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.     

Recycling of waste fly ash for production of porous mullite ceramic membrane supports with increased porosity

Low-cost porous mullite ceramic membrane supports were fabricated from recycling coal fly ash with addition of natural bauxite. V₂O₅ and AlF₃ were used as additives to cause the growth of mullite crystals with various morphologies via an in situ reaction sintering. Dynamic sintering, microstructure and phase evolution of the membrane supports were characterized in detail and open porosity, pore size, gas permeation and mechanical properties were determined. It showed the membrane support with 3 wt.% V₂O₅ and 4 wt.% AlF₃ addition exhibits an open porosity of ∼50%, mechanical strength of 69.8 ± 7.2 MPa, an interlocking microstructure composed of anisotropically grown mullite whiskers with an aspect ratio of 18.2 ± 3.6 at 1300 °C. Addition of more V₂O₅ lowered the secondary mullitization temperature, resulting in more mullite formation at lower temperatures. The fabricated membrane supports feature high porosity without mechanical strength degradation, possible strengthening mechanism of the mullite whiskers was further discussed.     

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.     

Preparation and characterization of low-cost ceramic microfiltration membranes for the removal of chromate from aqueous solutions

Low-cost ceramic microfiltration membranes were prepared using clay of IIT Guwahati. Two membranes were prepared by paste casting followed by sintering at different temperatures, the first one from clay only (membrane A) and the second one from clay with small amounts of sodium carbonate, sodium metasilicate and boric acid (membrane B). Both the membranes were characterized by TGA, SEM, XRD, water permeability test and acid–base treatment. With the increase of sintering temperature, pore size as well as permeability and flexural strength were increasing while porosity and pore density were decreasing. The overall performance of membrane B was better than membrane A. The average pore size, porosity, pore density and flexural strength of membrane B sintered at 1000 °C were 4.58 μm, 0.42, 2.06 × 10¹⁰ m^− 2 and 11.55 MPa respectively. This membrane was used for the removal of chromate from aqueous solutions by micellar enhanced microfiltration (MEMF) using cetylpyridinium chloride (CPC). 100% rejection of chromate ions were obtained at a feed ratio (CPC/chromate) of 10. Based on raw material prices, the membrane cost was estimated to be $19/m². The prepared low-cost membrane showed good promise for the treatment of wastewater containing such heavy metals.     

Preparation of microfiltration membrane supports using coarse alumina grains coated by nano TiO2 as raw materials

To increase the mixing uniformity of coarse alumina grains with a small amount of nano TiO₂ particles, TiO₂ particles were prepared on the surface of coarse Al₂O₃ grains by in-situ hydrolysis of TiCl₄. The coated coarse Al₂O₃ powder was used to prepare microfiltration membranes supports. The effects of TiO₂ content and sintering temperatures on the bending strength, porosity and pore size distribution of the obtained supports were studied. The results show that the melted nano TiO₂ grains locate mainly at the neck of Al₂O₃ grains, which increases the bending strength of the support by increases the neck area. However, the bending strength is weakened if the TiO₂ content is excessive. No aggregated nano TiO₂ grainsare found. The resulting supports sintered at 1650 °C for 2 h yields a bending strength of 55.4 MPa, a porosity of 38% with a mean pore size of 8.0 μm.     

Preparation of mullite ceramic microfilter membranes using Response surface methodology based on central composite design

In this paper effect of free silica removal from mullite microfilter membranes using different sodium hydroxide (NaOH) concentrations at different temperatures and for different removal times was studied. The prepared membranes were subjected to XRD, SEM, porosity analysis, and mechanical strength measurement. Response surface methodology (RSM) based on central composite design (CCD) was used to design the experiments and analyze three operating parameters including; NaOH solution concentration, NaOH solution temperature and removal time. The optimum porosity of 49.4 was obtained with NaOH solution concentration of 35 wt% at temperature 75 °C and removal time equal to 8 h.Water flux and mechanical strength as important characteristics were measured for all the membranes. For the membrane with the optimum porosity, water flux, mechanical strength, and free silica removal percentage were 61.7 kg/m² h, 21.6 MPa, and 28.2%, respectively. The maximum rejection percentage was 97.2% and emulsion flux for this state was 15.6 kg/m² h at temperature 25 °C and cross flow velocity of 1.5 m/s.     

