Influence of PEG-PPG-PEG Block Copolymer Concentration and Coagulation Bath Temperature on the Structure Formation of Polyphenylsulfone Membranes.

The effect of amphiphilic block copolymer polyethylene glycol (PEG)-polypropylene glycol (PPG)-PEG concentration in the polyphenylsulfone (PPSU) casting solution and coagulation bath temperature (CBT) on the structure, separation, and antifouling performance of PPSU ultrafiltration membranes was studied for the first time. According to the phase diagram obtained, PPSU/PEG-PPG-PEG/N-methyl-2-pyrrolidone (NMP) systems are characterized by a narrow miscibility gap. It was found that 20 wt.% PPSU solutions in NMP with the addition of 5-15 wt.% of PEG-PPG-PEG block copolymer feature upper critical solution temperature, gel point, and lower critical solution temperature. Membrane composition and structure were studied by Fourier-transform infrared spectroscopy, scanning electron and atomic force microscopies, and water contact angle measurements. The addition of PEG-PPG-PPG to the PPSU casting solution was found to increase the hydrophilicity of the membrane surface (water contact angle decreased from 78° for the reference PPSU membrane down to 50° for 20 wt.%PPSU/15 wt.% PEG-PPG-PEG membrane). It was revealed that the pure water flux increased with the rise of CBT from 18-20 L·m-2·h-1 for the reference PPSU membrane up to 38-140 L·m-2·h-1 for 20 wt.% PPSU/10-15 wt.% PEG-PPG-PEG membranes. However, the opposite trend was observed for 20 wt.% PPSU/5-7 wt.% PEG-PPG-PEG membranes: pure water flux decreased with an increase in CBT. This is due to the differences in the mechanism of phase separation (non-solvent-induced phase separation (NIPS) or a combination of NIPS and temperature-induced phase separation (TIPS)). It was shown that 20 wt.% PPSU/10 wt.% PEG-PPG-PEG membranes were characterized by significantly higher antifouling performance (FRR-81-89%, DRr-26-32%, DRir-10-20%, DT-33-45%) during the ultrafiltration of bovine serum albumin solutions compared to the reference PPSU membrane prepared at different CBTs (FRR-29-38%, DRr-6-14%, DRir-74-89%, DT-88-94%).

Effect of the Addition of Polyacrylic Acid of Different Molecular Weights to Coagulation Bath on the Structure and Performance of Polysulfone Ultrafiltration Membranes.

Membrane fouling is a serious issue in membrane technology which cannot be completely avoided but can be diminished. The perspective technique of membrane modification is the introduction of hydrophilic polymers or polyelectrolytes into the coagulation bath during membrane preparation via non-solvent-induced phase separation. The influence of polyacrylic acid (PAA) molecular weight (100,000, 250,000 and 450,000 g·mol-1) added to the aqueous coagulation bath (0.4-2.0 wt.%) on the polysulfone membrane structure, surface roughness, water contact angle and zeta potential of the selective layer, as well as the separation and antifouling performance, was systematically studied. It was found that membranes obtained via the addition of PAA with higher molecular weight feature smaller pore size and porosity, extremely high hydrophilicity and higher values of negative charge of membrane surface. It was shown that the increase in PAA concentration from 0.4 wt.% to 2.0 wt.% for all studied PAA molecular weights yielded a substantial decrease in water contact angle compared with the reference membrane (65 ± 2°) (from 27 ± 2° to 17 ± 2° for PAA with Mn = 100,000 g·mol-1; from 25 ± 2° to 16 ± 2° for PAA with Mn = 250,000 g·mol-1; and from 19 ± 2° to 10 ± 2° for PAA with Mn = 450,000 g·mol-1). An increase in PAA molecular weight from 100,000 to 450,000 g·mol-1 led to a decrease in membrane permeability, an increase in rejection and tailoring excellent antifouling performance in the ultrafiltration of humic acid solutions. The fouling recovery ratio increased from 73% for the reference membrane up to 91%, 100% and 136% for membranes modified with the addition to the coagulation bath of 1.5 wt.% of PAA with molecular weights of 100,000 g·mol-1, 250,000 g·mol-1 and 450,000 g·mol-1, respectively. Overall, the addition of PAA of different molecular weights to the coagulation bath is an efficient tool to adjust membrane separation and antifouling properties for different separation tasks.

