The effects of mechanical activation on the sintering of mullite produced from kaolin and aluminum powder

In this work, the effects of mechanical activation on the sintering of mullite produced from kaolin and aluminum metal powder was investigated. Because of the higher content of silica in kaolin it is necessary to add alumina or aluminum oxide in order to obtain the stoichiometric mullite composition. After mechanical treatment for different milling time, the reactions and phase transformations between kaolin and aluminum metal powder were studied using thermal techniques (DTA/TG), X-ray diffraction (XRD) and infrared spectroscopy (FT-IR). The heated samples at different temperatures were studied by XRD, apparent density, open porosity measurements and SEM analysis. The results showed the formation of silicon, quartz and small amount of nacrite after 40 h of milling at room temperature. All mixture powders milled for different time showed the formation of several alumina transitions during heat treatment. The formation of alumina transitions, α-alumina, cristobalite crystallization of and mullite (primary and secondary) formation was affected by ball milling time. The mixture of kaolin and aluminum milled for 40 h show the formation of kyanite (Al₂SiO₅) at 1300 °C. The mechanical treatment enhances the formation and sintering of mullite.     

Structural study of mullite based ceramics derived from a mica-rich kaolin waste

Mullite-based ceramics have been synthesized by reactive sintering of a mixture containing kaolin and a mica-rich kaolin waste. Samples fired in the temperature range from 1300 to 1500 °C were characterized by X-ray diffraction (XRD). The quantitative phase analysis and unit cell parameters of the mullite were determined by Rietveld refinement analysis of the XRD data. Mullite-based ceramics with 1.2 wt% quartz, 56.3 wt% glass (amorphous phase), 2.64 g/cm³ of apparent density, and 35±1.2 MPa of flexural strength were obtained after firing at 1500 °C. A liquid phase sintering mechanism activated by a total mica content of 13.3 wt% allowed to increase the mullite content to 47.6 wt% (2.3 wt% quartz and 50.1 wt% glass phase) and improve the flexural strength (70±3.9 MPa) after firing at 1400 °C.     

Firing transformations of Chilean clays for the manufacture of ceramic tile bodies

This contribution is focused on the study of the mineralogical changes occurring in the ceramic body after heating ceramic clays. Chile has an important local ceramic industry. Five deposits of clays with industrial applications were studied. The clays came from San Vicente de Tagua-Tagua (SVTT), Litueche (L), Las Compañías-Río Elqui (LC), La Herradura-Coquimbo (LH) and Monte Patria-Coquimbo (MP). The samples were heated to 830, 975, 1080 and 1160 °C keeping at the maximum temperature for 35 min. The bending strength of each ceramic body was determined at 1100 °C. Mineralogical analysis of the fired samples was carried out by X-ray diffraction. The SVTT contained quartz, spinel, cristobalite, microcline, albite, anorthite, hematite and enstatite; the LC clays quartz, mullite, spinel, microcline, albite, anorthite, hematite, diopside, enstatite, illite/muscovite and talc; the LH clays quartz, cristobalite, microcline, albite, anorthite, hematite, diopside, illite and augite; the MP clays quartz, cristobalite, microcline, albite, anorthite, hematite, diopside, gehlenite, enstatite and wollastonite and the L clays quartz, microcline and mullite. The persistence of illite at at least 900 °C was observed for LC and LH. SVTT and LH showed the required specifications for earthenware. The L clays were refractory clays with very low bending strength.     

Porcelain containing anatase and rutile nanocrystals

The aim of this work is to study the dielectric of two porcelains containing TiO₂ in the form of anatase and rutile. TiO₂ was added in compositions by means of raw kaolin with a relative high quantity of anatase, or the addition of anatase powder (10 wt%) in the initial mixture. An alternative porcelain containing kaolin–anatase mixture was obtained by a preliminary firing at 1300 °C. Beside kaolin, compositions also contain quartz and alkaline feldspar.The microstructural observations show various crystalline phases and micropores, which also have an effective role in affecting the properties. The dielectric characterization of fired porcelain, in the frequency range of 10⁵–10⁹ Hz, shows that permittivity value can be increased from 7.19 to 8.41, depending in TiO₂ crystal type, morphology and content. Permittivity depends also on mullite, quartz and cristobalite, quantities, but the role of TiO₂ phase is predominant. The macroscopic permittivity of porcelains can be calculated using a mixing rule, which fit accurately experimental results.     

