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Polyvinylidene fluoride (PVDF) electrospun nanofibrous membranes (ENMs), consolidated with a heatpress process and of various thicknesses were fabricated and tested in a DCMD cell at five different operating conditions. Membranes as thin as 27 μm were sufficiently robust for evaluation and gave a transmembrane flux as high as 60 L/h m 2 . An analytical model was created to estimate the optimal membrane thickness for DCMD operations. It is found that the value of optimal thickness increases with reduced heat transfer coefficients; decreased feed inlet temperature; increased membrane permeability; and increased salinity. Even for 10% NaCl the predicted optimum was estimated to be 13 μm which was too thin for experimental confirmation. Based upon this analysis but with due allowance for the variation of heat transfer coefficients with temperature dependent physical properties a single Matlab model was created to fit the five sets of data. With the introduction of a structural derivation factor, which reflected the experimentally determined variation of porosity and pore size with thickness, the model was found to fit the data very well. [ABSTRACT FROM AUTHOR]

Abstract: Due to the unique properties of amphiphilic Pluronic block copolymers, they have been blended with other polymers such as PVDF to prepare membranes. Considering the stability issue, the strong pore-forming ability of Pluronic F127, and the mechanical strength of the resultant membranes, Pluronic/LiCl mixed additive consisting of a very low concentration of Pluronic has been used in this study. The effects of spinning conditions on PVDF hollow fiber fabrication have also been studied. It is found that the use of merely 0.2wt% of Pluronic is sufficient to impose significant impacts on the morphology, filtration performance, and mechanical properties of the resultant fibers. Hollow fibers spun using higher coagulant temperature, higher take-up speed, and water as the bore fluid exhibit better mechanical properties and filtration performance. PVDF hollow fiber membranes with PWP of 1180L/m2 hMPa and MWCO of 5kDa were obtained when spun with optimized spinning conditions and using 3wt% of LiCl and 0.2wt% of Pluronic as the mixed additive. The fibers can withstand a pressure of 0.55MPa from the lumen. [Copyright &y& Elsevier]

Abstract: This study aims at developing an effective method to modify hydrophobic polyvinylidene fluoride (PVDF) membranes for membrane distillation (MD) which is tolerant to salty feed solution containing mineral oil. A novel approach was explored to obtain a highly hydrophilic membrane surface via plasma induced grafting of polyethylene glycol (PEG) and subsequent TiO2 particles deposition onto the membrane surface. The mechanism of oil affinity onto a membrane surface was quantitatively investigated by the extended Derjaguin–Landau–Verwey–Overbeek (XDLVO) theory. A series of characterizations were conducted for the virgin and modified membranes. Membrane distillation tests for synthetic seawater containing 0.01wt% of mineral oil were also performed to investigate the influences of membrane hydrophobicity, membrane surface structure, pH value of the feed solution and hydrodynamic conditions on oil fouling behavior. The SEM and FTIR measurements confirmed the presence of PEG and TiO2 particles on the PVDF membrane substrate. The hydrophilically modified PVDF-PT membrane exhibits a positive interfacial free energy with oil in the feed, indicating the TiO2 deposition effectively improve the anti-fouling property of PVDF-P membrane and PVDF membrane. It was also found that the PVDF-PT membrane presents a stable water flux over 24h of operation without fouling and wetting due to combined effects of enhanced surface hydrophilicity and reduced membrane pore sizes. In addition, the pH value of the feed solution plays an important role in oil fouling. More severe fouling can be observed at the pH which made the membrane surface and oil droplets carry opposite charges. Moreover, a higher flow velocity enhances the shear force exerted on the oil droplets, thus leading to less oil present on the membrane surface and less oil fouling of the membrane. [Copyright &y& Elsevier]

Abstract: The use of additives in the polymer dope solutions is one of the most powerful strategies to control the pore structure of poly(vinylidene fluoride) (PVDF) membranes for various applications. In present work, the effects of amphiphilic pluronic block copolymer as an additive on PVDF membrane formation has been studied and a membrane formation mechanism involving pluronic has been proposed. The surface tension–concentration curve reveals that no micelles are formed in pluronic/N-methyl-2-pyrrolidone (NMP) solutions while the thermodynamics and kinetics are found to be similar for the systems containing pluronic and polyethylene glycol (PEG), respectively. The membranes prepared with pluronic as the additive exhibit larger surface pore, porosity, and macrovoids than that with PEG, indicating that pluronic has a stronger pore-forming ability. Instead of the commonly used concept of instantaneous or delayed demixing, it is believed that the stronger pore-forming ability of pluronic is caused by the hydrophobic–hydrophobic interaction between pluronic and PVDF that delays the solidification process. Since pluronic is not completely stable in PVDF membrane matrix, the membranes are soaked in 2-propanol (IPA) to purposely wash out pluronic. The loss of pluronic after IPA-treatment causes an increase in water permeation and a decrease in rejection, indicating that the presence of pluronic on the membrane pore surface can narrow down the pore size. By adding lithium chloride as a second additive, the growth of macrovoids is suppressed. Moreover, the resultant membranes exhibit both higher permeability and selectivity. [Copyright &y& Elsevier]

