Modification of poly(vinylidene fluoride) membranes with aluminum oxide nanowires and graphene oxide nanosheets for oil–water separation

To improve the hydrophilic and oleophobic properties of membrane, we adopted aluminum oxide (Al₂O₃) nanowires and graphene oxide (GO) nanosheets to modify poly(vinylidene fluoride) (PVDF) membranes. The experimental results show that the intercalation of Al₂O₃ nanowires between GO nanosheets effectively improved the roughness of the GO–Al₂O₃–PVDF membrane, and the permeability of the membrane with an optimal mass ratio of Al₂O₃ to GO of 7.5 was 31 times that of the GO–PVDF membrane. Furthermore, the addition of Al₂O₃ nanowires significantly enhanced both the hydrophilic and oleophobic properties of the GO–Al₂O₃–PVDF membrane. On the basis of the extended Derjaguin–Landau–Verwey–Overbeek theory, the energy barriers between the oil droplets and GO–PVDF and GO–Al₂O₃–PVDF membranes were 0.63 and 0.9 KT, respectively; this indicated improvements in the anti-oil-fouling ability of the GO–Al₂O₃–PVDF membranes. We also found that both the GO–PVDF and GO–Al₂O₃–PVDF membranes had great oil–water separation rates (97.9 and 99.4%, respectively) with an initial oil concentration of 200 mg/L. The findings of this study show that the GO–Al₂O₃–PVDF membrane is a promising oil–water separation membrane, and further investigation of the cleaning procedure is needed to promote its practical application in oil–water separation. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47493.     

Electrospun nanofibrous polyvinylidene fluoride-co-hexafluoropropylene membranes for oil–water separation

Effective separation of oil from water is of significant importance globally for various applications such as wastewater treatment, oil spill cleanup, and oil purification. Among the numerous approaches for oil removal, membrane separation is considered one of the most promising approaches due to its selectivity and ease of operation. Electrospinning is a promising technique for producing polymeric membranes with tunable structures with interconnected pores, large surface area, and high porosity. In this study, hydrophobic poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) nanofibrous membranes were electrospun and used for this purpose. The effects of various parameters (e.g., polymer concentration, applied voltage, tip to collector distance, and feed rate) were investigated to find the optimum electrospinning conditions. Further, the electrospun membranes were characterized according to average fiber diameter, morphology, average pore size, and wettability to identify the combinations most likely to succeed in oil–water filtration. The physical–chemical properties of the membranes (i.e., thickness, areal density, porosity, average pore size, water/oil contact angle, hydrostatic pressure head, and oil filtration flux) were studied based on standard test methods. The separation efficiency of eight electrospun membranes with various pore sizes and average fiber diameters were tested for diesel/water mixtures. A linear relation was found between the initial oil flux and the average pore size of the membranes. The maximum oil filtration flux of about 224 L/m²/h, achieving over 75% oil recovery in 10 min, was obtained for the electrospun membrane with the average pore size of 4.5 μm. The membranes were successfully used for eight consecutive oil–water separation cycles without noticeable loss of flux.     

Reduced graphene oxide–gold nanoparticle membrane for water purification

The reduced graphene oxide–gold nanoparticle (rGO–Au NP) membranes are prepared by vacuum filtration method. The sizes of the Au NPs on the surface of the rGO are about 8–10 nm, and the lattice spacing of Au NPs is 0.0241 nm, which is relative to the cubic lattice of the gold crystal. The layer-by-layer stacking structure of rGO–Au NP membrane can be observed clearly by field emission scanning electron microscopy. The water flux of the rGO–Au NP membrane is as high as 204.1 L m^?2 h^?1 bar^?1, and its retention for Rhodamine B (RhB) is as high as 99.79%.     

