Effect of the calcined andalusite aggregates on the micro-crack formation and thermal shock resistance of mullite castables

The effect of calcined andalusite aggregates on the micro-crack formation and thermal shock resistance of mullite castables was investigated and analyzed. The mullite castables were prepared from andalusite aggregates calcined at high temperatures. The results show that the micro-cracks from the transformation of andalusite to mullite can effectively relieve thermal stress, improving the thermal shock resistance of mullite castables. The micro-cracks generated decreased with increasing calcine temperatures of the andalusite aggregates. When the calcine temperature was increased from 1300 °C to 1500 °C, the thermal shock resistance of mullite castables was found to continuously increase. However, the thermal shock resistance of mullite castables with the andalusite aggregates calcined at 1600 °C is lower than those with the andalusite aggregates calcined at 1500 °C.     

Optimized microstructure with nano-alumina and its effects on properties of corundum spinel castables

The mechanical properties, thermal shock resistance, and microstructure evolution of corundum spinel castables with different nano-alumina contents were investigated. The results show that the addition of nano-alumina has advantages on the microstructure evolution and properties of castables. An optimum nano-alumina amount is 2 wt%. When nano-alumina addition changes from 0 to 2 wt%, the cold modulus of rupture (CMOR) and cold compressive strength (CCS) improved by 69.7% and 78.1% after firing at 1100°C, respectively. The CMOR and CCS increased by 42.5% and 35.2% after firing at 1500°C, respectively. Meanwhile, the hot modulus of rupture (HMOR) was enhanced by 21.5% to 13.4 MPa. The retained Young's modulus values of castables were improved from 49.6% to 59.6% after eight thermal shock cycles. Furthermore, the HMOR and the retained Young's modulus values of castables slightly reduced when nano-alumina content up to 3 wt%. XRD, DSC, SEM, and EDS analyses revealed that the addition of nano-alumina leads to the formation of calcium dialuminate (CaO·2Al₂O₃) at 1100°C and it is beneficial to the formation of more platelet hibonite (CaO·6Al₂O₃) at 1500°C. As a result of using nano-alumina with large surface area, the solid phase sintering of the nanoscale particles can occur at lower temperatures. Moreover, the mechanical properties and thermal shock resistance of the castables were improved remarkably.     

Microstructure and reactivity evolution of colloidal silica binder in different systems at elevated temperatures

Colloidal silica as nanostructured binder for refractory castables has attracted many attentions in recent years. In the present study, phase composition, microstructure and reactivity evolution of silica gel at different heating conditions were investigated to find suitable system for colloidal silica application. The results showed that atmosphere and carbon slightly affected phase composition of the silica gel at elevated temperatures, and the crystalline phases were composed of major α-cristobalite and minor α-tridymite. The morphology and particle size of the silica gel were greatly affected by atmosphere and carbon during heating. The spherical nano-silica particles with sizes of 40–50 nm rapidly grew into macroscale rod-like particles with temperature increasing from 800-1000 °C to above 1200 °C in air, and sintering of silica particles was observed. However, the size and morphology of the spherical nano-silica particles retained at high temperature in a reducing atmosphere, and many well developed columnar mullite crystals and some SiC whiskers formed on heating silica gel, alumina fines and carbon at 1500 °C, which was due to carbon inclusions retarding the growth of nano-silica particles and the nano silica remained high reactivity at high temperature. Thus, colloidal silica was suitable for application in carbon-containing refractory castables.     

Effects of curing time on the pore structure evolution and fracture behavior of CAC bonded alumina-spinel castables

The present work investigated the pore structure evolution and fracture behavior of calcium aluminate cement (CAC)-bonded alumina-spinel castables treated at 110 and 1600 °C after curing at 25 °C for 1 day and 3 days. The pore structure and fracture behavior were characterized by mercury intrusion combined with micro-CT scanning and a wedge splitting test coupled with acoustic emission, respectively. The results showed that the hydration degree was enhanced by extending the curing time, and more hydrates were conducive to the generation of complex pore structures after drying. In comparison, the heat treatment at 1600 °C resulted in a substantial reduction in nano-sized pores, the 3 d sample obtained developed and complex micro-sized pores than 1 d sample. Therefore, specimens cured for 3 d had better hot modulus of rupture (HMOR) and thermal shock resistance compared to those cured for 1 d, which could be attributed to the induced tortuous microcrack propagation within the matrix and along the aggregate-matrix interfaces.     

