Seed assisted in-situ synthesis of porous anorthite/mullite whisker ceramics by foam-freeze casting

Porous anorthite/mullite whisker ceramics with both high strength and low thermal conductivity have been successfully prepared by combining seed-assisted in situ synthesis and foam-freeze casting techniques. The addition of mullite seed was conducive to a reduction in the sintering shrinkage, pore size, and anorthite grain size. This increased the high aspect ratio of mullite whiskers, which enhanced the strength and diminished the thermal conductivity. Mullite whiskers overlapped to form a stable three-dimensional network structure similar to the bird's nest, which was also beneficial to heighten the mechanical properties of the prepared porous ceramics. Through this method, the prepared materials had a high apparent porosity of 87.7–90.2%, a low bulk density of 0.29–0.36 g/cm³, a high compressive strength of 0.65–3.31 MPa, and low thermal conductivity of 0.067–0.112 W/m·K. The results indicated that the method described here can fabricate porous ceramics with excellent properties for further thermal insulating applications.     

Low sintering shrinkage porous mullite ceramics with high strength and low thermal conductivity via foam-gelcasting

Excessive sintering shrinkage leads to severe deformation and cracking, affecting the microstructure and properties of porous ceramics. Therefore, reducing sintering shrinkage and achieving near-net-size forming is one of the effective ways to prepare high-performance porous ceramics. Herein, low-shrinkage porous mullite ceramics were prepared by foam-gelcasting using kyanite as raw material and aluminum fluoride (AlF₃) as additive, through volume expansion from phase transition and gas generated from the reaction. The effects of AlF₃ content on the shrinkage, porosity, compressive strength, and thermal conductivity of mullite-based porous ceramics were investigated. The results showed that with the increase of content, the sintering shrinkage decreased, the porosity increased, and mullite whiskers were produced. Porous mullite ceramics with 30 wt% AlF₃ content exhibited a whisker structure with the lowest shrinkage of 3.5%, porosity of 85.2%, compressive strength of 3.06 ± 0.51 MPa, and thermal conductivity of 0.23 W/(m·K) at room temperature. The temperature difference between the front and back sides of the sample reached 710°C under high temperature fire resistance test. The low sintering shrinkage preparation process effectively reduces the subsequent processing cost, which is significant for the preparation of high-performance porous ceramics.     

Ultra-low cost porous mullite ceramics with excellent dielectric properties and low thermal conductivity fabricated from kaolin for radome applications

Near-net-shape mullite ceramics with high porosity were prepared from ultra-low cost natural aluminosilicate mineral kaolin as raw material and polystyrene micro-sphere (PS) as pore-forming agent. Microstructure, flexural strength, thermal conductivity and dielectric properties of the ceramics were systematically researched. Results show that the porous mullite ceramics possess fibrous skeleton structure formed by a large quantity of interlocked mullite whiskers, which results in good mechanical properties and low-to-zero sintering shrinkage. Flexural strength of the porous mullite ceramics can be up to 41.01 ± 1.12 MPa, even if the porosity is as high as 62.44%. The dielectric constant and loss tangent of the porous mullite ceramics at room temperature are lower than 2.61 and 5.9 × 10⁻³, respectively. Besides, dielectric constant is very stable with the rising of temperature, and the dielectric loss can be consistently lower than 10⁻² when the temperature is not higher than 800 °C. In addition, thermal conductivity at room temperature is as low as 0.163 W/m/K when the porosity of mullite ceramics is 80.05%. The infiltration of SiO₂ aerogels (SiO₂ AGs) can further decrease the thermal conductivity to 0.075 W/m/K, while has just little effects on the dielectric properties. Excellent mechanical, thermal and dielectric properties show that the porous mullite ceramics have potential applications in radome fields. The porous mullite ceramics prepared from kaolin not only have low cost, but also can achieve near-net-shape.     

Preparation and properties of mullite-bonded porous fibrous mullite ceramics by an epoxy resin gel-casting process

Porous fibrous mullite ceramics with a narrow range of pore size distribution have been successfully prepared utilizing a near net-shape epoxy resin gel-casting process by using mullite fibers, Al₂O₃ and SiC as raw materials. The effects of sintering temperatures, different amounts of fibers and Y₂O₃ additive on the phase compositions, linear shrinkage, apparent porosity, bulk density, microstructure, compressive strength and thermal conductivity were investigated. The results indicated that mullite-bonded among fibers were formed in the porous fibrous mullite ceramics with a bird nest pore structure. After determining the sintering temperatures and the amount of fibers, the tailored porous fibrous mullite ceramics had a low linear shrinkage (1.36–3.08%), a high apparent porosity (61.1–71.7%), a relatively high compressive strength (4.4–7.6 MPa), a low thermal conductivity (0.378–0.467 W/m K) and a narrow range of pore size distribution (around 5 µm). The excellent properties will enable the porous ceramics as a promising candidate for the applications of hot gas filters, thermal insulation materials at high temperatures.     

