Preparation of mullite by the reaction sintering of kaolinite and alumina

In the present study, mullite specimens and mullite/alumina composites are prepared by reaction sintering kaolinite and alumina at a temperature above 1000°C. The phase and microstructural evolution of the specimens and their mechanical properties are investigated. Primary mullite appears at a temperature around 1200°C. The alumina particles are inert to the formation of primary mullite. Alumina starts to react with the silica in glassy phase to form secondary mullite above 1300°C. The formation of secondary mullite decreases the amount of glassy phase. Furthermore, the addition of alumina reduces the size of mullite grains and their aspect ratio. The strength and toughness of the resulting mullite increase with the increase of alumina content; however, the mechanical properties of the mullite and mullite/alumina composites are lower than those of alumina for their relatively low density.     

Wear behavior and microstructure of alumina-mullite-zirconia composites prepared by a novel method: Coating of zircon powder by aluminum alkoxide

The formation of the mullite phase is the main challenge in the preparation of alumina-mullite-zirconia (AMZ) composites. To overcome this limitation, a novel method based on the coating of zircon powder with aluminum alkoxide was proposed in this study. Reaction sintering of alumina and coated zircon was carried out at 1630 °C for 3 h. The microstructural, physical, mechanical, and tribological properties of samples were compared with the conventional AMZ composites prepared by common mixing of alumina and zircon. The microstructural analysis indicated the higher alumina phase of the sample prepared with the conventional method. On contrary, the samples prepared with the proposed method included higher percentages of mullite phase. In terms of mechanical properties, the conventional AMZ samples performed better. However, due to the beneficial effect of the mullite phase in tribological applications, the samples prepared with this new method show superior wear resistance. Especially, the samples prepared from 30 wt% aluminum alkoxide exhibited the best wear resistance. The delamination and adhesive wear mechanisms govern the wear process.     

Improvement of the mechanical properties of SiC reticulated porous ceramics with optimized three-layered struts for porous media combustion

Silicon carbide reticulated porous ceramics (SiC RPCs) with three-layered struts were fabricated by polymer replica method, followed by infiltrating alumina slurries containing silicon (slurry-Si) and andalusite (slurry-An), respectively. The effects of composition of infiltration slurries on the strut structure, mechanical properties and thermal shock resistance of SiC RPCs were investigated. The results showed that the SiC RPCs infiltrated with slurry-Si and slurry-An exhibited better mechanical properties and thermal shock resistance in comparison with those of alumina slurry infiltration, even obtained the considerable strength at 1300 °C. In slurry-Si, silicon was oxidized into SiO₂ in the temperature range from 1300 °C to 1400 °C and it reacted with Al₂O₃ into mullite phase at 1450 °C. Meantime, the addition of silicon in slurry-Si could reduce SiC oxidation of SiC RPCs during firing process in contrast with alumina slurry. With regard to slurry-An, andalusite started to transform into mullite phase at 1300 °C and the secondary mullitization occurred at 1450 °C. The enhanced mechanical properties and thermal shock resistance of SiC RPCs infiltrated alumina slurries containing silicon and andalusite were attributed to the optimized microstructure and the triangular zone (inner layer of strut) with mullite bonded corundum via reaction sintering. In addition, the generation of residual compressive stress together with better interlocked needle-like mullite led to the crack-deflection in SiC skeleton, thus improving the thermal shock resistance of obtained SiC RPCs.     

Effect of zirconia content on mechanical and thermal properties of mullite–zirconia composite

Abstract

Mullite–zirconia composites were prepared by adding various zirconia contents in the mullite ranging from 0 to 30 wt-% and sintering at 1400–1600°C for 2 h. The phase composition examined by X-ray diffraction showed that mullite was the major phase combined with developed t-ZrO₂ and m-ZrO₂ phase as a function of zirconia content, especially at 1600°C, wherein m-ZrO₂ predominated. Density increased when the zirconia content and sintering temperature were increased ranging from 2·2 to 3·53 g cm^?3. The morphology of mullite grain showed elongated grains, whereas dispersed zirconia showed equiaxed and intergranular grains. Flexural strength was continuously improved by adding zirconia during the sintering temperature ranging from 1400 to 1500°C, whereas flexural strength was initially improved up to 5 wt-% of zirconia addition and deteriorated with more than 5 wt-% of zirconia content during sintering between 1550 and 1600°C. The maximum strength, 190 MPa, was obtained when sintering mullite with 30 wt-% of zirconia content at 1500°C. The degradation of strength at high sintering temperature may be a result from more occurrence of m-ZrO₂ phase. Thermal expansion of sintered specimens indicated linear change and hysteresis loop change. The hysteresis loop obtained with increased zirconia content resulted in the t–m phase transformation. Martensitic start temperature M_s was determined to be 530°C for 15 wt-% zirconia sintered at 1500°C, implying that the t–m phase transformation occurred.     

