Influence of compatibility between sol and intermediate layer on the performance of yttria-stabilized zirconia nanofiltration membrane

This paper reports the synergistic effect of the sol and intermediate layer on the performance of yttria-stabilized zirconia (YSZ) nanofiltration (NF) membranes. We have focused on the characterization of the microstructure, pure water permeance, and molecular weight cut-off (MWCO) of the NF membranes derived from zirconia sols of different precursor concentrations on two types of supported ZrO₂ ultrafiltration (UF) membranes. We found that the performance of YSZ membranes strongly depends on the sol concentration and the pore size of the intermediate layer. In addition, YSZ gel membrane formation was found to follow the filtration process. Therefore, it is essential to maintain the compatibility between the sol and intermediate layer to fabricate high-performance NF membranes. A crack-free thin YSZ layer with an MWCO of 816 Da (pore size: 1.4 nm) and a water permeance of 25 L m^-2 h^-1 bar^-1 was fabricated using a precursor concentration of 0.03 mol/L, on ZrO₂ UF membrane with a pore size of 5.5 nm. The YSZ NF membrane exhibited a relatively high retention rate towards MgCl₂ (71%), whereas a lower retention rate was observed for NaCl (35%).     

Preparation and characterization of Al3+-doped TiO2 tight ultrafiltration membrane for efficient dye removal

Al³⁺-doped TiO₂ (AT) tight ultrafiltration membrane with stable anatase phase was prepared by a modified sol-gel process using butyl titanate and aluminum chloride as the precursor and aluminum source respectively. The removal of Alizarin red-S was investigated by filtration experiment. A dip-coating process on homemade flat Al₂O₃ intermediate layer by TiO₂ sol followed by heat treatment was adopted to obtain the desired AT membrane. The addition of Al³⁺ inhibits the phase transformation of nanosized TiO₂ from anatase to rutile and restrains the growth of crystallite, resulting in the pore size of the separation layer reducing to 3.5 nm. The prepared AT1-500 membrane exhibits enhanced hydrophilicity with no cracks or pinholes, and shows a water permeability of 9.6 L m^-2 h⁻¹ bar⁻¹ and cut-off molecular weight (MWCO) of 4650 Da. The membrane demonstrated a retention rate of 96.9% for Alizarin Red-S (250 ppm) and maintained almost constant under repeated using.     

Preparation of yttria-stabilized ZrO2 nanofiltration membrane by reverse micelles-mediated sol-gel process and its application in pesticide wastewater treatment

8 mol% yttria-stabilized ZrO₂ (8YSZ) nanofiltration (NF) membranes were prepared from size-controlled spherical ZrO₂ nanoparticles with an average diameter of ˜10 nm and a particle roundness value greater than 0.90, and the nanoparticles were efficiently fabricated by a reverse micelles (RMs)-mediated sol-gel process. It was found that yttria doping not only suppressed the tetragonal to monoclinic (t-m) phase transition, ensuring the membranes integrity, but also decreased the tetragonal grain size, increased the specific surface area, narrowed the pore size distribution and thus optimized the NF performance. The as-prepared 8YSZ NF membranes with a thickness of ˜260 nm exhibited high NF performances, while the pure water permeability and molecular weight cut-off (MWCO) were 3.9-4.2 L m⁻² h^-1 bar^-1 and 800 ± 50 Da respectively. In the treatment of pesticide wastewater, the removal rate of carbofuran by 8YSZ NF membranes was more than 82%, while the maximum removal rate could reach 89%. Furthermore, the contaminated membranes could be restored as ever after alkali wash and low-temperature calcination, implementing multiple reuses.     

