Blend Membranes Research Articles

Bead-Free PSF/PVP Blend Membrane as Potential Material for Water Desalination

We herein report successful fabrication of bead-free PSF/PVP blend membrane using electrospinning technique.

Blend membranes of sulphonated poly(arylene ether sulphone) and sulphonated polybenzimidazole and their characterization for desalination applications

Blend membranes of sulphonated poly(arylene ether sulphone) and sulphonated polybenzimidazole and their characterization for desalination applications

Hybrid Protocells Based on Coacervate-Templated Fatty Acid Vesicles Combine Improved Membrane Stability with Functional Interior Protocytoplasm.

Prebiotically-plausible compartmentalization mechanisms include membrane vesicles formed by amphiphile self-assembly and coacervate droplets formed by liquid-liquid phase separation. Both types of structures form spontaneously and can be related to cellular compartmentalization motifs in today's living cells. As prebiotic compartments, they have complementary capabilities, with coacervates offering excellent solute accumulation and membranes providing superior boundaries. Herein, protocell models constructed by spontaneous encapsulation of coacervate droplets by mixed fatty acid/phospholipid and by purely fatty acid membranes are described. Coacervate-supported membranes form over a range of coacervate and lipid compositions, with membrane properties impacted by charge-charge interactions between coacervates and membranes. Vesicles formed by coacervate-templated membrane assembly exhibit profoundly different permeability than traditional fatty acid or blended fatty acid/phospholipid membranes without a coacervate interior, particularly in the presence of magnesium ions (Mg2+). While fatty acid and blended membrane vesicles are disrupted by the addition of Mg2+, the corresponding coacervate-supported membranes remain intact and impermeable to externally-added solutes. With the more robust membrane, fluorescein diacetate (FDA) hydrolysis, which is commonly used for cell viability assays, can be performed inside the protocell model due to the simple diffusion of FDA and then following with the coacervate-mediated abiotic hydrolysis to fluorescein.

Novel pervaporation separation of PVA/CS blend membranes for the removal of DMF from industrial wastewater

AbstractAchieving satisfactory separation of N, N‐Dimethylformamide (DMF)/water is still challenging in industrial wastewater treatment. To address this issue, a novel method involving pervaporation (PV) separation using polyvinyl alcohol/chitosan (PVA/CS) blend films is proposed. Various characterization methods confirmed the strong compatibility between PVA and CS, and the blending improved their mechanical properties and thermal stability. Heat treatment significantly reduced the swelling degree of the membranes. In a binary aqueous system with low concentrations of DMF, controlled separation can be achieved by adjusting the blending ratio of PVA to CS. The membranes exhibited preferential selectivity for DMF when the CS content is 40–75 wt%, which allowed for the concentration and recovery of DMF. At 20 °C with a feed of 10 wt% DMF solution, 2 h heat‐treated PVA/CS‐50 membrane exhibited the best performance, which could be attributed to its strong hydrogen bonding force, with a total flux of 484.09 g m−2 h−1 and a separation factor of 5.41 for DMF. The PVA/CS blend membranes exhibit excellent acid and alkali resistant and are promising candidates for the separation and recovery of DMF from industrial wastewater by membrane technology.

High‐performance polybenzimidazole blend membranes based on a commercially available anion‐exchange polymer and F6PBI for vanadium redox flow batteries

AbstractRenewable energy is essential for the transition to a carbon‐neutral society. Due to their intermittent nature, temporary storage is required. The all‐vanadium redox flow battery (VRFB) is a promising technology for this purpose. Commercially available membranes, such as the FAPQ330 from Fumatech BWT, already show reasonable performance but still have room for improvement in selectivity and conductivity. In this study, we developed new ductile porous blend membranes based on the polybenzimidazole F6PBI by mixing it with poly(diallyldimethylammonium bis(trifluoromethane)sulfonimide), which was prepared from the commercially available poly(dimethylammonium chloride) (PDADMAC). Three types of membranes with different amounts of PDADMA*TFSI in the blend solution were prepared and characterized. Ex‐situ conductivity measurements showed conductivities between 8.3 and 30.5 mS cm−1. Ex‐situ permeability tests revealed significantly lower permeabilities compared to the reference membrane FAPQ330. No change in ex‐situ conductivity was measured after the ex‐situ stability test. F6PBI‐PDAD37 reached the highest energy efficiency at 50, 100, and 200 mA cm−2 among all tested membranes. For example, a VRFB single‐cell equipped with F6PBI‐PDAD37 showed an improved EE of 76.5% at 200 mA cm−2, which is higher than the EE of FAPQ330 (74.3%).