Abstract: Recently membrane distillation (MD) has received intensive interests for a range of applications such as desalinations of seawater and brine. One of the major obstacles for MD application is the lack of an optimized MD membrane that can produce a high and stable flux in long-term operation. Two types of superhydrophobic PVDF nanofiber membranes, integrally-modified and surface-modified PVDF membranes, have been successfully fabricated by electro-spinning followed by surface modification, which includes dopamine surface activation, silver nanoparticle deposition and hydrophobic treatment. The modification is convenient because of mild reactions and wide applicability. These novel composite nanofiber membranes have been characterized by a series of measurements and benchmarked against commercial PVDF flat sheet membrane for MD application. The characterizations reveal that the modifications have altered the membrane surface morphology and topology and made the membrane superhydrophobic due to their hierarchical structures. Compared with unmodified membrane, the integrally-modified membrane (I-PVDF) can achieve a high and stable MD water flux of 31.6Lm−2 h−1 using a 3.5wt% NaCl as the feed solution while the feed and permeate temperatures were fixed at 333K and 293K, respectively. To the best of our knowledge, this result is superior to all other PVDF flat-sheet membranes tested under the same or similar conditions, which is believed to be attributed to the open-surface pore structure and thin thickness of the PVDF nanofiber membrane with the aid of electro-spinning. The superhydrophobic nature of the membrane surface brought by the integral modification on all nanofibers renders the membrane anti-wetting property while remaining high water flux. [Copyright &y& Elsevier]

Abstract: The main challenges for membranes used in membrane distillation (MD) are well-designed porous structure and hydrophobic surface property. Hydrophobic nanofiber membranes possess high hydrophobicity, high surface porosity and adjustable pore sizes and membrane thickness, which make them an attractive candidate as MD membrane. The current study aims to fabricate and optimize polyvinylidene fluoride (PVDF) nanofiber membranes for MD application. Scanning electron microscopy (SEM), capillary flow porometer, geniometer, a homemade setup for liquid entry pressure (LEP) measurement and direct contact MD (DCMD) setup were used to characterize the resultant nanofiber PVDF membranes. Polymer dope compositions, spinning parameters such as sprayer moving speed and chamber moisture were optimized to examine their effects on pore size distribution of the membranes. Inorganic additives were also added into the dope to improve the electro-spinability of diluted polymer dopes in order to further decrease membrane pore size. Meanwhile, a heat-press post-treatment was considered as a necessary step to improve fresh nanofiber membrane integrity, enhance water permeation flux and help prevent membrane pores from wetting in DCMD operation. The experiment confirmed that all the electrospun membranes exhibit a rough surface with high hydrophobicity (>135° water contact angle). The post-treated PVDF nanofiber membranes were able to present a steady water permeation flux of about 21kgm−2 h−1 throughout the entire testing period of 15h, using a 3.5wt% NaCl solution as the feed under the feed and permeate inlet temperatures of 323K and 293K, respectively. This result was better than these of commercial PVDF membranes and the nanofiber PVDF-clay membrane reported in literature, suggesting the competency of PVDF nanofiber membranes for DCMD applications. [Copyright &y& Elsevier]

This report demonstrates the fabrication of a composite hollow fiber membrane that efficiently recovers dissolved methane (dCH 4) from anaerobic wastewater treatment effluents via membrane contactor (MC) process. We first fabricated highly porous hollow fiber membranes (∼85% porosity) using polyvinylidene difluoride (PVDF). Then, we coated the whole structure (bulk), or lumen side of PVDF supports with polydimethylsiloxane (PDMS), a hydrophobic polymer possessing high gas permeability. The adjustment of the concentration of PDMS precursor mix could effectively serve for tuning the performance characteristics of MC membranes and helped suppress membrane wetting, a major performance-reducing factor. Despite their denser skin layers, the lumen-modified membranes demonstrated superior dCH 4 recovery flux. Mass transfer analyses have confirmed the importance of preserving bulk porosity while coating the membrane surfaces. The long-term performance tests performed using actual anaerobic effluents suggested that the PDMS coating did not accelerate fouling, such that the lumen-modified MC membranes showed an almost steady flux for 8 days with an anaerobic membrane bioreactor effluent. A high-strength effluent, obtained from an up-flow anaerobic sludge blanket reactor, induced faster fouling. However, we observed only a ∼20% flux decline in a 10-day operation. Thus, we propose that the designed PDMS-PVDF composite membranes are promising for industrial practices. Image 1 • We prepared PDMS-coated PVDF porous hollow fiber membranes for membrane contacting. • Both lumen- and bulk-modified PVDF membranes were successful in methane recovery. • Lumen-modified PDMS-PVDF membrane outperformed commercial PP and PDMS membranes. • Lumen-modified PVDF achieved long-term performance with actual anaerobic effluents. [ABSTRACT FROM AUTHOR]

