercial products continue to be manufactured from petrochemical resources. Two different families of high value, functional materials synthesized from vegetable oils were studied. These materials demonstrate superior and unique performance to comparable petrochemical analogues currently on the market. In the first approach, 3 amphiphilic thermoplastic polytriazoles with differing lipophilic segment lengths were synthesized in a polymerization process without solvents or catalysts. Investigation of monomer structure influence on the resultant functional behaviour of these polymers found distinctive odd/even behaviour reliant on the number of carbon atoms in the monomers. Higher concentrations of triazole groups, due to shorter CH2 chains in the monomeric dialkynes, resulted in more brittle polymers, displaying higher tensile strengths but reduced elongation to break characteristics. These polymers had similar properties to commercial petroleum derived thermoplastics. One polymer demonstrated self-assembled surface microstructuring, and displayed hydrophobic properties. Antimicrobial efficacy of the polymers were tested by applying concentrated bacterial solutions to the surfaces, and near complete inhibition was demonstrated after 4 hours. Scanning electron microscope images of killed bacteria showed extensive membrane damage, consistent with the observed impact of other amphiphilic compounds in literature. These polytriazoles are suited for applications in medical devices and implants, where major concerns over antibiotic resistance are prevalent. In the second approach, a series of symmetric, saturated diester phase change materials (PCMs) were also synthesized with superior latent heat values compared to commercial petrochemical analogues. These diesters exhibit melting temperatures between 39 °C and 77 °C, with latent heats greater than 220 J/g; much greater than paraffin waxes, which are currently the industry standard. Assessment of the trends between differing monomer lengths, in terms of number of CH2 groups of the 24 diesters synthesized exhibited structure/function dependencies in latent heat values and phase change temperatures, providing an understanding of the influence of each monomer on PCM thermal properties. A synthetic procedure was developed to produce these PCMs from a low value biodiesel feedstock. Application of these PCMs in the thermoregulation of hot beverages was demonstrated using a representative diester. This PCM cooled a freshly brewed hot beverage to a desired temperature within 1 minute, compared to 18 minutes required for the control. Furthermore, the PCM kept the beverage within the desired temperature range for 235 minutes, 40 % longer than the control. Author Keywords: Antimicrobial Surface, Click Chemistry, Green Chemistry, Phase Change Material, Polytriazole, Renewable
Novel Aliphatic Lipid-Based Diesters for use in Lubricant Formulations
Structure-property relationships are increasingly valued for the identification of specifically engineered materials with properties optimized for targeted application(s). In this work, linear and branched diesters for use in lubricant formulations are prepared from lipid-based oleochemicals and their structure-property relationships reported. It is shown that the branched diesters possess exceptional physical property profiles, including suppression of crystallization, and are superior alternatives for use in lubricant formulations. For the linear aliphatic diesters, both high and low temperature properties were predictable functions of total chain length, and both were differently influenced by the fatty acid versus diol chain length. Symmetry did not influence either, although thermal stability decreased and thermal transition temperatures increased with increasing saturation. All of the linear diesters demonstrated Newtonian flow behaviour. Viscosity was also predictable as a function of total chain length; any microstructural features due to structural effects were superseded by mass effects. Author Keywords: Crystallization, Phase behaviour, Rheology, Structure-Function, Thermogravimetric analysis, Vegetable Oils
Molecular Dynamics Simulations of Aqueous and Confined Systems Relevant to the Supercritical Water Cooled Nuclear Reactor
Supercritical water (SCW) is the intended heat transfer fluid and potential neutron moderator in the proposed GEN-IV Supercritical Water Cooled Reactor (SCWR). The oxidative environment poses challenges in choosing appropriate design materials, and the behaviour of SCW within crevices of the passivation layer is needed for developing a corrosion control strategy to minimize corrosion. Molecular Dynamics simulations have been employed to obtain diffusion coefficients, coordination number and surface density characteristics, of water and chloride in nanometer-spaced iron hydroxide surfaces. Diffusion models for hydrazine are evaluated along with hydration data. Results demonstrate that water is more likely to accumulate on the surface at low density conditions. The effect of confinement on the water structure diminishes as the gap size increases. The diffusion coefficient of chloride decreases with larger surface spacing. Clustering of water at the surface implies that the SCWR will be most susceptible to pitting corrosion and stress corrosion cracking. Author Keywords: Confinement, Diffusion, Hydration, MD Simulations, Supercritcal Water
Modelling the Lanthanum Aluminate-Strontium Titanate Interface with a Modified Transverse Ising Model
In 2004 it was discovered that a two-dimensional electron gas (2DEG) forms at the interface between lanthanum aluminate (LAO) and strontium titanate (STO). This 2DEG exhibits a variety of electronic and magnetic phenomena, motivating intense research into its applicability to electronic devices. Over the years several models have been developed in theoretical exploration of this system. Here, the transverse Ising model is applied to the LAO/STO interface for the first time. It is shown that the model as it is traditionally formulated cannot accurately predict the structure of the electron density at the interface. I show that this can be fixed with a simple modification of the model, and discuss how this modification affects both the polarization distribution in ferroelectric thin films and the electron density at the LAO/STO interface. The importance of including the depolarizing field when modelling spatially inhomogeneous ferroelectric systems is also explored. Author Keywords: ferroelectric thin film, lanthanum aluminate, strontium titanate, transverse Ising model, two-dimensional electron gas

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