Biomass assisted microfiltration of chromium(VI) using Baker's yeast by ceramic membrane prepared from low cost raw materials

This work deals with the preparation of ceramic microfiltration membrane from inexpensive raw materials such as kaolin, quartz, calcium carbonate by uniaxial dry compaction method. The prepared green membrane was initially dried at 100 °C for 24 h, 200 °C for 24 h and finally sintered at 900 °C for 6 h. The properties of the membrane such as porosity, flexural strength, chemical stability and hydraulic permeability were investigated. The fabricated membrane possessed an average pore diameter of 1.32 μm, porosity of 30% and flexural strength of 34 MPa. Furthermore, the chemical stability of the membrane was found to be excellent. Eventually, the separation performance of the membrane in terms of flux and removal of chromium(VI) ion using baker's yeast biomass as a function of applied pressure, pH, metal ion concentration and biomass dosage was also studied. The removal of Cr(VI) was found to be strongly dependent on the initial pH of the solution. At lower pH, the metal solution shows higher removal due to higher binding of the metal ion with biomass. It was also observed that the removal of Cr(VI) ion increases with increasing the biomass concentration and decreases with increasing the metal ion concentration. The removal of Cr(VI) was found to be independent of the applied pressure. The maximum removal of Cr(VI) was found to be 94% with the permeate flux of 2.07 × 10^-5 (m³/m² s) for a metal solution concentration of 100 mg/L.     

Effect of TiO2 doping on the characteristics of macroporous Al2O3/TiO2 membrane supports

A cost-effective tubular macroporous ceramic support consisting of alumina and titania was prepared by extrusion and subsequent heat treatment. An Al₂O₃/TiO₂ composite support with high porosity (41.4%), an average pore size of 6.8 μm and sufficient mechanical strength (32.7 MPa) was obtained after sintering at 1400 °C. The formation mechanism of this support as investigated with X-ray micromapping, SEM and XRD indicated that the appearance of Al₂TiO₅ plays a key role in the fabrication of high performance composite membrane supports at relatively low temperature. The amount of Al₂TiO₅ present in the composite has a strong impact on the properties of supports, especially with regard to the mechanical strength. A composite of 85 wt.% Al₂O₃/15 wt.% TiO₂ sintered at 1400 °C for 2 h exhibited both high permeability (pure water flux of 45 m³ m^?2 h^?1 bar^?1), together with an excellent corrosive resistance towards hot NaOH and HNO₃ solutions.     

Effect of polymer concentration on porosity and pore size characteristics of alumina membrane substrates prepared by gelcasting

The effect of urea–formaldehyde (UF) polymer concentration on porosity and average pore size of alumina membrane substrates prepared by gelcasting has been studied. The soluble UF oligomers formed in the initial stages of polymerization act as steric stabilizer for alumina particles in the suspension. The porosity and average pore size of the substrate samples decreased with both the decrease of amount of polymer in the gelcast body and the increase of sintering temperature. Membrane substrates obtained by sintering of gelcast bodies containing UF polymer concentrations from 24.3 to 15.6 wt% at temperatures from 1250 to 1450 °C showed porosity and average pore size of 62.5–27 vol% and 0.43–0.20 μm, respectively. The membrane substrates prepared by the gelcasting method had narrow pore size distribution.     

A new and economic approach to fabricate resistant porous membrane supports using kaolin and CaCO3

This new and economic approach to fabricate resistant porous membrane supports consists of Algerian kaolin and calcite (CaCO₃) instead of Al₂O₃. The porous mullite (3Al₂O₃·2SiO₂) and anorthite (CaO·Al₂O₃·2SiO₂) based ceramics were obtained by solid state reaction. Different calcite amounts (10–28 wt%) have been added into kaolin halloysite type (Al₂O₃·2SiO₂·4H₂O) in order to control pores forming with appropriate distribution and sizes. Based on a pore distribution and formed phases, a kaolin + 15 wt% calcite (K15C) mixture was selected for flat and tubular configurations. A porosity of 45–52% was also obtained when K15C compacts were sintered at 1100–1250 °C. For example, porosity, average pore size (APS) and 3 point flexural strength were 49%, 3 μm and 87 MPa (same as Al₂O₃ value), respectively when K15C compacts were sintered at 1250 °C for 1 h. Finally, a correlation between microstructure and mechanical properties of elaborated supports has been discussed.     