Recyclable porous polyurethane sponge for highly efficient oil–water separation

Oil spills and chemical leakages have caused severe environmental problems. Physical absorption of the spilled oils and chemical reagents by absorbing materials is an efficient and economical approach to solve these problems. Herein, we have prepared a porous thermoplastic polyurethane (TPU) sponge by combining the thermally induced phase separation method with the selective dissolution of water-soluble PEG components. The selective removal of PEG components from the walls of TPU sponges could increase the intensities of free volume holes and surface areas of TPU sponges. The content of free volume holes and surface areas of TPU sponge reached its maximum with the TPU/PEG ratio of 1:1. The increased roughness could improve the absorption capacities of TPU sponges for various oils/organic solvents. Moreover, due to its excellent compressibility, this TPU sponge could be reused 20 times with little loss of saturated absorption capacity. In addition, this TPU sponge exhibited excellent separation ability for the toluene from the toluene/water mixture and emulsion. In all, we have developed a facile method to prepare TPU sponge absorbent with excellent absorption performance, which holds great potential in the application of large-scale oil/water separation.     

Simultaneously spray-assisted assembling reversible superwetting coatings for oil–water separation

Here, superhydrophobic cuprous oxide(Cu_2O) with hierarchical micro/nanosized structures was synthesized via spray-assisted layer by layer assembling. The as-prepared superhydrophobic meshes with high contact angle(159.6°) and low sliding angle(1°) are covered with Cu_2O ‘‘coral reef"-like micro/nanosized structures. Interestingly, the superhydrophobic mesh surfaces became superhydrophilic again due to the oxidization of Cu_2O to CuO by annealing at a higher temperature(300 ℃). And the superhydrophobic properties would be recovered by heating at 120 ℃. Furthermore, the superwetting meshes were applied to design a miniature device to separate light or heavy oil from the water–oil mixtures with excellent separation efficiency. These superwetting surfaces by simultaneously spray-assisted layer by layer assembling technique show the potential application in universal oil–water separation.     

Experimental study of a vane-type pipe separator for oil–water separation

An experimental study of a new vane-type pipe separator (VTPS) was conducted for the possible application in the well-bore for oil–water separation and reinjection. Results by using particle image velocimetry (PIV) reveal a better flow field distribution for oil–water separation, which is formed in VTPS than that in hydrocyclone. The effects of split ratio, the oil content, guide vanes’ installation and number of guide vanes on oil–water separation performance have been investigated experimentally. Compared to a traditional single hydrocyclone, VTPS shows a good separation performance as the water content at the inlet of VTPS reaches 79.9%, the oil content at the water-rich outlet is about 400 ppm while the split is near 0.70. These results are helpful to provide a possibly new design for downhole oil–water separation.     

Enhancing oil–solid and oil–water separation in heavy oil recovery by CO2-responsive surfactants

Interfacial properties are of critical importance to various separation applications. In heavy oil recovery, for example, a low oil–water interfacial tension (IFT) benefits the separation of heavy oil from their host rocks, which becomes problematic in the later stage of oil–water separation. CO₂-responsive surfactants were investigated to enhance the overall heavy oil recovery by switching their interfacial activity to the desired state in each stage. The surfactants at interfacially active state greatly enhanced the separation of heavy oil from hosting solids, as demonstrated by measuring contact angle and oil liberation using a custom-designed on-line visualization system. Meanwhile, the resulting heavy oil-in-water emulsions could also be easily demulsified by the bubbling of CO₂ gas, which switched off the interfacial activity of the surfactants. Furthermore, CO₂-responsive surfactants could be partially recycled in process water to improve sustainability, making CO₂-responsive surfactants to be promising chemical aids in heavy oil production and many other vital industries.     

