Special refractory grog with increased alumina content are not currently produced in the Czech Republic. The price of these grogs produced abroad is high, so there is an effort to produce grogs using domestic waste fractions of claystones, which have been stored for decades. The theoretical part of the thesis describes the current results and experience with the processing of fine waste parts of claystone W super and BVP. Suitable raw materials for the preparation of grog with an increased content of alumina are characterized. In the experimental part of the thesis is verified the possibility of production of grogs with increased content of Al2O3 according to the proposed prescriptions.

When firing calcium ceramic materials creates a new crystalline phase anorthite. It can significantly improve the properties of ceramic body. This work deals with the possibilities of development anortitové ceramics using non-plastic raw materials, particularly alumina cement compared with conventional ceramics based on mullite.

<p><strong>Apstrakt je obrađen tehnologijama za optičko prepoznavanje teksta (OCR).</strong></p><p>Mehanizam nastanka mulita zavisi od načina doziranja polaznih oblika reaktanata kao &scaron;to su alumina i silika. Dobijanje mulita sol-gel postupkom je u velikoj meri pobolj&scaron;ano u odnosu na klasično procesiranje zbog mogućnosti homogenog me&scaron;anja AI₂O₃ i SiO₂ komponenti i kontrole dodataka. Sol-gel metod omogućuje pripremu vrlo homogenih i reaktivnih gelova koji mogu da sinteruju na nižim temperaturama pri čemu se može postići vrlo fina mikrostruktura. U ovom radu koji se odnosio na procesiranje mulita sol-gel postupkom, hipoteza je bila da se na samom početku procesiranja aluminijumovi joni iz alkoholnog rastvora Al-soli uključuju u polimernu gel strukturu koju formira silika. Svrha ovog rada, je proučavanje uticaja procesnih promenjivih, dodatka fluornog jona i &ldquo;seedinga&rdquo; na temperaturu nastanka sol-gel mulita pri čemu se očekuje &scaron;to je moguće niža tempertura nastanka mulita (niža od 980⁰C). Polimerni sol je dobijen u prvom slučaju me&scaron;anjem TEOS-a i aluminijum nitrata nanohidrata koji je prethodno rastvoren u etil alkoholu. U drugom slučaju, u polimerni sol je dodavan fluorni jon u koncentraciji 2 do 5 % mas. u odnosu na očekivani prinos mulita i u trećem slučaju je dodavana različita količina mulitnih klica (2-4 % mas.). Eksperimantalno je potvrđeno da procesne promenljive; pH, temperatura geliranja i R odnos imaju, veliki uticaj na brzinu geliranja i na nastanak mulita. U slučaju dodavanja fluornog jona, potvrdena je hipoteza da fluorni jona na različite načine utiče na mehanizam nastanka mulita, pri čemu u prvom slučaju prisustvo fluornog jona obezbeduje mesta u oblastima razdvajanja granica faza nakon geliranja koja utiču na proces nukleacije. Ova mesta slično procesu kristalizacije stakla, omogućuju lak&scaron;u nukleaciju mulita prilikom njegove transformacije iz gela. Mesta na granici razdvanja faza postaju mesta na kojima se uspostavlja proces heterogene nukleacije &scaron;to je jedan od mogućih načina za snižavanje temperature nastanka mulita. Pored ovoga, dodavanje fluornog jona je doprinelo promeni mulitnih gel struktura, pri čemu je promena brzine hidrolize silike imala za posledicu promenu sadržaja vezane vode u toku geliranja &scaron;to se takođe značajno odražavalo na temperaturu nastanka mulita. Eksperimentalni rezultati termički obradenih gelova su pokazali, da dodavanje lluornog jona u polimerni mulitni sol stvara uslove za snižavanje temperature obrazovanja mulita sve do 890⁰C. U ovom radu je takođe pokazano da mulitne čestice, kao nukleanti pri &ldquo;seeding&quot; procesiranju, doprinose nastanku mulitnog gela koji nakon termičke obrade na 1000⁰C pokazuje veoma finu mikrostrukturu.</p> / <p><strong>Abstract was processed by technology for Optical character recognition (OCR).</strong></p><p>The mechanism of mullite formation depends upon the method of combining the alumina and silica containing reactants. Mullite can be obtained through the sol-gel process and can be greatly improved by the control of some reaction conditions particulaiiy by homogeneous mixing of Al2O3 and SiO2, and controlling of the additions. Sol-gel method allow preparation of very homogenous and reactive gels which can be sintering at low temperature and consequently submicronic microstructure can be reached. In this study of the mullite formation by sol-gel method, the hypothesis was that aluminium ions from alcoholic solulion of its salts incorporate to polymeric silica gel structure. The aim of this work was the investigation of the effect processing variables, fluorine addition and &ldquo;seeding&rdquo;on the temperature of sol-gel mullite formation and to obtain as lower temperature of mullite formation as possible (smaller than 980&deg;C). Polymeric sols, were prepared by the mixing of TEOS and aluminum nitrate nanohydrate dissolved in absolute ethyl alcohol and by adding fluorine ions in the second case from 2 wt.% to 5 wt.