Fabrication of ceramic membranes on porous ceramic supports by electrophoretic deposition

Abstract

Nanoporous alumina membrane and continuous zeolite L membrane were fabricated on the inner surface of microporous alumina tubes. In the former case, an electrophoretic deposition (EPD) technique was used for the deposition of bimodal alumina particles for the subsequent low temperature sintering. In the latter case, the EPD was used for the seeding process of zeolite L particles for the subsequent hydrothermal synthesis. A thin layer of polypyrrole was synthesised on the inside wall of the porous tubes by the chemical polymerisation of pyrrole to give the wall electric conduction for the EPD electrode. The thickness of the coating layers was controlled by altering the applied voltage and deposition time. The interfacial connection of the alumina or zeolite coated layer and the substrate was evaluated by SEM observations before and after the thermal treatment. The nanoporous structure of the alumina membrane was also characterised by a pore size analyser.     

Asymmetric porous cordierite ceramic membranes prepared by phase inversion tape casting and their desalination performance

Asymmetric porous cordierite ceramic membranes were fabricated by phase inversion tape casting method. It is shown that the membranes consist of a relatively dense skin layer on the top, a sponge layer at the bottom and a finger-like layer in the middle. The membranes have a hierarchical pore structure, where macrovoids (denoted as dozens-micron-sized (DMS) pores) are present in the finger-like layer and micron-sized (MS) pores are located in the skin layer, sponge layer and the wall of macrovoids. After surface silylation by post-grafting with 1H,1H,2H,2H-perfluorodecyltriethoxysilane (FAS), the sample with a starting powder/polyethersulfone (PESf) weight ratio of 9 (M − 4) becomes hydrophobic, with a water contact angle of 150°. At a NaCl concentration of 3.5 wt%, a feed rate of 18L/h and a feed temperature of 80 °C, the hydrophobic M − 4 membrane exhibits a water permeate flux of 22.33 kg/m²h, which is considerably larger than that of the membranes prepared by dry pressing method previously, and a salt rejection of 99.9%. The higher water permeate flux is attributed to the much lower transport resistance of water vapor in the membranes of the present work.     

Fabrication of highly porous mullite microspheres via oil-drop molding accompanied by freeze casting

Porous mullite microspheres with a highly open porosity and average diameter of more than 800 µm were fabricated via an oil-drop molding method accompanied by a freeze casting process. After sintering, a highly porous structure was formed due to interlocking whisker-shaped mullite grains and formation of interconnected skeletons during the freeze-casting process. Additionally, it was found that a high porosity and large pore size in the microspheres green bodies are favorable for the synthesis of mullite whiskers with high aspect ratio.     

Preparation of high strength lamellar porous calcium silicate ceramics by directional freeze casting

In this study, porous calcium silicate (CS) ceramics with oriented arrangement of lamellar macropore structure were prepared by directional freeze casting method. The lamellar macropores were connected by the micropores on the pore wall, which had good pore interconnectivity. The effects of solid loading of the slurry, freezing temperature, sintering additive content, and sintering temperature on the microstructures and compressive strength of the synthesized porous materials were investigated systematically. The results showed that with the increase of solid loading (≤20 vol%) and sintering additive content, the sizes of lamellar pores and pore walls increased gradually, the open porosity decreased and the compressive strength increased. The sintering temperature had little effect on the pore size of the ceramics, but increasing the sintering temperature (≤1050 °C) promoted the densification of the pore wall, reduced the porosity, and improved the strength. The decrease of freezing temperature had little effect on porosity, but it reduced the size of lamellar pore and pore wall, so as to improve the strength. Finally, porous CS ceramics with lamellar macropores of about 300–600 μm and 2–10 μm micropores on the pore wall were obtained. The porous CS ceramics had high pore interconnectivity, an open porosity of 66.25% and a compressive strength of 5.47 MPa, which was expected to be used in bone tissue engineering.     

Structure control of hydroxyapatite ceramics via an electric field assisted freeze casting method

Using H₂O₂ aqueous solution as pore-forming agent, hydroxyapatite (HA) porous scaffolds with both lamellar and spherical pores were fabricated by a freeze casting method. The highest porosity was obtained in HA scaffolds prepared using 5 vol% H₂O₂ aqueous solution. The relationship between the electric field intensity and the properties of HA scaffolds was investigated. Results showed that when the electric field intensity was increased from 0 to 90 kV/m, the average diameters of lamellar and spherical pores of HA scaffold were increased from 460 μm to 810 μm, and from 320 μm to 420 μm, respectively. Vitro cellular assay indicated that HA scaffold with both the lamellar and the spherical pores has a better biocompatibility, compared with that with single pores.     

