Synthesis and characterization of mullite-ZrO2 porous fibrous ceramic for highly efficient oil-water separation

This work aimed to proposing a new strategy for preparing the mullite-ZrO₂ porous fibrous ceramic used as alternative matrix material for oil-water separation by the aqueous gel-casting method. The properties of the fabricated porous fibrous ceramics in terms of microstructure, phase composition, apparent porosity, bulk density and compressive strength were investigated and the separation behavior was predicted by analyzing the structural changes. It is demonstrated that the phase composition of green bodies consisted of bayerite, boehmite, ZrSiO₄ and YSZ, and the sintered sample contained mullite, ZrO₂ and YSZ. As the YSZ fibers increased, the porosity of the fabricated porous ceramic increased with the maximum value of 70.65% due to the formation of more pores caused by YSZ fibers. Moreover, a significant increase in compressive strength (up to 9.52–21.86 MPa) was observed with the increase of YSZ fibers. Therefore, the fabricated porous ceramics could be appropriative for advanced applications of separation membranes for oil-water separation.     

Porous fibrous ZrO2-mullite ceramics prepared via tert-butyl alcohol-based gel-casting

Mullite fiber was used to fabricate ZrO₂-mullite based porous ceramic via tert-butyl alcohol (TBA)-based gel-casting process using zirconite and bauxite as raw materials. Phase compositions, microstructure, pore size distribution, linear shrinkage, bulk density, apparent porosity, thermal conductivity, and compressive strength were analyzed to investigate influences of mullite fiber content and added Y₂O₃ on prepared porous ceramics. Results show that bird nest-like three-dimensional fibrous reticular skeleton structure was constructed with mullite fibers that evenly enwrapped rod-like mullite and ZrO₂ grains. Prepared porous fibrous ZrO₂-mullite ceramics had narrow pore size distribution that consisted of mullite and m-ZrO₂. With an increase in mullite fiber content, linear shrinkage and bulk density decreased, apparent porosity increased, and relatively good thermal conductivity was obtained. In addition, added Y₂O₃ reacted with Al₂O₃ and SiO₂ to form Y-Al-Si-O glass phase, which promoted sintering and densification of the ceramic, thus improving its compressive strength.     

Microstructure and permeability of porous YSZ ceramics fabricated by freeze casting of oil-in-water suspension

Porous yttria-stabilized zirconia (YSZ) ceramics are fabricated through freeze casting of oil-in-water suspension followed by sintering at 1250−1550 °C. The pore structure, compressive strength and permeability of porous YSZ ceramics are tailored via altering the emulsion content and sintering temperature. The samples obtained using higher emulsion content or at lower sintering temperature show larger Darcian and non-Darcian constants due to their higher open porosity and larger pore size. Furthermore, the investigation on individual contributions of viscous and inertial resistances on the total pressure drop during permeation process indicates that the viscous resistance increases but the inertial resistance decreases with increasing the emulsion content or decreasing the sintering temperature for samples. Porous YSZ ceramics obtained in this work with a k₁ range of 3.14 × 10⁻¹³–1.12 × 10⁻¹² m² are appropriate for applications in filters and membrane supports.     

YSZ/Al2O3/YSZ多层陶瓷叠层制备方法的研究

本文分别采用三种叠层方式制备YSZ/Al2O3/YSZ多层陶瓷,通过实验得出:由于YSZ与Al2O3陶瓷烧结性能的差异,导致YSZ与Al2O3陶瓷叠层共烧时容易分层翘曲,YSZ与Al2O3主要依靠层间的物理啮合作用而结合。通过在流延YSZ层与丝网印刷Al2O3层之间增加印刷YSZ过渡层的叠层方法,可以改善YSZ流延层与Al2O3丝网印刷层之间的结合,而得到结合良好的YSZ/Al2O3/YSZ多层陶瓷共烧结合界面。     

Preparation of calcium hexaluminate porous ceramics by gel-casting method with polymethyl methacrylate as pore-forming agent

Calcium hexaluminate (CA₆) porous ceramics were prepared by gel-casting method, with α-Al₂O₃ and CaCO₃ as raw materials and polymethyl methacrylate (PMMA) microspheres as pore-forming agent. The effects of the amount of pore-forming agent PMMA microspheres on the phase composition, bulk density, apparent porosity, flexural strength, microstructure, thermal shock stability and thermal conductivity of CA₆ porous ceramics were systematically studied. The pores of CA₆ porous ceramics are mainly formed by the burning loss of PMMA microspheres and the decomposition of organic matter. Adding an appropriate amount of PMMA microspheres as pore-forming agent has a positive effect on the thermal shock stability of CA₆ porous ceramics. When the amount of pore-forming agent is 15 wt%, the volume density of CA₆ porous ceramics is 1.33 g/cm³, the porosity is 63%, the flexural strength is 13.9 MPa, the thermal shock times can reach 9 times, and the thermal conductivity is 0.293 W/(m·K), which can meet the application in refractory, ceramics or high temperature cement industries.     