Corrosion resistant ZrO2/SiC ultrafiltration membranes for wastewater treatment and operation in harsh environments

This work focused on the fabrication of a ZrO₂/SiC ultrafiltration membrane by dip coating a high porous SiC support with a ZrO₂ slurry prepared by ceramic processing. The membranes were sintered in different temperatures (1000−1300 °C). With the optimal temperature, it was obtained a mechanically strong, homogenous, and defect free separation layer with 45 μm of thickness and average pore size of 60 nm. A pure water permeability of 360 L.m⁻² h⁻¹ bar^-1 and high retentions of humic acid, indigo dye, and hemoglobin were observed. In a pilot test with an olive oil/water emulsion, 99.91 % of oil was removed without fouling. Long-term corrosion tests at basic and acid baths did not cause change in pore size and morphology. In conclusion, the ZrO₂/SiC membrane has potential to operate in harsh conditions (e.g. heavily contaminated industrial effluents or urban wastewaters) and when severe membrane cleaning and disinfection are required, such as food and pharmaceutical industries.     

Green and feasible fabrication of loose nanofiltration membrane with high efficiency for fractionation of dye/NaCl mixture by taking advantage of membrane fouling

Loose nanofiltration membrane emerges as required recently, since it is hard for conventional nanofiltration membrane to fractionate mixture of dyes and salts in textile wastewater treatment. However, the polymeric membranes unavoidably suffer from membrane fouling, which was caused by the adsorption of organic pollutants (like dyes). Normally, the dye fouling layer will shrink membrane pore size, thus resulting in flux decline and rejection increase. It is thought that membrane fouling may be a double-edged sword and can be an advantage if properly utilized. Thereby, loose nanofiltration membranes were constructed here by a green yet effective method to fractionate dyes/salt mixture by taking advantage of membrane fouling without using poisonous ingredients. A commercially available polyacrylonitrile (PAN) ultrafiltration membrane with high permeability was chosen as the substrate, and dyes were used to contaminate PAN substrate and formed a stable barrier layer when adsorption of dyes reached dynamic equilibrium. The resultant PAN-direct red 80 (DR80) composite membranes displayed superior permeability (~128.4 L m⁻² h⁻¹) and high rejection (~99.9%) to DR80 solutions at 0.4 MPa. Moreover, PAN-DR80 membranes allowed fast fractionation of dyes/sodium chloride (NaCl) mixture, which maintained a negligible dye loss and a low NaCl rejection (~12.4%) with high flux of 113.6 L m⁻² h⁻¹ at 0.4 MPa. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47438.     

Preparation of highly selective nanofiltration composite membranes based on a novel soluble rigidly contorted monomer

Nanofiltration composite membranes with high selectivity are one of the most critical cores in water treatment, and regulating the surface charge and pore structure of active separation layers in thin film composite membranes is one of the most effective means to improve the selectivity of composite membranes. This article synthesized a novel monomer with positive charge and a rigid twisted Tröger's base structure (named TBDA-SO₃), which was manipulated to improve the microporous structure and surface charge of the composite membrane. By interfacial polymerization, TBDA-SO₃, and piperazine were co-reacted with trimesoyl chloride to successfully prepare positively charged, highly selective, and strongly microporous polyamide composite nanofiltration membranes. The best-performing composite nanofiltration membrane in this article has a permeability similar to that of the control group's poly(piperazine amide) (PPA) membrane (pure water flux, 7.8 L m⁻² h⁻¹ bar⁻¹), but has excellent divalent cation selectivity (52.57), which is 4.4 times that of the control group's PPA membrane.     

Asymmetric TiO2 hybrid photocatalytic ceramic membrane with porosity gradient: Effect of structure directing agent on the resulting membranes architecture and performances

