Improvement of porous polyvinylidene fluoride-co-hexafluropropylene hollow fiber membranes for sweeping gas membrane distillation of ethylene glycol solution

Porous polyvinylidene fluoride-co-hexafluropropylene (PVDF-HFP) hollow fiber membranes were fabricated through a wet spinning process. In order to improve the membrane structure, composition of the polymer solution was adjusted by studying ternary phase diagrams of polymer/solvent/non-solvent. The prepared membranes were used for sweeping gas membrane distillation (SGMD) of 20 wt% ethylene glycol (EG) aqueous solution. The membranes were characterized by different tests such as N₂ permeation, overall porosity, critical water entry pressure (CEP_w), water contact angle and collapsing pressure. From FESEM examination, addition of 3 wt% glycerol in the PVDF-HFP solution, produced membranes with smaller finger-likes cavities, higher surface porosity and smaller pore sizes. Increasing the polymer concentration up to 21 wt% resulted in a dense spongy structure which could significantly reduce the N₂ permeance. The membrane prepared by 3 wt% glycerol and 17 wt% polymer demonstrated an improved structure with mean pore size of 18 nm and a high surface porosity of 872 m^-1. CEP_w of 350 kPa and overall porosity of 84% were also obtained for the improved membrane. Collapsing pressure of the membranes relatively improved by increasing the polymer concentration. From the SGMD test, the developed membrane represented a maximum permeate flux of 28 kg·m^-2·h^-1 which is almost 19% higher than the flux of plain membrane. During 120 h of a long-term SGMD operation, a gradual flux reduction of 30% was noticed. In addition, EG rejection reduced from 100% to around 99.5% during 120 h of the operation.     

Improvement of porous polyvinylidene fluoride-co-hexafluropropylene hollow fiber membranes for sweeping gas membrane distillation of ethylene glycol solution

Porous polyvinylidene fluoride-co-hexafluropropylene (PVDF-HFP) hollow fiber membranes were fabricated through a wet spinning process. In order to improve the membrane structure, composition of the polymer solution was adjusted by studying ternary phase diagrams of polymer/solvent/non-solvent. The prepared membranes were used for sweeping gas membrane distillation (SGMD) of 20 wt% ethylene glycol (EG) aqueous solution. The membranes were characterized by different tests such as N₂ permeation, overall porosity, critical water entry pressure (CEP_w), water contact angle and collapsing pressure. From FESEM examination, addition of 3 wt% glycerol in the PVDF-HFP solution, produced membranes with smaller finger-likes cavities, higher surface porosity and smaller pore sizes. Increasing the polymer concentration up to 21 wt% resulted in a dense spongy structure which could significantly reduce the N₂ permeance. The membrane prepared by 3 wt% glycerol and 17 wt% polymer demonstrated an improved structure with mean pore size of 18 nm and a high surface porosity of 872 m⁻¹. CEP_w of 350 kPa and overall porosity of 84% were also obtained for the improved membrane. Collapsing pressure of the membranes relatively improved by increasing the polymer concentration. From the SGMD test, the developed membrane represented a maximum permeate flux of 28 kg·m⁻²·h⁻¹ which is almost 19% higher than the flux of plain membrane. During 120 h of a long-term SGMD operation, a gradual flux reduction of 30% was noticed. In addition, EG rejection reduced from 100% to around 99.5% during 120 h of the operation.     

Preparation of blend polyethersulfone/cellulose acetate/polyethylene glycol asymmetric membranes for oil–water separation

Blend PES/CA hydrophilic membranes were prepared via a phase-inversion process for oil–water separation. PEG-400 was introduced into the polymer solution in order to enhance phase-inversion and produce high permeability membranes. A gas permeation test was conducted to estimate mean pore size and surface porosity of the membranes. The membranes were characterized in terms of morphology, overall porosity, water contact angle, water flux and hydraulic resistance. A cross-flow separation system was used to evaluate oil–water separation performance of the membranes. From FESEM examination, the prepared PES/CA membrane presented thinner outer skin layer, higher surface porosity with larger pore sizes. The outer surface water contact angle of the prepared membrane significantly decreased when CA was added into the polymer solution. The higher water flux of the PES/CA membrane was related to the higher hydrophilicity and larger pore sizes of the membrane. From oil–water separation test, the PES/CA membrane showed stable oil rejection of 88 % and water flux of 27 l/m² s after 150 min of the operation. In conclusion, by controlling fabrication parameters a developed membrane structure with high hydrophilicity, high surface porosity and low resistance can be achieved to improve oil rejection and water productivity.     