Transient liquid phase diffusion process for porous mullite ceramics with excellent mechanical properties

Porous mullite ceramics were fabricated by the transient liquid phase diffusion process, using quartz and fly-ash floating bead (FABA) particles and corundum fines as starting materials. The effects of sintering temperatures on the evolution of phase composition and microstructure, linear shrinkage, porosity and compressive strength of ceramics were investigated. It is found that a large amount of quartz and FABA particles can be transformed into SiO₂-rich liquid phase during the sintering process, and the liquid phase is transient in the Al₂O₃-SiO₂ system, which can accelerate the mullitization rate and promote the growth of mullite grains. A large number of closed pores in the mullite ceramics are formed due to the transient liquid phase diffusion at elevated temperatures. The porous mullite ceramics with high closed porosity (about 30%) and excellent compressive strength (maximum 105?MPa) have been obtained after fried at 1700?°C.     

Fabrication and properties of mullite fiber matrix porous ceramics by a TBA-based gel-casting process

A bird nest-like structure was designed by using the mullite fiber as the matrix and SiO₂ as the high temperature binder. This special material was successfully prepared by a TBA-based gel-casting process. The randomly arranged fiber laps bonded by SiO₂ binder was the most important structure characteristic of this porous material. The effect of sintering temperature on the properties, i.e. porosity, bulk density, linear shrinkage, compressive strength, thermal conductivity and the microstructure was studied. The composite exhibited significant pseudoductility. The fracture mechanism of this composite under compression was discussed. The results indicated that the sintering temperature ranging from 1500 to 1600 °C was suitable for yielding mullite fiber matrix porous ceramics which had a low thermal conductivity (0.19–0.22 W/m K), a relatively high compressive strength (3–13 MPa) and a high resilience (66–70%) for applications in the thermal insulators and high-temperature elastic seal field.     

In situ formation of mullite strengthened SiC porous ceramics via gelcasting with high strength and good alkali resistance

Mullite-bonded porous SiC ceramics sintered in air by gelcasting are still challenges due to the high porosity induced severe oxidation of SiC, which results in the formation of large amount of detrimental cristobalite phase. Here in this work, small amounts of Y₂O₃ and CaF₂ were added in SiC and Al(OH)₃ raw materials as sintering additives for the in situ growth of mullite reinforcement. This additive system promoted the reaction between oxidation-derived SiO₂ from SiC and Al₂O₃ decomposed from Al(OH)₃ to mullite phase. Almost no cristobalite phase was detected when sintered at 1450℃/2 h with CaF₂ addition of more than 2.0 wt%. Mullite whisker reinforcement was in situ formed due to the gas reaction mechanism caused by CaF₂ addition. Thus obtained porous SiC ceramics exhibited a flexural strength of 67.6 MPa at porosity of 41.3%, which maintained exceeding 36 MPa after 8 h corrosion in 10 wt% NaOH 80℃ solution, being the best performance up to now. This high performance of porous SiC was attributed to the additive induces proper phase control and in situ formation of whisker-like mullite reinforcement.     

Fabrication and properties of porous anorthite/mullite ceramics with both high porosity and high strength

Porous anorthite/mullite ceramics with both high porosity and high strength have been successfully fabricated by foam-gelcasting and pressureless sintering technology, using α-Al₂O₃, SiO₂, and CaCO₃ as starting materials and MnO₂ as sintering aids. The porous mullite ceramics prepared in this study had 83.3% porosity and 0.3 W/m·K thermal conductivity, exhibited compressive strength value as high as 6.1 MPa. The samples fabricated with mullite content of 30 mol% possessed 79.4% porosity and 5.9 MPa compressive strength showed thermal conductivity as low as 0.19 W/m·K. With the addition of MnO₂, the properties of the prepared materials varied slightly when mullite content changed in a large scale. The results showed that the addition of MnO₂ promoted the reaction, affected sintering and grain growth, and contributed to high strength and low-thermal conductivity.     