Asymmetric TiO₂ hybrid photocatalytic ceramic membranes with porosity gradient have been fabricated via acid-catalyzed sol–gel method. Different structure directing agents (SDAs) i.e. Pluronic P-123, Triton X-100, Tween 20 and Tween 80 were incorporated in the preparation of TiO₂ sol to obtain a porous multilayered TiO₂ coated on the alumina ceramic support. Six different SDA-modified membrane specimens were fabricated. Four of which were coated with the TiO₂ sols prepared using only one type of SDA. The remaining two specimens were fabricated via multilayer coating of different TiO₂ sols prepared using different types of SDAs. Physico-chemical and morphological properties of different TiO₂ layers were thoroughly investigated. The membrane M1 which had the most porous TiO₂ sub-layers showed a high pure water permeability of 155 L m⁻² h⁻¹ bar⁻¹. The membrane showed a relatively high Rhodamine B (RhB) removal of 2997 mg m⁻² over 8 h treatment duration in the batch photoreactor, second only to the Pluronic-based TiO₂ membrane (specific RhB removal of 3050 mg m⁻²). All membrane specimens exhibited good performances while operated in the flow-through photocatalytic membrane reactor. Over 91% of RhB removal capability was retained after 4 treatment cycles. All membranes also showed self-cleaning property by retaining >90% of initial flux after 4 treatment cycles. The flexibility of optimizing membrane performances by fine-tuning the porosity gradient configuration of the photocatalytic layer has also been demonstrated.     

Preparation of poly(ether sulfone) hollow fiber UF membrane for removal of NOM

In this study, a high performance poly(ether sulfone) (PES) hollow fiber ultrafiltration (UF) membrane has been prepared for removal of natural organic matter (NOM). The membrane was spun from a dope solution containing PES/poly (vinyl pyrrolidone) (PVP 40K)/N‐methyl‐2‐pyrrolidone (NMP) by using a wet‐spinning process. Characterization of the membrane in terms of pure water flux, molecule weight cut‐off (MWCO), and retention for a model humic acid (HA) were conducted, and the fouling resistance was analyzed. The experimental results showed that the membrane had a pure water permeability of 20 × 10^?5 L m^?2 h^?1 Pa^?1 and a nominal MWCO of 6000 Da. The results also showed that the membrane retention for humic acid was over 97% and both productivity and selectivity for HA increased with increasing feed velocity. The PES membrane in this study exhibited a much lower fouling tendency than the commercial polysulfone membrane. SEM images revealed that the membrane had an outer dense skin and a porous inner surface. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 430–435, 2006     

Potential of DMSO as greener solvent for PES ultra‐ and nanofiltration membrane preparation

In this article, the performance of polyethersulfone (PES) ultra‐ and nanofiltration membranes, prepared with the non‐toxic solvent dimethyl sulfoxide (DMSO), was investigated. The membranes were prepared by immersion precipitation via phase inversion. Experimental results proved that DMSO is a better alternative to N‐methyl‐2‐pyrrolidone (NMP) as solvent for PES ultrafiltration membranes as the membranes had a higher permeability and rejection of bovine serum albumin (BSA). An explanation was found based on experimental cloud point data and scanning electron microscopy images showing the morphology. The rejection of BSA and rose Bengal (RB) was proportional to the polymer concentration. On the contrary, the permeability decreased with increasing polymer concentration. For a casting thickness of 250 µm, an optimal balance between permeability and rejection of macromolecules for ultrafiltration was found at 24 wt % PES. The permeability was inversely proportional to the casting thickness, but a small decrease in rejection was observed when lowering the thickness. A good balance between permeability and rejection of RB was found, using a reference nanofiltration membrane of 28.5 wt % PES with 150 µm casting thickness. This membrane achieved a RB rejection of 95.3% and a pure water flux of 2.03 L m^?2 h^?1 bar^?1. The membrane thickness and polymer concentration did not have a clear influence on the hydrophilicity of the membranes. It can be concluded that DMSO is a benign alternative as compared to traditional solvents such as NMP and also results in better PES membrane performances. DMSO is a perfectly suitable solvent for ultrafiltration applications and has potential to be used for nanofiltration applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46494.     

