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.

A Biofouling Resistant Zwitterionic Polysulfone Membrane Prepared by a Dual-Bath Procedure

This study introduces a zwitterionic material to modify polysulfone (PSf) membranes formed by a dual bath procedure, in view of reducing their fouling propensity. The zwitterionic copolymer, derived from a random polymer of styrene and 4-vinylpyrridine and referred to as zP(S-r-4VP), was incorporated to the PSf solution without any supplementary pore-forming additive to study the effect of the sole copolymer on membrane-structuring, chemical, and arising properties. XPS and mapping FT-IR provided evidence of the modification. Macrovoids appeared and then disappeared as the copolymer content increased in the range 1–4 wt%. The copolymer has hydrophilic units and its addition increases the casting solution viscosity. Both effects play an opposite role on transfers, and so on the growth of macrovoids. Biofouling tests demonstrated the efficiency of the copolymer to mitigate biofouling with a reduction in bacterial and blood cell attachment by more than 85%. Filtration tests revealed that the permeability increased by a twofold factor, the flux recovery ratio was augmented from 40% to 63% after water/BSA cycles, and irreversible fouling was reduced by 1/3. Although improvements are needed, these zwitterionic PSf membranes could be used in biomedical applications where resistance to biofouling by cells is a requirement.

Effect of Polyphenylsulfone and Polysulfone Incompatibility on the Structure and Performance of Blend Membranes for Ultrafiltration

This study deals with the modification of polyphenylsulfone ultrafiltration membranes by introduction of an incompatible polymer polysulfone to the polyphenylsulfone casting solution to improve the permeability. The correlation between properties of the blend polyphenylsulfone/polysulfone solutions and porous anisotropic membranes for ultrafiltration prepared from these solutions was revealed. The blend polyphenylsulfone/polysulfone solutions were investigated using a turbidity spectrum method, optical microscopy and measurements of dynamic viscosity and turbidity. The structure of the prepared blend flat sheet membranes was studied using scanning electron microscopy. Membrane separation performance was investigated in the process of ultrafiltration of human serum albumin buffered solutions. It was found that with the introduction of polysulfone to the polyphenylsulfone casting solution in N-methyl-2-pyrrolidone the size of supramolecular particles significantly increases with the maximum at (40–60):(60:40) polyphenylsulfone:polysulfone blend ratio from 76 nm to 196–354 nm. It was shown that polyphenylsulfone/polysulfone blend solutions, unlike the solutions of pristine polymers, are two-phase systems (emulsions) with the maximum droplet size and highest degree of polydispersity at polyphenylsulfone/polysulfone blend ratios (30–60):(70–40). Pure water flux of the blend membranes passes through a maximum in the region of the most heterogeneous structure of the casting solution, which is associated with the imposition of a polymer-polymer phase separation on the non-solvent induced phase separation upon membrane preparation. The application of polyphenylsulfone/polysulfone blends as membrane-forming polymers and polyethylene glycol (Mn = 400 g·mol−1) as a pore-forming agent to the casting solutions yields the formation of ultrafiltration membranes with high membrane pure water flux (270 L·m−2·h−1 at 0.1MPa) and human serum albumin rejection of 85%.

PREPARATION OF POLYACRYLONITRILE MEMBRANES WITH ANTIBACTERIAL PROPERTIES

We describe the method of formation of polyacrylonitrile membranes with antibacterial properties by addition into the casting solution casting of antibacterial polymeric compounds: polyhexamethyleneguanidine chloride, oligourethanesemicarbazide with terminal cationic pyridinium chloride groups, and the polyvinylpyrrolidone-iodine complex. We investigated the effect of the addition of antibacterial compounds to the casting solution casting on the physicochemical, transport and antibacterial properties of the obtained membranes. We show that increasing the concentration of the bactericidal additives in the casting solution to 3% (wt.) leads to a change in the investigated physicochemical characteristics, water flux and membrane rejection, of polyethyleneglycol and low molecular weight electrolyte type 2-1 (CaCl2). We found that membranes prepared from the casting solution with 3% (wt.) of antimicrobial substances are characterized by high antibacterial activity.