Preparation of self-reinforcement of porous mullite ceramics through in situ synthesis of mullite whisker in flyash body

Self-reinforced porous mullite ceramics were fabricated by a starch consolidation method with flyash, different aluminium sources (Al(OH)₃ and Al₂O₃) and the additive AlF₃ as raw materials. The reinforcement mechanism of needle-like mullite whiskers through in situ synthesis in ceramic body was investigated. The bulk density, apparent porosity and bending strength of the samples were tested. Phase compositions and microstructures of the sintered samples were measured by XRD and SEM, respectively. It showed that AlF₃ as additive was helpful to the formation of mullite whiskers at a low temperature. As the aluminium sources, Al(OH)₃ was more suitable for the preparation of mullite whiskers than Al₂O₃. The in situ synthesized mullite whiskers formed an interlocking structure, which enhanced the mechanical strength of the porous mullite ceramics. Porous mullite ceramics with bending strength of about 100 MPa and apparent porosity of about 55% were made at 1550 °C.     

Effect of mullite phase formed in situ on pore structure and properties of high-purity mullite fibrous ceramics

Porous mullite ceramics are potential advanced thermal insulating materials. Pore structure and purity are the main factors that affect properties of these ceramics. In this study, high performance porous mullite ceramics were prepared via aqueous gel-casting using mullite fibers and kaolin as the raw materials and ρ-Al₂O₃ as the gelling agent. Effects of addition of mullite fibers on the pore structure and properties were examined. The results indicated that mullite phase in situ formed by kaolin, and ρ-Al₂O₃ ensured the purity of mullite samples and mullite fibers bonded together to form a nest-like structure, greatly improving the properties of ceramic samples. In particular, the apparent porosity of mullite samples reached 73.6%. In the presence of 75% of mullite fibers, the thermal conductivity was only 0.289 W/m K at room temperature. Moreover, the mullite samples possessed relatively high cold compressive strength in the range of 4.9–9.6 MPa. Therefore, porous mullite ceramics prepared via aqueous gel-casting could be used for wide applications in thermal insulation materials, attributing to the excellent properties such as high cold compressive strength and low thermal conductivity.     

Porous mullite ceramics with enhanced compressive strength from fly ash-based ceramic microspheres: Facile synthesis,structure, and performance

Porous mullite ceramics are widely used in heat insulation owing to their high temperature and corrosion resistant properties. Reducing the thermal conductivity by increasing porosity, while ensuring a high compressive strength, is vital for the synthesis of high-strength and lightweight porous mullite ceramics. In this study, ceramic microspheres are initially prepared from pre-treated high-alumina fly ash by spray drying, and then used to successfully prepare porous mullite ceramics with enhanced compressive strength via a simple direct stacking and sintering approach. The influence of sintering temperature and time on the microstructure and properties of porous mullite ceramics was evaluated, and the corresponding formation mechanism was elucidated. Results show that the porous mullite ceramics, calcined at 1550 °C for 3 h, possess a porosity of 47%, compressive strength of 31.4 MPa, and thermal conductivity of 0.775 W/(m?K) (at 25 °C), similar to mullite ceramics prepared from pure raw materials. The uniform pore size distribution and sintered neck between the microspheres contribute to the high compressive strength of mullite ceramics, while maintaining high porosity.     

High-strength thermal insulating mullite nanofibrous porous ceramics

Mullite fibrous porous ceramics is one of the most commonly used high temperature insulation materials. However, how to improve the strength of the mullite fibrous porous ceramics dramatically under the premise of no sacrificing the low sample density has always been a difficult scientific problem. In this study, the strategy of using mullite nanofibers to replace the mullite micron-fibers was proposed to fabricate the mullite nanofibrous porous ceramics by the gel-casting method. Results show that mullite nanofibrous porous ceramics present a much higher compressive strength (0.837 MPa) than that of mullite micron-fibrous porous ceramics (0.515 MPa) even when the density of the mullite nanofibrous porous ceramics (0.202 g/cm³) is only around three quarters of that of the mullite micron-fibrous porous ceramics (0.266 g/cm³). The obtained materials that present the best combination of mechanical and thermal properties can be regarded as potential high-temperature thermal insulators in various thermal protection systems.     