Development and Investigation of Hierarchically Structured Thin-Film Nanocomposite Membranes from Polyamide/Chitosan Succinate Embedded with a Metal-Organic Framework (Fe-BTC) for Pervaporation.

Thin-film composite membranes (TFC) obtained by the formation of a selective layer on a porous membrane-substrate via interfacial polymerization (IP) are indispensable for separation procedures in reverse osmosis, nanofiltration, pervaporation, and gas separation. Achieving high selectivity and permeability for TFC membranes is still one of the main challenges in membrane science and technology. This study focuses on the development of thin film nanocomposite (TFN) membranes with a hierarchically structured polyamide (PA)/chitosan succinate (ChS) selective layer embedded with a metal-organic framework of iron 1,3,5-benzenetricarboxylate (Fe-BTC) for the enhanced pervaporation dehydration of isopropanol. The aim of this work was to study the effect of Fe-BTC incorporation into the ChS interlayer and PA selective layer, obtained via IP, on the structure, properties, and performance of pervaporation TFN membranes. The structure and hydrophilicity of the developed TFN membranes were investigated using scanning electron microscopy (SEM) and atomic force microscopy (AFM), along with water contact angle measurements. The developed TFN membranes were studied in the pervaporation dehydration of isopropanol (12-30 wt % water). It was found that incorporation of Fe-BTC into the ChS interlayer yielded the formation of a smoother, more uniform, and defect-free PA ultrathin selective layer via IP, due to the amorpho-crystalline structure of particles serving as the amine storage reservoir and led to an increase in membrane selectivity toward water, and a slight decrease in permeation flux compared to the ChS interlayered TFC membranes. The best pervaporation performance was demonstrated by the TFN membrane with a ChS-Fe-BTC interlayer and the addition of 0.03 wt % Fe-BTC in the PA layer, yielding a permeation flux of 197-826 g·m-2·h-1 and 98.50-99.99 wt % water in the permeate, in the pervaporation separation of isopropanol/water mixtures (12-30 wt % water).

Synthesis of Aromatic Polyimides Based on 3,4'-Oxydianiline by One-Pot Polycondensation in Molten Benzoic Acid and Their Application as Membrane Materials for Pervaporation.

A series of aromatic polyimides based on the asymmetrical diamine 3,4'-oxydianiline and various tetracarboxylic acid dianhydrides, both "rigid" and "flexible" structure, have been synthesized using the original method of one-pot high-temperature catalytic polycondensation in molten benzoic acid. The synthesized polyimides were investigated using fourier-transform infrared (FTIR) and 1H NMR spectroscopy, gel permeation chromatography (GPC), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), thermomechanical analysis (TMA) and wide-angle X-ray scattering (WAXS). It was found that the synthesized polyimides, depending on the used dianhydride, are characterized by different solubility in organic solvent and molten benzoic acid, molecular weight, glass transition temperature (Tg) from 198 to 270 °C, an amorphous or semi crystalline structure with the degree of crystallinity from 41 to 52%. The influence of the method of synthesis on the formation of the crystalline phase of polyimides was studied, and the obtained results were compared with the literature data. The effect of dianhydride chemical structure on the performance of polyimide in pervaporation more specifically, dehydratation of azeotropic isopropanol solution was investigated and compared with the commercially available polyetherimide Ultem 1000™. Membrane structure was studied using scanning electron microscopy. It was found that polyimide PI-DA is the most effective for separation of 88 wt.% isopropanol/12 wt.% water mixture compared to the polyimide PI-6FDA and commercial polyetherimide Ultem 1000™ demonstrating normalized permeation flux of 2.77 kg µm m-2 h-1 and separation factor of 264 (water content in permeate 97 wt.%).

Modification of Thin Film Composite PVA/PAN Membranes for Pervaporation Using Aluminosilicate Nanoparticles.