Tailoring the hydrophobic properties of membranes is an important requirement in gas-liquid membrane contactor processes because the membrane can be wetted by liquid. This paper describes the hydrophobic modification of the chemical surface of a polyvinylidene fluoride hollow-fiber membrane using a commercial perfluoropolyether, Fluorolink S10. The contact angle of the modified membrane was influenced by the modification parameters, and hence parameter optimization was required to obtain a highly hydrophobic membrane. The sodium hydroxide concentration (pH 8, 10 and 12), dehydrofluorination time (30, 60 and 90 min), and chemical solution grafting time (30, 60 and 90 min) were identified as the control parameters of this modification and were optimized using the Taguchi approach. The optimized membrane was then applied to recover methane from anaerobic membrane bioreactor effluent and benchmarked with a commercial polypropylene membrane manufactured for degasification of water. The contact angle of the polyvinylidene fluoride membrane was improved by 32% after the surface modification (under the optimal modification condition indicated by the Taguchi method). The membrane mass transfer coefficient was measured as 1.53 × 10 −4 m/s. Our membrane showed better methane recovery performance than the commercial polypropylene membrane and a very stable flux without pore wetting during 10 days of operation with synthetic effluent (made by saturating a 60:40 methane/carbon dioxide mixture into tap water). In addition, the membrane prepared in this study could be operated without significant fouling (7% flux drop during 8 days of operation) with real anaerobic membrane bioreactor effluent. [ABSTRACT FROM AUTHOR]

To separate oil/water mixtures and emlusions, superwetting membranes have been developed via synergy between surface chemistry and topography. However, challenges remain as most of them exhibit unsatisfactory performance, limited strength and durability. Herein, we report a novel membrane with switchable super-wettability for oil and water. This novel composite membrane was developed by electrospinning a hierarchically porous polyvinylidene fluoride (PVDF)-silica composite nano/micro-beaded top layer and a PVDF nanofibrous intermediate layer on a non-woven support. The surface of the composite membrane was modified to exhibit high surface free energy. The membrane is in-air superamphiphilic, underwater superoleophobic and under-oil superhydrophobic. It can treat various types of oil/water mixtures, from simple layered solutions to emulsions (including surfactant-free or surfactant-stabilized oil-in-water and water-in-oil emulsions) without external driving force or under an ultralow pressure (0.1 bar) in a cross-flow filtration process. It shows a flux up to 2000 L/m 2 h and high separation efficiency (> 99.99% in terms of water and oil purities in the permeation) in the cross-flow filtration process. The membrane also exhibits an excellent robustness under harsh conditions, including strong acidic or alkaline solutions, hot water and petroleum. In addition, it presents remarkable antifouling and easy-cleaning properties, which were demonstrated in a 50-h continuous operation. [ABSTRACT FROM AUTHOR]

