Acrolein is an indispensable chemical intermediate with a rising demand in recent years. The concern of the increase of propylene prices due to the shrinking supply of nonrenewable crude oil makes the acid-catalyzed gas-phase glycerol dehydration to acrolein a prime candidate for research. Our analysis showed that the sustainable acrolein production from glycerol was both technically and economically viable. Alumina2700® (Al) and Silica1252® (Si) loaded with silicotungstic acid (HSiW) possessed distinct features while provided equally good acrolein yield (73.86mol% and 74.05mol%, respectively) optimally. Due to the unique non-equilibrium characteristics, non-thermal plasma (NTP) could promote a variety of chemical reactions; however, its application in a dehydration process remained blank. This study used the reaction of glycerol dehydration to acrolein to probe whether NTP could 1) improve acrolein yield during dehydration, 2) suppress the coke formation and regenerate the catalyst, and 3) modify the properties of the catalyst. The dielectric barrier discharge configuration was used to generate NTP; various NTP field strengths and also their interaction with temperature and the catalyst were investigated. The results showed that NTP improved the glycerol conversion and that NTP with a proper field strength increased acrolein selectivity. The optimal acrolein yields of 83.6 mol% and 83.1 mol% were achieved with 3.78 kV/cm NTP and 4.58 kV/cm NTP at 275°C for HSiW-Al and HSiW-Si, respectively. The application of NTP-O2 (5% oxygen in argon, 4.58 kV/cm) during glycerol dehydration significantly suppressed coke formation on HSiW-Si. NTP-O2 could regenerate the deactivated HSiW-Si at low temperatures by removing both soft and hard coke at various rates. NTP-O2 with higher field strength, at medium operation temperature (150ºC) and in argon atmosphere was more effective for coke removal/catalyst regeneration. Applying NTP to the catalyst fabrication showed some capabilities in modifying catalyst properties, including enlarging surface area, preserving mesopores, increasing acid strength and Brønsted acidity. NTP with argon as the discharge gas performed better in these modifications than NTP with air as the discharge gas.

Microfluidic technology has been grown rapidly in the past decade. Microfluidics can find wide applications in multiple fields such as medicine, electronics, chemical and biology. Micro-pumping is an essential part of a microfluidic system. This thesis presents the optimization process of AC electro-thermal micropump with respect to the geometry of electrode array and channel height. The thesis first introduces the theories of AC electrokinetic including dielectrophoresis, AC electro-osmosis (ACEO) and AC electro-thermal (ACET). Also presented are the basic theory and governing equations of microfluidics, the continuity equation, the Navier-Stokes equation, and the conservation of energy equation. AC electro-thermal effect results from the interplays between electric field, temperature field and fluid mechanics. Since the governing equations are highly non-linear, numerical simulation is extensively used to understand the effects of factors such as the electrode dimensions and channel height. By interfacing finite element analysis software COMSOL Multiphysics with Matlab, to the simulation model is able to scan the geometry variables so as to find the optimal micropump design. The optimization has been performed with respect to flow rate and power efficiency of the micropump.

La déformation en traitement thermique est associée à des mécanismes complexes du fait de l'interaction d'un grand nombre de paramètres technologiques et physiques. Dans ce contexte, la méthode développée dans ces travaux de thèse définit un cadre générique pour étudier l'influence de ces paramètres sur la déformation d'un produit. Cette méthode comporte trois facettes d'intérêt. La première est la qualification de la déformation au moyen de signatures géométriques 3D significatives, choisies pour leur réalité physique : les phénomènes de déformations. Ceux-ci sont ensuite quantifiés et leur pertinence est évaluée par un indicateur de niveau de confiance. La deuxième facette de la méthode est la possibilité de confronter directement les résultats expérimentaux et ceux issus de la simulation numérique. La prédiction de la déformation est ainsi vérifiée en comparant les amplitudes des signatures géométriques. La troisième et dernière facette est la compréhension des mécanismes de la déformation. Elle s'effectue par le suivi des amplitudes des phénomènes de déformations en fonction des effets thermiques, métallurgiques et mécaniques survenant lors du traitement thermique. Appliquée à l'éprouvette croissant, la méthode a permis d'illustrer l'influence de deux paramètres sur la déformation : la nuance d'acier et le milieu de trempe. Pour cela, les phénomènes de déformations ont été séparés en deux catégories : la première correspond à la variation homogène des dimensions dues aux effets thermomécaniques, la seconde, à la partie hétérogène due aux effets métallurgiques et mécaniques. L'application de la méthode à un cas issu de la simulation numérique 3D a révélé la prédiction satisfaisante des signatures géométriques, y compris celles locales. Les investigations numériques ont permis d'appréhender les mécanismes de la déformation du croissant et de mettre en évidence la forte sensibilité de certains phénomènes de déformations face à la variation des paramètres expérimentaux, utilisés comme données initiales dans les simulations.