多孔PZT压电陶瓷膜的制备及其抗污染性能

以 PbZr_xTi_1-xO₃（PZT）压电陶瓷粉体为原料,通过干压成型的方法制备多孔PZT陶瓷膜,考察了煅烧温度对多孔PZT陶瓷膜的机械强度、孔隙率以及纯水渗透性能的影响。当煅烧温度为950℃时,可制备出纯水渗透率为850 L·m^-2·h^-1·MPa^-1,孔径为300 nm,机械强度为47.8 MPa,孔隙率为34%的多孔PZT陶瓷膜。在此基础上,考察了极化温度与极化电压对多孔PZT陶瓷膜压电性能的影响,并对极化后的PZT压电陶瓷膜进行萃取和表面等离子刻蚀处理。结果表明：极化温度为120℃、极化电压强度为4 kV·mm^-1,极化后经热乙醇萃取及表面等离子刻蚀4 min后,多孔PZT压电陶瓷膜在外加交流电为20 V时,产生的共振振幅信号值达34.8 mV。将制备的多孔PZT压电陶瓷膜在粒径为600 nm的含油乳化液中进行过滤实验,发现陶瓷膜两端未加交流电时,其通量在2 h内衰减至4%。而加交流电后,其稳定通量可维持在20%左右,表明制备的多孔PZT压电陶瓷膜具有良好的抗污染效果。     

Porous silicate cement membranes generated by the novel method combining freeze casting and heat-dry curing

Porous silicate cement membranes (PSCMs) fabricated by the freeze casting method show great potential to be utilized in seawater pretreatment, fermentation broth separation, and industrial wastewater treatment due to its merit of high-temperature resistance, low-cost, and hierarchically ordered porous structures, while the freeze casting method is complex and time-consuming. In this work, a combination of freeze casting and heat-dry curing was initially applied to generate PSCMs. The preparation periods of PSCMs could be shortened by simplifying preparation processes and reducing curing time. The resulting membranes presented double-layer structures, containing a nucleation zone (N-zone) with dense structures and a stability zone (S-zone) with lamellar pore structures. The X-ray diffraction pattern of membranes displayed the mixed hexagonal and rhombohedral structures. This novel method could save more than half of energy consumption compared with the traditional preparation technology of silicate cement samples. The membranes with a mesopore size of 3.794 nm showed high permeation performance with pure water flux reaching 207.23 L m⁻² h⁻¹ under 0.15 MPa and room temperature. The separation efficiency of oil-water was 78.05% under operating pressure of 0.05 MPa. Molecular dynamics simulation was applied to narrate the microscopic process of transformation during heat-dry curing, and obtained a good similarity of consequences between the computational method simulation and experimental operation.     

Preparation of porous Al2TiO5-Mullite ceramic by starch consolidation casting and its corrosion resistance characterization

Stabilized Al₂TiO₅ (AT)-mullite (M) porous ceramics were fabricated by starch consolidation casting using corn starch as curing agent and their microstructure, mechanical properties, pore size distribution and corrosion resistance were examined. Results showed that AT-M porous ceramic with the flexural strength of 11.5 MPa, apparent porosity of about 54.7% and pore size distribution in the range of 1–15 µm could be obtained with 10 wt% corn starch addition. Corrosion resistance results showed mass losses in hot H₂SO₄ solution and NaOH solution for 10 h to decreased from 1.03% to 0.36% and 4.39–2% when the calcination temperature increased from 1400 °C to 1450 °C, which proved these AT-M porous ceramics to possess an excellent corrosion resistance in acidic condition when calcined at 1450 °C.     

聚合物先驱体转化法制备陶瓷MEMS器件

简述了聚合物先驱体转化陶瓷(PDC)法在制备陶瓷纤维、陶瓷涂层和陶瓷粘接等方面的应用,重点介绍了PDC法在微机电系统(MEMS)器件制造中的发展概况。耐高温MEMS的发展面临两大挑战:高温材料的选择和发展合适的微加工技术。指出了传统加工技术制备陶瓷MEMS的不足,着重介绍了PDC法制备陶瓷MEMS的优缺点。以国外采用PDC法制备陶瓷MEMS的几种典型器件为例,指出该方法在制备陶瓷MEMS器件中存在的问题和未来的发展方向。     