New morphological Ba0.5Sr0.5Co0.8Fe0.2O3−α hollow fibre membranes with high oxygen permeation fluxes

Perovskite Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3?α (BSCF) hollow fibre membranes were fabricated by a combined phase inversion and sintering technique. The membranes were characterised by XRD, SEM and tested for air separation. The membrane possesses a novel morphology consisting of one dense layer and one porous layer. Oxygen permeation fluxes through the obtained hollow fibre membranes were measured in the temperature range 650–950 °C using helium sweep gas rates from 50 to 200 mL min^?1. Experimental results indicated the oxygen permeation flux through the BSCF hollow fibre membrane sintered at 1050 °C was approximately 11.46 mL min^?1 cm^?2 at 950 °C when the helium sweep rate was kept at 200 mL min^?1. The BSCF hollow fibre membrane showed a stable oxygen permeation flux of 8.60 mL min^?1 cm^?2 over the investigated period of 120 h at 900 °C.     

Development of asymmetric BTDA-TDI/MDI (P84) copolyimide flat sheet and hollow fiber membranes for ultrafiltration: Morphology transition and membrane performance

In this paper, the effects of γ-butyrolactone (GBL) weight ratio (w_GBL) and membrane thickness on the formation of asymmetric flat sheet membranes prepared with P84 (BTDA-TDI/MDI co-polyimide)/N-methyl-2-pyrrolidone (NMP)/GBL casting solutions are investigated. With the increase of membrane thickness, the transition of membrane morphology from sponge-like to finger-like structure occurs at critical structure-transition thickness L_c. L_c and the general sponge-like structure thickness (L_gs) increase with w_GBL. For 20 wt.% P84/NMP/GBL casting solution, the membrane morphology changes from finger-like to sponge-like structure at the critical weight ratio of GBL (w^? = 0.69). The membrane morphology and performance of hollow fibers spun with various w_GBL are observed. Compared with the hollow fiber membranes made of 18 wt.% P84/NMP/GBL dope solution with w_GBL = 0.75, the hollow fiber membranes spun with w_GBL = 0.25 present a higher permeation flux and a larger MWCO. As w_GBL increases from 0.25 to 0.75, the membrane morphology transfers from finger-like to sponge-like structure. An increase in shear rate shifts the rejection curves towards left, and lowers the MWCO of hollow fiber membranes. For hollow fiber membranes spun with w_GBL = 0.75, a relatively high permeation flux and a large MWCO are obtained by the wet spinning process.     

Positively charged loose nanofiltration membrane grafted by diallyl dimethyl ammonium chloride (DADMAC) via UV for salt and dye removal

A novel positively charged loose nanofiltration (NF) membrane was fabricated feasibly by UV-induced photografting polymerization of diallyl dimethyl ammonium chloride (DADMAC) on Polysulfone ultrafiltration membrane. A possible reaction mechanism was proposed that a linear chain structure and/or pyrrole like five-membered nitrogen heterocycles structure on the side chain were grafted to form the active barrier layer. NF membrane demonstrated a looser average pore size of 8.6 nm and positive charges surface. Owing to the nanoscale ultrathin nanoscale barrier layer and the combination of Donnan exclusion and steric hindrance, NF membrane exhibited good hydrophilicity, a high pure flux of 60 L/m² h (0.5 MPa), a good salt rejection to Mg²⁺ (90.8%), Al³⁺ (94.0%), Ca²⁺ (91.5%), and a high dye rejection to methylene blue (99.4%) and congo red (100.0%) respectively. The salts rejection of NF membrane to different salts followed the order of AlCl₃ > CaCl₂ > MgCl₂ > NaCl > LiCl > MgSO₄ > Na₂SO_4. NF membrane showed certain fouling resistance to seawater and BSA solution. The grafting polymerization kinetics were comprehensively investigated including irradiation time, monomer concentration and irradiation intensity. X-ray Photoelectron Spectroscopy (XPS), scanning electron microscopy (SEM), atomic force microscopy (AFM) and contact angle measurement were employed to investigate membrane chemistry, morphologies, and hydrophilicity.     

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.     

