Thesis (M.Sc. (Physics)) -- University of Limpopo, 2015 / Nanocrystalline materials of defect free anatase and rutile SnO2 together with Ti and Y in anatase SnO2 have been modelled successfully using classical molecular dynamics simulations together with Buckingham potential. The structural properties of these SnO2 phases were analysed using radial distribution functions (RDFs). The effect of increasing temperature in pure SnO2 and doped SnO2 were studied. In both pure and doped materials, RDFs suggest phase transition at higher temperature, where anatase SnO2 transforms to rutile SnO2. Rutile SnO2 was found to be more stable than anatase SnO2. The results showed that the dopants have different effects on the SnO2 material. Ti defect is found to lower the transformation temperature of anatase to rutile SnO2. Y defect is found not to have any effect on the anatase to rutile SnO2 transformation. Thermodynamic properties such as volume thermal expansion coefficient and specific heat capacity were also calculated from above Debye temperature. Volume thermal expansion coefficient was obtained from volume versus temperature curves. Volume thermal expansion coefficient for rutile and Ti-anatase SnO2 were found to be not of the same order with the calculated results. Specific heat capacity calculated from energy versus temperature curves was found to be in agreement with the Dulong and Petit law of solids. Nanocrystalline Al/Y co-doped SnO2 powders were successfully synthesized using the sol-gel method. The samples were subjected to different temperatures 100 (as prepared) 200, 400, 600, 800 and 1000 oC. The effects of co-doping and temperature on the structural and optical properties of Al/Y co-doped SnO2 nanoparticles as well as morphology were investigated. The characterization techniques used were X-ray powder diffraction (XRD), Raman spectroscopy, Scanning electron microscopy (SEM) and UV-visible spectroscopy (UV-vis). The average particle sizes were found to be in the range between 2.5–8 nm and the strains were calculated to be 2.76–0.53 with increasing temperature for as prepared and the sample sintered at different tempe-ratures. The Raman bands were found to correspond with the literature. At a higher temperature of about 800 oC the materials were found to contain the second phase which is yttrium stannate. However no information about aluminium was found. The optical band gap were found to be between 3.3–3.99 eV in the temperature range 200–1000 oC.

Nanocrystalline materials with grain size less than 100 nm have been receiving much attention because of their unparallel properties compared with their microcrystalline counterparts. Because of its high hardness, nanocrystalline nickel has been used for MEMS. Long term thermomechnical properties and deformation mechanism at both ambient and elevated temperatures need to be evaluated which is vital for reliability of its applications as structural material. In this thesis, nanoindentation creep of nanocrystalline nickel with an as-deposited grain size of 14 nm was characterized at elevated temperatures. The nanoindentation creep rate was observed to scale with temperature and applied load (or stress), and could be expressed by an empirical power-law equation for describing conventional crystalline solids. Creep activation energy was found to be close to that for grain boundary self-diffusion in nickel. The activation volume was also evaluated using a stress relaxation technique. The creep results were compared with those for fine-grained nickel in the literature. Possible mechanisms were discussed in light of the creep rate and temperature ranges. To provide a direct comparison, uniaxial creep tests were conducted on nanocrystalline nickel with an as-deposited grain size of 14 nm at 398 K. It was found that stress exponents under the two test conditions are almost the same, indicating a similar creep mechanism. However, the strain rate measured by nanoindentation creep was about 100 times faster than that by uniaxial creep. The rate difference was discussed in terms of stress states and the appropriate selection of Tabor factor. To further explore the time-dependent plastic behavior, multiple unload-reload tests were conducted on electrodeposited nanocrystalline nickel in both compression and tension. A hysteresis was observed during each unload-reload cycle, indicating irreversible energy dissipation. The dissipated energy was evaluated and the energy dissipation rate was found to increase with the flow stress to the third power and sensitive to the stress state (tension or compression). A mechanistic model based on grain boundary sliding was proposed to describe the unload-reload behavior. Experimental results were found to be in good agreement with the model predictions, suggesting the observed hysteresis was indeed caused by grain boundary sliding.

