Doctor of Philosophy / Department of Grain Science and Industry / Sajid Alavi / The Renewable Fuel Standard (RFS) in the Energy Independence and Security Act of 2007 has set the goal of 36 billion gallons of annual ethanol production in the U.S. by 2022, which is equivalent to 17.5% of the current gasoline consumption in the U.S. However, corn ethanol is expected to plateau at a level of 7.3% of current gasoline consumption on an energy-equivalent basis. Thus, it is essential to utilize a variety of substrates including lignocellulosic biomass from perennial energy crops such as switch grass, crop residues such as corn and sorghum stover, and agri-industrial co-products such as soybean hulls and wheat bran. Lignocellulosic substrates have a recalcitrant nature and require a pretreatment step that is critical for efficient enzymatic hydrolysis of cellulose and hemicellulose to fermentable sugars. In this study, soybean hulls were used as a model substrate for cellulosic ethanol. A novel thermo-mechanical pretreatment process using extrusion was investigated and compared with two traditional pretreatment methods, dilute acid and alkali hydrolysis, with regard to structural changes in the lignocellulosic substrate, and glucose and ethanol yields. The effect of extrusion parameters, such as barrel temperature, in-barrel moisture and screw speed, on glucose yield from soybean hulls was determined. Optimum processing conditions were screw speed of 350 rpm, maximum barrel temperature of 80C and 40% in-barrel moisture content, resulting in 95% cellulose conversion to glucose. Compared with untreated soybean hulls, the cellulose to glucose conversion of soybean hulls increased by 69.5, 128.4 and 132.2% for dilute acid, alkali and thermo-mechanical pretreatments, respectively. Glucose and other hexose sugars such as mannose and galactose were effectively fermented by Saccharomyces cerevisiae, resulting in ethanol yields of 13.04–15.44 g/L. Fermentation inhibitors glycerol, furfural, 5-(hydroxymethyl)-2-furaldehyde (HMF) and acetic acid were found in the thermo-mechanically pretreated substrate, ranging in concentrations from 0.072–0.431, 0–0.049, 0–0.023 and 0.181–0.278 g/L, respectively, which were lower than those reported from acid hydrolyzed substrates. The economic feasibility of commercial cellulosic ethanol production processes employing dilute acid hydrolysis and thermo-mechanical pretreatment were compared using a system dynamics modeling approach. It was concluded that low feedstock cost and high sugar conversion are important factors that can make cellulosic ethanol production commercially viable. Thermo-mechanical pretreatment was a more promising technology as compared to dilute acid hydrolysis because of the lower capital and operating costs, and higher sugar conversion.

Doctor of Philosophy / Department of Grain Science and Industry / Yong Cheng Shi / This study focused on in-vitro digestibility and pasting properties of cross-linked (CL) starch with different amylose contents and different cross-linking levels, as well as physicochemical properties of extruded wheat flours with different amylose contents and functionality of amylopectin and cross-linking in improving the textural and physical properties of oat flour extrudates. Starch was CL by phosphorylation using a mixture of sodium trimetaphosphate and sodium tripolyphosphate at the ratio of 99:1 under alkaline condition. The digestibility of highly CL maize starches with different amylose contents was determined by Englyst, Available Carbohydrate Dietary Fiber and Association of Official Analytical Chemists (AOAC) Method 991.43 methods. CL waxy and normal maize starch granules swelled much more at higher temperatures, resulting in significantly lower total dietary fiber content than high-amylose maize starch. The alkali treatment study on low levels of cross-linking in starch affected the ratios of total bound phosphate esters which changed the degree of starch swelling, crytallinity and pasting properties of the CL starch. The study on the mechanism of the digestive enzymes and the extent of digestion during the incubation of CL wheat starch in AOAC Method 2009.01 showed progressive digestion after 16 h of incubation, which may not reflect in-vivo response in human. Extrusion of normal and waxy wheat flours resulted in the breakdown of starch and an increase in the insoluble protein, which affected the textural and structural properties of extrudate. High energy input played a major role in radial expansion of normal hard wheat extrudate, whereas higher amylopectin in soft waxy wheat flour was a dominant factor in determining the radial expansion when compared to normal soft wheat. Inclusion of soft waxy wheat in the oat flour formulations at 18% moisture content improved the textural and structural properties of extrudates. Low cross-linking level of CL waxy maize starch in oat flour formulation increased the void fraction and reduced the breaking strength of extrudates, whereas higher cross-linking levels of CL starches improved the resistant starch level on oat flour formulation but had very poor structural and textural properties.The study offers a good insight on the properties and digestibility of CL starch, as well as using low levels of CL starch to improve textural properties of nutritional extruded products. In addition, study on the extrusion of wheat flours with different amylose and protein contents provides knowledge on the influence of chemical compositions and energy input on the physico-chemical properties of extrudates.