Mathematical modelling of a hydrocyclone for the down-hole oil–water separation (DOWS)

In this study, a mathematical model is developed to predict the efficiency of a down-hole oil–water separation hydrocyclone. In the proposed model, the separation efficiency is determined based on droplet trajectory of a single oil droplet through the continuous-phase. The droplet trajectory model is developed using a Lagrangian approach in which single droplets are traced in the continuous-phase. The droplet trajectory model uses the swirling flow of the continuous-phase to trace the oil droplets. By applying the droplet trajectory, a trial and error approach is used to determine the size of the oil droplet that reaches the reverse flow region, where they can be separated. The required input for the proposed model is hydrocyclone geometry, fluid properties, inlet droplet size distribution and operational conditions at the down hole. The model is capable of predicting the hydrocyclone hydrodynamic flow field, namely, the axial, tangential and radial velocity distributions of the continuous-phase. The model was then applied for some case studies from the field tested DOWS systems which exist in the literature. The results show that the proposed model can predict well the split ratio and separation efficiency of the hydrocyclone. Moreover, the results of the proposed model can be used as a preliminary evaluation for installing a down-hole oil–water separation hydrocyclone system in a producing well.     

Mechanical milling of thermoresponsive poly(N-isopropylacrylamide) hydrogel for particle-oriented oil–water separation

The separation of oil and water is widely studied because of the promise of cleaning up oil spills. One pathway is with thermosensitive polymer-based hydrogels. As hydrogels are raised to the lower critical solution temperature (LCST), they undergo a change of state, from hydrophilic to hydrophobic. Oil–water separation using hydrogels in particle form that are responsive to external stimuli (e.g., magnetic field and temperature) are of great interest. This work uses a novel approach of ball milling dry hydrogel into different sizes and testing oil–water separation efficacy. This study investigated the potential for ball milling P(NIPAAm) bulk hydrogel into small particles size ranges (0–45, 45–90, 90–106, 106–150, and 150+ μm) and the resulting impact on oil–water separation. It was observed that the LCST for the p(NIPAAm) in gel form was 32 °C while increasing to ~40 °C for the powdered form. It was found that the hydrogel particles of different size ranges managed to capture 196, 207, 208, 162, and 124% of its weight in oil, respectively. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48771.     

Reduced graphene oxide for Li–air batteries: The effect of oxidation time and reduction conditions for graphene oxide

Reduced graphene oxide (rGO) has shown great promise as an air-cathode for Li–air batteries with high capacity. In this article we demonstrate how the oxidation time of graphene oxide (GO) affects the ratio of different functional groups and how trends of these in GO are extended to chemically and thermally reduced GO. We investigate how differences in functional groups and synthesis may affect the performance of Li–O₂ batteries. The oxidation timescale of the GO was varied between 30 min and 3 days before reduction. Powder X-ray diffraction, micro-Raman, FE-SEM, BET analysis, and XPS were used to characterize the GO’s and rGO’s. Selected samples of GO and rGO were analyzed by solid state ¹³C MAS NMR. These methods highlighted the difference between the two types of rGO’s, and XPS indicated how the chemical trends in GO are extended to rGO. A comparison between XPS and ¹³C MAS NMR showed that both techniques can enhance the structural understanding of rGO. Different rGO cathodes were tested in Li–O₂ batteries which revealed a difference in overpotentials and discharge capacities for the different rGO’s. We report the highest Li–O₂ battery discharge capacity recorded of approximately 60,000 mAh/g_carbon achieved with a thermally reduced GO cathode.     

Preparation of blend polyethersulfone/cellulose acetate/polyethylene glycol asymmetric membranes for oil–water separation

Blend PES/CA hydrophilic membranes were prepared via a phase-inversion process for oil–water separation. PEG-400 was introduced into the polymer solution in order to enhance phase-inversion and produce high permeability membranes. A gas permeation test was conducted to estimate mean pore size and surface porosity of the membranes. The membranes were characterized in terms of morphology, overall porosity, water contact angle, water flux and hydraulic resistance. A cross-flow separation system was used to evaluate oil–water separation performance of the membranes. From FESEM examination, the prepared PES/CA membrane presented thinner outer skin layer, higher surface porosity with larger pore sizes. The outer surface water contact angle of the prepared membrane significantly decreased when CA was added into the polymer solution. The higher water flux of the PES/CA membrane was related to the higher hydrophilicity and larger pore sizes of the membrane. From oil–water separation test, the PES/CA membrane showed stable oil rejection of 88 % and water flux of 27 l/m² s after 150 min of the operation. In conclusion, by controlling fabrication parameters a developed membrane structure with high hydrophilicity, high surface porosity and low resistance can be achieved to improve oil rejection and water productivity.     

