Materials Science

Coherent anti-Stokes Raman scattering (CARS) microscopy is a label-free chemical imaging modality that uses CARS as a contrast mechanism to spatially resolve materials based on their molecular vibrational spectra. Due to the presence of a non resonant background that obfuscates the chemical information contained in CARS spectra, CARS images suffer from poor contrast and cannot be readily used for quantitative chemical analysis. Over the past two decades, spectral retrieval methods have been developed to obtain Raman-like spectra from CARS spectra. These methods promise to improve image contrast and enable reliable quantitative analysis. In this work I systematically evaluate a selection of the forefront spectral retrieval methods, including both analytical and machine learning approaches, to determine how well they perform at the task of non resonant background removal. The more recent machine learning methods demonstrate remarkable performance on spectra resembling the training dataset but are not as suitable as the analytical methods in general. The analytical methods based on the discrete Hilbert transform thus remain preferable due to their ease-of-use and general applicability.

Author Keywords: chemical imaging, coherent anti-stokes raman scattering, kramers-kronig analysis, machine learning, non-resonant background, spectral phase retrieval

Naphthenic acids are a major contaminant of concern and a focus of much research around remediation of oil sand process affected waters, OSPW. Using activated carbon adsorbents are an attractive option given their low cost of fabrication and implementation. A deeper evaluation of the effect naphthenic acid structural differences have on uptake affinity is warranted. In this thesis an in-depth exploration of naphthenic acid adsorption onto activated carbon is provided including many more model naphthenic acid species than what have been assessed previously in adsorption studies. Both adsorption kinetics and isotherms at the relevant alkaline pH of OSPW using several different carbon adsorbents with pH buffering to simulate the behaviour of real OSPW were evaluated. Given the time sensitive application of most adsorbents towards treating contaminated waters such as OSPW, achieving fast adsorption rates for model naphthenic acids is an important goal worth considering. Textural properties of activated carbon most conducive for fast adsorption kinetics were assessed using several candidate model species. Clear evidence is presented, demonstrating the influence of both the pore size distribution and particle size of porous adsorbents on uptake rates of naphthenic acids, demonstrating that careful optimization of these adsorbent properties can result in adequate uptake rates. Adsorption isotherms were used to assess model naphthenic acid affinity towards activated carbon. Uptake for the model naphthenic acids varied considerably regardless of the activated carbon used, ranging from 350 mg g-1 to near zero highlighting recalcitrant species. The equilibrium data was explored to identify important structural features of these species and key physiochemical properties that influence adsorption. It was demonstrated that certain naphthenic acids are resistant to adsorption when hydrophobic adsorbents are used. Adsorption isotherm modelling helped explore interactions occurring at the interface between naphthenic acids and adsorbent surfaces. Naphthenic acid hydrophobicity was identified as an importance physiochemical property for achieving high adsorption capacities onto activated carbon. Evidence is also presented that indicates favorable hydrogen bonding between naphthenic acids and surface site hydroxyl groups, demonstrating the importance of adsorbent surface functionality for naphthenic acid uptake. The adsorption mechanism was further explored through use of a thermodynamic analysis of the model naphthenic acid system using activated carbon. Standard state enthalpy and isosteric enthalpy of adsorption values were used to further support the proposed mechanisms occurring between model species and activated carbons. This research highlights the challenges associated with removing naphthenic acids from OSPW through adsorption and identifies how adsorbent surface chemistry modification will need to be used to increase the removal efficiency of recalcitrant naphthenic acid species when using activated carbon.

Author Keywords: Activated Carbon, Isotherms, Kinetics, Modelling, Naphthenic Acids, Thermodynamics

The oil sands industry is producing large volumes of tailings waste reaching 2 billion cubic meters by 2034 In this study, the industrial standard flocculant, high molecular weight PAM, was grafted from the surface of activated carbon (AC). This material was designed to increase the flocculant's hydrophobicity and density. Different molecular weight PAM was grafted from AC with different AC contents and particle sizes (AC-PAMs). The AC-PAMs were synthesized by surface-initiated atom transfer radical polymerization (SI-ATRP). The AC-PAMs achieved molecular weights 107 – 5,600 kg/mol and AC content of 0.2 – 5.8% on <0.1 and 0.1 – 0.5 mm AC particle diameters. AC-PAM achieved higher solids contents up to 51 wt% using AC-PAM with 5.1 wt% AC due to the grafting from a hydrophobic AC core. To summarize, our work shows the successful grafting of PAM from AC and its potential as a flocculant for mature fine tailings.

