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 and characteristics of porous anorthite ceramics with high porosity and high-temperature strength

High-temperature properties including compressive strength, thermal shock behavior, and thermal conductivity of porous anorthite ceramics with high specific strength were tested and analyzed. The results showed that the prepared materials merit high-temperature compressive strength, thermal stability, and conductivity. With the appropriate fabrication parameters, even though containing 0.33 g/cm³ bulk density and 88.2% porosity, its compressive strength could reach 2.03 MPa at 1000°C, 147% of that at room temperature; the residual strength ratio kept as 114.7% after a thermal shock at 1200°C. The X-ray diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscope (TEM) showed that anorthite grains refinement and intergranular voids filling by liquid phase were main factors for the high strength. From room temperature to 1200°C, its thermal conductivity only varied from 0.085 to 0.258 W·(m·K)⁻¹. High porosity, a large number of nanoregions in anorthite grains and amorphous phase in grain boundary were main reasons for low thermal conductivity.     

Fibrous porous mullite ceramics modified by mullite whiskers for thermal insulation and sound absorption

In order to meet the demand for thermal insulation and sound absorption, fibrous porous mullite ceramics (FPMC) with high porosity and an interconnected pore structure were prepared, followed by a pore structure modification with in situ grown mullite whiskers on the three-dimensional framework of the FPMC. The resultant hierarchical material exhibited superior sound absorption performance in the low-to-medium frequency to most reported sound-absorbing materials, as well as a sufficient compressive strength of 1.26 MPa with low thermal conductivity of 0.117 W·m^?1·K^?1. Moreover, the effects of solid content and mullite whiskers on the microstructure and physical properties of the material were analyzed. The increase of solid content led to increased compressive strength and thermal conductivity and decreased frequency corresponding to the first sound absorption peak. The thermal conductivity and compressive strength of the material increased as the mullite whiskers grew, while the median pore size decreased.     

Enhanced mechanical properties for porous ceramics with an in situ formation of anorthite crystals during vitrification

Porous anorthite ceramics are widely applied as catalysis supports, separation membranes, and thermal insulations at high temperatures. In situ formation of anorthite crystals during vitrification is herein employed to improve mechanical properties of porous anorthite with modulated grain sizes on pore walls. Sintering parameters of shrinkage (5%–30%), open porosity (31.0%–58.3%), density (1.18–1.71 g/cm³), and mass loss (12.20%–18.26%) are estimated to investigate the influences of sintering aids of calcite, fused mullite, and silicon carbide or talcum on the densification processes of porous anorthite. The Kissinger equation is used to determine the activation energy of 783 kJ/mol for the crystallization of anorthite, which is significantly low for the formation of anorthite crystals through surface nucleation mechanism in present flux-rich melt. In situ crystallization and simultaneous densification under liquid drainages are favored for whiskers-reinforced mechanism to enhance flexural strengths (6.9–19.4 MPa) for porous anorthite with the porosity of 49.6%–58.3% through the formation of hierarchical nano- and microscale structures during vitrification.     

In-situ growth of mullite whiskers and their effect on the microstructure and properties of porous mullite ceramics with an open/closed pore structure

Porous mullite ceramics with an open/closed pore structure were prepared by protein foaming method combined with fly ash hollow spheres. Both the open porosity and total porosity of samples were enhanced by increasing the hollow sphere content. Mullite whiskers with a diameter of 0.2–4 μm were grown in-situ in the porous mullite ceramics with an AlF₃ catalyst, conforming to a vapor-solid growth mechanism. The pore structure of the porous mullite ceramics was significantly affected by the mullite whiskers which increased the open porosity and total porosity. Moreover, the median pore size was reduced from 65.05 μm to 36.92 μm after the introduction of mullite whiskers. The flexural strength and the thermal conductivity of the samples decreased with increasing total porosity. The porosity dependence of the thermal conductivity was well described by the universal model, providing a reference for the prediction of thermal conductivity of porous ceramics with open/closed pores.     

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.     

木炭添加量对多孔莫来石陶瓷性能的影响

为了改善以木炭为造孔剂的多孔莫来石陶瓷的性能,以烧结莫来石(0.25~0.3 mm)、SiO2微粉、Al2O3微粉、滑石粉、球黏土、膨润土、甲基纤维素、木炭粉(≤0.044 mm)为原料,研究了不同量的木炭粉(外加质量分数分别为0、2%、4%、6%、8%、10%、12%)对多孔莫来石坯体的成型外观、烘干后的常温耐压强度及1 400℃保温3 h热处理后的显气孔率和常温耐压强度的影响,并对不同木炭添加量的多孔莫来石试样进行了显微结构分析。结果表明:外加质量分数≤8%的木炭,制成的多孔莫来石坯体可较好成型;外加质量分数2%~8%木炭的莫来石坯体与不添加木炭的相比,烘干后试样的常温耐压强度明显提高;多孔莫来石热处理后的显气孔率随着木炭添加量的增加而增加,常温耐压强度随之降低。综合考虑多孔莫来石陶瓷各项性能,木炭外加质量分数不宜超过8%。     

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.     