Fabrication of superhydrophobic electrospun polyimide nanofibers modified with polydopamine and polytetrafluoroethylene nanoparticles for oil–water separation

The oil–water separation technologies of removing oil pollutants from water in an efficient and economical way is a challenge. The current methods used for oil–water separation suffer many shortcomings, including a low separation efficiency, complex separation equipment, high operation costs, and secondary pollution. In this study, we fabricated a highly flexible, high-intensity, quite stable superhydrophobic and superoleophilic polyimide (PI) nanofibrous membranes, which are much more efficient and cost efficient for oil–water separation by modifying the membranes with a polydopamine (PDA) solution and polytetrafluoroethylene (PTFE) dispersion. The fabricated membrane (PDA–PTFE–PI) possesses both the high tensile stress of PI and the superhydrophobic and superlipophilic properties of the PDA–PTFE coating. The modified membrane could separate various oil–water mixtures efficiently at a high flux (6000 L·m⁻²·h⁻¹) and an extremely high efficiency (>99%). Furthermore, even when the membrane was under an extremely hostile environment (with an ultrahigh temperature, strong acidity, or strong basicity), it still remained quickly stable with a good separation efficiency and recyclability after 10 cycles. We anticipate that our study will provide a new technology for the highly efficient mass production of oil–water mixture management. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47638.     

A facile method to functionalize engineering solid membrane supports for rapid and efficient oil–water separation

A facile and low-cost method is developed to functionalize engineering metal membrane supports, such as stainless steel (SS), with epoxy-containing polymer poly(glycidyl methacrylate) (PGMA) to produce a versatile and universal platform for subsequent surface modification. With a PGMA anchoring layer, we have demonstrated that hydrogel particles, such as polyacrylamide-co-poly(acrylic acid) (PAM-co-PAA), can be subsequently grafted to form functional polymer membranes for rapid and efficient oil–water separation. By contact angle and AFM measurement, we have confirmed that PAM-co-PAA hydrogel particle layer grafted on a PGMA-modified SS surface exhibits excellent selectivity as required for liquid–liquid separation, showing high affinity to water but not to oils as an ideal membrane for oil–water separation. To evaluate the separation efficiency, a simple flow-through device is employed to separate free-floating oil from water in the mixture of varied initial oil volume fraction and oil composition. Under substantially high pump flow rate up to 1.3 L/min, PAM-co-PAA hydrogel treated SS mesh can achieve excellent separation efficiency with less than 5% oil or water in the respective filtrate at the flux of as high as 540 m³/(m²·h) and retentate at the flux of 1.95 m³/(m²·h). This separation efficiency is better than, or comparable to, the maximal performance achieved using conventional gravity methods at much lower flow rate. Similar approach could be also adapted to graft superhydrophobic and superoleophilic polymer membranes with PGMA-treated engineering support to separate water from oil.     

Hydrophobic and fire-resistant carbon monolith from melamine sponge: A recyclable sorbent for oil–water separation

Here we report a new strategy for fabrication of macro/mesoporous carbon monolith from commercially available and low-cost melamine sponge. This synthesis route involves the cooperative self-assembly and coating of block copolymer mixed with resol on the melamine sponge, followed by pyrolysis at different temperatures. The as-fabricated carbon monolith exhibits high porosity and excellent hydrophobicity, thus can be used as a potential sorbent for the removal of oil from water. The intrinsic fire-resistant property of obtained carbon monolith makes it a recyclable sorbent for oil–water separation. More importantly, benefiting from the low-cost, available raw material and simple synthesis route, the production of the carbon monolith can be easily scaled up. This work offers a simple pathway to prepare carbon monolith, which is a promising candidate in the field of oil spill cleanup.     

