Cette thèse porte sur la croissance de films minces d’oxydes de zinc/fer (ZnxFe1-xO1+δ par ablation laser pulsée (PLD) et sur la possibilité de contrôler leurs propriétés structurales et physico-chimiques en variant les conditions d’élaboration : pression d’oxygène et température de croissance, proportions respectives de zinc/fer. Pour de fortes valeurs de x (x > 65%), les films sont monophasés de structure wurtzite type ZnO (films Fe:ZnO), avec une transparence optique dans la gamme UV-visible de 80% mais sans propriété ferromagnétique ; en fonction de leur teneur en fer (1-x), ils évoluent de très bons conducteurs électriques à quasi-isolants. Pour de faibles valeurs de x (x < 15%), les films sont également monophasés de structure spinelle type Fe3O4 (films Zn:Fe3O4). Ils présentent de très bonnes propriétés ferromagnétiques dès la température ambiante ainsi qu’une bonne conductivité électrique, les effets de localisation des porteurs de charge se manifestant en dessous de la température de Verwey. Le nombre de parois d’antiphase peut être diminué par une croissance en deux étapes, comme l’atteste les mesures de magnétorésistance. Aux taux intermédiaires de zinc (15% < x < 65%), les films sont nano-composites. Dans le cas d’une coexistence des phases Fe:ZnO et Zn:Fe3O4, la bonne conductivité de Zn:Fe3O4 jointe à la multiplicité des variantes épitaxiales et donc des interfaces fournit un matériau adapté à la thermoélectricité. Dans le cas d’une coexistence de la phase ferrromagnétique Zn:Fe3O4 avec la phase Zn:FeO antiferromagnétique de type sel gemme, un fort couplage d’échange ainsi qu’une anisotropie magnétique perpendiculaire élevée sont mis en évidence. / This thesis deals with the growth of thin films of zinc/iron oxides (ZnxFe1-xO1+δ) by pulsed laser deposition (PLD) and the possibility of controlling their structural and physicochemical properties by varying the elaboration conditions: oxygen pressure and growth temperature, respective proportions of zinc/iron. For high values of x (x> 65%), the films are single-phase with a ZnO-type wurtzite structure (Fe:ZnO films), with 80% optical transparency in the UV-visible range but without ferromagnetic properties; depending on their iron (1-x) content, they evolve from very good electrical conductors to near-insulators. For small values of x (x <15%), the films are also single-phase with a Fe3O4-type spinel structure (Zn:Fe3O4 films). They exhibit very good ferromagnetic properties at ambient temperature as well as good electrical conductivity, the localization effects of charge carriers occurring below the Verwey temperature. The number of antiphase walls can be decreased by a two-step growth, as evidenced by magnetoresistance measurements. At intermediate zinc rates (15% <x <65%), the films are nano-composites. In the case of a coexistence of the Fe:ZnO and Zn:Fe3O4 phases, the good conductivity of Zn:Fe3O4 combined with the multiplicity of epitaxial variants and thus of the interfaces provides a material suitable for thermoelectricity. In the case of a coexistence of the ferrromagnetic Zn:Fe3O4 phase with the Zn:FeO antiferromagnetic rocksalt phase, strong exchange coupling as well as high perpendicular magnetic anisotropy are demonstrated.

The course of polymer film functioning has been a crucial concern in the advent of packaging technology. The thesis project aims towards obtaining an understanding of mechanical properties for a class of these materials, namely LDPE and PET. A constitutive understanding of this behavior in the case of LDPE is acquired through incorporating a plastic stress strain relationship in an iterative approach with focus put on the sensitivity of a few parameters by following a simple linear curve-fit technique in a way that the global as well as the local response are predictable. FE-models also developed in this way are validated with experimental data. An inverse analysis testing validity or usefulness of DIC technique in identifying a material model is done and some discussions are drawn towards this area. A relative numerical study with respect to experimentally obtained global response for tearing of these polymers is done through use of a similar material model developed from tensile tests and the challenges faced in this area have been addressed.

