Scientific evidence shows that dietary intake of the omega-3 polyunsaturated fatty acids is beneficial to human health. Fish oil is a rich source of omega-3 fatty acids. However, fish oil with high levels of omega-3 PUFA is very susceptible to oxidative deterioration during storage. The objective of this study was to investigate the effect of xanthan gum (XG)-locust bean gum (LBG) mixtures on the physicochemical properties of whey protein isolate (WPI) stabilized oil-in-water (O/W) emulsions containing 20% v/v menhaden oil. The O/W emulsions containing XG/LBG mixtures were compared to emulsions with either XG or LBG alone. The emulsions were prepared using a sonicator by first mixing menhaden oil into the WPI solution and then either XG, LBG or XG/LBG mixtures were added. WPI solution (2 wt%) and gum solutions (0.0,0.05, 0.1, 0.15, 0.2 and 0.5 wt%) were prepared separately by dissolving measured quantities of WPI in distilled water. XG and LBG gums were blended in a synergistic ratios of 50:50 for the mixture. The emulsions were evaluated for apparent viscosity, microstructure, creaming stability and oxidative stability. Addition of 0.15, 0.2 and 0.5 wt% XG/LBG mixtures greatly decreased the creaming of the emulsion. The emulsion with 0.15, 0.2 and 0.5 wt% XG/LBG mixtures showed no visible serum separation during 15 d of storage. The apparent viscosity of the emulsions containing XG/LBG mixtures was significantly higher (p < 0.05) than the emulsions containing either XG or LBG alone. The viscosity was sharply enhanced at higher concentrations of XG/LBG mixtures. Microstructure images showed depletion flocculation for LBG (0.05-0.5 wt%), XG (0.05- 0.2 wt%) and XG/LBG mixtures (0.05 and 0.1 wt%) emulsions. Flocculation was decreased with the increased biopolymer concentration in the emulsion. The decrease in flocculation was much pronounced for the emulsion containing XG/LBG mixtures. The rate of lipid oxidation for 8 week storage was significantly (p < 0.05) lower in emulsions containing XG/LBG mixtures than in emulsions containing either of the biopolymer alone. The results suggested that the addition of XG/LBG mixtures greatly enhanced the creaming and oxidative stability of the WPI-stabilized menhaden O/W emulsion as compared to either XG or LBG alone.

The comprehension of the viscoelastic behaviour of metals is of high interest as these materials are subjected to dynamic loads in most of their structural applications, and also because it enables a deeper understanding of several technologically essential properties, like mechanical damping and yielding. Thus, research on this field is needed not only because it may lead to new potential applications of metals, but also because predictability of the fatigue response may be greatly enhanced. Indeed, fatigue is the consequence of microstructural effects induced in a material under dynamic loading, while the viscoelastic behaviour is also intimately linked to the microstructure. Accordingly, the characterization of the viscoelastic response of a material offers an alternative method for analysing its microstructure and ultimately its fatigue behaviour. This research is aimed at the identification, characterization and modelling of the effects of temperature, excitation frequency and microstructure/phase transformations (when present) on the viscoelastic behaviour of aluminium alloys AA 7075-T6 and AA 2024-T3, and of pure aluminium in the H24 temper. The identification of the mechanical relaxation processes taking place and the relation between the viscoelastic response of AA 7075-T6 and AA 2024-T3 and the fatigue behaviour will be attempted for all these materials. Finally, we intend to investigate possible influences of the dynamic loading frequency on fatigue, and especially the existence of a threshold frequency marking the transition from a static-like response of the material to the advent of fatigue problems. AA 7075-T6 and AA 2024-T3 were selected for this study because these alloys are key representatives of their important families and are highly suitable to a number of industrial applications in the aerospace sector and transport industry. Pure aluminium was selected because of the inherent interest of this metal, for comparison purposes and for discussing the phenomena observed for the alloys. To accomplish the objectives, the viscoelastic response of the materials was measured experimentally with a Dynamic- Mechanical Analyser (DMA). The results were combined with Transmission Electron Microscopy (TEM) and Differential Scanning Calorimetry (DSC). An analytical model was proposed which fits the storage modulus up to 300 ºC. The model takes into account the effect of temperature, the excitation frequency and the concentration of some precipitates for the alloys. This allows us to test models proposed for the reaction rates of the associated microstructural transformations, to