Porous polyethersulfone hollow fiber membrane in gas–liquid contacting processes

Porous polyethersulfone hollow fiber membranes were fabricated via dry–wet phase inversion method with the polymer concentration in the spinning dope either 13 wt% or 15 wt%. The fabricated hollow fiber membranes were characterized by different test methods and the performance of membranes in contactor applications was tested by CO₂ absorption. The mean pore size, effective surface porosity and membrane porosity decreased while the membrane density and Liquid Entry Pressure (LEPw) increased as polymer concentration increased. The CO₂ absorption flux of the fabricated membranes was measured in two cases; i.e. when the absorbent, distilled water, was in the lumen side or in the shell side. The CO₂ flux for the membrane, fabricated from 13 wt% PES solution, was compared with some commercial and in-house made membranes. The former membrane had 111% higher flux than a commercial PTFE membrane.     

Morphological and structural formation of the regenerated cellulose membranes recovered from its cuprammonium solution using aqueous sulfuric acid

Morphological and structural formation of the regenerated cellulose membranes from its cuprammonium hydroxide solution by acid coagulation was investigated. Scanning electron microscopic observation revealed that the morphology of the membranes changed drastically as functions of both the cellulose concentration in the original cellulose solution C_Cell and the concentration of sulfuric acid as a coagulant C_H2SO4. It was found that at a constant polymer concentration (8 wt %) the membrane prepared by using 5 wt % aqueous sulfuric acid exhibits higher water flux, far smaller swelling anisotropy parameter L_t, and larger porosity P_r with a thinner skin structure, and these parameters were proven to be associated with lower (11 0) crystal plane orientation coefficient f_{∥(11 0)} compared with those for the membranes obtained by aqueous sulfuric acid with more than 10 wt %. On the other hand, at constant coagulant concentration (10 wt %) the membrane prepared by using the polymer solution with 5 wt % shows far greater P_r with practically no distinct skin structure; hence, a higher flux. The drastic changes in the morphology and structural parameters as functions of C_Cell and C_H2SO4 were found to be well correlated with abrupt changes in material transportation (copper ion, ammonium ion, and water) from the polymer solution to aqueous coagulants as a function of C_Cell and C_H2SO4. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1669–1678, 1999     

Fabrication of basalt embedded composite fiber membrane using electrospinning method and response surface methodology

In this study, a novel basalt embedded fiber membranes was prepared by the electrospinning method. The effects of the feed rate, voltage, tip to collector distance, and the basalt content on the prepared composite fiber membranes were investigated and optimized using the response surface method. Four models were built to compare the fibers in terms of deionized water flux (DWF), activated sludge flux, chemical oxygen demand (COD) removal, and porosity of fiber membranes. All the developed models were significant and adequately precise. The maximum flux of DWF was obtained when the voltage was 17.25 kV, the tip to collector distance of 19 cm, and a basalt content in polymer of 1.25%. COD removal decreased at higher voltage values as the feed rate increased. The porosity, pore size, and the contact angle values decreased for basalt embedded fiber membrane. The increases in the basalt percentage in polymer increased the hydrophilicity of the fiber. The flux decline for the basalt embedded fiber membrane was compared with the pristine fiber membrane. The permeate fluxes of pristine and basalt embedded fiber membranes were 42.3 and 59.6 L/m²/h, respectively. The biofouling performances of pristine and basalt embedded fiber membranes were also examined. Irreversible fouling decreased from 42.9% to 8.0%, and reversible fouling increased from 56.5% to 91.1% after modification of the membrane with basalt powder. Scanning electron microscopy with energy dispersive X-ray analysis (SEM–EDX) analysis showed that basalt powder was successfully embedded into polyether sulfone polymer.     

