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%).

Anti-marine biofouling adhesion performance and mechanism of PDMS fouling-release coating containing PS-PEG hydrogel.

Polystyrene microspheres compounded with polyethylene glycol-based hydrogel (PS-PEG)/polydimethylsiloxane (PDMS) coatings were prepared using the physical blending method. The chemical structure, surface and interface properties, interlayer adhesion, and tensile properties were tested in this paper. Furthermore, the antifouling performance was evaluated through bovine serum albumin fluorescent protein adsorption testing, marine bacteria adhesion testing, and benthic diatom adhesion testing. The results showed that the coating performance was best when 20 wt% PS-PEG hydrogel was added. Its surface energy was only 19.21 mJ/m2, the maximum breaking strength was 1.24 MPa, the maximum elongation rate was 675 %, the elastic modulus was 2.53 MPa, and the anti-stripping rate was 100 %. In addition, the coating with added 20 wt% PS-PEG hydrogel bacterial adherence rate was 5.36 % and 2.45 % after rinsing and washing, respectively, and the removal rate was 54.29 %. In the benthic diatom adhesion test, the chlorophyll concentration a-value was only 0.0017 mg/L after washing with added 20 wt% hydrogel, and the protein desorption rate was 84.19 % higher than PDMS in the fluorescent protein adsorption test. This coating has the 'low adhesion' and 'desorption' characteristics in the three growth stages of biofouling. Meanwhile, the low surface energy of the silicone is stable, and the hydrogel also dynamically migrates to the surface to gradually form a hydration layer, both are synergistic. When 20 wt% PS-PEG hydrogel was added, the coating demonstrated excellent antifouling performance due to its high hydration layer, low surface energy, high elasticity, and high interlayer adhesion. This research is expected to contribute to the practical applications of hydrogel coatings in marine antifouling.

Straightforward fabrication of electrochemical aptasensors with outstanding antifouling performance.

Self-assembled monolayers (SAMs) are popular tools for many different applications - SAMs of commercially available chemicals that convincingly inhibit unspecific binding for electrochemical sensors, however, have yet to be developed. While adsorption of foulants prohibits the reliable analysis of biological samples, unspecific binding of the analyte similarly impedes the investigation of binding characteristics from buffer solutions. In this communication, diglycolamine is introduced for the modification of electrodes with outstanding antifouling performance. The presented sensor design, solely consisting of diglycolamine and an aptamer of choice, convinces with its ease of preparation, low cost, and, most importantly, an exceptional specificity. The latter was found to rely on a gentle but potent cleaning of the electrodes, as only our optimized cleaning procedure granted the diglycolamine layer its excellent fouling minimization performance, while literature standard protocols failed to do so. Each step of the sensor fabrication protocol was optimized by electrochemical impedance spectroscopy, while square-wave voltammetry, surface-enhanced Raman spectroscopy, and zeta potential measurement were performed for further characterization. The presented approach of surface modification with diglycolamine is a versatile method applicable not just to electrochemical measurements, but to a variety of other detection techniques, too, and has the potential to change the way we investigate binding characteristics and fabricate sensors for the analysis of complex biological samples.

Integration of Antifouling and Underwater Sound Absorption Properties into PDMS/MWCNT/SiO2 Coatings.

Any surface immersed in sea water will suffer from marine fouling, including underwater sound absorption coatings. Traditional underwater sound absorption coatings rely heavily on the use of toxic, biocide-containing paints to combat biofouling. In this paper, an environmentally-friendly nanocomposite with integrated antifouling and underwater sound absorption properties was fabricated by adopting MWCNTs-COOH and SiO2 into PDMS at different ratios. SEM, FTIR and XPS results demonstrated MWCNTs were mixed into PDMS, and the changes in elements were also analyzed. SiO2 nanoparticles in PDMS decreased the tensile properties of the coating, while erosion resistance was enhanced. Antibacterial properties of the coatings containing MWCNTs-COOH and SiO2 at a ratio of 1:1, 1:3, and 1:5 reached 62.02%, 72.36%, and 74.69%, respectively. In the frequency range of 1500-5000 Hz, the average sound absorption coefficient of PDMS increased from 0.5 to greater than 0.8 after adding MWCNTs-COOH and SiO2, which illustrated that the addition of nanoparticles enhanced the underwater sound absorption performance of the coating. Incorporating MWCNTs-COOH and SiO2 nanoparticles into the PDMS matrix to improve its sound absorption and surface antifouling properties provides a promising idea for marine applications.

