Engineering design of outer‐selective tribore hollow fiber membranes for forward osmosis and oil‐water separation

Outer‐selective thin‐film composite (TFC) hollow fiber membranes offer advantages like less fiber blockage in the feed stream and high packing density for industrial applications. However, outer‐selective TFC hollow fiber membranes are rarely commercially available due to the lack of effective ways to remove residual reactants from fiber's outer surface during interfacial polymerization and form a defect‐free polyamide film. A new simplified method to fabricate outer‐selective TFC membranes on tribore hollow fiber substrates is reported. Mechanically robust tribore hollow fiber substrates containing three circular‐sector channels were first prepared by spinning a P84/ethylene glycol mixed dope solution with delayed demixing at the fiber lumen. The thin wall tribore hollow fibers have a large pure water permeability up to 300 L m^?2 h^?1 bar^?1. Outer‐selective TFC tribore hollow fiber membranes were then fabricated by interfacial polymerization with the aid of vacuum sucking to ensure the TFC layer well‐attached to the substrate. Under forward osmosis studies, the TFC tribore hollow fiber membrane exhibits a good water flux and a small flux difference between active‐to‐draw (i.e., the active layer facing the draw solution) and active‐to‐feed (i.e., the active layer facing the feed solution) modes due to the small internal concentration polarization. A hyperbranched polyglycerol was further grafted on top of the newly developed TFC tribore hollow fiber membranes for oily wastewater treatment. The membrane displays low fouling propensity and can fully recover its water flux after a simple 20‐min water wash at 0.5 bar from its lumen side, which makes the membrane preferentially suitable for oil‐water separation. © 2015 American Institute of Chemical Engineers AIChE J, 61: 4491–4501, 2015     

Positively charged hollow‐fiber composite nanofiltration membrane prepared by quaternization crosslinking

Poly(N,N‐dimethylaminoethyl methacrylate) (PDMAEMA) can be crosslinked by interfacial polymerization to develop a positively charged dense network structure. According to this mechanism, a positively charged hollow‐fiber composite nanofiltration (NF) membrane was prepared by quaternization to achieve a crosslinked PDMAEMA gel layer on the outer surface of polysulfone hollow‐fiber ultrafiltration (UF) membranes with a PDMAEMA aqueous solution as a coating solution and p‐xylylene dichloride as an agent. The preparation conditions, including the PDMAEMA concentration, content of additive in the coating solution, catalyzer, alkali, crosslinking temperature, and hollow‐fiber substrate membrane, were studied. Fourier transform infrared spectroscopy and scanning electron microscopy were used to characterize the structure of the membranes. This membrane had a rejection to inorganic salts in aqueous solution. The rejection of MgSO₄ (2 g/L aqueous solution at 0.7 MPa and 25°C) was above 98%, and the flux was about 19.5 L m^?2 h^?1. Moreover, the composite NF membranes showed good stability in the water‐phase filtration process. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Development of a chlorine‐resistant polyamide nanofiltration membrane and its field‐test results

For the development of chlorine‐resistant nanofiltration membranes, a thin‐film‐composite membrane was prepared by the interfacial polymerization of N‐phenylethylenediamine and 1,3,5‐benzenetricarbonyl trichloride on a microporous polysulfone support substrate. The polymerization on the substrate surface was confirmed by Fourier transform infrared measurements, and membrane surface properties such as the roughness and ζ potential were characterized. Rejections of NaCl and isopropyl alcohol of the prepared membrane were 95 and 50%, respectively. The membrane showed much higher chlorine resistance than a commercial polyamide membrane when the membranes were immersed in an aqueous NaOCl solution. A field test was carried out with a spiral‐type membrane module. Tap water was treated by this module for more than 70 days under the condition of continuous NaOCl injection. The prepared membrane module was quite stable, and no distinguished change in the rejection and flux was recognized. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Robust and high performance pressure retarded osmosis hollow fiber membranes for osmotic power generation