Properties of silica sol bonded corundum‐spinel castables for steel ladles

In order to overcome the shortcoming of the calcium aluminate cement (CAC) bonded castables, we prepared corundum‐spinel castables using silica sol as binder and tabular corundum, sintered magnesia‐alumina spinel, and reactive alumina as raw materials in this study. The effect of spinel grain size and solid content of silica sol on the flow value, sintering, mechanical strength and microstructure of the specimens treated at varying temperature of 400, 1000, 1500, and 1650°C for 5 hours in an air atmosphere were studied by SEM and EDS analyses. The results indicate that silica sol is suitable as a binder for corundum‐spinel systems. And silica sol with solid content of 25% bonded samples containing ≤90 μm spinel perform quite better than the others. At the same time, silica sol bonded samples had high strength in medium temperature. This is because that the closer proximity of silica sol and alumina powder and the high activity of nanometer SiO₂ in silica sol are beneficial for the reaction of SiO₂ and Al₂O₃ to generate mullite needed for reinforcement of castables matrix.     

B4C mineralizing role for mullite generation in Al2O3-SiO2 refractory castables

Based on refractory end-users’ requirements, continuous efforts have been made to design engineered products able to withstand high temperatures (800–1500 °C) and severe thermal gradients. One alternative to enhance the mechanical properties of alumina-based compositions consists of inducing in situ generation of phases with platelet or acicular shape within their matrix fraction, which may improve crack deflection and grain bridging mechanisms. Mullite and Al₁₈B₄O₃₃ are some compounds that present such interesting features. Thus, this work addresses the evaluation of alumina refractory castables bonded with SioxX-Zero and/or microsilica, containing 0 or 1 wt% of B₄C (sintering additive), aiming to: (i) induce transient liquid sintering, (ii) point out which silica source could favor a more effective mullite formation at high temperatures, and (iii) analyze the influence of B₄C in the phase transformation and thermo-mechanical properties of the designed compositions. Comparing SioxX-Zero and microsilica-bonded refractories, the latter showed more likelihood to give rise to the mullite phase during the samples’ thermal treatments. Moreover, adding B₄C to the castables containing 3 wt% of SiO₂ induced the generation of a boron-rich liquid phase with transient features during the samples’ firing step, favoring earlier sintering and faster mullite and Al₁₈B₄O₃₃ formation. These transformations resulted in refractories with enhanced creep, thermal shock resistance and HMOR behavior in a broader temperature range (600–1550 °C), which may enable them to be used in various industrial applications (petrochemical, steel-making, etc.).     

Mechanical properties of refractory castables bonded with hydratable magnesium carboxylate-boric acid

Hydratable magnesium carboxylate (HMC), which is similar to the properties of cement, can be used as a potential binder for refractory castables. However, its decomposition may lead to poor mechanical properties at medium temperatures (300 °C–1100 °C). This work investigated the effects of boric acid on the mechanical properties and microstructural evolution of castables bonded with hydratable magnesium carboxylate. The mechanical strength, bulk density, apparent porosity, thermal shock resistance, and sintering properties of the castables were evaluated. The results showed that the mechanical properties of HMC-bonded castables (HMCC) at various temperatures can be improved by adding boric acid. Boric acid reacts with HMC to form magnesium carboxylate borate ester (MCBE), which improves the bonding strength between HMC molecules. Thus, the cold modulus of rupture of HMCC containing boric acid dried at 110 °C are higher than that of calcium aluminate cement-bonded refractory castables (CACC). The decomposition temperature of MCBE is 77 °C higher than that of HMC, so MCBE can endow castables with better mechanical properties at 110 °C–500 °C. The B₄C obtained by MCBE pyrolysis could form a boron-rich liquid phase, which can accelerate the structural densification of castables via transient liquid phase sintering, thus improving the mechanical properties of castables at 500 °C–1100 °C. Moreover, boric acid can improve the thermal shock resistance of HMCC. The residual strength rate first increases and then decreases with an increasing boric acid, and reaches a maximum value of 29.7% (1 wt% boric acid is added), which is 2.3 times that of the CACC. The nanoindentation test showed that the microcracks in the matrix of 1 wt% boric acid castables are easy to initiate but difficult to propagate, so the microcracks are many and wavy.     