Influence of Dispersed TiO2 Nanoparticles via Steric Interaction on the Antifouling Performance of PVDF/TiO2 Composite Membranes.

Herein, the influence of various contents of polyethylene glycol (PEG) on the dispersion of TiO2 nanoparticles and the comprehensive properties of PVDF/TiO2 composite membranes via the steric hindrance interaction was systematically explored. Hydrophilic PEG was employed as a dispersing surfactant of TiO2 nanoparticles in the pre-dispersion process and as a pore-forming additive in the following membrane preparation process. The slight overlap shown in the TEM image and low TSI value (<1) of the composite casting solution indicated the effective dispersion and stabilization under the steric interaction with a PEG content of 6 wt.%. Properties such as the surface pore size, the development of finger-like structures, permeability, hydrophilicity and Zeta potential were obviously enhanced. The improved antifouling performance between the membrane surface and foulants was corroborated by less negative free energy of adhesion (about −42.87 mJ/m2), a higher interaction energy barrier (0.65 KT) and low flux declination during the filtration process. The high critical flux and low fouling rate both in winter and summer as well as the long-term running operation in A/O-MBR firmly supported the elevated antifouling performance, which implies a promising application in the municipal sewage treatment field.

Planting Anion Channels in a Negatively Charged Polyamide Layer for Highly Selective Nanofiltration Separation.

A nanofiltration (NF) membrane with high salt permeation and high retention of small organics is appealing for the treatment of high-salinity organic wastewater. However, the conventional negatively charged NF membranes commonly show high retention of divalent anions (e.g., SO42-), and the reported positively charged NF membranes normally suffer super low selectivity for small organics/Na2SO4 and high fouling potential. In this work, we propose a novel "etching-swelling-planting" strategy assisted by interfacial polymerization and mussel-inspired catecholamine chemistry to prepare a mix-charged NF membrane. By X-ray photoelectron spectroscopy depth profiling and pore size distribution analysis, it was found that such a strategy could not only deepen the positive charge distribution but also narrow the pore size. Molecular dynamics confirm that the planted polyethyleneimine chains play an important role to relay SO42- ions to facilitate their transport across the membrane, thus reversing the retention of Na2SO4 and glucose (43 vs 71%). Meanwhile, due to the high surface hydrophilicity and smoothness as well as the preservation of abundant negatively charged groups (-OH and -COOH) inside the separation layer, the obtained membrane exhibited excellent antifouling performance, even for the coking wastewater. This study advances the importance of vertical charge distribution of NF membranes in separation selectivity and antifouling performance.

Are silicone foul-release coatings a viable and environmentally sustainable alternative to biocidal antifouling coatings in the Baltic Sea region?

To combat unwanted fouling on immersed hulls, biocidal antifouling coatings are commonly applied to vessels trafficking the Baltic Sea. Here, the efficacy, environmental sustainability and market barriers of silicone foul-release coatings (FRCs) was assessed for this region to evaluate their viability as replacements for biocidal coatings. Coated panels were exposed statically over a 1 year period at three locations in the Baltic Sea region to assess the long-term performance of a biocide-free FRC and two copper coatings. The FRC was found to perform equally well or significantly better than the copper coatings. Even though most silicone FRCs on the market are biocide-free, a review of the literature regarding toxic effects and the identity and environmental fate of leachables shows that they may not be completely environmentally benign, simply for the lack of biocides. Nonetheless, FRCs are substantially less toxic compared to biocidal antifouling coatings and their use should be promoted.

