Phase and microstructural evolution during the heat treatment of Sm-Ca-alpha-sialon ceramics

The phase and microstructural evolution of multi-cation Sm-Ca-alpha-sialon ceramics was investigated. Six samples were prepared, ranging from a pure Sm-sialon to a pure Ca-sialon, with calcium replacing samarium in 20 eq% increments, thus maintaining an equivalent design composition in all samples. After pressureless sintering at 1820 degreesC for 2 It, all samples were subsequently heat treated up to 192 h at 1450 and 1300 degreesC. The amount of grain boundary glass in the samples after sintering was observed to decrease with increasing calcium levels. A M-ss' or M-ss',-gehlenite solid solution was observed to form during the 1450 degreesC heat treatment of all Sm-containing samples, and this phase forms in clusters in the high-Sm samples. The thermal stability of the alpha-sialon phase was improved in the multi-cation systems. Heat treatment at 1300 degreesC produces SmAlO3 in the high-Sm samples, a M-ss',-gehlenite solid solution in the high-Ca samples, and a Sm-Ca-apatite phase in some intermediate samples. (C) 2002 Elsevier Science Ltd. All rights reserved.

Phase equilibrium data and liquidus for the system "MnO"-CaO-(Al2O3+SiO2) at Al2O3/SiO2 of 0.41

Phase-equilibrium data and the liquidus for the system. "MnO"-CaO-(Al2O3-SiO2) at a manganese-rich alloy saturation have been determined in the temperature range from 1423 to 1723 K. The results are presented in the form of a pseudoternary section "MnO"-CaO-(Al2O3 + SiO2) with an Al2O3/SiO2 weight ratio of 0.41. The following primary phases are present in the range of conditions investigated:, 3Al(2)O(3).2SiO(2); SiO2; MnO.Al2O3-2SiO(2); (Mn,Ca)O.SiO2; 2(Mn,Ca)O.SiO2; MnO.Al2O3; (Mn,Ca)O; alpha-2CaO.SiO2; alpha'-2CaO.SiO2; 2CaO.Al2O3.SiO2; CaO.SiO2, and CaO.Al2O3.2SiO(2). The presence of alumina in this system is shown to have a significant effect on the liquidus compared to the system "MnO"-CaO-SiO2, leading to, the stabilization of the anorthite and gehlenite phases.

Cerâmicas Medievais e Modernas de Azamor (Marrocos) – Análise textural, mineralógica e química

Entre 2008 e 2011 foi recuperado, por uma missão arqueológica portuguesa na cidade de Azamor (Marrocos), um vasto conjunto de artefactos cerâmicos. Estes foram divididos em dois grupos cronológicos distintos: o medieval (séculos XIV-XV), constituído principalmente por despejos de uma unidade de produção oleira, e o moderno (séculos XVII-XVIII), constituído por fragmentos recuperados em vários contextos domésticos. O presente trabalho é um estudo arqueométrico de 17 fragmentos cerâmicos representativos de todo o espólio. Consiste na caracterização textural, mineralógica e química das pastas e vidrados, tendo por fim determinar se a fonte de matérias-primas e as técnicas de produção se mantiveram as mesmas em ambos os períodos cronológicos. Foi feita a observação à lupa binocular e uma análise petrográfica (lâminas delgadas) dos fragmentos cerâmicos com o objetivo de caracterizar a textura da matriz cerâmica e de identificar os componentes mineralógicos e a sua distribuição espacial. Estas análises foram complementadas por análises de difração de raios X (difração de pós) e microscopia Raman. Para a caracterização química das pastas e vidrados utilizou-se a micro-fluorescência de raios X dispersiva de energias. Os resultados indiciam que, a nível textural, designadamente no que se refere à coesão e porosidade da pasta e à quantidade de elementos não-plásticos, os dois grupos cerâmicos se assemelham bastante. Também são muitas as semelhanças quer a nível mineralógico, tendo sido identificados predominantemente quartzo, calcite, feldspato, gehlenite e piroxena, quer a nível químico, revelando a composição comum de pastas calcíticas. Foi ainda possível estimar uma temperatura de cozedura acima dos 800-950ºC para as cerâmicas dos dois grupos. Os vidrados analisados apresentam as características de vidrados plúmbicos verdes, coloridos com Cu e Fe. Assim, existe uma forte probabilidade de que as fontes de matérias-primas e técnicas de produção empregues em Azamor sejam as mesmas, em ambos os períodos cronológicos.

