Bio‐inspired method to fabricate poly‐dopamine/reduced graphene oxide composite membranes for dyes and heavy metal ion removal

Due to the narrow layer spacing, graphene oxide (GO) composite membrane usually exhibits a relatively low water flux in the process of wastewater treatment. In this study, GO was reduced to reduced graphene oxide through a bio‐inspired method, which was functionalized modified by poly‐dopamine (PDA). Then a series of PDA/reduced graphene oxide sheet films were prepared by vacuum filtration on the surface of cellulose acetate membrane (under the pressure of −0.1 MPa). The result indicated that the novel membranes had an excellent stability owing to the cross‐link of PDA. In addition, the hydrophilicity of membrane was increased significantly after PDA modification, which presented a superior water flux than pure GO composite membrane. More importantly, as‐prepared membranes were successfully applied for the removal of dyes (including Congo red, methylene blue, and rhodamine B) and heavy mental ion (Cu(II)) from simulated wastewater. This work might provide a new method for preparation and application of GO composite membranes.     

Chitosan‐modified graphene oxide as a modifier for improving the structure and performance of forward osmosis membranes

Chitosan (CS) with good hydrophilicity and charged property was used to modify graphene oxide (GO), the obtained GO‐CS was used as a novel modifier to fabricate thin film composite forward osmosis (FO) membranes. The results revealed that the amino groups on CS reacted with carboxyl groups on GO, and the lamellar structure of the GO nanosheets was peeled off by CS, resulting in the reducing of their thicknesses. The GO‐CS improved the hydrophilicity of polyethersulfone (PES) substrate, and their contact angles decreased to 64° with the addition of GO‐CS in the substrate. GO‐CS also increased the porosity of the substrate and surface roughness of FO membrane, thereby optimizing the water flux and reverse salt flux of FO membrane. The average water flux of the FO membrane reached the optimal flux of 21.34 L/(m² h) when GO‐CS addition was 0.5 wt%, and further addition of GO‐CS to the substrate would decrease the water flux of FO membrane, and the reverse salt flux also decreased to the lowest value of 2.26 g/(m² h). However, the salt rejection of the membrane increased from 91.4% to 95.1% when GO‐CS addition increased from 0.5 to 1.0 wt% under FO mode using 1 mol/L sodium chloride (NaCl) solution as draw solution (DS). In addition, high osmotic pressure favored water permeation, and at the same concentration of DS, magnesium chloride (MgCl₂) exhibited better properties than NaCl. These results all suggested that GO‐CS was a good modifier to fabricate FO membrane, and MgCl₂ was a good DS candidate.     

Interlaboratory studies of highly permeable thin‐film composite polyamide nanofiltration membrane

The aim of this paper is to survey interlaboratory studies of performance data to produce highly permeable thin‐film composite (TFC) polyamide nanofiltration (NF) membrane in the form of flat sheet at bench scale. TFC polyamide NF membranes were fabricated via interfacial polymerization of 1,3‐phenylenediamine and trimesoyl chloride on porous polyethersulfone (PES) membrane. The NF membranes were characterized by atomic force microscopy (AFM), scanning electron microscopy (SEM), and cross‐flow filtration. The AFM and SEM analyses indicated that a rough and dense film was formed on the PES support membrane. The permeability and NaCl rejection of the NF membrane prepared at the presence of camphor sulfonic acid as pH regulator and triethylamine as accelerator in the aqueous solution were 21 l m^?2 h^?1 and 70%, respectively. In order to estimate the repeatability and reproducibility standard deviations, the development of an interlaboratory study was conducted by measurements of permeation flux and salt rejection of the synthesized membranes. Repeatability standard deviation of the permeation flux data for the membrane based on optimum formulation was 1.99, and reproducibility standard deviation was 3.55. Also based on this trend, repeatability standard deviation of the salt rejection data was 1.57, and reproducibility standard deviation was 4.11. The American Society for Testing and Materials standard E691‐05 was used for data validation of the repeatability and reproducibility standard deviations and consistency statistics. Copyright © 2011 John Wiley & Sons, Ltd.     