Master of Science / Department of Grain Science and Industry / Sajid Alavi / Extrusion is a widely used processing technology for various food products and is also commonly applied in non-food applications involving plastics, rubber and metal. Expanded products for human and animal consumption such as snacks, breakfast cereal, pet food and aquatic food typically consist of a biopolymer matrix of starch and proteins that have natural physical, chemical and polymeric variability. Additionally, variability in extrusion parameters such as water injection and screw speed is often observed depending on the process controls employed. This can potentially lead to inconsistency in product quality. Stochastic modeling helps in studying the impact of variability of various parameters on the end product, which in turn helps in better process and product quality control. The primary purpose of this research was to develop a mathematical model for flow behavior of biopolymer melts inside extruder barrel and bubble growth dynamics after exiting the extruder using mass, heat and momentum transfer equations. This model was integrated with a Monte-Carlo based stochastic interface for input of randomly generated process data (based on experimental data acquisition) and output of simulated distributions of end-product properties such as expansion ratio and cellular architecture parameters (cell size and wall thickness). The mathematical model was experimentally validated using pilot-scale twin screw extrusion for processing of cereal-based cellular products. Process and product data were measured at different in-barrel moisture contents (19-28% dry basis) and experimental screw speeds (250-330 rpm). Experimental process parameters such as specific mechanical energy (212.8-319.3 kJ/kg), die temperature (120.7-170.6oC), die pressure (3160-7683 kPa) and product characteristics such as expansion ratio (3.29-16.94) and cell size or bubble radius (435-655 microns) compared well with simulated results from the mathematical model viz., specific mechanical energy (217.6-323.9 kJ/kg), die temperature (116.8-176.1oC), die pressure (3478-6404 kPa), expansion ratio (4.56-19.4) and bubble radius (426-728 microns). Experimental variability in product characteristics was quantified using coefficient of variation which compared well with simulation results (example, 2.5-4.9% versus 0.24-3.1% respectively for expansion ratio). The stochastic model was also used to conduct sensitivity analysis for understanding which raw material and process characteristics contribute most to product variability. Sensitivity analysis showed that the water added in extruder affects the magnitude and variability of expansion ratio the most, as compared to screw speed and consistency index.

The most popular and convenient route of drug administration remains the oral route, however, protein and peptide drugs such as insulin have poor membrane permeability and stability in the gastrointestinal tract. Absorption enhancers can be added to drug delivery systems to overcome the epithelial cell membrane permeability problem. Although previous studies have shown that aloe leaf materials improve the transport of drugs across intestinal epithelia, their performance in solid oral dosage forms has not yet been investigated. Beads containing insulin and each of the selected absorption enhancers (i.e. Aloe ferox, Aloe marlothii and Aloe vera gel materials) were produced by extrusion-spheronisation, using a full factorial design to optimise the formulations based on transepithelial electrical resistance (TEER) reduction of Caco-2 cell monolayers as response. The optimum bead formulations were evaluated in terms of friability, mass variation, particle surface texture, shape, size and dissolution. The transport of insulin across excised pig intestinal tissue from the optimised bead formulations was determined over a 2 h period. The samples obtained from the transport studies were analysed for insulin content by means of high-performance liquid chromatography (HPLC). The results showed that the TEER reduction, as an indication of tight junction modulation, obtained for the bead formulations containing aloe materials was concentration dependent. Furthermore, inclusion of croscarmellose sodium (Ac-di-sol®) as a disintegrant showed an enhanced TEER reduction effect in combination with the aloe gel materials. Dissolution profiles indicated that the beads containing aloe leaf materials in conjunction with insulin, released the insulin within an hour. In accordance with the TEER reduction results, the A. marlothii and A. vera materials containing beads showed similar increased insulin delivery across excised pig intestinal tissue, which was pronouncedly higher than that of the control group (insulin alone). It can be concluded that beads containing aloe leaf materials have high potential as effective delivery systems for protein therapeutics such as insulin via the oral route of administration. / MSc (Pharmaceutics), North-West University, Potchefstroom Campus, 2015