Fe-Cr based steels, i.e. stainless steels, possessing a combination of excellent corrosion resistance and good mechanical properties, have indispensable applications ranging from low-end cooking utensils, to sophisticated components for nuclear power plants. However, the bcc/bct phase containing stainless steels which have a miscibility gap (MG) suffer from the so-called “475 oC embrittlement” leading to hardness increase and toughness deterioration. It occurs due to demixing of Fe and Cr leading to the formation of Fe-rich (α) and Cr-rich (α′) regions in bcc/bct phases. The demixing is referred to as phase separation (PS). The goal of this work was to study PS in ferrite containing stainless steels mainly by small-angle neutron scattering (SANS). Firstly, the application of different experimental techniques for the study of phase separation in Fe-Cr based steels was reviewed and supplemented by new measurements. SANS was shown to be very sensitive to the nanostructure change caused by PS and capable of characterizing the early stages of PS in Fe-Cr alloys. However, atom probe tomography and transmission electron microscopy are complementary to SANS. Therefore, in order to have a more complete view of the microstructure, the combination of these techniques should be pursued. Secondly, the factors affecting the initial microstructure prior to aging treatment and the effect of the resulted initial microstructure on PS were systematically investigated using binary Fe-Cr model alloys. The critical temperature of the MG was determined to be located between 560 and 580 oC in binary Fe-Cr. The results indicate that the solution treatment temperature above the MG and the cooling rate after solution treatment have significant effects on the initial microstructure and thus on PS during subsequent aging. The mechanisms responsible for the changed aging behavior are Cr clustering, quenched-in vacancy and decomposition during cooling. Therefore, computational simulations should take into account these factors and the initial microstructure to make predictions that are more accurate. Thirdly, the study was extended to PS in commercial duplex stainless steels (DSSs) which are of practical importance in various industries, e.g., nuclear power. It is found that alloying elements have an important effect on PS in DSSs. The grade 2507 (25 %Cr, 7 %Ni) experiences stronger PS than grade 2205 (22 %Cr, 5 % Ni) for the same heat treatment. Moreover, the fracture mechanisms as well as the mechanical properties depend on the extent of PS.  Finally, the fundamental aspects regarding the neutron scattering behavior for Fe-Cr alloys were examined. The results show that the nuclear and magnetic scattering of neutrons depend on the evolution of the nanoscale compositional fluctuation in Fe-Cr alloys. The ratio of the magnitude of nuclear scattering versus magnetic scattering varies with the extent of PS. / Stål baserade på Fe-Cr systemet, det vill säga rostfria stål, som har en kombination av utmärkta korrosionsegenskaper och bra mekaniska egenskaper, har många tillämpningar; allt från köksredskap, till sofistikerade komponenter för kärnkraftverk. Rostfria stål som innehåller Bcc / bct-fasen och som således har en blandningslucka, är känsliga för den så kallade "475 °C försprödningen" som leder till en hårdhetsökning men kraftigt försämrad slagseghet. Detta uppstår på grund av en uppdelning av Fe och Cr som leder till bildandet av Fe-rika (a) och Cr-rika (a’) regioner i bcc / bct-fasen. Denna uppdelning brukar kallas fasseparation. Målet med detta arbete var att studera fasseparationen i ferrit-innehållande rostfria stål främst genom lågvinkel-spridning av neutroner (SANS). Till att börja med studerades och jämfördes olika experimentella tekniker för undersökning av fasseparation i Fe-Cr-baserade stål med nya SANS- mätningar. SANS visade sig vara mycket känslig för förändringar på nano-skala orsakad av fasseparation och tekniken visade sig även kapabel att karakterisera de tidiga stadierna av fasseparation i Fe-Cr-legeringar. För att få en mer fullständig bild av mikrostrukturen efter fasseparation, bör emellertid en kombination av SANS och komplementära tekniker, såsom atomsond och transmissions-elektronmikroskopi, användas. Vidare undersöktes de faktorer som påverkar den ursprungliga mikrostrukturen före åldringsbehandling, och effekten av den initiala mikrostrukturen på fasseparation studerades systematiskt med användning av binära modell-legeringar av Fe-Cr. Den kritiska temperaturen för blandningsluckan i Fe-Cr bestämdes vara belägen mellan 560 och 580 °C. Resultaten indikerar att temperaturen för upplösningsbehandling ovanför blandningsluckan och kylhastigheten har en signifikant inverkan på den initiala mikrostrukturen och därmed på fasseparationen under efterföljande åldring. Mekanismerna som är ansvariga för det förändrade åldringsbeteendet är: Cr-klustring, insläckta vakanser och fasseparation under kylning. Simuleringar av fasseparationen bör därför ta hänsyn till dessa faktorer och den ursprungliga mikrostrukturen för att göra mer exakta förutsägelser av hur mikrostrukturen utvecklar sig med åldringstiden. Fasseparationen i kommersiella duplexa rostfria stål (DSS), som är av stor praktisk betydelse i olika branscher, t ex kärnkraft, studerades också med SANS. Det visade sig att mängden av olika legeringselement har en viktig effekt på graden av fasseparation i DSS. Legeringen 2507 uppvisade en tydligare fasseparation jämfört med legering 2205 för samma värmebehandling. Brottmekanismerna såväl som de mekaniska egenskaperna visade sig bero på omfattningen av fasseparationen. Slutligen undersöktes de grundläggande aspekterna hos neutronspridnings-beteendet för binära Fe-Cr-legeringar. Resultaten visade att kärn- och magnetisk spridning av neutroner beror på utvecklingen av sammansättningsfluktuationerna på en nanoskala i Fe-Cr-legeringar. Förhållandet mellan magnetisk- och kärnspridning varierar med omfattningen av fasseparationen. / <p>QC 20171117</p>