Novel fabrication perspectives have been demonstrated to molecularly construct robust hollow fiber membrane supports for high performance thin‐film composite (TFC) pressure retarded osmosis (PRO) membranes. For the first time, we found that the desirable hollow fiber supports should possess high stretch resistance and acceptable ductility. The microstructure strength of the hollow fiber support may have more weights on overall robustness of the TFC PRO membranes than the apparent cross‐section morphology. Effectively manipulating the kinetics of phase inversion during spinning by maneuvering bore fluid chemistry, and polymer solution composition is a promising method to tailor the strength of hollow fiber supports. Prestabilization of the TFC membranes at elevated lumen pressures can significantly improve their PRO performance. The newly developed TFC PRO hollow fiber membranes exhibit a power density as high as 16.5 W/m² and a very low specific reverse salt flux (J_s/J_w) of 0.015 mol/L at a hydraulic pressure of 15 bar using synthetic seawater brine (1.0 M NaCl) as the draw solution. © 2014 American Institute of Chemical Engineers AIChE J, 60: 1107–1119, 2014     

Recognition properties of poly(vinylidene fluoride) hollow‐fiber membranes modified by levofloxacin‐imprinted polymers

Through the use of thermal polymerization, poly(vinylidene fluoride) (PVDF) hollow‐fiber membranes modified by a thin layer of molecularly imprinted polymers (MIPs) were developed for the selective separation of levofloxacin. To demonstrate the changes induced by thermal polymerization, PVDF hollow‐fiber membranes with different modification degrees by repeated polymerization were weighed. The total weight of the imprinted membranes increased by 14 μg/cm² after a five‐cycle polymerization. An increase in the membrane weight indicated the deposition of an MIP layer on the external surface of PVDF hollow‐fiber membranes during each polymerization cycle, which was also characterized by scanning electron microscopy. MIP membranes with different degrees of surface modification provided highly selective binding of levofloxacin. Both hollow‐fiber MIP membranes and nonimprinted membranes showed enhanced adsorption of levofloxacin and ofloxacin gradually with an increase in the modification degrees of PVDF hollow‐fiber membranes to a maximum value followed by a decrease. These results indicate that thermal polymerization indeed produces an MIP layer on the external surface of PVDF hollow‐fiber membranes and that it is feasible to control the permeability by repeated polymerization cycles. Different solvent systems in the permeation experiments were used to understand the hydrophobic interaction as one of the results of the binding specificity of MIP membranes. Selective separation was obtained by multisite binding to the template via ionic, hydrogen‐bond, and hydrophobic interactions. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Pervaporation of water/alcohol mixtures through chitosan/cellulose acetate composite hollow‐fiber membranes

For the purpose of separating aqueous alcohol by the use of pervaporation technique, a composite membrane of chitosan (CT) dip‐coated cellulose acetate (CA) hollow‐fiber membranes, CT‐d‐CA, was investigated. The effects of air‐gap distance in the spinning of CA hollow‐fiber membranes, chitosan concentration, and sorts of aqueous alcohol solutions on the pervaporation performances were studied. Compared with unmodified CA hollow‐fiber membrane, the CT‐d‐CA composite hollow‐fiber membrane effectively increases the permselectivity of water. The thickness of coating layer increases with an increase in chitosan concentration. As the concentration of chitosan solution increased, the permeation rate decreased and the concentration of water in the permeate increased. In addition, the effects of feed composition and feed solution temperature on the pervaporation performances were also investigated. The permeation rate and water content in permeate at 25°C for a 90 wt % aqueous isopropanol solution through the CT‐d‐CA composite hollow‐fiber membrane with a 5‐cm air‐gap distance spun, 2 wt % chitosan dip‐coated system were 169.5 g/m² h and 98.9 wt %, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1562–1568, 2004     

Effect of polyethylene glycol molecular weights and concentrations on polyethersulfone hollow fiber ultrafiltration membranes