The most popular and convenient route of drug administration remains the oral route, however, protein and peptide drugs such as insulin have poor membrane permeability and stability in the gastrointestinal tract. Absorption enhancers can be added to drug delivery systems to overcome the epithelial cell membrane permeability problem. Although previous studies have shown that aloe leaf materials improve the transport of drugs across intestinal epithelia, their performance in solid oral dosage forms has not yet been investigated. Beads containing insulin and each of the selected absorption enhancers (i.e. Aloe ferox, Aloe marlothii and Aloe vera gel materials) were produced by extrusion-spheronisation, using a full factorial design to optimise the formulations based on transepithelial electrical resistance (TEER) reduction of Caco-2 cell monolayers as response. The optimum bead formulations were evaluated in terms of friability, mass variation, particle surface texture, shape, size and dissolution. The transport of insulin across excised pig intestinal tissue from the optimised bead formulations was determined over a 2 h period. The samples obtained from the transport studies were analysed for insulin content by means of high-performance liquid chromatography (HPLC). The results showed that the TEER reduction, as an indication of tight junction modulation, obtained for the bead formulations containing aloe materials was concentration dependent. Furthermore, inclusion of croscarmellose sodium (Ac-di-sol®) as a disintegrant showed an enhanced TEER reduction effect in combination with the aloe gel materials. Dissolution profiles indicated that the beads containing aloe leaf materials in conjunction with insulin, released the insulin within an hour. In accordance with the TEER reduction results, the A. marlothii and A. vera materials containing beads showed similar increased insulin delivery across excised pig intestinal tissue, which was pronouncedly higher than that of the control group (insulin alone). It can be concluded that beads containing aloe leaf materials have high potential as effective delivery systems for protein therapeutics such as insulin via the oral route of administration. / MSc (Pharmaceutics), North-West University, Potchefstroom Campus, 2015

Les nouveaux matériaux qui ont fait leur apparition récemment dans l'industrie, tels que les matériaux composites et les mousses métalliques par exemple, ont trouvé de nombreuses applications. Cependant, en raison de leur complexité grandissante, la modélisation de leurs lois de comportement est de plus en plus difficile. D'où l'idée d'employer des méthodes d'imagerie tridimensionnelle telle que la microtomographie rayons-X, et d'utiliser la corrélation d'images digitales pour mesurer les champs de déplacements entre des images de l'échantillon au repos et sous compression. Cela permettrait ensuite de remonter aux paramètres de la loi de comportement. C'est le but du projet développé en collaboration entre l'École Polytechnique de Montréal et l'Université de Sherbrooke. La partie du projet menée à l'Université de Sherbrooke constitue l'objet de ce mémoire, et comprend deux tâches. La première consiste à concevoir un matériau modèle qui servira de base pour développer un algorithme de mesure des champs de déplacements à partir des images microtomographiques. La seconde consiste à obtenir lesdites images. Le matériau modèle conçu dans le cadre des travaux de recherche est un matériau composite à matrice de polyéthylène à basse densité linéaire, texturée par de l'oxyde de titane, et à renfort de billes de verre. Ces matériaux ont été choisis entre autres raisons pour leur bon contraste aux rayons-X et leur facilité de mise en forme. Le composite a été fabriqué par extrusion, pour assurer une bonne dispersion des particules de renforts, et les échantillons ont été réalisés par moulage. La microtomographie à rayons-X est une technique d'imagerie permettant de reconstruire le volume d'un objet à partir d'une série de projections radiographiques de celui-ci. C'est une méthode qui permet en général une appréciation qualitative de la structure d'un objet ( e.g. des anomalies). Par contre, la qualité des images peut être parfois insuffisante pour une analyse quantitative. Des bruits et des artefacts de reconstructions (e.g. artefacts d'anneaux, durcissement du faisceau, désalignement...) peuvent dégrader les microtomographies. Le développement d'une procédure de calibration était donc nécessaire avant de pouvoir utiliser la cellule de charge pour imager des échantillons au repos puis compressés in situ .