Friction stir spot welding (FSSW) is a solid-state welding process which is especially useful for joining precipitation-hardened aluminium alloys that undergo adverse property changes during fusion welding. It also has potential as an effective method for solid-state joining of dissimilar alloys. In FSSW, heat generation and plastic flow are strongly linked, and the scale of the process in time and space is such that it is difficult to separate and control the influence of all the relevant input parameters. The use of modelling is well-established in the field of welding research, and this thesis presents an analysis of the thermal and mechanical aspects of FSSW, principally using the finite element (FE) technique. Firstly, a thermal FE model is shown, which is subsequently validated by reference to experimental temperature data in both aluminium-to-aluminium and aluminium-to-steel welds. Correlations between high-quality welds and temperature fields are established, and predictions are made for peak temperatures reached under novel welding conditions. Deformation and heating are strongly linked in FSSW, but existing modelling tools are poorly suited to modelling flow processes in the conditions extant in FSSW. This thesis discusses the development and optimisation of two novel techniques to overcome the limitations of current approaches. The first of these uses greatly simplified constitutive behaviour to convert the problem into one defined purely by kinematics. In doing so, the boundary conditions reduce to a small number of assumptions about the contact conditions between weld material and tool, and the model calculation time is very rapid. This model is used to investigate changes in the slip condition at the tool to workpiece interface without an explicit statement of the friction law. Marker experiments are presented which use dissimilar composition but similar strength alloys to visualise flow patterns. The layering behaviour and surface patterns observed in the model agree well with observations from these experiments. The second approach extends the FE method to include deformation behaviour without the need for a fully-coupled approach, guided by the kinematic model. This is achieved using an innovative sequential small-strain analysis method in which thermal and deformation analyses alternate, with each running at a very different timescale. This technique avoids the requirement to either remesh the model domain at high strains or to use an explicit integration scheme, both of which impose penalties in calculation time and model complexity. The method is used to relate the purely thermal analysis developed in the work on thermal modelling to welding parameters such as tool speed. The model enables predictions of the spatial and temporal evolution of heat generation to be made directly from the constitutive behaviour of the alloy and the assumed velocity profile at the tool-workpiece interface. Predictions of the resulting temperature history are matched to experimental data and novel conditions are simulated, and these predictions correlate accurately with experimental results. Hence, the model is used to predict welding outcomes for situations for which no experimental data exists, and process charts are produced to describe optimum welding parameters. The methods and results presented in this thesis have significant implications for modelling friction stir spot welding, from optimising process conditions, to integration with microstructural models (to predict softening in the heat-affected zone, or the formation of intermetallics at the interface in dissimilar welds). The technique developed for sequential small strain finite element analysis could also be investigated for use in other kinematically constrained solid-state friction joining processes.

No description available.

