Thermal conductivity of ceramic/metal composites from preforms produced by freeze casting

Porous alumina and zirconia preforms, processed by ice templating, have been used to manufacture ceramic/metal composites by aluminium alloy infiltration. The aim of the present work is to study the influence of the ceramic material nature and of the initial porous structure on the thermal conductivity anisotropy of the composite in order to assess potential applications in the field of thermal management. The materials are characterised in terms of pore volume fraction and pore size before and after metal infiltration. The freeze casted preforms exhibit anisotropic lamellar structures with ellipsoidal pores ranging from 35 µm to 40 µm and porosity fractions from 64 to 67%. After metal infiltration, composite parts present the same anisotropic morphology, which correspond to alternating ceramic and metal layers. Thermal conductivities have been determined, with an average of 80 W m⁻¹ K⁻¹ and 13 W m⁻¹ K⁻¹ parallel and perpendicular to the freezing direction respectively, for zirconia/metal composites. Theoretical values of thermal conductivity can be calculated using the Maxwell-Eucken relation, to handle the residual porosity, in combination with series and parallel resistance models to describe the overall anisotropic character. These give good agreement to experiment.     

Effect of phase composition of natural quartz raw material on characterization of microfiltration ceramic membranes

The results of development of multi-layer ceramic membranes on the basis of natural quartz raw material from Mongolia are presented. The influence of the phase composition and temperature of calcination on the porosity, morphology and mechanical strength of large-porous ceramic support obtained by the method of isostatic pressing was studied. It was established that multi-layer ceramic membranes obtained by the application of water suspension of high-disperse quartz sand of Mongolia and alumosilicate binder with the addition of 15–35 wt% of quartz are characterized by optimal properties. The developed tubular ceramic membranes with the average pore size 5.3 µm, coefficient of air permeability (4.17–4.41)×10⁻¹³ m², productivity by water 46.3–48.0 m³/(h×m²×bar) and mechanical strength 2.27–2.53 MPa are perspective for wide use in microfiltration processes.     

Processing of alumina-coated clay–diatomite composite membranes for oily wastewater treatment

Crack-free alumina-coated clay–diatomite composite membranes were successfully prepared by a simple pressing and dip-coating route using inexpensive raw materials at a temperature as low as 1000 °C in air. The changes of porosity, flexural strength, pore size, flux, and oil rejection rate of the membranes were investigated while changing the diatomite content. A simple burn-out process subjected to the used membranes in air completely recovered the specific surface area, steady state flux, and oil rejection rate of the virgin membranes. The recycled membranes showed an exceptionally high oil rejection rate (99.9%) with a feed oil concentration of 600 mg/L at an applied pressure of 101 kPa. The typical porosity, pore size, flexural strength, oil rejection rate, and steady state flux of the recycled alumina-coated clay–diatomite composite membrane were 36.5%, 0.12 μm, 32 MPa, 99.9%, and 6.91×10⁻⁶ m³ m⁻² s⁻¹, respectively, at an applied pressure of 101 kPa.     

The membrane properties of alumina-coated alumina support layers and alumina-coated diatomite–kaolin composite support layers

ABSTRACT

Porous ceramic membranes are a current research focus because of their outstanding thermal and chemical stability. Recent research has utilised inexpensive natural materials such as diatomite to reduce the expense of these porous ceramic membranes. However, insufficient data exist for microfiltration applications using the diatomite-based membranes. The measured membrane properties of alumina-coated alumina support layers and alumina-coated diatomite–kaolin composite support layers have been compared. These experiments have been used to determine whether the average pore size could be reduced effectively by controlling the thickness of the alumina coating layer, while maintaining acceptable water permeability. The membrane properties of the alumina-coated alumina support layers and the alumina-coated diatomite–kaolin composite support layers were examined using the scanning electron microscopy, mercury porosimetry, and a dead-end microfiltration system.     

Preparation and characterization of porous MgAl2O4 spinel ceramic supports from bauxite and magnesite

Porous magnesium aluminate spinel (MgAl₂O₄) ceramic supports were fabricated by reactive sintering from low-cost bauxite and magnesite at different temperatures ranging from 1100 to 1400 °C and their sintering behavior and phase evolution were evaluated. The effects of sintering temperature on the pore structure, size and distribution as well as on the main properties of spinel ceramic supports such as flexural strength, nitrogen permeation flux and chemical resistance were investigated. The supports prepared at 1300 °C showed a homogeneous pore structure with the average pore size of 4.42 μm, and exhibited high flexural strength (35.6 MPa), high gas permeability (with nitrogen gas flux of 3057 m³ m⁻² h⁻¹ under a trans-membrane pressure of 0.1 MPa) and excellent chemical resistance.     

