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.

Preparation of hydrophilic modified polyvinylidene fluoride (PVDF) ultrafiltration membranes by polymer/non-solvent co-induced phase separation: effect of coagulation bath temperature

Membrane separation technology is widely used in wastewater purification, but the issue of membrane fouling could not be ignored. Hydrophilic modification is an effective method to reduce membrane fouling. Therefore, in this work, a hydrophilic modified polyvinylidene fluoride (PVDF) ultrafiltration membrane was prepared by polymer/non-solvent co-induced phase separation, and the effect of coagulation bath temperature on the membrane structure and performance was systematically investigated based on the previous study. With the increased of the coagulation bath temperature, the phase separation process changed from delayed to instantaneous, and the membrane surface changed from porous to dense, while the macropore structures and sponge-like pores appeared on the cross-section. Meanwhile, the pure water flux decreased from 229.3 L/(m2·h) to 2.08 L/(m2·h), the protein rejection rate increased from 83.87% to 100%, and the surface water contact angle increased from 63° to 90°. Thus, excessively high coagulation bath temperature adversely affected the permeate and separation performance, as well as antifouling performance of the membrane. This study enriched the research for preparing separation membranes by polymer/non-solvent co-induced phase separation and provided a practical and theoretical reference for controlling the membrane structure and properties by changing the coagulation bath temperature.

Nonwoven Textiles from Hyaluronan for Wound Healing Applications

Nonwoven textiles are used extensively in the field of medicine, including wound healing, but these textiles are mostly from conventional nondegradable materials, e.g., cotton or synthetic polymers such as polypropylene. Therefore, we aimed to develop nonwoven textiles from hyaluronan (HA), a biocompatible, biodegradable and nontoxic polysaccharide naturally present in the human body. For this purpose, we used a process based on wet spinning HA into a nonstationary coagulation bath combined with the wet-laid textile technology. The obtained HA nonwoven textiles are soft, flexible and paper like. Their mechanical properties, handling and hydration depend on the microscale fibre structure, which is tuneable by selected process parameters. Cell viability testing on two relevant cell lines (3T3, HaCaT) demonstrated that the textiles are not cytotoxic, while the monocyte activation test ruled out pyrogenicity. Biocompatibility, biodegradability and their high capacity for moisture absorption make HA nonwoven textiles a promising material for applications in the field of wound healing, both for topical and internal use. The beneficial effect of HA in the process of wound healing is well known and the form of a nonwoven textile should enable convenient handling and application to various types of wounds.

Modification of the Surface Morphology and Properties of Graphene Oxide and Multi-Walled Carbon Nanotube-Based Polyvinylidene Fluoride Membranes According to Changes in Non-Solvent Temperature

The effect of changes in non-solvent coagulation bath temperature on surface properties such as morphology and hydrophilicity were investigated in multi-walled carbon nanotubes (MWCNTs) and graphene oxide (GO)-based polyvinylidene fluoride (PVDF) membranes. The properties of pores (size, shape, and number) as well as membrane hydrophilicity were investigated using field emission scanning electron microscopy, Raman spectroscopy, optical microscopy, water contact angle, and water flux. Results showed that the pore size increased with an increase in coagulation temperature. The hydrophilic functional groups of the added carbon materials increased the solvent and non-solvent diffusion rate, which significantly increased the number of pores by 700% as compared to pure PVDF. Additionally, these functional groups changed the hydrophobic properties of pure PVDF into hydrophilic properties.

Tamisolve® NxG as an Alternative Non-Toxic Solvent for the Preparation of Porous Poly (Vinylidene Fluoride) Membranes

Tamisolve® NxG, a well-known non-toxic solvent, was used for poly(vinylidene fluoride) (PVDF) membranes preparation via a non-solvent-induced phase separation (NIPS) procedure with water as a coagulation bath. Preliminary investigations, related to the study of the physical/chemical properties of the solvent, the solubility parameters, the gel transition temperature and the viscosity of the polymer–solvent system, confirmed the power of the solvent to solubilize PVDF polymer for membranes preparation. The role of polyvinylpyrrolidone (PVP) and/or poly(ethylene glycol) (PEG), as pore former agents in the dope solution, was studied along with different polymer concentrations (10 wt%, 15 wt% and 18 wt%). The produced membranes were then characterized in terms of morphology, thickness, porosity, contact angle, atomic force microscopy (AFM) and infrared spectroscopy (ATR-FTIR). Pore size measurements, pore size distribution and water permeability (PWP) tests placed the developed membranes in the ultrafiltration (UF) and microfiltration (MF) range. Finally, PVDF membrane performances were investigated in terms of rejection (%) and permeability recovery ratio (PRR) using methylene blue (MB) in water solution to assess their potential application in separation and purification processes.

