Materials Science

In electron-doped ferroelectrics, the free electrons can become concentrated along the domain walls which act like a conducting surface. We consider the impact of free electrons occupying the t2g orbitals on the domain walls of an electron-doped perovskite ferroelectric. We build an analytical model based on Landau-Ginzburg-Devonshire theory, and a trio of tight-binding Hamiltonians for free electrons. We self-consistently solve for the polarization, potential, and electron density using a finite-difference approximation. We find that the ferroelectric is effectively charge neutral. The free electrons are attracted to the positively-charged domain wall, leaving it with a small residual charge. As the electron density increases, the domain walls tilt to form zig-zag domain walls. Orbital selectivity of the t2g orbitals depends on the relative orientations of the orbital plane and the domain wall. This property influences the rate at which the domain wall tilts as a function of the electron density.

Author Keywords: Charged Domain Wall, Domain Wall, Ferroelectric, Landau-Ginzburg, Perovskite, Strontium Titanate

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

The synthesis of biaryls through transition metal catalyzed cross-coupling reactions has been instrumental for synthetic organic chemists. The Hiyama reaction, which features organosilicon derived cross-coupling partners with aryl chlorides, remains relatively underdeveloped compared to other cross-coupling reactions. In this thesis, it is demonstrated that bench stable Palladium N-Heterocyclic Carbene (NHC) precatalysts of the general type [(NHC)Pd(allyl)Cl] are highly active in the Hiyama cross-coupling of activated aryl chlorides with low catalyst loading. Notably, this research demonstrates that catalysts featuring sterically less demanding NHCs display higher activity in this reaction, which contrasts with other cross-coupling reactions. Preliminary mechanistic investigations including in situ reaction monitoring by 19F NMR spectroscopy have uncovered side reactions. These side reactions may explain the low catalytic performance observed with unactivated substrates. These studies could help to further develop this reaction and improve catalytic performance. Additional investigations have also been made into ligand development by altering the electronics of sterically hindered NHC ligands for use in other cross-coupling reactions.

Author Keywords: Catalysis, Cross-coupling, Organic Chemistry, Organometallics, Side Reactions, Synthesis

In this work, a deep learning approach proposed by Valensise et al. [3] for extracting Raman resonant spectra from measured broadband CARS spectra was explored to see how effective it is at removing NRB from our experimentally measured "spectral-focusing"-based approach to CARS. A large dataset of realistic simulated CARS spectra was used to train a model capable of performing this spectral retrieval task. The non-resonant background shape used in creating the simulated CARS spectra was altered, to mimic our experimentally measured NRB response. Two models were trained: one using the original approach (Specnet) and one using the updated NRB "Specnet Plus", and then tested their ability to retrieve the vibrationally resonant spectrum from simulated and measured CARS spectra. An error analysis was performed to compare the model's retrieval performance on two simulated CARS spectra. The modified model's mean squared error value was five and two times lower for the first and second simulated CARS spectra, respectively. Specnet Plus was found to be more effective at extracting the resonant signals. Finally, the NRB extraction abilities of both models are tested on two experimentally measured CARS hyperspectroscopy samples (starch and chitin), with the updated NRB model (Specnet Plus) outperforming the original Specnet model. These results suggest that tailoring the approach to reflect what we observe experimentally will improve our spectral analysis workflow and increase our imaging potential.

The appearance of a two-dimensional electron gas (2DEG) in oxide interfaces between strontium titanate (STO) and other materials has become a major area of study. The behaviour of the 2DEG in STO is not well understood in part because the dielectric properties of STO are not well characterized. The differential susceptibility has a major impact on the electric fields within strontium titanate, and therefore to understand the 2DEG a better understanding of the susceptibility is needed. An expression for the soft mode phonon frequency of bulk strontium titanate is derived and used to model the susceptibility as a function of spatially homogeneous electric field, temperature and wavevector. This model is used to discuss the effect of spatially inhomogeneous electric fields and the local vs. nonlocal nature of the susceptibility. The critical exponents and the free energy are determined and discussed.

Author Keywords: critical exponents, differential susceptibility, quantum paraelectric, strontium titanate

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

This thesis is divided into two parts, each of which supports constructing and using a lithium magneto-optical trap for cold collision studies:

Part I

One outgoing channel of interest from cold collisions is the production of ion pairs. We describe an effective method for calculating bound-to-continuum cross-sections for charged binary systems by examining transitions to states above the binding energy that become bound when the system is placed within an infinite spherical well. This approach is verified for ionization of a hydrogen atom, and is then applied to the heavy Rydberg system Li+...I-.

Part II

A wavemeter previously built in the lab is redesigned for increased reliability and ease of use by replacing the optical hardware with a rocker system, which can be aligned in mere minutes rather than half a day as was previously the case. The new wavemeter has been tested through saturated absorption spectroscopy of lithium.

Author Keywords: cross-section, dissociation, lithium, magneto-optical trap, Michelson, wavemeter

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

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

The present thesis explores the cold flow properties of biodiesel and the effect of vegetable oil derived compounds on the crystallization path as well as the mechanisms at play at different stages and length scales. Model systems including triacylglycerol (TAG) oils and their derivatives, and a polymer were tested with biodiesel. The goal was to acquire the fundamental knowledge that would help design cold flow improver (CFI) additives that would address effectively and simultaneously the flow problems of biodiesel, particularly the cloud point (CP) and pour point (PP). The compounds were revealed to be fundamentally vegetable oil crystallization modifiers (VOCM) and the polymer was confirmed to be a pour point depressant (PPD).

The results obtained with the VOCMs indicate that two cis-unsaturated moieties combined with a trans-/saturated fatty acid is a critical structural architecture for depressing the crystallization onset by a mechanism wherein while the straight chain promotes a first packing with the linear saturated FAMEs, the kinked moieties prevent further crystallization. The study of model binary systems made of a VOCM and a saturated FAME with DSC, XRD and PLM provided a complete phase diagram including the thermal transformation lines, crystal structure and microstructure that impact the phase composition along the different crystallization stages, and elicited the competing effects of molecular mass, chain length mismatch and isomerism. The liquid-solid boundary is discussed in light of a simple thermodynamic model based on the Hildebrand equation and pair interactions.

In order to test for synergies, the PP and CP of a biodiesel (Soy1500) supplemented with several VOCM and PLMA binary cocktails were measured using a specially designed method inspired by ASTM standards. The results were impressive, the combination of additives depressed CP and PP better than any single additive. The PLM and DSC results suggest that the cocktail additives are most effective when the right molecular structure and optimal concentration are provided. The cocktail mixture achieves then tiny crystals that are prevented from aggregating for an extended temperature range. The results of the study can be directly used for the design of functional and economical CFI from vegetable oils and their derivatives.

Author Keywords: Biodiesel, Microstructure, Polymorphism, Pour point depressants, Triacylglycerol, Vegetable Oil Based Crystal Modifier