Characteristics of microbubbles generated by porous mullite ceramics prepared by an extrusion method using organic fibers as the pore former

Porous mullite ceramics with unidirectionally oriented pores were prepared by an extrusion method using rayon fibers as the pore formers and the characteristics of microbubbles generated by these porous ceramics were investigated. The 1200 mm long ceramics were tubular and of thick or thin types of 20–30 mm inner diameter and 30–50 mm outer diameter, respectively. The thin and thick samples had porosities of 47 and 49% and average pore radii of 7.8 μm. The gas permeabilities of the thick and thin samples were 4.1 × 10^?14 and 5.4 × 10^?14 m², respectively. Microbubbles were generated by introducing N₂ gas through the ceramic tube by immersing it into water. The minimum pressure (bubble point pressure) for generation of microbubbles was 20 kPa, much lower than for other bubble-forming methods. The average microbubble radii ranged from about 70 to 105 μm at flow rates of 0.15–0.25 L/min in the thin sample and 0.3–0.7 L/min in the thick sample. These bubble sizes are much smaller than calculated for a Fritz-type bubble such as generally formed by bubbling from pores and/or orifices. However, the present bubble sizes agree well with the calculated value based on nanobubbles, indicating that bubble formation occurs by mixing the gas with water in small pores. Since microbubbles enhance the dissolution rate of a gas phase in water, they are potentially useful for improving water environments, especially oxygen-deficient water. The effectiveness of gas dissolution in water was confirmed by determining the dissolution behavior of CO₂ gas using these porous ceramics.     

Capillary rise properties of porous geopolymers prepared by an extrusion method using polylactic acid (PLA) fibers as the pore formers

The geopolymers were prepared from sodium silicate, metakaolinite, NaOH and H₂O at SiO₂:Al₂O₃:Na₂O:H₂O of 3.66:1:1:x, where x = 8–17, and curing temperatures of 70–110 °C. Since the bending strength of the geopolymers was highest (36 MPa) where H₂O/Al₂O₃ = 9 and the curing temperature = 90 °C, these conditions were adopted. The porous geopolymers were prepared by kneading PLA fibers of 12, 20 and 29 μm diameter into the geopolymer paste, at fiber volumes of 13–28 vol%. The resulting paste was extruded using a domestic extruder, cured at 90 °C for 2 days then dried at the same temperature. The PLA fibers in the composites were removed by alkali treatment and/or heating. The highest capillary rise was achieved in the porous geopolymers containing 28 vol% of 29 μm fibers. The capillary rise of this sample, estimated by the equation of Fries and Dryer¹ was 1125 mm.     

Preparation and properties of porous alumina ceramics with uni-directionally oriented pores by extrusion method using a plastic substance as a pore former

Porous alumina ceramics with uni-directionally aligned pores were prepared by an extrusion method using 0–40 vol.% poly (vinyl acetate) (PVAC) as the pore former. A paste was prepared by mixing 25 mass% distilled water, 4 mass% methylcellulose, 8 mass% oleic acid and 0.8 mass% ammonium poly (carboxylic acid). This paste was molded into a 10 mm Ø body using a ram-type extruder, dried at room temperature for 24 h, calcined at 600 °C for 1 h and sintered at 1500 °C for 2 h in air. The PVAC added to the paste was homogeneously dispersed and formed particles 0.1–150 μm in size which extended in the extrusion direction and were converted to through-hole pores after sintering. The resulting pore size distribution in the samples was bimodal, centered at about 0.4 μm with a broad peak at about 70 μm dia. The resulting porous alumina ceramics showed high gas permeability because of their uni-directionally oriented through-hole pore structure.     

助烧剂和造孔剂对真空烧结SiC多孔陶瓷性能的影响

以粒度≤0.063mm的SiC为主要原料,分别加入30%(质量分数)的Al2O3-Y2O3与10%的Al2O3-高岭土复合助烧剂,并外加不同量(分别为12.8%、26.3%、30.0%和36.4%)的造孔剂羧甲基纤维素钠(CMC),制样后首先在空气炉中经过300℃2h或1100℃4h的预烧,然后在真空炉中于1550℃4h真空烧结而制备成SiC多孔陶瓷,并研究了助烧剂种类以及造孔剂CMC外加量对SiC多孔陶瓷显微组织、显气孔率及抗折强度的影响。结果显示:采用Al2O3-Y2O3作为助烧剂的SiC多孔陶瓷比Al2O3-高岭土作助烧剂的具有较高的抗折强度,显气孔率稍有减小;随着羧甲基纤维素钠量的增加,加入两种助烧剂的SiC多孔陶瓷均表现为显气孔率增加,抗折强度降低。     

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.     