Ag/AgBr/AgVO3 Photocatalyst-Embedded Polyacrylonitrile/Polyamide/Chitosan Nanofiltration Membrane for Integrated Filtration and Degradation of RhB.

A nanofiltration (NF) membrane containing a NaOH-treated electrospun polyacrylonitrile (HPAN) substrate, an interfacial polymerization (IP) polyamide (PA) layer, a chitosan (CS) coating layer, and an Ag/AgBr/AgVO3 photocatalyst loading layer was prepared. The structural evolution of the membranes was investigated, and their performance was estimated in accordance with the water flux and rejection rate. A probable mechanism for the photocatalytic activity of Ag/AgBr/AgVO3 was proposed. The loading of the Ag/AgBr/AgVO3 heterojunction on the HPAN/PA/CS NF membrane endowed the membrane with excellent self-cleaning properties owing to the photolytic degradation of the dye. The filtration and degradation processes of the Ag/AgBr/AgVO3-loaded membrane constantly promoted each other, and the treatment efficiency achieved with the integrated (filtration + degradation) process was superior to those obtained with the filtration and degradation processes alone. The Ag/AgBr/AgVO3-NF membrane exhibited excellent recyclability and stability when subjected to five integrated filtration-degradation processes. In addition, the Ag/AgBr/AgVO3-NF membrane exhibited an elastic modulus of 65.75 MPa and a toughness of 38.9 kJ/m3 along with a good disinfection effect on Escherichia coli in visible light. The as-prepared photocatalyst-loaded NF membrane with excellent antifouling performance, antimicrobial activity, high strength, and recyclability showed potential for continuous water purification operation.

Fouling Release Coatings Based on Acrylate-MQ Silicone Copolymers Incorporated with Non-Reactive Phenylmethylsilicone Oil.

Copolymers containing MQ silicone and acrylate were synthesized by controlling the additive amount of compositions. Subsequently, fouling release coatings based on the copolymer with the incorporation of non-reactive phenylmethylsilicone oil were prepared. The surface properties of the coating (CAMQ40) were consistent with that of the polydimethylsiloxane (PDMS) elastomer, which ensured good hydrophobicity. Moreover, the seawater volume swelling rate of all prepared coatings was less than 5%, especially for CAMQ40 with only 1.37%. Copolymers enhanced the mechanical properties of the coatings, while the enhancement was proportional to the molar content of structural units from acrylate in the copolymer. More importantly, the adhesion performance between the prepared coatings and substrates indicated that pull-off strength values were more than 1.6 MPa, meaning a high adhesion strength. The phenylmethylsilicone oil leaching observation determined that the oil leaching efficiency increased with the increase in the structural unit's molar content from MQ silicone in the copolymer, which was mainly owing to the decrease in compatibility between oil and the cured coating, as well as the decrease in mechanical properties. High oil leaching efficiency could make up for the decrease in the biofouling removal rate due to the enhancement of the elastic modulus. For CAMQ40, it had an excellent antifouling performance at 30 days of exposure time with more than 92% of biofouling removal rate, which was confirmed by biofilm adhesion assay.

Polysulfone-Polyvinyl Pyrrolidone Blend Polymer Composite Membranes for Batik Industrial Wastewater Treatment.