% and by different content of mullite seeded (2- 4 wt. %). Experimentally is determined that the processing variables as pH, gelling temperature and R ratio have high influence on the gelling rate and mullite formation. The hypothesis in the case of fluorine addition was that addition of fluorine ions could have different effects on the mechanism of mullite formation; the first it makes the sites at boundary of phase separation regions after gelling which influence at the process of the nucleation. These sites will act as a place for easy mullite nucleation, similar to process of the glass crystallization. The boundaries of the phase separation are the sites for heterogeneous nucleation which is one of the condition for lowering the temperature of mullite formation. Besides, fluorine addition could change the mullite gel structure (by changing the rate of hydrolyses of silica and it could change the content of bonded water during gelling), which should be very important for the temperature of mullite formation, too. The experimental results of heat treated gels showed that the addition of fluorine ion does decrease the temperature of mullite formation (in respect to classical sol-gel mullite processing) up to 8900C. As a nucleant in this study the mullite powder by &ldquo;seeding&rdquo; process contribute to muillite gel formation that after heat treatment up to 10000C showed very fine microstructure.</p>

Melhorias na eficiência energética motivam o desenvolvimento de isolamentos térmicos cada vez mais eficazes e duráveis. Cerâmicas porosas à base de mulita (Al6Si2O13 ou 3Al2O3.2SiO2) são ideais para essa aplicação devido à alta resistência à corrosão e à densificação. Apesar de rara sua forma mineral, esta é uma das fases mais importantes em cerâmicas tradicionais e avançadas, visto que pode ser obtida a partir de fontes de alumina e sílica, por meio de diversas rotas de processamentos. Sua formação in situ por sinterização reativa tem se destacado dentre os métodos de produção pelos bons resultados mecânicos e eficácia na formação e manutenção de porosidade, entretanto, ainda existem pontos a serem investigados como a influência do tamanho de partícula e porosidade inicial de suas matérias-primas nas propriedades finais das estruturas. Neste trabalho, foram produzidas peças porosas de alumina-mulita in situ a partir de suspensões de sílica coloidal com diferentes concentrações (30, 40 e 50 %) e hidróxidos de alumínio de diferentes granulometrias (fino, HAF e grosso, HAG) pré-calcinados em várias temperaturas (500-1500 °C), pelo processo de moldagem direta para aplicação como isolante térmico em temperaturas acima de 1000 °C. As amostras (verdes e tratadas termicamente - 1500 °C) foram submetidas à ensaios mecânicos (módulo elástico e resistência à ruptura por compressão e flexão), análise microestrutural (MEV e DRX) e de propriedades físicas (porosidade total, densidades e variação térmica dimensional). As aluminas de transição provenientes da calcinação agiram como agentes porogênicos no sistema e juntamente com a sílica coloidal (com funções simultâneas de fluido de mistura, agente ligante, aditivo de secagem e fonte de SiO2 amorfa) formaram estruturas com grande variação de propriedades. Estruturas com HAF apresentaram porosidade próxima a 40% e elevadas propriedades mecânicas, e com HAG foram obtidos níveis de porosidade acima de 50 % e baixas resistências. As composições mistas, contendo tanto HAF como HAG, obtiveram bons resultados mecânicos e porosidades acima de 50 %, mostrando-se bons candidatos para uso como isolamento térmico. Todos os sistemas contiveram a fase de mulita em maior quantidade coexistindo com alfa alumina (Coríndon). / Improvements in energy efficiency motivate the development of more effective and durable thermal insulation. Porous ceramics based on mullite (Al6Si2O13 or 3Al2O3.2SiO2) have great potential for this application due its high resistance to corrosion and densification. Although rare in its mineral form, this is one of the most important phases in traditional and advanced ceramics because it can be obtained from alumina and silica sources, through various processing routes. Among them, the solid-state in situ reactions by reactive sintering stands out for its good mechanical properties and efficiency in the formation and maintenance of pores. However, how particle size and initial porosity of its raw materials influences the final properties still requires investigation. In this work, porous ceramics of alumina-mullite were produced in situ from aqueous suspensions of colloidal silica with different concentrations (30, 40 and 50 %) and aluminum hydroxides of different grain sizes (fine, HAF and coarse, HAG) pre-calcined in several temperatures (500-1500 °C) by direct casting process for application as a thermal insulation at temperatures above 1000 °C. The samples (green and thermally treated - 1500 °C) were submitted to mechanical tests (elastic modulus and resistance to rupture by compression and flexural), microstructural analysis (SEM and XRD) and physical properties characterization (total porosity, densities and dimensional thermal variation). The transition aluminas acted as porogenic agents in the system and with the colloidal silica (with simultaneous functions of mixing fluid, binding agent, drying additive and source of amorphous SiO2), formed structures with great properties\' variation. Samples with HAF had porosity close to 40% and high mechanical properties, and with HAG, porosity levels above 50 % and low resistances were obtained. The mixed compositions, containing both HAF and HAG, obtained good mechanical results and porosities above 50 %, showing great potential to thermal insulation. All systems contained most of mullite coexisting with alpha alumina phase (Corundum).

