M.Tech. (Department of Chemistry, Faculty of Applied Sciences), Vaal University of Technology / Many oxidic iron compounds—iron oxides; oxy-hydroxides and hydroxides—not only play an important role in a variety of disciplines but also serve as a model system of reduction and catalytic reactions. There are more than 16 identifiable oxidic iron compounds. The reduction of these compounds has been investigated for centuries. Despite this, the reduction behavior of the oxides is not fully understood as yet. To date the reduction mechanism is still plagued with uncertainties and conflicting theories, partly due to the complex nature of these oxides and intermediates formed during the reduction. Thermodynamically, the reduction of iron oxide occurs in steps. For example, during the reduction of hematite (a-Fe2O3) magnetite (Fe3O4) is first formed followed by non-stoichiometric wüstite (Fe1-yO) and lastly metallic iron (a-Fe). The rate of transformation depends on the reduction conditions. Further, this reduction is accompanied by changes in the crystal structure. The reduction behavior of iron oxides using graphite under ball-milling conditions was investigated using Planetary mono mill (Fritsch Pulverisette 6), Mössbauer Spectroscopy (MS), X-ray Diffraction (XRD), Scanning electron microscopy (SEM) and Transmission Electron Microscopy (TEM). It was found that hematite transformed into magnetite, Wüstite and or cementite depending on the milling conditions. The study shows that by increasing the milling time, the rotational speed and / or the ball to powder ratio, the extent of the conversion of hematite to its reduction products increased. Further investigations are required for the elucidation of the reduction mechanism. The reaction og magnetite and graphite at different milling conditions lead to the formation of Fe2+ and Fe3+ species, the former increasing at the expense of Fe3O4. Fe3O4 completely disappeared after a BPR of 50:1 and beyond. The Fe2+ species was confirmed to be due to FeO using XRD analysis. HRSEM images Fe2O3 using scanning electron microscopy prior to and after milling at different times showed significant changes while the milling period was increased, HRSEM images showed that the once well defined hematite particles took ill-defined shapes and also became smaller in size, which was a results of the milling action that induced reaction between the two powders to form magnetite. EDX spectra at different milling times also confirmed formation of magnetite. EDX elemental analysis and quantification confirmed the elemental composition of starting material consisting mainly of iron. Similarly, HRSEM images of Fe3O4 using Scanning electron microscopy (SEM) prior to and after milling at different BPR showed significant changes when the milling period was increased. EDX spectra at different milling times also confirmed formation of partial FeO and EDX elemental analysis and quantification confirmed the elemental composition of starting material consisting mainly of iron than Fe2O3. TEM images of both Fe2O3 and Fe3O4 particles at different milling conditions displayed observable particle damages as a function of milling period.The once well - defined particles (Fe2O3 and Fe3O4 ) successively took ill – defined shapes, possibly accompanied by crystallite size reduction. MAS showed that the reactive milling of α- Fe2O3 and C resulted in reduction to Fe3O4 , FeO and or cementite depending on the milling conditions etc Time, milling speed and BPR variation which influenced the reduction. The study shows that by increasing the milling time, the rotational speed and / or the ball to powder ratio, the extent of the conversion of hematite to its reduction products increased. XRD study investigations even though were unable to detect spm species (Fe2+ and Fe3+ ) which has smaller crystallites below detection limits ,the variation in time showed an increment in the magnetite peaks accompanied by recession of hematite and graphite peaks as the milling time was increased which relates to the MAS observation.XRD also corroborated the data obtained from MAS that showed that the main constituent was magnetite and further evidence in support of the reduction of hematite to magnetite under reactive milling was obtained using XRD . Overall, the work demonstrated selective reduction of Fe2O3 to Fe3O4 and Fe3O4 to FeO by fine tuning the milling conditions. It is envisaged that the reduction of FeO to Fe and possible carburization to FexC could also be achieved.

The topic of this master’s thesis is the design of a sample manipulator for TEM. Regarding which the segment of the sample manipulator used to move the sample in the direction of the x-axis (so-called x-stage) was designed. The introductory theoretical part is concerned with a brief description of transmission electron microscopy focused on the imaging methods used in TEM and the procedures of preparing and loading TEM samples. The theoretical part follows with the design of precise mechanisms, especially with respect to the inaccuracies of their operation and the technological aspect of the design. In the practical part, a detailed analysis of the design of the x-stage is presented. Kinematics and dynamics of the mechanism is analyzed in depth, following with the description of the overall design of the mechanism and some of its parts in detail.

