Combustion synthesis of mullite–titanium boride composite

Mullite/TiB₂ composite has been prepared successfully by combustion synthesis from blends of fine TiO₂–B₂O₃–Al–SiO₂ powders. Despite the dilution effect due to silica addition and the endothermic character of mullite formation reaction, thermodynamic calculation shows that the overall reaction between the reactants is still highly exothermic. Depending on the silica grain size and the preheating temperature, partial to full conversion of reactants into products can be achieved during the process. At 550 °C preheating temperature, complete conversion of the reactants to mullite/TiB₂ was achieved. Adiabatic combustion temperature and mullite molten fraction are calculated as a function of preheating temperature.     

Anisotropic grain growth of mullite in high-energy ball milled powders doped with transition metal oxides

Dense mullite ceramics with anisotropic grains were derived from the high-energy ball milled mixtures of Al₂O₃ and amorphous silica with the presence of transition metal oxides (FeO_1.5, CoO and NiO). The mullitization and grain growth behavior of the unmilled mixture without the addition of the transition metal oxides and the undoped system of Al₂O₃ and amorphous silica with and without milling were also investigated and compared. The mullitization temperature was about 1200 °C in the milled systems, 100 °C lower than that required by the conventional solid-state reaction process. The lowered mullitization temperature, as well as the anisotropic grain growth, was attributed to the refined structure of the oxide powders, as a result of the high-energy ball milling. The experimental results have been explained by a dissolution-precipitation mechanism.     

Recycling photovoltaic silicon waste for fabricating porous mullite ceramics by low-temperature reaction sintering

In this study, porous mullite ceramics with coral-like structures were fabricated at a low temperature of 900 °C by using photovoltaic silicon waste (PSW) as the silicon source directly. The effects of additive content and sintering temperature on the mullitization reaction of green bodies were studied. The results showed that ammonium molybdate tetrahydrate molybdenum (H₂₄Mo₇N₆O₂₄·4H₂O) as an additive could reduce the reaction temperature for mullitization from 1100 °C to 900 °C. The research on the influence of catalyst on material properties showed that porous mullite ceramics with a flexural strength of 52.83 MPa, a 41.78 % porosity, a sintering expansion rate of 0.49 % and an average pore size of 0.23 μm could be fabricated by introducing 7.5 % H₂₄Mo₇N₆O₂₄·4H₂O at the sintering temperature of 1000 °C. This study develops an environment-friendly recycling method of PSW and provides a new idea for the low-cost preparation of porous mullite ceramics with high purity.     

Low-cost porous mullite ceramic membrane supports fabricated from kyanite by casting and reaction sintering

Porous mullite supports are firstly fabricated by casting and reaction sintering based on kyanite with Al(OH)₃ as porogenic agent. The effects of composition and sintering temperature on phase evolution, microstructure, apparent porosity, pore size distribution, linear shrinkage, gas permeation flux and mechanical property of supports are systematically investigated. Results show that the mullitization of kyanite generates needle-like mullite crystals, which form skeleton structures and improve the apparent porosity and strength of supports. Al(OH)₃ addition not only promotes the formation of needle-like mullite but also enhances the apparent porosity of supports. Temperature promotes the development of mullite, from 1450 to 1500 °C, the amount and size of needle-like mullite crystals increase, ≥1500 °C, they reveal columnar morphology. The support prepared with kyanite+40 wt%Al(OH)₃ sintered at 1500–1550 °C exhibits high apparent porosity, good gas permeation flux, excellent mechanical performance and interlocked network structure composed of well development needle-like mullite.     

DTA characterisation of three types of Al2O3SiO2 gels made from TEOS-Al (OBu)3 mixture with variation of water

Mixtures of TEOS and Al (OBu)₃ had been hydrolysed by varying the water contents at a fixed acid concentration. This led to the formation of three different kinds of gels. Diphasic gel formed when excess of water was used, which transformed to mullite at 1320 °C in exothermic reaction. When the amount of water content was reduced, the resultant monophasic gel completed its mullitization at lower temperatures from an amorphous aluminosilicate phase and cubic mullite by two paths at 1150 °C and 1250 °C exothermic reactions, respectively. When less water is used, the monophasic gel converted directly to tetragonal mullite at 980 °C in exothermic reaction. Thus, the variation of water contents during the gelation caused great variations in the course of mullitization processes.     