Recycling of waste red mud for fabrication of SiC/mullite composite porous ceramics

SiC/mullite composite porous ceramics were fabricated from recycled solid red mud (RM) waste. The porous ceramics were formed using a graphite pore forming agent, RM, Al(OH)₃ and SiC in the presence of catalysts. The influence of firing temperature and the pore-forming agent content on the mechanical performance, porosity and the microstructure of the porous SiC ceramics were investigated. Optimal preparation condition were determined by some testing. The results indicated that the flexural strength of specimens increased as a function of firing temperature and a reduction in graphite content, which concomitantly decreased porosity. The ceramic prepared under optimal conditions having 15?wt% graphite and sintered at 1350?°C, demonstrated excellent performance. Under optimal preparation conditions the flexural strength and porosity of the ceramic were 49.4?MPa and 31.4%, respectively. Scanning electron microscopy observation result showed that rod-shape mullite grains endowed the samples with high flexural strength and porosity. X-ray diffraction analysis indicated that the main crystallization phases of the porous ceramics were 6H-SiC, mullite, cristobalite and alumina. This work demonstrates that RM can be sucessfully reused as a new raw material for SiC/mullite composite porous ceramics.     

Preparation and characterization of mullite microspheres based porous ceramics with enhancement of in-situ mullite whiskers

High-strength insulating ceramic materials were prepared using lightweight mullite microspheres with dense surfaces and high internal porosity as the main raw material and silica sol as a binder. The effects of AlF₃·3H₂O content on the in situ formation and growth of mullite whiskers were analyzed by X-ray diffraction and scanning electron microscopy. The obtained results showed that mullite whiskers were formed in large quantities at 1200 °C using AlF₃·3H₂O and V₂O₅ as additives; their optimal growth was observed at 4 wt% AlF₃·3H₂O and 1 wt% V₂O₅. The apparent porosity of the produced specimens was 39%; the MOR and CCS of the specimens were 31 and 152 MPa, respectively; the HMOR at 1300 °C was 11.32 MPa; and the thermal conductivity at 900 °C was 0.783 W m⁻¹ K⁻¹. The staggered whisker network structure formed between mullite microspheres not only improved the mechanical properties of the material, but also refined its pore size, reduced the thermal conductivity, and enhanced the thermal insulation properties.     

Synthesis of hierarchically porous mullite ceramics with improved thermal insulation via foam-gelcasting combined with pore former addition

ABSTRACT

To further improve the thermal insulation performance of porous mullite ceramics used in important industrial sectors, a combined foam-gelcasting and pore-former addition approach was investigated in this work, by which hierarchical porous mullite ceramics with excellent properties, in particular, thermal insulation property, were prepared. Both mesopores (2–50?nm) and macropores (117.8–202.7?μm) were formed in porous mullite ceramics resultant from 2?h firing at 1300°C with various amounts of submicron-sized CaCO₃ pore former. The former mainly arose from the decomposition of CaCO₃, and the latter from the foam-gelcasting process. The porous samples prepared with CaCO₃ addition had low linear shrinkage of 2.35–4.83%, high porosity of 72.98–79.07% and high compressive strength of 5.52–14.82?MPa. Most importantly, they also exhibited a very low thermal-conductivity, e.g. 0.114?W?m^?1?K^?1 at 200°C, which was much lower than in the cases of their counterparts prepared via the conventional foam-gelcasting route.     

High-toughness mullite ceramics fabricated by hot-press sintering of pyrophyllite and AlOOH at low temperatures

High-toughness mullite ceramics were fabricated through hot-press sintering (HPS) of pyrophyllite and AlOOH, which were wet-milled and well mixed using a planetary ball mill. The impacts of sintering temperatures and contents of AlOOH on mullite phase formation, densification, microstructure and mechanical properties in ceramic materials were investigated through XRD, SEM and mechanical properties determination. The results indicated that high-toughness mullite ceramics could be successfully prepared by HPS at temperatures higher than 1200°C for 120 min. Increasing the sintering temperature from 1000 to 1300°C significantly enhanced the flexural strength and fracture toughness of samples. The highest flexural strength of 297.97±25.32 MPa and fracture toughness of 4.64±0.11 MPa⋅m^1/2 were obtained for samples sintered at 1300°C. Further increase of temperature to 1400°C resulted in slight decrease of flexural strength and fracture toughness. Compared with the mullite ceramics prepared only using pyrophyllite as raw material, incorporation of AlOOH into raw material significantly increased the mechanical properties of final mullite ceramics. And stoichiometric AlOOH and pyrophyllite as starting material gave the best performance in fracture toughness. The high-toughness of mullite ceramics were ascribed to the high mullite phase content, fine mullite whiskers and in situ formed, intertwined three-dimensional network structure obtained through HPS at a low temperature of 1300°C.     