The effect of the modification of the polyvinyl alcohol (PVA) selective layer of thin film composite (TFC) membranes by aluminosilicate (Al2O3·SiO2) nanoparticles on the structure and pervaporation performance was studied. For the first time, PVA-Al2O3·SiO2/polyacrylonitrile (PAN) thin film nanocomposite (TFN) membranes for pervaporation separation of ethanol/water mixture were developed via the formation of the selective layer in dynamic mode. Selective layers of PVA/PAN and PVA-Al2O3·SiO2/PAN membranes were formed via filtration of PVA aqueous solutions or PVA-Al2O3·SiO2 aqueous dispersions through the ultrafiltration PAN membrane for 10 min at 0.3 MPa in dead-end mode. Average particle size and zeta potential of aluminosilicate nanoparticles in PVA aqueous solution were analyzed using the dynamic light scattering technique. Structure and surface properties of membranes were studied using scanning electron microscopy (SEM), atomic force microscopy (AFM) and water contact angle measurements. Membrane performance was investigated in pervaporation dehydration of ethanol/water mixtures in the broad concentration range. It was found that flux of TFN membranes decreased with addition of Al2O3·SiO2 nanoparticles into the selective layer due to the increase in selective layer thickness. However, ethanol/water separation factor of TFN membranes was found to be significantly higher compared to the reference TFC membrane in the whole range of studied ethanol/water feed mixtures with different concentrations, which is attributed to the increase in membrane hydrophilicity. It was found that developed PVA-Al2O3·SiO2/PAN TFN membranes were more stable in the dehydration of ethanol in the whole range of investigated concentrations as well as at different temperatures of the feed mixtures (25 °C, 35 °C, 50 °C) compared to the reference membrane which is due to the additional cross-linking of the selective layer by formation hydrogen and donor-acceptor bonds between aluminosilicate nanoparticles and PVA macromolecules.

Novel Thin Film Nanocomposite Membranes Based on Chitosan Succinate Modified with Fe-BTC for Enhanced Pervaporation Dehydration of Isopropanol.

The application of environmentally friendly and energy-efficient membrane processes allows improvement the ecological safety and sustainability of industrial production. However, the effective application of membrane processes requires novel high-performance thin film composite (TFC) membranes based on biopolymers to solve environmental problems. In this work for the first time novel thin film nanocomposite (TFN) membranes based on biopolymer chitosan succinate (ChS) modified with the metal organic framework iron 1,3,5-benzenetricarboxylate (Fe-BTC) were developed for enhanced pervaporation dehydration. The formation of a selective layer of TFN membranes on the porous membrane-support was carried out by two methods-dynamic technique and physical adsorption. The effect of the membrane formation method and Fe-BTC content in ChS layer on the structure and physicochemical properties of TFN membranes was investigated. The developed TFN ChS-based membranes were evaluated in the pervaporation dehydration of isopropanol (12-30 wt.% water). It was found that TFN ChS-Fe-BTC membranes prepared by two methods demonstrated improved permeation flux compared to the reference TFC ChS membrane. The best transport properties in pervaporation dehydration of isopropanol (12-30 wt.% water) were possessed by TFN membranes with 40 wt.% Fe-BTC prepared by dynamic technique (permeation flux 99-499 g m-2 h-1 and 99.99% water in permeate) and TFN membranes with 5 wt.% Fe-BTC developed by physical adsorption (permeation flux 180-701 g m-2 h-1 and 99.99% water in permeate).

Development of High Flux Nanocomposite Polyphenylsulfone/Oxidized Multiwalled Carbon Nanotubes Membranes for Ultrafiltration Using the Systems with Critical Solution Temperatures.

The study deals with the investigation of the effect of the modification of polyphenylsulfone (PPSU) flat sheet membranes for ultrafiltration using oxidized multiwalled carbon nanotubes (O-MWCNT) in order to enhance membrane permeability and antifouling performance. The effect of O-MWCNT loading to the PPSU-polyethylene glycol (PEG-20,000, Mn = 20,000 g·mol-1)-polyvinylpyrrolidone (PVP K-30, Mn = 40,000 g·mol-1)-N-methy-2-pyrrolidinone (NMP) colloid systems on the phase state and viscosity was studied. It was found that PPSU-PEG-20,000-PVP K-30-O-MWCNT-NMP colloid systems feature a gel point (T = 35-37 °C) and demixing temperature (T = 127-129 °C) at which two bulk phases are formed and a polymer system delaminates. According to the study of the phase state and viscosity of these colloid systems, a method for the preparation of high flux PPSU membranes is proposed which includes processing of the casting solution at the temperature higher than gel point (40 °C) and using a coagulation bath temperature lower than gel point (25 °C) or lower than demixing temperature (40 °C and 70 °C). Membrane structure, topology and hydrophilic-hydrophobic balance were investigated by scanning electron microscopy (SEM), atomic force microscopy (AFM) and water contact angle measurements. The effect of coagulation bath temperature and O-MWCNT concentration on the membrane separation and antifouling performance in ultrafiltration of human serum albumin and humic acids solutions was studied. It was found that the modification of PPSU ultrafiltration membranes by O-MWCNTs yielded the formation of a thinner selective layer and hydrophilization of the membrane surface (water contact angle decreased from 53-56° for the reference PPSU membrane down to 33° for the nanocomposite membrane with the addition of 0.19 wt.% O-MWCNT). These changes resulted in the increase in membrane flux (from 203-605 L·m-2·h-1 at transmembrane pressure of 0.1 MPa for the reference membrane up to 512-983 L·m-2·h-1 for nanocomposite membrane with the addition of 0.19 wt.% O-MWCNT depending on coagulation bath temperature) which significantly surpasses the performance of PPSU ultrafiltration membranes reported to date while maintaining a high level of human serum albumin rejection (83-92%). It was revealed that nanocomposite membrane demonstrated better antifouling performance (the flux recovery ratio increased from 47% for the reference PPSU membrane up to 62% for the nanocomposite membrane) and higher total organic carbon removal compared to the reference PPSU membrane in humic acids solution ultrafiltration.