Simple fabrication of Cu~(2+) doped calcium alginate hydrogel filtration membrane with excellent anti-fouling and antibacterial properties

Herein,copper ion doped calcium alginate(Cu~(2+)/CaAlg) composite hydrogel filtration membranes were prepared by using natural polymer sodium alginate(NaAlg) as raw material.The thermal stability and structure of the composite membranes were characterized by thermogravimetric analysis and infrared spectroscopy.The mechanical strength,anti-fouling performance,hydrophilicity and filtration performance of the membrane were studied.The results show that Cu~(2+)/CaAlg hydrogel membrane has excelle nt mechanical properties and thermal stability.The anti-swelling ability of the membrane was greatly enhanced by doping Cu~(2+).After three alternate filtration cycles,the flux recovery rate of Cu~(2+)/CaAlg hydrogel membrane can still reach 85%,indicating that the membrane has good antipollution performance.When the operation pressure was 0.1 MPa,the rejection of coomassie brilliant blue G250 reached 99.8% with a flux of 46.3 L m ~2 h ~1,while the Na_2 SO_4 rejection was less than 10.0%.The Cu~(2+)/CaAlg membrane was recycled after 24 h in the filtration process,and its flux and rejection rate did not decrease significantly,indicating that the hydrogel membrane has long-term application potential.The Cu~(2+)/CaAlg membrane has a wide range of applications prospect in dye desalination,fine separation and biopharmaceutical technology fields.     

Salt‐Induced Fabrication of Superhydrophilic and Underwater Superoleophobic PAA‐g‐PVDF Membranes for Effective Separation of Oil‐in‐Water Emulsions

Conventional polymer membranes suffer from low flux and serious fouling when used for treating emulsified oil/water mixtures. Reported herein is the fabrication of a novel superhydrophilic and underwater superoleophobic poly(acrylic acid)‐grafted PVDF filtration membrane using a salt‐induced phase‐inversion approach. A hierarchical micro/nanoscale structure is constructed on the membrane surface and endows it with a superhydrophilic/underwater superoleophobic property. The membrane separates both surfactant‐free and surfactant‐stabilized oil‐in‐water emulsions under either a small applied pressure (<0.3 bar) or gravity, with high separation efficiency and high flux, which is one to two orders of magnitude higher than those of commercial filtration membranes having a similar permeation property. The membrane exhibits an excellent antifouling property and is easily recycled for long‐term use. The outstanding performance of the membrane and the efficient, energy and cost‐effective preparation process highlight its potential for practical applications.     

Exploring the characteristics,performance, and modification of Matrimid for development of thin‐film composite and thin‐film nanocomposite reverse osmosis membranes

Reverse osmosis (RO) membrane technology is widely employed to address the demands for freshwater. In this study, fabrication and performance evaluation of customized RO membranes comprised of Matrimid and polyacrylonitrile (PAN) is carried out. While exploring adoption of slip coating procedure, the effects of various modification techniques including incorporation of TiO₂ nanoparticles and polyethylene glycol (PEG) into the skin layer as well as cross‐linking were investigated. The individual and combined effects of parameters on membrane morphology, surface characteristics and performance were also examined. Despite the distinctive characteristics of involved materials, delamination‐free composite membranes were successfully formed with an intimate contact at the interface of two layers. The results also indicated that increasing concentration of Matrimid in dope solution led to increase in membrane thickness and consequently decline in water flux. In the best case, membrane prepared using 1 wt.% Matrimid in dope exhibited water flux of 0.98 LMH and NaCl rejection of 95.7%. Also, incorporation of 3 wt.% TiO₂ nanoparticles offered membranes with improved water flux of 1.37 LMH and salt rejection of 95.8%. On the other hand, water flux and salt rejection in membranes containing 5 wt.% PEG were 1.18 LMH and 96.2%, respectively. The co‐presence of both nanoparticles and PEG provided more insights about the contributing factors in tuned membranes. Modification of skin layer by cross‐linking significantly improved salt rejection at the expense of water flux. The results are scientifically interpreted and compared to the values reported in literature.     