determine their kinetic parameters and to characterize their influence on the viscoelastic behaviour, showing that the DMA is a good tool for studying the material microstructure, phase transformation kinetics and the influence of transformations on the viscoelastic properties of materials. The Time-Temperature Superposition (TTS) principle has been successfully applied to the DMA data, providing master curves for the storage and loss moduli. Also, it is proposed that the decrease of yield and fatigue strength with temperature observed in some aluminium alloys may be due to the internal friction increase with temperature. Finally, the existence of a threshold frequency is suggested, below which materials subjected to dynamic loading exhibit a static-like, elastic response, such that creep mechanisms dominate and deterioration due to fatigue may be neglected. A procedure to estimate this transition frequency is proposed. / La comprensión del comportamiento visco-elástico de los metales es de gran interés ya que estos están sometidos a cargas dinámicas en la mayoría de sus aplicaciones estructurales, y también porque posibilita un conocimiento más profundo de varias propiedades esenciales tecnológicamente, como el amortiguamiento mecánico y el límite elástico. Así, la investigación en este campo es necesaria no sólo porque puede conducir hacia nuevas aplicaciones potenciales de los metales, sino también porque la capacidad de predecir el comportamiento en fatiga de los mismos puede verse ampliamente mejorada. De hecho, la fatiga de los metales es consecuencia de efectos microestructurales inducidos en el material bajo cargas dinámicas, y el comportamiento visco-elástico está también íntimamente relacionado con la microestructura. Así, la caracterización de la respuesta visco-elástica de un material ofrece un método alternativo para analizar su microestructura y, en último término, su respuesta en fatiga. Este trabajo tiene por objetivos la identificación, caracterización y modelización de los efectos de la temperatura, la frecuencia de excitación y la microestructura/transformaciones de fase en el comportamiento visco-elástico de las aleaciones de aluminio AA 7075-T6 y AA 2024-T3, y de aluminio puro en estado H24. Se aborda también la identificación de los procesos de relajación mecánicos que tienen lugar en estos materiales y la identificación de la relación entre el comportamiento visco-elástico de AA 7075-T6 y 2024-T3 y su respuesta en fatiga. Finalmente, se intentará investigar posibles influencias de la frecuencia de la carga dinámica en la fatiga, y en especial la existencia de una frecuencia umbral que marque la transición desde una respuesta cuasi-estática del material hacia la aparición de problemas de fatiga. AA 7075-T6 y AA 2024-T3 fueron seleccionadas porque son representantes clave de sus importantes familias de aleaciones, y son altamente adecuadas para un gran número de aplicaciones en los sectores aeroespacial y del transporte. El aluminio puro fue seleccionado para este estudio por su interés inherente, y para realizar comparaciones y discutir algunos de los fenómenos observados en las aleaciones. Para cumplir los objetivos, el comportamiento visco-elástico de los materiales fue medido experimentalmente con un Dynamic-Mechanical Analyser (DMA). Los resultados se combinaron con microscopía electrónica y calorimetría. Se propuso un modelo analítico que ajusta la componente real del módulo elástico dinámico (el storage modulus) hasta 300 ºC. El modelo toma en consideración los efectos de la temperatura, la frecuencia de la carga dinámica y la concentración de ciertos precipitados para el caso de las aleaciones. Esto permitió testear modelos propuestos para las velocidades de reacción de las transformaciones microestructurales asociadas, determinar sus parámetros cinéticos y caracterizar su influencia en el comportamiento visco-elástico, demostrando que el DMA es una buena herramienta para estudiar la microestructura del material, la cinética de las transformaciones de fase y la influencia de las transformaciones en las propiedades visco-elásticas de los materiales. El principio de superposición de tiempo y temperatura ha sido aplicado con éxito, proporcionando curvas maestras para las componentes del módulo elástico dinámico. Asimismo, se sugiere que el descenso en el límite elástico y la resistencia a fatiga con la temperatura observado en algunas aleaciones de aluminio puede ser debido al incremento de la fricción interna con la temperatura. Finalmente, se propone la existencia de una frecuencia umbral, por debajo de la cual los materiales sometidos a cargas dinámicas exhiben una respuesta cuasi-estática y elástica, de tal modo que mecanismos de termofluencia son dominantes y el deterioro del material debido a fatiga puede ser despreciado. Se propone un procedimiento para estimar esta frecuencia de transición.