Nanocrystalline materials have generated immense scientific interest, primarily due to observations of significantly enhanced strength and hardness resulting from Hall-Petch grain size strengthening into the nano-regime. Unfortunately, however, most previous studies have been unable to present material strength measurements using established tensile tests because the most commonly accepted tensile test protocols call for specimen geometries that exceeded the capabilities of most nanocrystalline material synthesis processes. This has led to the development of non-standard mechanical test methodologies for the evaluation of miniature specimens, and/or the persistent use of hardness indentation as a proxy for tensile testing. This study explored why such alternative approaches can be misleading and revealed how reliable tensile ductility measurements and material strength information from hardness indentation may be obtained. To do so, an electrodeposition-based synthesis method to produce artifact-reduced specimens large enough for testing in accordance with ASTM E8 was developed. A large number of 161 samples were produced, tested, and the resultant data evaluated using Weibull statistical analysis. It was found that the impact of electroforming process control on both the absolute value and variability of achievable tensile elongation was strong. Tensile necking was found to obey similar processing quality and geometrical dependencies as in conventional engineering metals. However, unlike conventional engineering metals, intrinsic ductility (as measured by maximum uniform plastic strain) was unexpectedly observed to be independent of microstructure over the grain size range 10-80nm. This indicated that the underlying physical processes of grain boundary-mediated damage development are strain-oriented phenomena that can be best defined by a critical plastic strain regardless of the strength of the material as a whole. It was further shown that the HV = 3•σUTS expression is a reliable predictor of the relationship between hardness and strength for electrodeposited nanocrystalline materials, provided the material is ductile enough to sustain tensile deformation until the onset of necking instability. The widely used relationship HV = 3•σY was found to be inapplicable to this class of materials owing to the fact that they do not deform in an “ideally plastic” manner and instead exhibit plastic deformation that is characteristic of strain hardening behaviour.

Nanocrystalline materials have generated immense scientific interest, primarily due to observations of significantly enhanced strength and hardness resulting from Hall-Petch grain size strengthening into the nano-regime. Unfortunately, however, most previous studies have been unable to present material strength measurements using established tensile tests because the most commonly accepted tensile test protocols call for specimen geometries that exceeded the capabilities of most nanocrystalline material synthesis processes. This has led to the development of non-standard mechanical test methodologies for the evaluation of miniature specimens, and/or the persistent use of hardness indentation as a proxy for tensile testing. This study explored why such alternative approaches can be misleading and revealed how reliable tensile ductility measurements and material strength information from hardness indentation may be obtained. To do so, an electrodeposition-based synthesis method to produce artifact-reduced specimens large enough for testing in accordance with ASTM E8 was developed. A large number of 161 samples were produced, tested, and the resultant data evaluated using Weibull statistical analysis. It was found that the impact of electroforming process control on both the absolute value and variability of achievable tensile elongation was strong. Tensile necking was found to obey similar processing quality and geometrical dependencies as in conventional engineering metals. However, unlike conventional engineering metals, intrinsic ductility (as measured by maximum uniform plastic strain) was unexpectedly observed to be independent of microstructure over the grain size range 10-80nm. This indicated that the underlying physical processes of grain boundary-mediated damage development are strain-oriented phenomena that can be best defined by a critical plastic strain regardless of the strength of the material as a whole. It was further shown that the HV = 3•σUTS expression is a reliable predictor of the relationship between hardness and strength for electrodeposited nanocrystalline materials, provided the material is ductile enough to sustain tensile deformation until the onset of necking instability. The widely used relationship HV = 3•σY was found to be inapplicable to this class of materials owing to the fact that they do not deform in an “ideally plastic” manner and instead exhibit plastic deformation that is characteristic of strain hardening behaviour.