Waste cigarette filters-based polymer blends membrane for filtration of high loaded natural organic matter river water

Waste cigarette filter (WCF) is one of the most common wastes found in the environment. Cigarette filters contain up to 96% cellulose acetate (CA), which can be used as a material for membrane fabrication. However, the CA-based membrane from WCF posed a weak mechanical property (brittle). Therefore, the objective of this work is to improve mechanical property of CA-based membrane from WCF by preparing blend membranes with polyvinylidene fluoride (PVDF) polymer and evaluate their performance for filtration of real river water containing high natural organic matter (NOM) concentrations. The variations of WCF and PVDF used were 100:0, 75:25, 50:50, 25:75, and 0:100. The membranes were then characterized to determine the morphology, pore size and pore size distribution, hydrophilicity, mechanical properties, and filtration performance of the membrane using clean water and river water. The SEM test results showed the presence of spherulites on the surface of the blend membrane, indicating that crystallization occurred during membrane formation. The spherulites resulted in smaller pore size, narrower pore size distribution, higher hydrophilicity, and mechanical properties. Meanwhile, the filtration test results showed that blend membranes produced higher permeability compared to pristine WCF, PVDF, and commercial-based CA membranes, where the result of river water permeability was in the range of 875–1062.5 L/m2.h.bar. The membrane fouling formation was aligned well with the result of permeability and is dominated by irreversible fouling formation from the dynamic cake layer built on the membrane surface, with NOM rejections of 26.6–33.8%, suggesting the need for further developments.

Novel, Fluorine-Free Membranes Based on Sulfonated Polyvinyl Alcohol and Poly(ether-block-amide) with Sulfonated Montmorillonite Nanofiller for PEMFC Applications.

Novel blend membranes containing S-PVA and PEBAX 1657 with a blend ratio of 8:2 (referred to as SPP) were prepared using a solution-casting technique. In the manufacturing process, sulfonated montmorillonite (S-MMT) in ratios of 0%, 3%, 5%, and 7% was used as a filler. The crystallinity of composite membranes has been investigated by X-ray diffraction (XRD), while the interaction between the components was evaluated using Fourier-transform infrared spectroscopy (FT-IR). With increasing filler content, good compatibility between the components due to hydrogen bonds was established, which ultimately resulted in improved tensile strength and chemical stability. In addition, due to the sulfonated moieties of S-MMT, the highest ion exchange capacity (0.46 meq/g) and water uptake (51.61%) can be achieved at the highest filler content with an acceptable swelling degree of 22.65%. The composite membrane with 7% S-MMT appears to be suitable for application in proton exchange membrane fuel cells (PEMFCs). Amongst the membranes studied, this membrane achieved the highest current density and power density in fuel cell tests, which were 149.5 mA/cm2 and 49.51 mW/cm2. Our fluorine-free composite membranes can become a promising new membrane family in PEMFC applications, offering an alternative to Nafion membranes.

Structure and properties of homogeneous toughened poly(vinyl alcohol) blended membrane and exploration of application in membrane separation

Polyvinyl alcohol (PVA) has excellent physical and chemical properties; however, its rigidity easily leads to brittleness and breakage during use. Additionally, due to intramolecular hydrogen bonding, the dense structure of the film limits its application. This research used a self-toughening approach by homogeneously blending PVA 0588 and PVA 0499 with different molecular weights to enhance the toughness of PVA and create a porous structure for broader application in membrane separation. Porous PVA membranes were then produced through mechanical stretching. Rheological testing, differential scanning calorimetry, and dynamic thermomechanical analysis confirmed that the blend system is partially compatible. Mechanical characterization revealed that adding PVA 0499 decreased the tensile modulus, strength, and bending modulus of the blended film but increased the elongation at break, reaching a maximum of 179 %. This result indicates that homogeneous blending effectively achieved PVA self-toughening. After this, the PVA blended membrane underwent mechanical stretching. Results showed that the stretched membrane developed a porous structure with a PVA 0588 content of 60 wt%, yielding a pure water flux of 70.3 L m−2 h−1 MPa−1 and a glucan rejection rate of 91.07 %. The molecular weight cut-off test demonstrated that the resulting porous membrane was suitable for water treatment, effectively filtering substances with a molecular weight of ≥70 kDa. The membrane also exhibited notable antifouling properties. The hydrophilicity and high roughness of the porous membrane facilitated the formation of additional hydrogen bonds between the membrane surface and water molecules, thereby reducing direct contact between pollutants and the membrane surface. This study provides preliminary theoretical and experimental insights into enhancing PVA toughness and expanding its applications in membrane separation. Furthermore, homogeneous blending opens new avenues for improving the mechanical performance of polymers.

