Manufacturing process and properties of spherical granules in the MgO — Al2O3 — SiO2 system

A kaolin-talc mixture is used for developing a manufacturing process of spherical granules to be used as a propping agent in the oil industry. The functional properties of the granules are determined.     

Phase equilibria studies in the CaO–SiO2–Al2O3–MgO system with CaO/SiO2 ratio of 0.9

Phase equilibria and liquidus temperatures in the CaO–SiO₂–Al₂O₃–MgO system at a CaO/SiO₂ weight ratio of 0.9 in the liquid phase have been experimentally determined employing high-temperature equilibration and quenching technique followed by electron probe X-ray microanalysis. Isotherms at 1573, 1623, 1673, and 1773 K were determined and the primary phase fields of wollastonite, melilite, olivine, periclase, spinel, and corundum have been located. Compositions of the olivine and melilite solid solutions were analyzed and discussed. Comparisons between the newly constructed diagram, existing data, and FactSage predicted phase diagrams were performed and differences were discussed. The present study will be useful for guidance of industrial practices and further development of thermodynamic modeling.     

Glass-ceramics in the CaO–MgO–Al2O3–SiO2 system as potential dental restorative materials

This paper reports on development of novel alumina-containing glass-ceramics (GCs) with a high content of Al₂O₃ (12.5 wt.%) in the CaO–MgO–Al₂O₃–SiO₂ system aimed for dental restorations. The thermal properties of the parent glasses, the microstructure and the mechanical properties of the produced sintered and crystallized GCs along with bio-inertia performance were experimentally studied. Dense, white, and bio-inert GCs, comprised of melilite, either as a single-phase or with diopside, were produced. The values of flexural strength ranged between 120 and 171 MPa, the modulus of elasticity varied between 28 and 42 GPa, while the values of the hardness and the fracture toughness (measured by the indentation–Niihara equation) ranged from 6.3 to 7.0 GPa, and from 2.6 to 2.8 MPa m^0.5, respectively. The mechanical properties of the produced GCs, after being meticulously compared with the mechanical properties of GCs of various compositions reported in literature, including commercial ones, are a good match to the properties of dental hard tissues, and satisfy the requirements of the ISO 6872 “Dentistry-Ceramic Materials”.     

Crystallisation and characterisation of dielectric glass ceramics in Li2O–Al2O3–SiO2 system

Abstract

Glass ceramics in the Li₂O–Al₂O₃–SiO₂ system have been synthesised to produce bulk materials grown in a glass phase via quenching followed by controlled crystallisation. The crystallisation and microstructure of Li₂O–Al₂O₃–SiO₂ (LAS) glass–ceramic with nucleating agents (B₂O₃ and/or P₂O₅) are investigated by differential thermal analysis, X-ray diffraction and scanning electron microscopy and the effects of B₂O₃ and P₂O₅ on the crystallisation of LAS glass are also analysed. The introduction of both B₂O₃ and P₂O₅ promotes the crystallisation of LAS glass by decreasing the crystallisation temperature and adjusting the crystallisation kinetic parameters, allows a direct formation of β spodumene phase and as a result, increases the crystallinity of the LAS glass ceramic. Microstructural observations show that the randomly oriented, nanometre sized crystalline is found with residual glass concentrated at crystallite boundaries. Furthermore, it is interesting that codoping of B₂O₃ and P₂O₅ creates not much effect on the crystallisation temperature. The dielectric properties of the glass–ceramics formed through controlled crystallisation have a strong dependence on the phases that are developed during heat treatment. The dielectric constant is continuously increased and the dielectric loss is decreased with addition of additives where mobile alkali metal ions (e.g. Li⁺) are incorporated in a crystal phase and minimise the residual glass phase.     

