<p>Nano-powders of BaTiO₃, SrTiO₃, Ba_0.6Sr_0.4TiO₃, a mixture of the composition (BaTiO₃)_0.6(SrTiO₃)_0.4 with particle sizes in the range of 60 to 80 nm, and Bi₄Ti₃O₁₂ with an average particle size of 100 nm were consolidated by spark plasma sintering (SPS). The kinetics of reaction, densification and grain growth were studied. An experimental procedure is outlined that allows the determination of a “kinetic window” within which dense nano-sized compacts can be prepared. It is shown that the sintering behaviour of the five powders varies somewhat, but is generally speaking fairly similar. However, the types of grain growth behaviour of these powders are quite different, exemplified by the observation that the kinetic window for the (BaTiO₃)_0.6(SrTiO₃)_0.4 mixture is 125 ^oC, ~75 ^oC for Bi₄Ti₃O₁₂, ~25^oC for BaTiO₃ and SrTiO₃, while it is hard to observe an apparent kinetic window for obtaining nano-sized compacts of Ba_0.6Sr_0.4TiO₃. During the densification of the (BaTiO₃)_0.6(SrTiO₃)_0.4 mixture the reaction 0.6BaTiO₃+0.4SrTiO₃ → Ba_0.6Sr_0.4TiO₃ takes place, and this reaction is suggested to have a self-pinning effect on the grain growth, which in turn explains why this powder has a large kinetic window. Notably, SPS offers a unique opportunity to more preciously investigate and monitor the sintering kinetics of nano-powders, and it allows preparation of ceramics with tailored microstructures.</p><p>The dielectric properties of selected samples of (Ba, Sr)TiO₃ ceramics have been studied. The results are correlated with the microstructural features of these samples, <i>e.g.</i> to the grain sizes present in the compacts. The ceramic with nano-sized microstructure exhibits a diffuse transition in permittivity and reduced dielectric losses in the vicinity of the Curie temperature, whereas the more coarse-grained compacts exhibit normal dielectric properties in the ferroelectric region.</p><p>The morphology evolution, with increasing sintering temperature, of bismuth layer-structured ferroelectric ceramics such as Bi₄Ti₃O₁₂ (BIT) and CaBi₂Nb₂O₉ (CBNO) was investigated. The subsequent isothermal sintering experiments revealed that the nano-sized particles of the BIT precursor powder grew into elongated plate-like grains within a few minutes, via a dynamic ripening mechanism.</p><p>A new processing strategy for obtaining highly textured ceramics is described. It is based on a<i> directional dynamic ripening mechanism</i> <i>induced by superplastic deformation</i>. The new strategy makes it possible to produce a <i>textured</i> microstructure within minutes, and it allows production of textured ferroelectric ceramics with tailored morphology and improved physical properties.</p><p>The ferroelectric, dielectric, and piezoelectric properties of the textured bismuth layer-structured ferroelectric ceramics have been studied, and it was revealed that all textured samples exhibited anisotropic properties and improved performance. The highly textured Bi₄Ti₃O₁₂ ceramic exhibited ferroelectric properties equal to or better than those of corresponding single crystals, and much better than those previously reported for grain-orientated Bi₄Ti₃O₁₂ ceramics. Textured CaBi₂Nb₂O₉ ceramics exhibited a very high Curie temperature, <i>d</i><i>33</i>-values nearly three times larger than those of conventionally sintered materials, and a high thermal depoling temperature indicating that it is a very promising material for high-temperature piezoelectric applications.</p>

