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The construction of bonds in a controlled and selective manner and the development of operationally simple, general and reliable methods to achieve these aims remains a key goal of chemical synthesis and the countless industries it impacts upon. With this in mind, the chemo-, regio- and stereoselective introduction of a number of functionalities into small molecules was investigated. Traditionally the majority of functionalisations have used precious metals; the scope of transformations that can be achieved using these catalysts is remarkable. Palladium in particular has found widespread application in new bond-forming processes and, in addition to cross-coupling reactions, palladium catalysis has been used to effect a wide variety of asymmetric reactions. This work describes investigations into the palladium-catalysed enantioselective electrophilic fluorination of azaarylacetates and amides A2 and the oxidative annulation of ferrocene derivatives A4 (Scheme A1). Both products have structural significance; heterocycles and stereogenic fluorinated centres, present in A3, are important motifs in the pharmaceutical industry, and ferrocenes are important rigid scaffolds in chiral ligands such as those in the Josiphos family e.g. A7. Scheme A1. Palladium catalysis for a) enantioselective fluorination and b) oxidative annulation Whilst a general catalyst remained elusive for the asymmetric fluorination of azaarylacetates and amides, benzoxazole-containing substrates were consistently fluorinated with excellent enantioselectivity (up to 96% ee) using palladium catalyst A1 (Scheme 1a). The oxidative annulation of ferrocene derivatives proved challenging and although the reaction was successful, the product could only be isolated in up to 24% yield (Scheme 1b). In order to determine the yield-limiting step of the reaction, mechanistic studies were conducted and palladacycle A6 was synthesised as a possible reaction intermediate. Recently there has been a shift towards the development of more sustainable, environmentally benign and economic catalyst systems and iron is quickly becoming recognised as a viable alternative owing to its high natural abundance and low toxicity. A general iron-catalysed hydrofunctionalisation procedure is described that was used to form a wide variety of carbon-carbon and carbon-heteroatom bonds (Scheme A2). Scheme A2. Iron catalysis for carbon-carbon and carbon-heteroatom bond formation With just 0.5 mol% iron catalyst, the broad scope formal hydrofunctionalisation of styrene derivatives was achieved using commercially available and bench-stable catalysts and reagents. An iron-catalysed highly regioselective hydromagnesiation gave a common benzylic Grignard reagent, which was reacted with an array of electrophiles in a highly chemo- and regioselective manner. Significantly, the products of formal hydroboration, hydrosilylation and cross-coupling reactions were obtained.

Machine tool coolant concentration and pH data.

<p>Metal forming processes have been widely applied in many industries. With the severe competition in the market, a reliable and robust metal forming process becomes crucial for the manufacturer to reduce product development time and cost. For the purpose of supplying engineers with an effective tool for a reliable and robust design of metal forming process, this research investigates the application of traditional reliability theory and robust design methods in metal forming processes for the ultimate goal of increasing quality and reducing cost in manufacturing.</p> <p> A method to assess the probability of failure of the process based on traditional reliability theory and the forming limit diagram (FLD) is presented. The forming limit of a material is chosen as the failure criteria for analysis of reliability.</p> <p> A study of prediction of forming limit diagrams using finite element simulation without pre-defined geometrical imperfection or material imperfection is presented. A 3D model of the dome test is used to predict the FLD for AA 5182-0. The FE predicted forming limit diagram is in good agreement with the experimental one. The uncertainty sources for the scatter of forming limits are categorized and investigated to see their effects on the shape of FLD.</p> <p>A novel method of improving the reliability of a forming process using the Taguchi method at the design stage is presented. The thickness-thinning ratio is chosen as the failure criteria for the reliability analysis of the process. A Taguchi orthogonal array is constructed to evaluate the effects of design parameters on the thinning ratio. A series of finite element simulations is conducted according to the established orthogonal array. Based on the simulation results, Taguchi S/N analysis and ANOVA analysis are applied to identify the optimal combination of design parameters for minimum thinning ratio, minimum variance of thinning ratio, and maximum expected process reliability.</p> <p> A multi-objective optimization approach is presented, which simultaneously maximizes the bulge ratio and minimizes the thinning ratio for a tube hydroforming process. Taguchi method and finite element simulations are used to eliminate the parameters insignificant to the process quality performance. The significant parameters are then optimized to achieve the multiple optimization objectives. The optimization problem is solved by using a goal attainment method. An illustrative case study shows the practicability of this approach and ease of use by product designers and process engineers.</p> / Thesis / Doctor of Philosophy (PhD)