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.     

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.     

Thermo-mechanical properties of mullite ceramics: New data

Coefficients of elastic stiffnesses and thermal expansion of hot isostatically pressed, reaction-sintered and technical fused-mullite ceramics were measured between 100 and 1673 K in comparison with single crystal mullite employing resonant ultrasound spectroscopy and dilatometry, respectively. Additionally, chemical and phase compositions and the microstructure of the ceramics were studied using X-ray diffraction techniques and scanning electron microscopy. Our studies revealed that despite polycrystallinity and slight porosity of up to 1.6%, the elastic behavior of the hot isostatically pressed ceramics is near to ideal aggregate elastic properties of mullite single crystal, for example, their bulk moduli fit within 0.7% to B = 170.0 GPa of single crystal mullite. On the other hand, with B = 155 GPa, the reaction-sintered mullite behaves significantly softer. The difference can be explained with more tight grain to grain contacts in hot isostatically pressed ceramics as compared to reaction-sintered materials. The thermal expansion of both types of ceramics almost coincides with the corresponding averaged behavior of single crystal mullite. For example, between 573 and 1273 K, the volume expansion coefficients of all these materials are (18.0 ± 0.3)·10⁻⁶ K⁻¹. Obviously, the microstructural features are less important for the macroscopic thermal expansion. Due to heterogeneous microstructure and high α-alumina and zirconia contents, the corresponding properties of fused-mullite refractory deviate strongly from those of the other mullite materials.     

Effects of firing temperature on the microstructures and properties of porous mullite ceramics prepared by foam-gelcasting

Porous mullite ceramics were prepared at 1300–1600°C for 2?h via a foam-gelcasting route using industrial-grade mullite powders as the main raw material, Isobam 104 as the dispersing and gelling agent, triethanolamine lauryl sulphate as the foaming agent and sodium carboxymethyl cellulose as the foam stabilising agent. The effects of firing temperature on the sintering behaviour of green samples as well as microstructures and properties of final porous mullite products were investigated. With increasing the temperature from 1300 to 1600°C, linear shrinkage and bulk density values of fired samples increased, whereas their porosity decreased. Mechanical strength and thermal conductivity values of fired samples decreased with increasing their porosities. Even at a porosity level as high as 79.4%, compressive and flexural strengths of fired samples (with average pore size of 314?μm) remained as high as 9.0 and 3.7?MPa, respectively, and their thermal conductivity (at 200°C) remained as low as 0.21?W?(m^?1?K^?1).     

Using Si/SiC solid waste to design urchin-like mullite whiskers for oil-water separation

Using recyclable industrial waste Si/SiC and Al₂(SO₄)₃ as starting materials, urchin-like mullite whiskers were successfully synthesized via the molten salt method. The characterizations were focused on the phase transformations and morphology evolution of mullite whiskers. The circular oxidation-dissolution-precipitation mechanism was proposed for the growth of urchin-like mullite whiskers. Then, the pressing-sintering process was used for fabricating porous whisker-structured mullite ceramics for oil-water separation applications. Physical properties of porous ceramic, including bulk density, apparent porosity, mechanical and thermal shock resistance were measured. It was found that excessive reaction temperature could decompose the mullite, and a suitable temperature for pure urchin-like mullite whiskers was found to be 900°C. To achieve oil-water separation, bionic surface grafting technology was used for coating a hydrophobic and lipophilic material (octadecylamine, ODA) on mullite ceramic. Oil adsorption capacities of the ceramic/ODA for various oils, that is, .27 and .24 g/g for cooking and motor oil, respectively, were successfully achieved.     

Synthesis and characterization of porous Y2SiO5 with low linear shrinkage,high porosity and high strength

The emerging porous Y₂SiO₅ ceramic is regarded as a promising candidate of thermal insulator owing to its very low thermal conductivity. However, recent works on porous Y₂SiO₅ are confronted with severe problems such as large linear shrinkage (18.51–20.8%), low porosity (47.74–62%) and low strength (24.45–16.51 MPa) at high sintering temperatures (1450–1500 °C). In this work, highly porous Y₂SiO₅ ceramic with low shrinkage and excellent high-temperature strength was fabricated by in-situ foam-gelcasting method at 1550 °C. The as-prepared sample has unique multiple pore structures, low linear shrinkages of 6.3–4.5%, controllable high porosities of 60.7–88.4%, high compressive strengths of 38.2–0.90 MPa, and low thermal conductivities of 0.126–0.513 W/(m K) (porosity: 87.1–60.2%). The effects of relative density on relative strength, as well as porosity on thermal conductivity were quantitatively discussed. The present results indicate that porous Y₂SiO₅ is the potential high-temperature thermal insulation material of light weight, low thermal conductivity, and high strength.     