Effects of different potassium salts on the formation of mullite as the only crystal phase in kaolinite

The phase transition in kaolinite from 1050 °C to 1600 °C without and with different potassium salts (KF, KNO₃ and K₂SO₄) as mineralizers and the changes of the composition and morphologies of mullite formed in kaolinite have been investigated. The adding of enough potassium has been found to inhibit the formation of cristobalite in kaolinite. The fluorine is found to be beneficial to increase the reaction activity of aluminium from metakaolinite and so the potassium fluoride has promoted more pseudotetragonal mullite formed at 1100 °C than the other two mineralizers. The influence of potassium salts on the composition and microstructure of mullite formed from kaolinite with increasing the heating temperature has been scrutinized in detail. The formation condition for the only crystal phase of mullite from kaolinite has been shown.     

Time-resolved powder neutron diffraction study of the phase transformation sequence of kaolinite to mullite

Mullite formation from kaolinite was studied by means of high-temperature in situ powder neutron diffraction by heating from room temperature up to 1370 °C. Neutron diffractometry under this non-isothermal conditions is suitable for studying high-temperature reaction kinetics and to identify short-lived species which otherwise might escape detection. Data collected from dynamic techniques (neutron diffraction, DTA, TGA and constant-heating rate sintering) were consistent with data gathered in static mode (conventional X-ray diffraction and TEM). The full process occurs in successive stages: (a) kaolinite dehydroxylation yielding metakaolinite in the ∼400–650 °C temperature range, (b) nucleation of mullite in the temperature range ∼980–992 to ∼1121 °C (primary mullite) side by side with a crystalline cubic phase (Si-Al spinel) detected in the ∼983–1030 °C temperature interval; (c) growth of mullite crystals from ∼1136 °C, (d) high (or β) cristobalite crystallization at T > ∼1200 °C and (e) secondary mullite crystallization at T > ∼1300 °C. The calculated activation energy for the kaolinite dehydration was 115 kJ/mol; for the mullite nucleation was 278 kJ/mol and for the growth of mullite process was 87 kJ/mol; finally for cristobalite nucleation the calculated apparent activation energy was 481 kJ/mol.     

A kinetic study of gaseous potassium capture by coal minerals in a high temperature fixed-bed reactor

The reactions between gaseous potassium chloride and coal minerals were investigated in a lab-scale high temperature fixed-bed reactor using single sorbent pellets. The applied coal minerals included kaolin, mullite, silica, alumina, bituminous coal ash, and lignite coal ash that were formed into long cylindrical pellets. Kaolin and bituminous coal ash that both have significant amounts of Si and Al show superior potassium capture characteristics. Experimental results show that capture of potassium by kaolin is independent of the gas oxygen content. Kaolin releases water and forms metakaolin when heated at temperatures above 450 °C. The amounts of potassium captured by metakaolin pellet decreases with increasing reaction temperature in the range of 900–1300 °C and increases again with further increasing the temperature up to 1500 °C. There is no reaction of pre-made mullite with KCl at temperatures below 1300 °C. However, the weight gain by mullite is only slightly smaller than that by kaolin in the temperature range of 1300–1500 °C. A simple model was developed for the gas–solid reaction between potassium vapor and metakaolin pellet at 900 °C.     

Influence of iron on the occurrence of primary mullite in kaolin based materials: A semi-quantitative X-ray diffraction study

Iron-enriched reference kaolins (KGa-1b, KGa-2 and KF) were used to study the effect of iron on the development of mullite phases during the sintering of kaolin-based materials. Up to 1050 °C, primary mullite formation occurred at earlier temperature within iron-enriched kaolins than in the case of iron-free kaolins. At 1150 °C, the presence of ferric ions tended to promote the transformation of the spinel (γ-Al₂O₃-like) phase into primary mullite. This action was correlated with an enhancement of the diffusion mechanism of the main constitutive species of the samples (Al, Si). In the range 1300–1400 °C, iron-enriched kaolins exhibited an abnormal grain growth of secondary mullite crystals and a partial reduction of hematite (Fe₂O₃) into magnetite (Fe₃O₄). These two iron compounds reacted with mullite and cristobalite, leading to the occurrence of eutectic liquids as expected from phase equilibrium diagrams.     