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).     

Microstructure and properties of lightweight fibrous porous mullite ceramics prepared by vacuum squeeze moulding technique

A novel fibrous porous mullite network with a quasi-layered microstructure was produced by a simple vacuum squeeze moulding technique. The effects of organic binder content, inorganic binder and adsorbent on the microstructure and the room-temperature thermal and mechanical properties of fibrous porous mullite ceramics were systematically investigated. An anisotropy microstructure without agglomeration and layering was achieved. The fibrous porous mullite ceramics reported in this study exhibited low density (0.40 g/cm³), low thermal conductivity (~0.095 W/(m K)), and high compressive strength (~2.1 MPa in the x/y direction). This study reports an optimal processing method for the production of fibrous porous ceramics, which have the potential for use as high-temperature thermal insulation material.     

Multi-functional mullite fiber-based porous ceramics with a multilevel pore structure assembled by alumina platelets and mullite whiskers

Mullite fiber-based porous ceramics have been widely used in the field of heat insulation. To further broaden their applications in other fields, such as filtration and sound absorption, mullite whiskers and alumina platelets were introduced as the secondary structural materials in mullite fiber-based porous ceramics by a sol-gel combining heat-treating method, and new fiber-based porous ceramics with a unique multilevel pore structure were developed. By adjusting the molar ratios of aluminium tri-sec-butoxide to aluminium fluoride and calcination temperature, these fiber-based porous ceramics not only presented the characteristics of lightweight (maximum density of 0.38 g/cm³) and good heat insulation (minimum thermal conductivity of 0.11 W/mK) comparable to traditional fiber-based porous ceramics, but also showed a superior specific surface area (up to 11.5 g/m²) and excellent sound absorption performance (average sound absorption coefficient as high as 0.728). Owing to these outstanding characteristics, the corresponding porous ceramics are expected to be promising multifunctional materials in diverse fields, especially thermal insulation and sound absorption.     

Elastic properties of porous oxide ceramics prepared using starch as a pore-forming agent

The elastic properties, in particular the tensile modulus (Young's modulus) and Poisson ratio, of porous alumina, zirconia, and alumina–zirconia composite ceramics are studied using the resonance frequency method and the results compared with theoretical predictions. Starch is used as a pore-forming agent, so that the resulting microstructure is essentially of the matrix-inclusion type (with large bulk pores, connected by small throats when a percolation threshold is exceeded). It is found that for this type of microstructure the porosity dependence of the Young's modulus is significantly below the upper Hashin–Shtrikman bound and the power-law prediction; it corresponds well, however, to a recently proposed exponential relation and to an empirical volume-weighted average of the upper and lower Hashin–Shtrikman bounds. Results for all three types of ceramics indicate that – in the porosity range considered, i.e. up to approximately 50% – the Poisson ratio depends only slightly on porosity.     

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.     

Microstructure and properties of pore-created SiC ceramics with calcium chloride as pore former

Pore-created silicon carbide (SiC) ceramics were liquid phase sintered (LPS) by using Al₂O₃–Y₂O₃ as sintering additive and calcium chloride (CaCl₂) as pore former. The CaCl₂ did not react with other compositions, and accumulatively formed CaCl₂ crystals on the grain boundary of SiC ceramics. The addition of CaCl₂ decreased the sintering and mechanical properties of SiC ceramics, but obviously reduced the dry friction coefficient. The pores on the surface and inside of SiC ceramics could be continuously created by the solubility and non-volatility of calcium chloride.     

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%。     

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.     

Effects of SiC addition on the structure and properties of reticulated porous mullite ceramics

Reticulated porous mullite ceramics (mullite RPCs) were produced by the polymer replica method using alpha alumina and kaolin to form in situ mullite. Up to 30% particulate silicon carbide (SiCp) was added to ceramic mixtures to explore its effect on the structure and properties of the sintered products. The ceramic slurry was coated onto polyurethane sponge using preset roller method, then recoating was applied by the spray coating technique. The strength of the mullite RPCs was found to depend greatly on the phase composition of the structures and on the amount of SiCp addition.     