Efforts have been made in thermally induced phase separation (TIPS) process to modify the morphology of polyvinylidene fluoride (PVDF) membranes in order to improve their permeation performance and mechanical properties. Nevertheless, many methods not only altered the outer surface but also impacted the overall membrane structure, resulting in a trade-off between permeability and mechanical properties. In this study, we utilized a modified TIPS process to refine the outer surface morphology without altering the bulk structure. This was achieved by introducing NaCl in the coagulation bath. The PVDF membranes were fabricated using a dope with water insoluble diluent dimethyl phthalate (DMP) as main solvent and water-soluble additives polyethylene glycol 400 (PEG400)/triethylene glycol (TEG) as pore formers. The inclusion of NaCl in the coagulation bath serves to decrease the solubility of PEG within this medium, owing to the salting-out effect. Consequently, the NaCl concentration in the coagulation bath emerges as a crucial factor in regulating the migration of PEG400 toward the membrane surface. This control mechanism facilitates the precise adjustment of the outer surface morphology in the fabrication of membranes. As the NaCl concentration increases in the coagulation bath, the outer surface of the fabricated membrane transited from a mesh-like structure to a spherulite structure. As 0.5 mol L−1 NaCl was added to the coagulation bath, the membranes displayed a pure water permeability of 1073.9 L m−2 h−1 bar−1 while maintaining a narrow pore size distribution. Compared to the membranes fabricated without NaCl addition, the increment of the PWP contributed to the slight increase in mean pore size from 65 nm to 84 nm. Meanwhile, the water-insoluble diluent DMP was not affected by the addition of NaCl, which means that the bulk structure of the membrane could be maintained. Consequently, the increase in permeability did not compromise the mechanical properties of the membranes. All the membranes fabricated in this study maintained a reasonable tensile strength of approximately 3 MPa. This study introduces a simple and environmental method to increase the permeability effectively and fine-tune the pore size of the TIPS membranes while having little effect on the bulk structure. Furthermore, the study provides valuable insights into how changes in outer surface morphology can impact the pore size and permeability of TIPS PVDF membranes. [Display omitted] • Ultrafiltration PVDF membranes was fabricated by a modified TIPS method. • NaCl coagulation bath could control the outflow of PEG toward membrane surface. • The surface of the membranes could be fine-tuned without altering the bulk structure. • The ultrafiltration membranes present a narrow pore size distribution and high permeability. [ABSTRACT FROM AUTHOR]

The use of amphiphilic pore formers and hydrophilic non-solvents has demonstrated its effectiveness in improving the surface porosity and permeability of polyvinylidene fluoride (PVDF) ultrafiltration (UF) membranes through the nonsolvent induced phase separation (NIPS) process in literatures. However, in the thermally induced phase separation (TIPS) process, few reports illustrated how the amphiphilic pore-former and water-soluble non-solvent interact with water-insoluble diluents. In this study, water-insoluble dimethyl phthalate (DMP) was used as the main diluent to rule out the effect of diluent outflow. The amphiphilic pore former polyethylene glycol 400 (PEG400) failed to open pores on the outer surface of the membranes because of its amphiphilic nature. On the contrary, UF membranes with a mean pore size of 55 nm could be obtained by adding hydrophilic triethylene glycol (TEG) to the dope with a satisfactory pure water permeability (PWP) of 262.6 L m−2 h−1 bar−1. Moreover, PEG400 can serve as a stabilizer for the TEG droplets during the phase separation if both were added to the polymer dope solution. The addition of both PEG400 and TEG could significantly increase the membrane's PWP to 645.4 L m−2 h−1 bar−1 with moderate enlargement of the mean pore size of the membrane to 84 nm. Additionally, the well-connected membrane structure resulted in the tensile strength of the membranes ranging from 3.07 to 6.65 MPa. This study expands the range of additives used in the TIPS process and demonstrates the different roles of amphiphilic and hydrophilic non-solvents in the TIPS process. [Display omitted] • The effects of hydrophilic and amphiphilic non-solvent in the TIPS process are analyzed. • Hydrophilic non-solvent TEG could tailor the surface morphologies of the PVDF membranes. • Amphiphilic PEG failed to open pores on the outer surface of the PVDF membrane. • Amphiphilic PEG served as the stabilizer of TEG in the PVDF dope, increasing the porosity and pore size of the membranes. • The resulting PVDF membranes sit within the UF range, presenting narrow pore distribution and high pure water permeability. [ABSTRACT FROM AUTHOR]

Gas-liquid membrane contactor (GLMC) has been regarded as a promising alternative to conventional contacting processes for CO 2 absorption. In this work, a composite hollow fiber (HF) membrane with an aminosilane-modified zeolitic imidazolate framework-8 (mZIF-8) based dense skin layer was designed and synthesized for high-efficiency biogas upgrading in the GLMC process, by dispersing mZIF-8 nanocrystals into poly(dimethylsiloxane) matrix and then depositing on a porous polyvinylidene fluoride (PVDF) substrate. (3-aminopropyl)triethoxysilane was introduced to modify the ZIF-8 nanocrystals, thereby enabling the chemical bonding with PDMS chains for avoiding interfacial voids and further enhancing hydrophobicity. Compared with the control membrane, the newly developed mZIF-8 based composite membrane with a dense skin exhibited competitive hydrophobicity with a contact angle of 130°, ensuring its anti-wetting ability. It exhibited an enhanced biogas upgrading performance with the absorption fluxes of 2.3 and 3.8 × 10−3 mol m−2·s−1 using water and 1 M monoethanolamine (MEA) as absorbents, respectively (liquid velocity = 0.25 m s−1). In particular, a comparable selectivity of CO 2 /CH 4 with the value of ∼20 was achieved by using MEA as absorbent in the GLMC process. A robust long-term stability of the mZIF-8 based composite HF membrane was also achieved in a 15-day operation. This work offers a new perspective for promoting CO 2 mass transfer with mZIF-8 based composite HF membranes, thereby improving the biogas upgrading performance in GLMC applications. • A composite hollow fiber membrane with a ZIF-8 based dense skin layer was designed and synthesized. • The ZIF-8 nanocrystals were modified to cross-link with PDMS chains for further hydrophobicity enhancement. • The newly developed membrane exhibited competitive hydrophobicity, ensuring its anti-wetting ability. • An enhanced biogas upgrading performance was achieved in gas-liquid membrane contact applications. [ABSTRACT FROM AUTHOR]