Spark Plasma Sintering (SPS) is a promising rapid consolidation technique that allows a better understanding and manipulating of sintering kinetics and therefore makes it possible to obtain Si3N4-based ceramics with tailored microstructures, consisting of grains with either equiaxed or elongated morphology. The presence of an extra liquid phase is necessary for forming tough interlocking microstructures in Yb/Y-stabilised α-sialon by HP. The liquid is introduced by a new method, namely by increasing the O/N ratio in the general formula RExSi12-(3x+n)Al3x+nOnN16-n while keeping the cation ratios of RE, Si and Al constant. Monophasic α-sialon ceramics with tailored microstructures, consisting of either fine equiaxed or elongated grains, have been obtained by using SPS, whether or not such an extra liquid phase is involved. The three processes, namely densification, phase transformation and grain growth, which usually occur simultaneously during conventional HP consolidation of Si3N4-based ceramics, have been precisely followed and separately investigated in the SPS process. The enhanced densification is attributed to the non-equilibrium nature of the liquid phase formed during heating. The dominating mechanism during densification is the enhanced grain boundary sliding accompanied by diffusion- and/or reaction-controlled processes. The rapid grain growth is ascribed to a dynamic ripening mechanism based on the formation of a liquid phase that is grossly out of equilibrium, which in turn generates an extra chemical driving force for mass transfer. Monophasic α-sialon ceramics with interlocking microstructures exhibit improved damage tolerance. Y/Yb- stabilised monophasic α-sialon ceramics containing approximately 3 vol% liquid with refined interlocking microstructures have excellent thermal-shock resistance, comparable to the best β-sialon ceramics with 20 vol% additional liquid phase prepared by HP. The obtained sialon ceramics with fine-grained microstructure show formidably improved superplasticity in the presence of an electric field. The compressive strain rate reaches the order of 10-2 s-1 at temperatures above 1500oC, that is, two orders of magnitude higher than that has been realised so far by any other conventional approaches. The high deformation rate recorded in this work opens up possibilities for making ceramic components with complex shapes through super-plastic forming.

Nano-powders of BaTiO3, SrTiO3, Ba0.6Sr0.4TiO3, a mixture of the composition (BaTiO3)0.6(SrTiO3)0.4 with particle sizes in the range of 60 to 80 nm, and Bi4Ti3O12 with an average particle size of 100 nm were consolidated by spark plasma sintering (SPS). The kinetics of reaction, densification and grain growth were studied. An experimental procedure is outlined that allows the determination of a “kinetic window” within which dense nano-sized compacts can be prepared. It is shown that the sintering behaviour of the five powders varies somewhat, but is generally speaking fairly similar. However, the types of grain growth behaviour of these powders are quite different, exemplified by the observation that the kinetic window for the (BaTiO3)0.6(SrTiO3)0.4 mixture is 125 oC, ~75 oC for Bi4Ti3O12, ~25oC for BaTiO3 and SrTiO3, while it is hard to observe an apparent kinetic window for obtaining nano-sized compacts of Ba0.6Sr0.4TiO3. During the densification of the (BaTiO3)0.6(SrTiO3)0.4 mixture the reaction 0.6BaTiO3+0.4SrTiO3 → Ba0.6Sr0.4TiO3 takes place, and this reaction is suggested to have a self-pinning effect on the grain growth, which in turn explains why this powder has a large kinetic window. Notably, SPS offers a unique opportunity to more preciously investigate and monitor the sintering kinetics of nano-powders, and it allows preparation of ceramics with tailored microstructures. The dielectric properties of selected samples of (Ba, Sr)TiO3 ceramics have been studied. The results are correlated with the microstructural features of these samples, e.g. to the grain sizes present in the compacts. The ceramic with nano-sized microstructure exhibits a diffuse transition in permittivity and reduced dielectric losses in the vicinity of the Curie temperature, whereas the more coarse-grained compacts exhibit normal dielectric properties in the ferroelectric region. The morphology evolution, with increasing sintering temperature, of bismuth layer-structured ferroelectric ceramics such as Bi4Ti3O12 (BIT) and CaBi2Nb2O9 (CBNO) was investigated. The subsequent isothermal sintering experiments revealed that the nano-sized particles of the BIT precursor powder grew into elongated plate-like grains within a few minutes, via a dynamic ripening mechanism. A new processing strategy for obtaining highly textured ceramics is described. It is based on a directional dynamic ripening mechanism induced by superplastic deformation. The new strategy makes it possible to produce a textured microstructure within minutes, and it allows production of textured ferroelectric ceramics with tailored morphology and improved physical properties. The ferroelectric, dielectric, and piezoelectric properties of the textured bismuth layer-structured ferroelectric ceramics have been studied, and it was revealed that all textured samples exhibited anisotropic properties and improved performance. The highly textured Bi4Ti3O12 ceramic exhibited ferroelectric properties equal to or better than those of corresponding single crystals, and much better than those previously reported for grain-orientated Bi4Ti3O12 ceramics. Textured CaBi2Nb2O9 ceramics exhibited a very high Curie temperature, d33-values nearly three times larger than those of conventionally sintered materials, and a high thermal depoling temperature indicating that it is a very promising material for high-temperature piezoelectric applications.