Production of nepheline/quartz ceramics from geopolymer mortars

This research has investigated the mechanical properties and microstructure of metakaolin derived geopolymer mortars containing 50% by weight of silica sand, after exposure to temperatures up to 1200 °C. The compressive strength, porosity and microstructure of the geopolymer mortar samples were not significantly affected by temperatures up to 800 °C. Nepheline (NaAlSiO₄) and carnegieite (NaAlSiO₄) form at 900 °C in the geopolymer phase and after exposure to 1000 °C the mortar samples were transformed into polycrystalline nepheline/quartz ceramics with relatively high compressive strength (～275 MPa) and high Vickers hardness (～350 HV). Between 1000 and 1200 °C the samples soften with gas evolution causing the formation of closed porosity that reduced sample density and limited the mechanical properties.     

In-situ synthesis and textural evolution of the novel carbonaceous SiC/mullite aerogel via polymer-derived ceramics route

A novel carbonaceous SiC/mullite composite aerogel is derived from catechol-formaldehyde/silica/alumina hybrid aerogel (CF/SiO₂/AlOOH) via polymer-derived ceramics route (PDCR). The effects of the reactants concentrations on the physicochemical properties of the carbonaceous SiO₂/Al₂O₃ aerogel and SiC/mullite aerogel are investigated. The mechanism of the textural and structural evolution for the novel carbonaceous SiC/mullite is further discussed based on the experimental results. Smaller reactants concentration is favorable to formation of mullite. Reactants concentration of 25% is selected as the optimal condition in considering of the mullite formation and bulk densities of the preceramic aerogels. Spherical large silica particles are also produced during heat treatment, and amorphous silica is remained after this reaction. With further heat treatment at 1400 °C, silicon carbide and mullite coexist in the aerogel matrix. The mullite addition decreases the temperature of SiC formation, when compared with the conventional methods. However, after heat treatment at 1450 °C, the amount of mullite begins to decrease due to the further reaction between carbon and mullite, forming more silicon carbide and alumina. The carbonaceous SiC/mullite can be transferred to SiC/mullite binary aerogel after carbon combustion under air atmosphere. The carbonaceous SiC/mullite has a composition of SiC (31%), mullite (19.1%), SiO₂ (14.4%), and carbon (35%). It also possesses a 6.531 nm average pore diameter, high surface area (69.61 m²/g), and BJH desorption pore volume (0.1744 cm³/g). The oxidation resistance of the carbonaceous SiC/mullite is improved for 85 °C when compared with the carbon based aerogel.     

Thermal evolution and structural study of 2:1 mullite from monophasic gels

Single phase mullite gels with composition 2Al₂O₃·SiO₂ (2:1) were prepared by the slow hydrolysis method using aluminium nitrate nonahydrate and tetraethylorthosilicate as reagents. The evolution to mullite from gels was studied by infrared (IR) spectroscopy and X-ray diffraction (XRD). Gels thermally treated under fast schedules showed mullite formation below 900 °C. Compositional and microstructural changes in 2:1 mullites through the range of temperature from 900 to 1600 °C were determined by the measurement of lattice parameters and field emission scanning electron microscopy. The alumina-rich mullites formed at low temperatures become almost the nominal 2:1 at 1600 °C. This result is consistent with available thermodynamic data for mullite formation from alumina and silica. Microstructural examination indicated an almost constant grain size for mullite from 900 to 1600 °C.     

A kinetic study of the quartz–cristobalite phase transition

Cristobalite is a common silica polymorph in ceramics, as it can crystallize in SiO₂-rich systems during high temperature processes. Its occurrence in final traditional ceramic bodies remarkably affects their thermal expansion, thus playing an important role in the shrinkage upon cooling. The quartz–cristobalite transformation kinetics is investigated by in-situ isothermal X-ray powder diffraction experiments and then correlated to the average particle size (〈d〉) of the starting quartz using a model here developed. An Avrami-like rate equation, i.e. α(t) = 1 ? exp(? k × t)ⁿ, in which the n-term is assumed to account for the dependence on the average particle size, has provided the best fitting of theoretical to experimental data, yielding activation energy values that range from 181 to 234 kJ mol^?1, and exponential n-coefficients from 0.9 to 1.5. Ex-situ observations have demonstrated that the formation of cristobalite from quartz after 50 min, 2, 4 and 6 h at 1200 and 1300 °C, exhibits a remarkable dependence on 〈d〉 of quartz, showing comparable behaviours in the case of 〈d〉 equal to 15.8 and 28.4 μm, but significant differences for 〈d〉 of 4.1 μm. The formation of cristobalite is boosted remarkably at temperature higher than 1200 °C, with an increase by weight even of 500%, with respect to its content at lower temperature. The method of sample preparation (dry powder, wet powder and tablet of compressed dry powder) seems to influence the results only at temperature > 1200 °C and in the case of fine powder.     