Abstract The combination of nonsolvent and thermally induced phase separation (N-TIPS) method has shown promising ability in harvesting the features from the nonsolvent induced phase separation (NIPS) and thermally induced phase separation (TIPS) processes for developing membranes with a tailorable surface pore structure. However, previous approaches have been subjected to either the formation of macrovoids or dense layer due to the dominant NIPS effect, or required sophisticated instruments and operation skills. In this work, a facile attempt was carried out to fabricate novel polyvinylidene fluoride (PVDF) hollow fiber membranes with tunable surface pore structure while maintaining the narrow pore size distribution and mechanical strength. A modified N-TIPS method was developed by using mixed diluents: dimethyl phthalate (DMP) as a water-immiscible poor solvent for TIPS process, and triethyl phosphate (TEP) as a water-miscible neutral solvent to bridge the TIPS and NIPS processes. To further control the membrane formation especially near the membrane surface, an amphiphilic additive Pluronic F127 was also added as a potential pore-former and surface hydrophilicity modifier. PVDF hollow fiber membranes with a highly porous structure and a narrow pore size distribution were successfully synthesized by using TEP and Pluronic F127 in the N-TIPS process. The mechanism of N-TIPS process was thoroughly discussed. The water permeability of the membrane increased significantly from 389 ± 30–922 ± 36 L m–2 h–1 bar–1, with overall porosity improved from 50 ± 2.2–69 ± 2.9%, and a mean pore size of ~ 0.18 µm. The membranes produced by N-TIPS method also exhibited a good tensile strength ranging from 5.6 ± 0.1–6.5 ± 0.2 MPa, showing a great potential for a broad range of water applications after further modifications. Besides, the formation of piezoelectric β-phase crystals of the PVDF membrane was observed when the mixed diluent was used, which sheds light on the possible applications of resultant membranes in electrochemical separation process. Highlights • PVDF hollow fiber membranes were developed via a modified N-TIPS method using mixed diluents together with Pluronic F127. • The NIPS effect could be induced at the outer surface with the co-occurrence of TIPS process along the bulk of membrane. • The surface pore structure of membrane could be tailored without the formation of mechanically weak macrovoids. • The prepared membranes possess a hydrophobic surface with good porosity, permeability and mechanical strength. [ABSTRACT FROM AUTHOR]

Abstract A highly efficient biocatalytic carbonic anhydrase (CA)-polydopamine (PDA)/polyethylenimine (PEI)-polyvinylidene fluoride (PVDF) (referred to as CA-m-PVDF) composite membrane was fabricated for CO 2 conversion and capture in the gas-liquid membrane contactor (GLMC) process. The co-deposition of PDA/PEI with amino functional groups was employed to amine-functionalize a PVDF substrate as support for subsequent in-situ CA immobilization by cross-linking with glutaraldehyde. This enhances the enzyme stability and prolongs its lifespan, thus facilitates CO 2 hydration efficiency in the GLMC process. In this work, different immobilization CA protocols were compared based on the CA activity and activity recovery. For biocatalytic CA-m-PVDF membranes, the best activity of 498 U m−2 (membrane) and a corresponding activity recovery of 31.5% were achieved (m(5 h)-PVDF as support, 0.67 (v/v)% GLU as cross-linking agent, 600 μg mL−1 CA solution, pH 8.0, temperature at 25 °C, and 24 h reaction time). By using water as absorbent with a liquid velocity of 0.25 m s−1 in a bench-scale GLMC setup, a high-efficiency CO 2 absorption flux of 2.5 × 10−3 mol m−2 s−1 was obtained, which was ~165% higher than that of the non-biocatalytic m-PVDF membrane. The long-term stability test showed a good enzyme activity for CO 2 hydration capacity for the CA-m-PVDF membranes during 40 days of test duration. Overall, the results achieved in this work may provide promising insights into enzyme immobilization on polymeric supports for the development of high-efficiency biocatalytic membranes for CO 2 capture in GLMC applications. Highlights • A highly efficient biocatalytic composite membrane was fabricated for CO 2 conversion and capture. • PDA/PEI with amino functional groups was co-deposited to amine-functionalize a PVDF substrate. • Subsequent in-situ carbonic anhydrase (CA) immobilization was conducted by cross-linking. • The resultant membrane shows a high CO 2 absorption flux of 2.5 × 10-3 mol m-2 s-1 in the gas-liquid membrane contactor. [ABSTRACT FROM AUTHOR]