Polyethersulfone (PES) hollow‐fiber membranes were fabricated using poly(ethyleneglycol) (PEG) with different molecular weights (MW = PEG200, PEG600, PEG2000, PEG6000, and PEG10000) and poly(vinyl pyrrolidone) PVP40000 as additives and N‐methyl‐2‐pyrrolidone (NMP) as a solvent. Asymmetric hollow‐fiber membranes were spun by a wet phase‐inversion method from 25 wt % solids of 20 : 5 : 75 (weight ratio) PES/PEG/NMP or 18 : 7 : 75 of PES/(PEG600 + PVP40000)/NMP solutions, whereas both the bore fluid and the external coagulant were water. Effects of PEG molecular weights and PEG600 concentrations in the dope solution on separation properties, morphology, and mechanical properties of PES hollow‐fiber membranes were investigated. The membrane structures of PES hollow‐fiber membranes including cross section, external surface, and internal surface were characterized by scanning electron microscopy and the mechanical properties of PES hollow‐fiber membranes were discussed. Bovine serum albumin (BSA, MW 67,000), chicken egg albumin (CEA, MW 45,000), and lysozyme (MW 14,400) were used for the measurement of rejection. It was found that with an increase of PEG molecular weights from 200 to 10,000 in the dope solution, membrane structures were changed from double‐layer fingerlike structure to voids in the shape of spheres or ellipsoids; moreover, there were crack phenomena on the internal surfaces and external surfaces of PES hollow‐fiber membranes, pure water permeation fluxes increased from 22.0 to 64.0 L m^?2 h^?1 bar^?1, rejections of three protein for PES/PEG hollow‐fiber membranes were not significant, and changes in mechanical properties were decreased. Besides, with a decrease of PEG600 concentrations in the dope solution, permeation flux and elongation at break decreased, whereas the addition of PVP40000 in the dope solution resulted in more smooth surfaces (internal or external) of PES/(PEG600 + PVP40000) hollow‐fiber membranes than those of PES/PEG hollow‐fiber membranes. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3398–3407, 2004     

Effective incorporation of TiO2 nanoparticles into polyamide thin‐film composite membranes

The effectiveness of TiO₂ nanoparticles in improving the performance of polyamide (PA) thin‐film composite (TFC) membranes has been investigated. PA TFC membranes were prepared by interfacial polymerization with m‐phenylenediamine (MPD) and 1,3,5‐benzene tricarbonyl trichloride (TMC) where TiO₂ particles were added during and after interfacial polymerization. To distribute the TiO₂ nanoparticles uniformly in the PA films, colloidally stable TiO₂ sols were synthesized and added to the aqueous MPD solution rather than to an organic TMC solution. Through the use of different incorporation methods, TiO₂ particles were located on the top surface, in PA film layer, and in both positions. In the case of dense PA layers, the hydrophilicity of the membranes was significantly improved due to the presence of TiO₂ particles, resulting in an increased water flux. On the other hand, the enhancement of water flux was less significant when TiO₂ particles were incorporated into a loose PA film that was prepared with additives. In addition, a BSA fouling test confirmed that TiO₂ nanoparticles effectively improve the antifouling properties of the membranes for both dense and loose PA films. This effect is possibly due to increased hydrophilicity, covering of the fouling space, and a reduction in surface roughness. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43383.     

Direktes Herstellungsverfahren von Komposit‐Hohlfasermembranen mit sinusförmiger Geometrie

Composite hollow fiber membranes are fabricated in a one‐step process by superimposing the phase inversion process with interfacial polymerization on the lumen side of the fiber. A pulsation module in the bore fluid channel pulsates the bore fluid flow and leads to hollow fiber membranes with sinusoidal geometry. The fabrication of composite hollow fiber membranes with sinusoidal geometry is focus of this work. The sinusoidal geometry leads to reduced concentration polarization effects in membrane applications.     