With respect to nitrides being considered as potential fast reactor fuels, research is conducted on the out-of-pile thermophysical properties, sintering and fabrication processes, gas migration mechanisms, self-diffusion and point defect behaviour of actinide nitrides, their surrogate materials, and the inert matrix material ZrN . The experimental research, carried out in the framework of qualifying fuel for the European Lead Cooled Training Reactor (ELECTRA), shows that sintered ZrN and (Dy,Zr)N pellet densities are influenced by the oxygen concentration in the material. The effect is confirmed in sintered (Pu,Zr)N pellets. Oxygen concentration also plays a role in the thermophysical properties of inert matrix nitride fuels, but does not have an impact on the electrical properties of these materials. With the fuel fabrication methods applied here, clean nitride powders can be synthesized. However, the subsequent fabrication phases, including milling and solid solution formation, increases the impurity levels significantly. Research of equal importance is performed on materials free of fabrication-induced impurities, whose properties are studied by employing first-principles methods. ZrN, UN and (U,Zr)N are studied, whereas the results from ZrN are expected to be applicable for actinide nitrides as a first approximation. The migration of noble gases in ZrN, on the atomic scale, confirms the experimentally observed tendency for noble gases with higher atomic number to be retained in the fuel matrix, while the majority of He is released to the fuel pin. Materials modelling implies that self-diffusion of nitrogen and metal atoms in inert matrix nitride fuels is accelerated under irradiation, since noble gas retention reduces migration barriers which govern self-diffusion. Unlike Kr and Xe, He has the capacity to be released into the fuel matrix, after having been trapped in a vacancy. The results are expected to aid in providing an explanation to the macroscopic diffusion phenomena in nitride fuels, as the diffusion behaviour of noble gases is sparsely studied. In addition, a study on the miscibility of ZrN and UN in a narrow composition range suggests solubility, based on the negative mixing energies. The results obtained from research on inert matrix nitride fuel underline several beneficial properties which are desirable in a fast reactor fuel. The relevance of these results is analyzed and contextualized in the thesis, from the perspective of current research and development in the field. / <p>QC 20130611</p>