Morphological Study of Fabricated PVDF Based Hydrophobic Membrane for Different Additives and Coagulation Bath Temperature

The demand of membrane distillation (MD) has increased since last few decades for numerous applications. The membrane used in MD is hydrophobic; therefore, the focus has been emphasised on the development of a suitable membrane with desired microstructure. In this study, the flat sheet hydrophobic membrane of suitable properties has been casted with various additives such as water, ethane-di-ol, and propan-2-ol in dope solution using a non-solvent induced phase separation (NIPS) technique. The effect of water content in dope solution has been studied on casted membrane porosity and contact angle. The maximum contact angle and porosity were found to be 96° and 53.23% at 4 weight percent of water content in dope solution of PVDF polymer and di.methyl.acetamide as solvent. It was found that SEM micrograph when ethane-di-ol and propan-2-ol are used as an additive shows more finger-like pores and nodules, respectively, in the microstructure of the casted membrane. Furthermore, synergistic effects using water with other additives were also identified using SEM micrograph of casted membrane and it was observed that water with ethane-di-ol and propan-2-ol form contact angle of 98° and 105°, respectively, for 2 weight percent each additive in dope. In this study, the membrane was also cast by dissolving PVDF powder in di.methyl.acetamide solvent with lithium chloride and the effect of the temperature difference between coagulation bath and film temperature was investigated using an SEM micrograph. Overall, it was found that water content and temperature difference aid in developing hydrophobic porous membrane of desired properties for MD applications.

The Effect of Temperature, Sulfonation, and PEG Addition on Physicochemical Characteristics of PVDF Membranes and Its Application on Hemodialysis Membrane

Polyvinylidene fluoride (PVDF) membrane and its derivative have been investigated the permeation ability for creatinine and urea. The membrane was made by an inversion precipitation system in N,N-dimethyl acetamide (DMAc) and water as non-solvents. In this study, the modification of PVDF membrane permeability with PEG additives, CBT variations, and sulfonation was successfully carried out. The membrane solidification process was carried out on three variations of the coagulation bath temperature (CBT): 30, 45, and 60 °C. Eight types of membranes were characterized by using FT-IR and TGA/DSC, followed by the analysis of their porosity, hydrophilicity, water uptake, swelling degree, tensile strength, and permeability of creatinine and urea. The FT-IR spectra indicate that PVDF modification has been successfully carried out. The porosity, hydrophilicity, water uptake, and swelling degree values increase with the modification of functional groups. Furthermore, improvements in creatinine and urea permeability and clearances are achieved by increasing CBT and sulfonation in the PVDF/PEG membrane. The presence of sulfonate groups improves the membrane permeability through the interaction of intermolecular hydrogen with water and dialysate compounds. The existence of PEG as a porogen enhanced membrane porosity. Creatinine and urea clearance values increase from 0.29–0.58 and 6.38–20.63 mg/dL, respectively.

Simulation on Pore Formation from Polymer Solution at Surface in Contact with Solid Substrate via Thermally Induced Phase Separation

The formation of porous structures from polymer solutions at the surface in contact with various solid surfaces via a thermally-induced phase separation (TIPS) process is investigated. The pore formation process at the bulk and the surface of the poly(methyl methacrylate)/cyclohexanol solution is simulated with a model based on the phase field method. When the compatibilities between the polymer-rich phase formed by the phase separation and the solid surface are high or low, surface porosity decreases. In contrast, for the solid surface having similar compatibilities with the polymer and solvent, high surface porosity is achieved. This indicates that the compatibility between the solid surface and polymer solution is important, and that optimal compatibility results in high surface porosity. The knowledge obtained in this work is useful to design the coagulation bath component in the membrane preparation process by TIPS for achieving high surface porosity.