The mineralogy and chemistry of the German and Portuguese tiles used to face a historic building in the Amazon region and their natural susceptibility to tropical weathering

During the 19th century, the most prominent buildings of the city of Belém were faced entirely with tiles manufactured in Portugal and Germany, which now exhibit distinct degrees of degradation. The Pinho mansion is one of the most important of these buildings and was selected for the investigation of the action of the tropical Amazonian climate on the degradation of the tiles. To achieve this objective, the tiles were mapped for organic and inorganic degradation, and samples were collected for analysis. The minerals were determined by XRD, the chemical composition by classical wet methods and SEM/EDS, and the microorganisms under the microscope. The results show that the German and Portuguese tiles are quite different in their composition. While both ceramic bodies are composed of SiO2 and Al2O3, CaO was found only in the Portuguese tile. The low Na2O and K2O contents indicate the addition of materials to reduce the fusion temperature. SiO2 and PbO are the main constituents of the glaze, with CoO and FeO being added as pigment. The ceramic body of the German tiles is constituted of quartz, mullite, and cristobalite, in contrast with the Portuguese tiles, which are made of quartz, gehlenite, diopside, calcite, and feldspars. The glazes are XRD-amorphous. The chemical and mineralogical differences between the German and Portuguese tiles indicate that they were produced from different raw materials under distinct thermal processes. The most prominent weathering-related modifications are the thin layers (German tiles), oxidation stains, dark stains, the detachment of the tile (Portuguese tiles), loss of the glaze and powdering of the ceramic body (Portuguese tiles) through the establishment of Cyanophyta and Bacillariophyta.. The distinct degradation patterns of the tiles exposed to the tropical Amazon climate are a consequence of their distinct mineralogy and chemistry.

Glass-ceramic material from the SiO 2-Al 2O 3-CaO system using sugar-cane bagasse ash (SCBA)

Brazil is the world's largest producer of alcohol and sugar from sugarcane. Currently, sugarcane bagasse is burned in boilers to produce steam and electrical energy, producing a huge volume of ash. The major component of the ash is SiO 2, and among the minor components there are some mineralizing agents or fluxing. Published works have shown the potential of transforming silicate-based residues into glass-ceramic products of great utility. This work reports the research results of SCBA use to produce glass-ceramics with wollastonite, rankinite and gehlenite as the major phases. These silicates have important applications as building industry materials, principally wollastonite, due to their special properties: high resistance to weathering, zero water absorption, and hardness among others. The glasses (frits) were prepared mixing ash, calcium carbonate and sodium or potassium carbonates as flux agents, in different concentrations. X-ray fluorescence was used to determine the chemical composition of the glasses and their crystallization was assessed by using thermal analysis (DTA/DSC/TGA) and X-ray diffraction. The crystallization kinetics was evaluated using the Kissinger method, giving activation energies ranging from 200 to 600 kJ/mol. © 2011 Ceramic Society of Japan.

Caracterização química e mineralógica de azulejos portugueses do centro histórico de São Luís-MA (Brasil): Uma aproximação à mineralogia e à temperatura de queima das matérias-primas

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

The mineralogy and chemistry of the German and Portuguese tiles used to face a historic building in the Amazon region and their natural susceptibility to tropical weathering