Synthesis of SBA 15 graphene oxide composite membrane using phenol–formaldehyde resin pore modifier for CO2 separation

Present study highlights the development of carbon-loaded SBA 15 membrane on clay-alumina tubular support and its performance on the CO₂ separation efficiencies from different mixture gases. To modify the large pores of SBA 15 by graphitic carbon, low molecular weight phenol–formaldehyde (PF) resin was incorporated into the mesoporous channel followed by calcination under inert atmosphere. The modified ordered pore structure of the membrane has been characterized by low-angle XRD, TEM, and pore size distribution analysis. The chemical state of the deposited carbon phase into the SBA 15 pores was analyzed by X-ray photoelectron and Raman spectroscopy. Carbon having graphitic nature mainly in graphene oxide has been deposited into the mesopore of SBA 15 resulting decrease in pore size from 8.9 to 1.0 nm. Finally, the developed SBA 15 carbon membranes were characterized by CO₂ permeation and separation selectivity of CO₂/CH₄, CO₂/CO. Highest CO₂/CH₄ separation factor was achieved as 16.9 with CO₂ permeance 13.6 × 10^–8 mol/m²/s/Pa at 200 kPa feed pressure by the 20% resin with 2 times coated membrane. In flue gas analysis, highest CO₂/CO separation factor of 32.8 was achieved. This study offers an observation on CO₂ separation from simulated BF gas for the first time and the results show the potential of the developed SBA 15/C composite membranes in commercial application.     

Superhydrophobic–superoleophilic electrospun nanofibrous membrane modified by the chemical vapor deposition of dimethyl dichlorosilane for efficient oil–water separation

Superhydrophobic and superoleophilic functionalized electrospun poly(vinylidene fluoride) (PVDF) membranes with water repellence, breathability, and oil-sorption and oil–water separation properties were achieved with a combination of an electrospinning technique and the chemical vapor deposition of dichlorodimethyl silane. The samples were laterally characterized by scanning electron microscopy, atomic force microscopy, water contact angle measurement, and Fourier transform infrared spectroscopy. The maximum water contact angle value was 152.0 ± 2.5° for the PVDF nanofibrous membranes with 500 μL of deposited silane (PMS2) obtained under certain conditions. The PMS2 membranes showed 100.0, 93.7, 23.3, 35.0, and 100.0% separation efficiencies for n-hexane, kerosene, crude oil, frying oil, and toluene, respectively. The understudy membrane exhibited reasonable waterproofness and remarkable breathability (water vapor transition rate = 215.21 g/m².h). Moreover, the superhydrophobic and superoleophilic nanofibrous membranes also showed good reusability, stability, moderate water-repellent properties, breathability, antifouling properties, and oil–water separation ability after several cycles. These properties confirmed potential in feasible applications, including protective cloths and in the purification of oil-polluted water. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47621.     

Hierarchical superhydrophobic surfaces for oil–water separation via a gradient of ammonia content controlling of dopamine oxidative self-polymerization

Superhydrophobic three-dimensional porous materials have been considering as one of the most promising candidate absorbents for removal and collection of oil spills or organic contaminants from water. In this work, we report a novel and straightforward method for construction of hierarchical superhydrophobic surfaces on the commercial melamine sponge by controlling of the dopamine oxidative selfpolymerization via a gradient of ammonia content. The surface roughness of the sponge was enhanced by the deposited polydopamine coatings whose surfaces exhibited different morphologies at solutions of varied ethanol-ammonia ratios. Thereafter the low-surface free energy moieties were decorated on the surfaces by utilizing a secondary modification platform of polydopamine. Correspondingly, the obtained superhydrophobic melamine sponge achieved a water contact angle of 162.6° ± 1. Furthermore, the superhydrophobic sponge exhibited excellent absorption performances and extraordinary recyclabilities toward a variety of oils and organic solvents. These findings presented in this study offer an effective and versatile approach for oil spills and organic solvents containment removal and environmental remediation in more fundamental and practical fields. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48044.     