叔丁醇基凝胶注模成型制备氧化铝多孔陶瓷

以微米级Al2O3粉料为原料,叔丁醇为溶剂,采用凝胶注模成型工艺制备了氧化铝多孔陶瓷,并研究了Al2O3浆料的固相体积分数(分别为8%、10%、13%和15%)对1 500℃保温2 h烧后氧化铝多孔陶瓷的气孔率、气孔孔径分布、耐压强度、热导率和显微结构的影响.结果表明:当Al2O3浆料的固相体积分数从8%增加到15%时,氧化铝多孔陶瓷烧结体的总气孔率从71.2%逐渐降低至61.2%,气孔平均孔径从1.0 μm逐渐减小至0.78 μm,耐压强度从16.0 MPa逐渐增大至45.6 MPa,而热导率从1.03 W·(m·K)-1逐渐增大至1.83W·(m·K)-1.     

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.     

Effect of organic fibers addition on digital light processing for Al2O3 porous ceramics

Porous ceramics based on additive manufacturing have great application potential in many industries, including filtration, catalysis, and heat insulation. In this research, we propose a method for manufacturing porous ceramics with connected channels structure through ceramic digital light processing (DLP) and organic fiber decomposition. The crossed fibers in the green body, working as a pore-forming agent, were decomposed and removed to form connected channels in ceramic. It was confirmed that ball milling changed the fiber morphology during slurry preparation, which was beneficial to promote fibers crossing. Besides, we focused on the influence of the “Sponge Compression effect” during the DLP process, which affected the fibers distribution. The existence of fibers in the green body resulted in uneven pressure distribution during the debinding process, providing a potential source of cracks. Results show that this method can produce channels with a diameter of 100 μm and high connectivity, providing great potential in fabricating high connectivity porous ceramics with complex shapes and structures.     

Effects of Al2O3 crystal types on morphologies,formation mechanisms of mullite and properties of porous mullite ceramics based on kyanite

Porous mullite ceramics with different crystal shapes of mullite are fabricated by in-situ reaction with middle-grade kyanite as raw material, Al(OH)₃, γ-Al₂O₃, ρ-Al₂O₃ and α-Al₂O₃ as alumina sources. Effects of Al₂O₃ crystal types on morphology evolution and formation mechanisms of mullite, and properties of porous ceramics are investigated. Results show that mullite in the sample with Al(OH)₃ mainly shows acicular morphology, because its (001) plane has the minimum interplanar crystal spacing and maximal attachment energy, it grows fast along [001] direction by screw dislocation mechanism. With a successive slowdown in reactivities of Al(OH)₃, γ-Al₂O₃, ρ-Al₂O₃ and α-Al₂O₃, the amount and aspect ratio of mullite reduce, its growth mechanism gradually transforms into two-dimensional nucleation. Acicular mullite not only reinforces samples, but makes effective pore sizes smaller, which enable the sample with Al(OH)₃ to present low bulk density, high apparent porosity and linear changes, small average pore size and good mechanical strength.     

Effects of AlF3 and MoO3 on properties of Mullite whisker reinforced porous ceramics fabricated from construction waste

Mullite-whisker-reinforced anorthite-mullite-corundum porous ceramics were prepared from construction waste and Al₂O₃ powder by adding AlF₃ and MoO₃ as the additive and crystallization catalyst, respectively. The effects of AlF₃ and MoO₃ content on the properties of mullite whiskers, such as open porosity, mechanical properties, pore size distribution, microstructure and phase structure, were investigated in detail. The results showed that the morphology of the mullite whiskers and properties of the porous ceramics were greatly influenced by the AlF₃ and MoO₃ content. The specimen obtained by co-adding 12 wt% AlF₃ and 3 wt% MoO₃, and sintering at 1350 °C for 1 h, exhibited excellent properties, including an open porosity of 67.4±0.5% and biaxial flexural strength of 24.0±0.8 MPa. The mullite whiskers were uniformly distributed; the whiskers had a diameter of 0.05–0.5 µm, length of 8–10 µm, and aspect ratios (length to diameter ratio) of 20–30 on average.     

