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This dissertation will investigate how Product Performance Contracts are organized in Multi Component Systems contexts that proliferate contemporary OEM industries. The last two decades have seen a big change in both practice as well as the product engineering technologies that form the ecosystem within which suppliers and buyers negotiate the scale and scope of their transaction contracts. While we have seen the focus of industrial procurement move from specifications based contracts to performance based contracts, we are also witnessing a burgeoning technological capability that allows remote monitoring of product performance. These capabilities are part of the interconnectivity driving the much-touted Internet of Things (IoT) technology and at the heart of the Industrial Big Data ecosystem. The dissertation will attempt to explain three major phenomena in the industrial buyer and seller relationship in the context of Multi Component System Industries. First, we uncover the factors that explain the choice of product performance contract specificity between the OEM and suppliers. We first set up an analytical model to explain the notion of an optimal contract specificity level and predict and further empirically test the role of different factors in the choice of contract specificity. We find that while the technology uncertainty decreases the level of optimal contract specificity, OEM’s transaction specific investment, unconstrained mixing-and-matching of branded component, and extent of product monitoring technology increases the level of optimal contract specificity. Second, we provide empirical evidence that any deviation from optimal contract specificity erodes value in the form of an increase in total transaction cost. In our transaction cost efficiency model, we also illustrate with a precise granularity that under-specified contracts lead to more ex-post dispute costs, and over-specified contracts lead to more ex-post contract monitoring cost and ex-ante contract writing cost. Third, we investigate how contracts, investments in strategic capabilities such as monitoring technology, the overall firm strategy, and transaction costs determine the firm performance. We find that not every transaction cost is a dead weight loss in terms of product performance. Most notably we find that ex-post dispute costs are associated with higher product performance when there is a major incident such as component failure between the OEM and the supplier. Methodologically, this dissertation proposes to use a combination of field work, mathematical modeling, conceptual theory building, and empirical analysis of primary data about firm practices. / Thesis / Doctor of Philosophy (PhD)

In Situ Thermal Treatment (ISTT) is a candidate remediation technology for dense non-aqueous phase liquids (DNAPLs). However, the relationships between gas production, gas flow, and contaminant mass removal during ISTT are not fully understood. A laboratory study was conducted to assess the degree of mass removal, as well as the gas generation rate and the composition of the gas phase as a function of different heating times and initial DNAPL saturations. The temperature of the contaminated soil was measured continuously using a thermocouple to identify periods of heating, co-boiling and boiling. Samples were collected from the aqueous and DNAPL phase of the condensate, as well as from the source soil, at different heating times, and analyzed by gas chromatography/mass spectrometry. In addition to laboratory experiments, a mathematical model was developed to predict the co-boiling temperature and transient composition of the gas phase during heating of a uniform source. Predictions for single-component sources matched the experiments well, with a co-boiling plateau at 88°C ± 1°C for experiments with tetrachloroethene (PCE) and water. A comparison of predicted and observed boiling behaviour showed a discrepancy at the end of the co-boiling period, with earlier temperature increases occurring in the experiments. The results of this study suggest that temperature observations related to the co-boiling period during ISTT applications may not provide a clear indication of complete NAPL mass removal, and that multi-compartment modeling associated with various NAPL saturation zones is required to consider mass-transfer limitations within the heated zone. Predictions for multi-component DNAPL, containing 1,2-Dichloroethane (1,2-DCA), PCE and Chlorobenzene, showed no co-boiling plateau. CB is the least volatile component and dominates in the vapour phase at the end of the co-boiling process, and it can be used as an indicator of the end of the co-boiling stage. Two field NAPL mixtures were simulated using the screening-level analytical model to demonstrate its potential application on ISTT. The two mixtures with similar composition but different mass fractions result in distinct co-boiling temperature and mass transfer behaviour. The non-volatile component in the NAPL mixture results in larger amounts of water consumption and longer ISTT operation time. / Thesis (Master, Civil Engineering) -- Queen's University, 2013-09-30 09:26:00.857