Preparation and characterization of novel ceramic membranes for micro-filtration applications

Porous microfiltration range ceramic membranes were prepared using kaolin and other suitable materials like feldspar, quartz, boric acid, activated carbon, sodium metasilicate and titanium dioxide following standard paste casting route. The membranes were casted as circular disks of 40 mm ID and 5 mm thickness. They were characterized using thermo gravimetric analysis (TGA), particle size distribution (PSD), X-ray diffraction (XRD) and scanning electron microscope (SEM) to evaluate the effect of maximum sintering temperature on the structure, porosity and mechanical integrity. The prepared membranes were initially dried at 120 °C and 250 °C for 24 h each and finally sintered at 850 °C, 900 °C and 950 °C for 6 h. Morphological parameters viz. pore size distribution, porosity, average pore size of the prepared membranes were determined and the membrane performance were evaluated by carrying out the permeation experiment with pure water. Results show that the average pore size of the membranes increases from 1.59 µm to 2.56 µm and porosity of the membrane supports decreases from 18.88% to 5.59% with increase in sintering temperature from 850 °C to 950 °C. The membrane corrosion resistance was also tested using acid and base and it is observed that there is no significant weight loss in the process. Based on market price of the inorganic precursors, the membrane cost was estimated to be $92/m² which can be considered low cost in the microfiltration range for industrial applications.     

Fabrication and optimization of a clay-bonded SiC flat tubular membrane support for microfiltration applications

SiC has excellent structural and mechanical properties and also has excellent properties related to membrane performance. High processing temperature increases the costs of SiC products and thus limits their use. In this study, we fabricated SiC-based ceramic support layers using a clay-bonding technique. Kaolin, a well-known clay, was used as a binder for silicon-carbide particles. Three different SiC powders were used on the basis of particle size for fabrication by the extrusion method, which converts powders into flat tubular form. The resultant supports are sintered at 1300–1500 °C in air and evaluated for their structural properties, pore characteristics and permeability. It is evident from the study that we can produce a support layer with small-sized SiC powder that has a high open porosity and high strength with a smaller pore size and lower permeability in comparison with layers produced with a large-sized starting SiC powder. Additionally, the produced support layer could be used as a stand-alone membrane for 1 µm particles.     

Design and preparation of high permeability porous mullite support for membranes by in-situ reaction

The natural mineral kaolin combined with alumina additives Al(OH)₃,α-Al₂O₃ and AlF₃ was used to prepare porous mullite ceramic membrane supports using an in-situ reaction. The effects of composition and sintering temperature on the sintering behavior, pore structure, permeability and microstructure of the resulting porous mullite supports were extensively investigated. The experimental results showed that excess SiO₂ in kaolin can be consumed by adding alumina precursors, which resulted in a stiff skeleton of interlinked needle-like mullite crystals in-situ during the sintering. The needle-like mullite crystals touched each other and formed a short network, which acted as a porous skeletal network structure. This network resulted in a highly permeable porous structure. The resulting support is suitable for the preparation of asymmetric ceramic membranes. The densification and pore structure of the support can be effectively adjusted by control of the quantity of alumina precursors in the composition and the sintering temperature. Sintering the subject mullite compositions at 1500 °C for two hours resulted in support structures with an average porosity of 45.9%, an average pore size of 1.3 µm and a penetrating porosity of 35.9%.     

Composite ceramic membranes from natural aluminosilicates for microfiltration applications

This work concerns to the development and characterisation of support, active layer and tubular composite membranes (CM) from natural aluminosilicates as principal components (clay, bentonite, feldspar, quartz, alumina). The selection of these raw materials was primarily based on their low cost and they are locally produced. In the substrates preparation, the effect of materials compositions, additives, particle sizes, paste rheological properties, and drying-sintering temperatures was investigated. The consolidated ceramic substrates were characterised by SEM, DTA–TG, X-Ray diffraction, Hg intrusion, mechanical resistance, and water flux measurements. Extrusion has been used as the forming process of tubular support. The CM was fabricated depositing a thin active layer by slip-casting method on the support. The CM sintered at 1200 °C showed the best structural characteristics, porosities of 50%, active layer pore size between 0.08 and 0.55 μm. The CM hydraulic permeabilities (10–274 L/h m² kPa) were comparable and greater than several inorganic commercial membranes and CM obtained from other researches. The CM microfiltration effectiveness was tested with different substances from food industry, i.e. slaughterhouse wastewater treatment and goat milk pasteurisation. The obtained results, insoluble residue rejections (100%) and high bacterial removal (87–99%), make the ceramic CM suitable for microfiltration processes.     

