Ultra high temperature ceramics (UHTC) are candidate materials for high temperature applications such as leading edges for hypersonic flight vehicles, thermal protection systems for spacecraft, and rocket nozzle throat inserts due to their extremely high melting points. Tantalum and Niobium Carbide (TaC and NbC), with melting points of 3950°C and 3600°C, respectively, have high resistivity to chemical attack, making them ideal candidates for the harsh environments UHTCs are to be used in. The major setbacks to the implementation of UHTC materials for these applications are the difficulty in consolidating to full density as well as their low fracture toughness. In this study, small amounts of sintering additive were used to enhance the densification and Graphene Nanoplatelets (GNP) were dispersed in the ceramic composites to enhance the fracture toughness. While the mechanisms of toughening of GNP addition to ceramics have been previously documented, this study focused on the anisotropy of the mechanisms. Spark plasma sintering was used to consolidate both bulk GNP pellets and near full relative density TaC-NbC ceramic composites with the addition of both sintering aid and GNP and resulted in an aligned GNP orientation perpendicular to the SPS pressing axis that allowed the anisotropy to be studied. In situ high load indentation was performed that allowed real time viewing of the deformation mechanisms for enhanced analysis. The total energy dissipation when indenting the bulk GNP pellet in the in-plane GNP direction was found to be 270% greater than in the out-of-plane orientation due to the resulting deformation mechanisms that occurred. In GNP reinforced TaC-NbC composites, the projected residual damaged area as a result of indentation was 89% greater when indenting on the surface of the sintered compact (out-of-plane GNP orientation) than when indenting in the orthogonal direction (in-plane GNP orientation) which is further evidence to the anisotropy of the GNP reinforcement.

Les batteries au lithium tout solide présentent un grand intérêt pour le développement de systèmes de stockage de grande densité (volumique) d'énergie et sûrs notamment en raison de leur excellente stabilité thermique par rapport aux technologies lithium-ions à électrolyte liquide. Cependant, avec l'épaisseur de la batterie, de fortes limitations cinétiques sont observées, en raison i/ de la relativement faible mobilité des ions dans les matériaux inorganiques et ii/ de la présence de joints de grains généralement bloquants aux interfaces solide/solide. De plus au cours de la charge/décharge de la batterie, les matériaux actifs (réservoir de l'énergie) changent de volume ce qui induit des contraintes mécaniques interfaciales qui provoquent la formation de micro-fractures très dommageables à la cyclabilité de ces systèmes. Cette thèse concerne la réalisation et la caractérisation de batteries inorganiques monolithiques (avec les électrodes composites) en utilisant une méthode de frittage: Spark Plasma Sintering (SPS). La formulation des électrodes composites est fondamentale car ce sont de multi-matériaux qui doivent présenter de nombreuses fonctionnalités: 1) une grande densité d'énergie 2) une bonne percolation électronique (resp. ionique) enfin 3) une bonne tenue mécanique avec des interfaces électrodes/electrolyte stables afin d'assurer la durée de vie des cellules.Le principal objectif est de trouver des relations, pour des matériaux donnés, entre la texture des poudres initiales, la microstructure des céramiques obtenues par frittage SPS et les propriétés électriques (électronique et ionique) ainsi que les performances électrochimiques. / All-solid batteries with inorganic solid electrolytes are attractive candidates in electrochemical energy storage since they offer high safety, reliability and energy density. Aiming to increase the surface capacity strong efforts have been made to increase the thickness of the electrode. However, the thicker electrode, the more stress is generated at the solid/solid interfaces because of the volume change of the active material during lithium insertion/desinsertion upon cycling, which leads to formation of micro-cracks between the components and finally a bad cycling life. The possible answer to this issue is to build in place of a dense phase pure electrode, a composite electrode which is a multifunctional material. This composite electrode should contain a lot of electrochemically active material, the reservoir of energy; together with electronic and ionic conductor additives, to ensure efficient and homogeneous transfer of electrons and ions in the electrode volume.The main scope of this thesis was to develop all-solid-state batteries prepared by SPS method for applications at elevated temperatures. These batteries consist of a two composite electrodes separated by the NASICON-type solid electrolyte Li1.5Al0.5Ge1.5(PO4)3. The main objective was to find relationships, for given materials, between the initial powder granulometry (grain size, size distribution, agglomeration), the microstructure of ceramics obtained by SPS sintering, and the electrochemical performances of the final batteries. By creating electrodes with novel materials and better composition, the trade-off of power density and energy density can be minimized.