Synthesis and sintering of pre-mullite powders obtained via carbonate precipitation

Ultrafine pre-mullite powders, which yield mullite at high temperatures, have been prepared from colloidal silica and aluminium nitrate via carbonate coprecipitation and followed by calcination. The chemical and structural evolutions of the as-prepared precipitation powder during thermal treatment were studied and the sinterability of pre-mullite powders were investigated. The as-prepared powders are comprised of ammonium aluminum carbonate hydroxide and amorphous silica, which convert to mullite via the Al–Si spinel phase at 1250 °C. Calcination of the as-prepared powders at 1000 °C gives a very active powder which can be reactively sintered to 98.2% theoretical density at 1550 °C. The sintered body possesses a relatively uniform chemical composition with Al₂O₃/SiO₂ mole ratio of 1.48 and exhibits a very fine interlocking equiaxed and polygonal grain morphology with grain size of 100–200 nm.     

Fabrication and properties of porous mullite ceramics from calcined carbonaceous kaolin and α-Al2O3

High purity calcined carbonaceous kaolin and α-Al₂O₃ powders were employed to prepare porous mullite ceramics (Sample A) using graphite as pore former with the reaction sintering method. For the purpose of comparison, porous mullite ceramics (Sample B) was also fabricated from the uncalcined carbonaceous clay incorporated with α-Al₂O₃ powders. Mullitization in the two samples was both nearly complete at 1500 °C, despite the fact that calcination of the clay remarkably depressed mullitization and promoted the formation of glass phase. The Sample A sintered at 1500 °C fractured mainly in an intergranular way, while the Sample B mainly underwent transgranular fracture. The experimental results revealed that densification behavior/open porosity of the Sample A was far more sensitive to sintering temperature. The pore size of the Sample A as well as the Sample B sintered at 1500 °C was in a narrower range of 0.3–5 μm.     

Study on preparation of thermal storage ceramic by using clay shale

Shale was used as main raw material for developing thermal storage ceramics. The samples were fabricated via semi-dry pressing followed by pressureless sintering. The result showed that the sample (75% shale, 10% kaolin, 10% potash feldspar and 5% soda feldspar) fired at 1080 °C exhibited the best comprehensive performance. Ocular examination reveals that no cracks were observed after 30 cycle times thermal shock tests (wind cooling from 600 °C to room temperature). The results presented that the high bending strength remained after 20 cycle times thermal shock tests but plummeted at the thirtieth time. Other properties were given as follows: bulk density: 2.60 g/cm³; thermal conductivity: 2.33 W/(m °C); and heat storage density: 578.50 mJ/m³. XRD analysis indicated that the quartz and hematite were the main solid phases in the sample. Some isolated pores, quartz crystals, granular hematite crystals and needle-like mullite crystals were observed in the matrix according to the SEM (Scanning Electron Microscope) analysis. More pores were found with temperature rizing according to SEM analysis. The relatively high content of Fe₂O₃ contributed to the formation of the vitreous phase and favored the densification. Overall, the introduction of shale effectively reduced the firing temperature and performed the better thermal storage properties.     

Re-formation of metastable ε-Fe2O3 in post-annealing of Fe2O3/SiO2 nanostructure: Synthesis,computational particle shape analysis in micrographs and magnetic properties

Several Fe₂O₃/SiO₂ nanostructures were synthesized by the combination of the microemulsion and a sol-gel methods. Based on X-ray powder diffraction (XRD) and magnetic measurements (giant coercivity ~2.13 T) we identified ε-Fe₂O₃ (hard magnet) as the dominant crystalline phase. TEM analysis showed a wide size distribution of iron oxide nanoparticles (from 4 to 50 nm) with various morphologies (spherical, ellipsoidal and rod-like). We quantitatively described (computational analysis, MATLAB code) morphological properties of nanoparticles using the ellipticity of the shapes. The as-synthesized hard magnetic material was subjected to a post-annealing treatment at different temperatures (200, 500, 750, 1000 and 1100 °C) in order to investigate stability, formation and transformation of the ε-Fe₂O₃ polymorph. We found decreasing coercivity in the thermally treated samples up to the temperature of 750 °C (H_c=1245 Oe), followed by an observation of a surprising jump in coercivity H_C~1.5 T after post-annealing at 1000 °C. We conclude that the re-formation of the ε-Fe₂O₃ structure during post-annealing at 1000 °C is the origin of the observed phenomena. The phase transformation ε-Fe₂O₃→α-Fe₂O₃ and crystallization of amorphous silica in quartz and cristobalite were observed in the sample treated at 1100 °C.     