As proeminentes edificações da cidade de Belém foram revestidas durante o século 19 com azulejos produzidos em Portugal e Alemanha que já apresentam distintos graus de degradação. O Palacete Pinho é uma das mais importantes destas edificações e foi selecionado para se investigar a ação do clima tropical amazônico sobre a degradação destes azulejos. Para atingir estes objetivos mapearam-se os azulejos desta edificação visando identificar as modificações de origem orgânica e inorgânica e coletas de amostras para análises. Os minerais foram determinados por DRX, a composição química por métodos clássicos úmidos e MEV/SED e os micro-organismos por microscopia. Os resultados obtidos mostram que os azulejos Portugueses e Alemães são distintos entre si. Enquanto o biscoito é composto de SiO₂ e Al₂O₃, CaO foi encontrado apenas nos Portugueses. Os baixos conteúdos de Na₂O e K₂O indicam adição de materiais para redução da temperatura de fusão. SiO₂ e PbO compõem o vidrado, já CoO e FeO foram adicionados como pigmentos. O biscoito dos azulejos Alemães é constituído de quartzo, mullita e cristobalita, ao contrário do Português com quartzo, gehlenita, diopsídio, calcita e feldspatos. Os vidrados são amorfos ao DRX. As diferenças químicas e mineralógicas entre os azulejos Portugueses e Alemães indicam que foram produzidos por matéria prima distinta, bem como processo termal. As alterações relacionadas com o intemperismo são as finas camadas de detritos (nos Alemães), manchas de oxidação, manchas escuras, descolamento do azulejo (no Português); perda de vidrado e biscoito tornando-se pulverulento como consequência do estabelecimento de Cyanophyta e bacillariophyta (Português). As distintas feições de degradação dos azulejos refletem as suas diferenças mineralógicas e químicas expostas ao clima tropical Amazônico.

Chemical and mineralogical characterization of portuguese ceramic tiles in the historic center of São Luís do Maranhão (Brazil): an approximation of the mineralogy and firing temperature of the raw materials

Nesse trabalho, foram caracterizados, pela primeira vez, azulejos históricos portugueses do Centro Histórico de São Luís (CHSL) do Maranhão. A caracterização foi realizada através dos ensaios de microscopia ótica, difração de raios X (DRX) e análise química, visando ao uso dessa informação para a determinação das possíveis matérias-primas utilizadas na sua fabricação, bem como a provável temperatura de queima desses materiais. Os resultados mostraram que a microestrutura desses materiais é constituída por poros de tamanhos variados, apresentando incrustações de calcita e grãos de quartzo de tamanhos inferiores a 500 µm, distribuídos numa matriz de cor rosa-amarelo, onde foram identificadas, por DRX, as fases minerais calcita, gelhenita, wollastonita, quartzo e amorfo. A partir da informação obtida, é possível inferir que as matérias-primas originais estiveram constituídas, provavelmente, por mistura de argilas caoliníticas (Al₂O₃•2SiO,₂•2H₂O), ricas em carbonatos de cálcio e quartzo ou misturas de argilas caoliniticas, quartzo e calcita. Essas matérias-primas originais não atingiram a temperatura de cocção de 950ºC.

Caracterização mineralógica de azulejos de Salvador e Belém dos séculos XVI, XVII e XIX

O presente artigo trata da caracterização da composição mineralógica de azulejos antigos pertencentes aos séculos XVI, XVII e XIX, coletados em Salvador e Belém, visando à identificação da sua provável matéria-prima e a possível temperatura de queima. Quartzo foi identificado em todas as amostras. As demais fases cristalinas encontradas foram: mullita, cristobalita, calcita, anortita, hematita, gehlenita, diopsídio e wollastonita. Foi possível dividir as amostras em três grupos, em função da possível matéria-prima e temperatura de queima: grupo 1 - caulinita e quartzo, T entre 1200º e 1728º C; grupo 2 - quartzo, caulinita, calcita e/ou dolomita e óxido ou hidróxido de ferro, T entre 900º e 1200ºC; grupo 3 - quartzo, argilominerais (provavelmente caulinita), calcita e/ou dolomita e hidróxido ou óxido de ferro, T entre 1200º e 1565º C.

Metakaolin as a cement extender

The effect of 10% and 20% replacement metakaolin on a number of aspects of hydration chemistry and service performance of ordinary Portland cement pastes has been investigated. The analysis of expressed pore solutions has revealed that metakaolin-blended specimen pastes possess enhanced chloride binding capacities and reduced pore solution pH values when compared with their unblended counterparts. The implications of the observed changes in pore solution chemistry with respect to chloride induced reinforcement corrosion and the reduction in expansion associated with the alkali aggregate reaction are discussed. Differential thermal analysis, mercury intrusion porosimetry, and nuclear magnetic resonance spectroscopy have been employed in the analysis of the solid phase. It is suggested that hydrated gehlenite (a product of pozzolanic reaction) is operative in the removal and solid state binding of chloride ions from the pore solution of metakaolin-blended pastes. Diffusion coefficients obtained in a non-steady state chloride ion diffusion investigation have indicated that cement pastes containing 10% and 20% replacement metakaolin exhibit superior resistance to the penetration of chloride ions in comparison with those of plain OPC of the same water:cement ratio. The chloride induced corrosion behaviour of cement paste samples, of water:cement ratio 0.4, containing 0% , 10%, and 20% replacement metakaolin, has been monitored using the linear polarization technique. No significant corrosion of embedded mild steel was observed over a 200 day period.