Effect of microsilica addition on the properties of colloidal silica bonded bauxite-andalusite based castables

Colloidal silica bonded bauxite-andalusite based castables were prepared using homogenized bauxite and andalusite as aggregates, andalusite fines, corundum fines, ultrafine Al₂O₃ as matrixes and colloidal silica as binders. Effects of microsilica addition on the green strength, physical properties, hot strength and thermal shock resistance of castables were investigated. Moreover, phase composition and morphological evolution of specimens were characterized by XRD and SEM analysis. Green strength after demoulding, cold strength and hot strength as well as thermal shock resistance of the castables are enhanced with microsilica addition, which attribute to generating more chemical bond (–Si–O–Si–) after demoulding and heating at intermediate temperature (up to 1100 °C), and creating a stronger mullite bonding at higher temperature (1400 °C) compare to the specimens without microsilica.     

Preparation and properties of porous mullite-based ceramics fabricated by solid state reaction

In this study, the effect of the alumina particle size on the formation of mullite using a silica gel powder and micro- and nano-scale Al₂O₃ powders as raw materials was investigated. The optimized Al₂O₃ source was then reacted with the silica gel to prepare porous mullite-based ceramics. The results revealed that the highly reactive nano-Al₂O₃ powder could form mullite at a relatively low firing temperature. Therefore, the nano-Al₂O₃ powder was used to prepare porous mullite-based ceramics by firing at 1600 °C, 1650 °C and 1700 °C. The pore size of the prepared porous mullite-based ceramics ranges from tens to hundreds of micrometres, with the apparent porosity being 42.8–58.0%. Further, the mullite content in the samples increased with increasing firing temperature, and a higher firing temperature promoted sintering, resulting in improved strength of the sample. After calcination at 1700 °C, the mullite content in the sample reached 81.8%, and the sample showed excellent thermal shock resistance. The strengths of the samples before and after thermal shock were found to be 23.6 and 15.58 MPa, with the residual strength ratio being 66%.     

Low Temperature Synthesis of High Alumina Cements by Novel Co‐Melt Precursors and Their Implementation as Castables with Some Micro Fine Additives

In the present investigations nano size high alumina cements (HAC) were prepared by very effective co‐melt precursor sintering technique from their metal nitrate precursors. The prime cementing phases observed were CA, CA₂, and C₁₂A₇. The addition of nano structured cements in refractory castables has improved the thermo‐chemical‐mechanical properties to a significant extent. Each batch of low cement castables (LCC) was prepared from calcined Chinese bauxite, HAC, and superfine additives. The effect of HAC in bauxite castable with the additives similar to Silicon Carbide, reactive alumina, and micro‐fine silica on the sinterability and properties of these castables was investigated. Physical properties such as apparent porosity and bulk density, mechanical properties such as hot modulus of rupture (HMOR), cold and hot modulus of rupture (CMOR), and cold crushing strength (CCS) of hydrated and sintered castables were studied. The sintered castables were also characterized for their solid phase compositions and microstructure using X‐ray diffraction (XRD) and FE‐SEM, respectively. In the castables new phases such as mullite, α‐alumina were formed at the expense of bauxite and silica. Solid solution of mullite formed at high temperature acts as a bonding phase and is accounted for high HMOR, CMOR, and CCS values. These excellent properties of such castables may enable their uses in various applications such as refractory lining for fabrication of steel, aluminium, copper, glass, cement, chemicals, and ceramics.     

