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Every moment of every day, at least hundreds of thousands of tires roll across a surface throughout the world. Tires are indisputably important in our daily life. The tire's primary component is rubber, which consumes energy when it rotates on a substrate due to the viscoelastic material's internal friction: a phenomenon referred to as rolling resistance. The interaction between the tire and the road surface is one of the most intricate and crucial phenomena in an automobile, because it is responsible for creating forces, moments, and deformation in the tire. Additionally, the road's roughness interacts with the tire and contributes significantly to its performance. This dissertation aims to develop a comprehensive physics-based model for predicting the rolling resistance of a viscoelastic material due to dynamic deformations caused by tire rotation using an analytical approach. The model was developed by proposing a Gaussian wave function propagating across a tire circumference's viscoelastic medium. The wave function was selected to describe the displacement field produced by tire-road interaction. Additionally, by adopting a multi-scale modeling technique, the model was upgraded to estimate rolling resistance while taking into account surface roughness at all length scales, from macroscopic to microscopic. Additionally, another mathematical model was developed using the Fourier series approach to evaluate the steady-state stress response and energy dissipation for any harmonic and non-harmonic periodic strain signals. Additionally, the dissertation strove to build a continuum damage mathematical model using a combined testing/modeling methodology to predict the aging of Styrene-Butadiene Rubber (SBR) after continuous exposure to the atmosphere. The obtained model was developed through the implementation of optimization techniques while formulating a mathematical model, which was then combined with a physics-based model to predict rolling resistance while taking into account rubber aging. Calibration of hyperelastic and viscoelastic material models with testing data was performed using an optimization technique that yielded sufficient results. The results of all mathematical models obtained in this dissertation are reported subsequently. The stress response of a viscoelastic material under harmonic and non-harmonic strain input yielded good agreement with the FEA model obtained using ABAQUS. The rolling resistance behavior under various operating conditions, including texture and aging effects, was reported, and the results aligned with the experimental results found in the literature. / Doctor of Philosophy / Every moment of every day, hundreds of thousands of automobile tires roll across a surface somewhere in the world. A tire is an undeniably important part of everyday life. Rubber is the tire's main component, and when it rotates on a surface, it loses energy, resulting in a force that resists motion, known as rolling resistance force. The contact between the tire and the road is one of the most complicated and important phenomena that happens in an automobile because it is responsible for the vehicle's dynamic performance in areas such as acceleration, stopping distance, and stability. Another factor that affects tire and car performance and should be taken into account is the road's roughness. This dissertation used an analytical method to come up with an accurate physics-based model for predicting the rolling resistance force of a viscoelastic material caused by tire rotation. The model was developed by assuming a Gaussian wave function would move across the tire circumference. Additionally, using a multi-scale modeling technique, the model was improved so that it could calculate the value of rolling resistance force considering surface roughness in all lengths of scale. This project also developed an additional mathematical model using the Fourier series method to determine how the stress response and energy dissipation would behave for any harmonic and nonharmonic periodic strain signals. Additionally, the dissertation presents the developing of a continuum damage mathematical model that could predict the material property of styrene-butadiene rubber (SBR) after being exposed to the air for a long time (i.e., aged). The model was developed based on experimental data and optimization techniques. This model was then combined with a physics-based model to predict rolling resistance force while taking aging into account. The material models were defined using an optimization method that yielded good results. The stress response of a viscoelastic material when it was subjected to harmonic and non-harmonic strain was in good agreement with the Finite Element Analysis (FEA) model made with ABAQUS. Rolling resistance behavior was observed, and the results were consistent with those found in the literature.