The unique features of the Spark plasma sintering (SPS) were used to investigate the sintering and deformation behaviour of titanium and titanium–titanium diboride composites, and to control the sintering and grain growth of ferroelectric Na0.5K0.5NbO3 (NKN) and of hydroxyapatite (HAp). In the SPS the samples experience a temperature different from that recorded by the thermocouple (pyrometer) used and this temperature difference has been estimated for Ti and NKN.   Sintering and deformation of titanium was investigated. Increasing heating rate and/or pressure shifted the sintering to lower temperatures, and the sintering and deformation rates changed when the α→β phase transition temperature was passed. Fully dense Ti/TiB2 composites were prepared. The Ti/TiB2 composites could be deformed at high temperatures, but the hardness decreased due to the formation of TiB.    The kinetic windows within which it is possible to obtain fully dense NKN and HAp ceramics and simultaneously avoid grain growth are defined. Materials have a threshold temperature above which rapid and abnormal grain growth takes place. The abnormal grain growth of NKN is due to a small shift in the stoichiometry, which in turn impairs the ferroelectric properties. Fully transparent HAp nanoceramics was prepared, and between 900 and 1050 oC elongated grains are formed, while above 1050 oC abnormal grain growth takes place.NKN samples containing grains of the sizes 0.35–0.6 µm yielded optimum ferroelectric properties, i.e. a high remanent polarization (Pr = 30 µC/cm2) and high piezoelectric constant (d33= 160 pC/N). The ferroelectric domain structure was studied, and all grains exhibited a multi-domain type of structure. / At the time of doctoral defense the following articles were unpublished and had a status as follows: Article 4: Manuscript; Article 5 : Manuscript

Currently, there is a high demand for lightweight aerospace materials, driven by the desire to provide enhanced fuel efficiency by reducing vehicular weight. Aluminum alloys are attractive due to their excellent mechanical properties and high strength to weight ratios. Powder metallurgy (PM), which converts metal powder into a high performance product, presents an alternative to traditional forming techniques, which are often unable to provide adequate dimensional tolerances. The challenge is to determine if aluminum PM alloys and technologies can be successfully employed within aerospace applications. This research focuses on the PM processing technologies (die compaction, cold isostatic pressing (CIP), and spark plasma sintering (SPS)) of two alloys, PM2024 and PM7075. Processing parameters were assessed using attributes such as density, hardness, and tensile properties. Both powders showed comparable densities and tensile properties to their wrought equivalents. Ultimately, the groundwork was laid for future research into these alloys and their processing methods.