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.     

Recycling of aluminum dross and silica fume wastes for production of mullite-containing ceramics: Powder preparation,sinterability and properties

The improper disposal of industrial wastes causes environmental pollution so their recycling for fabrication of new products became an interesting research issue. In this work, sintered mullite-containing ceramics were prepared from aluminum dross and silica fume (up to 40 wt%) waste materials after sintering up to 1500 °C. Before sintering, the starting waste materials were converted into nano powders by mechanical milling alloying method up to 15 h. The obtained waste nano powders were investigated using different techniques as X-ray diffraction (XRD), transmission electron microscope (TEM) and scanning electron microscope (SEM). On the other hand, phase identification by XRD, physical properties determination (bulk density and apparent porosity), microstructure by SEM, mechanical and electrical properties of sintered bodies were investigated. The results revealed that mullite phase was formed in higher amounts with increasing both sintering temperature (1500 °C) and silica fume content. At 1300 °C, amorphous mullite was formed in addition to the alumina phase. It is also noted that the apparent porosity and bulk density were reduced with increasing silica content. However, they exhibited opposite trend when the temperature increased from 1300 into 1500 °C. Moreover, with increasing the mullite content, the microhardness, compressive strength, Younges modulus and electrical conductivity were decreased and reached 10.2 GPa, 216.9 MPa, 119.7 GPa and 4.9 × 10 ^?12 S/m, respectively, for the sample that contained higher amount of mullite, while the fracture toughness was improved and reached to 3.44 MPa m^0.5.     

Effect of spinel content on hot strength of alumina-spinel castables in the temperature range 1000–1500°C

Hot modulus of rupture of Al₂O₃-spinel castables containing 5–15 wt% alumina-rich magnesia alumina spinel and 1·7 wt% CaO generally increases with increase in spinel content and temperature from 1000 to 1500°C. The magnitudes of hot modulus of rupture of castables containing 15 wt% spinel and 1·7 wt% CaO are 14·3 MPa at 1400°C and 15·6 MPa at 1500°C, while those of castables containing 20 wt% spinel and 1·7 wt% CaO are 12·5 MPa at 1400°C and 14·7 MPa at 1500°C. The former castables contained 15 wt% spinel of −75 μm size, while the latter contained 10 wt% spinel of +75 μm size and another 10 wt% spinel of −75 μm size. The bond linkage between the CA₆ and spinel grains in the matrix is believed to cause both the spinel content and temperature dependence of hot strength of Al₂O₃-spinel castables, as well as fine grain spinel even in amount less than coarser grain spinel to be more effective for enhancing hot strength. The trend of the magnitude of thermal expansion under load (0·2 MPa) above 1500°C of the castables is not necessarily indicative of the magnitude of hot modulus of rupture at 1400 or 1500°C. ©     

Effect of carbon black on corrosion resistance of Al2O3–SiC–C castables to SiO2–MgO slag

Metallurgical solid waste recycling is the shape of things to come in green development of Chinese iron and steel industry. Utilization of ironworks slag for producing mineral wool at high temperature is an important approach. However, refractory lining is seriously corroded by the SiO₂–MgO based slag at 1600 °C during the production process. Different production steps need different atmospheres, the changeable service atmospheres (air and reducing atmosphere) put forward high requirements for slag resistance. The Al₂O₃–SiC–C castables containing carbon black are usually used in iron runner, which faces high-temperature service condition of 1450 °C–1500 °C. Nevertheless, the function of carbon black in the Al₂O₃–SiC–C castables at 1600 °C is till essentially unknown. In the current study, the carbon black was introduced to tabular alumina based Al₂O₃–SiC–C castables to improve corrosion resistance to SiO₂–MgO based slag at 1600 °C. The result showed that 0.4 wt% carbon black was suitable for the castables, which the slag resistance of castables was significantly improved. The carbon black had contributed to block slag by wettability resistance. By comparison with the castables without carbon black, the corrosion index and penetration index had been reduced by 20.2% and 28.0%, respectively, under air atmosphere. And there were little corrosion or penetration under reducing atmosphere for castables with 0.4 wt% carbon black. For the mechanical properties, the Al₂O₃–SiC–C castables with 0.4 wt% carbon black could serve production process although the carbon black impaired the physical properties.     