The present thesis deals with synthesis of free alloy nanoparticles in immiscible alloy systems by the process of laser ablation under a liquid. In this process the alloy target is submerged in a liquid and the plume formed by the laser beam interaction with the target is confined in the liquid. The nanoparticles formed inside this plume and get quenched by the surrounding liquid yielding suspension of nanoparticles in the liquid. By the addition of suitable surfactants, these nanoparticles can be protected from other reactions and their size can be controlled by preventing further growth. We have selected immiscible alloys for the present study. These alloys tend to phase separate in melt as well as in solid depending on the value of the positive heat of mixing. We have used two binary alloys for the present study. These are alloys in Ag-Cu system and Fe-Cu system. In both these systems, there are reports of formation of extended solid solution due to kinetic factors during nonequilibrium processing like rapid solidification and mechanical alloying. In the present thesis we report synthesis of alloy nanoparticles of different compositions and sizes in these two systems and explore the nature of the phases that form in the small (nano) particles and their evolutionary pathways leading to the final microstructure. Microscopic techniques, especially transmission electron microscope, were used for characterization of these nanoparticles. The phase evolution was further studied using in situ microscopic techniques. After introducing the thesis in the Chapter 1, we describe briefly the relevant literatures in Chapter 2. The experimental details, in particular the experimental set up for laser ablation with targets under liquid are described in chapter 3. This chapter also includes the experimental details of the characterization. Transmission electron microscopy was used as primary characterization tool in the present study. The Chapter 4 presents the result of our study of alloy nanoparticles in Fe-Cu system. This system exhibits a submerged liquid miscibility gap. Although we have studied alloy targets of different compositions, the results of alloy nanoparticles obtained from targets with compositions Cu-40at.%Fe and Cu-60at.%Fe were primarily presented in this chapter. The nanoparticles that were synthesized had a size range of approximately 40nm to more than 100 nm. These particles have spherical morphology. The measurements of local compositions of different locations in the particle indicate the presence of a layer of Fe3O4 oxide at the spherical surface. This layer is devoid of copper. Most of the copper exist in the core of the particle. Fe rich spherical particles of much smaller size (~15 nm) are found to be embedded in the copper rich core. The copper formed solid solution with Fe and a copper concentration gradient exists in the particle below oxide layer due to oxidation of Fe. In contrast the nanoparticles obtained from alloy target with composition Fe-40at.% Cu have a spherical morphology. These have a composite structure with a Fe core in addition to Fe3O4 oxide layer at the surface. We have attempted to explain the phase evolution taking into account under cooling of the melt condensate that forms in the plume and their subsequent solidification through submerged miscibility gap. The chapters 5-7 deals with alloys of Ag-Cu system. In Chapter 5, we have carried out a detailed study of morphological evolution of the nanoparticles of Ag-Cu system. After optimizing the ablation parameters using pure Ag and Cu targets, we have synthesized alloy nanoparticles using different target compositions over the entire range of compositions with sizes having a mode of 25 nm. The evolution of the two phase structure is shown to be composition dependent with particles near equiatomic composition exhibit solid solution with uniformly distributed segregations of composition (Cu & Ag rich) while copper rich alloys exhibit a core shell structure with outer layer being Ag rich. The isothermal experiments again reveal emergence of core-shell morphology at intermediate time for particles with equiatomic composition. In order to compare the results of Ag-Cu nanoparticles with particles produced by other techniques we have synthesized Ag-Cu nanoparticles of near equiatomic composition by chemical route using nitrate salts and NaBH4 as reducing agent. PVP was used as capping agent. The results are presented in chapter 6. Depending on time of reaction, it is possible to synthesis free alloy particles from 2-3 nm to a network of chains. The nanoparticles contain Ag rich and Ag deficient region with Ag tends to segregate near surface. We have also presented mechanism for the formation of chain structure with prolonged reaction. The thermodynamic basis of phase formation in the immiscible system and evolution of phases under nonequilibrium situation have been discussed in chapter 7. This also includes a model to estimate size dependent surface energy. The analysis presented allows a discussion of possible pathways for phase evolution observed in the present work. The thesis ends with a final chapter that discussed the critical issues remains to be addressed and possible future work.

Canada produces about one-third of the global supply of medical radioisotopes. The nuclear power reactors in Ontario, Quebec and New Brunswick have generated about 17 percent of the electricity in the country every year (NWMO, 2010; Noorden; 2013). Since the 1960s, more than 2 million used (or spent) fuel bundles (high-level radioactivity) and 75,000 m³ of low- and intermediate-level radioactive waste have been produced, which is increasing by 2000 to 3000 m³ every year after reducing the processed volume (Jensen et al., 2009). More than 30 countries around the world, including Canada, have proposed construction of very deep geological repositories (DGRs) to store this nuclear waste for design periods 1,000,000 years. DGR concepts under development in Canada (the DGR is likely to be constructed in Ontario) are based on a multi-barrier system (NWMO, 2012). A crucial component of the multi-barrier system is the engineered barrier system (EBS), which includes a buffer, backfill, and tunnel sealing materials to physically, chemically, hydraulically and biologically isolate the nuclear waste. Bentonite-based material has been chosen for this critical use because of its high swelling capacity, low hydraulic conductivity, and for its good ability to retain radionuclides in the case of failed canisters. However, the presence of bentonite-based material in DGRs, surrounded by an aggressive environment of underground saline water, nuclear waste heat decay, and corrosion products under confining stress, may lead to mineralogical changes. Consequently, the physical and physiochemical properties of bentonite-based materials may change, which could influence the performance of bentonite in an EBS as well as the overall safety of DGRs. The objective of this research is to investigate the impact of the underground water salinity, heat generated by nuclear waste, and corrosion products of nuclear waste containers in Ontario on the engineering and micro-/nano-structural properties of bentonite-sand engineered barrier materials. Free-swelling, swelling pressure and hydraulic conductivity tests have been performed on bentonite-sand mixtures subjected to various chemical (groundwater chemistry; corrosion water with iron as a corrosion product) and thermal (heat generated) conditions. Several techniques of micro- and nano-structural analyses, such as x-ray diffraction (XRD), X-Ray microanalysis (DES), surface area and pore size distribution analyses (BET, BJH) and differential gravimetric (TGA and DTG) analyses have also been conducted on the bentonite-sand materials. Valuable results have been obtained for better understanding the durability and performance of the bentonite-sand barrier for the DGR which may be located in Ontario. The obtained results have shown that the groundwater chemistry and corrosion products of the nuclear containers significantly deteriorate the swelling and permeability properties of the tested bentonite-sand barrier materials, while temperature has little or no effect.