Preparation and characterization of a composite nanofiltration membrane interfacially polymerized from cis,cis‐1,3,5‐triaminocyclohexane and trimesoyl chloride

cis,cis‐1,3,5‐Triaminocyclohexane (TAC) was synthesized and used to prepare composite nanofiltration (NF) membranes by interfacial polymerization with trimesoyl chloride (TMC). The surface elemental composition, morphology, and hydrophilicity of the prepared NF membranes were characterized. The separation performances were examined with various salts and polyethylene glycol (PEG400, PEG600) solutions. The effects of preparation conditions were also systematically studied. The NF membrane was negatively charged and exhibited a salt rejection in the order Na₂SO₄ (98.2%) > MgSO₄ (90.8%) > MgCl₂ (84.5%) > NaCl (54.6%). The water permeability was 1.56 L m^?2 h^?1 bar^?1, and the molecular weight cutoff was 600 Da. The TAC/TMC membrane exhibited some characteristics that were different from the ones made from common diamines such as m‐phenylenediamine: (1) the surface was smoother, without a ridge‐and‐valley structure; (2) there were two kinds of crosslinking points in the polyamide chains; (3) the active layer was formed faster (only 5 seconds was required to reach a Na₂SO₄ rejection of 98%). © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43511.     

Novel high performance hollow fiber ultrafiltration membranes spun from LiBr doped solutions

The objective of this research is to evaluate the performance of the polyethersulfone (PES) hollow fiber ultrafiltration membranes spun from LiBr doped solutions prepared using the newly developed microwave heating technique. In addition the resultant hollow fiber membranes were introduced to a new post-treatment method where the membranes were placed in water and irradiated using the microwave technique. Various concentrations of the additive, LiBr, (1-4 wt.%) were added into the PES dope solutions. The dissolution of PES and LiBr in DMF was facilitated by the microwave heating technique. The performance of the membranes was evaluated in terms of pure water permeation and polyethylene glycol separation and its molecular weight cutoff (MWCO) was determined. The results revealed that the microwave post-treatment technique was proven to be effective in producing higher performance membranes. The best performance was obtained at 3% LiBr with MWCO at 90% rejection in the range of 2.83 kDa and high flux range of 222.18 (Lm^− 2 h^− 1 bar^− 1). LiBr interacts in the membrane matrix resulting in the enhancement of the hydrophilic property of the membrane and this is confirmed by the contact angle measurement.     

Preparation and characterization of a novel positively charged nanofiltration membrane based on polysulfone

The goal of this study was to prepare positively charged nanofiltration (NF) membranes to remove cations from aqueous solutions. A composite NF membrane was fabricated by the modification of a polysulfone ultrafiltration support. The active top layer was formed by the interfacial crosslinking polymerization of poly(ethylene imine) (PEI) with p‐xylene dichloride (XDC). Then, it was quaternized by methyl iodide (MI) to form a perpetually positively charged layer. The chemical and morphological changes of the membrane surfaces were studied by Fourier transform infrared spectroscopy, scanning electron microscopy (SEM), and atomic force microscopy. To optimize the membrane operation, the PEI solution concentration, PEI coating time, XDC concentration, crosslinking time, and MI concentration were optimized. Consequently, high water flux (5.4 L m^?2 h^?1 bar^?1) and CaCl₂ rejection (94%) values were obtained for the composite membranes at 4 bars and 30°C. The rejections of the NF membrane for different salt solutions, obtained from pH testing, followed the order Na₂SO₄ < MgSO₄ < NaCl < CaCl₂. The molecular weight cutoff was calculated by the retention of poly(ethylene glycol) solutions with different molecular weights, and finally, the stoke radius was calculated as 1.47 nm. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41988.     

Preparation and characterization of hydrophilic and antifouling poly(ether sulfone) ultrafiltration membranes modified with Zn–Al layered double hydroxides

Zn–Al layered double hydroxide (LDH)‐entrapped poly(ether sulfone) (PES) ultrafiltration membranes with four different weight percentages, 0.5, 1.0, 2.0, and 3.0%, were prepared by a phase‐inversion method. Characterization by scanning electron microscopy, atomic force microscopy and contact angle (CA), equilibrium water content, porosity, average pore size, mechanical strength, and ζ potential measurement were used to evaluate the morphological structure and physical and chemical properties of membranes. Static protein adsorption, filtration, and rejection experiments were conducted to study the antifouling properties, water permeability, and removal ability of the modified membranes. The results show that significant change occurred in the membrane morphology and that better hydrophilicity, water permeability, and antifouling ability were also achieved for the PES/LDH membranes when a proper amount of LDH was used. For example, the CA value decreased from 66.60 to 50.21°, and the pure water flux increased from 80.21 to 119.10 L m^?2 h^?1 bar^?1 when the LDH loading was increased from 0 to 2.0 wt %. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43988.     