In this project, the TMP method was employed to produce “active sites.” These active sites are for influencing and controlling the Co₃O₄ growth. One of the aims was to investigate what effect the grafting of the molecular precursor has on the nature and distribution of active sites on the various support materials. The second aim was to investigate the effect an increase in molecular precursor loading, in various impregnation steps, has on the nature and distribution of the active sites. The third aim was to investigate the effect of the steric constraints of ligand groups, by changing the molecular precursor, on the nature and distribution of active sites. The fourth aim was to use the different aspects discussed above and apply them to investigate what effect the above-mentioned modifications have on Co₃O₄ morphology. While another aim was to investigated what effect varying the quantity of Co(NO₃)₂•6H₂O has on Co₃O₄ morphology. Lastly, we investigated what effect varying the impregnation procedure and calcination temperature have on the Co₃O₄ morphology. The effect the support has on the phase of titanium molecular precursor was investigated using molecular precursor, ⁱPrOTi[OSi(O[superscript(t)]Bu₃)]₃. The supports used were Silica 922, NanoDur, Aerosil 200, Stöber spherical silica, SBA-15, mod MCM-41 and sMCM-41. The molecular precursor ⁱPrOTi[OSi(O[superscript(t)]Bu₃)]₃ was revealed to be in the orthorhombic TiO₂ with space group P(cab), normal brookite lattice, on Silica 922 after calcination but only an isolated area displaying this morphology. Generally we do not observe any TiO₂ on the support, which indicates that we have produce site-isolated sites, suggesting the TMP method has been successful on all of the various supports. The emphasis is placed on the effect of this molecular precursor and the respective support has on the Co₃O₄ morphology in Chapter 3. In this Chapter, a unique morphology was observed on Silica 922 which showed Co₃O₄ nanorods of cubic Co₃O₄ in the space group Fd-3m. Silica 922 was used for the remainder of the thesis to investigate the effect the quantity of molecular precursor has on the nature of active sites and Co₃O₄ morphology in Chapter 4. This support was also used to investigate the effect the amount of Co(NO₃)₂•6H₂O has on Co₃O₄ morphology in Chapter 5. This support was lastly used to investigate the steric constraints of the ligand groups, Ti[OSi(O[superscript(t)]Bu)₃]₄ (TiSi4), ⁱPrOTi[OSi(O[superscript(t)]Bu)₃]₃ (TiSi3), (OtBu)₃TiOSi(O[superscript(t)]Bu)₃ (TiSi) and the least sterically constrained Ti(OⁱPr)₄ has on the loading of precursor and Co₃O₄ morphology in Chapter 6.

No description available.

No description available.

