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.

Resumen (Castellano) El aumento del consumo de energía global junto con las preocupaciones ambientales ha generado mucho interés por las fuentes de energía alternativas y limpias, como la energía solar fotovoltaica. Los investigadores en la comunidad fotovoltaica han estado buscando formas de reducir costos mientras mantienen o aumentan las eficiencias. Una mejor comprensión de los materiales implicados es esencial para el rápido desarrollo de nuevas tecnologías. Las películas delgadas I-III-VI2 ofrecen sistemas prometedores para lograr células solares de alta eficiencia a un costo menor. De hecho, al adaptar la composición de los compuestos, es posible cambiar la banda prohibida del material para captar la luz solar de manera más eficiente. Esta tesis se centra en la preparación y caracterización del material de la capa absorbente, especialmente las películas delgadas nanocristalinas y la consideración de las características estructurales y eléctricas de dicha capa principal absorbente de células. La tesis examina cómo las diferentes técnicas de preparación y uso del material podrían afectar las propiedades del películas delgadas sintetizadas. Películas delgadas CuInSe2 y CuInS2 se depositaron sobre sustratos de vidrio ITO usando la técnica de electrodeposición en solución acuosa. Las películas electrodepositadas se caracterizaron por difracción de rayos X (XRD), microscopía electrónica de barrido (SEM) y análisis de rayos X de energía dispersiva (EDS). Se investigaron los efectos de recocido sobre los precursores electrodepositados. La estructura de calcopirita de CuInSe2/CuInS2 mostró una mejora de la cristalinidad después del tratamiento posterior de selenización/sulfurización en atmósfera Se/S, respectivamente. Los estudios de XRD y SEM revelaron una mejora de la calidad cristalina de las películas de CIS después de los tratamientos térmicos. Las propiedades ópticas de las películas delgadas recocidas CuInSe2-Se y CuInSe2-S se han estudiado para determinar el efecto del proceso de recocido en diferentes ambientes de selenio y azufre. Además, modificamos el CuInxCryGa1-x-ySe2 de cobre indio, donde x = 0.4, y = (0.0, 0.1, 0.2, 0.3) la capa de superestrato por el proceso de recubrimiento por centrifugado. CuInxCryGa1-xySe2 donde x = 0.4, y = (0.0, 0.1, 0.2, 0.3) nanopartículas han sido sintetizadas en primer lugar usando un método hidrotermal químico húmedo que se basa en un proceso térmico sin vacío sin ningún proceso de selenización adicional. Introduciendo diferentes fuentes de metal en un autoclave con etilenamina como solvente, se obtuvieron nanopartículas de CIGS a diferentes temperaturas en un rango de 190-230 °C. Los resultados de la difracción de rayos X (XRD) confirmaron la formación de una estructura de calcopirita CuInxCryGa1-x-ySe2 tetragonal. Finalmente, se estudió el efecto de la temperatura de recocido en los materiales tipo Kesterita (como el Cu2ZnSnS4) que son materiales de muy bajo costo y que no dañan el medio ambiente. Estudiamos el crecimiento de las películas delgadas cuaternarias Cu2ZnSnS4 (CZTS) de kesterita mediante un depósito electroquímico de un solo paso seguido de un recocido a baja temperatura. La influencia de diferentes atmósferas de recocido a tiempos de recocido constantes (t = 45 min) y parámetros de control de preparación fijos; es decir, concentración de la solución de materiales de partida (sales de metales precursores), tiempo de deposición y potencial de electrodeposición. Se estudiaron las propiedades estructurales, de composición, morfológicas y ópticas, así como las propiedades fotoelectroquímicas. / Abstract Increasing global energy consumption together with environmental concerns has led to much interest in alternative, cleaner sources of energy such as solar photovoltaic. Researchers in the solar cell community have been looking for ways to reduce costs while maintaining or increasing already high efficiencies. A fundamental understanding of the materials under consideration is essential to rapid development of new technologies. The I-III-VI2 thin films offer promising systems for achieving high efficiency solar cells at lower costs. In fact, by tailoring the chemistry of the compounds it is possible to change the bandgap of the material in order to collect sunlight more efficiently. First of all, this thesis focuses on absorber layer material preparation and characterization, especially nanocrystalline thin films and consideration of both structural and electrical characteristics of such main cell absorber layer.The thesis examines how different preparation techniques and material usage could affect the properties of the synthesized thin films (absorber layer). In this study CuInSe2 and CuInS2 thin films were deposited onto ITO glass substrate using the electrodeposition technique in aqueous solution. The electrodeposited films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDS). The annealing effects on the electrodeposited precursors were investigated. The chalcopyrite structure of CuInSe2/CuInS2 showed an enhancement of crystallinity after subsequent selenization/sulfurization treatment in Se/S atmosphere, respectively. XRD and SEM studies revealed a dramatic improvement of the crystalline quality of CIS films after annealing treatments. The optical