Preparation and characterization of novel PES‐(SiO2‐g‐PMAA) membranes with antifouling and hydrophilic properties for separation of oil‐in‐water emulsions

In the present study, modification of nanoparticles (NPs) was investigated to mitigate aggregation of SiO₂ nanoparticles and improve the polymeric membrane's performance. For this purpose, the surface of SiO₂ nanoparticles was activated with amine groups, and polymethacrylic acid (PMAA) was grafted on the surface of NPs by atom transfer radical polymerization. Modified NPs were characterized by Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA) tests. Polyethersulfone (PES) membranes were fabricated with both SiO₂ and SiO₂‐g‐PMAA NPs via nonsolvent‐induced phase separation method. The fabricated membranes were characterized regarding their permeability, hydrophilicity, and porosity properties, and their separation efficiency was tested using the synthetic oil‐in‐water emulsion. The surface and cross‐sectional morphologies of membranes were observed by field emission scanning electron microscopy (FESEM). The experimental trials showed that modified NPs dispersed more uniformly in the structure of membranes and hydroxyl groups on the surface of NPs acted more effectively. Modification of NPs enhance the membrane performance in terms of permeate flux, hydrophilicity, and porosity. NPs modification improved the permeate flux about 46%. Oil rejection for all tested membranes was more than 98%, and modification of NPs did not reduce the rejection of membranes. The optimum concentration was obtained as 1 wt.% and 1.5 wt.% for SiO₂ and SiO₂‐g‐PMAA, respectively. Aggregation effect dominated at concentrations beyond the optimum values that decreased the permeate flux, consequently.     

Fabrication of cellulose triacetate/graphene oxide porous membrane

Cellulose triacetate (AC)/graphene oxide (GO) porous membranes were successfully fabricated by combining ultrasonication and phase inversion method. The structures and morphologies of the resultant composite membranes were investigated by X‐ray diffraction (XRD), scanning electron microscopy, and transmission electron microscopy, respectively. Microscopic and X‐ray diffraction measurements revealed that GO sheets were uniformly dispersed within the AC matrix. The pore size and structure were modulated by changing GO concentration from 0.25 to 1 wt%. Membrane thermal properties were also studied. Among all tested membranes, the most favorable GO amount was 1 wt%, giving Td_3% of 274°C, which represents a 22°C enhancement compared with AC. Conversely, the membranes showed improved barrier properties against water and ethanol. The decrease of both ethanol and water fluxes was assigned to the stabilization of composite membrane structure, as a result of GO progressive addition. Bovine serum albumin rejection assay indicated an increasing from 78% in the case of CA membrane to 99% in the case of CA/GO 1 wt% of the rejection degree after 90 min. Copyright © 2015 John Wiley & Sons, Ltd.     

Effect of aqueous and organic solutions on the performance of polyamide thin‐film‐composite nanofiltration membranes

Polyamide/polyacrylonitrile thin‐film‐composite (TFC) nanofiltration (NF) membranes for the separation of oleic acid dissolved in organic solvents (methanol and acetone) were interfacially prepared by the reaction of trimesoyl chloride in an organic phase with an aqueous phase containing piperazine and m‐phenylene diamine. The interfacial reaction was confirmed by an investigation of the attenuated total reflection infrared spectrum. The surface morphology of the polyamide TFC membranes was examined with scanning electron microscopy. The hydrophilic properties of the membrane surfaces were conjectured on the basis of the ζ potential and contact angle. The effects of the monomer concentrations of the monomer blends (aliphatic and aromatic diamines) and drying times on various aspects of membrane performance, such as the solvents (water, alcohols, ketones, and hexane), permeation rates, and organic solute [poly(ethylene glycol) 200 and oleic acid] rejection rates, were investigated. All the membranes showed good solvent resistance. The polar solvent flux for water and methanol was higher than that for a nonpolar solvent (hexane). The membranes gave good rejection rates of oleic acid dissolved in methanol and acetone. The NF membranes were compared with various commercial membranes. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2151–2163, 2002     

Ultrathin pH‐Sensitive Nanoporous Membranes for Superfast Size‐Selective Separation