Development of Antifouling Polysulfone Membranes by Synergistic Modification with Two Different Additives in Casting Solution and Coagulation Bath: Synperonic F108 and Polyacrylic Acid.

This study deals with the development of antifouling ultrafiltration membranes based on polysulfone (PSF) for wastewater treatment and the concentration and purification of hemicellulose and lignin in the pulp and paper industry. The efficient simple and reproducible technique of PSF membrane modification to increase antifouling performance by simultaneous addition of triblock copolymer polyethylene glycol-polypropylene glycol-polyethylene glycol (Synperonic F108, Mn =14 × 103 g mol-1) to the casting solution and addition of polyacrylic acid (PAA, Mn = 250 × 103 g mol-1) to the coagulation bath is proposed for the first time. The effect of the PAA concentration in the aqueous solution on the PSF/Synperonic F108 membrane structure, surface characteristics, performance, and antifouling stability was investigated. PAA concentrations were varied from 0.35 to 2.0 wt.%. Membrane composition, structure, and topology were investigated by Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and scanning electron microscopy (SEM). The addition of PAA into the coagulation bath was revealed to cause the formation of a thicker and denser selective layer with decreasing its pore size and porosity; according to the structural characterization, an interpolymer complex of the two additives was formed on the surface of the PSF membrane. Hydrophilicity of the membrane selective layer surface was shown to increase significantly. The selective layer surface charge was found to become more negative in comparison to the reference membrane. It was shown that PSF/Synperonic F108/PAA membranes are characterized by better antifouling performance in ultrafiltration of humic acid solution and thermomechanical pulp mill (ThMP) process water. Membrane modification with PAA results in higher ThMP process water flux, fouling recovery ratio, and hemicellulose and total lignin rejection compared to the reference PSF/Synperonic F108 membrane. This suggests the possibility of applying the developed membranes for hemicellulose concentration and purification.

Novel High Flux Poly(m-phenylene isophtalamide)/TiO2 Membranes for Ultrafiltration with Enhanced Antifouling Performance.

Wide application of ultrafiltration in different industrial fields requires the development of new membranes with tailored properties and good antifouling stability. This study is devoted to the improvement of ultrafiltration properties of poly(m-phenylene isophtalamide) (PA) membranes by modification with titanium oxide (TiO2) particles. The introduction of TiO2 particles improved membrane separation performance and increased antifouling stability and cleaning ability under UV irradiation. The developed membranes were characterized by scanning electron and atomic force microscopy methods, the measurements of water contact angle, and total porosimetry. The transport properties of the PA and PA/TiO2 membranes were tested in ultrafiltration of industrially important feeds: coolant lubricant (cutting fluid) emulsion (5 wt.% in water) and bovine serum albumin (BSA) solution (0.5 wt.%). The PA/TiO2 (0.3 wt.%) membrane was found to possess optimal transport characteristics in ultrafiltration of coolant lubricant emulsion due to the highest pure water and coolant lubricant fluxes (1146 and 32 L/(m2 h), respectively), rejection coefficient (100%), and flux recovery ratio (84%). Furthermore, this membrane featured improved ability of surface contamination degradation after UV irradiation in prolonged ultrafiltration of BSA, demonstrating a high flux recovery ratio (89-94%).