Titania ultrafiltration membrane: Preparation,characterization and photocatalytic activity

A mesoporous photocatalytic titania (TiO₂) membrane on alumina support is successfully fabricated via the sol–gel processing method. Several techniques such as dynamic light scattering, X-ray diffraction (XRD), TGA, N₂-sorption, and SEM are utilized to investigate the optimized processing parameters and their influence on the final properties of the developed membrane. The prepared titania sol containing organic additives (HPC and PVA) has an average particle size of 55.6 nm with a narrow distribution. The resulting TiO₂ membrane with thickness of 1 μm exhibits homogeneity with no cracks or pinholes. It also maintains small pore size (4.7 nm), large specific surface area (75 m²/g), and small crystallite size (8.3 nm).The permeability and photocatalytic properties of the titania membrane were measured. The permeability coefficient of the fabricated membrane is 30.09 cm³ min^?1 bar^?1 cm^?2. These measurements indicate an optimum processing condition for the preparation of the membrane. The prepared titania membrane has a great potential in developing high efficient water treatment and reuse systems because of its multifunctional capability such as decomposition of organic pollutants and physical separation of contaminants.     

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.     

From nanometric zirconia powder to transparent polycrystal

Coprecipitated zirconia-yttria (8 mol%) gel subjected to hydrothermal treatment at 240 °C resulted in the solid solution powder of 8 nm particle sizes and specific surface area 132.7 m²/g. Uniaxial compaction followed by cold isostatic pressing under 300 MPa resulted in samples of the extremely small and narrow pore size distribution. Such samples start to shrink at about 200 °C which is related to the desorption of water layers surrounding particles. The state of closed porosity is achieved at 1150 °C. Pore closing was performed in air or oxygen atmosphere. Hot isostatic pressing at 1150 °C for 2 h under 250 MPa argon pressure led to transparent materials. Some pores remained in the material whose preliminary pore closure was performed in air. The samples initially sintered in oxygen atmosphere show no porosity and higher light transmittance than the former ones.     

Surface hierarchical porosity in poly (ɛ-caprolactone) membranes with potential applications in tissue engineering prepared by foaming in supercritical carbon dioxide

This article describes the preparation of porous poly (ɛ-caprolactone), PCL, membranes by supercritical CO₂ (SCCO₂) foaming, displaying surface hierarchical macroporosity which could be tailored by careful control of the pressure, in the range of 150–250 bar, and depressurization processes in several steps, showing also pore interconnectivity between both membrane faces. The membranes exhibited two distinct types of surface macroporosity, the larger with diameter sizes of 300–500 μm were surrounded by and also composed of smaller pores of 15–50 μm (same size as inner pores). Membranes were prepared by solvent casting and submitted to different SCCO₂ foaming. Parameters such as membrane thickness, CO₂ flow, foaming time, pressure, temperature and the depressurization processes (rate and profiles), were varied to determine their influence on final porosity and to decipher which parameters were the most critical ones in terms of surface hierarchical pore organization. No remarkable changes in PCL crystallinity were found when membranes were processed under SCCO₂. Finally, biological evaluation of the porous membranes was achieved by seeding human skin fibroblasts on the prepared membranes. The results, in terms of cell adhesion, spreading, proliferation and metabolic activity indicate that these membranes could hold promise for the fabrication of meshes with controlled porosity for tissue engineering applications.     

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 of porous Y2SiO5 ceramics with relatively high compressive strength and ultra-low thermal conductivity by a TBA-based gel-casting method

Porous Y₂SiO₅ ceramics with relative high compressive strength (as high as 24.45 MPa) and ultra-low thermal conductivity (～0.08 W/m K) were successfully fabricated by a tert-butyl alcohol based gel-casting method. The formation mechanism of the 3D interconnected pores and the properties of the green body are discussed. The porosity, pore size, compressive strength and thermal conductivity could be controlled by varying the initial solid loading and the sintering temperature. When regulating the initial solid loading (from 20 to 50 wt%) and sintering temperature (from 1200 to 1500 °C), the porosity can be controlled between 47.74% and 73.93%, and the compressive strength and the thermal conductivity of porous Y₂SiO₅ ceramics varied from 3.34 to 24.45 MPa and from 0.08 to 0.55 W/m K, respectively. It should be noted that the porous Y₂SiO₅ ceramics with 30 wt% solid loading and sintering at 1400 °C had an open porosity of 61.80%, a pore size of 2.24 μm, a low room-temperature thermal conductivity of 0.17 W/m K and a relatively high compressive strength of 13.91 MPa, which make this porous Y₂SiO₅ ceramics suitable for applications in high-temperature thermal insulators.