properties of annealed CuInSe2-Se and CuInSe2-S thin films have been studied in order to determine the effect of annealing process in different selenium and sulfur atmosphere. In the second step we modified copper indium CuInxCryGa1-x-ySe2 where x=0.4, y= (0.0, 0.1, 0.2, 0.3)superstrate layer by spin coating process. CuInxCryGa1-x-ySe2 where x=0.4, y= (0.0, 0.1, 0.2, 0.3) nanoparticles have been synthesized firstly using a wet chemical hydrothermal method that is based on a non-vacuum thermal process without any additional selenization process. Introducing different metal sources in an autoclave with ethylenediamine as solvent, CIGS nanoparticles were obtained at different temperatures range 190-230°C. The X-ray diffraction (XRD) results confirmed the formation of a tetragonal CuInxCryGa1-x-ySe2 chalcopyrite structure. Finally, we turned again to the study of the annealing temperature effect onKesterite materials but this time in those of very low-cost materials and environmentally friendly Cu2ZnSnS4. We studied the growth of quaternary Cu2ZnSnS4 (CZTS) kesterite thin films by a single step electrochemical deposition followed by annealing at low temperature. The influence of different annealing atmospheres at constant annealing times (t = 45 min) and fixed preparation controlling parameters; i.e., starting materials (precursor metal salts) solution concentration, time of deposition and electrodeposition potential. Structural, compositional, morphological, and optical properties, as well as photoelectrochemical properties were studied. / Resum (Valencià) L'augment del consum d'energia global juntament amb les preocupacions ambientals ha generat molt d'interès per les fonts d'energia alternatives i netes, com ara l'energia solar fotovoltaica. Els investigadors de la comunitat fotovoltaica han estat buscant formes de reduir costos mentre mantenen o augmenten les eficiències. Una millor comprensió dels materials implicats és essencial per al ràpid desenvolupament de noves tecnologies. Les pel·lícules primes I-III-VI2 ofereixen sistemes prometedors per aconseguir cèl·lules solars d'alta eficiència a un cost menor. De fet, en adaptar la composició dels compostos, és possible canviar la banda prohibida del material per captar la llum solar de manera més eficient. Aquesta tesi se centra en la preparació i caracterització del material de la capa absorbent, especialment les pel·lícules primes nanocristal·lines i la consideració de les característiques estructurals i elèctriques d'aquesta capa principal absorbent de cèl·lules. La tesi examina com les diferents tècniques de preparació i ús del material podrien afectar les propietats del pel·lícules primes sintetitzades. Pel·lícules primes CuInSe2 i CuInS2 es van dipositar sobre substrats de vidre ITO usant la tècnica d'electrodeposició en solució aquosa. Les pel·lícules electrodepositadas es van caracteritzar per difracció de raigs X (XRD), microscòpia electrònica de rastreig (SEM) i anàlisi de raigs X d'energia dispersiva (EDS). Es van investigar els efectes de recuit sobre els precursors electrodepositados. L'estructura de calcopirita de CuInSe2/CuInS2 va mostrar una millora de la cristal·linitat després del tractament posterior de selenització/sulfurització en atmosfera de Se o S, respectivament. Els estudis de XRD i SEM van revelar una millora de la qualitat cristal·lina de les pel·lícules de CIS després dels tractaments tèrmics. Les propietats òptiques de les pel·lícules primes recuites CuInSe2-Es i CuInSe2-S s'han estudiat per determinar l'efecte del procés de recuit en diferents ambients de seleni i sofre. A més, modifiquem el CuInxCryGa1-x-ySe2 de coure indi, on x = 0.4, i = (0.0, 0.1, 0.2, 0.3) la capa d'superstrat pel procés de recobriment per centrifugat. CuInxCryGa1-x-ySe2 on x = 0.4, i = (0.0, 0.1, 0.2, 0.3) nanopartícules han estat sintetitzades en primer lloc fent servir un mètode hidrotermal químic humit que es basa en un procés tèrmic sense buit sense cap procés de selenización addicional. Introduint diferents fonts de metall en un autoclau amb etilenamina com solvent, es van obtenir nanopartícules de CIGS a diferents temperatures en un rang de 190- 230 °C. Els resultats de la difracció de raigs X (XRD) van confirmar la formació d'una estructura de calcopirita CuInxCryGa1-x-ySe2 tetragonal. Finalment, es va estudiar l'efecte de la temperatura de recuit en els materials tipus kesterita (com el Cu2ZnSnS4) que són materials de molt baix cost i que no danyen el medi ambient. Vam estudiar el creixement de les pel·lícules primes quaternàries Cu2ZnSnS4 (CZTS) de kesterita mitjançant un dipòsit electroquímic d'un sol pas seguit d'un recuit a baixa temperatura. La influència de diferents atmosferes de recuit a temps de recuit constants (t = 45 min) i paràmetres de control de preparació fixos; és a dir, concentració de la solució de materials de partida (sals de metalls precursors), temps de deposició i potencial d'electrodeposició. Es van estudiar les propietats estructurals, de composició, morfològiques i òptiques, així com les propietats fotoelectroquímiques / Kamal Abdelhamied Saber, S. (2018). Synthesis and characterization of some nano-selenides and their applications in solar cells [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/107389 / TESIS

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.