Preparation of novel reticulated prickly porous ceramics with mullite whiskers

Porous materials are widely used in heat exchangers, sewage treatment, electromagnetic shielding, thermal insulation, gas adsorption, photocatalytic due to their high specific surface area. The specific surface area of materials plays a pivotal role in them. It can be enhanced by increasing the porosity of the material, but the cost of this improvement is reducing the strength of the material. In order to improve performance, it is necessary to increase its surface area without reducing the strength of the material. In this work, mullite porous ceramics with mullite whisker on the inside and outside surfaces structures, which known as prickly porous ceramics(PPCs). They were fabricated using polyurethane foam coated with slurries as the pore-forming agents, sintered after secondary impregnation with silica sol and ammonium fluoroaluminate. The the sintering temperature as well as slurry composition of secondary impregnation were tuned to tailor the strength and surface structures of the PPCs. In addition, the potential of PPCs as high-temperature catalyst supports was demonstrated. Overall, the PPCs demonstrated large surface areas and high mechanical strength. This study paved the way for the fabrication of high-performance porous ceramics.     

Preparation study for the low thermal expansion spodumene/mullite composites

In this work, spodumene/mullite ceramics with low thermal expansion were successfully prepared from spodumene, quartz, talc, and clay. The effects of spodumene content and sintering temperature on the mechanical properties of spodumene/mullite ceramics were investigated. The formed phases were then detected by X-ray diffraction analysis and the microstructures of the sintered bodies were determined by scanning electron microscopy. The interaction effects of the spodumene content and sintering temperature on the apparent porosity and bulk density were studied by response surface methodology. The results demonstrate that an appropriate sintering temperature and spodumene content can promote densification, improve the mechanical properties, and reduce the coefficient of thermal expansion (CTE) of spodumene/mullite ceramics. At the spodumene content of 40 wt.%, the sintering temperature of 1270°C, and the holding time of 90 min, the bending strength was 60.45 MPa, the CTE was 1.73 × 10^–6/°C (α_{[25–650°C]} < 2 × 10^–6/°C), the bulk density was 2.28 g cm^-3, and the apparent porosity was 0.43%. Therefore, this study was of guiding significance for reducing the production cost of spodumene low thermal expansion ceramics and improving product quality.     

Porous YSZ Ceramics Reinforced by Different Kinds of Fibers

Porous YSZ ceramics reinforced by different fibers were prepared by gel‐casting with 15% solid content and pressureless sintering. The four kinds of fibers (mullite, aluminosilicate, Al₂O₃, and YSZ fibers) were added into the YSZ ceramics with the same 10% vol content. After sintered at 1500°C for 2 h, aluminosilicate and mullite fibers could not be found in the samples of porous YSZ ceramics, which showed they reacted with YSZ ceramics at high temperature, while YSZ and Al₂O₃ fibers still kept perfect after sintering. Furthermore, the influences of fiber content, sintering temperature, porosity of matrix materials on compressive strength and porosity of the porous YSZ ceramics were studied. The results showed that Al₂O₃ fiber showed more obvious reinforcing effect than YSZ fiber on porous YSZ ceramics. The fiber‐reinforcing effects depend on fiber content, sintering temperature, and porosity of matrix materials. The fiber addition can improve the shrinkage behavior of porous ceramics during sintering and strengthen the skeleton of porous ceramics.     

Effects of holding time on structure and the properties of spodumene/mullite composite ceramics

In this paper, spodumene/mullite ceramics with good thermal shock resistance were prepared from spodumene, quartz, talc, and clay when the sintering temperature was 1270℃. In the sintering process, the effect of holding time on densification, mechanical properties, phase transformation, microstructure, and thermal shock resistance of the composite ceramics were investigated. The phase transition and microstructures of the ceramics were identified via X-ray diffraction (XRD) and scanning electron microscopy (SEM). The interaction between holding time and bulk density was studied by response surface methodology. The result show that an appropriate holding time can improve the mechanical properties of spodumene/mullite ceramics. When the holding time was kept 90 min, the spodumene/mullite ceramics with the apparent porosity was .47%, the bulk density was 2.28 g/cm³, and bending strength was 63.46 MPa. Furthermore, since no cracks formed after 20 thermal shock cycles for the composite ceramics with a bending strength decreasing rate of 12.66%, it is revealed that spodumene/mullite ceramics exhibit good thermal shock resistance. Therefore, this study can provide beneficial guidance for both industrial production and energy conservation.