Modification of Polysulfone Ultrafiltration Membranes via Addition of Anionic Polyelectrolyte Based on Acrylamide and Sodium Acrylate to the Coagulation Bath to Improve Antifouling Performance in Water Treatment.

Surface modification of polysulfone ultrafiltration membranes was performed via addition of an anionic polymer flocculant based on acrylamide and sodium acrylate (PASA) to the coagulation bath upon membrane preparation by non-solvent induced phase separation (NIPS). The effect of PASA concentration in the coagulant at different coagulation bath temperatures on membrane formation time, membrane structure, surface roughness, hydrophilic-hydrophobic balance of the skin layer, surface charge, as well as separation and antifouling performance was studied. Scanning electron microscopy (SEM), atomic force microscopy (AFM), Fourier transform infrared (FTIR) spectroscopy, contact angle and zeta potential measurements were utilized for membrane characterization. Membrane barrier and antifouling properties were evaluated in ultrafiltration of model solutions containing human serum albumin and humic acids as well as with real surface water. PASA addition was found to affect the kinetics of phase separation leading to delayed demixing mechanism of phase separation due to the substantial increase of coagulant viscosity, which is proved by a large increase of membrane formation time. Denser and thicker skin layer is formed and formation of macrovoids in membrane matrix is suppressed. FTIR analysis confirms the immobilization of PASA macromolecules into the membrane skin layer, which yields improvement of hydrophilicity and change of zeta potential. Modified membrane demonstrated better separation and antifouling performance in the ultrafiltration of humic acid solution and surface water compared to the reference membrane.

Effect of the Formation of Ultrathin Selective Layers on the Structure and Performance of Thin-Film Composite Chitosan/PAN Membranes for Pervaporation Dehydration.

The aim of the study is to improve the performance of thin-film composite (TFC) membranes with a thin selective layer based on chitosan (CS) via different approaches by: (1) varying the concentration of the CS solution; (2) changing the porosity of substrates from polyacrylonitrile (PAN); (3) deposition of the additional ultrathin layers on the surface of the selective CS layer using interfacial polymerization and layer-by-layer assembly. The developed membranes were characterized by different methods of analyses (SEM and AFM, IR spectroscopy, measuring of water contact angles and porosity). The transport characteristics of the developed TFC membranes were studied in pervaporation separation of isopropanol/water mixtures. It was found that the application of the most porous PAN-4 substrate with combination of formation of an additional polyamide selective layer by interfacial polymerization on the surface of a dense selective CS layer with the subsequent layer-by-layer deposition of five bilayers of poly (sodium 4-styrenesulfonate)/CS polyelectrolyte pair led to the significant improvement of permeance and high selectivity for the entire concentration feed range. Thus, for TFC membrane on the PAN-4 substrate the optimal transport characteristics in pervaporation dehydration of isopropanol (12-90 wt.% water) were achieved: 0.22-1.30 kg/(m2h), 99.9 wt.% water in the permeate.

One-Step Preparation of Antifouling Polysulfone Ultrafiltration Membranes via Modification by a Cationic Polyelectrolyte Based on Polyacrylamide.

A novel method for one-step preparation of antifouling ultrafiltration membranes via a non-solvent induced phase separation (NIPS) technique is proposed. It involves using aqueous 0.05-0.3 wt.% solutions of cationic polyelectrolyte based on a copolymer of acrylamide and 2-acryloxyethyltrimethylammonium chloride (Praestol 859) as a coagulant in NIPS. A systematic study of the effect of the cationic polyelectrolyte addition to the coagulant on the structure, performance and antifouling stability of polysulfone membranes was carried out. The methods for membrane characterization involved scanning electron microscopy (SEM), atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FTIR), contact angle and zeta-potential measurements and evaluation of the permeability, rejection and antifouling performance in human serum albumin solution and surface water ultrafiltration. It was revealed that in the presence of cationic polyelectrolyte in the coagulation bath, its concentration has a major influence on the rate of "solvent-non-solvent" exchange and thus also on the rate of phase separation which significantly affects membrane structure. The immobilization of cationic polyelectrolyte macromolecules into the selective layer was confirmed by FTIR spectroscopy. It was revealed that polyelectrolyte macromolecules predominately immobilize on the surface of the selective layer and not on the bottom layer. Membrane modification was found to improve the hydrophilicity of the selective layer, to increase surface roughness and to change zeta-potential which yields the substantial improvement of membrane antifouling stability toward natural organic matter and human serum albumin.