Amorphous ribbons of alloy composition Fe75B10Si15 are cast by melt spinning and annealed to partially nanocrystalline states. The magnetic properties are investigated by VSM and MTGA. Structure is examined using XRD and SEM. Results obtained show nanostructured material with excellent soft magnetism in samples annealed at temperatures below the crystallization temperature as well as enhancement of magnetic hardness for annealing at high temperatures. This validates Herzer’s Random Anisotropy model of magnetism in nanostructured materials and provides basis for further inquiry into tweaking alloy compositions and/or manipulating annealing parameters. Also, increase of Curie temperature is noted with respect to increasing annealing temperatures arising from stress relaxation, validating a study on the relationship between the two.

Ball milling has been shown to produce nanostructures in metal powders through severe repetitive deformation. Ball milling at cryogenic temperatures (cryomilling) is more effective in this capacity due to the low temperature by slowing recovery and minimizing diffusion distances between different components. Nanostructured metals are of interest because of their unique physical and mechanical properties. The result of cryomilling is powder consisting of crystallites on the order of 30 – 50 nm. In order to characterize the properties of this material, it is often necessary to consolidate the powder, which is often difficult without causing significant grain growth. In this work, aluminum-rich and magnesium-rich alloys of varying composition are produced by cryomilling and characterized by x-ray diffraction. A novel consolidation process called high shear powder consolidation (HSPC) is used to densify as-received and as-milled powders with minimal growth. The construction of a cryomill, along with a modification for improving process yield, has provided a platform for the study of nanocrystalline metals. It has been shown that bulk nanocrystalline materials are attainable and that alloy composition influences mechanical properties. / Master of Science

Un enjeu majeur de l’industrie aéronautique de demain est de concevoir et développer un avion « plus » électrique. En effet, sur un avion de ligne, les principaux systèmes utilisent des types d'énergies différents tels que l'énergie hydraulique ou pneumatique. La tendance actuelle est à la conversion de ces systèmes à l'énergie électrique car elle présente de nombreux avantages et permettrait des économies de masse, d’énergie, et de coûts de maintenance. Avec l’augmentation croissante des systèmes électriques dans l’avion se posent par conséquent des problèmes d’interférences et de compatibilité électromagnétique entre ces différents dispositifs. Par ailleurs ces systèmes électriques sont soumis à des conditions de travail très sévères, notamment des températures extrêmes. Dans le cadre du projet FEMINA (Filtrage Electromagnétiques et Matériaux pour l’INtégration en Aéronautique), l’objectif de notre équipe était d’étudier un filtre électrique soumis à des conditions de températures extrêmes. Ce filtre composé d’éléments passifs (condensateurs et inductances) est destiné à éliminer les interférences provoquées par le convertisseur électrique placé à proximité de la source d’énergie et de chaleur (le propulseur). Dans le cadre de mes travaux de thèse, je me suis intéressé plus particulièrement à l’effet de la température sur le comportement des inductances au travers des matériaux magnétiques qui les composent. J’ai ainsi déterminé les matériaux magnétiques que j’estimais capable de remplir leur rôle de filtrage en hautes températures, puis j’ai élaboré un modèle de comportement magnétique dynamique, tenant compte de l’effet de peau et de l’effet de la température et enfin j’ai testé ce nouveau modèle en l’incluant dans un simulateur circuit, afin de modéliser un filtre de mode commun répondant au cahier des charges de nos partenaires industriels. / A major challenge in the aviation industry is to design and develop “more” electric aircraft. Indeed, the main systems use different types of energy such as hydraulic or pneumatic energy. The current trend is to convert these systems to electric power because it has many advantages and would allow economies of mass, energy and maintenance costs. With the increasing electrical systems in the aircraft, arise problems of interference and electromagnetic compatibility between these systems. Moreover, these power systems are subjected to severe working conditions, including extreme temperatures. As part of the FEMINA project (Filtrage Electromagnétiques et Matériaux pour l‟INtégration en Aéronautique), the goal of our team was to study an EMC filter subjected to extreme temperature conditions. This filter is composed of passive elements (capacitors and inductors) and designed to remove interference caused by electrical converter located close to the source of energy and heat (the propeller). As part of my thesis work, I focused on the effect of temperature on the behavior of inductors through the magnetic materials that compose them. I have thus determined the magnetic materials that I felt able to fulfill their role at high temperatures, then I developed a dynamic model of magnetic behavior, taking into account the skin effect and the effect of temperature and finally I tested this new model by including it in a circuit simulator to model a common mode filter that meets the specifications of our industrial partners.

