Hlavním cílem této diplomové práce byl popis závislosti kritické hustoty (tj. hustota, při které se tubulární póry zcela přemění na póry izolované a uzavřené) a průměrné velikosti zrn při této hustotě na rozdílných rychlostech ohřevu během druhého stádia slinovacího procesu. Dosažené výsledky jsou velice důležité, např. pro produkci transparentních balistických pancířů, vysoce výkonných řezných nástrojů či kostních a kloubních implantátů, jelikož poskytují informace pro výběr nejvhodnější slinovací metody, jejímž výsledkem jsou vzorky v předslinutém stavu s minimální velikostí zrn pro následnou metodu izostatického lisování za tepla (post –HIP). Bylo zjištěno, že kritická hustota všech studovaných oxidových materiálů (Al2O3, tetragonální ZrO2 a kubické ZrO2) není významně závislá na rychlosti ohřevu v rozmezí od 2°C/min do 200°C/min a průměrné hodnoty kritických hustot jsou 96.3 %; 92,4 % a 93,0 % pro Al2O3, t- ZrO2 a c-ZrO2. Výsledky z dosavadní literatury prokázali, že kritická hustota není taktéž závislá na mikrostruktuře keramického polotovaru, a tedy je možné usuzovat, že kritická hustota je materiálovou konstantou závislou na dihedrálním úhlu materiálu. Slinovací trajektorie (tj. závislost průměrné velikosti zrn na relativní hustotě) byly vyhodnoceny jak pro všechny tři způsoby slinování lišící se rychlostí ohřevu (2, 10 a 200 °C/min s dobou výdrže 5 min), tak pro takzvaný způsob slinování- long-dwell (nízké slinovací teploty s dobou výdrže 5 – 10 h). Výsledky nepotvrdily, že by některá z alternativních metod slinování vedla ke snížení průměrné velikosti zrn při kritické hustotě materiálu, a tudíž v současnosti nejvyužívanější metoda pro přípravu materiálů v předslinutém stavu, tzv. metoda konvenčního slinování (rychlost ohřevu 10 °C/min, doba výdrže 5 min), zůstává i nadále vhodnou metodou pro přípravu vzorků s optimální mikrostrukturou pro následný post-HIP proces.

Táto práca sa zaoberá prispôsobením (tailoring) mikroštruktúry vybraných pokročilých keramických materiálov (oxid hlinitý, kubický a tetragonálny oxid zirkoničitý) metódou izostatického lisovania za tepla (post-HIPing) s cieľom pripraviť vzorky s teoretickou hustotou and minimálnou veľkosťou zŕn. Vzhľadom na to, že izostatické lisovanie je vo väčšine prípadov používané ako dokončovacia metóda, pred-slinovanie (príprava vzoriek v štádiu uzavretej pórovitosti) bolo tiež dopodrobna študované. Extenzívny teoretický a experimentálny výskum pred-sintrovania pokročilých keramických materiálov ukázal niekoľko výsledkov. Bolo zistené, že uzatváranie pórov je materiálová charakteristika riadená medzi-povrchovými energiami (uzatváranie pórov nastáva pri 92-96 % t.d. pre skúmané materiály), je nezávislé na technológii prípravy keramického polotovaru a je nezávislé na histórii sintrovacieho procesu. Pre analýzu mikroštruktúry skenovacím elektrónovým mikroskopom a výrazné zvýšenie efektivity mikroštruktúrnej analýzy, bola vyvinutá nízkoteplotná metóda termálneho leptania. Táto metóda umožňuje zviditeľnenie leštenej mikroštruktúry pri leptacej teplote 900 °C a výdrži 1 hodina čiastočne sintrovaných a plne hutných vzoriek bez teplotnej kontaminácie (zvýšenie hustoty a veľkosti zŕn). Pred-sintrované vzorky boli post-HIPované nadizajnovaným kombináciami teploty (1200-1400 °C), aplikovaného tlaku (50 a 200 MPa) a času výdrže (0,5 až 9 hodín) s cieľom štúdia vplyvu týchto post-HIPovacích parametrov na mikroštruktúru vzoriek. Najdôležitejší výsledok experimentov je, že aplikovaný tlak vykazuje iba minimálny vplyv na rast zŕn v priebehu post-HIPovania, pričom výrazne posilňuje zhutňovanie. Sintrovacia teplota a čas výdrže tiež vykazovali zhutňovací potenciál, avšak s negatívnym efektom na veľkosť zŕn počas post-HIPovania rešpektujúc kinetickú rovnicu rastu zŕn – exponenciálny rast pre teplotu a parabolický rast pre čas. Tieto výsledky boli použité pre optimalizáciu post-HIPovacích cyklov pre študované materiály. Výsledné vzorky boli zhutnené nad 99,7 % t.d. a s minimálnym (pod 10 %) nárastom veľkosti zŕn v porovnaní s pred-sintrovanou veľkosťou zŕn. Aplikáciou získaných znalostí bola pripravená transparentná korundová keramika dopovaná erbiom s fotoluminiscenčnými vlastnosťami. Pripravená vzorka s tvrdosťou HV 10 26,9 GPa a so skutočnou inline priepustnosťou RIT 56 % vykazuje najlepšie hodnoty tvrdosti a priepustnosti v doposiaľ publikovaných korundových keramických materiáloch dopovaných prvkami vzácnych zemín.