Stimuli‐responsive nanoporous membranes have attracted increasing interest in various fields due to their abrupt changes of permeation/separation in response to the external environment. Here we report ultrathin pH‐sensitive nanoporous membranes that are easily fabricated by the self‐assembly of poly(acrylic acid) (PAA) in a metal hydroxide nanostrand solution. PAA‐adsorbed nanostrands (2.5–5.0 nm) and PAA‐Cu^II nanogels (2.0–2.5 nm) grow competitively during self‐assembly. The PAA‐adsorbed nanostrands are deposited on a porous support to fabricate ultrathin PAA membranes. The membranes display ultrafast water permeation and good rejection as well as significant pH‐sensitivity. The 28 nm‐thick membrane has a water flux decrease from 3740 to 1350 L m^?1 h^?1 bar^?1 (pH 2.0 to 7.0) with a sharp decrease at pH 5.0. This newly developed pH‐sensitive nanoporous membranes may find a wide range of applications such as controlled release and size‐ and charge‐selective separation.     

Nanofiltration membrane cross‐linked by m‐phenylenediamine for dye removal from textile wastewater

In this work, m‐phenylenediamine (MPD) is used to prepare cross‐linked polyetherimide (PEI)‐based nanofiltration (NF) membrane for treatment of dye containing wastewater. The effects of dope solution composition, cross‐linking time, and dye concentration on membrane performance are investigated. Results indicate that the rejection of dye is increased with the increase of acetone concentration in the dope solution, cross‐linking time, and dye concentration. Meanwhile, membrane flux showed the opposite trend. With the aid of SEM and FTIR analysis, the cross‐linking between MPD and PEI is confirmed. The cross‐linked membrane has thicker and dense selective layer compared to the unmodified membrane. The cross‐linked NF membrane (PEI: 15 wt%; acetone: 20 wt%; cross‐linking time: 10 minutes) showed good performance in filtration of synthetic dye wastewater (Reactive Red 120, 1500 ppm) with 98% dye rejection and 0.013 L m^?2 hour^?1 of flux at relatively low operating pressure (60 psi).     

Self‐Assembled Asymmetric Block Copolymer Membranes: Bridging the Gap from Ultra‐ to Nanofiltration

The self‐assembly of block copolymers is an emerging strategy to produce isoporous ultrafiltration membranes. However, thus far, it has not been possible to bridge the gap from ultra‐ to nanofiltration and decrease the pore size of self‐assembled block copolymer membranes to below 5 nm without post‐treatment. It is now reported that the self‐assembly of blends of two chemically interacting copolymers can lead to highly porous membranes with pore diameters as small as 1.5 nm. The membrane containing an ultraporous, 60 nm thin separation layer can fully reject solutes with molecular weights of 600 g mol^?1 in aqueous solutions with a water flux that is more than one order of magnitude higher than the permeance of commercial nanofiltration membranes. Simulations of the membrane formation process by dissipative particle dynamics (DPD) were used to explain the dramatic observed pore size reduction combined with an increase in water flux.     

Preparation and characterization of modified polyphenylsulfone membranes with hydrophilic property for filtration of aqueous media

In the present research, the low water flux of polyphenylsulfone membranes was addressed, and a novel improvement in their water permeation and fouling resistance was achieved using polyethylene glycol (PEG) as the hydrophilic additive. Scanning electron microscopy and field emission scanning electron microscopy, atomic force microscopy, attenuated total reflection Fourier‐transform infrared spectroscopy, thermogravimetric analysis, and tensile test were applied for the investigation of membrane morphology, surface topography, surface chemical structure, thermal stability, and mechanical properties, respectively. Moreover, the relative hydrophilicity/hydrophobicity of the membranes was assessed via determination of membrane water uptake capacity and water contact angle. The membrane performance was studied and compared by determination of pure water flux and filtration of canned beans production wastewater as well as bovine serum albumin solution. The filtration results indicated a remarkable pure water flux and 100% turbidity rejection provided by the polyphenylsulfone/PEG 20 000 membrane. In addition, it was confirmed that the amount of residual PEG within the membrane was increased with increasing PEG molecular weight and concentration.     