Spark plasma sintering (SPS), also known as direct current sintering (DCS) is an advanced sintering technique that and uses a continuous pulsed direct current to rapidly process materials through Joule heating and offers significant advantages and versatility over conventional sintering methods. The technique features in energy saving owing to high heating rates and is very suitable for consolidation as well as diffusion bonding of electrical conductive advanced ceramic materials such as ultra high temperature ceramics (UHTCs). However, cooling rate in SPS also plays an important role as it directly influences the generation of residual stress especially for specimens consist of dissimilar phases such as composites and laminates primarily due to CTE mismatch. Therefore, in order to produce high quality materials, a zirconium diboride with addition of silicon carbide (ZrB2-SiC) ultra high temperature ceramic composite is selected to investigate the effect of cooling rate in SPS on microstructure and mechanical properties. After being densified at the target temperature, ZrB2-25vol%SiC specimens are cooled from 1800°C using controlled cooling rates of 10 °C/minute to ~225.5 °C/minute (free cooling). A time dependent finite element analysis (FEA) model is used to simulate the temperature gradients across the specimens at dwell times and during the cooling processes. The residual stress within the specimens are experimentally verified using X-ray diffraction (XRD) and Raman spectrometry, and found maximum residual stress within the specimen cooled at 225.5 °C/minute. Peak Hardness and moderate elastic modulus is found for specimen sintered at 1800 °C and cooled at 100 °C/minute, which make this temperature and cooling rate appropriate conditions for future fabrication of UHTCs with similar thermal and electrical properties. These materials are of great interest for their excellent high-temperature capabilities, wear and corrosion resistance, and are regarded as material candidates for engineering applications in extreme environments. Therefore, development of an effective joining technique is important since near-net shape fabrication is challenging, and joints formed by brazing or conventional solid-state diffusion bonding limit the mechanical strength and high temperature applications of the base materials. Using SPS we have rapidly and successfully joined ZrB2 to hafnium diboride (HfB2) at 1750 and 1800 °C within a minute through electric current assisted solid-state diffusion bonding. The electric current enables localized Joule heating as well as plastic deformation of the mating surface asperities, and enhances the elemental interdiffusion process at the HfB2/ZrB2 interfaces owing to electromigration, which leads to the formation of ZrxHf1-xB2 solid solution. A series of characterization and analytical techniques including scanning electron microscopy (SEM), wavelength dispersive spectroscopy (WDS), electron backscatter diffraction (EBSD), and scanning transmission electron microscopy (S/TEM) are employed to study the microstructure and chemical composition at of the HfB2/ZrB2 interfaces. Apart from enhanced diffusion as a result of electromigration, the applied electric current can also be use to promote plastic deformation in ZrB2, which does not go through gross plastic deformation due to its extremely high melting point and brittle nature even when elevated temperature and pressure are applied. Through “electroplastic effect” (an effect based on electromigration) the mobility and multiplication of the existing dislocations in ZrB2 is enhanced, and a “metal-like” primary recrystallization phenomenon in the ZrB2 is observed meaning the material has experienced a sufficient amount of plastic deformation and reached the critical dislocation density and configuration for nucleation of “strain-free” grains. The average grain size of the recrystallized grain is only ½ of its original value. These findings suggest great potentials in microstructural tailoring and grain refinement of conductive advanced ceramics using SPS, and provide promising ideas for future fabrications and applications.

Tantalum carbide (TaC) and hafnium carbide (HfC) possess extremely high melting points, around 3900 oC, which are the highest among the known materials. TaC and HfC exhibit superior oxidation resistance under oxygen deficient and rich environments, respectively. A versatile material can be expected by forming solid solutions of TaC and HfC. However, the synthesis of fully dense solid solution carbide is a challenge due to their intrinsic covalent bonding which makes sintering challenging. The aim of the present work is to synthesize full dense TaC-HfC solid solutions by spark plasma sintering with five compositions: pure HfC, HfC-20 vol.% TaC (T20H80), HfC- 50 vol.% TaC (T50H50), HfC- 80 vol.% TaC (T80H20), and pure TaC. To evaluate the oxidation behavior of the solid solutions carbides in an environment that simulates the various applications, an oxygen rich, plasma assisted flow experiment was developed. While exposed to the plasma flow, samples were exposed to a temperature of approximately 2800 oC with a gas flow speed greater than 300 m/s. Density measurements confirm near full density was achieved for all compositions, with the highest density measured in the HfC-contained samples, all consolidated without sintering aids. Confirmation of solid solution was completed using x-ray diffraction, which had an excellent match with the theoretical values computed using Vegard’s Law, which confirmed the formation of the solid solutions. The solid solution samples showed much improved oxidation resistance compared to the pure carbide samples, and the T50H50 samples exhibited the best oxidation resistance of all samples. The thickness of the oxide scales in T50H50 was reduced more than 90% compared to the pure TaC samples, and more than 85% compared to the pure HfC samples after 5 min oxidation tests. A new Ta2Hf6O17 phase was found to be responsible for the improved oxidation performance. Additionally, the structure of HfO2 scaffold filled with molten Ta2O5 was also beneficial to the oxidation resistance by limiting the availability of oxygen.