Submitted by Angela Maria de Oliveira (amolivei@uepg.br) on 2019-03-11T20:36:23Z No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) THAYS ALLANA OLCOSKI.pdf: 2638999 bytes, checksum: 786ecaaa8b03350890f4a8a81ad27819 (MD5) / Made available in DSpace on 2019-03-11T20:36:23Z (GMT). No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) THAYS ALLANA OLCOSKI.pdf: 2638999 bytes, checksum: 786ecaaa8b03350890f4a8a81ad27819 (MD5) Previous issue date: 2018-10-30 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / A mulita é a única fase cristalina formada no sistema SiO2-Al2O3, sendo um material refratário, com elevado ponto de fusão, excelente resistência ao choque térmico, resistividade elétrica e baixa condutividade térmica. Pode ser usada tanto em aplicações tradicionais quanto avançadas. Para a sua obtenção são necessárias elevadas temperaturas e longos tempos de sinterização, devido a necessidade de alta energia de ativação para ocorrer a difusão dos íons na rede da mulita. Para otimizar o processo, pode ser usado precursores em pó com tamanho de grãos submicrométricos ou usar aditivos de sinterização. Neste estudo foi usado como aditivo o MgO, para obter a mulita por sinterização reativa, a partir da mistura de Al(OH)3 e SiO2 coloidal, e da mistura de Al2O3 e SiO2 coloidal. Para verificar o seu efeito na mulitização e sinterização da mulita nessas composições, foram adicionadas 0,8; 1,6; 2,4; 3,1 e 3,9 % em peso de MgO. As composições foram sinterizadas à 1350, 1450 e 1550 ºC por 4 horas. Inicialmente as composições foram analisadas por dilatometria e análise térmica diferencial e termogravimétrica. E após sinterização foram analisadas por difração de raios X, fluorescência de raios X, medidas de densidade e porosidade aparentes, microscopia eletrônica de varredura, resistência à flexão em três pontos e espectroscopia de impedância. Pelos resultados obtidos, observou-se que a adição de MgO reduziu a temperatura de mulitização e a temperatura de sinterização das composições estudadas, de 1400 ºC para em torno de 1350 ºC. Além disso, observou-se que, quanto maior o teor de MgO e a temperatura de sinterização, maiores e mais anisotrópicos são os grãos de mulita formados e maior é a sua resistência a flexão. Sendo que a composição M5 sinterizada à 1550 ºC obteve o maior valor de resistência de 28 MPa. Houve uma redução drástica da porosidade à 1450 e 1550 ºC, ao contrário do que ocorreu à 1350 ºC, podendo ser observado nas imagens de MEV e pelos valores de porosidade aparente. Sendo que a composição M5 sinterizada à 1550 ºC obteve o menor valor de porosidade de 2 %, sendo que a composição M0 sinterizada na mesma temperatura obteve 13,1 %. As composições derivadas da mistura com alumina, obtiveram microestruturas mais densas, com menor porosidade e maior resistência à flexão. A composição MA1 sinterizada à 1450 ºC, obteve o maior valor de resistência no valor de 65,2 MPa, devido ao aparecimento da fase vítrea, que reforçou a sua microestrutura. Com o aumento da quantidade de MgO, houve a formação da fase espinélio, juntamente com a mulita, restando ainda α-alumina residual em algumas composições. No ensaio de espectroscopia de impedância, obteve-se apenas um semicírculo na representação de Nyquist, associado a contribuição apenas do interior do grão, com uma capacitância em torno de 10-11-10- 12 F. Notou-se que a condutividade elétrica do material é dependente da temperatura de ensaio, que quanto maior a temperatura maior a condutividade. Além do que, o aparecimento de fases como, espinélio, alumina e fase vítrea favoreceram a resistividade elétrica do material, consideravelmente. / The mullite is the only crystalline phase formed in the SiO2-Al2O3 system, being a refractory material with high melting point, excelente resistance to termal shock, electrical resistivity and low termal conductivity. It can be used traditional and advanced applications. High temperatures and long sintering times are required due to the high activation energy required to diffuse the ions in the mullite network. To optimize the process, power precursors with submicron grain size or using sintering additives. In this study, MgO was used to obtain the reactive sintering mullite from the mixture of Al(OH)3 and coloidal SiO2, and the mixture of Al2O3 and coloidal SiO2. To verify its effect on mulitization and sintering of mullite in these compositions, 0,8; 1,6; 2,4; 3,1 and 3,9 wt% MgO were added. The compositions were sintered at 1350, 1450 and 1550 ºC for 4 hours. Initially the compostions were analyzed by dilatometry and differential termal and thermogravimetric analysis. After sintering, they were analyzed by X ray diffraction, X ray fluorescence, apparent density and porosity measurements, scanning eléctron microscopy, three-point flexural strength and impedance spectroscopy. From the obtained results, it was observed that the addition of MgO reduced the mulitization temperature and the sintering temperature of the compositions studied, from 1400 ° C to around 1350 ° C. In addition, it has been observed that the higher the MgO contente and the sintering temperature, the larger and more anisotropic the mullite grains are formed and the greater their flexural strength. The composition M5 sintered at 1550 ºC obtained the highest resistance value of 28 MPa. There was a drastic reduction of porosity at 1450 and 1550 ºC, contrary to what happened at 1350 ºC, which can be observed in the SEM images and the values of apparent porosity. In which the composition M5 sintered at 1550 ºC obtained the lowest porosity value of 2%, and the composition M0 sintered at the same temperature obtained 13,1%. The composition MA1 sintered at 1450 ºC, obtained the highest value of resistance in the value of 65,2 MPa, due to the appearance of the glassy phase, which reinforced its microstructure. With the increase of the amount of MgO, there was formation of the spinel phase, together with the mullite, remaining residual α-alumina in some compositions. In the impedance spectroscopy test, only a semicircle was obtained in the Nyquist representation, associated with the contribution of only the interior of the grain, with a capacitance around 10-11-10-12 F. It was noted that the electrical conductivity of the material is dependent on the test temperature, that the higher the temperature the higher the conductivity. In addition, the appearance of phases such as spinel, alumina and vitreous phase favored the electrical resistivity of the material, considerably.

