abstract: III-nitride InGaN light-emitting diodes (LEDs) enable wide range of applications in solid-state lighting, full-color displays, and high-speed visible-light communication. Conventional InGaN quantum well LEDs grown on polar c-plane substrate suffer from quantum confined Stark effect due to the large internal polarization-related fields, leading to a reduced radiative recombination rate and device efficiency, which limits the performance of InGaN LEDs in high-speed communication applications. To circumvent these negative effects, non-trivial-cavity designs such as flip-chip LEDs, metallic grating coated LEDs are proposed. This oral defense will show the works on the high-modulation-speed LEDs from basic ideas to applications. Fundamental principles such as rate equations for LEDs/laser diodes (LDs), plasmonic effects, Purcell effects will be briefly introduced. For applications, the modal properties of flip-chip LEDs are solved by implementing finite difference method in order to study the modulation response. The emission properties of highly polarized InGaN LEDs coated by metallic gratings are also investigated by finite difference time domain method. / Dissertation/Thesis / Masters Thesis Electrical Engineering 2016

This research investigated the thermal properties of the polarization switching (PS) in vertical-cavity surface-emitting lasers (VCSELs). The investigations were performed by experiments and numerical simulations. In the experiments, the current modulation frequency and ambient temperature of VCSELs were varied to study their thermal effects on PS, resulting in rich dynamics. The current-heating effect on PS was also investigated by a step function current experiment. Based on an assumption that PS is activated as the temperature in the active region reaches a certain temperature, we model a simplified temperature rate equation to simulate the experiment of the step function. The consistency of the experiments and simulations concludes that the thermal effect plays a major role in PS and PS¡¦s hysteresis. These results contribute to the understanding of the mechanism of VCSEL¡¦s polarization switching.

An estimated 1000 trillion cubic meters of gas in the unconventional hydrocarbon resource of gas hydrates in the world?s ocean floors far exceeds the known hydrocarbons in conventional reserves like coal, petroleum, and natural gas. These hydrate deposits also contain massive amounts of the greenhouse gases like methane and carbon dioxide. As relatively little is known about the oceanloor natural gas hydrates, mechanisms leading to the formation of these hydrates in ocean sediments need to be investigated before the significant technical challenges of recovery and environmental hazards are addressed. The subject research focuses on possible catalytic effects of biosurfactants on the formation of natural gas hydrates in oceanloor sediments. Sand/clay packs were saturated with seawater containing 1000 ppm of biosurfactant and pressurized with natural gas of 90 mole% methane, 6 mole% ethane and 4 mole% propane. The experimental results showed that gas hydrates formation in porous media is catalyzed by biosurfactants at very low concentrations. Commercially available representatives from the five biosurfactant classifications that microbes produce were purchased and evaluated in sand/clay packs at hydrateorming conditions. The rate of formation and induction time differed in the presence of bentonite and kaolin. The surface activities of biosurfactants were either specific to sand or clay surfaces. While in the presence of bentonite, Surfactin decreased hydrate induction time by 71% over a reference test with no biosurfactant in the seawater; Surfactin lowered induction time by 25% in the presence of kaolin. Rhamnolipid reduced the induction time by 58% in the presence of bentonite and by 66% in the presence of kaolin. Snomax and Emulsan, belonging to the classification of polysaccharide lipid complexes, reduced induction time by 30 to 40% in the presence of both kaolin and bentonite. Fatty acids reduced the induction time by 55% in the presence of bentonite and by 20% in the presence of kaolin. Surfactin enhanced the rate of formation by 400% in the presence of bentonite, but it had minimal effect in the presence of kaolin. Emulsan and Snomax increased the rate of formation by 250%, while rhamnolipid and phospholipids doubled formation rate in the presence of bentonite. Emulsan increased the rate of formation by 800%. In seawater, at hydrateorming conditions, rhamnolipid was found to have a critical micellar concentration of 12 ppm. This very low value of CMC suggests that minimal bacterial activity in ocean sediments could greatly catalyze hydrate formation. The recent analysis by Lanoil et al. (2001) of sediments from around gas hydrate mounds in the Gulf of Mexico gives a direct association between microbes and gas hydrates and supports the conclusions of the subject work.

This thesis reports a model to predict the auto-ignition time of single droplets of n-paraffin fuel mixtures using the method of continuous thermodynamics. The model uses experimental data for pure fuels to fit rate parameters for a single-step global chemical reaction equation; from this, correlations for rate parameters as a function of species molecular mass are derived, which are integrated to produce a continuous thermodynamics expression for mixture reaction rate. Experiments were carried out using the suspended droplet-moving furnace technique. The model was then tested and compared to experimental data for three continuous mixtures with known compositions: one ranging from ¬n-octane to n-hexadecane, the second ranging from n-dodecane to n-eicosane, and the third being a combination of the first two mixtures to produce a “dumbbell” mixture. Discrete and continuous mixture models of the ASTM standard distillation test were compared to design the experimental mixtures and provide the distribution parameters of the continuous mixtures intended to simulate them. The results of calculations were found to agree very well with measured ignition times for the mixtures.