Synthesis and Characterization of Chitosan/Sericin Composite Blend Membranes Containing Silver Nanoparticles for Effective Antibacterial Applications

AbstractDue to drug‐resistant bacteria, antimicrobial composite materials that will replace antibiotics are among the current research topics. In this study, environmentally‐friendly, low‐cost, easy‐to‐synthesize chitosan/silk sericin/silver nanoparticles (Cht/SS/AgNPs) membranes were obtained for use in antibacterial applications. For material synthesis, firstly, AgNPs were obtained by mixing solution of 2 % sericin (at pH 11)‐10 mM AgNO3 at 100 °C with hydrothermal method and AgNPs formation was confirmed by UV‐Vis measurements. Then, sericin/AgNPs solution was added to chitosan solutions at different ratios and Cht/SS/AgNPs composites were obtained by solvent casting method. The final forms of the membranes were characterized by fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM)‐energy dispersive X‐ray spectroscopy (EDS), and thermogravimetric analysis (TGA). Water retention capacities and mechanical properties of the membranes were also determined. Finally, antibacterial and biocompatibility properties were evaluated by disc diffusion test method on Escherichia coli and Staphylococcus aureus and MTT on L929 fibroblast cell line, respectively. The obtained membranes had homogeneous appearance, high swelling ratios, good mechanical properties. The composites also showed excellent antibacterial activity, especially on S. aureus and good biocompatibility. In summary, Cht/SS/AgNPs composites can be used as an alternative polymeric antibacterial materials especially as the wound‐dressing materials or functional packaging materials.

Development of a Superior Anion Exchange Membrane with Hyperbranched Polymer for Anion Exchange Membrane Water Electrolysis

The production of hydrogen using membrane-based electrolyzersposes significant advantages and benefits compared to traditionalelectrolysis methods. Among the electrolyzers, anion exchangemembrane water electrolysis (AEMWE) has emerged as one of thepromising technologies owing to its unique advantages. However,the development of efficient AEMs for water electrolysis presentssignificant challenges, particularly in achieving enhanceddimensional stability and conductivity. In this study, ahyperbranched polyesteramide (HPEA) was synthesized andblended with poly(ether sulfone) (PES) to address the challenges.The resulting QPES-HPEA blend membrane exhibited a lowswelling ratio and high water uptake, which are critical formaintaining dimensional stability and enhancing the hydroxide iontransport efficiency of AEM. The enhanced physical properties andoptimized structure of the membrane make it a promising candidatefor next-generation AEMs in water electrolysis systems.

Fabrication of charged and zwitterionic nanofiltration membranes and anti-adhesion analysis using quartz crystal microbalance with dissipation and atomic force microscopy