Matérias-primas cerâmicas são tecnologicamente muito importantes, pois são aplicadas desde a indústria de base, como isolamento térmico dos fornos siderúrgicos feito pelas cerâmicas refratárias, por exemplo; até a produção de materiais para a construção civil, componentes eletrônicos, entre outros. Devido a essa ampla aplicação, muitos estudos se desenvolveram com o intuito de conhecer as propriedades desses materiais, bem como suas interações com o processamento. Tais propriedades são determinantes para as aplicações e também para as rotas de produção que podem ser empregadas. A principal técnica de processamento cerâmico para consolidação das peças e ganho de propriedades mecânicas é a sinterização. Este processo sofre grande influência das propriedades físicas das partículas que compõem as matérias-primas. O presente estudo se propõe a investigar e monitorar, através de modificações estruturais controladas, quais as características das partículas que mais afetam esta etapa do processamento. Para tal estudo escolheu-se o sistema Al2O3-SiO2 em proporção estequiométrica (3:2) para obtenção de Mulita. Dentre as matérias-primas componentes do sistema, a sílica (SiO2) é a que mais sofre modificações estruturais em uma faixa de temperatura relativamente baixa; logo, foi selecionada para ter suas propriedades modificadas mediante tratamentos térmicos variados, de 700°C, 900°C e 1100°C. As modificações causadas nas propriedades físicas e seus efeitos foram monitorados. Avaliou-se a influência causada na obtenção de mulita estequiométrica, as alterações nas propriedades mecânicas dos corpos de prova sinterizados em temperaturas diferentes (1100°C, 1300°C e 1500°C) durante 3 horas, e a estabilidade dimensional. A sílica aplicada no estudo foi uma sílica amorfa precipitada, disponível comercialmente. Os resultados mostraram que a sílica teve sua área superficial específica (ASE) variando de cerca de 150 m²/g até valores próximos de 0,5 m²/g. Ficou evidente ainda que a variação da ASE das partículas foi responsável por grandes interferências na sinterização ou densificação das estruturas. Este processo depende da movimentação dos átomos para regiões da superfície onde ocorrerá o contato entre as partículas e sua junção. Com a redução da ASE, a sinterização se torna menos efetiva e a estabilidade dimensional é favorecida. Por outro lado, quando a sinterização das partículas é proeminente, a densificação das estruturas dá origem a componentes com boas propriedades mecânicas, aplicáveis em situações estruturais. Os resultados mostraram ainda que é possível obter estruturas com propriedades mecânicas semelhantes, como resistência à ruptura e módulo elástico, mesmo tendo partido de matérias-primas muito diferentes, permitindo o nivelamento e adequação dessas propriedades às aplicações desejadas. / Ceramic raw-materials are technologically very important, once they are applied since basic industry, such as thermal insulating for steel furnace made by refractory ceramics until the production of materials for construction, electronics compounds and others. Due to its wide hall of applications, many studies were developed for understand these materials\' properties and its interaction with processing. Such properties are application and processing route determinant. The main processing technique for consolidating and gaining of mechanical properties is sintering. This process is highly influenced by particles\' physical properties. This very study is proposed to investigate and monitor, by controlled structure modifications, which particles\' characteristics affects sintering more intensely. For such objective, the system Al2O3-SiO2 on stoichiometric proportion (3:2) for mullite obtaining was chosen. Among system\'s raw-material, silica (SiO2) is easier to be modified by temperature in a relatively low range, so it was selected to have its properties changed by different thermal treatment of 700°C, 900°C and 1100°C. Physical properties\' modifications and its effects were monitored. The influence on stoichiometric mullite obtaining, variations on mechanical properties of 3 hours long sintered samples (1100°C, 1300°C and 1500°C), and dimensional stability were measured. Market-available precipitate amorphous silica was employed. Results showed that thermal treatment of silica was able to vary its specific surface area (SSA) from 150 m2g-1 to values near of 0,5 m2g-1. It was also clear that SSA variation was responsible for interfering on sintering. This process depends on atoms movement to surface regions where will occur contact and particles bonding. With SSA reduction, sintering is less effective and dimensional stability is favored. On the other hand, when particles\' sintering is more effective structure densification will end on components with good mechanical properties, finding uses on structural application. Results also showed that is possible to obtain similar mechanical properties structures even when raw-materials exhibit different characteristics.