De nombreux alliages de structure doivent leurs propriétés mécaniques à la présence de précipités inter ou intragranulaires. Ainsi les superalliages à base nickel, de matrice austénique γ, sont souvent renforcés par des précipités de phases intermétalliques ordonnées. Au sein de l’alliage Inconel 718, outre la phase γ’ de structure L12 (cubique simple), on trouve des précipités de Ni3Nb sous la forme métastable γ" (D022 - tétragonal centré) ou sous la forme stable δ (D0a - orthorhombique). Le rôle des précipités γ’, γ" et δ sur les propriétés macroscopiques de l'alliage est connu et largement utilisé en contexte industriel. Cependant les mécanismes de précipitation et de transformation de ces précipités ne sont toujours pas complètement élucidés, ce qui a motivé ce travail. La microstructure de l’alliage a été caractérisée par microscopie optique (MO) et électronique (à balayage et en transmission ; MEB et MET) dans l’état de livraison et après des traitements thermiques isothermes et anisothermes. Les essais d’analyse thermique différentielle (ATD) nous ont permis de préciser les domaines de température de précipitation et de dissolution des différentes phases présentes (γ’, γ" et δ). Différents états de précipitation ont été obtenus à l’aide de traitements thermiques isothermes basés sur les diagrammes temps-températuretransformation (T.T.T.) disponibles dans la littérature. Les observations en MET « à haute résolution » des précipités des phases δ et γ’’ ont permis de caractériser certains des défauts structuraux présents dans ces précipités. Nous montrons ainsi que les défauts d’empilement au sein de la phase γ’’ peuvent servir de germes pour la précipitation de . Alors que la structure des interfaces δ/γ ainsi que les défauts d’orientation au sein des lamelles de δ suggèrent que la croissance de la phase δ a lieu directement à partir de la matrice . / Many structural alloys are strengthened by the presence of precipitates in the grains or at grain boundaries. Nickel based superalloys often present an austenitic γ matrix in which ordered intermetallic phases precipitate. In the alloy Inconel 718, one can find γ’ L12 cubic ordered precipitates together with the compound Ni3Nb in its metastable form γ" (D022 - tetragonal) or the stable phase δ (D0a - orthorhombic). The incidence of those precipitates on macroscopic properties of the alloy 718 is well known and widely used in industrial applications. However the mechanisms responsible for the precipitation and transformation of these phases are not fully understood, which motivated the present study. The alloy microstructure has been observed by optical microscopy (OM) and electron microscopy (scanning and transmission, SEM and TEM) in the as received state as well as after heat treatment (isothermal and anisothermal). Differential thermal analysis (DTA) was used to determine the precipitation and dissolution temperatures of the phases γ', γ" and δ. Various precipitation microstructures were obtained by heat treatments based on available TTT diagrams. Some of the structural defects present in γ" and δ precipitates have been characterised by lattice imaging TEM observations. It is shown that stacking faults in γ’’ phase can act as a seed for the germination of . The structure of the δ/γ interface and the orientation defects in δ lamellae suggest that the growth of δ phase occurs directly from the matrix (and not by transformation of the γ’’ phase).

A large number of proteins interact with biological membranes, either integrated in the membrane (PepTSo2), embedded on a membrane surface (5-lipoxygenase) or encircling a cutout of lipid bilayer (apolipoprotein1 (apoA-I). They function as transporters, receptors or biocatalysts in cellular processes like inflammation or cholesterol transport which are touched upon here. Malfunction of specific membrane proteins are the cause for several diseases or disorders. Knowledge of protein structure supports understanding of its mechanism of function. Here, transmission electron microscopy (TEM) was used for structure determination. To obtain structure information to high resolution for membrane proteins, normally surrounded by lipids, demands specific methods and materials for stabilization. Stabilized in detergent the structure of the bacterial transporter PepTSo2 was shown to form a tetramer even bound to substrate. However, with a protein based stabilizer, Salipro, the structure of PepTSo2 could be determined to high resolution. High density lipoprotein (HDL) in blood plasma, involved in the removal of cholesterol from peripheral tissues, have a central role in cardiovascular function, metabolic syndrome and diabetes. The HDL-particle is composed of two copies of ApoA1 and around hundred lipid molecules. From TEM data, for the first time the clearly discoidal shape could be shown by 3-dimendional reconstructions. These were used for modelling the ApoA1 protein dimer by a "biased fitting" procedure. The results indicate how ApoA1 folds around a lipid bilayer in a disc-shaped structure. Modified HDL called nanodiscs were here used to show the Ca2+ dependent binding of 5-lipoxygenase on the nanodisc bilayer and thereby increased production of the inflammatory mediator leukotrieneA4. Dimerization of 5-lipoxygenase inactivates these functions. / <p>QC 20170323</p>