Pyrrolidine and pyrrolidinone rings are common motifs found in many biologically active natural products and drugs. Accordingly, our work focuses on the development of new methodologies for their one-pot synthesis. An efficient diastereoselective nitro-Mannich / lactamisation reaction cascade of methyl 3-nitropropanoate with cyclic and acyclic imines for the direct preparation of trans-monocyclic and fused tricyclic pyrrolidinone derivatives was developed. The reaction is easy to perform, broad in scope and tolerates a wide variety of functional groups. For the monocyclic methodology, 28 examples with a very good average yield of 72% and excellent diastereocontrol (typical dr >98:2) were obtained using optimized conditions and varying the amine and the aldehyde reagents. The methodology has been extended to the synthesis of 1,3,5-trisubstituted 4-nitropyrrolidinone derivatives using α-substituted 3-nitropropanoate. Using a one-pot protocol, 22 derivatives were synthesised in good yields (65% average) and diastereomeric ratios ranging from 3:1 to 30:1 in favor of the trans/trans diastereoisomer. In addition, the nitro-Mannich / lactamisation cascade of methyl 3-nitropropanoate was developed further to allow the rapid synthesis of 5-isopropyl-4-nitropyrrolidin-2-one from reaction with ammonium acetate and 1-butyl-4-nitropyrrolidin-2-one from reaction with formaldehyde. Also, the synthetic utility of the nitro-pyrrolidinones formed was exemplified through various functional group modifications: the selective reduction of the lactam carbonyl, the reduction of the nitro group in the presence or absence of a carbonyl group and the reductive removal of the nitro group. The development of an enantioselective version of the cascade under chiral Brönsted acid catalysis provided promising results (up to 90% ee). Moreover, various studies were undertaken to understand the mechanism of the reaction and the nitro-Mannich / latamisation cascade is now well understood. Furthermore, a formal synthesis of rac-Slaframine in 8 steps and 15% overall yield was achieved and it inspired additional work towards a nitro-Mannich / epoxide ring opening cascade.

Heat insulation is the process of blocking the transfer of thermal energy between objects at different temperatures. Heat transfer occurs due to conduction, convection, or radiation, as well as any combination of these three mechanisms. Fibrous insulations can completely suppress the convective mode of heat transfer for most applications, and also help to reduce the conductive and radiative modes to some extent. In this study, an attempt has been made to computationally predict the effects of microstructural parameters (e.g., fiber diameter, fiber orientation and porosity) on the insulation performance of fibrous materials. The flexible simulation method developed in this work can potentially be used to custom-design optimal multi-component fibrous insulation media for different applications. With regards to modeling conductive heat transfer, a computationally-feasible simulation method is developed that allows one to predict the effects of each microstructural parameter on the transfer of heat across a fibrous insulation. This was achieved by combining analytical calculations for conduction through interstitial fluid (e.g., air) with numerical simulations for conduction through fibrous structures. With regards to modeling radiative heat transfer, both Monte Carlo Ray Tracing and Electromagnetic Wave Theory were implemented for our simulations. The modeling methods developed in this work are flexible to allow simulating the performance of media made up of different combinations of fibers with different materials or dimensions at different operating temperatures. For example, our simulations demonstrate that fiber diameter plays an important role in blocking radiation heat transfer. In particular, it was shown that there exists an optimum fiber diameter for which maximum insulation against radiative transfer is achieved. The optimum fiber diameter is different for fibers made of different materials and also depends on the mean temperature of the media. The contributions of conduction and radiation heat transfer predicted using the above techniques are combined to define a total thermal resistance value for media with different microstructures. Such a capability can be of great interest for design and optimization of the overall performance of fibrous media for different applications.