To offer better solutions for the recycling of salt cake from secondary aluminum melting, several innovative investigations were carried out based on hydrometallurgical and pyrometallurgical views. Thermal diffusivity measurements as a function of temperature on salts-Al composites having various compositions (0, 2, 4, 6, 8, 10, 12wt pct metallic Al) were carried out. Its attempt to derive theoretical relationships between aluminium contents in the salt-Al composites and the thermal conductivities so that these would serve as calibration curves for industrial samples taken out from secondary aluminium re-melting at a later stage. The AlN hydrolysis behavior in NaCl solution was investigated by immersing pure AlN powder in deionized water, 0.3mol/l NaCl aq, 0.6mol/l NaCl aq and NaCl solution respectively with CO2 bubbling at 291K. The results showed that AlN powder underwent enhanced hydrolysis in NaCl aq than that in deionized water, while, the introduction of CO2 was found to hinder the hydrolysis even in the presence of NaCl. The characterization of the products after hydrolysis was carried out using XRD, SEM and TEM analyses. It was shown that the hydrolysis process included a slow-reaction period involving the dissolution of aluminum hydroxide layer around raw AlN particle, followed by the precipitation of aluminum hydroxide gel and the crystallization of boehmite, bayerite and gibbsite. The effects of sodium chloride concentration on the hydrolysis behavior are presented. The leaching process in CO2-saturated water showed that, at a solid to liquid ratio of 1:20 and 3h at 291K, the extraction of Na and K from the dross could be kept as high as 95.6% and 95.9%, respectively. At the same time, with continuous CO2 bubbling, the mass of generated NH3 during the leaching process decreased significantly, also the escaping NH3 gas decreased from 0.25mg in pure water down to &lt;0.006mg. The above results showed that the introduction of CO2 causes hindrance to the hydrolysis of AlN, meanwhile, effective absorption of ammonia. The plausible mechanisms for the observed phenomena are discussed. The concept of the leaching of the salt cake by carbonated water and the consequent retention of AlN in the leach residue opens up a promising route towards an environment-friendly recycling process for the salt cake viz. recovery of the salts, utilization of CO2 and further processing of the dross residue, towards the synthesis of SiAlON from the leach residues.   In alternative route to the processing of salt cake, the ammonia gas evolved by hydrolysis of AlN was collected by CO2-saturated water during water leaching at 373K. The products, i.e. ammonium carbonates which are free of chlorides, has application as a fertilizer, besides that, this method also has the advantage of fixing carbon from CO2, which is the subject of many investigations around the world. The oxidation behavior of composites SiMgAlON phases (β-SiAlON, MgAlON and 15R) synthesized from the residue during the leaching treatment of salt cake and corresponding synthetic samples was investigated in air by thermogravimetric measurements. The oxidation studies reveal the effects of impurities, namely, Fe2O3 and CaO present in the salt cake residue. From the view of kinetics, the addition of Fe2O3 brings a lower activation energy and more aggressive oxidation. The additive of CaO caused the shrinkage during the synthesis and liquid formation during the oxidation above 1673K, thus retard the oxidation rate. The impurities of CaO and Fe2O3 in the leaching residue can result in an aggressive oxidation at low temperature and a protective oxidation at temperatures above the eutectic point. From the view of phase evolution, with the progress of oxidation, the composition of the material being oxidized moved towards the Al2O3-rich corner of MgO-Al2O3-SiO2 or CaO-MgO-Al2O3-SiO2 phase diagrams relevant to SiMgAlON composite. At lower temperatures, the addition of Fe2O3 and CaO facilitated the formation of cordierite and anorthite, respectively. With the increasing of temperature, islands of silicate melt were formed dissolving these oxides, with the liquidus temperature getting lowered as a consequence. The liquid phase formed engulfed the adjacent solid phases providing strong mobility for the cations and enabling the crystal growth. As a result, intermediate products, i.e. cordierite, anorthite, spinel, which formed earlier during oxidation are found to get dissolved in the liquid phase. / <p>QC 20120912</p>

In this diploma thesis was analysed layer of corroded material created on refractory lining of reactors for mazut gasification. Samples of corroded material were analysed for SiO2, Al2O3, ZrO2, Fe2O3 a TiO2. Corroded material was further analysed by x-ray and IR spectroscopy to acquire more precise data about chemical composition. This thesis studies the exact effect of microstructure on static corrosion kinetics in system SiO2-Al2O3.