Optimization of wastepaper sludge ash (WSA) in robust cementitious systems

Abstract : Wastepaper sludge ash (WSA) is generated by a cogeneration station by burning wastepaper sludge. It mainly consists of amorphous aluminosilicate phase, anhydrite, gehlenite, calcite, lime, C2S, C3A, quartz, anorthite, traces of mayenite. Because of its free lime content (~10%), WSA suspension has a high pH (13). Previous researchers have found that the WSA composition has poor robustness and the variations lead to some unsoundness for Portland cement (PC) blended WSA concrete. This thesis focused on the use of WSA in different types of concrete mixes to avoid the deleterious effect of the expansion due to the WSA hydration. As a result, WSA were used in making alkali-activated materials (AAMs) as a precursor source and as a potential activator in consideration of its amorphous content and the high alkaline nature. Moreover, the autogenous shrinkage behavior of PC concrete at low w/b ratio was used in order to compensate the expansion effect due to WSA. The concrete properties as well as the volume change were investigated for the modified WSA blended concrete. The reaction mechanism and microstructure of newly formed binder were evaluated by X-ray diffraction (XRD), calorimetry, thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX). When WSA was used as precursor, the results showed incompatible reaction between WSA and alkaline solution. The mixtures were not workable and provided very low compressive strength no matter what kinds of chemical activators were used. This was due to the metallic aluminum in WSA, which releases abundant hydrogen gas when WSA reacts with strong alkaline solution. Besides, the results of this thesis showed that WSA can activate the glassy phase contained in slag, glass powder (GP) and class F fly ash (FFA) with an optimum blended ratio of 50:50. The WSA/slag (mass ratio of 50:50) mortar (w/b of 0.47) attained 46 MPa at 28 days without heat curing assistance. A significant fast setting was noticed for the WSA-activated binder due to the C3A phase, free lime and metallic aluminum contained in the WSA. Adding 5% of gypsum can delay the fast setting, but this greatly increased the potential risk of intern sulfate attack. The XRD, TGA and calorimetry analyses demonstrated the formation of ettringite, C-S-H, portlandite, hydrogarnet and calcium carboaluminate in the hydrated binder. The mechanical performance of different binder was closely related to the microstructure of corresponding binder which was proved by the SEM observation. The hydrated WSA/slag and WSA/FFA binder formed a C-A-S-H type of gel with lower Ca/Si ratio (0.47~1.6). A hybrid gel (i.e. C-N-A-S-H) was observed for the WSA/GP binder with a very low Ca/Si ratio (0.26) and Na/Si ratio (0.03). The SEM/EDX analyses displayed the formation of expansive gel (ettringite and thaumasite) in the gypsum added WSA/slag concrete. The gradual emission of hydrogen gas due to the reaction of WSA with alkaline environment significantly increased the porosity and degraded the microstructure of hydrated matrix after the setting. In the last phase of this research WSA-PC blended binder was tailored to form a high autogenous shrinkage concrete in order to compensate the initial expansion. Different binders were proportioned with PC, WSA, silica fume or slag. The microstructure and mechanical properties of concrete can be improved by decreasing w/b ratios and by incorporating silica fume or slag. The 28-day compressive strength of WSA-blended concrete was above 22 MPa and reached 45 MPa when silica fume was added. The PC concrete incorporating silica fume or slag tended to develop higher autogenous shrinkage at low w/b ratios, and thus the ternary binder with the addition of WSA inhibited the long term shrinkage due to the initial expansion property to WSA. In the restrained shrinkage test, the concrete ring incorporating the ternary binder (PC/WSA/slag) revealed negligible potential to cracking up to 96 days as a result of the offset effect by WSA expansion. The WSA blended regular concrete could be produced for potential applications with reduced expansion, good mechanical property and lower permeability.