Permeability and thermal expansion properties of porous LAS ceramic prepared by gel-casting method

The porous lithium aluminosilicate (LAS) ceramics with controllable pore structure were fabricated by gel-casting method. The porosity, pore structure, compression strength, gas permeability, and coefficient of thermal expansion (CTE) of the porous LAS ceramics with different monomer content were investigated. The sample with 5 wt.% monomer content has maximum value of compression (26.62 ± 0.54 MPa). When the monomer content increased to 20 wt.%, the porosity, Darcian gas permeability, and thermal expansion coefficient increased to maximum (63.66 %, 13.3 × 10⁻¹³ m², and 1.1–2.6 × 10⁻⁶ K⁻¹). The non-Darcian gas permeability showed irregular variation (1.35–3.61 m) with the increase of monomer content. A thermal vibration model was induced to investigate the effect of temperature and monomer content on the CTE. The results showed that the CTE increased with the increase of temperature due to the nonlinear thermal vibration of the atoms in lattice and the asymmetry of the force between particles.     

Properties of porous zirconia ceramics fabricated by using various pore-forming agents

The present work proposes a new method for fabrication partially stabilized porous zirconia ceramics using monoclinic zirconia as raw material, yttrium nitrate and magnesium compounds as pore-forming agents and stabilizers. Effects of different pore-forming agents, firing temperatures and firing time on properties of samples were investigated. Thermal decomposition of yttrium nitrate and magnesium compounds creates a large number of pores, and thus porous zirconia ceramics were fabricated. ZrO₂ can be partially stabilized by Y₂O₃ and MgO derived from the precursors. The porous ZrO₂ ceramics obtained by using Y(NO₃)₃·6H₂O and 4MgCO₃·Mg(OH)₂·6H₂O as pore-forming agents had relatively high stabilization ratio, uniform pores and high strength. The optimum firing temperature and firing time are 1400 °C and 3 h, and the samples have the stabilization ratio of 45.7%, high cold crushing strength (26 MPa), uniform pores, and apparent porosity is about 40%.     

Preparation of porous Al2O3 ceramics by starch consolidation casting method

Porous alumina ceramics were fabricated by starch consolidation casting using corn starch as a curing agent while their microstructure, mechanical properties, pore size distribution, and corrosion resistance were examined. Results showed that the porous alumina ceramics with the flexural strength of about 44.31MPa, apparent porosity of about 47.67% and pore size distribution in the range of 1‐4 μm could be obtained with 3wt% SiO₂ and 3wt% MgO additives. Corrosion resistance results showed mass losses: hot H₂SO₄ solution and NaOH solution for 10 hours were 0.77% and 2.19%, which showed that these porous alumina ceramics may offer better corrosion resistance in acidic conditions.     

Gelcasting of dense and porous ceramics by using a natural gelatine

An improved gel-casting procedure was successfully exploited to produce porous ceramic bodies having controlled porosity features in terms of mean pore size, total pore volume as well as pore geometry. The gel-casting process in which a natural gelatine for food industry is used as gelling agent was firstly set-up to prepare dense alumina and zirconia components. Then, commercial PE spheres, sieved to select proper dimensional ranges, were added to the starting slurries as pore-forming agent. Both alumina and zirconia porous bodies were then produced, having a porosity ranging between 40 and 50 vol%. The fired components were characterised by spherical pores surrounded by highly dense ceramic walls and struts, having a homogeneous and fine microstructure. Their mean pore size was directly dependent on the sieved fraction of the starting PE spheres selected as pore-forming phase.     

Preparation and properties of porous ceramics from nickel slag by aerogel gelcasting

To further resource industrial solid waste, porous ceramics with high porosity were prepared by a gelcasting method using nickel slag and kaolin as raw materials and hydrophilic nontoxic SiO₂ aerogel as a gelling agent. The effects of nickel slag content, dispersant and solid content on the properties and microstructure of porous ceramics were investigated in detail in terms of density, compressive strength, porosity, phase composition and micromorphology. The results confirmed that a certain amount of nickel slag can effectively improve the porosity of porous ceramics, while the addition of dispersant can promote the flow of the slurry, enhanced the denseness of the raw billet and significantly improved the compressive strength. However, its excessive use had a negative effect on the ceramic density and porosity. At the same time, the solid content played a key role in the performance of porous ceramics prepared by gelcasting, and too much solid content was also not conducive to the generation of pores. When the nickel slag content was 55%, the amount of dispersant was 2%, and the solid content was 60 vol%, the porous ceramic had a better overall performance, the density of the porous ceramic was 510 kg/m³, the compressive strength was 1.3 MPa, and the porosity reached 80.1%. The major crystalline phases of porous ceramics prepared by nickel slag were cordierite and anorthite.     