Abstract A highly-efficient zeolitic imidazolate framework-8 (ZIF-8) embedded polydimethylsiloxane (PDMS) mixed matrix membrane (MMM) supported by a polyvinylidene fluoride (PVDF) nanofibrous substrate was developed for phenol removal in an aqueous-aqueous membrane extractive process. Homogeneous nano-scaled dispersion of ZIF-8 in the PDMS matrix was achieved by direct incorporation without intermediate drying process, where the interaction of the randomly-moved nanofillers could be prevented, leading to evenly dispersed ZIF-8 nanofillers and defect-free ZIF-8@PDMS/PVDF nanofibrous composite membranes. The newly-developed ZIF-8@PDMS/PVDF membrane exhibited an exceptionally high overall mass-transfer coefficient, k 0 of 35.7 ± 1.1 × 10−7 m/s, doubling that of the pristine membrane in the membrane extractive process. The high performance was maintained for over 360 h without loss of salt rejection. These results could be attributed to the organophilic-assisted "bi-mode" transporting mechanism of ZIF-8 nanofillers in PDMS matrix, namely: (1) the solution-diffusion transport mode; (2) the pore-flow transport mode, where the synergistic effects are expected to significantly improve the phenol transfer efficiency through the membranes. Overall, the results achieved in this work demonstrate promising potential of highly-efficient ZIF-8@PDMS/PVDF nanofibrous composite membranes used for aqueous-aqueous membrane extractive processes for organic-containing wastewater treatments. Highlights • A drying-free method for incorporating ZIF-8 nanofillers into membrane was proposed. • The membrane is used for phenol removal in membrane extractive process. • Presence of ZIF-8 nanofillers in PDMS matrix enhances mass transfer efficiency. • Membrane properties can be tuned by controlling ZIF-8 nanofillers doping. [ABSTRACT FROM AUTHOR]

Porous hydrophobic polyvinylidene fluoride (PVDF) membranes have been extensively used in direct-contact membrane distillation (DCMD) processes. However, these PVDF membranes are vulnerable to membrane fouling and pore wetting in low surface tension feeds, restricting its application for water recovery from challenging industrial wastewaters. Therefore, it is of paramount importance to engineer fouling- and wetting-resistant MD membranes for robust long-term applications. In this study, a superoleophobic composite hollow fiber membrane with sandwich structure has been developed via accelerated oxidant-induced polydopamine (PDA) deposition on both the outer and inner surfaces of a commercial hydrophobic PVDF membrane under slightly acidic conditions (pH = 5). The modified surface prevents organics adhesion ascribing to its underwater superoleophobicity while the unmodified pores remain hydrophobic for vapor transport. The long-term robustness of the PDA-decorated membrane in highly saline feeds containing low surface tension contaminants has been evaluated via bench-scale DCMD experiments. In contrast to the pristine PVDF membrane, the PDA-decorated membrane exhibits excellent fouling- and wetting-resistant properties in different surfactant solutions as well as oil-in-water emulsion. The PDA-decorated membrane has also been used for seawater desalination, during which it maintains a stable flux and high salt rejection rate. Furthermore, the PDA-decorated membrane presents a flux enhancement of up to 70% over the pristine PVDF membrane in 3.5 wt% NaCl solution at 333 K. This study demonstrates the potential of the PDA-decorated membrane for extended DCMD applications such as water recovery from industrial wastewater containing low surface tension substances. [ABSTRACT FROM AUTHOR]