The commercially available solar cells suffer from low conversion efficiency due to the thermalization and transmission losses arising from the mismatch between the band gap of the semiconductor materials and the solar spectrum. Advanced device architectures based on nanomaterial have been proposed and being successfully used to enhance the efficiency of the solar cells. Quantum dots (QDs) and nanowires (NWs) are the nanosclae structures that have been exploited for the development of the third generation solar cell devices and nanowire based solar cells, respectively. The optical and electrical properties of these materials can be tuned by their size and geometry; hence they have great potential for the production of highly efficient solar cell. Application of QDs and NWs with enhanced optoelectronic properties and development of low-cost fabrication processes render a new generation of economic highly efficient PV devices. The most significant contribution of this PhD study is the development of simple and cost effective methods for fabrication of nanowires and quantum dots for advanced solar cell architectures. In advanced silicon nanowires (SiNWs) array cell, SiNWs have been widely synthesised by the well-known vapor-liquid-solid method. Electron beam lithography and deep reactive ion etching have also been employed for fabrication of SiNWs. Due to the high price and complexity of these methods, simple and cost effective approaches are needed for the fabrication of SiNWs. In another approach, to enhance the cell efficiency, organic dyes and polymers have been widely used as luminescent centers and host mediums in the luminescent down shifting (LDS) layers. However, due to the narrow absorption band of the dyes and degradation of the polymers by moisture and heat, these materials are not promising candidates to use as LDS. Highly efficient luminescent materials and transparent host materials with stable mechanical properties are demanded for luminescent down shifting applications. In this project, simple fabrication processes were developed to produce SiNWs and QDs for application in advanced cell architectures. The SiNWs array were successfully fabricated, characterized and deployed in new cell architectures with radial p-n junction geometry. The luminescence down shifting of layers containing QDs in oxide and glass mediums was verified. The silica coated quantum dots which are suitable for luminescence down shifting, were also fabricated and characterized for deployment in new design architectures. Silicon nanowires were fabricated using two simplified methods. In the first approach, a maskless reactive ion etching process was developed to form upright ordered arrays of the SiNWs without relying on the complicated nano-scale lithography or masking methods. The fabricated structures were comprehensively characterized. Light trapping and photoluminescence properties of the medium were verified. In the second approach, combination of the nanosphere lithography and etching techniques were utilized for wire formation. This method provides a better control on the wire diameters and geometries in a very simple and cost effective way. The fabricated silicon nanowires were used for formation of the radial p-n junction array cells. The functionality of the new cell structures were confirmed through experimental and simulation results. Quantum dots are promising candidates as luminescent centers due to their tunable optical properties. Oxide/glass matrices are also preferred as the host medium for QDs because of their robust mechanical properties and their compatibility with standard silicon processing technology. Besides, the oxide layers are transparent mediums with good passivation and anti-reflection coating properties. They can also be used to encapsulate the cell. In this work, ordered arrays of QDs were incorporated in an oxide layer to form a luminescent down shifting layer. This design benefits from the enhanced absorption of a periodic QD structure in a transparent oxide. The down shifting properties of the layer after deployment on a crystalline silicon solar cell were examined. For this purpose, crystalline silicon solar cells were fabricated to use as test platform for down shifting. In order to examine the down-shifting effect, different approaches for formation of a luminescence down shifting layer were developed. The LDS layer consist of cadmium selenide- zinc sulfide (CdSe/ZnS) quantum dots in oxide and glass layers to act as luminescent centers and transparent host medium, respectively. The structural and optical properties of the fabricated layers were studied. The concept of spectral engineering was proved by the deployment of the layer on the solar cell. To further benefit from the LDS technique, quantum efficiency of the QDs and optical properties of the layer must be improved. Demand for the high quantum efficiency material with desired geometry leaded us to synthesis quantum dots coated with a layer of grown oxide. As the luminescence quantum efficiency of the QDs is correlated to the surface defects, one advantage of having oxide on the outer shell of the QDs, is to passivate the surface non-radiative recombination centers and produce QDs with high luminescent quantum yield. In addition, nanoparticles with desired size can be obtained only by changing the thickness of the oxide shell. This method also simplifies the fabrication of QD arrays for luminescence down shifting application, since it is easier to form ordered arrays from larger particles. QD superlattices in an oxide medium can be fabricated on a large area by a simple spin-coating or dip coating methods. The photonic crystal properties of the proposed structure can greatly increase the absorption in the QDs layer and enhance the effect of down shifting.

Composites have been developed with great success by the use of fiber reinforcements in metallic materials. Fiber reinforced metal matrices possess great potential to be the next generation of advanced composites offering many advantages compared to fiber reinforced polymers. Specific advantages include high temperature capability, superior environmental stability, better transverse modulus, shear and fatigue properties. Although many Metal Matrix Composites (MMCs) are attractive for use in different industrial applications, Aluminium Matrix Composites (AMCs) are the most used in advanced applications because they combine acceptable strength, low density, durability, machinability, availability, effectiveness and cost. The present study focuses on the fabrication of aluminium matrix composite plates by squeeze casting using plain weave carbon fiber preform (AS4 Hexcel) as reinforcement and a matrix of wrought aluminium alloy 1235-H19. The objective is to investigate the process feasibility and resulting materials properties such as hardness at macro- and micro-scale, impact and bend strength. The properties obtained are compared with those of 6061/1235-H19 aluminium plates that were manufactured under the same fabrication conditions. The effect of fiber volume fraction on the properties is also investigated. Furthermore, the characterization of the microstructure is done using Optical Microscopy (OM) and Scanning Electron Microscopy (SEM) in order to establish relationships between the quality of the fiber/aluminium interface bond and mechanical properties of the composites. In conclusion, aluminium matrix composite laminate plates were successfully produced. The composites show a good chemical bond between the fiber and the aluminium matrix. This bond resulted from heterogeneous precipitation of aluminium carbides (Al4C3) at the interface between aluminium matrix and carbon fiber. The hardness at macro- and micro-scale of the composites increases by over 50% and the flexural modulus increases by about 55%. The toughness of the composite decreases due to the presence of brittle phases which can be improved by better oxidation prevention. Also, an optimal carbon volume fraction was observed that provides optimal properties including peak hardness, peak stiffness and peak toughness.