Diphasic aluminosilicate gels with two stage mullitization in temperature range of 1200–1300 °C

The crystallization of mullite in amorphous diphasic gel aged for 6 months has been studied using non-isothermal differential scanning calorimetry (DSC) and powder X-ray diffraction with Rietveld structure refinement analysis. The diphasic premullite gels undergo structural changes by aging even when they are calcined at 700 °C. These changes imply segregation of the sample to Al₂O₃-rich and SiO₂-rich regions. From the Al₂O₃-rich region crystallizes poorly defined AlSi spinel at 977 °C followed by two-step mullite crystallization in the temperature interval of 1200–1300 °C. Two overlapped exothermic peaks on DSC scan of aged gel were observed; the first at 1233 °C and the second at 1261 °C. The former is attributed to mullite crystallization by transformation of AlSi spinel, by which excess alumina occurs, which in the second step of mullitization reacts with amorphous SiO₂-rich phase. The activation energy for mullite crystallization in the first step was E_a=935±14 kJ mol⁻¹ and the Avrami exponent n=2.5. The values E_a=1119±25 kJ mol⁻¹ and n=1.2 were obtained for mullite formation in the second step. If amorphous SiO₂-rich phase is extracted from the sample, the value E_a=805±26 kJ mol⁻¹ is obtained. Mullite crystallizing from AlSi spinel (when SiO₂-rich phase has been extracted) differentiates compositionally from that formed by both reactions. Smaller unit cell parameters and higher amount of oxygen vacancies are incorporated into tetrahedral positions of mullite structure, as was determined by Rietveld structure refinement method.     

Industrial waste silica-alumina gel recycling: Low-temperature synthesis of mullite whiskers for mass production

The increasing demand for mullite whisker-reinforced, toughened ceramic materials and mullite raw materials that meet industrial requirements has prompted the search for new and alternative sources, as well as effective technologies to obtain the target products. In this work, mullite whiskers of high purity were synthesized by a vapor-liquid–solid (V-L-S) process using industrial waste silica-alumina gel and Al₂(SO₄)₃·18H₂O as raw materials, with AlF₃·3H₂O and Na₂SO₄ as additives. The effects of sintering temperatures on the mullitization reactions and mullite morphology were investigated by XRD, TG-DTA, SEM and so forth. The results suggest that the introduction of AlF₃·3H₂O and Na₂SO₄ alters the mullitization reaction path, which leads to an initial mullitization reaction temperature of 720 °C. The SEM results demonstrate that mullite whiskers transformed from secondary growth to anisotropic growth when the sintering temperature was increased from 720 °C to 825 °C. By analyzing the experimental results, the mechanism of AlF₃·3H₂O-assisted growth of mullite whiskers with Na₂SO₄ as the liquid phase template is proposed based on the “dissolution-precipitation” process. Herein, a novel and feasible solution for the recycling of silica-rich industrial waste is proposed, which offers new and simple insights into the high value-added recycling of industrial waste, which provides new ideas for the actual mass production of mullite whiskers.     

Synthesis of high-performance mullite ceramics based on associated rare-earth kaolin

The objective of this work was to prepare high-purity, high-strength mullite ceramics from low-cost, associated rare-earth kaolin (AREK). A reaction sintering process using calcined AREK and γ-Al₂O₃ powders was used to synthesize high-performance mullite ceramics. Mineralogical, morphological, and chemical characteristics of AREK were given. The effects of associated REEs in kaolin and sintering temperature on the microstructural evolution, phase transformation, and physical properties of mullite were studied. The results showed that the mullite contents were 98.8%, the maximum aspect ratio was 8.22 μm, the relative density was 93.04%, and the micro-Vickers hardness and flexural strength were 10.63 GPa and 184.24 MPa, after sintering at 1500°C for 4 h. For comparison, calcined without rare-earth kaolin was also employed as a raw material to synthesize mullite ceramics, and the mullite content prepared by sintering the two kaolin clays at 1320–1480°C for 4 h was quite similar. However, mullite prepared using AREK forms secondary mullite in the temperature range of 1480–1500°C with a significantly higher mullite content, and therefore, the advantages of preparing mullite based on AREK as the raw material are high purity, low mullitization temperature, and high strength.     