Separation of phenol from aqueous solution by membrane pervaporation using modified polyurethaneurea membranes

Hydroxy‐terminated polybutadiene‐based porous and nonporous polyurethaneurea membranes were prepared and used to study the phenol separation efficiency from dilute aqueous solution. The porosity was developed by incorporation of lithium chloride in polymer matrix with subsequent leaching of the same in hot water. The porous membrane showed higher phenol flux over that of nonporous membrane. Permeate containing about 97 wt % phenol was obtained from feed containing 7 wt % phenol, when pervaporation was carried out with porous polyurethaneurea membrane at 75°C. The activation energies for diffusion, permeation, and pervaporation were calculated from Arrhenius plots. From the activation energy values, it was observed that the pervaporation process became easier with increased phenol concentration in the feed and porosity of the membrane used. The membrane boundary resistance was observed to decrease with increase in temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1857–1865, 2006     

Solvent‐stable UV‐cured acrylic polysulfone membranes

A systematic investigation of the effect of the presence of acrylate resin on polysulfone‐based membranes was performed with the aim of obtaining chemically stable crosslinked membranes without affecting their flux performances. The membranes were prepared via UV curing of the polymer dope followed by a non‐solvent‐induced phase separation process. Two different acrylic monomers were investigated and their amount was varied in the polymer dope, to study the influence of concentration on final results. High crosslinking degrees were achieved by irradiating the solution for one minute. Morphological investigations of the active surface and of the cross‐sections of the fabricated membranes showed that the typical porosity of ultrafiltration membranes was obtained starting from solutions containing a low amount of crosslinker (10 wt%), which is consistent with the water flux values which were comparable to that of the pristine polysulfone membrane. High concentrations of crosslinker resin in the initial polymer dope produced denser membranes with lower permeability. High rejection of 27 nm particles (>90%) was measured for all samples having measurable flux. The addition of the crosslinker allowed one to obtain stability in various solvents without affecting the flux and rejection performance of the porous membranes. © 2016 Society of Chemical Industry     

Poly(vinylidene fluoride-co-hexafluoro propylene) membranes prepared via thermally induced phase separation and application in direct contact membrane distillation

A non-toxic and environmentally safe diluent, acetyl tributyl citrate, was employed to prepare poly(vinylidene fluoride)-co-hexafluoropropylene membranes via thermally induced phase separation. Effects of the polymer concentration on the phase diagram, membrane morphology, hydrophobicity, pore size, porosity and mechanical properties (tensile stress and elongation at break) were investigated. The results showed that the pore size and porosity tended to decrease with increasing polymer concentration, whereas the contact angle, liquid entry pressure and mechanical properties showed the opposite trend. In direct contact membrane distillation operation with 3.5 wt-% sodium chloride solution as the feed solution, the prepared membranes performed high salt rejection (>99.9%). Furthermore, the prepared membranes retained excellent performance in long-term stability tests regarding the permeate flux and salt rejection.     

Preparation of Superhydrophobic Polypropylene Membrane Using Dip-Coating Method: The Effects of Solution and Process Parameters

Superhydrophobic polypropylene hollow fiber membranes were prepared through two-step dip-coating process. The effects of solution and process parameters were investigated. It was found that polymer solution concentration and temperature were crucial parameters to obtain homogeneous coating. High hydrophobicity could be achieved by controlling the polymer solution concentration and drying temperature. Using methyl ethyl ketone as nonsolvent, the membrane surface roughness was increased, resulting in superhydrophobicity with high contact angle of 151.3°. The modified membrane still exhibited lower flux than unmodified membrane in water–oil separation due to porosity decrease. However, their water rejections were comparable.     