Fabrication and electrochemical properties of SOFC single cells using porous yttria-stabilized zirconia ceramic support layer coated with Ni

A porous yttria-stabilized zirconia (YSZ) ceramic supported single cell with a configuration of porous YSZ support layer coated with Ni/Ni–Ce_0.8Sm_0.2O_1.9 (SDC) anode/YSZ/SDC bi-layer electrolyte/La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ cathode was fabricated. The porosity, mechanical strength, and microstructure of porous YSZ ceramics were investigated with respect to the amount of poly(methyl methacrylate) (PMMA) used as a pore former. Porous YSZ ceramics with 56 vol.% PMMA showed a mechanical strength of 24 ± 3 MPa and a porosity of 37 ± 1%. The electrochemical properties of the single cell employing the porous YSZ support layer were measured using hydrogen and methane fuels, respectively. The single cell exhibited maximum power densities of 421 mW/cm² in hydrogen and 399 mW/cm² in methane at 800 °C. Moreover, at a current density of 550 mA/cm², the cell maintained 91% of its initial voltage after operation in methane for 13 h at 700 °C.     

Enhanced water desalination performance through hierarchically-structured ceramic membranes

Developments of membrane water desalination are impeded by low water vapor flux across the membrane. We present an innovative membrane design to significantly enhance the water vapor flux. A bilayer zirconia-based membrane with a thick hierarchically-structured support and a thin functional layer is prepared using a combined freeze drying tape casting and screen printing method. The hierarchically-structured YSZ support has a porosity of 42.6%, pores of 4.5 μm or larger, and a relatively low tortuosity of 1.58 along the thickness direction. The bilayer membrane is then converted from naturally hydrophilic to hydrophobic via grafting with a fluoroalkylsilane. A water flux of 28.7 Lm⁻² h⁻¹ and a salt rejection of 99.5% are achieved by exposing the functional layer to 80 °C salt water of 2 wt.% NaCl and the support layer to 20 °C distilled water. These results are the best performing ones for ceramic membranes in direct contact membrane distillation operation.     

Design of ceramic filters using Clay/Sawdust composites: Effect of pore network on the hydraulic permeability

Clay based ceramic composite materials with hydraulic permeability were elaborated using sawdust as porogent agent. Their mechanical, morphological, microstructural and pore network properties were investigated. Mixtures in various ratios of two kaolinite clay minerals, Ba (highly plastic) and Va (sand-rich) constitute the five ceramic matrixes studied (CM1, CM2, CM3, CM4 and CM5). Due to their high flexural strength, CM3 and CM4 received 0%, 5%, 10% and 15% sawdust before firing, to improve the porosity of the final matrixes. Results revealed that 900–1000 °C is the range of temperature necessary to get good sintering and flexural strength (≥2 MPa). A typical clay-sawdust based materials (parallepipedic bricks) present porosity ≥40 vol% and 1.5 g/cm³ density. Characterizations such as FTIR, SEM, MIP and flow permeability of ceramic candles were performed. A Hydraulic permeability of ~10 mDarcy was obtained and the mean pore diameter varies from 0.05 to 0.1 µm, in agreement with the microstructure exhibited by the ceramic candles. In the presence of sawdust, pores with size up to 10 µm were observed, justifying the increase of flowing permeability. The elaborated matrixes are promising candidates for microfiltration.     

Fabrication of insulated metal substrates with organic ceramic composite films for high thermal conductivity

Insulated metal substrates (IMSs) were fabricated and characterized using an organic ceramic composite as a coating mixture. Organic‐inorganic sol solutions were prepared by a sol‐gel process using TEOS (tetraethylorthosilicate), MTMS (methyltrimethoxysilane) and PhTMS (phenyltrimethoxysilane). Ceramic fillers were composed of aluminum oxide (1 and 4 µm) and silicon nitride. The optimal ratio of ceramic filler in the coating mixture was found to be 70 wt%. A thermal conductivity of 3.16 W/mK and a breakdown voltage of 4 kV with a leakage current of 0.17 mA/cm² were obtained for the 122 µm-thick film. A well-networked microstructure between the sol resin and filler in the organic ceramic composite films enhanced the properties of the IMS, such as thermal conductivity and electric insulation.     