Author Keywords: activate carbon, atom transfer radical polymization, flocculation, grafting-from, polyacrylamide, surface-initiated polymerization

Access to human blood for forensic research and training in bloodstain pattern analysis (BPA) can be difficult due to many ethical, safety and cost concerns. Mammalian blood alternatives can be sourced, especially from local and willing abattoirs, but some concerns remain, and the added difficulties of high variation and species-specific differences in cellular components pose other issues. Therefore, synthetic alternatives to human blood provide practical options for the BPA community. This thesis explores the use of alginate hydrogels as a base material for forensic blood substitute (FBS) development. Hydrogels are first explored as a suitable environment for DNA stability and functionality and compared to other polymer systems. The ability of DNA to remain intact while undergoing electrospray ionization (ESI) is also investigated. The FBS design focuses on mimicking the fluid properties and genetic capabilities of whole human blood – a material not developed in FBSs previously. ESI was used to develop microparticles (MPs) that serve as cellular components of human blood (the red blood cells – RBCs, and white blood cells – WBCs). The microparticles were ionically crosslinked using calcium to provide small MPs (RBCs) or covalently crosslinked with functional DNA to provide larger WBC-like functional particles. The integration of these novel MPs into alginate-based materials is optimized and their use in BPA scenarios is explored. The FBS is tested in BPA scenarios of dripping experiments, impact patterns, and the ability to extract and amplify the contained DNA. In addition, the stability (or shelf-life) of the FBS was also assessed. The FBS exhibited similar spreading ratios to blood and demonstrated feasibility in use for impact angle (a) determination and impact pattern creation. Importantly, the DNA contained within the FBS could be processed with analogous protocols used in DNA evidence processing, enhancing its applicability to BPA research and training.

Author Keywords: Alginate hydrogels, Bloodstain pattern analysis, Electrospray ionization, Forensic blood substitutes, Forensic materials, Synthetic DNA design

Microwave resonances in isolated water-based spheres, dimers, and trimers are explored using simulations conducted with COMSOL Multiphysics. The study centers on morphology-dependent resonances (MDRs) and hotspot characteristics in cm-sized objects at microwave frequencies. Monomers subjected to microwave radiation exhibit four distinct resonant modes at specific sizes characterized by electric and magnetic field distributions which correspond to magnetic-dipolar, electric-dipolar, magnetic quadrupolar, and electric quadrupolar resonances, respectively. Dimer configurations reveal intriguing hotspot features, with axial hotspots emerging as a key resonant characteristic. The three fundamental dimer orientations dictate unique resonant behaviors, highlighting the sensitivity of hotspot intensity to orientation changes, but smooth and consistent trends during transitions between them. Investigations into trimer structures, as a more intricate geometry formed by interconnected dimers, reveal the subtle interactions of spheres in a trimer structure. Trimer hotspots largely reflect the sum of isolated dimer hotspot contributions, showcasing the energy conservation with no evidence of a newly formed hotpot. Our results, while arising as a consequence of the particularly high index of refraction of water at GHz frequencies, are generalizable to other length scales (such as nano-photonics), were materials with sufficiently high refractive index and transparency to be found.

Author Keywords: COMSOL simulations, Electromagnetic physics, Microwave frequencies, Morphology-dependent resonance, water-based objects

This thesis explores the remediation of naphthenic acids (NAs) from oil sands process-affected water (OSPW) using activated carbon (AC) derived from petroleum coke (PC) chemically activated with potassium hydroxide. The research aims to identify the most effective method for the adsorptive removal of NAs by optimizing the use of economically viable KOH quantities and to apply Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR-MS) for species-specific detection and characterization of NAs, crucial for targeting specific NAs in future studies.Prior research focused on single-species adsorption, establishing a foundational understanding of non-competitive adsorption before applying these findings to more complex NA mixtures and OSPW. This study builds upon this foundation, addressing a significant gap in the literature concerning the use of petcoke-derived AC with low KOH ratios and short activation times, which are economically advantageous for large scale applications. In this thesis, a comprehensive investigation into the kinetics and isotherms of NA adsorption on various ACs including PAC (petroleum coke AC), PWAC (pore-widened AC), HAC (heat-treated wood-based AC), and CAC (commercial AC) was conducted. The study specifically examines the adsorption behaviors of seven model NAs, reflecting the diverse molecular structures present in real world OSPW. The research also explores the impact of pore widening techniques on the adsorption efficiency of ACs, hypothesizing that increased mesoporosity enhances the adsorption of NA compounds. The findings demonstrate that FT-ICR-MS is an essential tool for precisely characterizing the NA species in OSPW, revealing that pore-widened ACs significantly improve the adsorption of NAFCs. This thesis contributes to the field of environmental remediation by offering new insights into the optimization of AC for NA removal, emphasizing the importance of surface chemistry and mesoporosity in enhancing adsorption efficiency. The study's outcomes have significant implications for the treatment of OSPW, providing a scalable and cost-effective solution to mitigate the environmental impacts of oil sands production.