Fabrication of Cu(OH)<Subscript>2</Subscript> Nanowires Blended Poly(vinylidene fluoride) Ultrafiltration Membranes for Oil-Water Separation

Cu(OH)2 nanowires were prepared and incorporated into poly(vinylidene fluoride) (PVDF) to fabricate Cu(OH)2-PVDF ultrafiltration (UF) membrane via immersion precipitation phase inversion process.The effect of Cu(OH)2 nanowires on the morphology of membranes was investigated by X-ray photoelectron spectroscopy (XPS),Fourier transform infrared (FTIR) spectroscopy,atomic force microscopy (AFM),scanning electron microscopy (SEM) and X-ray diffraction (XRD) measurements.The results showed that all the Cu(OH)2-PVDF membranes had wider fingerlike pore structure and better hydrophilicity,smoother surface than pristine PVDF membrane due to the incorporation of Cu(OH)2 nanowires.In addition,water flux and bovine serum albumin (BSA) rejection were also measured to investigate the filtration performance of membranes.The results indicated that all the Cu(OH)2-PVDF membranes had high water flux,outstanding BSA rejection and excellent antifouling properties.It is worth mentioning that the optimized performance could be obtained when the Cu(OH)2 nanowires content reached 1.2 wt％.Furthermore,the membrane with 1.2 wt％ Cu(OH)2 nanowires showed outstanding oil-water emulsion separation capability.     

Construction of superhydrophilic/underwater superoleophobic polydopamine‐modified h‐BN/poly(arylene ether nitrile) composite membrane for stable oil‐water emulsions separation

Oil/water emulsion separation in harsh environments remains a big challenge. Herein, a double layered nanofibrous composite membrane was developed by assembly of polydopamine‐modified hexagonal boron nitride (h‐BN‐PDA) onto a poly(arylene ether nitrile) (PEN) nanofibrous mat. Owing to the synergistic effect of a h‐BN‐PDA skin layer and a PEN nanofibrous mat supporting layer, as‐prepared composite membrane exhibited high thermal stability, corrosion resistance, and superhydrophilic/underwater superoleophobic property. Consequently, the PEN composite membrane showed good antifouling performance and a high rejection ratio (>99.0%) for various oil/water emulsions. After 10 cycles, the separation flux of PEN composite membrane still reached 588.1 L/m² h under the operating pressure of 0.04 MPa. Furthermore, the PEN composite membrane could still achieve high separation efficiency and high flux in high‐temperature (65 °C) and strongly corrosive conditions (pH = 1‐13). Therefore, the stable and efficient h‐BN‐PDA/PEN composite membrane showed potential application for treating oily wastewater in harsh environments.     

Performance enhancement of thin‐film composite membranes in water desalination process by wood sawdust

In this study, polysulfone/wood sawdust (PSf/WSD) mixed matrix membrane (MMM) was prepared as a novel substrate layer of thin‐film composite (TFC) membrane in water desalination. The main aim was to evaluate how different amounts of WSD (0‐5 wt%) and PSf concentrations (12‐16 wt%) in the porous substrate affect the properties of the final TFC membranes in the separation of organic and inorganic compounds. Morphological and wettability studies demonstrated that the addition of small amount of WSD (less than or equal to 1 wt%) in the casting solution resulted in more porous but similar hydrophobic substrates, while high loading (greater than or equal to 2 wt%) of WSD not only changed the substrate wettability and morphology but also increased and decreased the swelling and mechanical properties of substrate layer. Therefore, PA layer formed thereon displayed extensively varying film morphology, interfacial properties, and separation performance. Based on approximately stable permeate flux (ASPF) and apparent salt rejection efficiency (ASRE), the best TFC membrane was prepared over the substrate with 12 to 14 wt% of PSf and around 0.5 to 1 wt% of WSD. Although notable improvements in permeate flux were obtained by adding a small amount of sawdust, the results clearly indicate that the salt rejection mechanism of TFC membrane was different from the glycerin rejection mechanism. Furthermore, durability results of TFC membranes showed that in continuous operation for 30 days, TFC‐14/0.5 and TFC‐14/01 have the maximum plateau levels of stable permeate flux and salt rejection among the all TFC membranes.     