Die vorliegende Abhandlung befasst sich mit der Thematik der gezielten Festigkeitssteigerung silikatkeramischer Werkstoffe. Dabei liegt das Interesse auf der Korrelation der Bruchspannung verschiedener Versuchswerkstoffe, mit den sich in Abhängigkeit der Rohstoffzusammensetzung bildenden Gefügemerkmalen. Die Grundlage der Versuche ist die Modifikation eines chemisch-technischen Feinsteinzeuges, bestehend aus bildsamen Rohstoffen, den Tonen und zweier unbildsamen Komponenten, den Schamotten. Durch die Substitution der unbildsamen Schamotten mit Feldspatrohstoffen und Aluminiumoxid gelingt die Veränderung der Gefüge bei gleichzeitiger Steigerung der Festigkeit gegenüber dem Referenzwerkstoff. Dabei korrelieren die Substitute eng miteinander. Die Feldspatrohstoffe liefern die erforderliche Menge Alkaliionen zur Intensivierung der Flüssigphasensinterung. In dieser Konsequenz entsteht ein vermehrter Anteil röntgenamorpher Phase. Zudem wird die Mullitkristallisation begünstigt. Das kristalline Al2O3 führt zu einem Verbund mit der amorphen Matrix, der deutlich geringeren Spannungen unterliegt, als es der Fall für den durch die Rohstoffe eingebrachten und ungelösten Restquarz ist. Dieser zeichnet sich vorrangig durch ein vollständiges oder teilweises Ablösen von der Matrix und damit einer kritischen Gefügeschädigung aus. Die damit einhergehende Beeinträchtigung der Werkstoffe wird durch den Vergleich mit einem Werkstoff höheren Quarzanteils bekräftigt. Eingehende röntgenografische Analysen der heterogenen Werkstoffe ermöglichen es, Tendenzen hinsichtlich der Diskrepanz des thermischen Dehnungsverhaltens zwischen Glas- und Mineralphasen aufzuzeigen und somit einen Bezug zu inneren Spannungen herzustellen. Neben derartigen Spannungen im Gefüge zeigt sich die Relevanz des sich während der Werkstoffkonsolidierung bildenden Sekundärmullits. Mikro- und nanoskalige Mullitnadeln, eingebettet in der amorphen Matrix, münden in deren Bewehrung, wodurch ein Beitrag zur Festigkeitssteigerung des Werkstoffes geleistet wird. Die Ergebnisse liefern die grundsätzliche Erkenntnis, dass die unterschiedlichen Wirkmechanismen zur Steigerung der Festigkeit in silkatkeramischen Werkstoffen in kausalem Zusammenhang stehen und nicht ausschließlich individuell betrachtet werden sollten.:1 Einleitung und Problemstellung 1 2 Grundlagen und Stand der Technik 4 2.1 Merkmale des Feinsteinzeugs und Porzellans . . . . . . . . . . . . . . . 4 2.2 Relevante Rohstoffe und deren Eigenschaften . . . . . . . . . . . . . . . 5 2.2.1 Tone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 2.2.2 Schamotte . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 2.2.3 Aluminiumoxid . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 2.2.4 Feldspat und Feldspatvertreter . . . . . . . . . . . . . . . . . . . 9 2.3 Mechanische Eigenschaften keramischer Werkstoffe . . . . . . . . . . . 11 2.4 Bruchmechanisches Verhalten keramischer Werkstoffe . . . . . . . . . . 12 2.5 Festigkeitstheorien in Abhängigkeit bestimmter Gefügemerkmale . . . . 14 2.5.1 Mullit und die Mullithypothese . . . . . . . . . . . . . . . . . . 14 2.5.2 Gefügespannungstheorie . . . . . . . . . . . . . . . . . . . . . . 16 2.5.3 Dispersionsverstärkung der Matrix . . . . . . . . . . . . . . . . 19 2.5.4 Glasphase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20 2.5.5 Einfluss der Porosität . . . . . . . . . . . . . . . . . . . . . . . . 21 2.5.6 Statistische Auswertung der Bruchspannungsswerte - DieWeibull- Statistik . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22 2.6 Grundlagen zur Bestimmung des Mineralphasengehaltes . . . . . . . . . 23 3 Experimentelle Methodik 25 3.1 Grundlagen und Vorgehensweise zur Entwicklung der Masseversätze . . 25 3.1.1 Auswahl der Rohstoffe . . . . . . . . . . . . . . . . . . . . . . . 25 3.1.2 Grundlagen der Versatzberechnung . . . . . . . . . . . . . . . . 26 3.1.3 Erläuterung der Versuchsbezeichnungen . . . . . . . . . . . . . . 28 3.1.4 Zusammenstellung der Versuchsversätze . . . . . . . . . . . . . 