Application of piezoelectric quartz for self-cleaning membrane preparation

Separation membranes that are prepared from piezoelectric ceramics can generate ultrasound on-line to maintain surface cleanliness. Here, a lead-free piezoelectric support is presented consisting of quartz. The Na₂O and Al₂O₃ were employed as sintering aids to improve the mechanical performance of piezoelectric quartz support while avoid the formation of no-piezoelectric cristobalite. A ZrO₂-based thin microfiltration membrane layer was applied on the optimized support. The membrane structure, thus obtained had an average pore size and ultrasonic emission of 270 nm and 5.1 mV, respectively. The stationary permeance of the membrane in the treatment of oil-in-water emulsion was 163 L m^?2?h^?1?bar^?1 (LMH/bar). With the application of alternating voltages of 60 V and 100 V, the permeance increased to 198 and 225 LMH/bar, respectively, and the oil rejection was maintained above 97%. The in-situ ultrasound directly acted on membrane surface, so it removed more fouling resistance at lower power than the external one.     

Reaction-bonded robust SiC ceramic membranes sintered at low temperature with coal gangue

Herein, we report an in-situ reaction-bonded SiC membrane sintered at low temperature using a solid waste (i.e. coal gangue) as the sintering aid to form strong neck connections. The effects of sintering temperature and coal gangue proportion on their properties regarding pore size, open porosity, bending strength and pure water permeability were investigated. The single-channel tubular SiC membrane sintered at 1300 °C with a coal gangue proportion of 12 wt% was optimal, exhibiting an average pore size of 2.78 μm, a open porosity of 47.08%, a bending strength of 34.01 ± 1.3 MPa and a high water permeability of 83967 L m⁻² h⁻¹ bar⁻¹. The membrane could completely reject D₅₀ = 0.87 μm SiC solids and presented a steady-state water permeability of 458 L m⁻² h⁻¹·bar⁻¹. The SiC membrane could be regenerated through ultrasonication and its steady-state water permeability was almost unchanged for 3 cycles, proving its mechanical robustness. This work may appeal to the practical low-cost production of high-performance SiC membranes.     

Nanofiltration membranes for ionic liquid recovery

Nanofiltration membranes have been developed by interfacial polymerization using base PES ultrafiltration membranes. By varying the concentration of the reactive monomers present as well as the reaction conditions, the structure of the polymerized barrier layer has been modified. Here, the ability to concentrate low molecular weight sugars while allowing dissolved ionic liquids in aqueous solution to be recovered in the permeate has been investigated for application in biomass hydrolysis. The results obtained here indicate that the selectivity for 1-butyl-3-methylimidazoliumchloride (BmimCl) over glucose can be as high as 36.6. The membrane permeance was 2.31 L m^?2 h^?1 bar^?1.     

Perforative pore formation on nanoplates for 2D porous MXene membranes via H2O2 mild etching

MXene (Ti₃C₂T_x) is a novel, two-dimensional (2D) layered material that is atomically thin, exhibits good mechanical strength, and is ideal for fabricating efficient membranes for molecular separation. However, the applications of MXene membranes are limited by their low water permeability owing to narrow channels and high tortuosity. A novel strategy for introducing artificial pores on the surface of MXene nanosheets via gentle in situ chemical etching with hydrogen peroxide (H₂O₂) to prepare porous MXene nanosheets (PMS) is reported herein. This greatly increases the water permeability of MXene membranes while retaining the high rejection of small-molecule dyes. Permeable pores generated on MXene nanosheets transform the transport model of water molecules in the membrane from typical horizontal transport pathways dominated by interlayer channels to longitudinal–lateral three-dimensional transport pathways, affording increased water molecule transport channels and reduced transport distance. Based on different etching conditions, the obtained membranes exhibit high pure-water permeability ranging from 9.37 to 42.48 L m⁻² h⁻¹ bar⁻¹. Moreover, mild etching maintains the 2D structure of the membrane and retains a nearly complete rejection of congo red dye. This study provides a novel and effective strategy for preparing high-performance porous laminar MXene membranes for dye-separation applications.     