Batik wastewater, in general, is colored and has high concentrations of BOD (biological oxygen demand), COD (chemical oxygen demand), and dissolved and suspended solids. Polysulfone (PSf)-based membranes with the addition of polyvinyl pyrrolidone (PVP) were prepared to treat batik industrial wastewater. PSf/PVP membranes were prepared using the phase inversion method with N-methyl-2 pyrrolidone (NMP) as the solvent. Based on the membrane characterization through FESEM, water contact angle, porosity, and mechanical tests showed a phenomenon where the addition of PVP provided thermodynamic and kinetic effects on membrane formation, thereby affecting porosity, thickness, and hydrophilicity of the membranes. The study aims to observe the effect of adding PVP on polysulfone membrane permeability and antifouling performance on a laboratory scale through the ultrafiltration (UF) process. With the addition of PVP, the operational pressure of the polysulfone membrane was reduced compared to that without PVP. Based on the membrane filtration results, the highest removal efficiencies of COD, TDS (total dissolved solid), and conductivity achieved in the study were 80.4, 84.6, and 83.6%, respectively, on the PSf/PVP 0.35 membrane operated at 4 bar. Moreover, the highest color removal efficiency was 85.73% on the PSf/PVP 0.25 operated at 5 bar. The antifouling performance was identified by calculating the value of total, reversible, and irreversible membrane fouling, wherein in this study, the membrane with the best antifouling performance was PSf/PVP 0.25.

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.

The hierarchical flower-like MoS2 nanosheets incorporated into PES mixed matrix membranes for enhanced separation performance.

Membrane fouling is an issue of concern due to the hydrophobic properties of polyethersulfone (PES) membrane when applied in water treatment. In this work, a facile hydrothermal method was utilized to synthesize hierarchical flower-like structured molybdenum disulfide nanosheets (HF-MoS2 NSs) that then incorporated into PES membranes as composite membranes. We characterized their permeability, the separation performance, the antifouling performance, and the antibacterial activity systematically. Results showed that composite membranes exhibited a better pure water flux (286 LMH/bar) at the HF-MoS2 NSs content of 0.4 wt%, which was 1.8 times higher than the control membrane. Also, composite PES membranes achieved 98.2% and 96.9% rejection of BSA and HA in comparison with the control PES membrane (87.3%, and 84.5%, respectively). Compare to the control PES membrane, the flux recovery ratio of the composite membrane increased from 69% to 88% for BSA fouling and increased from 84% to 93% for HA fouling. The retention rate for the organic dyes also improved slightly after HF-MoS2 NSs incorporation into the membrane. Additionally, the composite membranes exhibited a relatively high antibacterial activity against E. coli and B. subtilis with antibacterial rates of 67.8% and 82.5%, respectively. In conclusion, HF-MoS2 NSs incorporated composite membranes were shown to have outstanding filtration performance and could be a promising candidate for practical application in water filtration.

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.

Cannabinoids and Terpenes as an Antibacterial and Antibiofouling Promotor for PES Water Filtration Membranes.

Plant phytochemicals have potential decontaminating properties, however, their role in the amelioration of hydrophobic water filtration membranes have not been elucidated yet. In this work, phytochemicals (i.e., cannabinoids (C) and terpenes (T) from C. sativa) were revealed for their antibacterial activity against different Gram-positive and Gram-negative bacteria. As such, a synergistic relationship was observed between the two against all strains. These phytochemicals individually and in combination were used to prepare polyethersulfone (PES) hybrid membranes. Membrane characterizations were carried out using scanning electron microscopy, Fourier transform infrared spectroscopy, energy-dispersive X-ray spectroscopy. Moreover, contact angle, water retention, surface roughness, mechanical testing, and X-ray florescence analysis were also carried out. According to results, the CT-PES hybrid membrane exhibited the lowest contact angle (40°), the highest water retention (70%), and smallest average pore size (0.04 µm). The hybrid membrane also exhibited improved water flux with no surface leaching. Quantitative bacterial decline analysis of the CT-PES hybrid membranes confirmed an effective antibacterial performance against Gram-positive and Gram-negative bacteria. The results of this study established cannabinoids and terpenes as an inexpensive solution for PES membrane surface modification. These hybrid membranes can be easily deployed at an industrial scale for water filtration purposes.

Role of trapped air and lubricant in the interactions between fouling and SiO2 nanoparticle surfaces.