L'addition de nanotubes de carbone multiparois (MWNT) dans une matrice de polyamide 12 (PA 12), électriquement isolante, permet d'augmenter les propriétés électriques vers un comportement conducteur. Cette modification est influencée par l'arrangement des MWNT en chemins de conduction qui permettent le transfert des charges électriques entre deux électrodes. La conductivité électrique des nanocomposites isotropes atteint une valeur asymptote (~10-2 S.m-1) pour des teneurs supérieures à 1,2% en masse (seuil de percolation électrique). En microinjection, les nanocomposites sont soumis à des taux de cisaillement très élevés (~104 s-1) et des gradients de températures extrêmes, qui conditionnent fortement la microstructure et les propriétés électriques de pièces mises en forme par ce procédé. Cette thèse a eu pour but d'expliquer l'influence de la vitesse de cisaillement (0,02 s-1 - 1 s-1) et la vitesse de refroidissement (3 °C.min-1) sur l'évolution des propriétés électriques du nanocomposite PA12/MWNT. L'analyse de ces propriétés a permis de déduire, à l'état fondu, l'évolution de l'arrangement de MWNT dans cette fenêtre de conditions. Dans les pièces microinjectées, nous constatons une perte complète du comportement conducteur dans la direction normale au plan d'écoulement et une chute de la conductivité dans les directions d'injection et transverse. Ces faits suggèrent alors un arrangement en forme d'agrégats faiblement orientés dans le plan d'écoulement, qui est corroboré par la très large distribution d'orientation déterminée par l'analyse en spectroscopie Raman des pièces micro-injectées. Lors du procédé de microinjection, les agrégats de MWNT seraient alors cassés dans des agrégats plus petits, mais fortement déconnectés les uns des autres, expliquant ainsi la chutedes propriétés électriques mais aussi l'observation d'une microstructure quasi isotrope à l'échelle macro et micro.

Plasma sprayed Thermal Barrier Coating systems (TBCs) are commonly used for thermal protection of components in modern gas turbine application such as power generation, marine and aero engines. The material that is most commonly used in these applications is Yttria Partially Stabilized Zirconia (YPSZ) because of this ceramic’s favourable properties, such as low thermal conductivity, phase stability to high temperature, and good erosion resistance. The coating microstructures in YPSZ coatings are highly heterogeneous, consisting of defects such as pores and cracks of different sizes which determine the coating’s final thermal and mechanical properties, and the service lives of the coatings. Determination of quantitative microstructure–property correlations is of great interest as experimental procedures are time consuming and expensive. Significant attention has been given to this field, especially in last fifteen years. The usual approach for modelling was to describe various microstructural features in some way, so as to determine their influence on the overall thermal conductivity of the coating. As the analytical models over-simplified the description of the defects, various numerical models were developed which incorporated real microstructure images.This thesis work describes two modelling approaches to further investigate the relationships between microstructure and thermal conductivity of TBCs. The first modelling approach uses a combination of a statistical model and a finite element model which could be used to evaluate and verify the relationship between microstructural defects and thermal conductivity. The second modelling approach uses the same finite element model along with a coating morphology generator, and can be used to design low thermal conductivity TBCs. A tentative verification of both the approaches has been done in this work.