Preparation of mullite whiskers from kaolin via the addition of tribasic calcium phosphate

Mullite whiskers are potential candidates for improving the mechanical and thermal properties of ceramic, glass, and composite material. In this work, well‐developed whisker‐shaped mullite has been produced by adding tribasic calcium phosphate (Ca₃(PO₄)₂) into kaolin before calcining in air. In the raw kaolin, rod‐like mullite crystal of ~0.5‐1.0 μm length and ~0.05‐0.2 μm diameter formed at 1350°C, and mullite whiskers were not be observed; however, by doping 6 wt% Ca₃(PO₄)₂ into kaolin, mullite whiskers of ~5.5 μm length and ~0.05‐0.10 μm diameter grew at 1250°C. The formation of high aspect ratio of mullite whiskers can probably be explained by the synergistic effect of P₂O₅ and CaO, resulting in the formation of liquid phase with a relatively higher content of Si and a lower viscosity at low temperature of 1250°C, which facilitates the growth of mullite displaying acicular morphology. The results are of interest in producing high aspect ratio of mullite whiskers from kaolin at reduced calcination temperatures.     

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.     

Low-temperature preparation of high-performance porous ceramics composed of anorthite platelets

Platelet-like anorthite based porous ceramics with improved mechanical strength were fabricated via direct gelcasting and firing at 1223-1473 K using CaCO₃, Al(OH)₃, and SiO₂ powders as the raw materials, along with H₃BO₃ and melamine sintering/crosslinking agents. Based on density functional theory calculations, H₃BO₃ promoted the formation of platelet-like anorthite at a relatively low temperature via covering the {130} facet of anorthite and reducing the corresponding adsorption energy, which led to the preferential growth along the a- and b-axes. The optimal amount of H₃BO₃ for the anorthite platelet formation was 0.9 wt%. The porous anorthite sample with an original solid content of 22.0 wt%, after firing at 1373 K, contained 71.0% porosity and exhibited a compressive strength as high as 5.7 MPa, which were comparable or even superior to those of porous anorthite ceramics prepared previously at a much higher temperature (1573-1723 K), indicating that the preparation strategy reported in this paper is feasible in fabricating high-performance porous anorthite ceramics at a much milder condition. The thermal conductivity of the porous anorthite sample at 1073 K was as low as 0.266 W/(m·K), much lower than that (0.645 W/(m·K)) of the control sample, suggesting that the former could be potentially used for thermal insulation at high temperatures.     

原位生长莫来石增强钙长石复合材料的制备

采用一步固相烧结法,以高岭土和氢氧化铝原位制备了莫来石晶相增强钙长石复合材料,利用XRD和SEM对材料的显微结构进行了分析.实验结果表明:原位生长莫来石/钙长石的配比组成对材料的显微结构有着极为重要的影响.当钙长石:莫来石=70:30时,该复合材料在1400～1420℃下烧成时,抗折强度高达107 ～ 123.9 MPa.该复合材料比纯的钙长石陶瓷材料的抗折强度提高了1.5 ～2倍.     

Preparation and characterization of porous mullite ceramics via foam-gelcasting

Porous mullite ceramics were prepared via foam-gelcasting using industrial grade mullite powder as the main raw materials, Isobam-104 as the dispersing and gelling agent, sodium carboxymethyl cellulose as the foam stabilizing agent, and triethanolamine lauryl sulfate as the foaming agent. The effects of processing parameters such as type and amount of additive, solid loading level and gelling temperature on rheological properties and gelling behaviors of the slurries were investigated. The green samples after drying at 100 °C for 24 h were fired at 1600 °C for 2 h, and the microstructures and properties of the resultant porous ceramic samples were characterized. Based on the results, the effects of foaming agent on the porosity level, pore structure and size and mechanical properties of the as-prepared porous mullite ceramics were examined. Porosity levels and pore sizes of the as-prepared samples increased with increasing the foaming agent content up to 1.0%, above which both porosity levels and pore sizes did not change. The compressive strength and flexural strength of the as-prepared sample with porosity of 76% and average pore size of 313 μm remained as high as 15.3±0.3 MPa and 3.7±0.2 MPa, respectively, and permeability increased exponentially with increasing the porosity.     

Preparation of elongated mullite self-reinforced porous ceramics

Elongated mullite was synthesized using mullite powder as a raw material and AlF₃·3H₂O as an additive, and characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). The effects of AlF₃·3H₂O content and reaction temperature on the formation of elongated mullite were investigated, and the relevant growth mechanism was discussed based on the experimental results and density functional theory (DFT) calculations. When the optimal amount of AlF₃·3H₂O (4?wt% in the present work) was used, the length and diameter of elongated mullite increased with increasing the reaction temperature, and elongated mullite of 22.3?µm in average length and 4.6?µm in average diameter was formed after 5?h at 1873?K. Based on the results, elongated mullite self-reinforced porous ceramics were prepared by a combined foam-gelcasting and solid-reaction method, and their mechanical properties were examined. Elongated mullite in-situ formed in the porous samples evidently enhanced their mechanical strength. The flexural strength of the elongated mullite self-reinforced porous sample with 67.0% porosity (prepared using 6?wt% AlF₃·3H₂O) was as high as 13.9?MPa, which was about 26.4% higher than that of a porous sample (11.0?MPa) prepared without AlF₃·3H₂O.