The present research aims to develop a novel technique for creation of composite riot helmet shells with reinforcing fibre continuity for better protection against low velocity impacts. In this research an innovative, simple and effective method of making a single-piece continuously textile reinforced helmet shell by vacuum bagging has been established and discussed. This technique also includes the development of solid collapsible moulding apparatus from non-woven fibres. Angle-interlock fabric due to its good mouldability, low shear rigidity and ease of production is used in this research. Several wrinkle-free single- piece composite helmet shells have been manufactured. Low-velocity impact test on the continuously reinforced helmet shells has been carried out. For this purpose an in-house helmet shell testing facility has been developed. Test rig has been designed in such a way that the impact test can be carried out at different locations at the riot helmet shell. Low-velocity impact test has been successfully conducted on the developed test rig. The practical experimentation and analysis revealed that the helmet shell performance against impact is dependent on the impact location. The helmet shell top surface has better impact protection as compared to helmet shell side and back location. Moreover, the helmet shell side is the most at risk location for the wearer. Finite Element models were created and simulated in Abaqus software to investigate the impact performance of single-piece helmet shells at different impact locations. Models parts have been designed in Rhinoceros software. Simulated results are validated by the experimental result which shows that the helmet top position is the safest position against an impact when it is compared to helmet back and helmet side positions.

The acceptance of the theory of the duties of protection isstrongly conditioned by systemic features of each legal order. if the premise and the scope of the doctrine are overlooked, and its historical and dogmatic location is dissociated from it, eventually it will be created a wasteful duplication of compensatory systems, in a legal order where the same result is obtained using the tort law. Nevertheless, it does not mean that creditor’s person or property will not be relevant with respect to contractual relationship. it is enough just to understand that this will only happen in a few situations in which the possibility to affect the rights of obligee falls within the specific contractual obligation. Out of these situations, any effort to turn tort damage into contractual damage will nothave otherwise forced and unsustainable consequences. / El acogimiento de la teoría de los deberes de protección y de la relación obligatoria compleja, está estrechamente condicionado por las características sistémicas de cada ordenamiento jurídico. si se desconocen tanto la premisa como el objetivo de dicha doctrina, y se la disocia de su ubicación histórico-dogmática, se terminará por crear una duplicación inútil de las tutelas resarcitorias en un sistema en donde el mismo resultado se obtiene recurriendo a la responsabilidad aquiliana. sin embargo, esto no quiere decir que la persona y el patrimonio del acreedor no asuman relevancia dentro de la relación obligatoria. será suficiente con comprender que esto sólo ocurrirá en determinadas hipótesis en las que la posibilidad de afectar la esfera jurídica del acreedor quede comprendida dentro de la prestación deducida en obligación. Fuera de estas, todo esfuerzo por convertir el daño aquiliano en contractual no tendrá si no consecuencias forzadas e insostenibles.

Esta tesina tiene como objetivo analizar la escala de valores subyacente al personaje de Cipriano Salcedo en la novela de Miguel Delibes El hereje. Además de realizar este análisis, la tesina analiza la posible existencia de intencionalidad por parte de Delibes de transmitir algún tipo de mensaje ético a través del relato. La metodología utilizada para alcanzar el objetivo es el método hermenéutico y las teorías sobre las que se asienta el análisis son el humanismo cristiano y las teorías axiológicas de los valores. La tesis realiza una identificación y clasificación de los valores que se muestra el personaje de Cipriano Salcedo y concluye demostrando la intención ética de Miguel Delibes al escribir esta novela.