<p>In sheet metal forming processes, friction has decisive effects on the strain distribution in the deformed sheets and the quality of the final product due to the large surface/thickness ratio of the blank sheets. It is well known that friction in sheet forming operations is dependent on local contact conditions such as surface roughness, contact pressure and sliding velocity. Adding complexity to this frictional behavior, some rolled sheets have oriented surface roughness and show considerable frictional anisotropy. A constant friction model without consideration of these relevant phenomena is regarded as the reason why sheet metal forming simulations often fail to produce satisfying results despite the well developed material models. </p> <p>To develop a friction model which considers both of the varying conditions of local contact and the frictional anisotropy was the aim of this thesis. For this purpose, the analysis method of the friction test (draw-bend test) had to be examined for the capability to evaluate these parameters independently. Through careful study using finite element simulations, it was found that the conventional method has shortcomings in addressing pressure dependent friction due to the pressure non-uniformity existing in the test. Therefore, a new analysis method, which can evaluate pressure dependency of a friction coefficient, was developed. In the new method, contact pressure maps obtained from simulations were included in the analysis of test data.</p> <p>The new analysis method was applied to friction measurement of aluminum sheets with known anisotropic mill finish, and friction coefficients were obtained as functions of contact pressure, sliding velocity and sliding direction. In the obtained friction model, a friction coefficient is a continuous surface over the domain of contact pressure and sliding velocity. Lastly, the new friction model was implemented into a finite element code and the model was validated through circular cup drawing experiments and simulations. The comparisons showed good agreements in the aspects of punch force, cup size and failure location. Thus, the newly developed model can accurately predict the effects of anisotropic friction in sheet metal forming processes. </p> / Thesis / Doctor of Philosophy (PhD)

The Master’s Thesis is focused on stamping of sheet metal parts. The analyzed part is a structural part of an automobile body. The part is made of DC04 (cold rolled mild steel) material. The annual pruduction volume is 10.000 pieces. Theoretical background research is a knowledge base for design of tooling that can produce parts which meet quality requirements. There are three technological processes proposed in the Thesis. An economic analysis identifies the optimal technological process for the production volume. The thesis contains a complex analysis that confirmes material formability. Computer simulation verifies the part design, material and technological parameters of the forming process.

The quality of continuous fiber reinforced polymer matrix composite parts and structures depends strongly on the friction during the composite forming process. The two major types of friction that cause deformations during this process are ply-ply friction and tool-ply friction. One of the challenges in the composite forming process is the occurrence of wrinkling and shape distortion of the fabric caused by the surface differences between the forming tool and surface of the laminate. Frictional measurements of composites can vary widely depending on processing parameters, measurement technique, and instruments used. In this study, a commercial rheometer was used to evaluate tool-ply friction of unidirectional carbon fiber epoxy prepreg at various contact pressures, temperatures and sliding velocities. Viscoelastic properties such as the complex viscosity (η*), storage modulus (G'), loss modulus (G"), and loss factor (tan δ) were used to determine the critical transition events (such as gelation) during cure. An understanding of changes in viscoelastic properties as a function of time, temperature, and cure provides insight for establishing a suitable processing range for compression forming of prepreg systems. Surface imaging results were coupled with rheological results to qualitatively examine the effects of processing parameters on prepreg distortions. Changes in gap height over the measurement interval qualitatively describe the changes in contact area and contact mechanisms between the tool-ply surfaces. The results indicate that friction behavior of the prepreg system is a contribution of adhesive and frictional forces, where increase in viscosity, reduction in gap height, and cure of the sample correlate to higher friction values. / Master of Science / The quality of composite parts and structures depends strongly on the friction present during the composite forming process. One of the major challenges in the forming process is the occurrence of wrinkling and shape distortions of the fabric caused by the surface differences between the forming tool and material. The presence of these defects can compromise the final material property and lead to failure when in use. Frictional measurements of composites can vary widely depending on processing parameters, measurement technique, and instruments used. The extent of interaction between the tool and surface of the material depends on the tooling height, and by extension, contact area, which cannot easily be monitored with traditional test designs. A commercial rheometer was used in this study to evaluate tool-ply friction of unidirectional carbon fiber epoxy prepreg at various contact pressures, temperatures, and sliding velocities. Gap height and torque were monitored to provide information on the frictional dependence of processing parameters. In addition, surface-imaging results were coupled with rheological results to examine the relationship between friction and fiber distortions. The understanding of changes in material property with respect to the tooling process is the key to optimizing the composite forming process.