Hierarchical amphiphilic high-efficiency oil–water separation membranes from fermentation derived cellulose and recycled polystyrene

A high-efficiency separation of oil and water can be achieved by using specially designed amphiphilic porous membrane. However, the preparation of such membranes often involves complex multistep chemical processes. Herein, we report an amphiphilic composite membrane (polystyrene [PS]/bacterial cellulose [BC] membrane) consisting of hydrophobic recycled PS and hydrophilic BC, fabricated by a facile in situ fermentation process. Not only these membranes exhibit a combination of contrasting wettability but also comprise of a hierarchical network of microfibers and nanofibers, which makes them ideal for oil–water separation. The structural and morphological properties of as-produced BC, recycled PS membrane, and PS/BC composite membrane were studied by Fourier transform infrared spectroscopy and scanning electron microscopy, respectively. The ability of the membranes to separate oil and water was tested by using an emulsion of hexane-in-water as the feed and the collected filtrates were characterized by optical microscopy and UV–Vis spectroscopy. PS membranes were unable to separate oil and water, while the PS/BC membrane efficiently separated water from the emulsion. PS/BC composite membranes showed a high water recovery of more than 90%, against only 57% recovery shown by BC. Mechanisms of oil–water separation for each membrane are discussed. The reusability of the PS/BC composite membrane was also demonstrated.     

Experimental determination of the Hamaker constants for solid–water–oil systems

The van der Waals interaction (vdW) is a fundamental interaction in colloid and interface science. Regardless of the methods used in deriving the vdW interaction between two bodies as a function of their separation distance, the Hamaker constant is always an essential parameter involved. In this paper, a simple experimental method is presented to determine the Hamaker constant. As an example, the Hamaker constant of a solid-water-oil system is related to its surface and interfacial energies, which can be measured accurately. Based on the proposed method, the effects of two typical solid surfaces and three kinds of aqueous solutions on the Hamaker constant and wettability of the solid-water-oil system are studied. It is found that hydrophilic and hydrophobic solid surfaces will lead to rather different Hamaker constants and wettability behaviour. The detailed experimental results also show that the ionic surfactant solutions have a strong influence, whereas the pH value of the aqueous phase has a limited effect on the Hamaker constant. In addition, the electrolyte solutions do not strongly affect the Hamaker constant for the oil phase interacting with the solid surface across an electrolyte solution. Such determined Hamaker constants are in reasonable agreement with the reported Hamaker constants for oils (dodecane and hexadecane), mica, and metals (Ag, Au, and Cu) interacting across a pure water phase.     

Robust,fluorine-free and superhydrophobic composite melamine sponge modified with dual silanized SiO_2 microspheres for oil–water separation

Massive oily wastewater discharged from industrial production and human daily life have been an urgent environmental and ecological challenge. Superhydrophobic materials have attracted tremendous attention due to their unique properties and potential applications in the treatment of wastewater. In this study, a novel superhydrophobic/superoleophilic composite melamine sponge modified with dual silanized Si O_2 microspheres was fabricated simply by a two-step sol–gel method using vinyltriethoxysilane and hexadecyltrimethoxysilane as functional agent, which exhibited a water contact angle of 153.2° and a water sliding contact angle of 4.8°. Furthermore, the composite sponge showed the excellent oil adsorption performance and the compressive elasticity reaching up to 130 g·g~(-1) of dichloromethane and 33.1 k Pa of compressive stress. It was worth noting that the composite sponge presented the excellent separation efficiency(up to 99.5%) in the processes of continuous oil/water separation. The robust superhydrophobic composite melamine sponge provided the possibility with the practical application for oil–water separation.