Three nanofiltration (NF) membranes (positive charge, negative charge and near charge neutrality) were fabricated to investigate the anti-adhesion mechanism. Among them, the NF membrane with positive charge was synthesized through an electrophilic substitution reaction between the amino group of polyethyleneimine (PEI) and the chloromethyl groups of chloromethyl polysulfone (CMPSf) on a supporting polysulfone (PSf)/CMPSf blend membrane. The NF membrane with negative charge was fabricated through polycondensation using 1, 3, 5-benzenetricarbonyl trichloride (TMC) as a reactive monomer on the positive charge NF membrane. Subsequently, the near charge neutral zwitterion NF membrane (ZNF) was prepared by grafting 3-((2-aminoethyl) dimethylammonio) propane-1-sulfonate (sulfobetaine) (ADSS) onto the negative charge NF membrane. The anti-adhesion behaviors of the NF membranes during the dye selective separation were analyzed by Atomic force microscopy (AFM) and quartz crystal microbalance with dissipation (QCM-D). The results demonstrated that the near charge neutral ZNF membrane displayed a higher dyes rejection (>94.4 %) and higher flux recovery rates (>88.1 %) than charged NF membranes. Meanwhile, the near charge neutral ZNF membrane demonstrated the lowest amounts of dye deposition compared with charged NF membranes, such as reactive blue 4 (R4) for 509.9 ng/cm2, basic blue 24 (BB 24) for 269.0 ng/cm2, rhodamine B (RB) for 197.4 ng/cm2). Additionally, the near charge neutral ZNF membrane with the thicker hydration layer (121.7 nm) displayed weaker interaction forces (−4.8 nN to −7.4 nN) with the dyes than the charged membranes (−10.4 nN to −28.6 nN). Finally, an anti-adhesion mechanism involved charged shielding effect and hydration layer formation was proposed. These observations provide comprehensive insights into the anti-adhesion mechanism of ZNF membrane.

Production Sericin/Poly(Vinyl Alcohol) Blend Membranes Containing One‐Step Synthesized Silver Nanoparticles by UV Radiation for Obtaining Versatile Antibacterial Materials

AbstractIn this study, silver nanoparticles (AgNPs) were in‐situ synthesized in silk sericin/poly(vinyl alcohol) (SS/PVA) mixtures by an easy one‐step synthesis method with the presence of ultraviolet (UV) radiation. Then, the SS/PVA composite membranes containing AgNPs were obtained by solvent casting method. The chemical structures of the membranes were investigated by fourier‐transform infrared spectroscopy (FTIR) and results showed that the membranes were a mixture of silk sericin and PVA. The morphological features of the membranes were investigated by field emission scanning electron microscopy (FE‐SEM) and it was seen that AgNPs containing membranes have heterogeneous structures. Energy dispersive spectroscopy (EDS) analysis revealed that the membranes contain carbon, oxygen, nitrogen, sulfur and silver. X‐ray diffractometer (XRD) and thermogravimetric (TGA) analyses also proved the presence of AgNPs in the structure of membranes. The antibacterial activities of membranes containing AgNPs were investigated on Staphylococcus aureus and Escherichia coli bacteria with disk diffusion test and liquid culture medium incubation. It was found that SS/PVA membranes containing 5 and 10 mM AgNPs have quite high antibacterial activity on both types of bacteria. The functional SS/PVA membranes have capacity to be used in biomedical applications such as wound care materials.

Adsorptive membrane separation for eco-friendly decontamination of chlorpyrifos via biochar-impregnated cellulose acetate mixed matrix membrane.

In this work, the phase inversion approach is used to synthesize a blended mixed matrix membrane from cellulose acetate polymer and sugarcane bagasse biochar. The experiments were carried out to estimate the extent of chlorpyrifos (CPS) pesticide removal. The results showed that the removal rate was more than 99% in making the filtered water suitable enough for domestic use. The physical and functional characteristics of the membranes, such as permeability, and contact angle were identified. The changes in the membrane characteristics were observed using scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray diffraction both before and after the experimental trials. Experiments were conducted to assess not only the rejection characteristics of CPS, as a function feed concentration, but also the effect co-ions on the rejection used to analyze the composition both before and after filtration. The effects of initial CPS concentration, biochar loading, and co-ions on the membrane were investigated. The membranes showed contact angles between 70° and 97° and a permeability between 0.25 × 1010 m Pa-1 s-1 and 0.31 × 1010 m Pa-1 s-1. The effective removal of CPS from the contaminated aqueous stream was attributed to a combination of adsorptive uptake and membrane-based separation. CPS was found to get adsorbed onto the membrane matrix through an intraparticle diffusion mechanism along with an irreversible monolayer adsorption. The membrane-solute adsorptive interaction was represented by Langmuir isotherm and intraparticle diffusion models with a maximum adsorption capacity of 192.3 mg g-1. The findings indicated the efficacy of biochar-cellulose acetate mixed matrix membrane for sustainable and eco-friendly treatment of chlorpyrifoscontaminated water.