Fabrication and development of interfacial polymerized thin-film composite nanofiltration membrane using different surfactants in organic phase; study of morphology and performance

The effects of addition of cationic cetyltrimethylammonium bromide (CTAB), non-ionic (Triton X-100) and anionic sodium dodecyl sulfate (SDS) surfactants in organic phase for preparing the composite nanofiltration membranes were investigated. The interfacial polymerization technique was employed by applying trimesoyl chloride (TMC) and piperazine (PIP) as the reagents for the preparation of poly(piperazineamide) on a UF support. The obtained thin layer membranes were placed in oven for 2 min at 70 °C. Water permeation performance, salt rejection, membrane surface charge, chemical structure and membrane morphology including top surface and cross-section were investigated for characterization of the prepared membranes using IR-ATR, SEM, filtration and zeta potential measurement. The prepared membranes using SDS showed higher flux compared to the other membranes. SEM surface images demonstrate some defects and cracks on the thin layer surface of the membrane prepared with SDS. For membrane containing CTAB, the salt rejection increased in the order of Na₂SO₄ > NaCl > MgCl₂ with variation around 50–90%.     

High flux nanofiltration membranes based on interfacially polymerized polyamide barrier layer on polyacrylonitrile nanofibrous scaffolds

Electrospun polyacrylonitrile (PAN) nanofibrous scaffold was used as a mid-layer support in a new kind of high flux thin film nanofibrous composite (TFNC) membranes for nanofiltration (NF) applications. The top barrier layer was produced by interfacial polymerization of polyamides containing different ratios of piperazine and bipiperidine. The filtration performance (i.e., permeate flux and rejection) of TFNC membranes based on electrospun PAN nanofibrous scaffold was compared with those of conventional thin film composite (TFC) membranes consisting of (1) a commercial PAN ultrafiltration (UF) support with the same barrier layer coating and (2) two kinds of commercial NF membranes (i.e., NF90 and NF270 from Dow Filmtec). The nanofiltration test was carried out by using a divalent salt solution (MgSO₄, 2000 ppm) and a cross-flow filtration cell. The results indicated that TFNC membranes exhibited over 2.4 times more permeate flux than TFC membranes with the same chemical compositions, while maintaining the same rejection rate (ca. 98%). In addition, the permeate flux of hand-cast TFNC membranes was about 38% higher than commercial NF270 membrane with the similar rejection rate.     

Ultrahigh flux of graphene oxide membrane modified with orientated growth of MOFs for rejection of dyes and oil-water separation

Metal organic frameworks (MOFs) has broad application prospect in separation, catalysis, and adsorption. By a facile green method, we successfully fabricated prGO@cHKUST-1 composite membrane with the modification of dopamine and orientated growth of MOFs. Mg/Al-layered double hydroxides (Mg/Al-LDHs) was used as a modulator to obtain cubic HKUST-1 (cHKUST-1) with excellent morphology and special properties. Scanning Electron Microscopy (SEM), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR) etc. characterization illustrated successful synthesis of cHKUST-1 and composite membranes. Cubic HKUST-1 can tune the inter-layer spacing of graphene oxide (GO) leading increase in hydrophilicity and flux of the membrane. Meanwhile, the reduction effect of PDA and intercalation effect of MOFs could change the stacked way of GO layers, forming several fuzzy pores and more active sites on membrane surface. The prGO@cHKUST-1 membrane has an excellent rejection for methylene blue (MB) (99.5%) and Congo red (CR) (71.2%). Moreover, the modified membrane exhibited 10 and 5 times higher permeation flux than that of original GO membrane and prGO membrane, respectively. Thus, using orientated growth of MOFs to synthesize GO based composite membrane will provide useful insights in ultrahigh permeation flux membranes of dye and oil-water emulsion separation.     

Temperature‐Modulated Water Filtration Using Microgel‐Functionalized Hollow‐Fiber Membranes

In the present work, we investigate the potential of aqueous polymer microgels in membrane technology, especially for filtration applications. The poly(N‐vinylcaprolactam)‐based microgels exhibit thermoresponsive behavior and were employed to coat hollow‐fiber membranes used for micro‐ and ultrafiltration. We discuss the preparation of microgel‐modified membranes (by “inside‐out” as well as “outside‐in” filtration in dead‐end mode). The clean‐water permeability and stability of these membranes was studied not only as a function of time, but also of temperature. The microgel‐modified membranes exhibit a reversible thermoresponsive behavior whereby both the resistance and the retention increased with decreasing temperature.