Sillimanite‐mullite transformation observed in synchrotron X‐ray diffraction experiments

High‐resolution synchrotron powder X‐ray diffraction (XRD) experiments were conducted to clarify the transformation of sillimanite to mullite (mullitization) and determine the mullitization temperature (T_c). We were able to distinguish sillimanite and mullite in the XRD patterns, despite their very similar crystallographic parameters, and to detect the appearance of small mullite peaks among sillimanite peaks. Analysis of the Johnson‐Mehl‐Avrami (JMA) equation for mullitization ratio (ζ) revealed that at temperatures T≥1240°C the mullitization had the same kinetics. The activation energy E at T≥1240°C obtained from the Arrhenius plot was 679.8 kJ mol^?1. In analysis using a time‐temperature‐transformation diagram for mullitization, a mullitization curve of ζ=1% can be described as where t is time, n is a reaction‐mechanism‐dependent parameter determined as 0.324 by JMA‐analysis, k₀ is the frequency factor, E_A is the activation energy for atomic diffusion, and represents the activation energy for nucleation. The results of fitting the data to this equation were T_c=1199°C, A=3.9×10⁶ kJ mol^?1 K^?2, E_A=605 kJ mol^?1, and k₀=3.65×10¹⁵. We conclude that the boundary between sillimanite and mullite+SiO₂ in the phase diagram is ~1200°C.     

Sintering characteristics of Chinese bauxites

The sintering behaviour of Chinese bauxites of the diaspore-kaolinite type proceeds in three stages, viz: decomposition stage (400–1200°C), secondary mullitization stage (1200–1400 or 1500°C) and recrystallization sintering stage (above 1400 or 1500°C). The sinterability of different grades of bauxites is dependent on the Al₂O₃ content. The closer is the composition of calcined bauxite to that of mullite, the more difficult is it to sinter. It is postulated that secondary mullitization and liquid phase action are the two principal factors influencing the sintering of these bauxites. Grade II bauxites characterised by maximum secondary mullite formation and relatively low glass content are found to be most difficult to sinter.     

Sintering and microstructural study of mullite prepared from kaolinite and reactive alumina: Effect of MgO and TiO2

Mullite ceramic was prepared using kaolinite and synthesized alumina (combustion route) by solid-state interaction process. The influence of TiO₂ and MgO additives in phase formation, microstructural evolution, densification, and mechanical strengthening was evaluated in this work. TiO₂ and MgO were used as sintering additives. According to the stoichiometric composition of mullite (3Al₂O₃·2SiO₂), the raw materials, ie kaolinite, synthesized alumina, and different wt% of additives were wet mixed, dried, and uniaxially pressed followed by sintering at different temperature. 1600°C sintered samples from each batch exhibit enhanced properties. The 1 wt% TiO₂ addition shows bulk density up to 2.96 g/cm³ with a maximum strength of 156.3 MPa. The addition of MgO up to 1 wt% favored the growth of mullite by obtaining a density and strength matching with the batch containing 1 wt% TiO₂. These additives have shown a positive effect on mullite phase formation by reducing the temperature for complete mullitization by 100°C. Both additives promote sintering by liquid phase formation. However, the grain growth, compact microstructure, and larger elongated mullite crystals in MgO containing batch enhance its hardness properties.     

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.     