Ce travail présente les résultats d'un modèle théorique de précipitation de particules Al$_2$Cu dans un alliage d'aluminium de fonderie de type 319 traité thermiquement T7, prenant en compte les équations de la théorie de la coalescence. L'utilisation d'une distribution de taille de particules expérimentale discrétisée comme point de départ du modèle rend possible l'utilisation d'une équation de flux afin de modéliser l'évolution du rayon moyen des particules dans un élément de volume représentatif de l'alliage. L'utilisation d'un schéma numérique implicite permet de ramener la résolution du problème physique à l'inversion d'une matrice tridiagonale. Ainsi, l'évolution du rayon critique de coalescence, du nombre total et de la fraction volumique de précipités sont obtenus pour plusieurs vieillissements. Les résultats du modèle a été confrontés aux résultats des mesures expérimentales qui ont été réalisées à l'aide d'observations en microscopie électronique à transmission et qui ont permis une mesure de la taille des précipités. Ces derniers ont été assimilés à des sphères de volume équivalent aux plaquettes réelles et ont été analysés numériquement. Les résultats fournis par le modèle théorique sont en bon accord avec les mesures expérimentales et ont permis le couplage du modèle de coalescence avec un modèle micromécanique fondé sur la théorie des dislocations et calibré à l'aide d'essais de traction en température. Il permet de déterminer la limite d'élasticité de l'alliage pour un vieillissement jusqu'à 1000h compris entre 23°C et 300°C. La limite d'élasticité est alors assimilée à une somme de trois contraintes~: une contrainte liée à la friction de réseau (contrainte de Peierls), une contrainte liée au contournement des précipités par les dislocations (contrainte d'Orowan) et une contrainte liée à la présence de solution solide. Enfin, des essais de fatigue oligocyclique à différentes températures ont permis de déterminer les variables internes de la loi de comportement macroscopique. Il s'agit d'une loi élasto-viscoplastique de type Lemaitre et Chaboche, à laquelle la limite d'élasticité calculée par le modèle micromécanique est couplée. Ainsi, le comportement physique macroscopique de l'alliage est fonction de la coalescence des précipités. Des calculs 1D ou 3D, par éléments finis, permettent alors de déterminer le comportement général d'une culasse soumise à de la fatigue thermomécanique / This work highlights the results of a theoretical Al$_2$Cu particles coarsening model in a T7 thermal treated 319 aluminum alloy. As an input of the model, the experimental and discretised size distribution of the precipitates, in a 1$mu$m$^3$ representative volume element of the alloy, is used and coupled to a flux equation. The use of a numerical implicit scheme allows us to solve the problem by the inversion of a tridiagonal matrix. Thus, the evolution of the critical radius of coarsening, of the total number and of the volumical fraction of particles are modeled in a range of temperature going from 23°C to 300°C up to 1000h ageing time. Results were then compared to transmission electron microscope observations and are in good agreement with experimental measurements. Hence, the model was then coupled to a micro-mechanical model which is based on the theory of dislocations. It determines the real yield stress of the alloy generated by the interaction of the dislocations with the lattice (Peierls stress), with the precipitates (Orowan stress) and with the atoms in solid solution. Both models were then combined into a mechanical macro-scale model in order to represent the LCF behavior of the material. An elasto-viscoplastic law has been used and all the internal variables were experimentally determined using LCF stress/strain loops for the mechanical steady state. The simulation results are in good agreement with the experiments. Finally, 1D and 3D finite element computations could be run, taking into account the evolution of the microstructure during ageing and its impact on the evolution of the mechanical properties, to determine the head cylinder behavior under thermomechanical fatigue

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Master of Science / Department of Biological and Agricultural Engineering / Donghai Wang / Currently, the majority of adhesives used for wood veneer, plywood, and composite applications are formaldehyde-based. Formaldehyde is derived from petroleum and natural gas, making it non-renewable and toxic. Therefore, extensive research has been conducted to develop bio-based adhesives to replace formaldehyde-based adhesives. Soy protein has shown great potential to partially replace formaldehyde adhesives, and canola protein has similar properties to soy protein. However, little research has been conducted on the feasibility of using canola protein for wood adhesive applications. The objective of this research was to study the adhesion performance of canola protein. Canola protein was modified with different chemical modifiers including sodium dodecyl sulfate (SDS), calcium carbonate (CaCO[subscript]3), zinc sulfate (ZnSO[subscript]4), calcium chloride (CaCl[subscript]2), and 2-octen-1-ylsuccinic anhydride (OSA) as well as combined chemical modifications. The wet, dry, and soak shear strengths of the adhesive formulations were determined. Viscosity testing, differential scanning calorimetry, and TEM and SEM imaging were used to characterize protein properties. Chemical modification with SDS (1%, 3%, and 5%), CaCO[subscript]3 (1%, 3%, and 5%), ZnSO[subscript]4 (1%), and OSA (2%, 3.5%, and 5%) improved the dry and soak shear strengths compared to unmodified canola protein. Canola protein modified with 3.5% OSA had improved wet, dry, and soak shear strengths. Combined chemical modification of canola protein did not show significant improvement on shear strength. Thermal modification of canola protein adhesives showed a trend of increasing shear strength with increasing press temperature. The data suggests that with further research, canola protein has potential to be used as a commercial adhesive or as an additive to formaldehyde-based adhesives to make them more environmentally-friendly.