Designing block copolymer architectures for targeted membrane performance

Using a combination of block copolymer self-assembly and non-solvent induced phase separation, isoporous ultrafiltration membranes were fabricated from four poly(isoprene-b-styrene-b-4-vinylpyridine) triblock terpolymers with similar block volume fractions but varying in total molar mass from 43 kg/mol to 115 kg/mol to systematically study the effect of polymer size on membrane structure. Small-angle X-ray scattering was used to probe terpolymer solution structure in the dope. All four triblocks displayed solution scattering patterns consistent with a body-centered cubic morphology. After membrane formation, structures were characterized using a combination of scanning electron microscopy and filtration performance tests. Membrane pore densities that ranged from 4.53 × 10¹⁴ to 1.48 × 10¹⁵ pores/m² were observed, which are the highest pore densities yet reported for membranes using self-assembly and non-solvent induced phase separation. Hydraulic permeabilities ranging from 24 to 850 L m⁻² h⁻¹ bar⁻¹ and pore diameters ranging from 7 to 36 nm were determined from permeation and rejection experiments. Both the hydraulic permeability and pore size increased with increasing molar mass of the parent terpolymer. The combination of polymer characterization and membrane transport tests described here demonstrates the ability to rationally design macromolecular structures to target specific performance characteristics in block copolymer derived ultrafiltration membranes.     

Preparation and characterization of new tubular kaolino-illitic ceramic membrane used for dairy wastewater treatment

Low cost asymmetric tubular ceramic membrane was developed from kaolino-illitic clay collected from the region of Medenin (Tunisia). The obtained membrane was designed to be used for ultrafiltration. The effect of pore forming agent on the plasticity, porosity, pore size distribution, mechanical strength, and permeability was evaluated. The support was performed by extrusion using the raw clay and olive pomace (OP) as pore forming agent. The effect of the use of OP was noticeable; it improved the plasticity of the paste. Also it helped to ameliorate both permeability and porosity of the obtained supports. Top layer was prepared using acid activated clay suspension. The obtained membrane had gas permeability of about 13 cm³.s⁻¹.cm⁻².bar⁻¹ at a pressure of 1.5 bar and water flux of 1700 L.h⁻¹.m⁻² at a pressure of 1 bar. The final membrane was successfully used to eliminate the fat present in a solution containing 10% of milk. Regeneration of the used membrane was carried out by calcination at 550°C. The performances of the used membrane were recovered by 97% after regeneration.     

Preparation and antifouling performance of thin inorganic ultrafiltration membrane via assisted sol-gel method with different composition of dual additives

A novel TiO₂ thin film was prepared on the ceramic hollow fiber by the sol-gel method using poly(vinylpyrrolidone) (PVP) and polyvinyl alcohol (PVA) as additives. SEM images verified the formation of TiO₂ layer with various thickness using different composition of titania sols. The effect of the PVP and PVA contents on the TiO₂ sol properties, the separation and the antifouling performance of the ultrafiltration membranes were investigated thoroughly. When the contents of PVP and PVA were 1.0 wt% and 0.8 wt%, respectively, the resultant membrane showed a thickness of 0.55 μm with a pure water flux of 255 L m^?2 h^?1. In addition, the adherent foulant bovine serum albumin was applied to evaluate the antifouling performance. During the three fouling-recovery cycles, the flux recovery ratio and the flux decay ratio maintained about 99% and 30%. The BSA flux and rejection were still 169 L m^?2 h^?1 and 96.9% after the cycles, indicating a superior antifouling property.