Mullite formation from the pyrolysis of aluminium-loaded polymethylsiloxanes: The influence of aluminium powder characteristics

Polymethylsiloxane (PMS) filled with a range of aluminium powders of different size and morphology have been used to produce precursor mixtures to form mullite bodies. The size and shape of the Al powder is shown to have a strong influence on the temperature and mechanism of mullite formation, on the final microstructure and phase composition of the product. The reaction proceeds by decomposition of the PMS producing amorphous SiO₂. Al oxidation occurs both by reaction with the atmosphere and by reduction of the amorphous SiO₂ to produce α-Al₂O₃. Crystallisation of cristobalite was also observed prior to mullitisation. It is these components of the microstructure that react to produce mullite. The onset of mullite formation occurs at different temperatures, depending on the initial Al powder size and morphology. Large, flake morphology Al powders produced the greatest quantity of mullite and showed the lowest temperatures for mullite formation. XRD analysis identified 3:2 mullite in samples using large Al particles after heating to 1400 °C and at 1700 °C in samples using small Al powders.     

Temperature-induced changes in morphology and microstructure of electrospun mullite nanofibers fabricated from a hybrid mullite sol

Mullite nanofibers with small diameter and high surface area are an ideal candidate as the reinforcements in composite materials, and have promising applications in the fields of catalysis, filtration, thermal storage and so forth. In this work, electrospun mullite nanofibers were successfully synthesized using a hybrid mullite sol. The morphology and microstructure of fibers calcined at different temperatures were investigated. The morphology of fibers synthesized at 900 °C is porous with coarse surface, and after crystallization it becomes compact with smooth surface. The densities of fibers increase with the increasing temperatures. At 1200 °C the surface of fibers becomes coarse again, as a result of the grain growth of mullite. The crystallization path of fibers was revealed that the Al-rich mullite (4Al₂O₃·SiO₂) together with amorphous silica formed at 1000 °C, changed into mullite with higher silica contents as temperature further increased, and finally transformed into a stable 3Al₂O₃·2SiO₂ phase at 1200 °C. During this crystallization process, the flow of amorphous silica phase and the formation of mullite crystal structure benefit the densification of fibers, leading to the resultant fibers with fine and compact microstructure. The present findings can provide a guideline for the preparation of the promising high-mechanical mullite nanofibers and the synthesized nanofibers display great potential as reinforcements in structural ceramic composites.     

Low-temperature sintering and microstructure control of mullite–Mo composites

Dense mullite–Mo (45 vol%) composites with homogeneous microstructure have been obtained by plasma activated sintering of a mixture of Mo and mullite precursors at a relatively low temperature (1350 °C) and a pressure of 30 MPa. The mullite precursor was synthesized by a sol–gel process followed by a heat-treatment at 1000 °C. The influence of different mullite precursors on the densification behavior and the microstructure of mullite–Mo composites has been studied. The precursor powder heat-treated at 1000 °C with only Si–Al spinel but no mullite phase shows an excellent sintering activity. Following the sintering shrinkage curves, a two-stage sintering process is designed to enhance the composite densification for further reducing the sintering temperature. The study reveals that viscous flow sintering of amorphous SiO₂ at low temperatures effectively enhances the densification. Moreover, microstructure of these composites can be controlled by selecting different precursors and sintering temperatures.     

Effects of densification and mullitization on the evolution of the elastic properties of a clay-based material during firing

The microstructural evolution of an illito-kaolinitic raw material has been characterized during firing at 10 °C/min up to 1200 °C. The strong evolution of porosity and amount of mullite formed from the viscous flux (from 1000 °C) has been quantified using dilatometric measurement, image analysis and X-ray diffraction. In situ ultrasonic echography has been used in order to determine the Young's modulus (E) evolution associated to the microstructural changes. This technique is highly sensitive to porosity elimination and mullite development even though an abundant viscous flux is present. For low amount of mullite (<24.7 vol.%), the E evolution observed can be easily related to porosity and mullite volume proportion changes by applying the Hashin & Shtrikman approach (lower bound). For higher mullite content, the strong experimental E increase observed between 25.9 and 51.2 GPa has been related to the transition from isolated rigid inclusions (mullite and quartz) in soft matrix (viscous flux) toward a percolating network.