A systematic study of propylene polymerization using a 4th generation Ziegler-Natta catalyst is presented in this thesis. The apparent kinetic rate constants for propylene polymerization were estimated in the presence and absence of hydrogen and/or donor. The estimated activation energies for activation, propagation, and deactivation were found to be close to values previously reported in the literature for similar catalysts. The polypropylene samples were characterized using high-temperature gel permeation chromatography (GPC), carbon-13 nuclear magnetic resonance (13C NMR), and crystallization elution fractionation (CEF). The effect of hydrogen and external electron donor on polypropylene microstructure was investigated at two polymerization temperatures. In addition to the expected electron donor positive effect on tacticity, hydrogen was also found to increase polypropylene tacticity. The effect of changing these polymerization conditions on molecular weight and polydispersity was also investigated. Finally, CEF profiles show how the distribution of polypropylene crystallizability changes by adding hydrogen and electron donor to the reactor. The concentrations of hydrogen and external donor were also varied to study their effect of polymerization kinetics and polymer microstructure. The estimated activation energies were close to those found in the first part of this investigation in the presence and/or absence of donor and hydrogen. A polypropylene microstructural study showed a positive effect of hydrogen concentration on mmmm pentad at low donor concentration, likely due to an increase in stereoselectivity of the aspecific sites by hydrogen. However, increasing donor concentration over a given threshold seems to transform the aspecific sitess into stereospecific sites that are no longer significantly affected by hydrogen. These experimental results were compared to a previously developed Monte Carlo model and found to agree with the trends predicted by simulation. Finally, the effect of diisopropyldimethoxysilane (P), n-propyltrimethoxysilane (N), paraethoxyethylbenzoate (PEEB), and dicyclopentyldimethoxysilane (D) external donors on catalyst activity and stereoselectivity was investigated. P and D donors were more stereoselective than N and PEEB donors; however, D donor had the best activity among all donors investigated. Therefore, D donor was mixed with PEEB to combine its high activity with the self-extinguishing properties of PEEB. The D/PEEB 90/10 (mol/mol) mixture generated a catalyst with good stereoselectivity but poor activity. When the ratio was increased to 95/5 and 98/2, the resulting catalyst had high activity and good stereoselectivity. Interestingly, the D/PEEB combination with just a small fraction of PEEB has a positive effect on the catalysts activation term which may decrease polymerization costs with this system.

Because of its low density and high strength, magnesium (Mg) and its alloys are being sought after in the automotive industry for structural applications. Although many road-going cars today contain cast Mg parts, in the fabrication of chassis structural members the wrought alloys are required. One of the challenges of fabrication with wrought Mg is welding and joining the formed sheets. Because of the commonly observed difficulties in fusion welding of Mg such as hot cracking and severe Heat Affected Zone (HAZ), this work aimed to establish the feasibility of the solid-state process Magnetic Pulse Welding in producing lap welds of Mg sheet. Mg AZ31 alloy sheets have been lap-welded with Magnetic Pulse Welding (MPW), an Impact Welding technique, using H-shaped symmetric coils connected to a Pulsar MPW-25 capacitor bank. MPW uses the interaction between two opposing magnetic fields to create a high speed oblique collision between the metal surfaces. The oblique impact sweeps away the contaminated surface layers and forces intimate contact between clean materials to produce a solid-state weld. Various combinations of similar and dissimilar metals can be welded using MPW. Other advantages of MPW are high speed, high strength, and the