Developing thin‐film‐composite forward osmosis membranes on the PES/SPSf substrate through interfacial polymerization

A new scheme has been developed to fabricate high‐performance forward osmosis (FO) membranes through the interfacial polymerization reaction on porous polymeric supports. p‐Phenylenediamine and 1,3,5‐trimesoylchloride were adopted as the monomers for the in‐situ polycondensation reaction to form a thin aromatic polyamide selective layer of 150 nm in thickness on the substrate surface, a lab‐made polyethersulfone (PES)/sulfonated polysulfone (SPSf)‐alloyed porous membrane with enhanced hydrophilicity. Under FO tests, the FO membrane achieved a higher water flux of 69.8 LMH when against deionized water and 25.2 LMH when against a model 3.5 wt % NaCl solution under 5.0 M NaCl as the draw solution in the pressure‐retarded osmosis mode. The PES/SPSf thin‐film‐composite (TFC)‐FO membrane has a smaller structural parameter S of 238 μm than those reported data. The morphology and topology of substrates and TFC‐FO membranes have been studied by means of atomic force microscopy and scanning electronic microscopy. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

A design of composite hollow fiber membranes with tunable performance and reinforced mechanical strength

A new design of hollow fiber membranes with high mechanical strength, great surface area per volume ratio and tunable filtration performance is presented. This newly developed hollow fiber membrane was produced by an intensified production process, in which the processes of thermally induced phase separation (TIPS), non‐solvent induced phase separation (NIPS), and interfacial polymerization (IP) were combined. PVDF (polyvinylidene difluoride) hollow fiber membranes (produced by TIPS) were used as support substrates. Afterwards, PES (polyethersulfone) (made by NIPS) and PA (polyamide) layers (manufactured by IP) were coated one by one. The pure water permeability, molecular weight cut off (MWCO), salt rejection, tensile stress together with surface and cross‐sectional morphology indicate that the properties of the hollow fiber membranes can be easily adjusted from microfiltration‐like to nanofiltration‐like membranes only by varying the presence of the IP step and the concentration in the PES layer in the production system. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41247.     

A novel hollow fiber membrane-assisted antisolvent crystallization for enhanced mass transfer process control

Herein, a novel hollow fiber membrane-assisted antisolvent crystallization (MAAC) was proposed to enhance the mass transfer control over the antisolvent crystallization. A polyethersulfone membrane module was introduced as the key device for antisolvent transfer and solution mixing. An antisolvent liquid film layer was formed on the membrane surface and mixed with the solution. The liquid film also prevented the membrane from directly contacting with crystallization solution. By controlling both the shell side flow velocity and the antisolvent transfer, the antisolvent permeation rate achieved sensitive, stable, and accurate control during long-term and repeated utilization. The interfacial mass transfer rate of MAAC was 0.66 mg cm⁻² s⁻¹, which was only 1/50 that of conventional droplet antisolvent crystallization. MAAC also provided crystal products with better morphologies and narrower size distributions than the conventional process. The stable performances of MAAC in terms of its accurate antisolvent mass transfer and antifouling capabilities were also highlighted. © 2018 American Institute of Chemical Engineers AIChE J, 65: 734–744, 2019     

Polyamide/polyacrylonitrile thin film composites as forward osmosis membranes

Thin film composites (TFCs) as forward osmosis (FO) membranes for seawater desalination application were prepared. For this purpose, polyacrylonitrile (PAN) as a moderately hydrophilic polymer was used to fabricate support membranes via nonsolvent‐induced phase inversion. A selective thin polyamide (PA) film was then formed on the top of PAN membranes via interfacial polymerization reaction of m‐phenylenediamine and trimesoyl chloride (TMC). The effects of PAN solution concentration, solvent mixture, and coagulation bath temperature on the morphology, water permeability, and FO performance of the membranes and composites were studied. Support membranes based on low PAN concentrations (7 wt %), NMP as solvent and low coagulation bath temperature (0 °C) demonstrated lower thickness, thinner skin layer, more porosity, and higher water permeability. Meanwhile, decreasing the PAN solution concentration lead to higher water permeance and flux and lower reverse salt flux, structural parameter, and tortuosity for the final TFCs. Composites made in N,N‐dimethylformamide presented lower permeance and flux for water and salt and higher salt rejection, structural parameter, and tortuosity. FO assay of the composites showed lower water permeance values in saline medium comparing to pure water. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44130.     