Macro-porous dolomite hollow fibers sintered at different temperatures toward widened applications

Ceramic hollow fibers from natural dolomite with different pore structures have been designed. The unique hollow fibers were produced by the phase inversion method and applying different sintering temperatures. The hollow fiber precursor presented coagulated polymers through the fiber thickness due to the high granulometric size of the used dolomite material (11.3–47.2 µm). The fiber sintered at 400 °C presented mechanical strength of 4.5 MPa and water permeability of 84.7 L h⁻¹ m⁻² kPa⁻¹. The increase in the sintering temperature up to 1250 °C resulted in fragile hollow fibers due to dolomite transformations that resulted in gas release and a significant mass loss of 33.7%. At 1350 °C, the liquid phase sintering mechanism occurred and the dolomite hollow fiber sintered at 1350 °C presented mechanical strength of 5.5 MPa and water permeability of 2219 L h⁻¹ m⁻² kPa⁻¹. Doloma dissolution in water was investigated and calcium concentration was increased from 0.72 (pure water) to 2.905 ppm for a contact time from 4 h between the fiber sintered at 1250 °C and pure water. However, this dissolution did not decrease the mechanical resistance of the fiber. These results suggest the potential of applying natural dolomite for producing low cost membranes or substrates. The hollow fiber sintered at 400 °C is suggested to be used as a proper separation medium, while the hollow fiber sintered at 1350 °C may be used as a substrate for the deposition of a separation layer to be used in gas separations. The high porosity of the fiber sintered at 1250 °C suggests its application as a support for the impregnation of functional materials. Thus, depending on the applied sintering temperature the dolomite membrane can be used in different applications.     

Pressure-assisted self-assembly technique for fabricating composite membranes consisting of highly ordered selective laminate layers of amphiphilic graphene oxide

We prepare highly ordered flexible layers of graphene oxide (GO) on modified polyacrylonitrile substrates by the pressure-assisted self-assembly technique. This composite membrane shows excellent performance during the pervaporation separation of a 70 wt.% isopropyl alcohol (IPA)/water mixture: 99.5 wt% water in permeate and 2047 g m⁻² h⁻¹ permeation flux. Despite the specific GO deposition increase from 4.3 to 43.3 × 10⁻⁵ g cm⁻² (ninefold layer thickness growth), its effect on the permeation flux is not significant, as manifested by only a little decrease in the flux. At 70 °C feed temperature, the permeate water concentration remains 99.5 wt% and the permeation flux reaches 4137 g m⁻² h⁻¹. The high selectivity may be due to the dense GO film consisting of highly ordered and packed laminates, allowing water but inhibiting IPA molecules to pass through. GO is demonstrated to be amphiphilic: water molecules adsorb first at the hydrophilic edge (hydroxides) and then rapidly diffuse through the hydrophobic core (mainly carbon), forming a water passage channel that promotes high permeation flux. When water molecules permeate through the GO layers, they accumulate and form a monolayer structure that pushes the successive layers away from each other, leading to widening of the d-spacing.     

Preparation of dual-phase composite BaCe0.8Y0.2O3/Ce0.8Y0.2O2 and its application for hydrogen permeation

Dual-phase ceramic membranes composed of BaCe_0.8Y_0.2O₃ (BCY) and Ce_0.8Y_0.2O₂ (CYO) were successfully synthesized by solid state reaction method for hydrogen permeation. The influences of the BCY/CYO volume ratios on phase composition, microstructure, chemical stability and electrical property were investigated. The hydrogen permeation of the dual-phase composite was characterized as a function of temperature and feed side hydrogen partial pressure. The results showed that there was no reaction between the two constituent oxides observed under the preparation conditions. The dual-phase composite with different BCY/CYO volume ratios after sintering at 1550 °C exhibited dense structure, as well as good stability in 4% H₂/Ar, wet Ar and pure CO₂ atmosphere. The conductivity of the dual-phase composite increased with the content of CYO increasing and 30BCY–70CYO exhibited the highest total conductivity of 2.6×10⁻² S cm⁻¹ at 800 °C in 4% H₂/Ar. The hydrogen permeability of 30BCY–70CYO sample was improved as the temperature and the hydrogen partial pressure in feed gas increased. The hydrogen permeation flux of 1.7 μmol cm⁻² s⁻¹ was achieved at 850 °C.     