Ce travail de thèse vise à une meilleure compréhension et prise en compte des mécanismes d'endommagement ductile au cours des procédés de mise en forme à froid. Le tréfilage, le laminage de fils et le laminage à pas de pèlerin sont pris comme exemples d'application. Une grande attention est portée également à la méthodologie d'identification des paramètres des modèles d'endommagement implémentés. Trois approches de l'endommagement ductile ont été étudiées : des critères de rupture phénoménologique, des modèles phénoménologiques couplés et des modèles micromécaniques. Ces modèles ont été implémentés dans Forge®, et les algorithmes ont dû être adaptés à sa formulation mixte vitesse-pression et à son élément fini (P1+/P1). Parallèlement aux développements numériques, différents essais mécaniques ont été effectués sur trois matériaux différents (acier haut carbone, acier inoxydable et alliage de zirconium) pour identifier les paramètres des modèles d'écrouissage et d'endommagement. Des essais de traction in situ sous micro-tomographie aux rayons X ont été exploités pour l'identification des mécanismes d'endommagement ductile (germination, croissance et coalescence), ainsi que l'identification du modèle micromécanique. Enfin, la dernière partie de ce travail a consisté à réaliser des études comparatives de ces différents modèles d'endommagement pour les différents procédés de mise en forme et différents matériaux. Concernant le tréfilage et le laminage de l'acier inoxydable, un bon accord entre les simulations numériques et les résultats expérimentaux a été obtenu. Pour l'acier à haute teneur en carbone (perlitique), le modèle micro-mécanique GTN a donné le meilleur résultat à la fois qualitativement et quantitativement pour le tréfilage ultime. Par ailleurs, la comparaison entre les différents modèles sur différents procédés (laminage du fil avec l'acier haut carbone, laminage à pas de pèlerin avec l'alliage de zirconium) a aidé d'une part à mettre en évidence le rôle important du troisième invariant de la contrainte déviatorique sur la localisation de l'endommagement dans les procédés de mise en forme où le cisaillement est dominant. D'autre part, elle montre que le processus d'identification lui-même devrait se fonder sur la mesure de la microstructure afin de garantir un résultat précis lors de l'application aux procédés. / The present PhD thesis aims at a better understanding and modeling of ductile damage mechanisms during cold forming processes, with wire drawing, rolling and cold pilgering as examples. In addition, special attention is paid to implemented damage models parameters identification methodology. All three approaches of ductile damage were investigated: uncoupled phenomenological fracture criteria; coupled phenomenological models; micromechanical model. These models have been implemented in Forge®, which required adaptation of algorithms to its mixed velocity-pressure formulation and to its finite element (P1+/P1). Parallel to the numerical work, various mechanical tests on three different materials (high carbon steel, stainless steel and zirconium alloy) were carried out for work hardening, and damage models parameters identification. In situ X-ray micro-tomography tensile tests have also been exploited for the identification of ductile damage mechanisms (nucleation, growth and coalescence) as well as the identification of micromechanical model. Finally, we carried out comparative studies of these models on our three abovementioned forming processes and materials. Regarding wire drawing and rolling of stainless steel, good agreement between numerical simulations and experimental results was found. For high carbon perlitic steel ultimate wire drawing, the GTN micro-mechanical model has given the best result, both qualitatively and quantitatively. Moreover, the comparison of the different models on different processes (wire rolling on high carbon steel, cold pilgering on zirconium alloy) highlights on the one hand the important role of the third deviatoric stress invariant in damage localization for shear-dominated forming processes. It shows on the other hand that the identification process itself should be based on microstructure measurements to provide accurate results in forming application.

The production of low cost, large area display systems requires a light emitting material compatible with the standard silicon (Si) based complementary metal oxide semiconductor (CMOS) technology. The crystalline bulk Si is an indirect band semiconductor with very poor optical properties. On the other hand, hydrogenated amorphous Si (a-Si:H) based wide gap alloys exhibit strong visible photoluminescence (PL) at room temperature, owing to the release of the momentum conservation law. Still, the electroluminescence (EL) intensity from the diodes based on these alloys is weak due to the limitation of the current transport by the localized states. In the frame of this work, first, the luminescent properties of amorphous silicon nitride (a-SiNx:H) thin films grown in a plasma enhanced chemical vapor deposition (PECVD) system were analyzed with respect to the nitrogen content. Then, the doping effciency of p- and n-type hydrogenated nanocrystalline Si (nc-Si:H) films was optimized via adjusting the deposition conditions. Next, the junction quality of these doped layers was checked and further improved in a homojunction pin diode. Heterojunction pin light emitting diodes (LEDs) were fabricated with a-SiNx:H as the luminescent active layer. The EL effciency of the fresh diodes was very low, as expected. As a solution, the diodes were electro-formed under high electric field leading to nanocrystallization accompanied by a strong visible light emission from the whole diode area. The current-voltage (I-V) and EL properties of these transformed diodes were investigated in detail.