L'objectif de la thèse est de créer et développer de nouvelles méthodes de résolution efficaces des problèmes combinatoires en configuration des lignes de fabrication. Deux problèmes ont été particulièrement étudiés: le problème d'équilibrage et de choix d'équipement pour des lignes dédiées et le problème de minimisation des coûts de changements de séries pour des lignes multi-produits. Une solution du premier problème consiste en une affectation admissible des ressources à un nombre de stations à déterminer de sorte que le coût total soit minimal. Afin de résoudre ce problème, nous l'avons réduit au problème de partition d'ensemble et l'avons résolu par des heuristiques gloutonnes et une méthode exacte de génération de contraintes. Les expérimentations sur différentes instances ont montré que la nouvelle approche de résolution surclasse les approches antérieures de la littérature en termes de qualité de solution et de temps de calcul. Pour le second problème deux critères sont considérés lexicographiquement : la minimisation du nombre de stations et la minimisation du coût de changement de séries. Nous avons examiné successivement les cas d'exécution parallèle et séquentielle des opérations. Des solutions approchées ont été trouvées par des heuristiques gloutonnes. Ensuite, nous avons proposé deux modèles de programmation linéaire en nombres entiers (PLNE) afin de trouver le nombre de stations minimal et ensuite d'obtenir le coût de changement de séries minimal. Les résultats des expérimentations sur ces nouveaux problèmes se sont avérés prometteurs à la fois en termes de qualité de solution et de temps de calcul.

Self-assembling peptides have emerged as new nanobiomaterials and received considerable attention in the areas of nanoscience and biomedical engineering. In this category are ionic-complementary peptides, which contain a repeating charge distribution and alternating hydrophobic and hydrophilic residues in the amino acid sequence, leading to the unusual combination of amphiphilicity and ionic complementarity. Although their self-assembled nanostructures have been successfully applied as scaffoldings for tissue engineering, novel materials for regenerative medicine and nanocarriers for drug and gene/siRNA delivery, aspects of the assembly process remain unclear. Since many of these applications involve peptide-modified interfaces and surfaces, a better understanding and control of the peptide assembly on a surface are very crucial for future development of peptide-based applications in nano-biotechnology. This thesis contains two major parts: (i) fundamental study of the assembly of a model ionic-complementary peptide EAK16-II on surfaces and (ii) potential applications of such a peptide in surface modification and nanofabrication. In the fundamental study, EAK16-II assembly on negatively charged mica was first investigated via in-situ Atomic Force Microscopy (AFM). It was found that EAK16-II nanofiber growth on mica is surface-assisted and follows a nucleation and growth mechanism involving two steps: (i) adsorption of nanofibers and fiber clusters (from the bulk solution) on the surface to serve as the seeds and (ii) fiber elongation from the active ends of the seeds. Such a process can be controlled by adjusting the solution pH since it modulates the adsorption of the seeds and the growth rates. Unlike what is observed on mica, EAK16-II formed well-ordered nanofiber patterns with preferential orientations at angles of 60° or 120° to each other on hydrophobic highly ordered pyrolytic graphite (HOPG) surfaces, resembling the crystallographic structure of the graphite. Nanofiber formation on HOPG is also surface-assisted and adopts a nucleation and growth mechanism that can be affected by solution pH. The pH-dependent adsorption of peptides to HOPG is attributed to the resulting changes in peptide hydrophobicity. It was also found that EAK16-II assembly can be induced by the mechanical force of a tapping AFM tip. It occurs when the tip cuts the adsorbed EAK16-II nanofibers into segments that then serve as seeds for new nanofiber growth. This finding allows one to locally grow nanofibers at specific regions of the surface. The tip cutting has been combined with the effect that solution pH has on peptide assembly to develop a new AFM lithography method to fabricate local patterned peptide nanostructures on HOPG. To study the use of EAK16-II for surface modification applications, the wettability and stability of the peptide-modified surfaces were characterized. EAK16-II-modified mica becomes slightly hydrophobic as the water contact angle increases from <10° to 20.3 ± 2.9°. However, the hydrophobicity of the HOPG surface is significantly reduced, as reflected in a contact angle change from 71.2 ± 11.1° to 39.4 ± 4.3°. The EAK16-II-modified mica surface is stable in acidic solution, while the modified HOPG surface is stable in both acidic and alkaline solutions. The peptide-modified HOPG shows potential as a biocompatible electrode for (bio)molecular sensing. The ability of EAK16-II to form nanofibers on surfaces has also promoted research on peptide-based metallic nanowire fabrication. Our approach is to provide EAK16-II with metal ion binding ability by adding a GGH motif to the C-terminus. This new peptide EAK16(II)GGH has been found to form one-dimensional nanofibers while binding to Cu2+ ions. The dimensions of the nanofibers were significantly affected by the nature of the anions (SO42-, Cl- and NO3-) in the copper salt solution. This work demonstrates the potential usage of EAK16-II for nanowire fabrication.