Author Keywords: activated carbon, FT-ICR-MS, naphthenic acids, oil sands, petroleum coke, process-affected water

Innovative strategies to manage copious waste streams by upcycling feedstocks to valorized products which are then used in environmental remediation applications is an attractive circular economy model. This thesis explores this approach using waste wood generated from the milling of Chlorocardium rodiei (greenheart), a tropical hardwood species abundant in Guyana. We evaluate the thermochemical conversion of this feedstock, using phosphoric acid as the activant, to super activated carbons with surface areas of more than 2200 m2/g. Owing to the presence of surface heteroatoms, these adsorbents are amenable to further surface modifications including base-treatment, O-functionalization and N-functionalization. Using a facile oxidation procedure and shrimp waste-based dopants, we increase oxygen and nitrogen content by 8-fold and 5-fold respectively. These increases are realized without catastrophic loss of surface area and porosity as generally occurs with many reported functionalization approaches. Functionalized materials demonstrated efficient removal of both metal ions and the chlorinated herbicides 2,4-dichlorophenoxy acetic acid and paraquat. Pristine and base-washed ACs removed more than 90% of iron, aluminum and manganese from natural pit-lake waters. O-functionalized adsorbents also showed excellent removal efficiencies for aluminum and lead but only removed moderate amounts of manganese. Nitrogen-enriched composites fabricated with the addition of commercial chitosan removed 67% 2,4-D and 89% paraquat from model solutions at environmentally relevant concentrations of 4 ppm and 40 ppm respectively. Their versatility is further demonstrated in their ability to remove both herbicides from binary mixtures albeit to different extents. Shrimp chitin-based composites were most effective at removing 2,4-D from model solutions with a maximum adsorption capacity of 101 mg/g. Both surface area and surface nitrogen had strong influences on the adsorption capacity of adsorbents. Mechanistically, physisorption interactions predominate the synergistic or antagonistic interaction between N-functionalized composites and herbicide species. These green adsorbent materials, fabricated from sustainable biopolymers, are promising candidates for diverse environmental remediation applications.

Author Keywords: adsorption, Environmental remediation, N-functionalization, O-functionalization, tropical hardwood waste, waste valorization

Petroleum coke (petcoke) is a waste by-product of the upgrading process in the oil refining industry. It has limited utility in other areas of application.1 High carbon content (over 85 wt.%), low ash content, and softness make petcoke a potentially valuable precursor for graphitization, where amorphous carbon can be transformed into graphitic carbon. The synthetic production of graphite is gaining more interest due to the increasing demand for battery materials.2,3 Without metal moderators, achieving graphitization requires significantly high temperatures (> 2500 °C). Magnesium (Mg) has been identified as a promising reactant because of its efficacy in promoting graphitization and its relatively simple removal from the final product.3–5 The optimized conditions of magnesium-assisted graphitization showed an electrical conductivity of (3552.0 ± 78.5) S/m at 10 mA. Furthermore, bimetallic metal mediators can exhibit improved catalytic activity in graphitization due to the synergistic effect.3,6,7 Raney nickel alloy (Ni-Al alloy) contains 50 wt.% nickel and 50 wt.% aluminum. Individually, nickel and aluminum have shown efficacy in graphitization.8 However, no research has been conducted on the efficacy of Raney nickel alloy as a metal mediator in petcoke graphitization. We present our work on the graphitization of petcoke and its derived activated carbon using magnesium and Ni-Al alloy at 1000 °C and 1500 °C, respectively. This study assesses the effects of heating time, temperature, and precursor particle size on the degree of graphitization. Additionally, magnesium was completely removed after the graphitization process, and the residual Raney nickel alloy percentage was minimal.

Author Keywords: activated carbon, magnesium, Petroleum coke, Raney nickel alloy, synthetic graphitization

There is a `universal' picture of a charged domain wall (CDW) in theoretical work, often depicted as residing in an infinite thickness film, charge neutral, and with no bias voltage applied. However, in experiment CDWs are shown with none of these assumptions. CDWs are produced in thin or ultra-thin films, the CDW is not charge neutral, and a bias voltage is being applied. We look to go beyond these assumptions. It was shown that a positively charged domain wall (DW) moves against an external electric field which is not expected. The free electron density was also shown to determine the DW displacement amount. When the film thickness is lowered (ultra-thin film) we get a negatively charged DW which still moves against an external electric field, which agrees with experiment of a CDW in a ultra-thin film. This suggests the charge on the DW does not determine displacement direction.

Author Keywords: charged domain wall, displacement

This thesis presents the design, synthesis, and evaluation of activated carbon polyacrylamide (AC-PAM) composites for oil sands tailings remediation, integrating flocculation and adsorption functionalities. Surface-initiated atom transfer radical polymerization (SI-ATRP) was employed to graft high molecular weight PAM brushes onto petroleum coke and commercial activated carbon, with SARA-ATRP yielding the most uniform architecture (Mn ≈ 5.2 kg/mol, Đ ≈ 1.25). Flocculation tests using mature fine tailings (MFT) revealed superior sedimentation and dewatering with SARA-ATRP composites, outperforming conventional PAM at lower dosages. Adsorption studies using benzoic acid and model naphthenic acids showed selective uptake governed by polymer brush morphology and molecular structure, with Dubinin–Radushkevich isotherms best capturing the behavior of ARGET-ATRP composites. Post-flocculation assays confirmed reduced metal and polymer contamination, validating dual-function efficacy. These findings underscore petcoke's viability as a sustainable substrate and highlight controlled polymerization as a critical driver for tuning composite performance in industrial water treatment.

Author Keywords: Activated Carbon, Adsorption, Atom Transfer Radical Polymerization, Dubinin–Radushkevich, Isotherm, Polyacrylamide