It was found that laser modified wood surfaces can be bonded together to create a wood composite without the need of any additive. This bonding method removes the need of applying adhesive, potentially lowers cost, and eliminates off gassing of petroleum resins, creating a wood product with many eco-friendly attributes. This body of work outlines a) initial chemical analysis of the laser modified surface b) its bond strength and c) the optimization of factors that control the strength of the bond. Surface chemical analysis on laser modified wood was conducted using photo acoustic Fourier transform infrared spectroscopy (PA-FTIR) and X-Ray photoelectron spectroscopy (XPS). Light microscopy and scanning electron microscopy were utilized for surface topology analysis.Differential scanning calorimetry (DSC) quantified the thermal properties of the modified wood surface. Screening of multiple factors that would contribute to surface modification and adhesion was performed utilizing mechanical testing. Optimization of significant factors that affect bond strength was determined statistically utilizing a design of experiment approach. Chemical analysis of the laser modified surface revealed changes in the carbonyl and aromatic regions indicating modification of the hemicellulose and lignin components, intensifying with increasing laser modification.The C1/C2 ratios found via XPS revealed that one or more of the following is occurring: more extractives have moved to the surface, condensation reactions among lignin units, and the loss of methoxy and breakage of aryl ether linkages occurred.Microscopy images showed color changes to a darker caramel color with a smoothing of surface topology, suggesting the occurrence of the softening and/or melting of wood polymers. DSC verified chemical and/or physical changes in the wood with the modified material now having a glass transition temperature between 130-150°C.DOE found that laser parameters (power and focus) as well as hot press parameters (temperature and pressure) were significant in optimizing the bond. The impact of the study is the first documentation of the ability to laser modifies wood surfaces and subsequently bond them together. The ability of the wood polymers at the surface to undergo flow at elevated temperature is implicated in the adhesion mechanism of the laser modified wood. / Master of Science

Yes / The aim of this work was to investigate the feasibility of cross-linker free polyelectrolyte complex formation at the nanoscale between carrageenan (CAR) and protamine (PROT). The properties of CAR/PROT nanoparticles (NPs) were dependent on the carrageenan type: kappa (KC), iota (IC) and lambda (LC), concentration of components, addition of divalent cations, weight mixing ratio (WMR) of constituents and mode of component addition. In the case of 0.1% w/v solutions, IC-based NPs had the smallest particle sizes (100-150nm) and low polydispersity indices (0.1-0.4). A decrease in the solution concentration from 0.1% to 0.05% w/v enabled the formation of KC/PROT NPs. All carrageenans exhibited the ability to form NPs with surface charge ranging from -190 to 40mV. The inclusion of divalent cations caused an increase in the particle size and zeta potential. Infrared analysis confirmed the presence of a complex between CAR and PROT and showed that IC chains undergo structural changes when forming NPs. Colloidal stability of NPs was related to the initial surface charge of particles and was time- and pH-dependent. IC was found to be the most suitable type of CAR when forming nanoplexes with PROT.