Cette thèse a consisté en la fabrication d’électrodes de charbon actif frittées par SPS destinées aux supercondensateurs à double couche électrochimique. L’influence des paramètres de frittage (température, pression, durée du palier isotherme et vitesses de chauffe et de refroidissement) sur les propriétés structurales et microstructurales des pastilles de charbon actif a été évaluée par diffraction des rayons X, microscopie électronique à balayage et en transmission, spectrométrie de photoélectrons X, mesures de surface spécifique et de volume microporeux et détermination des propriétés mécaniques. Les performances électrochimiques des pastilles de charbon actif frittées sélectionnées pour leurs bonnes propriétés de volume microporeux, de résistance mécanique à l’électrolyte et de masse volumique élevée ont été déterminées par mesures galvanostatiques et de spectrométrie d’impédance. Un gain en capacité volumique de 31% a été obtenu pour un supercondensateur composé d’électrodes de charbon actif pur de 200 μm d’épaisseur frittées à 1100°C – 50 MPa par rapport à un supercondensateur composé d’électrodes de production de Blue Solutions. Cependant sa résistance série est deux fois supérieure à celle d’un supercondensateur de production de volume identique. Des résultats prometteurs de frittage multi-pastilles, possédant des propriétés microstructurales proches, indiquent une voie possible d’industrialisation du procédé SPS pour la fabrication d’électrodes frittées de charbon actif destinées aux supercondensateurs. / This thesis has consisted in the manufacturing of activated carbon electrodes sintered by SPS for Electric Double-Layer Capacitors (EDLCs). The influence of sintering parameters (temperature, pressure, isothermal dwell duration, heating and cooling rates) on structural and microstructural properties of sintered activated carbon pellets has been evaluated by X-ray diffraction, scanning and transmission electron microscopy, X-ray photoelectron spectrometry, specific area and microporous volume measurements and determination of mechanical properties. The electrochemical performances of sintered activated carbon pellets selected for their good properties in terms of microporous volume, mechanical resistance in the electrolyte and high density were determined by galvanostatic and impedance spectrometry measurements. A 31% increase of the volumetric capacity was obtained for a supercapacitor composed of 200 μm thick electrodes of pure activated carbon sintered at 1100°C – 50 MPa, relative to a supercapacitor composed of industrial electrodes from Blue Solutions company. However, its serial resistance is twice larger than that of an industrial of identical volume. Promising results of multi-pellet sintering, possessing close microstructural properties, indicate a possible way of industrialization of SPS process for the manufacturing of sintered activated carbon electrodes for supercapacitors.

Master‘s thesis deals with the preparation and evaluation single-phase high-entropy alloy based on cobalt, chromium, iron, nickel and manganese and its variants strengthened by dispersion of oxidic particles. High-entropy alloy was prepared in powder form by mechanical alloying from the equiatomic proportions of atomic powders. Obtained powder was subsequently compacted by spark plasma sintering. By the method of mechanical alloying were successfully prepared single-phase high-entropy alloy and its variant strengthened by dispersion of nanometric yttria oxides. It has been found that the oxide particles present in the microstructure of high-entropy alloy significantly block mobility of grain boundary and dislocation at elevated temperatures. As a result of this behavior were observed doubling of alloy strength and decreasing of creep rate at 800 °C.

The subject of this thesis is preparation of CoCrFeMnNiNx high entropy mixtures via the methods of mechanical alloying and spark plasma sintering (SPS). Three series of specimens were fabricated in this thesis: samples milled in argon (benchmark materials), samples milled in nitrogen atmosphere (to observe their ability of nitrogen absorption) and samples microalloyed with CrN, FeN nitrides (to observe their dissociation into the solid solution potential). The fabricated powders and SPS compacts were subsequently observed by electron microscopy and their phase content by X-Ray diffraction (XRD) and elemental composition by EDS analysis were carried out. A method of reduction melting in inert atmosphere was used to determine the exact oxygen and nitrogen content in powders, while the respective particle size distribution measured by laser diffraction method. The influence of nitrogen content on the hardness of the samples was studied via the microhardness measured. After completing the process of mechanical alloying under the Nitrogen atmosphere was the maximal concentration of nitrogen in the structure 0,208% after 24 hours of milling (dependency on time was linear), which means, the method of milling under the Nitrogen atmosphere was successful. XRD of milled samples showed the existence of the only FCC single solid solution phase, while samples milled under the Nitrogen atmosphere showed the trend of the growth of the lattice parameter with the increasing nitrogen content. There was observed the presence of the chromium nitrides precipitates on the grain boundaries of the FCC phase in microalloyed samples. All specimen were contaminated by a mixture of metallic oxides and manganeese sulphides, which were present in the default manganeese powder. The greatest value of microhardness showed the duplex sample. The increase in values of microhardness (344 HV 0,3) in comparison with the standard sample (262,9 HV 0,3) was recorded on the samples milled under the nitrogen atmosphere, which conforms the positive influence of the nitrogen content on strength characteristics of this alloy.

This thesis gives a comprehensive characterization of lightweight non-oxide ceramic materials for ballistic applications, an overview of production technologies and processing of boron carbide B4C and its ceramic-based composites. A framework for evaluating the ballistic resistance of the material based on mechanical properties is shown there. It can be used in experiments without normalized equipment. The experiments including B4C + Si, B4C + Ti composites, and application of Spark plasma sintering (SPS) were designed according to outputs from the theoretical part. The volume fractions of Si, Ti dopants were optimized based on ongoing chemical reactions during sintering. The obtained samples were subjects of mechanical testing which results were compared to identify the ideal ratio of matrix and reinforcement. As the best suited material for ballistic protection, B4C + 1,0 obj. % reaches these values of parameters; hardness = 3502 ± 122 HV1; fracture toughness KIC = 2,97 ± 0,03 MPam^0,5.