Preparation and characterization of braided tube reinforced polyacrylonitrile hollow fiber membranes

Polyacrylonitrile (PAN) and polyester (PET) braided hollow tube that used as a special reinforcement are braided from their filaments via two‐dimensional weaving techniques. PAN braided tube reinforced homogeneous PAN hollow fiber membranes and PET braided tube reinforced heterogeneous PAN hollow fiber membranes are prepared by concentric circles squeezed‐coated spinning method. As for PAN hollow fiber membrane, the effects of PAN concentration on the performance of the prepared hollow fiber membranes are investigated in terms of pure water flux, protein rejection, mechanical strength, and morphology observations by a scanning electron microscope (SEM). The interfacial bonding state of the braided tube reinforced PAN hollow fiber membranes is studied by constant speed stretching method. Results show that the breaking strength of two‐dimensional braided tube reinforced PAN hollow fiber membranes is higher than 80 MPa. The structure of separation surface is similar to the structure of an asymmetric membrane. With the increase of polymer concentration, the membrane flux decreases while the retention rate of BSA increase. The membrane porosity and maximum pore size have the same decreasing tendency as the increase of PAN concentration. The results also show that the interfacial bonding state of the PAN two‐dimensional braided tube reinforced homogeneous PAN hollow fiber membranes is better than that of the PET two‐dimensional braided tube reinforced heterogeneous PAN hollow fiber membranes. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41795.     

Fabrication of innovative forward osmosis membranes via multilayered interfacial polymerization on electrospun nanofibers

Practical application of forward osmosis (FO) membranes is beset by low water flux and vulnerability of selective polyamide (PA) layers. Herein, novel composite membranes were fabricated with multilayered PA via cyclic interfacial polymerization (IP) on electrospun polyethersulfone (PES) nanofiber substrates to realize high performance FO. The membrane fabrication conditions were optimized detailedly with respect to the morphologies, physicochemical properties, and FO performances. It is indicated that the PES concentration has great impacts on the morphology, thickness, and fiber diameter of the electrospun substrates and the optimal concentration is proved to be 26 wt %. After multilayered IP, the membrane thickness, surface hydrophilicity, and mechanical strength increased with IP cycles. The optimized FO membranes with two PA layers show much higher water flux and membrane selectivity compared with the commercial thin film composite membranes, holding great promise for water purification and seawater desalination. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47247.     

Inhibiting the concentration polarization of FO membranes based on the wettable microporous supporting layer and the enhanced dense skin layer

A novel thin film composite‐type forward osmosis (FO) membrane with inhibited concentration polarization phenomenon and expectant separation performance was prepared by continuous interfacial polymerization method. The nylon‐6,6 microfiltration membrane with the average pore size of 5 μm and the self‐wetting property was for the first time used as the supporting layer of the FO membranes, which decreased the mass transfer resistance in the porous supporting layer. The skin layer was prepared via the continuous interfacial polymerization of polyamide as a relatively dense layer, with the reverse salt flux of less than 1 g/m^?2 h^?1. The mass transfer resistance and the reverse salt flux of the prepared FO membranes were remarkably reduced due to the functional design of the double‐layer structure, which effectively enhanced the separation selectivity and restrain the concentration polarization of the FO membranes. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45133.     

Second interfacial polymerization of thin-film composite hollow fibers with amine-cyclodextrins for pervaporation dehydration

High performance thin-film composite (TFC) hollow fiber membranes have been developed for pervaporation dehydration by second interfacial polymerization (SIP) modification with three kinds of amine-functionalized β-cyclodextrin (amine-CDs), which were synthesized by modifying β-CD with ammonia, ethylenediamine (EDA), and tris(2-aminoethyl)amine, respectively. The chemical properties of amine-CDs and SIP-modified TFC membranes were characterized by various techniques. The effects of amine-CD type and SIP parameters (pH or concentration of CD-EDA solution) were studied systematically to acquire the optimized selective layer of TFC membranes for ethanol dehydration. Among all SIP-modified TFC membranes, the one with SIP by 2 wt% CD-EDA aqueous solution (pH = 2) exhibited the most outstanding separation performance with a ultrahigh permeation flux (3,018.0 ± 12.0 g/m² hr) and permeate concentration (98.7 ± 0.2 wt% water) at 50°C (equivalent to separation factor of 415), contributed by the effectively incorporated CD with rich hydrophilic functional groups and intrinsic nanocavities facilitating the passage of water molecules.     