Lisovanie za tepla (HIP) je pokročilá technológia pre výrobu plne hutných keramických materiálov, ktoré majú množstvo štruktúrnych (napr. rezné nástroje), biologických (napr. implantáty hutných kostí a kĺbov) alebo funkčných (napr. transparentné štíty a okná) aplikácií. Pre úspešné použitie tejto technológie je potrebné, aby predspekané vzorky boli plynotesné, teda bez otvorených pórov. Výskum zaoberajúci sa premenou otvorených pórov na uzatvorené je preto veľmi dôležitý, avšak iba málo publikovaný v odbornej literatúre. Preto bolo experimentálne a teoretické štúdium tohto javu hlavným cieľom diplomovej práce. Analýzy teoretických modelov ukazujú, že transformácia z otvorenej na uzatvorenú pórovitosť je materiálová charakteristika, ktoré sa mení iba s dihedrálnym uhlom, nezávisle na veľkosti častíc prášku alebo na spôsobe tvarovania a nastáva od 92.6% t.d. do 93.7% t.d pre daný materiál (oxid hlinitý, oxid zirkoničitý a horečnato-hlinitý spinel). Tieto teoretické výpočty boli porovnané s experimentálnymi dátami z literatúry a dátami z experimentálnej časti diplomovej práce s úspešnou zhodou pre kubické systémy (spinel a kubický oxid zirkoničitý). Výsledky experimentov s oxidom hlinitým boli v dobrej zhode s experimentálnymi dátami publikovanými v literatúre, ale boli vyššie ako teoretické hodnoty. Na objasnenie týchto odlišností bolo vytvorených niekoľko hypotéz a tiež boli navrhnuté spôsoby riešenia tejto témy.

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The diploma work is focused on the ceramic tool materials and its effective use. The introductory part of the work contains the detail characteristic of the ceramic tool materials from the point of view of their dividing, physic-mechanical propertis, production methods and marking. The main part of the work is focused to judging of the ceramic portion at the production assortment of the top World producers of tool materials and to evaluation of cutting ability of the particular materials of these producers. The detail analysis of recommended cutting conditions, which is aimed to an effective use of the ceramic materials, had been worked up for this purpose. The technical economic analysis confirms, that the present effective aplications of ceramic are limited only for specific cases of machining cast irons, steels and alloys.

