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As technologies grow towards more demanding and complex applications, energy and environmental sectors carry a relevant fraction of the ecological burden for the next generations to come. Renewable energies, efficient industrial processes and clever management of environmental resources must be taken into serious account to reduce as much as possible our footprint. In this scenario, material science aims at finding solution for the most disparate scientific issues, these including the synthesis of multifunctional and performing materials able to fill the gap with innovative and green technologies. Among others, ceramic materials have shown a growing flexibility towards green and functional applications also thanks to the Polymer-Derived Ceramic route (PDC). This pathway to ceramic materials has the advantage of controlling their composition at the molecular level via chemical reactions, thus permitting to obtain complex ceramic systems with particular functionalities after controlled pyrolysis of preceramic polymers. Besides, Polymer-Derived Ceramic routes can be implemented with many processing solutions, such as the outgrowing fields of 3D printing and ceramic matrix composites. Among these, porous and cellular ceramics can be synthesized via PDC routes as well, laying the foundations for new, cheap and functional sorbents and scaffolds. In such a scenario, ceramic aerogels are ultraporous materials possessing high surface areas, low density and pore size distributions that easily reach few nanometers while maintaining rather high porosities, generally above 90%. Hence, when compared with other porous ceramics, aerogels present outperforming microstructural features that make them intriguing for applications in the energy and environmental fields, and when the PDC route is combined with aerogels processing, the outcome is something new. This thesis deals exactly with these two concepts, in the framework of innovative energy storage and environmental pollution mitigation. As a matter of fact, this work offers novel synthesis pathways for PDC ceramic aerogels belonging to the Si-C-N-O system, where their chemistry and microstructure have been tuned to serve for the abovementioned applications. Particular attention has been devoted to Si-N, Si-C-N, Si-C and Si-O-C aerogels, characterizing their thermal evolution when changing polymeric precursors and synthesis parameters. On this point, perhydropolysilazane (PHPS) and Durazane® 1800 were employed as precursors for silicon nitride and carbonitride aerogels, SPR-036 and polymethylhydrosiloxane (PHMS) as precursors for SiOC, and SMP-10 polycarbosilane as starting point for producing SiC aerogels. Our interest in making of these aerogels lies both on the urge of understanding the principles behind their synthesis steps, how each of them has an impact on the final aerogel chemistry, microstructure and thermal stability, and given this, how processing parameters can be exploited for novel applications of such peculiar materials. Overall, this thesis offers a paper collection of these novel aerogels featuring applications such as thermal and thermochemical energy storage, thermal insulation, electrochemistry and polluted water management, where we demonstrate the versatility and the potential of PDC routes towards the synthesis of ultraporous functional ceramics.

(a). The time required to dry a test specimen by the use of ultra-high frequency induced current until shrinkage ceases is only thirty percent of the time required when heat is supplied by resistance wire heating coils. (b). It is possible, with the use of the ultrahigh frequency energy, to dry complicated shapes evenly over their cross sections, which will enable much more rapid and safe drying of these shapes. (c). The structures of the pieces are not detrimentally affected by induced current, and the rapid drying of this method. (d). Drying with ultra-high frequency will probably prove to be of economical value in the drying of complicated shapes when additional research has further proved the effectiveness of the use of ultra-high frequency electrical energy. / Master of Science

Recently there has been an increased interest in the generation of ceranlic powders composed of nanosize particles with a narrow size-distribution and high purity. It has been shown that ceramics sintered from these ultrafine partic1es exhibit improved mechanical and electrical properties. The present research has attempted to control the growth of the ceramic particles in a relatively simple continuous flow process by placing charges on the forming particles and controlling their evolution with an electric field. Nanosize TiO₂ powder was produced using a multi-stream, co-annular reactor. The heat source was a cylindrical H₂/0₂ diffusion flame located around the outside of reaction zone. The effect on the powder size, shape, and size distribution due to particle charging, applied electric fields, and varying reactant concentrations were investigated. The temperature field within the reaction zone was uniform radially and ramped axially from 600 to 1100 K. The reactant stream passed through a 10 millicurie Po-21 0 alpha source within the burner with the intention of creating a bipolar ion concentration. In the presence of an electric field, this ionization can lead to either a unipolar-negative or unipolar-positive particle charging environment. The electric field across the reaction zone was varied in an attempt to control particle residence time. / Master of Science

Solid-state reaction and sol-gel, processing techniques were used extensively to form chemically-modified mullite solid solutions in an effort to lower their thermal expansion coefficients. TiO₂, B₂O₃, CrPO₄, P2O₅, Ga₂O₃, Cr2O₃, and WO₃ and the half-breed SiO₂ compounds AlPas, BPO₄, GaPO₄, BAsO₄, AIAsO₄, GaAsO₄, and GeO₂ were chosen as the modifiers. The results indicate that, apart from TiO₂, none of the substitutions made in mullite significantly change the thermal expansion properties. The solubility of 3 wt% TiO₂ in mullite reduces the coefficient of thermal expansion by about 10%; That corresponds to a reduction in AAl₂O₃/SiO₂ molar ratio ( < 1.5) compared to stoichiometric mullite (3Al₂O₃·2SiO₂). The formation of TiO₂-modified mullite depends on processing condition and heat treatment. The possible mechanism of lowering the CTE of mullite by the addition of TiO₂ is discussed in terms of the bond strength. The axial expansion of a Ga2O₃-modified mullite was measured' up to 1200°C to show that the expansion is increased along the c-axis compared with that of the stoichiometric mullite. / Master of Science