Taurine as an additive for improving the fouling resistance of nanofiltration composite membranes

A hydrophilic compound, taurine, was investigated as an additive in the interfacial polymerization between piperazine (PIP) and trimesoyl chloride (TMC) to prepare thin‐film composite (TFC) membranes. The resulting membranes were characterized by X‐ray photoelectron spectroscopy and attenuated total reflectance–Fourier transform infrared spectroscopy. The morphology and hydrophilicity of the membranes were investigated through scanning electronic microscopy and water contact angle measurements. The separation performance of the TFC membranes was investigated through water flux and salt rejection tests. The protein‐fouling resistance of the films was evaluated by water recovery rate measurements after the treatment of bovine serum albumin. The membrane containing 0.2 wt % taurine showed the best performance of 92% MgSO₄ rejection at a flux of 31 L m^?2 h^?1 and better antifouling properties than the PIP–TMC membranes. An appropriately low concentration of taurine showed the same MgSO₄ rejection as the PIP–TMC membranes but a better fouling resistance performance. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41620.     

Fabrication of polyamide thin film nanocomposite reverse osmosis membrane incorporated with a novel graphite-based carbon material for desalination

The properties of polyamide (PA) thin film composite (TFC) membranes are affected by many variables, especially the additives in the process of interfacial polymerization that play an important role in the properties of membranes. In this study, a new type graphite carbon was added into organic phase containing trimesoyl chloride for interfacial polymerization with aqueous phase containing m-phenylenediamine to prepare modified polyamide thin film nanocomposite (TFN) membranes for reverse osmosis (RO) adhibition. Polysulfone ultrafiltration membranes were used as the carrier of the interfacial polymerization. The concentration of graphite carbon was selected from 0.002 to 0.01 wt%. The polyamide nanocomposite membrane prepared with the concentration of 0.004 wt% graphite carbon showed the best RO desalination performance, which the water flux of this TFN membrane is over 2.3 times as much as pristine TFC membrane, and the salt rejection is over 99%. This article provides a well-performing polyamide thin film nanocomposite membrane modified by a new-type carbon nanoparticles consequently.     

Preparation and characterization of poly(vinyl chloride)/polystyrene/poly(ethylene glycol) hollow‐fiber ultrafiltration membranes

Hollow‐fiber ultrafiltration (UF) membranes were prepared from blends of poly(vinyl chloride) (PVC) and polystyrene (PS) with a dry/wet phase inversion method. Poly(ethylene glycol) (PEG) and N,N‐dimethylacetamide were used as the additive and solvent, respectively. The effects of the PEG concentration in the dope solution as an additive on the cross sections and inner and outer surface morphologies, permeability, and separation performance of the hollow fibers were examined. The mean pore size, pore size distribution, and mean roughness of both the inner and outer surfaces of the produced hollow fibers were determined by atomic force microscopy. Also, the mechanical properties of the hollow‐fiber membranes were investigated. UF experiments were conducted with aqueous solutions of poly(vinyl pyrrolidone) (PVP; K‐90, M_w = 360 kDa). From the results, we found that the PVC/PS hollow‐fiber membranes had two layers with a fingerlike structure. These two layers were changed from a wide and long to a thin and short morphology with increasing PEG concentration. A novel and until now undescribed shape of the nodules in the outer surfaces, which was denoted as a sea‐waves shape, was observed. The outer and inner pore sizes both increased with increasing PEG concentration. The water permeation flux of the hollow fibers increased from 104 to 367 L m^?2 h^?1 bar^?1) at higher PEG concentrations. The PVP rejection reached the highest value at a PEG concentration of 4 wt %, whereas at higher values (from 4 to 9 wt %), the rejection decreased. The same trend was found also for the tensile stress at break, Young's modulus, and elongation at break of the hollow fibers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 989‐1004, 2013