Fabrication of lightweight ZrO2 fiberboards using hollow ZrO2 fibers

ZrO₂ fiberboards with ultra-low densities (0.34–0.40 g/cm³) were fabricated using biomorphic ZrO₂ hollow fibers, which have a lower density and better thermal insulation than traditional ZrO₂ solid fibers. The effects of sol binder content, sintering temperature, and proportion of solid fibers on the density, microstructure, compressive strength, linear shrinkage, and thermal conductivity of lightweight ZrO₂ fiberboards were investigated. The results showed that the hollow features of biomorphic ZrO₂ fibers were successfully maintained after they were made into ZrO₂ fiberboards, which made them less dense and thermally conductive. The best conditions were found to be a sol binder content of 30 vol%, sintering temperature of 1400 °C, and 20 wt% sintered solid fibers to balance thermal insulation and compressive strength. The results show that the density and thermal conductivity of lightweight ZrO₂ fiberboard gives it obvious advantages as a heat-insulating ceramic. Specifically, when the sintering temperature was 1400 °C, the sample had an ultra-low density of 0.34–0.40 g/cm³, a thermal conductivity of 0.101–0.116 W/(m·K) (at 500 °C), a compressive strength of 0.05–0.24 MPa, and a linear shrinkage of 9.4–13%.     

Microstructure of TiO2 porous ceramics by freeze casting of nanoparticle suspensions

During freeze casting of TiO₂ porous ceramics, the porous architecture is strongly influenced by TiO₂ particle size, solids loading, and cooling temperature. This work investigates the influences of particle size, freezing substrate, and cooling temperature on the TiO₂ green bodies prepared by freeze casting. The results show that the lamellar channel width with 100 nm particles is larger than that of 25 nm particles, yet the ceramic wall thickness is noticeably decreased. The lamellar structure is more ordered when using a copper sheet than glass as its freezing substrate. A finer microstructure results when frozen at − 50 ℃ than − 30 ℃. Such porous materials have application potentials in a wide range of areas such as photocatalysis, solar cells, and pollutant removal and should be further studied.     

陶瓷纤维催化剂载体的制备及其性能

利用陶瓷纤维毡为原料,通过适当的成型工艺将纤维毡制备成陶瓷纤维催化剂载体.探讨浸润助剂(十二烷基硫酸钠,SDS)用量、纤维毡的干燥工艺及黏结剂浓度对陶瓷纤维催化剂载体的成型和性能的影响.确定最优的成型工艺,以质量分数0.2％的SDS作浸润助剂,150℃干燥2 min,质量分数30％的硅溶胶作黏结剂,浸渍粘结后烘干,即制...     

Influence of additive contents on the properties of SiC ceramic membranes and their performance in oil-water separation

The high processing cost is the key challenge for the economic industrial use of SiC membrane The aim of this research was to fabricate mullite bonded porous SiC ceramic membrane at low temperature from novel combinations of fly ash and alumina (FA) in weight ratio 44.5:55.5 as sintering additives. The influences of FA and pore former content on the porosity, morphology, crystalline phase composition, mechanical performance, permeability properties were investigated. The membrane prepared at 1300°C using 20 wt% FA showed pure water permeability 3690 Lm⁻²h⁻¹bar⁻¹ and exhibited high oil removal efficiency of ∼ 98% from the synthetic oil-water emulsion having oil concentration of 1000 mg/L. The corrosion behaviour of silicon carbide membrane in the strong acid and alkali solution and its mechanism were investigated. The utilization of fly ash successfully reduced the raw material cost and sintering temperature and the use of alumina reduced the amount of oxidation of SiC as well as increased the amount of mullite bond phase which resulted excellent mechanical strength to the final ceramics.     

Fabrication of a graded-index polymer optical fiber preform by using a centrifugal force

We have investigated a fabricating method for a graded index polymer optical fiber preform using a centrifugal force. When two monomers with different densities and refractive indices are polymerized under a centrifugal force, a concentration gradient is generated due to their density difference. Therefore, a graded refractive index can be obtained according to the concentration gradient. When a monomer is polymerized under a centrifugal force, a preform with a hollow is obtained because of volume shrinkage. To compensate for this practically, additional monomer should be filled into the hollow. Monomer should be fed to obtain a continuous gradient of refractive index at the interface before the first polymerized product is perfectly glassified. Two different types of feeding additional monomer were experimented with: monomer-monomer pair (case I) and monomer-polymer pair (case II). The graded index profile with a proper δn (about 0.01) was successfully obtained in either case.     

Additive manufacturing of fiber reinforced ceramic matrix composites: Advances,challenges, and prospects

Fiber reinforced ceramic matrix composites (FRCMCs) have been used in various engineering fields. Additive manufacturing (AM) technologies provide new methods for fabricating FRCMCs and their structures. This review systematically reviews the additive manufacturing technologies of FRCMCs. In this review, the progress for additive manufacturing of FRCMCs were summarized firstly. The key scientific and technological challenges, and prospects were also discussed. This review aims to motivate the future research of the additive manufacturing of FRCMCs.     