Particulate reinforced Al alloy composites (AlMCs) are recognized as important structural materials due to their lightweight, high modulus and strength and high wear resistance. In order to understand the effect of matrix, reinforcement and secondary processing techniques on the microstructure development and mechanical properties of AlMCs produced by powder metallurgy routes, Al alloy composites reinforced with three types of reinforcements by different secondary processing techniques have been produced and examined. Fabrication of Al or 6061Al alloy based composites reinforced with nano-sized SiC particles (~500nm), micro-sized (<25µm) quasicrystalline alloy particles (hereinafter referred to as “NQX”) and micro-sized Nb particles (~130µm) has been carried out by powder metallurgy routes followed by extrusion or cold rolling. After extrusion, a homogeneous distribution of secondary particles has been obtained with rare interfacial reaction products. The 6061Al/SiC composites exhibit superior mechanical properties than either monolithic alloys or composites reinforced with micro-sized particles with retained ductility while the 6061Al/NQX and 6061Al/Nb composites show limited improvement in tensile strength mainly due to their reinforcement size and poor interfacial bonding. After cold rolling, the evolution in microstructure, texture and strength has been analysed. A typical near β fibre texture with highest intensities near Copper and Brass orientations has been developed for 6061Al/NQX and 6061Al/Nb composites. For 6061Al/SiC composites, a randomized texture with very small grains has achieved due to the presence of the non-deformable SiC particles. Mechanical property tests including microhardness, three-point bending tests and tensile tests have been carried out on cold rolled samples and the results exhibit some level of improvement when compared with as-extruded samples due to work hardening. Finally, the work moves on to the general discussion based on the previous result chapters. The microstructural development related to reinforcement, matrix and interfacial areas during extrusion and cold rolling has been summarised and the correlation between microstructure and mechanical properties has been discussed. The thesis provides a thorough understanding of AlMCs produced by powder metallurgy routes in terms of matrix, reinforcement and processing techniques. It can provide reference to the future development of AlMCs for high strength applications.

No description available.

The Palmer Zone of Transpression (PZoT) in the Bronson Hill zone of central Massachusetts is an expression of late Paleozoic oblique convergence between Avalonia and Laurentia. The steeply W-dipping, N-S trending PZoT is defined by bounding high strain zones (Mt. Dumplin on west, Central Maine and Conant Brook on east) of opposing shear sense enclosing the Monson orthogneiss. Research was designed to establish the timing of deformation to test the hypothesis that strain in transpressional systems occurs contemporaneously. An understanding of the timing of deformation in this zone could elucidate the mechanisms that formed the zone and contribute to a greater overall understanding of fabric evolution in transpressional systems. U-Pb SIMS ages of zircon in deformed pegmatites in Monson orthogneiss and Paxton and Rangeley paragneisses are 369 to 364 Ma. Plutons that contain all fabrics associated with progressive transpression – lineations ranging from subhorizontal (initial) to steeply-plunging parallel to dip (final) – mark the maximum age of deformation. Ages range from 360-355 Ma in the Hardwick tonalite, Wachusett tonalite, West Warren diorite, Walker Mountain orthogneiss, and Nichewaug diorite, and indicate transpression in the PZoT initiated after ca. 355 Ma. Monazite from Rangeley paragneisses and schists selected in the context of petrofabrics and syn-deformational mineral assemblages yield U-Th-Pb EPMA chemical ages that indicate dextral transpression occurred continuously from 355 to 315 Ma. Monazite chemical ages also indicate that sinistral lateral displacement in the west-bounding Mt. Dumplin high strain zone initiated ca. 325 Ma and lasted for roughly 45 m.y., ending around 280 Ma. The data for the Central Maine zone, Conant Brook shear zone, and Greenwich syncline support the idea of contemporaneous deformation across the compartmentalized zones of a transpressive system (355-315 Ma), while the ages for the Mt. Dumplin high strain zone indicate sinistral lateral displacement overlapped dextral transpression by about 10 m.y. but generally continued later in time (325-280 Ma).

In this paper, processing effects of electroplating and post- plating annealing on via extrusion are investigated. The study is based on two TSV structures with identical geometry but different processing conditions. Via extrusion, stress and material behaviors of the TSV structures were first compared. Electron backscatter diffraction (EBSD) and time-of-flight secondary ion mass spectroscopy (TOF-SIMS) were used to characterize the microstructure of TSVs and the additives incorporated during electroplating. Based on the results, processing effects on via extrusion and its mechanism are discussed, including grain growth, local plasticity, and diffusional creep.