1250°C liquidus for the CaO–MgO–SiO2–Al2O3–TiO2 system in air

Ti-bearing blast furnace slags have been regarded as an important secondary material in modern society, and the efficient recycling of Ti oxides from it is of key interest. For this reason, more thermodynamic data is needed regarding the phase relations in different composition ranges and sections. Therefore, the equilibrium phase relations of CaO–MgO–SiO₂–Al₂O₃–TiO₂ system in a low w(CaO)/w(SiO₂) ratio of 0.6–0.8 at 1250 °C in air and fixed concentrations of MgO and Al₂O₃, were investigated experimentally using a high temperature equilibration and quenching method followed by SEM-EDS (Scanning Electron Microscope and Energy Dispersive X-ray Spectrometer) analyses. The equilibrium solid phases of perovskite (CaO·TiO₂), a pseudo-brookite solid solution (MgO·2TiO₂, Al₂O₃·TiO₂)_ss, and anorthite (CaO·Al₂O₃·2SiO₂) were found to coexist with the liquid phase at 1250 °C. The calculated results of Factsage and MTDATA were used for comparisons, and significant discrepancies were found between predictions and the experimental results. The 1250 °C isotherm has been constructed and projected on the CaO–SiO₂–TiO₂-8 wt.% MgO-14 wt% Al₂O₃ quasi-ternary plane of the phase diagram. The obtained results provide new fundamental data for Ti-bearing slag recycling processes, and they add new experimental features for thermodynamic modeling of the high-order titanium oxide-containing systems.     

Thermal Stability and Crystallization Kinetics of MgO–Al2O3–B2O3–SiO2 Glasses

To support commercialization of the MgO–Al₂O₃–B₂O–SiO₂-based low-dielectric glass fibers, crystallization characteristics of the relevant glasses was investigated under various heat-treatment conditions. The study focused on the effects of iron on the related thermal properties and crystallization kinetics. Both air-cooled and nucleation-treated samples were characterized by using the differential thermal analysis/differential scanning calorimeter method between room temperature and 1200°C. A collected set of properties covers glass transition temperature (T_g), maximum crystallization temperature (T_p), specific heat (ΔC_p), enthalpy of crystallization (ΔH_cryst), and thermal stability (ΔT=T_p—T_g). Using the Kinssiger method, the activation energy of crystallization was determined. Crystalline phases in the samples having various thermal histories were determined using powder X-ray diffraction (XRD) and/or in situ high-temperature XRD method. Selective scanning electron microscope/energy-dispersive spectroscopy analysis provided evidence that crystal density in the glass is affected by the iron concentration. Glass network structures, for air-cooled and heat-treated samples, were examined using a midinfrared spectroscopic method. Combining all of the results from our study, iron in glass is believed to function as a nucleation agent enhancing crystal population density in the melt without altering a primary phase field. By comparing the XRD data of the glasses in two forms (bulk versus powder), the following conclusions can be reached. The low-dielectric glass melt in commercial operation should be resistant to crystallization above 1100°C. Microscopic amorphous phase separation, possibly a borate-enriched phase separating from the silicate-enriched continuous phase can occur only if the melt is held at temperatures below 1100°C, that is, below the glass immiscibility temperature. The study concludes that neither crystallization nor amorphous phase separation will be expected for drawing fibers between 1200°C and 1300°C in a commercial operation.     

Preparation of α-cordierite through mechanochemical activation of MgO–Al2O3–SiO2 ternary system