This thesis reports a model to predict the auto-ignition time of single droplets of n-paraffin fuel mixtures using the method of continuous thermodynamics. The model uses experimental data for pure fuels to fit rate parameters for a single-step global chemical reaction equation; from this, correlations for rate parameters as a function of species molecular mass are derived, which are integrated to produce a continuous thermodynamics expression for mixture reaction rate. Experiments were carried out using the suspended droplet-moving furnace technique. The model was then tested and compared to experimental data for three continuous mixtures with known compositions: one ranging from ¬n-octane to n-hexadecane, the second ranging from n-dodecane to n-eicosane, and the third being a combination of the first two mixtures to produce a “dumbbell” mixture. Discrete and continuous mixture models of the ASTM standard distillation test were compared to design the experimental mixtures and provide the distribution parameters of the continuous mixtures intended to simulate them. The results of calculations were found to agree very well with measured ignition times for the mixtures.

This thesis reports a model to predict the auto-ignition time of single droplets of n-paraffin fuel mixtures using the method of continuous thermodynamics. The model uses experimental data for pure fuels to fit rate parameters for a single-step global chemical reaction equation; from this, correlations for rate parameters as a function of species molecular mass are derived, which are integrated to produce a continuous thermodynamics expression for mixture reaction rate. Experiments were carried out using the suspended droplet-moving furnace technique. The model was then tested and compared to experimental data for three continuous mixtures with known compositions: one ranging from ¬n-octane to n-hexadecane, the second ranging from n-dodecane to n-eicosane, and the third being a combination of the first two mixtures to produce a “dumbbell” mixture. Discrete and continuous mixture models of the ASTM standard distillation test were compared to design the experimental mixtures and provide the distribution parameters of the continuous mixtures intended to simulate them. The results of calculations were found to agree very well with measured ignition times for the mixtures.

This thesis reports a model to predict the auto-ignition time of single droplets of n-paraffin fuel mixtures using the method of continuous thermodynamics. The model uses experimental data for pure fuels to fit rate parameters for a single-step global chemical reaction equation; from this, correlations for rate parameters as a function of species molecular mass are derived, which are integrated to produce a continuous thermodynamics expression for mixture reaction rate. Experiments were carried out using the suspended droplet-moving furnace technique. The model was then tested and compared to experimental data for three continuous mixtures with known compositions: one ranging from ¬n-octane to n-hexadecane, the second ranging from n-dodecane to n-eicosane, and the third being a combination of the first two mixtures to produce a “dumbbell” mixture. Discrete and continuous mixture models of the ASTM standard distillation test were compared to design the experimental mixtures and provide the distribution parameters of the continuous mixtures intended to simulate them. The results of calculations were found to agree very well with measured ignition times for the mixtures.

Thesis (MSc)--Stellenbosch University, 2011. / ENGLISH ABSTRACT: Progress in computational systems biology depends crucially on the availability of generic rate equations that accurately describe the behaviour and regulation of catalysed processes over a wide range of conditions. Such equations for ordinary enzyme-catalysed reactions have been developed in our group and have proved extremely useful in modelling metabolic networks. However, these networks link to growth and reproduction processes through template-directed synthesis of macromolecules such as polynucleotides and polypeptides. Lack of an equation that captures such a relationship led us to derive a generic rate equation that describes catalysed, template-directed polymerisation reactions with varying monomer stoichiometry and varying chain length. A model describing the mechanism of a generic template-directed polymerisation process in terms of elementary reactions with mass action kinetics was developed. Maxima, a computational algebraic solver, was used to determine analytical expressions for the steady-state concentrations of the species in the equation system from which a steady-state rate equation could be derived. Using PySCeS, a numerical simulation platform developed in our group, we calculated the time-dependent evolution and the steadystates of the species in the catalytic mechanisms used in the derivation of the rate equations. The rate equation was robust in terms of being accurately derived, and in comparison with the rates determined with PySCeS. Addition of more elongation steps to the mechanism allowed the generalisation of the rate equation to an arbitrary number of elongations steps and an arbitrary number of monomer types. To test the regulatory design of the system we incorporated the generic rate equation in a computational model describing a metabolic system consisting of multiple monomer supplies linked by a template-directed demand reaction. Rate characteristics were chosen to demonstrate the utility of the simplified generic rate equation. The rate characteristics provided a visual representation of the control and regulation profile of the system and showed how this profile changes under varying conditions. / AFRIKAANSE OPSOMMING: Die beskikbaarheid van generiese snelheidsvergelykings wat die gedrag en regulering van gekataliseerde prosesse akkuraat oor ’n wye reeks omstandighede beskryf is van kardinale belang vir vooruitgang in rekenaarmatige sisteembiologie. Sulke vergelykings is in ons groep ontwikkel vir gewone ensiem-gekataliseerde reaksies en blyk uiters nuttig te wees vir die modellering van metaboliese netwerke. Hierdie netwerke skakel egter deur templaat-gerigte sintese van makromolekule soos polinukleotiede en polipeptiede aan groei- en voorplantingsprosesse. Die gebrek aan vergelykings wat sulke verwantskappe beskryf het ons genoop om ’n generiese snelheidsvergelyking af te lei wat gekataliseerde, templaatgerigte polimerisasie-reaksies met wisselende monomeerstoigiometrie en kettinglengte beskryf. ’n Model wat die meganisme van ’n generiese templaat-gerigte polimerisasie-proses in terme van elementêre reaksies met massa-aksiekinetika beskryf is ontwikkel. Maxima, ’n rekenaarmatige algebraïese oplosser, is gebruik om analitiese uitdrukkings vir die bestendige- toestand konsentrasies van die spesies in die vergelyking-stelsel te vind. Hierdie uitdrukkings is gebruik om ’n bestendige-toestand snelheidsvergelyking af te lei. Ons het die tyd-afhanklike progressie en die bestendige toestande bereken van die spesies in die katalitiese meganismes wat gebruik is in die afleiding van die snelheidsvergelykings. Die rekenaarprogram PySCeS is ’n numeriese simulasieplatform wat in ons groep ontwikkel is. Die snelheidsvergelyking blyk akkuraat afgelei te wees en is in ooreenstemming met snelhede deur PySCeS bereken. Die toevoeging van verdere verlengingstappe tot die meganisme het dit moontlik gemaak om die snelheidsvergelyking te veralgemeen tot ’n arbitrêre hoeveelheid verlengingstappe en monomeertipes. Om die regulatoriese ontwerp van die sisteem te toets het ons die generiese snelheidsvergelyking in ’n rekenaarmatige model geïnkorporeer wat ’n metaboliese sisteem bestaande uit verskeie monomeer-aanbodblokke en ’n templaatgerigte aanvraagblok beskryf. Snelheidskenmerkanalise is gekies om die nut van die vereenvoudigde generiese snelheidsvergelyking te demonstreer. Met hierdie snelheidskenmerke kon ons die kontrole- en reguleringsprofiel van die stelsel visualiseer en wys hoe hierdie profiel verander onder wisselende omstandighede.