γ-Valerolactone as Bio-Based Solvent for Nanofiltration Membrane Preparation

γ-Valerolactone (GVL) was selected as a renewable green solvent to prepare membranes via the process of phase inversion. Water and ethanol were screened as sustainable non-solvents to prepare membranes for nanofiltration (NF). Scanning electron microscopy was applied to check the membrane morphology, while aqueous rose Bengal (RB) and magnesium sulphate (MgSO4) feed solutions were used to screen performance. Cellulose acetate (CA), polyimide (PI), cellulose triacetate (CTA), polyethersulfone (PES) and polysulfone (PSU) membranes were fine-tuned as materials for preparation of NF-membranes, either by selecting a suitable non-solvent for phase inversion or by increasing the polymer concentration in the casting solution. The best membranes were prepared with CTA in GVL using water as non-solvent: with increasing CTA concentration (10 wt% to 17.5 wt%) in the casting solution, permeance decreased from 15.9 to 5.5 L/m2·h·bar while RB rejection remained higher than 94%. The polymer solubilities in GVL were rationalized using Hansen solubility parameters, while membrane performances and morphologies were linked to viscosity measurements and cloudpoint determination of the casting solutions to better understand the kinetic and thermodynamic aspects of the phase inversion process.

Effect of Solution Viscosity on the Precipitation of PSaMA in Aqueous Phase Separation-Based Membrane Formation

Aqueous phase separation (APS) is a recently developed sustainable alternative to the conventional organic solvent based nonsolvent-induced phase separation (NIPS) method to prepare polymeric membranes. In APS, polyelectrolytes are precipitated from aqueous solutions through pH or salinity switches. Although APS differs from NIPS in the polymer and solvents, they share many tuning parameters. In this work, we investigate the APS-based preparation of membranes from poly(styrene-alt-maleic acid) (PSaMA) with a focus on acid concentration in the coagulation bath, and polymer and additive concentration in the casting solution. Nanofiltration membranes are prepared using significantly lower concentrations of acid: 0.3 M HCl compared to the 2 M of either acetic or phosphoric acid used in previous works. It is shown that higher polymer concentrations can be used to prevent defect formation in the top layer. In addition, acetic acid concentration also strongly affects casting solution viscosity and thus can be used to control membrane structure, where lower acetic acid concentrations can prevent the formation of macrovoids in the support structure. The prepared nanofiltration membranes exhibit a very low molecular weight cutoff (210 ± 40 dalton), making these sustainable membranes very relevant for the removal of contaminants of emerging concern. Understanding how the parameters described here affect membrane preparation and performance is essential to optimizing membranes prepared with APS towards this important application.

Express Method of Preparation of Hollow Fiber Membrane Samples for Spinning Solution Optimization: Polysulfone as Example

This article describes a new technique for the preparation of hollow fiber (HF) membrane samples using an automatic manipulator unit. The manipulator uses a syringe needle to form a HF of a given geometry. The needle in automatic mode is sequentially immersed, first into the polymer solution and then into the coagulation bath. The possibility of using a manipulator to obtain HF samples was studied on the known polysulfone (PSf)/N-methylpyrrolidone (NMP)/pore-forming additive system. A series of HF membrane samples were made within 29 h from twelve 1 mL PSf casting solutions. This was 15 times faster than obtaining samples of HF membranes at the multifunctional research laboratory facility. From the point of view of the consumption of the components of the casting solution, the use of the manipulator was 30 times more economical, and the consumption of water for precipitation and washing was 8000 times less. The developed method made it possible to study samples of HF by scanning electron microscopy (SEM), ultrafiltration, and evaluate its mechanical properties without spinning the membranes. Using the new technique, the optimal composition of the casting solution for the wet spinning of HF PSf membranes was selected during two weeks. Thus, the manipulator makes it possible to significantly reduce the time of the new membrane preparation, reduce the volume of used polymer, and thus makes it promising to study expensive or new membrane materials.

Fabrication of a lead ion selective membrane based on a polycarbazole Sn(iv) arsenotungstate nanocomposite and its ion exchange membrane (IEM) kinetic studies

A polycarbazole-Sn(iv) arsenotungstate (Pcz-SnAT) nanocomposite cation exchanger membrane (CEM) was prepared via the casting solution technique utilizing polycarbazole-Sn(iv) arsenotungstate and PVC (polyvinyl chloride) as a binder.