Les travaux portent sur les multiplexeurs optiques fonctionnant à mi-IR pour la source à large bande dans l'application de détection de gaz. Deux configurations ont été étudiées: réseau de guides d'onde (AWG) et réseau concave planaire (PCG). Premièrement, le principe du fonctionnement a été compris afin de développer une solution analytique pour le champ de sortie en utilisant une approximation gaussienne du champ et de l'optique de Fourier. Ensuite, un outil de simulation semi-analytique de la réponse spectrale pour les deux configurations de multiplexeur a été développé dans MATLAB. La distribution normale des erreurs de phase a été introduite dans le modèle semi-analytique AWG, ce qui nous a permis d'étudier la corrélation entre l'écart-type des erreurs de phase et le niveau de diaphonie de la réponse spectrale AWG. AWG à 5,65 μm a été fabriqué à partir de la technologie SiGe / Si à l'aide de l'outil MATLAB pour le calcul des paramètres de conception et de l'outil P.Labeye pour le calcul de la géométrie AWG. Les dispositifs avec des paramètres légèrement variables ont été caractérisés: AWG1 avec guides d'ondes de 4,6 μm et MMI de 9 μm; AWG2 avec guides d'ondes de 4,6 μm et MMI de 11 μm; AWG3 avec guides d'ondes de 4,8 μm et MMI de 9 μm. Des mesures des dispositifs sur la puce 36 (centre de la plaquette) et sur la puce 32 (côté de la plaquette) ont été effectuées et analysées. Les mesures de température de AWG2 et AWG3 (puce 32 et puce 36) aux points cinq points de température ont montré une dépendance linéaire du déplacement spectral avec la température qui a une bonne corrélation avec les prédictions de simulation. / The work focuses on optical multiplexers operating in mid-IR for broadband source in gas sensing application. Two configurations were studies – arrayed waveguide grating (AWG) and planar concave grating (PCG). First, principle of operation was understood in order to develop analytical solution for output field using Gaussian approximation of the field and Fourier Optics. Then, semi-analytical simulation tool of the spectral response for both multiplexer configurations was developed in MATLAB. Normal distribution of phase errors was introduced to semi-analytical AWG model, which allowed us to study the correlation between standard deviation of phase errors and the level of crosstalk of AWG spectral response. AWG at 5.65 µm was fabricated based on SiGe/Si technology using the MATLAB tool for design parameters calculation and P.Labeye’s tool for AWG geometry calculation. Devices with slightly varying parameters were characterized: AWG1 with 4.6 µm waveguides and 9µm MMI; AWG2 with 4.6 µm waveguides and 11µm MMI; AWG3 with 4.8 µm waveguides and 9µm MMI. Measurements of devices on chip 36 (center of the wafer) and chip 32 (side of the wafer) were performed and analyzed. Temperature measurements of AWG2 and AWG3 (chip 32 and chip 36) at points five temperature points showed linear dependence of spectral shift with the temperature which has a good correlation with simulation predictions.

In this work, an electrochemical method based on a cyt c biosensor has been developed, for the detection of selected arsenic and cyanide compounds. Boron Doped Diamond (BDD) electrode was used as a transducer, onto which cyt c was immobilised and used for direct determination of Prussian blue, potassium cyanide and arsenic trioxide by inhibition mechanism. The sensitivity as calculated from cyclic voltammetry (CV) and square wave voltammetry (SWV), for each analyte in phosphate buffer (pH= 7) was found to be (1.087- 4.488 ×10-9 M) and the detection limits ranging from 0.0043- 9.1 μM. These values represent a big improvement over the current Environmental Protection Agency (EPA) and World Health Organisation (WHO) guidelines.

In this work, an electrochemical method based on a cyt c biosensor has been developed, for the detection of selected arsenic and cyanide compounds. Boron Doped Diamond (BDD) electrode was used as a transducer, onto which cyt c was immobilised and used for direct determination of Prussian blue, potassium cyanide and arsenic trioxide by inhibition mechanism. The sensitivity as calculated from cyclic voltammetry (CV) and square wave voltammetry (SWV), for each analyte in phosphate buffer (pH= 7) was found to be (1.087- 4.488 ×10-9 M) and the detection limits ranging from 0.0043- 9.1 μM. These values represent a big improvement over the current Environmental Protection Agency (EPA) and World Health Organisation (WHO) guidelines.

Magister Scientiae - MSc / In this work, an electrochemical method based on a cyt c biosensor has been developed, for the detection of selected arsenic and cyanide compounds. Boron Doped Diamond (BDD) electrode was used as a transducer, onto which cyt c was immobilised and used for direct determination of Prussian blue, potassium cyanide and arsenic trioxide by inhibition mechanism. The sensitivity as calculated from cyclic voltammetry (CV) and square wave voltammetry (SWV), for each analyte in phosphate buffer (pH= 7) was found to be (1.087- 4.488 ×10-9 M) and the detection limits ranging from 0.0043- 9.1 μM. These values represent a big improvement over the current Environmental Protection Agency (EPA) and World Health Organisation (WHO) guidelines. / South Africa