possibility of being mounted on a robotic arm. The present research focuses on the feasibility and mechanical performance of an MPW weld of 0.6 mm AZ31 Mg alloy sheets made in a lap joint configuration. Tensile shear tests were carried out on the joints produced. Load bearing capacity showed linear increase with capacitor bank discharge energy up to a certain value above which a parabolic increase was seen. Strength was estimated to be at least as high as base metal strength by measuring the fracture surface area of selected samples. The fracture surface of samples welded at higher discharge energy showed two regions. In the beginning of the bond a platelet-featured fracture brittle in appearance and a ductile, micro-voiding fracture in the latter part. The joint cross section morphology consisted of a flattened area that had two symmetric bond zones 1 mm wide each separated by an unbonded centre zone ~3mm wide. Reasons for the morphology were presented as a sequence of events based on the transient nature of the oblique collision angle. The interface microstructure was studied by optical and electron microscopy. Examination of the bonds has revealed sound and defect free interfaces. No microcracking, porosity, resolidification, or secondary phase formation was observed. Metallographic examination of the unbonded centre zone revealed anisotropic deformation and a lack of cleaning from the interface. This zone is formed as a result of normal impact in the initial stage of collision. The bond zone interface of the joint was characterized by a smooth interface consisting of refined grains. In samples welded at higher energy interfacial waves developed in the latter half of the bond zone. Transmission electron microscopy (TEM) of the bond zone revealed a continuous interface having an 8-25 μm thick interlayer that coincided with the waves and had a dislocation cell structure and distinct boundaries with adjacent material. Equiaxed 300 nm dynamic recrystallized (DRX) grains were found adjacent to the interlayer as well as other slightly larger elongated grains. The interlayer is thought to be formed in plasticized state at elevated temperature through severe shear strain heating. The interlayer corresponds to a ductile fracture surface and, along with the interfacial waves, is responsible for the joint’s high strength.

In this work, we investigate the relation between the diffusion behavior of Ti1-xAlxN at elevated temperatures and the microstructure. Thinfilm samples are synthesized by reactive co-sputtering with two cathodes. One cathode equipped with Ti target is connected to a highpower impulse magnetron sputtering (HiPIMS) power supply, and the other cathode equipped with Al target is operated with a directcurrent power source. The spinodal decomposition of cubic metastable Ti1-xAlxN controlled by thermally activated diffusion is observe fordiffusion behavior. Various HiPIMS pulsing frequencies are used to achieve different microstructure, while altered power applied to Altarget is used to change the Al content in films. In the phase composition analysis achieved by GI-XRD, the right-shift of (111) film peakalong with increasing Al-power is observed. A saturation of the right-shift and h-AlN peaks are also observed at certain Al-power. Thechemical composition determined by ERDA shows trends of reducing Al solubility limit in metastable phase and O contamination upondecreasing the pulsing frequency. More N deficiency is found in samples deposited with higher frequency. In the 500 Hz and 250 Hzsamples deposited into similar composition and thickness, no apparent difference of the microstructure is observed from the SEM crosssectionalimages. From HT-XRD, we observe higher intensity of TiO2 and h-AlN peaks in 500 Hz sample at elevated temperature ascompared with 250 Hz one. From the reduction of O contamination, denser Ti1-xAlxN films are able to be deposited with lower HiPIMSpulsing frequency. In addition, the higher intensity observed in HT-XRD patterns indicates that the 500 Hz sample is more open todiffusion and therefore allows the new formed phases to grow in larger grains.