The quasicrystals are characterized by unusual rotational symmetries that are not observed in the crystalline materials, which is the cause of their interesting material properties. Because of that a particular attention was paid to quasicrystalline structures in the literature research. The research also contains a description of electron beam technology, spark plasma sintering method and introduction to the problematics of wear. As the default materials for the experimental part were selected Titanium Grade 2 powder and Cristome A5 powder which was partially composed of quasicrystalline phase. The first series of samples was sintered only from powder Cristome A5. The second series was sintered from the mixture of 80 % Titanium Grade 2 powder and 20 % Cristome A5 powder. For the compaction of samples spark plasma sintering technology was selected. Samples were then systematically modified by electron beam and subjected to pin on disc tests. Samples modified at 750 °C had the best wear resistance. Samples modified at 1150 °C contained increased amount of quasicrystalline phase.

The diploma thesis deals with the preparation of the composite material based on the NiSi system using powder metallurgy supplemented by the sintering with the usage of SPS method (spark plasma sintering). Theoretical part contains general information about the mechanical-chemical process and sintering, while materials and methods used for experimental observation are explained in a separate chapter. Experimental part explains the procedure of the experiment and selected parameters of individual processes. In the experiment, two powder mixtures were created in order to form the NiSi phase in the maximum possible amount of powder material. After successfully reaching presence of the NiSi phase in the range of 87 to 89 wt. %, both mixtures were used to produce sintered samples at temperatures from 700 to 900 °C. Experiments showed the best results for sample number 2, which was sintered at 900 °C for 4 minutes. Resulting porosity was 0.9 % and hardness reached a maximum value of 718 HV 1. However, all sintered samples show cracks at room temperature associated with increased brittleness of the material.

Ceramic materials are in general characterized by high hardness, high modulus of elasticity, excellent abrasion resistance, etc. These properties make ceramics among others useful in optically transparent applications. An ideal form of optically transparent ceramic material is monocrystalline. However, the monocrystalline fabrication is expensive and/or time consuming. From this point of view polycrystalline ceramics is preferred. But the polycrystalline transparent ceramics fabrication is fraught with complications such as porosity, inappropriate grain size and insufficient purity. These circumstances could be solved by using sintering additives. This master’s thesis compiles literature research summarizing modern technologies of advanced ceramics sintering and ceramic polycrystalline microstructure dependence on its optical properties. The experimental part of this thesis focuses on the fabrication parameters of polycrystalline advanced ceramics based on Al2O3MgO and evaluation of their optical properties. Polycrystalline magnesium-aluminate spinel with sintering additive contents 0; 0.3 and 0.6 weight % LiOH was fabricated by optimalisation of Spark Plasma Sintering cycle. Fully dense ceramic samples of polycrystalline magnesium-aluminate spinel with favourable optical properties in visible spectrum radiation were achieved. Real In-line Transmission RIT and Total Forward Transmittance TFT were analysed. RIT exceeded 84 % at wavelength of 633 nm and TFT exceeded 83 % at wavelength above 860 nm. The decisive factors in terms of the optical properties of ceramics sintered with sintering additives were the amount of time-spending at high temperatures and the purity of ceramic powders.