Preparation of amphiphilic block copolymers via RAFT polymerization and preliminary properties exploration of blended membranes with PVDF

Preparation of amphiphilic block copolymers via RAFT polymerization and preliminary properties exploration of blended membranes with PVDF

Leveraging an innovative process integration using highly acid-immune blend membranes for enhanced acid recovery and selective salt separation

We investigate the efficiency and advantage of the integrated diffusion dialysis-electrodialysis (DD-ED) system over the DD process for acid recovery with highly acidic wastewater. The investigation uses various acid (HCl/H2SO4) /salt mixtures encompassing iron, copper and aluminium salts (FeCl2, CuCl2, AlCl3, and FeSO4) as simulated feed. The membrane is prepared using blend mixture of polyvinylidene fluoride (PVDF) and polymethyl methacrylate-co-poly chloromethyl styrene copolymer (PMMA-co-PCMSt) solution by non-solvent induced phase inversion on a nonwoven fabric followed by treatment with different tertiary amines. Representative AEM-Q3 membrane prepared by the post modification of blend membrane with a mixture of N, N, N’, N’- tetramethyl diamino hexane (TMDAH) and trimethyl amine (TMA) (1: 1 w/w %) exhibited the best-balanced performance. The membrane recovered a 84.2% AR (%) of acid with 96.28% purity (%) at a flux (JH+) of 7.08 × 10-4 mol cm-2 h-1 from 3 M HCl and 0.2M FeCl2 mixture making it suitable for further studies. A comprehensive comparative study drawn between the DD and integrated DD-ED showed that there was a 2.3 fold increment in acid recovery for the integrated process over the DD process (for the HCl-FeCl2 system). The membranes have also shown good monovalent (Cl-) and bivalent (SO42-) anion selectivity of 7.8. However, the selectivity was further improved to 12.28 by modification of AEM-Q3 membrane, which is double side cast (referred as AEM-Q3/b). The synthetic strategy of the membrane is easy and scalable and has potential for both acid recovery and selective salt separation by ED process.

Polyvinylidene fluoride-alkali lignin blend: A new candidate for membranes development

New blend membranes consisting of a tuned ratio of polyvinylidene fluoride (PVDF) and alkali lignin (AL) were studied. Through the use of a green solvent like dimethyl sulfoxide, effective mixing between PVDF and AL was achieved, leading to the development of highly hydrophilic membranes with robust mechanical stability. Characterization methods confirmed the suitability of the blend for membrane preparation and its hydrophilic nature.A key aspect of the strategy involved hydrophilizing PVDF during the preparation process by blending it with AL in the pot. This approach aimed to streamline production by reducing the number of steps compared to post-treatment methods such as grafting or coating. The presence of hydrophobic/hydrophilic groups in the AL structure addressed the challenge of compatibility between PVDF and conventional hydrophilic polymers, enhancing interaction between the components.The resulting hydrophilic material exhibited improved pure water permeance and demonstrated resistance to irreversible fouling. The membrane's ability to process wastewater streams and its resistance to fouling was demonstrated by separating stable and uniform submicron oil-in-water emulsions with high rejection (>99.9 %) up to a volume reduction factor (VRF) of 7.7.

Preparation of modified atmosphere and moisture packaging membranes by blending quaternized polyether ether ketone with polyvinylidene fluoride and its application in grape packaging

The modified atmosphere and moisture packaging membranes for preserving Vitis vinifera L. (V. vinifera) were developed by blending triethylamine-grafted quaternized polyether ether ketone (QPEEK) and polyvinylidene fluoride (PVDF) using thermally induced phase separation. With the addition of QPEEK, the blend membranes exhibited increased hydrophilicity, gas transmission rate, and gas permeability coefficient. For the 5 % QPEEK/PVDF membrane, the water vapor transmission rate is 48.4 g/(m²·24 h), the water contact angle is 82.2°, and the CO2/O2 separation coefficient is 2.06. Compared to other groups, this membrane exhibits better tensile, swelling, and relaxation properties. These properties facilitate achieving dynamic air equilibrium within 3 days, maintaining a suitable atmosphere inside the package (3.4–4.1 % CO2 and 16.1–18.1 % O2), and timely removing moisture to prevent water vapor condensation, thus extending the shelf life of grapes to more than 25 days. Grapes packaged in 5 % QPEEK/PVDF membrane box maintained 99.3 % mass, 85.1 % firmness, and 72.2 % total phenol content, and exhibited minimal changes in soluble solids, relative electrical conductivity, and water state and distribution compared to fresh grapes. These experimental results suggest significant potential for the use of QPEEK/PVDF membranes in fruit and vegetable packaging.