Broadband light emitters operation, which covers multiple wavelengths of the electromagnetic spectrum, has been established as an indispensable element to the human kind, continuously advancing the living standard by serving as sources in important multi-disciplinary field applications such as biomedical imaging and sensing, general lighting and internet and mobile phone connectivity. In general, most commercial broadband light sources relies on complex systems for broadband light generation which are bulky, and energy hungry. Recent demonstration of ultra-broadband emission from semiconductor light sources in the form of superluminescent light emitting diodes (SLDs) has paved way in realization of broadband emitters on a completely novel platform, which offered compactness, cost effectiveness, and comparatively energy efficient, and are already serving as a key component in medical imaging systems. The low power-bandwidth product is inherent in SLDs operating in the amplified spontaneous emission regime. A quantum leap in the advancement of broadband emitters, in which high power and large bandwidth (in tens of nm) are in demand. Recently, the birth of a new class of broadband semiconductor laser diode (LDs) producing multiple wavelength light in stimulated emission regime was demonstrated. This very recent manifestation of a high power-bandwidth-product semiconductor broadband LDs relies on interband optical transitions via quantum confined dot/dash nanostructures and exploiting the natural inhomogeneity of the self-assembled growth technology. This concept is highly interesting and extending the broad spectrum of stimulated emission by novel device design forms the central focus of this dissertation. In this work, a simple rate equation numerical technique for modeling InAs/InP quantum dash laser incorporating the properties of inhomogeneous broadening effect on lasing spectra was developed and discussed, followed by a comprehensive experimental analysis of a novel epitaxial structure design. The layered structure is based on chirping the barrier layer thickness of the over grown quantum dash layer, in a multi-stack quantum dash/barrier active region, with the aim of inducing additional inhomogeneity. Based on material-structure and device characterization, enhanced lasing-emission bandwidth is achieved from the narrow (2 u m)ridge-waveguide LDs as a result of the formation of multiple ensembles of quantum dashes that are electronically different, in addition to improved device performance. Moreover, realization of SLDs from this device structure demonstrated extra-ordinary emission bandwidth covering the entire international telecommunication union (O- to U-) bands. This accomplishment is a collective emission from quantum wells and quantum dashes of the device active region. All these results lead to a step forward in the eventual realization of more than 150 nm lasing bandwidth from a single semiconductor laser diode.

Master of Science / Department of Chemical Engineering / John R. Schlup / The cross-linking reaction of the polyimide Matrimid 5218 with ethylenediamine (EDA) in methanol was investigated using Fourier transform infrared (FTIR) spectroscopy. Peaks associated with breaking imide bonds and the formation of amide bonds were identified. Using an internal standard peak of 1014 cm⁻¹ allowed for quantitative analysis to be applied. The peak areas, calculated by slice area, were used for absorbance ratio analysis to follow the cross-linking reaction as a function of time. Lastly, the absorbance values for the decreasing peak 1718 cm⁻¹ were used to calculate the order of reaction for the reaction rate of the mechanism.