Macro-porous ceramic supports for membranes prepared from quartz sand and calcite mixtures

A new type of porous ceramic supports for membranes has been designed. The new supports have been fabricated from polycrystalline quartz sand and calcite raw materials. In this work, two configurations of support (tubular and flat) have been produced using extrusion method. The open porosity, the pore size distribution, the average pore size (APS), the strength and the permeability of sintered supports have been found to depend mainly on the weight ratio of calcite (CaCO₃) additive. The results showed that with the addition of 15–35 wt.% of calcite and sintering temperature of about 1375 °C for 1 h the best characteristics of sintered supports could be obtained. The developed tubular ceramic supports with the APS 6.3–12 μm, open porosity 42–55%, the water permeability (16–68 m³/h m² bar) and flexural strength 8–18 MPa hopefully offer many perspectives for a wide use in membranes technology.     

Fabrication and H2 flux measurement of asymmetric La27W3.5Mo1.5O55.5-δ − La0.87Sr0.13CrO3-δ membranes

Novel asymmetric hydrogen permeable membranes consist of a dense ceramic–ceramic (cercer) composite layer of La_0.87Sr_0.13CrO_3-δ and La₂₇W_3.5Mo_1.5O_55.5-δ deposited on a tubular porous support of the latter composition. The membranes were produced by extrusion and dip-coating with various thermal cycles required for adjusting the thermal shrinkage of the different layers and obtaining gas tight membrane layers. The produced asymmetric membranes have a dense cercer layer thicknesses ranging from 25 to 50 μm on supports exhibiting a porosity of up to 40 vol%. The effect of processing parameters, such as volume of pore former, coating steps, sintering temperature and soaking time on the microstructure of the membranes is discussed to highlight critical steps in the manufacturing protocol. Hydrogen fluxes were measured as a function of temperature with both wet and dry Ar sweep gas. Results are discussed with respect to membrane architectures and materials properties.     

Preparation and characterization of a nigerian mesoporous clay-based membrane for uranium removal from underground water

This study reports the removal of uranium in underground wastewater using a Nigerian clay-based membrane. The clay and sintered clay were characterized using XRD, XRF, TGA/DTA, FESEM and PSD. The raw clay was mixed with cassava starch (10, 15, 20 and 25 wt%) and sintered at a temperature of 1300 °C. A multi-point BET analysis of the produced clay-based membranes was conducted to determine the surface area, pore volume and average pore size. Sintering characteristics were determined by apparent porosity, bulk density and flexural strength. The radioactivity of the feed and the permeated water was counted using a gamma spectrometer with an HPGe detector. From the XRD, TGA and FESEM, 1300 °C was found to be optimum for the mullite formation from the clay. The average pore sizes of the produced membranes from the BET results were observed to be in the range from 51 to 70 Å and with a steady state flux range of the tested membranes in the range 1.92×10⁻⁵–2.09×10⁻⁴ m³ m⁻² s⁻¹. The permeation flux produced is of high quality with a rejection in the range of 1.78–2.56 Bq/l of the uranium activity by the tested membranes. This low-cost membrane will have an application for the treatment of uranium-containing wastewater from fracking, oil exploration and phosphate mining industries.     

Fabrication and thermal conductivity of highly porous alumina body from platelets with yeast fungi as a pore forming agent

A highly porous alumina body was fabricated by heating a green clinker body consisting of platelets and yeast fungi as a pore forming agent. Four kinds of alumina platelets were used. When green clinker bodies of platelet aggregates (A11) with 10 and 30 mass% of yeast fungi were heated at 1500 °C for 2 h, their porosities reached 72% and 78%, respectively. In contrast, when the green clinker bodies composed of platelets with an average size of 10 µm and an aspect ratio of 25–30 (SERATH①), and 20 mass% of yeast fungi were heated at 1400 °C for 2 h, the porosity of the resultant porous alumina body was also approximately 72%. However, the room temperature thermal conductivities of the porous alumina bodies with 72% porosity derived from A11 and SERATH① were 0.86 and 0.50 W m⁻¹ K⁻¹, respectively. The decrease in the thermal conductivity of the porous alumina body produced from SERATH① is caused by the long path route for heat transfer.