29 3.1.5 Aufbereitung der experimentellen Versätze . . . . . . . . . . . . 30 3.2 Charakterisierung der Werkstoffeigenschaften . . . . . . . . . . . . . . . 31 3.2.1 Vorgehensweise zur Bestimmung und statistischen Auswertung der Festigkeitswerte . . . . . . . . . . . . . . . . . . . . . . . . . 31 3.2.2 Bestimmung des Wärmeausdehnungskoeffizienten der Glasmatrix 33 3.2.3 Bestimmung der Deformation während des Sinterprozesses . . . 35 3.2.4 Analyse des Erweichungsverhalten mit dem Erhitzungsmikroskop 36 3.2.5 Wasseraufnahme, Rohdichte und offene Porosität . . . . . . . . 36 3.2.6 Reindichtebestimmung . . . . . . . . . . . . . . . . . . . . . . . 37 3.3 Röntgenographische Untersuchungen . . . . . . . . . . . . . . . . . . . 37 3.3.1 Röntgenbeugungsanalytik . . . . . . . . . . . . . . . . . . . . . 37 3.3.2 Rasterelektronenmikroskopie . . . . . . . . . . . . . . . . . . . . 40 3.3.3 Röntgenfluoreszenzanalyse . . . . . . . . . . . . . . . . . . . . . 40 4 Darstellung und Diskussion der Ergebnisse 42 4.1 Betrachtung der mechanischen Festigkeit . . . . . . . . . . . . . . . . . 42 4.2 Reproduzierbarkeit der Ergebnisse der Bruchspannungsmessungen . . . 48 4.3 Festigkeitsentwicklung in Abhängigkeit der Porosität . . . . . . . . . . 49 4.4 Ergebnisse der mineralogischen Zusammensetzung . . . . . . . . . . . . 55 4.4.1 Qualitative Darstellung der Mineralogie . . . . . . . . . . . . . . 55 4.4.2 Quantitative Darstellung der Mineralogie . . . . . . . . . . . . . 58 4.4.3 Verifizierung der Ergebnisse aus der Mineralphasenquantifizierung nach der modifizierten RIR-Methode . . . . . . . . . . . . 66 4.5 Elektronenmikroskopische Aufnahmen . . . . . . . . . . . . . . . . . . 67 4.5.1 Vergleichende Betrachtung der Gefüge in Abhängigkeit der unterschiedlichen Rohstoffe . . . . . . . . . . . . . . . . . . . . . . 68 4.5.2 Vergleich der Werkstoffgefüge mit Al2O3 und Feldspatrohstoff . 79 4.5.3 Betrachtung der Mullitkristallisation . . . . . . . . . . . . . . . 80 4.6 Wärmdehnungsverhalten der Glasphase . . . . . . . . . . . . . . . . . . 82 4.7 Deformationsverhalten während des Sinterprozesses . . . . . . . . . . . 87 5 Zusammenfassung und Ausblick 90 Literatur- und Quellenverzeichnis 95 Appendix 108 / The theme of the present work is the strength of silicate ceramic materials. In this regard it is of interest to correlate the fracture stress of various experimentally investigated materials with microstructural characteristics dependent on different raw material compositions. The basis of these investigations is the modification of a porcelain stoneware consisting of different types of clay and non plastic chamottes. Substitution of the chamottes with different types of feldspar and alumina leads to significant changes of the microstructure and to an associated increase in mechanical strength relative to the reference material. The feldspar raw materials provide the required concentration of alkali ions to enhance the liquid-phase sintering. As a result, the amount of the amorphous phase inreases and the crystallisation of mullite is promoted. The crystalline alumina becomes embedded in the glassy matrix and thereby leads to significantly lower stresses than would be the case for undissolved residual quartz introduced by the raw materials. Quartz is characterised by a complete or partial detachment from the matrix and thus a critical material failure. This is confirmed by comparison with a material consisting of a high quartz concentration. X-ray analysis of the heterogenous materials reveals trends regarding thermal expansion mismatch between the amorphous and crystalline phases. Thus a relationship to internal stresses is established. In addition, the relevance of the secondary mullite formed during the consolidation process is shown. Micro- and nanoscaled mullite needles, embedded in the amorphous matrix, contribute to the strength of the materials by reinforcing the matrix. The results provide the fundamental insight that the different mechanisms of increasing the strength in silicate ceramic materials are causally related and should not be considered in isolation.:1 Einleitung und Problemstellung 1 2 Grundlagen und Stand der Technik 4 2.1 Merkmale des Feinsteinzeugs und Porzellans . . . . . . . . . . . . . . . 