The fabrication of porous mullite ceramics based on the different sizes of aluminum hydroxide

In this research, for studying the influence of size and heat treatment temperature of initial Al(OH)₃ on the physical properties of porous mullite ceramics, porous mullite ceramics were prepared by in situ reaction sintering of amorphous silica and treated Al(OH)₃. The transition phases χ-Al₂O₃, к-Al₂O₃, and stable phase α-Al₂O₃ can be obtained in turn when the treatment temperature of raw Al(OH)₃ is 500, 1000, and 1500°C, respectively. The coarser the raw Al(OH)₃, the higher the strength of porous mullite ceramics. When the sintering temperature is 1500°C, the bending strengths of PS500-C, PS1000-C, and PS1500-C (PSx-C represents that the specimen was prepared by the coarse grade Al(OH)_3, which was previously treated at x°C) are 40.3 ± 2.1, 54.9 ± 5.2, and 64.8 ± 4.8 MPa, respectively. In addition, although the activated Al₂O₃ can decrease the formation temperature (∼100°C) of porous mullite ceramics, the strength and density of porous mullite ceramics prepared by activated Al₂O₃ will decrease at the same sintering temperature. It is believed that the increase of defects and pores during the phase transformation should be responsible for this phenomenon.     

Effect of yttria on sintering and microstructural behavior of reaction sintered mullite based on bauxite,fly ash and precipitated silica

The present investigation on the effect of Y₂O₃ towards the sintering behavior of mullite compacts revealed that rapid mullitization occurred through nucleation and normal grain growth due to the formation of yttrious silicate glassy phase. The intergranular voids were progressively eliminated by yttrious silicate glass leading to significant decrease in porosity with the corresponding remarkable rise in mechanical strength of sintered compacts. The uniform dispersion of microfine corundum grains into the mullite matrix with 1.5% Y₂O₃ content was noticed during sintering at 1550?°C and above.     

Effect of thermal exposure on the microstructure and strength of an alumina-silica ceramic fiber

The microstructure and mechanical properties of an alumina-silica ceramic fiber after thermal exposure at 1100–1300°C were investigated by X-ray diffraction, nuclear magnetic resonance, scanning electron microscopy, transmission electron microscopy analyses and room temperature tensile strength test. The results showed that the fiber was composed of γ-A1₂O₃ and amorphous SiO₂. A phase reaction of γ-A1₂O₃ and amorphous SiO₂ occurred when thermal exposure temperature exceeded 1150°C, and a new mullite phase formed. The grain size of the newly formed mullite increased with the increase of exposure temperature. Both the phase transition and grain growth of mullite had a significant impact on the mechanical properties of the fiber. Tensile strength of the fiber decreased slightly when thermal exposure temperature was below 1150°C, while the strength retention of the fiber decreased sharply to 65.36% as exposure temperature rose to 1200°C. A higher dispersion of tensile strength was also observed at higher exposure temperatures, as revealed by the Weibull statistical model.     

Mechanical properties of in situ synthesized mullite-based composite ceramics with three-dimensional network structure

Needle-like nanocrystalline mullite powders were prepared through the molten salt process at the temperature of 900°C using coal gangue as raw material. Then, mullite-based composite ceramics were prepared by a conventional solid-state reaction between in situ synthesized mullite and Al₂O₃ powders. Effects of Al₂O₃ content and sintering temperatures on phase compositions, microstructure, and mechanical properties of the mullite-based composite ceramics were also studied. The results show that mullite content productivity increase from 72% to 95%, as the sintering temperature increased from 1480°C to 1580°C, which led to the improvement in the bulk density and flexural strength of the samples. The three-dimensional interlocking structure for mullite-based composite ceramics was obtained by the in situ solid-state reaction process. The maximum bulk density, flexural strength, and fracture toughness for the sample with 15 wt% Al₂O₃ content are 2.48 g/cm³, 139.79 MPa, and 5.62 MPa··m^1/2, respectively, as it was sintered at the temperature of 1560°C for 3 h. The improved mechanical properties of mullite-based composite ceramics maybe ascribed to good densification and increased mullite phase content, as well as to the in situ three-dimensional network structure. Therefore, the results would provide new ideas for high-value utilization of coal gangue.     