This diploma thesis deals with the processing of the magnesium-based powder materials with the addition of zinc by the spark plasma sintering. The aim of this thesis is to evaluate influence of sintering parameters and zinc content on the microstructure and mechanical properties of the material. First part of the thesis is literary research which is divided into two main chapters. The first chapter describes magnesium-based materials and mentions their use as biomaterials. The second chapter discusses powder metallurgy, specifically magnesium powders and spark plasma sintering. In the experimental part the powders were sintered at temperatures 300 °C and 400 °C and an analysis was performed using optical microscope, scanning electron microscope, then also EDS analysis and hardness, microhardness and three-point bending tests were performed. An increase in hardness was observed with increasing zinc content and with increasing sintering temperature. The flexural strength was higher for materials sintered at a temperature of 400 ° C.

Title: Materials for fusion applications and their interaction with tokamak plasma Author: Veronika Klevarová Department: Department of Physics of Materials Supervisor: doc. RNDr. Miloš Janeček, CSc., Department of Physics of Materials Abstract: Tungsten represents a perspective option in the context of fusion devices first-wall materials. In the first part of this work, set of tungsten samples with variable grain size was prepared by spark plasma sintering. Specimens were exposed to steady state deuterium plasma beam and high energy heat pulses, simulating thus the normal operation in the tokamak. As a consequence of the exposure, samples surfaces were roughened, as-prepared grains were recovered and in some cases cracks were formed. Moreover, post-irradiation analysis of the damaged samples revealed activation of in-grain slip systems within the loaded surfaces. Threshold grain diameter for this mechanism was determined to be between 5.5 - 6.6 μm at the particular loading conditions. However, damaged features showed to depend more on the fabrication parameters than on the grain diameter. Synergistic effects of simultaneous loading were proven to be important since those reduced the heat propagation within the volume of the tested samples. In the second part of this thesis, introduction to plasma-surface...

Bulk commercially pure titanium was prepared by powder metallurgy, namely by cryogenic milling and spark plasma sintering, with aim to produce ultra-fine grained material with enhanced strength. The microstructure of milled powders was investigated in detail by a novel method called transmission EBSD, which allowed the first direct observation of texture within the powder particles. This texture is similar to rolling texture, because of the similar nature of the defor- mation during milling. Microstructure observations revealed grains with the size under 100 nm. The influence of sintering parameters on material properties were studied by scan- ning electron microscopy including EBSD, X-ray diffraction and by microhardness measurements. The trade-off relationship between porosity and grain size was identified, fully dense material with ultra-fine grained microstructure could not be produced. Increased oxygen content was identified as a main strengthening factor, while porosity has significant deteriorating effect on mechanical properties. The texture of powder was retained in the bulk material. The possibility of stabilizing the microstructure by mechanical alloying of Ti with yttrium oxide nanoparticles was investigated with mixed results. The stabiliza- tion was successful, but several issues...

Ionic conductivity of metal oxides is critical for the function of a broad range of different components, such as electrolytes in solid oxide fuel cells and alloys designed for high temperature applications. In both cases the ionic conductivity can be studied by in situ impedance spectroscopy, which is also able to reveal information on the dielectric properties of the metal oxides, and in some cases the influence of their microstructure. The focus of this thesis is on impedance spectroscopy measurements of α-alumina in the temperature range 400-1000 °C. This metal oxide has found extensive use as the protective scale on heat resistant alloys. Some unpublished work on oxygen ion conductivity of yttria-stabilized zirconia is also included. The low electrical conductivity of α-alumina can be a source for errors and misinterpretations during impedance spectroscopy measurements. A major disturbance originates from leakage currents that appear in the experimental setup. These leakage currents are due to conduction through the gas phase around the sample, conduction on the sample surface, or poor insulation in the sample holder. It was shown that below 700 °C, conduction on the sample surface could severely distort the measurement. The magnitude of the distortions appeared to be sensitive to the type of electrodes used. The use of a so-called guard electrode was shown to effectively block the surface conduction in the measurements. Conductivity of metal oxides is known to be dependent on their microstructure. Generally it is believed that ionic conductivity is favoured along grain boundaries and dislocations. The influence of microstructure on conductivity was studied for α-alumina in the temperature range 400-1000 °C. The conductivity of a series of highly pure and dense samples with narrow grain size distributions was measured by impedance spectroscopy. It appeared that the activation energy for conduction increased with decreasing grain size. Results based purely on impendence spectroscopy have some inherently weaknesses. For instance no information on the nature of the charge carrier can be found. Therefore the charge transport in single crystalline α-alumina was simulated by the molecular dynamics method. The results from the simulation were then compared to results from impedance measurements on single crystalline α-alumina. From the simulation it turned out that diffusion of aluminium ions had lower activation energy than diffusion of oxygen. The activation energy of oxygen was close to the measured activation energy, and the mobility of oxygen was higher than for aluminium. Therefore the dominating charge carrier was suggested to be oxygen ions.