4 2.2 Relevante Rohstoffe und deren Eigenschaften . . . . . . . . . . . . . . . 5 2.2.1 Tone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 2.2.2 Schamotte . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 2.2.3 Aluminiumoxid . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 2.2.4 Feldspat und Feldspatvertreter . . . . . . . . . . . . . . . . . . . 9 2.3 Mechanische Eigenschaften keramischer Werkstoffe . . . . . . . . . . . 11 2.4 Bruchmechanisches Verhalten keramischer Werkstoffe . . . . . . . . . . 12 2.5 Festigkeitstheorien in Abhängigkeit bestimmter Gefügemerkmale . . . . 14 2.5.1 Mullit und die Mullithypothese . . . . . . . . . . . . . . . . . . 14 2.5.2 Gefügespannungstheorie . . . . . . . . . . . . . . . . . . . . . . 16 2.5.3 Dispersionsverstärkung der Matrix . . . . . . . . . . . . . . . . 19 2.5.4 Glasphase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20 2.5.5 Einfluss der Porosität . . . . . . . . . . . . . . . . . . . . . . . . 21 2.5.6 Statistische Auswertung der Bruchspannungsswerte - DieWeibull- Statistik . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22 2.6 Grundlagen zur Bestimmung des Mineralphasengehaltes . . . . . . . . . 23 3 Experimentelle Methodik 25 3.1 Grundlagen und Vorgehensweise zur Entwicklung der Masseversätze . . 25 3.1.1 Auswahl der Rohstoffe . . . . . . . . . . . . . . . . . . . . . . . 25 3.1.2 Grundlagen der Versatzberechnung . . . . . . . . . . . . . . . . 26 3.1.3 Erläuterung der Versuchsbezeichnungen . . . . . . . . . . . . . . 28 3.1.4 Zusammenstellung der Versuchsversätze . . . . . . . . . . . . . 29 3.1.5 Aufbereitung der experimentellen Versätze . . . . . . . . . . . . 30 3.2 Charakterisierung der Werkstoffeigenschaften . . . . . . . . . . . . . . . 31 3.2.1 Vorgehensweise zur Bestimmung und statistischen Auswertung der Festigkeitswerte . . . . . . . . . . . . . . . . . . . . . . . . . 31 3.2.2 Bestimmung des Wärmeausdehnungskoeffizienten der Glasmatrix 33 3.2.3 Bestimmung der Deformation während des Sinterprozesses . . . 35 3.2.4 Analyse des Erweichungsverhalten mit dem Erhitzungsmikroskop 36 3.2.5 Wasseraufnahme, Rohdichte und offene Porosität . . . . . . . . 36 3.2.6 Reindichtebestimmung . . . . . . . . . . . . . . . . . . . . . . . 37 3.3 Röntgenographische Untersuchungen . . . . . . . . . . . . . . . . . . . 37 3.3.1 Röntgenbeugungsanalytik . . . . . . . . . . . . . . . . . . . . . 37 3.3.2 Rasterelektronenmikroskopie . . . . . . . . . . . . . . . . . . . . 40 3.3.3 Röntgenfluoreszenzanalyse . . . . . . . . . . . . . . . . . . . . . 40 4 Darstellung und Diskussion der Ergebnisse 42 4.1 Betrachtung der mechanischen Festigkeit . . . . . . . . . . . . . . . . . 42 4.2 Reproduzierbarkeit der Ergebnisse der Bruchspannungsmessungen . . . 48 4.3 Festigkeitsentwicklung in Abhängigkeit der Porosität . . . . . . . . . . 49 4.4 Ergebnisse der mineralogischen Zusammensetzung . . . . . . . . . . . . 55 4.4.1 Qualitative Darstellung der Mineralogie . . . . . . . . . . . . . . 55 4.4.2 Quantitative Darstellung der Mineralogie . . . . . . . . . . . . . 58 4.4.3 Verifizierung der Ergebnisse aus der Mineralphasenquantifizierung nach der modifizierten RIR-Methode . . . . . . . . . . . . 66 4.5 Elektronenmikroskopische Aufnahmen . . . . . . . . . . . . . . . . . . 67 4.5.1 Vergleichende Betrachtung der Gefüge in Abhängigkeit der unterschiedlichen Rohstoffe . . . . . . . . . . . . . . . . . . . . . . 68 4.5.2 Vergleich der Werkstoffgefüge mit Al2O3 und Feldspatrohstoff . 79 4.5.3 Betrachtung der Mullitkristallisation . . . . . . . . . . . . . . . 80 4.6 Wärmdehnungsverhalten der Glasphase . . . . . . . . . . . . . . . . . . 82 4.7 Deformationsverhalten während des Sinterprozesses . . . . . . . . . . . 87 5 Zusammenfassung und Ausblick 90 Literatur- und Quellenverzeichnis 95 Appendix 108