This thesis deals with an introduction to the theory of switching power supplies and with properties of magnetic materials. Special attention is paid to nanocrystalline materials. It also discusses the issues of simulating the behavior of ferromagnets. The properties of commonly used ferrite material and nanocrystalline materials was measured. Using the created program for the design of forward converter is designed a switching power supply to verify its proposal. Design optimization is based on using a nanocrystalline core, which allows to reduce the operating frequency.

Das Ziel der vorliegenden Arbeit ist es, nanokristalline und laserpuls-strukturierte Elektroden für die alkalische Wasserelektrolyse zu untersuchten und hinsichtlich ihrer elektrokatalytischen Eigenschaft zu bewerten. Dabei besteht die Hauptaufgabe in der Aufklärung der Zusammenhänge zwischen der elektrokatalytischen Aktivität und der Struktur der Elektroden. Es soll der Effekt der nanokristallinen Kristallstruktur auf die Elektrodenaktivität aufgeklärt werden. Zudem stellt die elektrokatalytische Wirkung von Mo in Ni-Elektroden für die Wasserstoffentwicklungsreaktion eine zentrale Untersuchung in der vorliegenden Arbeit dar. Für die Sauerstoffentwicklungsreaktion soll der Einfluss von Fe in nanokristallinen Ni-Materialien näher analysiert und unter industriell relevanten Betriebsbedingungen bewertet werden. Zum anderen richtet sich der Fokus auf die Nutzung eines Ultrakurzpulslasers zur Strukturierung von Ni-Elektrodenoberflächen. Besonderes Augenmerk wird auf die Korrelation zwischen den individuellen Strukturmerkmalen, der erzielten Oberflächenvergrößerung und der elektrokatalytischen Aktivität bezüglich der Wasserstoffentwicklung gelegt. Zudem werden Langzeituntersuchungen bei Stromdichten von bis 1 A/cm² durchgeführt, um die Stabilität zu bewerten und Degradationsmechanismen aufzuklären.

In der vorliegenden Dissertation werden verschiedene plasmonisch aktive Kern/Schale- Nanopartikel synthetisiert, experimentell und theoretisch charakterisiert und in analytischen Anwendungen der oberflächenverstärkten Raman-Spektroskopie (engl. surface-enhanced Raman scattering, SERS) eingesetzt. Es werden die optischen Eigenschaften von Gold/Silber-Nanoschalen mit durchstimmbaren Plasmonbanden behandelt. Motivation dafür ist die Frage nach optimalen SERS-Markern für die rote Laseranregung (λ = 632.8 nm). In SERS-Anwendungen gibt es die Möglichkeit mehrere Marker-Moleküle auf die Oberfläche der Nanopartikel aufzubringen, um so eine erhöhte Multiplexing-Kapazität zu generieren. Diese Option der gemischten Monolagen wird in der vorliegenden Arbeit untersucht. Es werden SERS-Marker-Konzepte für die rote Laseranregung basierend auf einzelnen Nanopartikeln gezeigt. Außerdem wird dargestellt, inwieweit sich durch die Anordnung von Nanopartikeln in allen drei Raumdimensionen neue SERS-Marker- Konzepte mit sehr guten plasmonischen Eigenschaften realisieren lassen. In den oben beschriebenen Kapiteln übernehmen Nanopartikel die Rolle des SERS-Substrats für den selektiven Nachweis eines bestimmten Zielmoleküls (z.B. Antigens). Neben diesen Anwendungen können Nanopartikel jedoch auch noch als SERS-Substrat für die markierungsfreie Detektion von Analytmolekülen eingesetzt werden. In dieser Dissertation wird die Herstellung, Charakterisierung und der Einsatz eines integrierten SERS-Substrats für die kombinierte Festphasensynthese und Analytik mittels plamonisch aktiver Gold/Glas-Kern/Schale-Nanopartikel auf Harz-Mikrokugeln behandelt.