En rupture avec les approches classiques de métallurgie consistant à allier un ou deux éléments majoritaires avec d'autres éléments en proportions minoritaires, un nouveau concept de matériaux est né : des alliages multi-composants formant une solution solide et pour lesquels tous les composants sont fortement concentrés. Ces nouveaux alliages, appelés alliages à haute entropie, présentent des propriétés mécaniques prometteuses, telles qu'une résistance mécanique élevée combiné à une grande ductilité. Par définition, ce nouveau concept de matériau rend possible l'exploration d'un champ quasi-infini de compositions chimiques. Toutefois, la stabilité thermodynamique de ces systèmes est mal connue, limitant fortement le choix des compositions. Dans ce contexte, le premier objectif de cette étude était de déterminer le domaine d'existence de la solution solide cubique à faces centrées (cfc) pour le système Co-Cr-Fe-Mn-Ni. Pour cela, la stabilité de phase cfc a été étudiée théoriquement et expérimentalement. En utilisant l'approche Calphad (Calculation of PHAse Diagram) et une nouvelle base de données (TCHEA-1), les phases stables de 10 626 compositions ont pu être calculées, à plusieurs températures. La comparaison entre calculs et résultats expérimentaux indique que la solution solide cfc est correctement décrite par cette base de données. Ainsi, il a été montré que la phase cfc est stable sur une large gamme de composition, décrite intégralement. Il est désormais possible de choisir une composition formant une solution solide stable à haute température pour ce système. Des calculs DFT (Density Functional Theory) ont ensuite permis d'analyser l'évolution de l'enthalpie de mélange en fonction de la composition mais aussi du nombre d'éléments. Des différences notables ont pu être constatées avec les prédictions faites par la base de données TCHEA-1. De plus, ces calculs ont mis en avant l'absence d'interaction ternaire et quaternaire pour le système d'étude. Ensuite, l'influence de la composition sur le durcissement par solution solide a été étudiée, pour permettre l'optimisation des propriétés mécaniques. Ainsi, l'évolution des propriétés structurelles et mécaniques des alliages multi-composants a été étudiée expérimentalement. Vingt-cinq alliages du système Co-Cr-Fe-Mn-Ni formant une solution solide cfc ont été traités. Le paramètre de maille a été mesuré par rayons X tandis que la dureté et le module d'élasticité ont été étudiés par nano-indentation. Le rôle de chaque élément sur le comportement mécanique fut ainsi explicité. Finalement, un modèle permettant d'estimer le durcissement de solution solide pour ce système est étudié / For a long time, development of alloys was restricted to one principal element, or two, with minor elements added for performance optimization. In 2004, a new concept of materials was born: multi-component alloys forming a solid-solution and in which all components are very concentrated. These new alloys, named high entropy alloys, can combine high mechanical resistance and large ductility. By definition this new material concept should make it possible to explore an almost infinite field of chemical compositions. But in the meantime, the thermodynamic stability of these systems was poorly known and severely limits the choice of alloy compositions. In this context, the first objective of this study was to fully determine the composition range of existence of a unique fcc solid solution within the multi-component Co-Cr-Fe-Mn-Ni system. To address this problem, the phase stability was theoretically and experimentally investigated. Using the Calphad approach and a new database (TCHEA-1), the stable phases of 10 626 compositions could be calculated, at several temperatures. The comparison between calculation and experimental results indicates that the fcc solid solution is accurately described by this database. Finally, it was shown that the fcc phase is stable over a wide range of composition, which was completely described. Now, it is possible to choose a priori a composition which will form a solid solution within this system. The heat of mixing of the fcc phase were compared between density functional theory (DFT) and Calphad calculations for binaries, ternaries, quaternaries and quinary systems. Significant differences were found with the predictions made by the TCHEA-1 database. In addition, these calculations have highlighted the absence of ternary and quaternary interaction for the Co-Cr-Fe-Mn-Ni system. However, the influence of the composition on the fcc solid solution strengthening was not fully understood, which limits mechanical optimization. So, the evolution of structural and mechanical properties of multi-components alloys was experimentally investigated. Several alloys from the Co-Cr-Fe-Mn-Ni system forming a unique fcc solid solution were processed. The lattice parameter was measured by XRD while the hardness and elastic modulus were measured by nano-indentation. The role of each element on the mechanical behaviour is presented. Finally, a model to assess the solid solution strengthening for this system is studied

Cation-exchange fast protein liquid chromatography separated whole casein into β-casein A2, A1, and B, K-casein, αs1-casein, and αs2-casein fractions as well as γ-caseins and several unidentified peaks using a urea-acetate buffer at pH 5 and a NaCl gradient. The whole casein fractions eluted in the following order: breakdown products of β-casein and unidentified peaks; β-casein A2, Al, and B; additional breakdown products of β-casein and unidentified peaks; K-casein; αs1-casein; and αs2-casein. The calculated composition of the four major caseins correlated well with values obtained using anion-exchange fast protein liquid chromatography at pH 7. An acid-PAGE gel confirmed that the three β-casein peaks were variants of β-casein. Incubating herd bulk whole casein with neuraminidase (EC 3.2.1.18) removed carbohydrate from K-casein. Anion-exchange fast protein liquid chromatography separated whole casein into β-casein breakdown products, K-casein A and B, β-casein, αs2-casein, and αs1-casein peaks as well as three unidentified fractions using bis-Tris-propane-urea buffer at pH 7 and a NaCl gradient. Fractions of whole casein eluted in the following order: breakdown products of β-casein and unidentified fractions A and B; K-casein fraction; unidentified C fraction; β-casein; αs2-casein; and αs1-casein. Following treatment with neuraminidase, K-casein eluted as K-casein B and A rather than a series of peaks. Casein samples from individual cows containing known combinations of K-casein A and B confirmed that the peaks were K-casein variants. Isoelectric focusing on a PhastSystem™ separated K-casein A and B; β-casein A1, A2, A3, and B; αs1-casein Band C; β-lactoglobulin A and B; αs2-casein A; and α-lactalbumin B. Minimal preparation and a short separation time enabled many whole milk and whole casein samples to be phenotyped daily. Stepwise regression equations derived to predict samples as homozygous or heterozygous for K-casein A and B and β-casein A1, A2, and B had coefficient of determination values of .18, .58, .82, and .72 for K-casein A and B, β-casein A1, β-casein A2, and β-casein B. Although amino acid analysis can identify whether β-casein A1, A2, or B variants are present, it cannot identify whether K-casein A and B variants are present. Percentages of K-casein, β-casein, αs1-casein, and αs2-casein obtained with isoelectric focusing, cation-exchange fast protein liquid chromatography, and anion-exchange fast protein liquid chromatography compare well with published results. Isoelectric focusing and anion-exchange fast protein liquid chromatography methods separated K-casein into its A and B variants. Isoelectric focusing and cation-exchange fast protein liquid chromatography separated β-casein into its A1, A2, and B variants. Individual cows homozygous for K-casein A or B expressed the same amount of K-casein. When results from individual cows heterozygous for K-casein are combined, the two alleles are expressed equally; on an individual cow basis, however, some cows expressed more K-casein B than K-casein A. Individual cows homozygous for β-casein A1, A2 or B expressed the same amount of β-casein. When the results for individual cows heterozygous for β-casein are combined, the two β-casein alleles are expressed equally. In milk from individual cows typed β-casein A2B, slightly more B than A2 was expressed with cation-exchange fast protein liquid chromatography.