Recent studies have proved the advantages of novel composite membranes in the extractive membrane bioreactor (EMBR) for recalcitrant organic wastewater treatment. However, more systematic research into membrane properties and mass transfer effects are required. This study investigates the role of internal concentration polarization (ICP), including concentrated and diluted ICP, in an aqueous-aqueous extractive process, and the coupled effects of membrane roughness and hydrodynamic conditions on membrane performance in both cross-flow EMBR (CF-EMBR) and submerged EMBR (S-EMBR) processes. To study these factors, a nanofibrous composite membrane with a four-tiered structure, consisting of a dense polydimethylsiloxane (PDMS) selective layer, a polyvinylidene fluoride (PVDF) nanofibrous sublayer, a non-woven mechanical support and a rough micro/nano-beaded layer, has been developed for the EMBR by electrospinning and spray-coating. A diluted ICP, which occurred when the selective layer faces receiving water (SL-R w ), was less severe than a concentrated ICP in the selective layer facing feed (SL-F) orientation. It resulted in higher overall membrane mass transfer coefficients ( k 0 's) in the SL-R w mode during the aqueous-aqueous extractive tests. In addition, less biofilm was observed on the smooth PDMS surface after 14-days CF-EMBR and S-EMBR operations in the selective layer facing biomedium (SL-R bio ) mode. In contrast, in the SL-F mode during EMBR operations, the ridges and valleys on the membrane surface were able to provide a more favourable micro-environment for microorganisms and protect them from external stresses. The mature micro-colonies that developed in the SL-F mode clogged the membrane support and enhanced concentrated ICP, resulting in a significant reduction of k 0 's by more than 58%. Moreover, as the shear force on the membrane surface due to up-flow of air bubbles in the S-EMBR could mitigate the biofilm attachment, the most effective biofilm control strategy found in this study was to operate the nanofibrous composite membrane in the S-EMBR configuration with a smooth selective layer facing the biomedium. This effectively decreased the amounts of protein by 86%, polysaccharides by 88% and total suspended solids (TSS) by 89% in the biofilms on membrane surface, and achieved the highest stable k 0 of 7.0 × 10 −7 m/s. [ABSTRACT FROM AUTHOR]

Increasing demand for oil and gas leads to the generation of substantial amount of produced water, bringing about deleterious impacts on the environment. Direct-contact membrane distillation (DCMD) could be a possible option for dewatering oil-in-water (O/W) emulsions because of many benefits brought by the DCMD process. However, these low surface tension solutions pose some difficult issues such as membrane fouling and pore wetting. The mechanisms involved are not fully understood due to the lack of study of the interaction between the emulsions and the membrane surface in the DCMD domain. To address the challenges, this study aims at developing a fundamental understanding of the relationship between surfactant-stabilized O/W emulsions and polyvinylidene fluoride (PVDF) membrane surface in DCMD operations. Effects of surfactant types (Span 20, Tween 20, and sodium dodecyl sulfate), oil concentration, and oil types (petroleum and vacuum pump oil) were systematically studied to better understand the fouling and wetting mechanisms involved. The results reveal that surfactant concentration and hydrophobicity had an influence on the membrane fouling and wetting behaviors. Surfactants with a lower hydrophilic-lipophilic balance (HLB) value could make the PVDF membrane surface less hydrophobic and cause less severe fouling by restraining the adsorption of oil droplets on the membrane surface. These findings suggest that membrane surface modification is required to achieve anti-fouling and anti-wetting properties to make DCMD an energy-efficient and effective technology for treating produced water. [ABSTRACT FROM AUTHOR]

Hydrophobic membranes suffer from wetting and scaling when treating hypersaline brine using membrane distillation (MD). Thus omniphobic membranes with re-entrant surfaces have been developed by diverse modifications to enhance anti-wetting/scaling properties. However, those post-modifications usually sacrifice membrane permeability in spite of improved stability. In this work, omniphobic membranes were fabricated by decorating polyvinylidene fluoride (PVDF) nanofibrous membranes with different silica nanoparticles (SiNPs) followed by fluorination. Compared to unmodified nanofibrous and commercial PVDF membranes, both smaller SiNPs coated membrane #P-Min and larger SiNPs coated membrane #P-Max can perfectly sustain liquids with low surface tensions on their surfaces without wetting. In contrast to #P-Max with an oil contact angle of 136 ± 1°, #P-Min exhibited better oleophobicity with an oil contact angle of 152 ± 1°. In addition, the rigidity of their omniphobic properties was confirmed by testing in harsh conditions. Moreover, #P-Min successfully overcame the trade-off relation between membrane permeability and rejection with an enhanced MD flux due to more effective water evaporation area on membrane surface and a higher membrane porosity. While #P-Max was wetted by a hypersaline feed solution composed of 25 wt% NaCl, #P-Min could maintain a stable flux of 15 L m−2h−1 in a continuous 7-h MD operation, which proved its excellent performance for brine treatment. Furthermore, #P-Min exhibited less scaling tendency when feed was a saturated gypsum solution. Compared to #P-Max , the better anti-scaling properties of #P-Min should be due to its higher surface energy barrier, better slippery property and less solid-liquid contact area, which effectively impede crystal nucleation and attachment. Image 1 • Effects of nano-scaled roughness on membrane omniphobicity were studied. • As-prepared omniphobic membranes were stable under harsh conditions. • Omniphobic membrane coated with smaller NPs exhibited better performance. • It should be due to high surface energy barrier, slippery property and less solid-liquid contact area. [ABSTRACT FROM AUTHOR]