The major objectives of this study were to examine electrical conduction properties of BaTiO3-based multilayer ceramic ( MLC ) capacitors in order to gain a better understanding of the conduction transport mechanisms inside the devices. The experiments involved mainly leakage current versus time measurements under both low temperature-low voltage stress and high temperature-high voltage stress. It was established that leakage current conduction in a MLC capacitor under temperature-voltage stress can be divided into three different conduction regions due to different mechanisms. Those regions are polarization current, DC conduction current and degradation current. The polarization current decreases with time as a power law relation, i.e. Ic(t) t-m where the exponent value m is strongly dependent on the type of capacitor and temperature, but is only weakly dependent on the applied voltage. It has been proposed that two degradation models ( a charge carrier concentration model and a reduction of grain boundary barrier height model ) can explain the degradation behavior for the Z5U devices tested. Degradation measurements indicate that the lifetime for Z5U capacitors can be described by Minford's expression. However, these models account only partly for X7R degradation. X7R behavior, is characterized by an early power law time dependence, followed by exponential voltage dependence. The most probable conduction transport mechanism in X7R capacitors is small polaron hopping, while grain boundary transmission may be the predominant conduction transport mechanism in Z5U capacitors. / Master of Science

Cordierite was adhered to molybdenum using various metallic interlayers of copper, nickel, and chromium. The development of a coating adhesion test methodology was required to choose between interface designs. An indentation method was chosen because of ease in testing and availability of fracture mechanics interpretations of test data. The interfacial fracture toughness was determined from indentation load vs. crack length data by examining the residual stress and critical buckling load of the ceramic coatings. The interfacial fracture toughness values obtained using a slightly different indentation analysis agree with those in the literature. Quantitative chemical analysis of the interface microstructure was used to explain differences in interfacial fracture toughness values for samples with different metallic interlayer designs. The best interface design for adhering cordierite glass-ceramic coatings to molybdenum was found to be molybdenum / 2 μm copper / 4 μm chromium / cordierite. / Master of Science

Silicon oxycarbide (SiOC) is a ceramic obtained through the heating of a polymer precursor, which undergoes partial decomposition to go from an organic polymer to an inorganic ceramic. The microstructure of SiOC is not uniform at the nanometer scale, and contains nanometer sized silicon dioxide, carbon, and silicon carbide. Porous SiOC has shown great promise in applications such as lithium ion batteries, gas separation, and thermal barriers. The microstructure, and thus the properties of the SiOC, is influenced by the initial polymer and the processing conditions. In this thesis, SiOC is fabricated using a base polysiloxane polymer using different gases during heating, different additives that change the initial polymer chemical composition or polymer shape, and polymers with different reactive groups. Porosity was introduced into the SiOC ceramics through either etching the SiOC with hydrofluoric acid, which removes the silicon dioxide and produces pores with diameters less than 20 nanometers, or through decomposition during heating of a certain polymer in a two polymer mixture, producing pores that are dozens of microns in diameter. The effects of the processing parameters on the porosity and pore size are used to understand the differences in the microstructure during pyrolysis. / Master of Science / Silicon oxycarbide (SiOC) is a ceramic obtained through the heating of a polymer precursor, which undergoes partial decomposition to go from an organic polymer to an inorganic ceramic. The microstructure of SiOC is not uniform at the nanometer scale, and contains nanometer sized silicon dioxide, carbon, and silicon carbide. Porous SiOC has shown great promise in applications such as lithium ion batteries, gas separation, and thermal barriers. The microstructure, and thus the properties of the SiOC, is influenced by the initial polymer and the processing conditions. In this thesis, SiOC is fabricated using a base polysiloxane polymer using different gases during heating, different additives that change the initial polymer chemical composition or polymer shape, and polymers with different reactive groups. Porosity was introduced into the SiOC ceramics through either etching the SiOC with hydrofluoric acid, which removes the silicon dioxide and produces pores with diameters less than 20 nanometers, or through decomposition during heating of a certain polymer in a two polymer mixture, producing pores that are dozens of microns in diameter. The effects of the processing parameters on the porosity and pore size are used to understand the differences in the microstructure during pyrolysis.

The electrical characteristics, including degradation, of high K (≅ 500) barium titanate based thick film capacitors were studied. It was found that a gold conductor made from Au metallo-organic paste is not compatible with the porous high K dielectric material. The leakage current of a thick film capacitor made from Ag/Pd thick film conducting paste and high K dielectric has shown ohmic and space charge limited current behavior with a 3/2 power voltage dependence. Voltage independence of thermal activation energy and time dependence of a leakage current have been observed. A healing effect by reversal of bias polarity and humidity effect on leakage current have also been studied. The 3/2 power voltage dependence can be attributed to point emission from surface indentations or clusters of Ag particles at the electrode. Two possible degradation mechanisms based either on simple vacancy movement or a reduced grain boundary potential barrier height are suggested. It has been found that an electronic conduction model based on reduced grain boundary barrier height is more reasonable than that of simple vacancy induced current model. / M.S.

Structure-property studies were carried out on a number of different hybrid sol·gel materials. Multifunctional silicon ethoxides were prepared and studied by solid state ²⁹Si NMR and Raman spectroscopy to determine the type of silicate structures formed and the degree of conversion attained by the sol-gel process under previously established reaction conditions. New procedures were developed to incorporate titaniumisopropoxide as well as Al, Zr and Zn acetylacetonates into functlonalized polyltetramethylene oxide) modified sol-gel systems. The physical properties of titanium containing poIy(tetramethyIene oxide) modified sol-gel materials were studied in detail and correlated to morphological and structural information gained from dynamic mechanical analysis, small angle x-ray scattering and scanning electron microscopy. The incorporation of titanium was found to increase the measured Young’s modulus and stress at break relative to comparable materials based solely on TEOS. / Ph. D.