Acrylonitrile copolymers: Synthesis,characterization, and formation of ultrafiltration membranes

A variety of poly(acrylonitrile‐co‐acrylamide) polymers of different compositions were synthesized by free radical copolymerization. Thin films were cast from polymer solutions, and coagulated into ultrafiltration membranes. The effect of preparative parameters on membrane gel structure was investigated. For nonsupported membranes, concentrated polymer solutions produce fine pore membranes with a lower flux; extending the drying time causes a diminution in membrane thickness, swelling index, and fluxes; the membrane thickness, swelling index, and permeate flux all increased with increasing coagulation bath temperature. For supported membranes, dilute polymer casting solutions, small casting gate opening, and added polyvinylpyrrolidone to the casting solution all increased the permeate flux. The membranes containing acrylamide were more hydrophilic, and had a smaller dispersion force component of the surface free energy than those prepared from the polyacrylonitrile homopolymer. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1271–1277, 1999     

Studies on cellulose acetate‐carboxylated polysulfone blend ultrafiltration membranes. III

Enhancement of the hydrophilicity in polymeric membrane materials results in membranes with higher flux and better membrane characteristics. Hence, polysulfone was carboxylated and ultrafiltration membranes were prepared from blends of cellulose acetate and carboxylated polysulfones having various degrees of carboxylation with a total polymer concentration of 20 wt % in casting solution and at different blend polymer compositions. The effects of degree of carboxylation on membrane characteristics such as compaction, pure water flux, and membrane hydraulic resistance (R_m) have been investigated. The influence of the polymer concentration in the blend solution on the performance of blend membranes at various blend polymer compositions has also been investigated and compared with that of blend membranes prepared from blends of cellulose acetate and polysulfone or carboxylated polysulfone with a total polymer concentration of 17.5 wt %. Further, the solute rejection performance of the membranes has also been investigated by subjecting the membranes to metal ion permeation studies using polyelectrolyte‐enhanced ultrafiltration. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 976–988, 2005     

Characterization of triple electrospun layers of PVDF for direct contact membrane distillation process

Recently, electrospinning technique was applied successfully to fabricate porous hydrophobic membranes for MD applications. In this work, a novel triple layer configuration with diameter gradient for PVDF nanofiber membranes is proposed, with the objective of to minimize mass transfer resistance and heat loss. In outer layers of these membranes, the minimum concentration of PVDF (20 wt%) was used to produce bead-free nanofibers with thinner diameters and middle layers were composed of thicker nanofibers formed at higher polymer concentrations (21.5-26 wt%). Characterization of prepared membranes was conducted by the measurement of porosity, thickness, liquid entry pressure (LEP), scanning electron microscopy (SEM), contact angle, thermal and mechanical properties. Direct contact membrane distillation performance of fabricated membranes was tested using 42 g/L NaCl as feed solution. Water permeate flux of triple layer membranes (27.8-31.5 kg/m² h) was found to be considerably higher than that obtained from single layer membrane (15.4 kg/m² h), indicating the proposed configuration can effectively improve evaporation efficiency.     

Hollow fine fiber vs. flat sheet membranes - a comparison of structures and performance

The reverse osmosis performance of polymeric membranes depends not only on the chemical structure of the polymer but also on the physical structure of the membrane. Percolation theory is used to describe water flux and salt passage as functions of the polymer density, or porosity, of the membrane. Water permeability increases with increasing porosity, or decreasing polymer density in the membrane. Salt passage is controlled primarily by the membrane polymer density in the surface layer on the feed side of the membrane. Experimental data on both hollow fine fiber and flat sheet membranes are consistent with the basic concepts of percolation theory.     

Characterization of asymmetric polysulphone membranes for gas separation

The mean pore size and surface porosity of the dense skin of polymeric asymmetric membranes were determined by the gas permeability method. When the contribution of the flux of a gas permeating through the dense skin is greater than 10% of the ‘slip’ flux in the pore, the dense skin thickness can be obtained from the equations developed in the present work. The method was applied to investigate the influence of the parameters involved in the preparation of polysulphone asymmetric membranes by the wet process of phase inversion. Electron microscopy was used to determine the structure and thickness of the dense skin. The results obtained with the microporous membranes synthesized indicate the following trends: pore size increases and surface porosity decreases with (i) increasing temperature of the coagulation bath; (ii) increasing concentration of polymer in the casting solution; and (iii) increasing casting thickness.     

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.     