Fabrication of porous fibrous alumina ceramics by direct coagulation casting combined with 3D printing

A novel forming method for preparing porous alumina ceramics using alumina fibers as raw materials by direct coagulation casting (DCC) combined with 3D printing was proposed. Porous fibrous alumina ceramics were fabricated through temperature induced coagulation of aqueous-based DCC process using sodium tripolyphosphate (STPP) as dispersant and adding K₂SO₄ as removable sintering additives. The sacrificial coated sand molds was fabricated by 3D printing technology, followed by the infiltration of silica sol solution for the subsequent suspension casting. Stable alumina suspension of 40 vol% solid loading was obtained by adding 2.0 wt% STPP and 40 wt% K₂SO₄. The controlled coagulation of the suspension could be realized after heating at 90 °C for about 35 min. The ceramic sample sintered at 1450 °C for 2 h showed the highest compressive strength of 24.33 MPa with porosity of 57.38%. All samples sintered at 1300–1450 °C had uniform pore size distributions with average pore size of 7.2 µm, which indicated the good structure stability when sintered at high temperature.     

Dendritic porous alumina with high porosity by directional freeze casting using a binary solution for bacterial removal

High-porosity dendritic porous alumina was fabricated by using tertiary butanol (TBA) hydrate crystals combined with directional freeze casting. The porosity of this porous alumina approximated 80 %, and its high porosity resulted in high water flux. Dendritic pores improved the physical interception capability of porous ceramics due to the intrinsic moving paths and intercepts from the pore structure. Changes in the TBA content (from 70 vol.% to 85 vol.%) caused a change in pore size from 36.58 μm to 11.54 μm and pore structure (change order: snowflake, dendritic, rod-like, and needle-like), which are important factors affecting water flux and interception capability. The interception and removal of Escherichia coli by 7 mm-height porous ceramics with dendritic structure and an average pore size of 27.90 μm reached 100 % at pH 7.2. This study provides a simple and low-cost method for the effective removal of bacteria.     

流延法制备Ni-YSZ/YSZ复合基膜及性能测试

采用传统有机流延法制备NiO-YSZ/YSZ复合基膜,其中包括流延浆料配制及流延工艺过程.采用共烧结方式制备均匀平整的SOFC多孔阳极支撑的致密电解质膜,阳极支撑层厚度1000 μm、阳极功能层20 μm、致密电解质层40 μm左右.并对阳极孔隙率和电解质气体渗透率、显微结构及膨胀系数等进行测试.结果表明通过复合流延的方式可以制备出具有良好组织结构和性能的SOFC阳极支撑系统.     

New insights into sodium alginate fouling of ceramic hollow fiber membranes by NMR imaging

Ceramic hollow fiber membranes are investigated with respect to the fouling behavior. Constant pressure dead‐end filtration experiments have been performed using alginate as model substance for extracellular polymeric substances. In addition to the evaluation of the filtration data using conventional cake filtration model, nuclear magnetic resonance imaging (MRI) was used to elucidate the influence of Ca²⁺ on the fouling layer structure for alginate filtration within ceramic hollow fiber membranes. To visualize the alginate layers inside the opaque ceramic hollow fiber membranes by means of MRI, specific contrast agents were applied. Supplementary to multi slice multi echo imaging, flow velocity measurements were performed to gain more insight into the hydrodynamics in the fouled membranes. MRI reveals the structure of the alginate layers with the finding that the addition of Ca²⁺ to the alginate feed solution promotes the formation of a dense alginate gel layer on the membrane's surface. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2459–2467, 2016     

Porous SiC using polycarbosilane/camphene solutions: Roles of freeze casting parameters

In order to control the pore characteristics and macroscopical performance of porous ceramics, roles of the freeze casting parameters are the key points. Herein, aligned dendritic porous SiC was fabricated by freeze casting of PCS-camphene solutions with different solid loading, freeze front velocity, temperature gradient, and freezing temperature. Influence of these parameters on the microstructure and compressive strength of porous SiC was investigated. With increasing the PCS content, freeze temperature, freeze front velocity or temperature gradient, degree of undercooling of the camphene was increased, resulting in the formation of smaller pore size, decreased porosity and increased compressive strength. Compared to variables of freeze temperature and temperature gradient, increased freeze front velocity was more efficiency in improving the compressive strength of porous SiC, owing to the formation of smaller pore size and longer secondary dendritic crystals. Promising micron-sized porous SiC with high porosity (79.93 vol%) and satisfactory strength (15.84 MPa) was achieved for 10% PCS-camphene solution under optimized freezing conditions.