This thesis contains two components of research: studies of supercontinuum pulses generated in the novel microstructure fiber, and research on spatio-temporal coupling in ultrafast laser beams. One of the most exciting developments in optics in recent years has been the invention of the microstructure optical fiber. By controlling the structural parameters of these novel fibers in design and manufacturing, their dispersion profile can be freely tailored, opening up a huge application base. One particularly interesting effect in the microstructure fiber is the generation of ultrabroadband supercontinuum with only nJ-level Ti:sapphire oscillator pulse pump. This supercontinuum is arguably the most complicated ultrafast pulse ever generated, with its huge time-bandwidth product (> 1000 from a 16-cm-long fiber). Although many applications have been demonstrated or envisioned with this continuum, its generation is a very complicated process that is poorly understood, and the characteristics of the continuum pulses are not clearly known. In this work, we make a full-intensity-and-phase measurement of the continuum pulses using cross-correlation frequency-resolved optical gating (XFROG). The results reveal surprising unstable fine spectral structure in the continuum pulses, which is confirmed by single-shot measurements. Our study on the coherence of the continuum, on the other hand, shows that the spectral phase of the supercontinuum is fairly stable. Numerical simulations are carried out whose results are in good agreement with experiments. The second component of this thesis is the study of spatio-temporal coupling in ultrafast beams. We propose two definitions of spatial chirp, point out their respective physical meanings, and derive their relationship. On the common perception of the equivalence between pulse-front tilt and angular dispersion, we show that the equivalence only holds for plane waves. We establish a generalized theory of ultrafast laser beams with first-order spatio-temporal couplings, and discover a new pulse-front tilt effect associated with the combination of spatial chirp and temporal chirp. For the measurement of spatio-temporal distortions, the effects of such distortions in the input beam to a GRENOUILLE trace are carefully studied. An algorithm is proposed and tested to retrieve information about the distortions from the GRENOUILLE trace.

This thesis describes the creation of a metrology system based upon an actively controlled diffraction grating interferometer, which measures relative linear distances. The dynamics of this sensor are estimated based on experimental testing, and a suitable controller is designed to maintain the position of the sensor in the most sensitive operating region. This controller is implemented on a field programmable gate array (FPGA) processor, which allows for flexible programming and real-time control. The sample under test is mounted atop a three axis linear stage system, which allows the diffraction grating interferometer to scan across the surface of the device, creating maps of the static and dynamic measurements. The controller is shown to maintain the sensitivity of the sensor during this operation. This insures all data are taken on the same scale, creating more accurate results. The controller increases the signal to noise ratio as compared to the system without the controller. The specifications of the entire metrology system are detailed including the sensor and controller bandwidth, the vertical and horizontal resolution, and the signal to noise ratio. A case study utilizing a capacitive micromachined ultrasonic transducer (cMUT) is presented. The sensor generates static and dynamic displacement maps of the surface of this MEMS device. The controller improves these measurements by maintaining a position of high sensitivity during operation. Finally, the preliminary results of a miniaturized version of this system are presented including the implementation of two fully independent parallel sensors. This allows for array implementation of these sensors, which is crucial for the batch fabrication photolithography techniques used to create many MEMS devices. Recommendations on the future work needed to complete the array implementation are given in conjunction with methods for increasing the resolution and robustness of the macroscale system described in this thesis.

An effective way to describe changes in the microstructure of a material or to assess fatigue damage at an early stage in fatigue life is by measuring the acoustic nonlinearity parameter beta. The nonlinearity parameter is defined for harmonic longitudinal plane waves and it depends on the ratio of the amplitudes of the first harmonic of the exciting signal and the second harmonic. A reliable measurement of the amplitudes of these harmonics is crucial since their amplitude of the second (higher) harmonic is much smaller than the amplitude of the first harmonic. This research investigates the influence of the apparent nonlinearity that can occur due to the signal processing and shows how this influence can be quantified and minimized to enable a more accurate evaluation of the acoustic nonlinearity parameter. Furthermore the concept of the nonlinear parameter is extended to Rayleigh surface waves by developing a connection between the harmonic amplitudes and the third order elastic constants, using the approximate model by Zabolotskaya. Finally the problem of modeling the influence of fatigue damage on the nonlinear parameter and the elastic constants is discussed. The reduction of the processing nonlinearity combined with Rayleigh surface waves - Rayleigh surface waves are more efficient in the detection of fatigue damage initiated and concentrated at the surface - helps improve the prediction of fatigue damage and the remaining life of a sample.