Thermal conductivity of porous alumina ceramics prepared using starch as a pore-forming agent

The thermal conductivity of porous alumina ceramics prepared using different types of starch (potato, wheat, corn, and rice starch) as pore-forming agents is investigated from room temperature up to 500 °C. The temperature dependence measured for alumina ceramics of different porosity (in the range 6–47%) is fitted with second-order polynomials and 1/T-type relations, and compared to available literature data for dense alumina. It is found that the porosity dependence of the relative thermal conductivity k_r = k/k₀ is well described by a modified exponential relation of the form k_r = exp(?1.5?/(1 ? ?)), where ? is the porosity. This finding is in agreement with other literature data and seems to indicate a common feature of all porous materials with microstructures resulting from fugitive pore-forming agents.     

Porous ceramics with controllable properties prepared by protein foaming-consolidation method

A new protein foaming-consolidation method for preparing porous alumina was developed using egg yolk both as consolidating and foaming agent. This method allows the control of properties of porous alumina not only by varying alumina-to-yolk ratio but also by managing the foaming process. After drying, the green bodies were burned at 600 °C for 1 h to remove the pore creating agent, followed by sintering at 1,550 °C for 2 h. The porous alumina ceramics with pore sizes of 25–1,000 μm and relative density of 29–50% were obtained. The compressive strength of the sintered samples varied within the range of 1.1–5.7 MPa, corresponding to porosity of 40–71%. The addition of dispersant with different concentration into alumina slurries shifted the rheological properties from shear thinning behavior to a Newtonian fluid, which resulted in changes in the pore sizes of the resulting ceramics. The main advantages of the process are the simplicity of the process and the low-cost processing equipment/materials needed. These results have opened a novel preparative way for porous ceramics especially alumina-based porous materials designed for biomedical applications.     

Mineralogical and dielectric properties of mullite and cordierite ceramics produced using wastes

In this work technical ceramics containing industrial inorganic wastes was carried out. Ceramic formulations prepared with clay, magnesium oxide and residues of kaolin and alumina as raw materials, were formed in a disk-shaped specimens using the uniaxial pressing process and sintering at temperatures from 950°C to 1400°C. The mineralogical, physical and dielectric characteristics of the fired samples were investigated. The dielectric properties, the relative dielectric constant (ε_r) and the loss tangent (tan δ) were evaluated at frequencies of 0.1, 1, 10, and 100?kHz at room temperature. Mullite and cordierite were present as major phases at the highest temperatures. Relative dielectric constant values closest to that of mullite (ε_r = ~ 5 to ~ 6) and cordierite (ε_r =?~ 4 to ~ 6) at 1?kHz. On the other hand, the lowest dielectric losses (tan δ ~ 0.06 to ~ 0.04) were observed for the formulations containing the mullite major phase, and tan δ ~ 0.009 to ~ 0.003 for formulations that showed cordierite as main phase. It was verified that an increase in temperature promoted a reduction of porosity, a property that had a direct influence on the dielectric properties of the formulations. The materials obtained from the residues presented low dielectric constants and loss tangents, which make them suitable for use in electrical and electronic systems.     

Enhancing the thermal insulating properties of lanthanum zirconate porous ceramics via pore structure tailoring

The potentially useful role of lanthanum zirconate (La₂Zr₂O₇, LZO) porous bulk ceramics has been rarely explored thus far, much less the optimisation of its pore structure. In this study, LZO porous ceramics were successfully fabricated using a tert-butyl alcohol (TBA)-based gelcasting method, and the pore structures were tailored by varying the initial solid loading of the slurry. The as-prepared ceramics exhibited an interconnected pore structure with high porosity (67.9 %–84.2 %), low thermal conductivity (0.083–0.207 W/(m·K)), and relatively high compressive strength (1.56–7.89 MPa). The LZO porous ceramics with porosity of 84.2 % showed thermal conductivity as low as 0.083 W/(m·K) at room temperature and 0.141 W/(m·K) at 1200 °C, which is much lower than the counterparts fabricated from particle-stabilized foams owing to its unique pore structure with a smaller size, exhibiting better thermal insulating performance.     

溶胶-凝胶法制备可纺莫来石溶胶的特性研究

以水作为分散剂,以异丙醇铝、氯化铝和正硅酸乙酯为原料,盐酸和醋酸做复合催化剂,聚乙烯醇为纺丝助剂,采用溶胶-凝胶法合成了可纺莫来石溶胶,并分析了获得适宜拉丝性的原料的较佳配比、不同水解时间对后续热处理的影响及溶胶粘度与温度的关系,为制取连续莫来石纤维提供必要借鉴.采用DTA-TG,IR,XRD及旋转粘度计分析测试了胶体各方面的性能.