The chemical crosslinking effect of polybenzimidazole/polyvinyl alcohol blend membranes for proton exchange membrane fuel cells: An experimental study

AbstractIn this survey, the different weight ratios of polybenzimidazole (PBI)/polyvinyl alcohol (PVA) blend polymer membranes were produced using the solution‐casting method. The crosslinking agents of phosphoric acid (PA) and glutaraldehyde (GA) were studied separately to prevent the PVA water solubility in the PBI/PVA blend membrane structure. The GA crosslinking (24 h) successfully prevented membrane solubility, reducing it to below 1%. The chemically crosslinked blend membrane (Cr‐PBI/PVA‐9:1) has the highest proton conductivity result which is 0.209 S cm−1 at 80°C and it has excellent oxidative stability since the membrane only lost 4% of its weight in a Fenton agent after 96 h. The Cr‐PBI/PVA‐9:1 also has higher proton conductivity than the commercial PBI membrane (0.122 S cm−1 at 80°C). The glass transition temperature of the synthesized Cr‐PBI/PVA‐9:1 blend membrane is greater than the synthesized PBI membrane (390°C). The current density and power density measured at 0.6 V for the synthesized Cr‐PBI/PVA‐9:1 membrane were found to be 504 mA cm−2and 251 mW cm−2. This work sheds light on the potential use of PVA in PEMFC applications by mixing PVA with a high‐temperature polymer like PBI and crosslinking the membrane with a prepared GA crosslinking agent.

Easy Fabrication of Ultrafiltration Membrane via Polyethersulfone-Fumed Silica

This study investigated the effect of low-concentration fumed silica (FS) in polyethersulfone (PES) membranes. The PES/FS blend membrane was fabricated using a wet phase inversion technique as a flat sheet membrane. Scanning electron microscopy analysis revealed improved pore connectivity and rounder middle structures due to the addition of fumed silica. The experimental results indicated that the fabricated membranes fell within the ultrafiltration range, with pure water flux increasing as fumed silica concentration rose. The pure water flux improved by 64% compared to the native PES membrane. Furthermore, the blend membranes exhibited better selectivity, rejecting pepsin and lysozyme 11% and 19% more efficiently, respectively. Although the low concentration of fumed silica had minimal impact on the water contact angles of the membrane surface, all membranes demonstrated hydrophilicity. This cost-effective approach enhances permeability while maintaining separation characteristics, making it suitable for clean water applications.

Facile infiltration of polyethyleneimine as a strong CO2 retardant in scalable dual-polymer membranes for H2/CO2 separation

Successful pre-combustion CO2 capture from synthetic gas for H2 production requires effective membrane separation technology. While polymer-based membrane materials offer promising industrial scalability, they generally lack a sufficiently high H2/CO2 selectivity to make this process energy-efficient. In this work, we have designed a scalable dual-polymer blend membrane consisting of sulfonated polyphenylsulfone (sPPSU) and polybenzimidazole (PBI), and then being infiltrated with amine-rich poly(ethyleneimine) (PEI) molecules as effective CO2 retardants to substantially elevate the H2/CO2 selectivity. PEI molecules were infiltrated into the dual-polymer matrix via solution-treatment to crosslink the polymer network and retard CO2 transport using its amine-rich nature. The PEI infiltration dramatically increased the H2/CO2 selectivity of the dual-polymer matrix from 4.6 to up to 59.3 while maintaining a minimum H2 permeability of 2.49 Barrer at a low temperature of 35 °C, which not only surpasses the Robeson upper bound but also places the newly developed membrane among the best-performing polymer-based membranes. More importantly, the solution infiltration of PEI incurs no phase segregation, maintaining the polymer mechanical robustness, which is crucial for industrial scaling. This study offers promising opportunities to develop three-polymer membrane systems for H2/CO2 separation using synergistic polymer blends and CO2-retarding molecules.