Hydrophilic modification of high‐strength polyvinylidene fluoride hollow fiber membrane

The polyvinylidene fluoride (PVDF)/polyvinyl alcohol (PVA) polymer solutions were coated on the outer surface of PVDF matrix hollow fiber membrane. On the principle of the homogeneous‐reinforced (HR) membrane technology, the reinforced PVDF/PVA (RFA) hollow fiber membranes prepared through the dry‐wet spinning method. The performance of the RFA membranes varies with the PVA concentration in the polymer solution and is characterized in terms of pure water flux (PWF), porosity, a mechanical strength test, and morphology observations by a scanning electron microscopy (SEM). The results of this study indicate that PVA can apparently improve the hydrophilicity of the PVDF hollow fiber membranes. The growing enrichment of the hydrophilic components PVA on the membrane surface is determined by X‐ray photoelectron spectroscopy. The RFA membranes have a favorable interfacial bonding between the coating layer (PVDF/PVA) and the matrix membrane (PVDF hollow fiber membrane), as shown by SEM. The elongation at break of the RFA membranes increases much more than that of the matrix membrane that is endowed with the better flexibility of the membrane performance. PWF decreases much more compared with that of the matrix membrane. The RFA membranes have a lower flux decline degree during the process of protein solution and ink solution filtration compared with that of the matrix membrane. POLYM. ENG. SCI., 54:276–287, 2014. © 2013 Society of Plastics Engineers     

A rationale for the preparation of Loeb-Sourirajan-type cellulose acetate membranes

An attempt has been made to rationalize the variables in the preparation procedure of Loeb-Sourirajan-type reverse-osmosis membranes. The quaternary phase diagram of the system cellulose acetate–acetone–formamide–water was determined and has proved a useful tool in the discussion of membrane structures and properties. A mechanism based on differences in the precipitation rate of the polymer during the membrane formation process has been suggested to explain the observed asymmetry in the membrane structure. The porosity of the membrane has been ascribed to the relative rates of water entering and solvent leaving the cast film. The effects of the casting solution composition, the evaporation time, the wash bath temperature, and the annealing procedure have been studied. X-Ray diffraction and electron microscopy were used to supplement flux and retention data of membranes made from a cellulose acetate–formamide–acetone casting solution.     

Effect of ethylene vinyl acetate content on the performance of VMD using HDPE co-blending membrane

Membranes were fabricated with high-density polyethylene(HDPE) and ethylene vinyl acetate(EVA) blend through thermally induced phase separation and were then used for vacuum membrane distillation(VMD).The membranes were supported by nonwoven polyester fabric with a special cellular structure. Different membrane samples were obtained by adjusting the polymer concentration, HDPE/EVA weight ratio, and coagulation bath temperature. The membranes were characterized by scanning electron microscopy(SEM) analysis, contact angle test, and evaluation of porosity and pore size distribution. A series of VMD tests were conducted using aqueous NaCl solution(0.5 mol·L~(-1)) at a feed temperature of 65 ℃ and permeate side absolute pressure of 3 kPa. The membranes showed excellent performance in water permeation flux, salt rejection, and long-term stability. The HDPE/EVA co-blending membranes exhibited the largest permeation flux of 23.87 kg·m~(-2)·h~(-1) and benign salt rejection of ≥99.9%.     

Synthesis and characterization of cellulose acetate-polysulfone blend microfiltration membrane for separation of microbial cells from lactic acid fermentation broth

This work is focused on synthesis and characterization of a polymer blend microfiltration membrane for separation of microbial cells from lactic acid fermentation broth in a continuous process. The membranes were prepared by blending hydrophilic cellulose diacetate (CA) polymer with hydrophobic polysulfone (PSF) polymer in wet phase inversion method. Polymers were blended in N-methyl-2-pyrrolidone (NMP) solvent (70 wt.%) where polyethylene glycol was added as a pore former. The membranes were characterized in terms of morphology, porosity, flux and microbial separation capability. The best prepared membrane with PSF/CA weight ratio of 25/75 yielded a pure water flux of 1830 LMH (liter/m² h) and a fermentation broth flux of 1430 LMH at around 1.5 bar TMP (trans-membrane pressure). The membrane was successful in complete retention of microbial cells from the broth in a continuous crossflow membrane module integrated with the fermentor.