Samples of the ternary system MgO–Al₂O₃–SiO₂ with stoichiometric composition in relation to α-cordierite (Mg₂A_l4Si₅O₁₈), consisting of 22.2 mol% MgO, 22.2 mol% Al₂O₃, and 55.6 mol% SiO₂, were activated in a low energy mill with a constant speed of 100 rpm, in an aqueous medium. The precursors used were corundum (Al₂O₃), silica gel HF254 type 60 (SiO₂), and periclase (MgO). The objective of the present study was to evaluate the effect of mechanochemical activation on the solid-state synthesis of α-cordierite, using a low energy ball mill. Another objective was to shed light on the effect of mechanochemical activation on the steps of α-cordierite formation. For this end several grinding conditions were evaluated, varying the time and mass ratio of precursors/grinding elements, as well as calcination at different temperatures between 950 °C and 1350 °C for 2 h. The samples were analyzed for the determination of the formed phases by Infrared (IR) and X-ray Diffraction (XRD). The phases identified in uncalcined samples were brucite (Mg(OH)₂), forsterite (Mg₂SiO₄), enstatite (MgSiO₃), spinel (MgAl₂O₃), amorphous silica (SiO₂), corundum (α-Al₂O₃), and zirconia (monoclinic and tetragonal ZrO₂). The lowest temperature corresponding to the formation of α-cordierite (α-Mg₂Al₄Si₅O₁₈) was 1150 °C and a considerable amount of this phase (16.2%) was observed at this temperature, for the sample with the higher mechanochemical activation. In a solid-state reaction, α-cordierite is normally obtained at around 1400 °C, therefore, the formation of this phase at 1150 °C confirms that the mechanochemical activation method, using a low-cost ball mill, is efficient in reducing the solid-state reaction temperature.     

On the mechanisms of solid-phase reversible chemical reactions in the MgO—Al2O3—SiO2 system

Results of an electron microscope study of metastable intermediate compounds formed due to the incompleteness of solid-phase processes in shaping materials of a corundum-mullite-cordierite phase composition are presented. The identification of high-temperature clinoenstatite in contact with cordierite grains has made it possible to model and analyze some variants of mass transfer in the solid-phase reversible chemical reaction between mullite and spinel with the formation of corundum and cordierite. Common features in the mass transfer are determined for four reversible chemical reactions that occur in the subsolidus region of the MgO-A1₂O₃-SiO₂ phase diagram under a normal pressure. This has made it possible to find and substantiate the most probable mechanisms of these reactions and the mechanisms of synthesis of triple oxide compounds, i.e., sapphirine and cordierite.     

Critical evaluation and thermodynamic optimization of the Na2O–FeO–Fe2O3–Al2O3–SiO2 system

A critical assessment and thermodynamic optimization of phase diagrams and thermodynamic properties of the entire Na₂O–FeO–Fe₂O₃–Al₂O₃–SiO₂ system were carried out at 1 atm total pressure. A set of optimized model parameters obtained for all phases present in this system reproduces available and reliable thermodynamic property and phase equilibrium data within experimental error limits from 298 K to above liquidus temperatures for all compositions and oxygen partial pressures from metallic Fe saturation to 1 atm. The Gibbs energy of liquid solution was described based on the Modified Quasichemical Model considering the possible formation of NaAlO₂ and NaFeO₂ associates in the liquid state. The solid solutions wüstite, spinel, feldspar, nepheline, carnegieite, mullite, corundum, clino-pyroxene, meta-oxides and Na-β″-alumina were treated within the framework of Compound Energy Formalism. The database of model parameters can be used to calculate any thermodynamic property and phase diagram section of the present system.     

Effect of MgO calcination temperature on the reaction products and kinetics of MgO–SiO2–H2O system

MgO-based binders have been widely studied for decades. Recently, the MgO–SiO₂–H₂O system was developed as a novel construction material, however, its reaction mechanism remains unclear. This paper investigated the reaction products and kinetics of MgO/silica fume (SF) pastes with MgO calcinated at different temperatures. The results indicate that MgO presented larger grain size after calcination at higher temperature. Mg(OH)₂ and magnesium silicate hydrate (M–S–H) gel were formed when using MgO calcined at 850, 950, and 1050°C. However, only M–S–H gel was formed when using MgO calcined at 1450°C. The reaction kinetics of MgO could be described using α = 1 − e^−k*t. The reaction rate of MgO increased with decreasing calcination temperature, increasing SF dosage, and the addition of sodium hexametaphosphate. Only M–S–H gel was formed when the reaction rate of MgO was below the demarcation line (about 0.250 × 10⁻⁶ s⁻¹), and the corresponding demarcation area was around 14 days.     