Porous mullite–ZrO2 composites from reaction sintering of zircon and aluminum

Mullite–zirconia porous bodies were prepared by reaction sintering of zircon and alumina derived from oxidation reaction of Al at sintering temperatures between 1200 and 1600 °C. The results show that the incorporation of TiO₂ improves the oxidation reaction of Al, dissociation of zircon subsequently formation of mullite and zirconia. Composites containing TiO₂ obtain a high tetragonal concentration at 1500 °C, which reduces by increasing sintering temperature to 1600 °C. No tetragonal zirconia phase was detected at 1500 °C in TiO₂-free composites while tetragonal concentration was increased over this temperature. The major oxidation reaction of Al proceeds with a liquid–gas mechanism that is suitable for producing low dense ceramics. In spite of the higher porosity of the composites containing TiO₂, they possess almost the same flexural strength values as obtained from the TiO₂-free composites.     

Phase formation,microstructure development,and mechanical properties of kaolin-based mullite ceramics added with Fe2O3

The effects of Fe₂O₃ on phase evolution, density, microstructural development, and mechanical properties of mullite ceramics from kaolin and alumina were systematically studied. X-ray diffraction results suggested that the ceramics consisted of mullite, sillimanite, and corundum, in the sintering range of 1450°C–1580°C. However, as the sintering was raised to 1580°C, mullite is the main phase with a content of 94%, and the corundum phase content is 5.9%. Simultaneously, high-temperature sintering had a positive effect on the densification of the mullite ceramics, where both the bulk density and flexural strength could be optimized by adjusting the content of Fe₂O₃. It was found that 6 wt% Fe₂O₃ was optimal for the formation of rod-shaped mullite after sintering at 1550°C for 3 h. The sample's maximum bulk density was 2.84 g/cm³, with a flexural strength of 112 MPa. Meanwhile, rod-shaped mullite grains with an aspect ratio of ~9 were formed. As a result, a dense network structure was developed, thus leading to mullite ceramics with excellent mechanical properties. The effect of Fe₂O₃ on the properties might be attributed to the fact that Al³⁺ ions in the [AlO₆] octahedron were replaced by Fe³⁺ ions, resulting in lattice distortion.     

Mechanical properties and microstructures of reaction sintered mullite–zirconia composites in the presence of an additive — dysprosia

Mullite–zirconia composites were prepared from Indian zircon flour and calcined alumina following the reaction sintering route. Zircon flour and calcined alumina with 0–4.5 mol% dysprosium oxide were attrition milled followed by isostatic pressing and sintering at 1400–1650°C for 2 h. Significant densification was achieved after dysprosia addition as an additive. The thermal expansion coefficient values were found to be reduced in the presence of dysprosia. Dysprosia helps in densification by liquid phase formation as well as by stabilisastion in tetragonal zirconia state. The thermo-mechanical and microstructural characteristics of the composites were discussed.     

Low-temperature synthesis of mullite-based ceramics from Moroccan naturally occurring andalusite and marble waste

The present work aims to prepare mullite-based ceramics at low temperature mainly from andalusite and marble byproduct by a solid-state interaction method. Marble powder byproduct was used, in the prospect of waste management, as a sintering aid. The influence of marble powder byproduct (5 wt.%) on the phase formation, microstructure-temperature evolution, densification, and mechanical strength was evaluated by means of XRD, TGA-DTA, and SEM. The results revealed that the andalusite remained present with mullite up to 1400°C, while the addition of 5 wt.% of marble byproduct involved its complete transformation into mullite and a trace of anorthite. The transformation of andalusite into mullite upon the heating in the range 1300–1400°C involved the densification of the matrix body and a significant increase in mechanical strength from 60 to 170 MPa, which promoted its application for refractory materials.     

Effect of heat treatment and zircon addition on the properties of low-cement castables based on recycled alumina grog

In this investigation, low-cement castables were prepared using 70% alumina grog aggregates obtained from crushed alumina brick waste. The aggregates were thermally treated at 1550 °C for 3 h. Four types of low-cement castables were prepared with various types of aggregates (alumina grog with or without thermal treatment) and fillers (with or without zircon addition), and they were evaluated in terms of their physical, thermal, and chemical properties. Microstructural analysis via scanning electron microscopy (SEM) was performed on the castables before and after slag attack. Compared to the other fabricated castables, the thermally treated alumina grog castables with zircon showed better physical properties, such as a higher bulk density, cold crushing strength, and modulus of rupture and a lower apparent porosity and water absorption. In addition, they had a higher positive linear thermal expansion, refractoriness under load, permanent linear change, and hot modulus of rupture. The results of the SEM with energy dispersive X-ray analysis of the prepared castables confirmed that the mullite and anorthite phases were predominant when zircon was not added and the zircon–mullite phase additionally appeared upon the incorporation of zircon. A quantitative elemental analysis via X-ray fluorescence spectroscopy was employed to determine the composition of the castables. X-ray diffraction analysis showed that the alumina grog castables had a high mullite and low anorthite content, and the thermally treated alumina grog had a high anorthite, low mullite, and high zircon content. The improvement in the mechanical and thermo-mechanical properties of the castables with thermally treated alumina grog and added zircon can be attributed to the formation of the zircon–mullite phase with a low mullite phase content.     