Effect of zirconia particle size on the properties of alumina-spinel castables

The industrial application of alumina-spinel refractory castables has crucial requirements on the service performance. Thus, the effects of different sized desilicated zirconia particles on the castables microstructure, thermal-mechanical properties and high temperature elastic modulus have been investigated. The zirconia particle sizes were varied from 1000 µm to 2.5 µm (d₅₀). It was observed that the finer (below 88 µm) zirconia particles were beneficial to improve the cold modulus of rupture (CMOR) and the hot modulus of rupture (HMOR), but could not effectively enhance the thermal shock resistance. Fine zirconia particles can homogeneously disperse in the matrix and significantly promote the sintering process. Accompanied with the phase transformation of zirconia, both the high density of matrix cracks and the strong ceramic bonding (between the coarse grains and the matrix) were found in the refractory castables, which was responsible for an increase of CMOR. However, the binding characteristic could also give rise to the high stored elastic energy that was adverse to the thermal shock resistance, and the excessive amount of preexisting matrix cracks could induce more microdamage during the thermal shock. Additionally, it was proposed that the second-phase dispersion reinforcement and the highly ceramics bonding resulted in the superior HMOR when introducing fine ZrO₂ particles.     

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.     

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.     

Influences of quartz and muscovite on the formation of mullite from kaolinite

A kaolin containing muscovite and quartz (K-SZ) and a pure kaolin (K-SX) with the addition of potassium feldspar, K₂SO₄ and quartz, respectively, were used to investigate the influences of muscovite and quartz on the formation of mullite from kaolinite in the temperature range 1000–1500 °C. In K-SZ formation of mullite began at 1100 °C, and in K-SX at 1000 °C. In K-SZ quartz accelerated the formation of cristobalite and restrained the reaction of mullite and silica. Muscovite in K-SZ acted as a fluxing agent for silica and mullite before 1400 °C and accelerated the formation of cristobalite. The FTIR band at 896.8 cm^− 1 was used to monitor the formation of orthorhombic mullite.     

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.     

Influence of bonding phases on properties of in-situ bonded porous SiC membrane supports

Porous SiC ceramic membrane supports are widely employed in a wide variety of high-temperature applications, such as hot flue gas filtration, porous burners and molten metal filters. Herein, SiC supports, with a porosity of ~37%, were prepared by using low-temperature bonding techniques and the influence of different bonding phases, such as mullite, cordierite and glass, on ambient-temperature flexural strength, hot modulus of rupture (HMOR), thermal shock resistance and oxidation resistance were systematically investigated. The results reveal that the glass-bonded SiC (GBSC) support exhibited the highest ambient-temperature flexural strength of 33.6 MPa, whereas the flexural strength of mullite-bonded SiC (MBSC) and cordierite-bonded SiC (CBSC) supports ranged from 22 to 25 MPa. However, the presence of glass phase deteriorated the high-temperature properties of the support. MBSC support rendered superior mechanical strength at high temperature and self-strengthening in a certain temperature range, such as HMOR improved 47.5% at 900 °C, but HMOR of glass-bonded support was only 57.4% of the ambient-temperature strength. Moreover, MBSC and CBSC supports exhibited better thermal shock resistance than GBSC supports and the critical temperature difference of water quenching for MBSC supports was ~200 °C higher than GBSC supports. In addition, MBSC support rendered superior oxidation resistance and exhibited a weight gain rate of ~0.1% at 1150 °C for 24 h, which is 54.4% and 42.2% lower than CBSC and GBSC supports, respectively.