The impact of nano-quartz on the structure of glass-ceramic glazes from the SiO2–Al2O3–CaO–MgO–Na2O–K2O system

The present study reports the impact of the introduction of nano-grained quartz (SA = 325 m²/g) into the composition on the structure and properties of the ceramic glaze of the CMAS-Na₂O–K₂O system. The results were compared to the glaze which had an identical oxide composition, with a difference that quartz was introduced in the form of quartz powder with a much smaller specific surface area SA = 1.41 m²/g. Both glazes are characterized by a large part of the glassy phase, above 90% by volume. The results obtained show a higher arrangement of the continuous glassy phase structure in the glaze with the addition of nano-quartz. This glaze also shows significantly higher values for all measured mechanical properties. It seems that if, in the near future, new cheaper methods for the production of nano-quartz are developed, it will be a new interesting direction of research aimed at improving the parameters of glazes and glass-ceramic materials of CMAS type.     

Experimental investigation on high temperature wettability and structural behaviour of SAW fluxes using MgO–TiO2–SiO2 and Al2O3–MgO–SiO2 flux system

To establish the relationship between wettability and structure with the change in SAW flux composition, the contact angle measurement study was performed at 1700 K. For MgO–TiO₂–SiO₂ and Al₂O₃–MgO–SiO₂ flux system the wetting behaviour was studied by evaluating the contact angle as well as surface tension properties. Sessile drop method was used to determine the wetting properties of SAW fluxes. Twenty-one SAW fluxes were designed & developed by applying mixture design approach of design of experiments. Chemical, phase and structural properties of SAW fluxes were measured using modern techniques such as X-ray fluorescence (XRF), X-ray diffraction (XRD) & Fourier Transform Infra-red spectroscopy (FTIR). As per the calculated contact angle value, different surface tension values for MgO–TiO₂–SiO₂ and Al₂O₃–MgO–SiO₂ flux system was calculated using Young's & Boni's equations. Using Dupre's equation the adhesion energy for twenty-one basic fluxes was also calculated. Measured contact angle value increased with increase in the TiO₂/MgO & TiO₂/Al₂O₃ flux ratio. Lower contact angle gives higher wettability between the flux and the heating substrate. With increase of TiO₂/SiO₂ ratio up to 1.5 to 2.0 the calculated surface tension value is decreasing while after that it is increased with increase in TiO₂/SiO₂ ratio.     

Preparation of glass–ceramic glazes in the SiO2–Al2O3–CaO–MgO–K2O–Na2O–ZnO system by variable content of ZnO

This paper is focused on glass–ceramic glazes from the SiO₂–Al₂O₃–CaO–MgO–K₂O–Na₂O system with ZnO additions (2.5, 5, 10, 15, 15, 20 and 25 wt%). The compositions were designed based on constant molar ratio of SiO₂/Al₂O₃. In the resulting glazes diopside (CaMg[Si₂O₆]), willemite (Zn₂SiO₄) and vitreous phase were identified by X-ray diffraction. Morphological and structural date of these glazes were supplementary determined by EPMA, FTIR and Raman Spectroscopy. DSC analysis was carried out to characterize thermal properties of the materials.     

Effect of MgO/Al2O3 ratio on the crystallization behaviour of Li2O–MgO–Al2O3–SiO2 glass-ceramic and its wettability on Si3N4 ceramic

The composition governs the crystallization ability, the type and content of crystal phases of glass-ceramics. Glass-ceramic joining materials have generated more research interest in recent years. Here, we prepared a novel Li₂O–MgO–Al₂O₃–SiO₂ glass-ceramic for the application of joining Si₃N₄ ceramics. We investigated the influence of the MgO/Al₂O₃ composition ratio on microstructure and crystallization behaviour. The crystallization kinetics demonstrated that the glasses had excellent crystallization ability and high crystallinity. β-LiAlSi₂O₆ and Mg₂SiO₄ were precipitated from the glass-ceramics, and the increase of MgO concentration was conducive to the precipitation of Mg₂SiO₄. Among the glass-ceramic samples, the thermal expansion coefficient of LMAS2 glass-ceramic was 3.1 × 10^?6/°C, which was very close to that of Si₃N₄ ceramics. The wetting test showed that the final contact angle of the glass droplet on the Si₃N₄ ceramic surface was 32° and the interface was well bonded.     