Formaldehyde-based adhesives have been reported to be detrimental to health. Petrochemical-based adhesives are non-renewable, limited and costly. Therefore, the improvement of environmental-friendly adhesive from natural agricultural products has awakened noteworthy attention. A novel adhesive for wood application was successfully prepared with enhanced shear strength and water resistance. The Fourier transmform infrared spectra showed the surface functionalities of the functionalized carbon nanotubes (FCNTs) and soy protein isolate nanocomposite adhesive. The attachment of carboxylic functional group on the surface of the carbon nanotubes (CNTs) after purification contributed to the effective dispersion of the CNTs in the nanocomposite adhesive. Hence, enhanced properties of FCNTs were successfully transferred into the SPI/CNTs nanocomposite adhesive. These unique functionalities on FCNTs however, improved the mechanical properties of the adhesive. The shear strength and water resistance of SPI/FCNTs was higher than that of the SPI/CNTs. SEM images showed the homogenous dispersion of CNTs in the SPI/CNTs nanocomposite adhesive. The carbon nanotubes were distributed uniformly in the soy protein adhesive with no noticeable clusters at relatively reduced fractions of CNTs as shown in the SEM images, which resulted into better adhesion on wood surface. Mechanical (shear) mixing and ultrasonication with 30 minutes of shear mixing both showed an improved dispersion of CNTs in the soy protein matrix. However, ultrasonication method of dispersion showed higher tensile shear strength and water resistance than in mechanical (shear) mixing method. Thermogravimetric analysis of the samples also showed that the CNTs incorporated increases the thermal stability of the nanocomposite adhesive at higher loading fraction. Incorporation of CNTs into soy protein isolate adhesive improved both the shear strength and water resistance of the adhesive prepared at a relatively reduced concentration of 0.3%.The result showed that tensile shear strength of SPI/FCNTs adhesive was 0.8 MPa and 7.25MPa at dry and wet state respectively, while SPI/CNTs adhesive had 6.91 MPa and 5.48MPa at dry and wet state respectively. There was over 100% increase in shear strength both at dry and wet state compared to the pure SPI adhesive. The 19% decrease in value of the new adhesive developed compared to the minimum value of ≥10MPa of European standard for interior wood application may be attributed to the presence of metallic particles remaining after purification of CNTs. The presence of metallic particles will prevent the proper penetration of the adhesive into the wood substrate. The type of wood used in this study as well as the processing parameters could also result into lower value compared to the value of European standard. Therefore, optimization of the processing parameter as well as the conversion of carboxylic acid group on the surface of the CNTs into acyl chloride group may be employed in future investigation. However, the preparation of new nanocomposite adhesive from soy protein isolate will replace the formaldehyde and petrochemical adhesive in the market and be of useful application in the wood industry. / Civil and Chemical Engineering / M. Tech. (Chemical Engineering)

La fonction barrière de la peau, qui protège l’organisme contre les molécules exogènes, limite la pénétration des actifs cosmétiques, ce qui réduit l’efficacité des molécules actives dans les couches profondes de l’épiderme. Il est alors apparu essentiel d'optimiser l'administration des actifs cosmétiques déjà existants afin d’en tirer tout le bénéfice escompté. Certaines innovations sont développées pour répondre à ce défi, notamment l’encapsulation des actifs cosmétiques dans des nanosystemes. En parallèle, il est nécessaire de s’intéresser aux méthodes analytiques capables de fournir une information qualitative et quantitative sur ces systèmes dispersés dans un produit fini complexe et de permettre une évaluation biologique à différents stades de développement des formulations. / The barrier function of the skin, which protects the body against exogenous molecules, limits the penetration of active cosmetic ingredients (ACI), thus reduce the effectiveness of molecules with a deep cellular target. Therefore, it appeared crucial to optimize the administration of existing active cosmetic in order to get the full benefits expected. Some innovations are explored to bypass this issue, including the encapsulation of existing active cosmetic in nanocarriers. In parallel, it is important to also focus on the development of analytical methodologies that could provide qualitative and quantitative information, in particular the determination of ACI contents and potentially excipients incorporated in a final form, and biological evaluation at different stages of formulation.