The purpose of the present study was to assess the feasibility of a laser layer manufacturing technique for realization of shape memory alloy (SMA) components with complex geometry. Pre-placed laser solid freeform fabrication (LSFF) was utilized to produce straight and curvaceous SMA parts from a mixture of 55.2 wt%Ni - 44.8 wt%Ti powder. A pulsed Nd:YAG laser was used; while laser pulse width and frequency were held constant at what are considered their optimal values (4 ms and 50 Hz, respectively), laser energy and scanning speeds were varied across samples to determine appropriate values for fabrication of high quality SMA parts . Different pre-placed powder thicknesses were deposited and then mechanically and physically studied. Optical microscopy, SEM, EDS, and XRD methods, as well as microhardness measurements, were used to examine the microstructural characteristics and hardness of the SMA samples. Also, differential scanning calorimetry (DSC) was performed to determine the transformation temperatures of the fabricated parts. The results confirmed the formation of crack-free solid surfaces in which two types of microstructure exist: solid (non-prose) and dendrite arms. EDS chemical composition analysis confirmed the absence of any impurity or oxidise in the cross section of the samples as well as the presence of only nickel and titanium. XRD spectrum analysis indicated the presence of Ni-Ti intermetallic phases, which are almost Ni-Ti but contain a small amount of Ti2Ni. The XRD results also indicated the presence of austenite and martensite phases, which are exchanged during heating or mechanical deformation. The hardness of these samples varied from 250 to 450 HV0.3. Several tests were carried out to investigate the shape memory effect (SME). It was observed that the fabricated SMAs can recover from the bent condition very quickly (i.e., 1 to 8 seconds) depending on their thickness. In general, the fabricated parts were first bent out of their original shapes then heated, in various ways, above the transformation temperature. To theoretically assess the SME performance of the fabricated SMAs with the proposed geometry two models were developed. The first model was established based upon a lump approach in which the part was exposed to an electrical current. The second model, however, was established based upon a finite element method in which a specific domain at one end of the sample was exposed to a source of heat. It was found that the theoretical outputs from both models were in good agreement with the experimental results.

Electrostatically actuated parallel-plate MEMS tunable capacitors are desired elements for different applications including sensing, actuating and communications and RF (radio frequency) engineering for their superior characteristics such as quick response, high Q-factor and small size. However, due to the nature of their coupled electrostatic-structural physics, they suffer from low tuning range of 50% and have nonlinear capacitance-voltage (C-V) responses which are very sensitive to the voltage change near pull-in voltage. Numerous studies in the literature introduce new designs with high tunability ranging from 100% to over 1500%, but improvement of the nonlinearity and high sensitivity of the capacitor response have not received enough attention. In this thesis, novel highly tunable capacitors with high linearity are proposed to reduce sensitivity to the voltage changes near pull-in. The characteristic equations of a perfectly linear capacitor are first derived for two- and three-plate capacitors to obtain insight for developing linear capacitance-voltage responses. The devices proposed in this research may be classified into three categories: designs with nonlinear structural rigidities, geometric modifications and flexible moving electrodes. The concept of nonlinear supporting beams is exploited to develop parallel-plate capacitors with partially linear C-V curves. Novel electrodes with triangular, trapezoidal, butterfly, zigzag and fishbone shapes and structural/geometric nonlinearities are used to increase the linearity and tuning ratio of the response. To investigate the capacitors' behavior, an analytical approximate model is developed which can drastically decrease the computation time. The model is ideal for early design and optimization stages. Using this model, design variables are optimized for maximum linearity of the C-V responses. The results of the proposed modeling approach are verified by ANSYS FEM simulations and/or experimental data. When the fabrication process has dimensional limitations, design modifications and geometric enhancements are implemented to improve the linearity of the C-V response. The design techniques proposed in this thesis can provide tunabilities ranging from 80% to over 350% with highly linear regions in resulting C-V curves. Due to the low sensitivity of the capacitance to voltage changes in new designs, the entire tuning range is usable. Furthermore, the effect of fabrication uncertainties on parallel-plate capacitors performance is studied and a sensitivity analysis is performed to find the design variables with maximum impact on the C-V curves. An optimization method is then introduced to immunize the design against fabrication uncertainties and to maximize the production yield for MEMS tunable capacitors. The method approximates the feasible region and the probability distribution functions of the design variables to directly maximize the yield. Numerical examples with two different sets of design variables demonstrate significant increase in the yield. The presented optimization method can be advantageously utilized in design stage to improve the yield without increasing the fabrication cost or complexity.