The Emergence for Multilamellar Ti–Al–N Solid Solution in Ti/AlN Composites Sintered at Various Temperatures

Nowadays, a variety of coatings such as Ti–Al–N and TiN have been proposed in titanium machining, but few results on fabrication of bulk Ti/AlN composites were reported. Here, we prepared bulk Ti‐60 wt%AlN composites via vacuum hot‐press sintering at 1250°C–1450°C under an applied pressure of 30 MPa for 1 h. With sintering temperature increasing, the mechanical properties of Ti/AlN composites improved and achieved the maximum values when the sintering temperature is 1450°C. SEM detected the multilamellar grains which are confirmed as Ti–Al–N solid solution by XRD and EDS. Finally, microstructure evolution and phase transformation of Ti/AlN composites were illustrated that Al and N atoms diffuse across the grain boundary and react with Ti atoms to form TiN phase and multilamellar Ti–Al–N solid solution. This work is interesting for producing high strength and toughens metal/ceramic composites.     

Mullitization,microstructure and physical properties of mechanically activated andalusite sintered by microwave

In this work, the effects of mechanical activation and microwave heating of andalusite on mullite formation have been investigated. XRD results revealed that andalusite peaks disappeared after 60 h of milling and the peaks of alumina were observed. The formation of mullite from activated and as-received andalusite occurred at 800° and 1250 °C, respectively, while mullitization was completed at 1100° and 1400 °C in the former and latter, respectively. Mullite samples prepared from activated andalusite showed better densification with an elongated morphology.     

Development of AMZ composites via mutual attraction of particles in wet processing

In this paper, three approaches were investigated for preparing alumina-mullite-zirconia (AMZ) composites. The weight ratio of alumina to zircon was selected to be 85/15. In the first approach, common well-known reaction sintering or solid-state mixing of alumina and zircon were used. In the second approach, suspensions of the raw materials were prepared to examine the effect of wet processing method. The third approach was based on the use of aluminum alkoxide coated zircon and alumina. The sintering of samples was carried out at the temperature of 1630°C for 3 hours. Phase composition and Rietveld refinement method, microstructural observation, EDS analysis, as well as physical and mechanical properties were used and determined to characterize the sintered samples. The results showed that aluminum alkoxide coating can develop the mentioned reaction sintering and mullite formation. However, the desired mechanical properties were not obtained. Wet processing approach resulted in more interesting data about the formation of mullite and could improve the microstructure homogeneity of final composites. Higher amount of tetragonal zirconia, good densification, high hardness, and fine microstructure were obtained by the wet approach. These interesting results were attributed to the fine discrete particles provided by mutual attraction in the wet preparation method.     

Chemical,phase and structural change of mullite synthesized during sintering of kaolin

Mullite is of great technological relevance but rarely occurs in nature and as a result different approaches have been adopted in its synthesis from alumina bearing minerals. In this study, chemical, phase and structural change of mullite synthesized from sintering of natural kaolinite clay is investigated. Thoroughly beneficiated kaolinite clay powder was obtained from Nigeria and uniaxially pressed into cylindrical compact of 40 × 30 mm followed by sintering at temperatures of 1200°C and 1300°C, respectively. The chemical composition, microstructure change, phase transformation, and reaction bonding were carried out using EDXRF, SEM, XRD, and FT-IR, respectively, to assess the synthesized mullite. The results showed that a well-dispersed primary mullite phase was obtained which was fully developed at increased temperature of 1300°C. Better mullite phase was also obtained with increasing alumina content at more elevated temperature of 1300°C while Si-O-Al bonding of mullite crystals was also obtained from the FT-IR spectra. However, the needle-shaped mullite structure was not achieved which might be attributed to the sintering temperatures 1200°C-1300°C utilized.     

Manufacture of mullite substrates from andalusite for the development of thin film solar cells

The purpose of this work is the manufacture of dense thin mullite substrates by tape casting of the natural silicate mineral andalusite. The targeted application for such substrates is the manufacture of thin film solar cells. Indeed, in addition to a good resistance at high temperature (up to 1200 °C), this application requires a good correspondence between the thermal expansion coefficient of the substrate and silicon film in order to lower the stresses in the film and in the substrate after cooling. The work was performed in three successive stages. First, the study of the transformation during sintering of andalusite+alumina mixtures. Second, the optimisation of the slurries and of the parameters for tape casting. Finally, green tapes prepared from various powder compositions were characterised before and after sintering. The addition of alumina to andalusite reduces the final amount of vitreous phase. This limits the risk of impurity diffusion in the silicon film. However, the addition of alumina also slows down the sintering process leading to more porosity in the substrates. A good compromise is obtained with an initial mixture of 80 wt.% andalusite with 20 wt.% alumina. In that case, the thermal expansion behaviour is very close to pure mullite and the mechanical properties of the substrates can be considered as sufficient for the targeted application.     

