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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: 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: 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]

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]

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]