Effect of Sitallization Conditions on the Hardness of Transparent Sitalls in the System ZnO–MgO–Al2O3–SiO2

Glass and Ceramics - Reliable protection of the screens of next-generation mobile devices requires the use of transparent materials which are stronger than glass. In the present work the influence...     

Effect of Al2O3 and K2O content on structure,properties and devitrification of glasses in the Li2O–SiO2 system

The effect of Al₂O₃ and K₂O content on structure, sintering and devitrification behaviour of glasses in the Li₂O–SiO₂ system along with the properties of the resultant glass–ceramics (GCs) was investigated. Glasses containing Al₂O₃ and K₂O and featuring SiO₂/Li₂O molar ratios (3.13–4.88) far beyond that of lithium disilicate (Li₂Si₂O₅) stoichiometry were produced by conventional melt-quenching technique along with a bicomponent glass with a composition 23Li₂O–77SiO₂ (mol.%) (L₂₃S₇₇). The GCs were produced through two different methods: (a) nucleation and crystallization of monolithic bulk glass, (b) sintering and crystallization of glass powder compacts.Scanning electron microscopy (SEM) examination of as cast non-annealed monolithic glasses revealed precipitation of nanosize droplet phase in glassy matrices suggesting the occurrence of phase separation in all investigated compositions. The extent of segregation, as judged from the mean droplet diameter and the packing density of droplet phase, decreased with increasing Al₂O₃ and K₂O content in the glasses. The crystallization of glasses richer in Al₂O₃ and K₂O was dominated by surface nucleation leading to crystallization of lithium metasilicate (Li₂SiO₃) within the temperature range of 550–900 °C. On the other hand, the glass with lowest amount of Al₂O₃ and K₂O and glass L₂₃S₇₇ were prone to volume nucleation and crystallization, resulting in formation of Li₂Si₂O₅ within the temperature interval of 650–800 °C.Sintering and crystallization behaviour of glass powders was followed by hot stage microscopy (HSM) and differential thermal analysis (DTA), respectively. GCs from composition L₂₃S₇₇ demonstrated high fragility along with low flexural strength and density. The addition of Al₂O₃ and K₂O to Li₂O–SiO₂ system resulted in improved densification and mechanical strength.     

Phase transformation and microstructure of MgO–Al2O3–SiO2 system glass–ceramics under different heat treatment conditions

Abstract

Effects of heat treatment conditions on phase transformation, microstructure and thermal expansion coefficient (TEC) in MgO–Al₂O₃–SiO₂ system glass–ceramics were investigated by means of differential thermal analysis, X-ray diffraction and scanning electron microscopy. The magnesium aluminium titanate (MAT) precipitated firstly at 850°C and β-quartz solutions (β-QSS) formed at 950°C. Further increasing temperature to 1000°C, MAT disappeared and β-QSS became master phase, following little amount of α-cordierite, MgTi₂O₅, rutile and sapphirine. When glass was treated at 1050°C, β-QSS content decreased and α-cordierite became master phase. As temperature reached higher than 1100°C, β-QSS and sapphirine disappeared, and α-cordierite became master phase accompany with rutile and MgTi₂O₅ as secondary phase. The microstructure transformed gradually from particle shape crystallites to slat shape network with the increase in heat treatment temperature. By controlling heat treatment condition, an ideal glass–ceramics with proper TEC for matching sealing to 4J29 alloy has been obtained.