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.     

A Novel Si3N4–SiC Ceramic Used for Volumetric Receivers

Si₃N₄–SiC composite ceramics used for volumetric receivers were fabricated by pressureless sintering of micrometer SiC, Si₃N₄, andalusite, and other minor additions powders. Mechanical, thermal expansion, thermal conductivity, and thermal shock resistance properties were tested at different sintering temperatures. The best sintering temperature of optimum formula A2 is 1360°C, and the bending strength reaches 79.60 Mpa. And moreover, its thermal expansion coefficient is 6.401 × 10^?6/°C, thermal conductivity is 7.83 W/(m K), and no crack occurs even subjected to 30 cycles thermal shock with a bending strength increase rate of 4.72%. X‐ray diffraction results show that the phase constituents of the sintered products mainly consist of SiC, Si₃N₄, mullite, and quartz. Microstructure that is most appropriate and exhibits maximal thermal shock resistance was detected using SEM. The porosity of Si₃N₄–SiC ceramic foam prepared from formula A2 is 95%, which provides a rapid and steady action for the receiver. The evaluation of the present foam shows that Si₃N₄–SiC ceramic composite is a good candidate for volumetric receivers.     

Development of mullite/zirconia composites from a mixture of aluminum dross and zircon

In order to obtain mullite/zirconia composites, mixtures of aluminum dross and zircon were sintered. Aluminum dross was collected and purified by a milling, sieving and washing process. Stoichiometric mixtures of aluminum dross and zircon were sintered at several temperatures (1400, 1450 and 1500 °C) for several periods of time (2, 4 and 6 h). After the purifying treatment the dross contained mainly Al₂O₃, AlN, MgAl₂O₄, SiO₂ and metallic Al. A homogeneous mullite matrix with small zirconia particles was obtained by sintering the aluminum dross–zircon samples at 1500 °C for 6 h.     

Reaction-Bonded Mullite/Zirconia Composites

The feasibility of fabricating dense, low-shrinkage, mullite/ ZrO₂ composites based on the reaction bonding of alumina (RBAO) process and the reaction sintering of zircon is examined. Compacts pressed from an attrition-milled powder mixture of Al, A1₂O₃ and zircon were heated in air according to a two-step heating cycle. The phase evolution and microstructural development during reaction bonding were traced by X-ray diffraction, nuclear magnetic resonance, and scanning electron microscopy on samples extracted from various points along the heating cycle. It is seen that, as in conventional RBAO, AI oxidizes to γ-Al₂O₃ which then transforms to α-AI₂O₃ between 1100° and 1200°C. The zircon dissociation commences at ∼1400°C and is practically complete by 1500°C. Mullite enriched in Al₂O₃ forms initially, but 3:2 stoichiometry is attained in the final product which consists of mullite, t - and m-ZrO₂, and residual α-AI₂O₃. The flexure strength of the composite is superior to that of pure mullite, and ∼80% of the strength is retained up to 1200°C. Although there was no toughness enhancement relative to mullite, this should be achievable by optimizing the fabrication procedure.     

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 Solids Loading on Sintering and Properties of Freeze‐Cast Kaolinite–Silica Porous Composites

Kaolinite–silica nanocomposites with a green porosity ranging from 75% to 87% were prepared using a freeze‐casting technique. The initial solids loading values (kaolinite platelets plus silica nanospheres) greatly influence the sintering behavior as well as the phase and strength of the resulting porous composites. The composites with lower solids loading exhibit faster sintering (e.g., larger shrinkage, more extensive thickening of the pore walls) when sintered at 1250°C, which in turn, results in a rapid increase in flexural strength. All the composites maintain a high porosity (above 50%) after sintering at 1250°C for 72 h, whereas the flexural strength of the composites increases from roughly 0.2 MPa for the green samples to 13.3, 7.5, and 6.5 MPa for 12, 18, and 24 vol% solids samples, respectively, after sintering. It is believed that solids loading affects kaolinite–silica packing during the sol‐to‐gel transition as a minimum amount of silica nanoparticles is required to build the gel network. This particle packing difference influences the amount of kaolinite–silica interfacial contact, which in turn affects the strength. The strength increase through solids loading change is a combined effect of changes in the porous structure during sintering plus the development of a new phase at the silica–kaolinite interface.