Graduate Theses & Dissertations

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was also predictable as a function of total chain length; any microstructural features due to structural effects were superseded by mass effects.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
effects of Dissolved Organic Matter (DOM) sources on Pb2+, Zn2+ and Cd2+ binding
Metal binding to dissolved organic matter (DOM) determines metal speciation and strongly influences potential toxicity. The understanding of this process, however, is challenged by DOM source variation, which is not always considered by most existing metal speciation models. Source determines the molecular structure of DOM, including metal binding functional groups. This study has experimentally showed that the allochthonous-dominant DOM (i.e. more aromatic and humic) consistently has higher level of Pb binding than the autochthonous-dominant DOM (i.e. more aliphatic and proteinaceous) by more than two orders of magnitude. This source-discrimination, however, is less noticeable for Zn and Cd, although variation still exceeds a factor of four for both metals. The results indicate that metal binding is source-dependent, but the dependency is metal-specific. Accordingly, metal speciation models, such as the Windermere Humic Aqueous Model (WHAM), needs to consider DOM source variations. The WHAM input of active fraction of DOM participating in metal binding (f) is sensitive to DOM source. The commonly-used f = 0.65 substantially overestimated the Pb and Zn binding to autochthonous-dominant DOM, indicating f needs to be adjusted specifically. The optimal f value (fopt) linearly correlates with optical indexes, showing a potential to estimate fopt using simple absorbance and/or fluorescence measurements. Other DOM properties not optically-characterized may be also important to determine fopt, such as thiol, which shows strong affinity to most toxic metals and whose concentrations are appreciably high in natural waters (< 0.1 to 400 nmol L-1). Other analytical techniques rather than Cathodic Stripping Voltammetry (CSV) are required to accurately quantify thiol concentration for DOM with concentration > 1 mg L-1. To better explain the DOM-source effects, the conditional affinity spectrum (CAS) was calculated using a Fully Optimized ContinUous Spectrum (FOCUS) method. This method not only provides satisfactory goodness-of-fit, but also unique CAS solution. The allochthonous-dominant DOM consistently shows higher Pb affinity than autochthonous-dominant DOM. This source-discrimination is not clearly observed for Zn and Cd. Neither the variability of affinity nor capacity can be fully explained by the variability of individual DOM properties, indicating multiple properties may involve simultaneously. Together, the results help improve WHAM prediction of metal speciation, and consequently, benefit geochemical modelling of metal speciation, such as Biotic Ligand Model for predicting metal toxicity. Author Keywords: Dissolved organic matter, Metal binding, Source, Windermere Humic Aqueous Model
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
Extraction and Characterization of Hyaluronic Acid and Collagen from Eggshell Membrane Waste
Connecting academia to industry is one important way to advance towards meeting the United Nations (UN) Sustainability Goals (SDGs).1 Sustainability can be applied to all industrial sectors with the SDGs being implemented by 2030.2 This research contributes to the SDGs by investigating a way to remediate an industrial waste stream in the egg-breaking industry. If adopted, this would reduce the amount of eggshell membrane (ESM) waste placed in landfill where it does not decompose properly. The work described in this thesis specifically targets extraction of collagen and hyaluronic acid (HA), two components of the ESM that are of commercial value in the cosmetic, pharmaceutical, and biomedical industries3,4 . Deliverables from this research include economically viable extraction methods, developed based on green chemistry approaches, that can be transferred from lab bench to industrial scale. The extraction development process was guided by the 12 Principles of Green Chemistry5,6,7 and the 12 Principles of Green Engineering.8 HA was most successfully extracted using a sodium acetate solution on ground ESM. Filtrate was collected, exhaustively dialyzed and lyophilized. High molecular weight HA was recovered. Fourier transform infrared attenuated total reflectance (FTIR-ATR) spectroscopy and proton nuclear magnetic resonance (NMR) spectroscopy compared extracted material to reference HA identifying successful extraction. Collagen was extracted using acetic acid or pepsin enzyme digestion. Hydrophilic interaction liquid chromatography (HILIC) coupled with mass spectrometry (MS) compared amino acid composition of extracted materials to reference collagen material. FTIR-ATR spectra also supported successful extraction of collagen. This work identifies that HA and collagen can be conveniently extracted from ESM using an economical approach that can be implemented into egg-breaking facilities. This work highlights the benefits of connecting academia to industry to advance green chemical approaches while implementing sustainable practices into existing industry. Author Keywords: collagen, eggshell membrane waste, extraction, green chemistry, hyaluronic acid, sustainability
Automated Separation and Preconcentration of Ultra-Trace Levels of Radionuclides in Complex Matrices by Online Ion Exchange Chromatography Coupled with Inductively Coupled Plasma Mass Spectrometry (ICP-MS)
Radionuclides occur in the environment both naturally and artificially. Along with weapons testing and nuclear reactor operations, activities such as mining, fuel fabrication and fuel reprocessing are also major contributors to nuclear waste in the environment. In terms of nuclear safety, the concentration of radionuclides in nuclear waste must be monitored and reported before storage and/or discharge. Similarly, radionuclide waste from mining activities also contains radionuclides that need to be monitored. In addition, a knowledge of ongoing radionuclide concentrations is often required under certain ‘special’ conditions, for example in the area surrounding nuclear and mining operations, or when nuclear and other accidents occur. Thus, there is a huge demand for new methods that are suitable for continuously monitoring and rapidly analyzing radionuclide levels, especially in emergency situations. In this study, new automated analytical methods were successfully developed to measure ultra trace levels of single or multiple radionuclides in various environmental samples with the goal of faster analysis times and less analyst involvement while achieving detection limits suitable for typical environmental concentrations. Author Keywords: automation, ICP-MS, ion exchange, radionuclide

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