Non-oxide porous ceramics exhibit many unique and superior properties, such as better high-temperature stability, improved chemical inertness/corrosive resistance, as well as wide band-gap semiconducting behavior, which lead to numerous potential applications in catalysis, high temperature electronic and photonic devices, and micro-electromechanical systems. Currently, most mesoporous non-oxide ceramics (e.g. SiC) are formed by two-step templating methods, which are hard to adjust the pore sizes, and require a harmful etching step or a high temperature treatment to remove the templates. In this dissertation, we report a novel technique for synthesizing hierarchically mesoporous non-oxide SiC ceramic from a block copolymer precursor. The copolymer precursors with vairing block length were synthesized by reversible addition fragmentation chain transfer polymerization. The block copolymers self-assemble into nano-scaled micelles with a core-shell structure in toluene. With different operation processes, hollow SiC nanospheres and bulk mesoporous SiC ceramics were synthesized after the subsequent pyrolysis of precorsur micelles. The resultant SiC ceramics have potential applications in catalysis, solar cells, separation, and purification processes.The polymer synthesis and pyrolysis process will investigated by NMR, FTIR, GPC, TEM, and TGA/DSC. The morphology and structure of synthesised SiC hollow spheres and mesoporous ceramics were analyzed by SEM, TGA/DSC and BET/BJH analysis. Besides forming core shell micelles in selective solvent Toluene, we found that PVSZ-b-PS could also exhibit this property in the air water interface. By inducing the Langmuir-Blodgett deposition, a precursor monolayer with homogeously distributed povinylsilazane particles deposited on silicon wafer synthesized by spreading the diblock copolymer PVSZ-b-PS in the air water interface. After the pyrolysis process, orderly arranging SiC nano particles formed from the polymer precursor monolayer doped on the surface of silicon wafer, which shows great potential as an optoelectronic material. The deposition process and the relationship between compress pressure and monolayer morphology were studies, and the structure of monolayer and SiC dots were investigated by AFM, SEM.

Novel ceramic membrane cells of BaCe₀.₅Zr₀.₃Y₀.₁₆Zn₀.₀₄O[subscript(3-δ)] (BCZYZ), a proton-conducting oxide, have been developed for electrocatalytic ammonia synthesis. Unlike the industrial Haber-Bosch process, in this work an attempt to synthesise ammonia at atmospheric pressure has been made. The membrane cell fabricated by tape casting and solution impregnation comprises of a 200 μm-thick BCZYZ electrolyte and impregnated electrode composites. Electrocatalysts for anode and cathode were investigated. For the anode, the co-impregnation of Ni and CeO₂ provided excellent electrode performance including high catalytic activity, sintering stability and compatibility with the BCZYZ electrolyte. The best composition was the mixture of 25 wt% NiO and 10 wt% CeO₂. A symmetrical cell prepared with this electrode composition revealed low polarisation resistances of 1.0 and 0.45 Ωcm² in humidified 5% H₂/Ar at 400 and 500 °C, respectively. For the cathode, 25 wt% of impregnated Fe oxide provided a satisfactory performance in non-humidified N₂ atmosphere. Significant amounts of ammonia were produced from the single cell with Ni-CeO₂ anode and Fe oxide cathode at 400-500 °C under atmospheric pressure. Ammonia formation rate was enhanced by Pd catalyst addition and electrochemical performance was improved by Ru addition. The highest ammonia formation rate of 4 x 10⁻⁹ mols⁻¹cm⁻² was attained using the cell with a Pd-modified Fe cathode at 450 °C. The formation reaction of ammonia typically consumed around 1-2.5 % of total applied current while most of the applied current was employed in H⁺ reduction. The total current efficiency of around 90-100 % could be obtained from the membrane cells.

Thesis dealing with cutting ceramics and its efficient use. Introduction describes the general characteristics of the cutting of ceramics, its history and development and production of various kinds. This section describes the mechanical and physical properties with potential application in machining. The se-cond part is an overview of cutting-frame in the range of selected world leaders. Ano-ther section focuses on general assessment of the power of cutting tools and other ma-terials comparison. The fourth part, is comparing the working conditions of producers and tools intended for cutting.