Novel iron-rich mullite solid solution synthesis using fused-silica and α-Al2O3 powders

An iron-rich mullite solid solution was synthesized by using α-Al₂O₃, fused-silica and Fe₂O₃ powders at elevated temperatures. The phase compositions and microstructures of the synthesized samples were characterized by X-ray diffraction (XRD), energy dispersive spectrometer (EDS) and field emission scanning electron microscope (FESEM). The occurrence states of Fe²⁺ and Fe³⁺ at different temperatures were analysed by X-ray photoelectron spectroscopy (XPS). The influence and the reaction mechanism of Fe₂O₃ addition on the synthesis of the mullite solid solution were clarified. The results showed that with the addition of Fe₂O₃, a liquid-solid sintered state was formed at 1300–1400?°C, which leaded to a reduction in the mullitization temperature. After sintering at 1600?°C, the quantitative analysis showed that the mullite phase content was 100%. Meanwhile, the Fe^3+/2+ ions entered completely into the mullite to form a stable solid solution, which exhibited the crystal morphology of a spherical shape and a short columnar shape with a low aspect ratio. The crystal grains were interwoven and squeezed each other, showing good structural stability. The refractoriness under load (RUL) property of the sample sintered at 1700?°C was slightly higher than that of the sample sintered at 1600?°C.     

Impact of inorganic waste fines on structure of mullite microspheres by reaction sintering

The impact of waste composition and morphology on the properties of the mullite microstructure were studied by reaction sintering two types of siliceous waste powders with calcined alum sludge. Stoichiometric mixtures of fly ash or rice husk ash with the alum sludge were shaped into mullite microspheres by droplet coagulation. The mullitization reaction was followed by HT-XRD with a distinct difference in onset temperature. The specific powder composition of fly ash (presence of primary mullite) shifted the onset temperature to higher values as compared to the rice husk ash mixture. After sintering at 1600?°C, the mullitization reaction resulted in the same yield for both samples. Although the mullite content in the microspheres was equal, distinct differences on the microstructure could be observed. Reaction sintering of the fly ash mixture resulted in lower total porosity with smaller pore sizes.     

Effect of Bi2O3 on phase formation and microstructure evolution of mullite ceramics from mechanochemically activated oxide mixtures

Mullite ceramics with hollow whisker structure have been synthesized firstly through ordinary sintering process. The effects of Bi₂O₃ and processing, on mullitization behavior and morphology development of mullite ceramics, derived from the mechanochemically activated mixture of Al₂O₃ and SiO₂, were investigated in this paper. When the content of Bi₂O₃ was less than 10?mol%, the mullite grains show a short rod-like morphology, without the formation of whisker. As the content of Bi₂O₃ was increased to more than 10?mol%, the formation temperature of mullite was decreased from 1400?°C to 1100?°C. After sintering at 1400?°C, well-developed mullite whiskers with hollow structure were formed. The formation process and growth mechanism of hollow structural whiskers in mullite ceramic doped with high content of Bi₂O₃ were discussed in detail.     

Microstructural evolution and densification behavior of porous kaolin-based mullite ceramic added with MoO3

Microstructural evolution and densification behavior of porous kaolin-based mullite ceramic added with MoO₃ were investigated. The results indicated that MoO₃ addition not only lowered the secondary mullitization temperature to below 950?°C, but also facilitated effectively the anisotropic growth of mullite grains. Fine mullite whiskers grew and interlocked with one another in the pre-existing pore regions, in-situ forming a stiff 3D skeleton structure of mullite whiskers, which arrested further densification of the sample. On the other hand, due to the great capillary attraction of small pores, the liquid phase tended to spread over small grains, which favored the growth from small mullite grains into whiskers at the expense of the liquid phase. Consequently, competitive mechanisms of sintering and crystal growth of mullite functioned, which further limited the sample densification. As a result, the total linear shrinkage of the sample added with MoO₃ after firing at 1400?°C was only ??2.75%, and its porosity was retained at as high as 67%.