Both biomimetic superhydrophobic surfaces and biomimetic slippery liquid-infused porous surfaces (SLIPSs) have been developed as potential alternatives for solving the problem of biofouling. Herein, a facile method was used to construct superhydrophobic surfaces and liquid infused porous surfaces on stainless steels for antifouling applications. The nano-structures were formed by electrostatic attraction between polycations and negatively charged SiO2 nanoparticles, providing a structural basis for superhydrophobic surfaces and liquid infused surfaces. Biofouling testing suggested excellent antifouling performances of the liquid infused porous surfaces by decreasing the adhesion of Chlorella pyrenoidosa by 93% and of Phaeodactylum tricornutum by 71%. The thermodynamic interpretation further indicated that the air layer captured by the superhydrophobic surfaces and the lubricant layer entrapped by the liquid infused porous surfaces played the dominant role in their antifouling performances. The inspiring results might show great potential for liquid infused porous surfaces in antifouling applications.

Bio-inspired robust superhydrophobic-superoleophilic polyphenylene sulfide membrane for efficient oil/water separation under highly acidic or alkaline conditions.

The separation of water-in-oil emulsions in harsh environment (strong acid/alkali) is a challenging subject. In this study, we prepared a superhydrophobic-superoleophilic polyphenylene sulfide (PPS) membrane by the mixture of hydrophobic SiO2 nanoparticles, diphenyl ketone (DPK), benzoin (BZ) and PPS via thermally induced phase separation (TIPS) technology. This superhydrophobic membrane displayed a lotus leaf-like micro-nano structure, and it could be used for oil/water separation in strong acidic or alkaline environment. The hydrophobic SiO2 nanoparticles played a key role in the membrane structure evolution and its performance. When SiO2 content was 4 wt%, the pure water contact angle of the prepared superhydrophobic-superoleophilic membrane reached 156.9° and the oil contact angle achieved 0°. The fluxes of water-in-oil emulsions (kerosene, toluene and chloroform) reached 1926, 3150 and 3416 L/(m2·h), respectively. However, the fluxes of their surfactant-stabilized water-in-oil emulsions declined to 531, 685 and 724 L/(m2·h), respectively, due to the great stability of surfactant-stabilized emulsions. Most importantly, all the water rejection rates exceeded 99.9% when the PPS membranes modified with 4 wt% hydrophobic SiO2 nanoparticles. In addition, the PPS-SiO2 hybrid membranes exhibited excellent self-cleaning antifouling performance, cycling performance and superior acid/alkali resistance.

Composite nanofiltration membrane with asymmetric selective separation layer for enhanced separation efficiency to anionic dye aqueous solution.

The development of high performance membrane is crucial for enhanced separation efficiency of nanofiltration process in treating wastewaters from dye and textile industries. In this work, a novel thin-film composite nanofiltration membrane with an asymmetric separation layer composed of relatively compact skin and loose body was designed and fabricated for improved perm-selectivity and antifouling property. Nascent composite membrane with loose poly(piperazine amide) (PA) separation layer was interfacially synthesized and performed with secondary surface reaction using an aqueous tannic acid (TA) solution. Membrane characterizations verified the formation of compact TA skin on top of the loose PA layer through forming covalent bonds via esterification reaction. Compared with the composite nanofiltration membrane with PA symmetric separation layer having the same glucose rejection of about 82.0%, the permeability to pure water of the composite membrane with PA/TA asymmetric separation layer was higher by 28.0%, the water fluxes to aqueous solutions dissolved with model anionic dyes of alizarin yellow R, sunset yellow and Congo red under steady state were higher by 50.3, 43.9 and 36.1%, and the steady-state flux declines were lowered by 27.8, 43.4 and 23.5%, respectively. Furthermore, the PA/TA-based membrane also exhibited better antifouling property and rejection ability to alizarin yellow R.

Silicalite-1 zeolite membrane: Synthesis by seed method and application in organics removal.