Health care facilities, offices, as well as workshops and other commercial occupancies, require ventilation and air conditioning for thermal comfort and removal of contaminants and other pollutions. A good design of ventilation and air conditioning provides a healthy and comfortable environment for patients, workers, and visitors. The increasing developments of computational fluid dynamics (CFD) in the recent years have opened the possibilities of low-cost yet effective method for improving HVAC systems in design phase, with less experiment required. This work presents numerical simulations of thermal comfort and contaminant removal for two typical working spaces where these factors are critical: a hospital operating room with various configurations of inlet and outlet arrangements, and an office with two cases of air distribution systems: underfloor and overhead, also with alternative cases. The 2-D simulation approach was employed. Temperature, relative humidity, contaminant concentration, thermal sensation, predicted mean vote (PMV), and contaminant removal factor were computed and used for assessing thermal comfort and contaminant removal characteristics of the office room and operating room. The result shows good agreements with experimental data taken from related literature.

A new integrated layout optimization method is proposed here for the design of multi-component systems. By introducing movable components into the design domain, the components layout and the supporting structural topology are optimized simultaneously. The developed design procedure mainly consists of three parts: (i). Introduction of non-overlap constraints between components. The Finite Circle Method (FCM) is used to avoid the components overlaps and also overlaps between components and the design domain boundaries. It proceeds by approximating geometries of components and the design domain with numbers of circles. The distance constraints between the circles of different components are then imposed as non-overlap constraints. (ii). Layout optimization of the components and supporting structure. Locations and orientations of the components are assumed as geometrical design variables for the optimal placement. Topology design variables of the supporting structure are defined by the density points. Meanwhile, embedded meshing techniques are developed to take into account the finite element mesh change caused by the component movements. Moreover, to account for the complicated requirements from aerospace structural system designs, design-dependent loads related to the inertial load or the structural self-weight and the design constraint related to the system gravity center position are taken into account in the problem formulation. (iii). Consistent material interpolation scheme between element stiffness and inertial load. The common SIMP material interpolation model is improved to avoid the singularity of localized deformation due to the presence of design dependent loading when the element stiffness and the involved inertial load are weakened with the element material removal. Finally, to validate the proposed design procedure, a variety of multi-component system layout design problems are tested and solved on account of inertia loads and gravity center position constraint.

This thesis is directed towards expanding and refining a free radical multi-component polymerization model. The model considers up to six monomers (unique in the literature), both in bulk and solution polymerization, for either batch or semi-batch reactor modes. As the simulator database contains 13 monomers, 5 initiators, 4 solvents, 3 chain transfer agents and 2 inhibitors, all tested over a wide range of polymerization conditions, from data in both academic and industrial laboratories, several hundred combinations of ingredients can be modeled. The many outputs generated by the model include conversion, molecular weight, polymer composition, branching indicators, sequence length, as well as many others polymerization characteristics related to both production rate and polymer quality. Although the only literature data found to-date contains a maximum of four monomers, model predictions for homo-, co-, ter- and tetra-polymerizations show reasonable agreement against the data at both regular and elevated temperatures. Recently, with the basic polymerization kinetics modeled sufficiently, several expansions to the simulation software have been added. Specifically, depropagation, multiple initiators, back-biting, and composition control have been incorporated and/or improved, each adding to the advancement of the polymerization simulation tool. Depropagation is a vital mechanism that should be accounted for at elevated temperatures. Currently the software has the functionality to implement depropagation but requires further literature resources for improving the kinetic predictions for conversion and polymer composition. Consequently, depropagation research is ongoing. Back-biting and beta-scission of butyl acrylate (BA) is a recent development in free radical polymerization. The completed extension can model BA under the same diverse conditions as the base model, in homo-, co- and ter-polymerizations with depropagation, if applicable. The ability to generate a polymer with a constant (or controlled) composition throughout the reaction has several practical uses. Originally, three composition control scenarios were considered. At present, several methods as well as combinations of methods have been integrated into the model. With these new expansions and the ability to simulate several initiators at the same time, this model is directed towards becoming a complete free radical polymerization tool for training and educational uses both in industry and academia.