The use of amphiphilic copolymer Pluronic F127 as an additive has shown effectiveness in fabricating polyethersulfone (PES) membranes with excellent antifouling properties due to its roles in enhancing pore structure and surface hydrophilicity. However, F127 was found to be unstable in polyvinylidene fluoride (PVDF) membranes as its hydrophilic modifying function was deactivated over time. In present work, we developed a novel approach to immobilize F127 in PVDF hollow fiber membranes using polytetrafluoroethylene (PTFE) particles as a binding agent through the combined nonsolvent and thermally induced phase separation (N-TIPS) method. The results suggest that the hydrophobic segment of F127 could adsorb firmly onto PTFE with the hydrophilic segments protruding outwards. The dual-functions of F127 were observed in pore formation and surface hydrophilization for PVDF membranes. The water contact angle of PVDF/PTFE/F127 membranes decreased from 102 ± 4° to 76 ± 3° compared with membranes without additives. The resultant membranes possess a pure water permeability (PWP) of 869 ± 39 L m−2h−1bar−1 with a mean pore size of 0.09 ± 0.01 μm and an outstanding tensile strength of 7.0 ± 0.3 MPa, suggesting the potential of N-TIPS method for tuning the membrane pore structure and hydrophilicity by using multifunctional additives. Image 1 • PTFE or Pluronic-F127 could effectively help tailor bulk and surface properties of PVDF membranes through N-TIPS method. • The instability of F127 in PVDF membranes was significantly relieved in the presence of PTFE. • The mediating effect of PTFE allowed F127 to be a pore-former and surface hydrophilic modifier for PVDF membranes. • The prepared PVDF/PTFE/F127 membranes possess a narrower pore size distribution. • The membrane has improved porosity, tensile strength, hydrophilicity and antifouling property. [ABSTRACT FROM AUTHOR]

Demulsification of oil-in-water emulsions is challenging but significant for oily wastewater treatment, especially for surfactant-stabilized oil-in-water (S–O/W) emulsions. Electrospun nanofibrous membranes exhibit promising performance as demulsification medium but the underline mechanisms are still unclear. In this work, the effects of membrane pore size and nanofiber surface wettability on the demulsification of the S–O/W emulsions were investigated. Two polyvinylidene difluoride (PVDF) nanofibrous membranes with different nanofiber diameter (#P2 : 200 nm and #P10 : 1000 nm) were developed by electrospinning. The superhydrophilic membranes (#Dopa-P2 and #Dopa-P10) were obtained by coating polydopamine layers on both membranes #P2 and #P10. The silver nanoparticle deposition and subsequent fluorination were conducted on the surfaces of the polydopamine-activated membranes to prepare superhydrophobic nanofibrous membranes (#Ag–P2 and #Ag–P10). The superhydrophilic membrane #Dopa-P10 with a membrane pore size matching the oil droplets performed the best demulsification result. The oil droplets size increased up to 15 times (from 6.5 ± 1.0 μm to 98 ± 7 μm) after passing through #Dopa-P10. The underlying mechanism should be the superhydrophilic nanofibers possessed excellent affinity to the surfactants layer surrounding oil droplets, which could destroy the stable status and facilitate the coalescence of the oil droplets in S–O/W emulsions. The hydrophobic and superhydrophobic membrane #P10 and #Ag–P10 showed little coalescence effects as they exhibited a negative repulsive force to oil droplets. The physical cutting effect dominated the coalescence process when oil droplets passing through the membranes (#P2 , #Dopa-P2 , and #Ag–P2) with pore size much smaller than oil droplets. The various surface wettability didn't show any obvious difference on the coalescence results. • Superhydrophilic and superhydrophobic PVDF membranes were fabricated for demulsification. • Effects of membrane pore size and nanofiber wettability on the demulsification of surfactant-stabilized oil-in-water emulsions were investigated. • Oil droplets size was increased by 15 times after passing through superhydrophilic membranes with a mean pore size close to oil droplet size. • The demulsification mechanisms are discussed. [ABSTRACT FROM AUTHOR]