In recent years bismuth-based, layer-structured perovskites such as SrBi2Nb2O9 (SBN) and SrBi2Ta2O9 (SBT) have been investigated extensively, because of their potential use in ferroelectric random access memories (FeRAMs). In comparison with non-layered perovskite ferroelectrics such as Pb(Zr,Ti)O3 (PZT), these offer several advantages such as fatigue free, lead free, low operating voltages and most importantly their ferroelectric properties are independent of film thickness in the 90 to 500 nm range. For FeRAM device applications, large remnant polarization (Pr), low coercive field (Ec) accompanied by high Curie temperature (Tc) are required for better performance and reliable operation. Much effort has been made to improve the ferroelectric properties of SBN and SBT ceramics by doping on A or B sites. It was known in the literature that partial substitution of Sr2+ by Bi3+ ions in SBN and SBT would increase the Curie temperature and improve the dielectric properties. The focus of the investigations that were taken up was to improve the electrical, dielectric and ferroelectric characteristics of SrBi2Nb2O9 ceramics. It was reported that the ferroelectric and nonlinear optical properties of LiNbO3 and LiTaO3 could be improved when vanadium, the lightest element in group V of the periodic table is substituted for Nb or Ta along with Li and three oxygens. It is with this background the investigations have been taken up to see whether one can extend the same argument to the Aurivillius family of oxides. Therefore, the central theme of the present investigations aimed at substituting Nb5+ by a smaller cation V5+ in SBN and study its influence on the formation temperature, sinterability, structural and microstructural characteristics apart from its physical properties. Recently the optical properties of this material have been recognized to be important from the optical device point of view. Unfortunately single crystal growth of vanadium doped SBN was hampered because of the bismuth and vanadium loss (high volatility) observed in the process of growth. One of the routes that attracted our attention has been the glass-ceramic. It would be interesting to visualize the behavior of crystallites of nano/micrometer size embedded in a glass matrix as these crystals were known to give rise to exotic properties. One of the crucial steps in the process of fabrication of a glass nanocrystalcomposite system in which crystalline phases have symmetries that would eventually give rise to basic non - centrosymmetric properties such as piezoelectric, pyroelectric and Pockels effects, has been to choose a compatible matrix material associated with easy glass forming capability and the ability to evenly disperse dipolar defects within itself. Recent investigations into strontium borate SrB4O7 (SBO), lithium borate Li2B4O7 (LBO) glasses indicated that LBO by virtue of its favorable structure, thermal and optical properties would form a suitable host glass matrix for dispersing layer structured ferroelectric oxides belonging to the Aurivillius family of oxides. Since lithium borate has wide transmission window, it was worth making an attempt to fabricate optical composite of Li2B4O7 (LBO) and vanadium doped SrBi2Nb2O9 (SBVN) and to study its structural, dielectric, pyroelectric, ferroelectric and optical properties. Therefore the present thesis reports detailed investigations into the effect of vanadium doping on the structural and various physical properties of an n = 2 member of the Aurivillius family of oxides in the polycrystalline form and novel glass composites comprising nano/microcrystallites of this phase. Chapter 1 comprises a brief introduction to the dielectric, pyroelectric, ferroelectric and nonlinear optical properties of materials. In addition to the principles and phenomena, the material aspects of these important branches of physics are discussed. It also forms a preamble to the glasses, criteria for glass formation, glass – ceramics and subsequently ferroelectric and nonlinear optical effects that were observed in glasses and glass - ceramics. Chapter 2 describes the material fabrication techniques adopted to prepare polycrystalline and grain – oriented ceramics, glasses and glass nanocrystalcomposites. The details of various structural, dielectric, pyroelectric, ferroelectric and optical measurement techniques employed to characterize these materials are also included. Chapter 3 discloses the fabrication of strontium bismuth niobate ceramics and their characterization for dielectric and impedance properties. The dielectric properties of strontium bismuth niobate ceramics have been modeled based on Jonscher’s Universal formalism. The coefficients of the Jonscher’s expression, exponent n(T) undergoes a minimum and A(T) exhibits a peak at the Curie temperature, Tc (723K). A strong low frequency dielectric dispersion (LFDD) associated with an impedance relaxation has been found to exist in these ceramics in the temperature range 573 - 823K. The Z′′ of the AC complex impedance showed two