Graduate Theses & Dissertations

Advanced broadband CARS microscopy based on a supercontinuum-generating photonic crystal fiber
I have developed and improved a coherent anti-Stokes Raman scattering (CARS) microscope based on the spectral focusing (SF) technique. The CARS microscope uses an 800 nm oscillator and a photonic crystal fibre module to generate the supercontinuum Stokes. The photonic crystal fibre was originally designed to generate light beyond 945 nm which is useful for CARS microscopy in the CH/OH frequencies but essentially prevents access to the important fingerprint region at lower frequencies. With expert and nontraditional approaches to generating supercontinuum with sufficient power at wavelengths below 945 nm, I substantially extend the usefulness of the module for SF-CARS microscopy deep into the fingerprint region. Moreover, with the invention of a dynamic supercontinuum generation scheme we call "spectral surfing," I improve both the brightness of the CARS signal and extend the accessible CARS frequency range to frequencies as low as 350 cm$^{-1}$ and as high as 3500 cm$^{-1}$---all in a single scan-window. I demonstrate the capabilities of our broadband SF-CARS system through CARS and four-wave mixing hyperspectroscopy on samples such as astaxanthin, lily pollen and glass; liquid chemicals such as benzonitrile, nitrobenzene and dimethyl sulfoxide; and on pharmaceutical samples such as acetaminophen, ibuprofen, and cetirizine. Furthermore, In search of more useful Stokes supercontinuum sources, I compare the performance of two commercial photonic crystal fibre modules for use in SF-CARS applications, ultimately finding that one module provides better spectral characteristics for static supercontinuum use, while the other provides improved characteristics when spectral surfing is implemented. Author Keywords: coherent anti-Stokes Raman scattering, nonlinear microscopy, scanning microscopy, spectroscopy, supercontinuum generation, vibrational spectroscopy
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
Model for the Differential Susceptibility of Strontium Titanate
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
Mitigating Cold Flow Problems of Biodiesel
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
Heavy Rydberg Photo-dissociation Cross-section Calculations and Experimental Progress Towards Cold Collisions in Lithium
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

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