Silicalite-1 (S-1) zeolite membrane synthesized by seed method with superior features attracts intensive attentions, while the influences of key parameters during synthesis process and its applications for organics removal require further investigation. This study revealed the morphology and the structure of the prepared membranes under different crystallization temperatures and seed concentrations by using a suite of characterization methods. The as-prepared membrane under optimal condition (crystallization temperature of 175 °C and seed concentration of 1.0 wt. %) possessed high membrane integrity, with ideal separation factor of 4.0. It also exhibited outstanding performance for organics removal, with dyes retention of 99.9% and 99.2% for 500 mg L-1 neutral red and 500 mg L-1 methyl blue, respectively. Excellent antifouling property of the synthesized membrane was also proved. Results of this work can guide the characteristic improvement of the S-1 zeolite membrane by adjusting key parameters and broaden its applications in dye wastewater treatment.

Dye Degrading and Fouling-Resistant Membranes Formed by Deposition with Ternary Nanocomposites of N-Doped Graphene/TiO2/Activated Carbon.

A ternary nanocomposite consisting of N-doped graphene (NGR)/TiO2/activated carbon (NGRT@AC) was prepared, and the components' synergetic effect on dye degradation was investigated after deposition on the surface of a polysulfone membrane (PSF). As far as we know, this ternary composite catalyst has never previously been used to degrade dyes nor been used as a functional layer for separation membranes. The surface morphology and structure of the as-prepared membranes were analyzed by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS). The NGRT@AC-modified PSF membrane (NGRT@AC-PSF) presents excellent photodegradation efficiency to methyl orange (MO) under both UV (95.2%) and sunlight (78.1%) irradiation, much higher than those values of PSF, TiO2- modified PSF (TiO2-PSF), and N-doped graphene/TiO2 (NGRT)-modified PSF membranes (NGRT-PSF) under the same conditions. The high flux recovery ratio (95.5%) demonstrates that the NGRT@AC-PSF membrane shows improved antifouling performance. The photocatalytic results prove that surface deposition method (95.2%) was better than the blending method (31.1%) for forming high-performance membranes. Therefore, the NGRT@AC-PSF membrane has the potential for broad applications in dye degradation to treat waste water from textile industries.

Antifouling performance of polytetrafluoroethylene and polyvinylidene fluoride ultrafiltration membranes during alkali/surfactant/polymer flooding wastewater treatment: Distinctions and mechanisms.

Alkali/surfactant/polymer (ASP) flooding wastewater is highly caustic, and membrane fouling is the main obstacle during ASP ultrafiltration (UF) treatment. To maintain favorable filtration performance, polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF) membranes were implemented here, and their antifouling properties and mechanisms were investigated based on the threshold flux theory. Compared with the PVDF membranes, the PTFE membranes exhibited superior antifouling properties with lower reductions in flux and smaller hydraulic resistance, and they presented a nearly identical pseudo-stable fouling rate at a later time point. In the fouling layers of the PTFE and PVDF membranes, anion polyacrylamide (APAM) was observed along with divalent/trivalent metal ions. The thermodynamic and molecular mechanisms of membrane fouling by APAM were elucidated using the Extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory and atomic force microscopy (AFM), respectively. The calculated total interfacial free energy (mJ/m2) of adhesion between the APAM and PTFE membranes was positive, and the value between the APAM and PVDF membranes was negative. Furthermore, the values and interaction distances of the measured intermolecular rupture and approaching forces were larger for APAM-PTFE than for APAM-PVDF. For the PTFE membranes, the positive free energies and smaller intermolecular interaction resulted in weaker APAM-PTFE adhesion and adsorption and therefore the lower levels of flux decline and the later achievement of the pseudo-stable fouling rate. Additionally, the total flux recoveries observed after physical cleaning reached 0.78-0.80 and 0.32-0.39 for the PTFE and PVDF membranes, respectively, which showed that the PTFE membranes can be cleaned easily. The PTFE membranes have considerable potential for extensive application in UF treatments for ASP wastewater. These results should promote understanding the essence of the threshold flux and the fouling control of UF membranes.