distinct slopes in the frequency range 100Hz-1MHz suggesting the existence of two dispersion mechanisms. The exponents m and n were obtained from the curve fitting. The exponent n was found to exhibit a minimum at the Curie temperature, Tc (723K) whereas the m was temperature independent. Chapter 4 deals with the fabrication of vanadium doped SrBi2Nb2O9 ceramics and their characterization for microstructural, dielectric, pyroelectric and ferroelectric properties. The average grain size of the SrBi2Nb2O9 (SBN) ceramic containing V2O5 was found to increase with increase in V2O5 content. The dielectric constant (εr) as well as the dielectric loss (D) increased with increase in grain size (6µm-17µm). The pyroelectric coefficient was found to be positive at 300K and showed an increasing trend with increasing grain size. Interestingly, the SrBi2(Nb0.7V0.3)2O9-δ ceramics consisting of 17µm sized grains showed higher remnant polarization (Pr) and lower coercive field (Ec) than those with grains of 7µm. Chapter 5 deals with the dielectric properties which were studied in detail in the 100Hz to 1MHz frequency range at various temperatures (300 – 823 K) for undoped and vanadium (10 mol%) doped SrBi2Nb2O9 (SBVN10) ferroelectric ceramics. A strong low frequency dielectric dispersion was encountered in these ceramics in the 573 – 823 K temperature range. The dielectric constants measured in the wide frequency and temperature ranges for both the samples were found to fit well to the Jonscher’s dielectric dispersion relations. The dielectric behavior of SBN and SBVN10 ceramics was rationalized using the impedance and modulus data. The electrical conductivity studies of layered SrBi2(Nb1-xVx)2O9-δ ceramics with x lying in the range 0 to 0.3 (30 mol%) were centered in the 573 – 823K temperature range as the Curie temperature lies in this range. The concentration of mobile charge carriers (n), the diffusion constant (D0) and the mean free path (a) were calculated using Rice and Roth formalism. The conductivity parameters such as ion hopping rate (ωp) and the charge carrier concentration (K′) term have been calculated using Almond and West formalism. The afore mentioned microscopic parameters were found to be V2O5 content dependent in SrBi2(Nb1-xVx)2O9-δceramics. Chapter 6 describes the fabrication of partially grain – oriented SrBi2(Nb1-xVx)2O9-δ (0 ≤x≤3.0 in molar ratio) ceramics and characterization for their structural, microstructural, dielectric, pyroelectric and ferroelectric properties. The grain – orientation factor and the microstructural features were studied by XRD and scanning electron microscopy as a fuction of sintering temperature and V2O5 content. The dielectric constant measured along the direction parallel and perpendicular to the pressing axis has shown a significant anisotropy. The pyroelectric and ferroelectric properties were superior in the direction perpendicular to the pressing axis (polar) to that in the parallel direction. The fabrication and characterization details of (100 – x) (Li2B4O7) – x (SrO - Bi2O3 - 0.7 Nb2O5 – 0.3 V2O5) (10 ≤ x ≤ 60, in molar ratio) glasses and glass nanocrystal composites are dealt within Chapter 7. The nanocrystallization of strontium bismuth niobate doped with vanadium (SrBi2(Nb0.7V0.3)2O9-δ(SBVN)) has been demonstrated in Li2B4O7 glasses. The glassy nature of the as – quenched samples was established by differential thermal analyses (DTA). The amorphous nature of the as – quenched glasses and crystallinity of glass nanocrystal composites were confirmed by X – ray powder diffraction studies. High resolution transmission electron microscopy (HRTEM) of the glass nanocrystal composites (heat – treated at 783K/6h) confirm the presence of nano rods of SBVN embedded in Li2B4O7 glass matrix. Chapter 8 presents the physical properties of the glasses and glass nanocrystal composites. Dielectric constant of both the as – quenched and glass nanocrystal composites was found to increase with increase in the composition, whereas the loss was observed to decrease with increasing SBVN composition. Different dielectric mixture formulae were employed to analyze the dielectric properties of the glass nanocrystal composite. The electrical behaviour of the glasses and glass nanocrystal composites was rationalized using impedance spectroscopy. The observed pyroelectric response and ferroelectric hysteresis of these composites confirmed the polar nature. Various optical parameters such as optical band gap (Eopt), Urbach energy (∆E), refractive index (n), optical dielectric constant (ε′∞) and ratio of carrier concentration to the effective mass (N/m*) were determined. The effects of composition of the glasses and glass nanocrystal composites on these parameters were studied. Transparent glasses embedded with nanocrystallites of SBVN exhibited intense second harmonic signals in transmission mode when exposed to IR laser light at λ = 1064 nm. The thesis ends with a summary of the important findings and conclusions.

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