Gel-casted porous Al<Subscript>2</Subscript>O<Subscript>3</Subscript> ceramics by use of natural fibres as pore developers

An approach using ceramic shaping by gel-casting and addition of natural tropical fibres as burnable pore developers has been explored for development of porous alumina materials with predetermined pore structures. The fibres used have been characterized in terms of size, shape, water uptake and surface charge. The degree of fibres loading in slurry has been varied. It has been shown that the amount of added fibres correlates well with the measured porosity, the shape of the developed pores however deviating slightly with that of the introduced fibres. The ceramic bodies have been characterised in terms of porosity, shrinkage and flexural strength. It could be assumed that at fibres amount in slurry above 30% V, an open porosity appears which is accompanied by a sharp drop in strength. In order to explore the benefits of the gel-casting method for complex bodies development, two key issues need to be addressed: air evacuation prior to casting and lowering slurry viscosity at fibre loadings higher than the tested ones. For reaching the latter objective, surface modification of fibres has been undertaken.     

Preparation and optical properties of highly transparent MgAl1.9Ga0.1O4 ceramics via aqueous gel-casting method

The aqueous gel-casting technology has been widely used to prepare high-quality green body for various transparent ceramics with large dimension and complex shape. However, owing to the severe hydrolysis of MgAl₂O₄ powder, it is challenging to obtain thick aqueous slurry with high homogeneity and flowability. In this paper, the surface chemical state of MgAl₂O₄ powder was modified by introducing Ga³⁺, and stable MgAl_1.9Ga_0.1O₄ aqueous slurry with high solid-phase loading (52 vol. %) and low viscosity (136 mPa·s, at a shear rate of 50 s^-1) was successfully prepared. After pressureless presintering and hot isostatic pressing, the gel-cast sample exhibited much higher optical transmittance and more homogeneous microstructure than the dry-pressed sample, which is mainly derived from the improved homogeneity and densification of the green bodies and ceramics. The optical band gap, infrared cutoff wavelength, static refractive index and dispersion of both MgAl_1.9Ga_0.1O₄ and MgAl₂O₄ transparent ceramics were systematically compared. It is indicated that the transparent MgAl_1.9Ga_0.1O₄ ceramic has the increscent static refractive index of 1.695, the decrescent direct band gap energy of 6.15 eV and absorption coefficient of 0.49 cm^-1 at 5 µm, which could be ascribable to the fact that Ga³⁺ has different electronic structure, higher electronic polarizability and larger ionic radius in comparison with Al³⁺. This work provides a dependable solution for preparation of spinel oxide ceramics with superior optical properties and large dimension.     

颗粒级配对发泡法-凝胶注模制备Al_2O_3多孔陶瓷性能的影响

为了降低Al2O3多孔陶瓷制备过程中的干燥后收缩和烧后收缩,提高成品率,将d50分别为25.1、9.4和1.1μm的粗、中、细Al2O3粉体按粗粉中粉细粉质量比分别为50 40 10、10 40 50和100%全细粉的级配方式制备Al2O3泡沫浆料,研究颗粒级配对浆料黏度、干燥生坯的线收缩、烧后试样的线收缩、烧后试样的热导率等性能的影响。结果表明:颗粒级配可以有效提高固含量,且颗粒级配后的发泡浆料在静置30 min后仍能保持稳定,颗粒级配可以明显降低生坯的干燥线收缩以及烧后线收缩,并能降低热导率,提高了发泡法-凝胶注模工艺制备氧化铝多孔陶瓷的成品率。     

Effect of the molecular weight and concentration of PEG solution on microstructure and mechanical properties of Si3N4 ceramics fabricated by gel-casting

Gel-casting is a promising preparation technology of Si₃N₄ structural ceramics. The process involves drying of the “green” gel-cast parts before densification. And the drying of green gel-cast bodies is an important step in the gel-casting manufacturing process. In this work, the Si₃N₄ gel-cast green bodies were dried in polyethylene glycol (PEG) solution with the purpose of obtaining Si₃N₄ ceramics with good mechanical properties. The effect of the molecular weight and concentration of PEG solution on drying rate, microstructure and mechanical properties of Si₃N₄ ceramics was studied. The results indicated that with the increase of molecular weight of PEG, the drying rate increased obviously and the structure became more uniform and dense when the concentration of solution was 20?wt%. The Si₃N₄ ceramics after sintering have the excellent flexural strength (662.6?MPa) under PEG600 drying condition. Furthermore, the concentration of PEG600 solution had a positive effect on drying and sintering of the green body. Therefore, the bending strength reached 871.1?MPa under 65?wt% PEG 600 solution drying condition. Overall, the drying process (drying in 65?wt% PEG600 solution) promotes the efficiency and quality of drying of Si₃N₄ gel-cast green bodies, which is beneficial for the subsequent drying and sintering process.     

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%.