Magnetic field induced orderly arrangement of Fe3O4/GO composite particles for preparation of Fe3O4/GO/PVDF membrane
Graphical abstract
Introduction
Nowadays, membrane technology has received significant attentions as a promising technology in many sectors of manufacturing industry water desalination, product recycling and recovering and pollution abatement, owing to its high efficiency, deeply cleaning and no chemical additives [1], [2], [3]. Exploitation of new membranes with excellent separation capability is still a major research goal in membrane technology. Recently, many effort are devoted to improve the performance of the existing membranes in terms of anti-fouling properties, excellent thermal stability, high mechanical strength and good chemical resistance [4]. In general, the true cure to membrane fouling lies in new fabrication methods or modification of key steps followed in membrane synthesis. The modification of membrane using hydrophilic components allows for alteration of the physical and chemical properties of the membrane surface to acquire more hydrophilic wetting properties that prompt an improvement in permeate flux and the prevention or minimization of membrane fouling [5]. Currently, polyvinylidene fluoride (PVDF) is a commercial membrane material with outstanding anti-oxidation activities and good mechanical properties, moreover it is resistant to corrosion by most chemicals and organic compounds [6], [7]. However, the inherent hydrophobicity of PVDF induces a high tendency toward membrane fouling, which can diminish the separation performance and shorten membrane life, thereby restricting its advancements [8]. Generally, hydrophilic modification of polymeric membranes which primarily consist of surface and blending modification, has enabled the integration of hydrophilic or super-hydrophilic materials on a membrane surface, thereby improving comprehensive performance of polymeric membranes [9]. However, most surface coating or grafting suffered flux reduction and unsustainability of the functional layer [2].
Over the past decades, significant interest has been focused on graphene oxide (GO) to attain high permeability selectivity and antifouling property in membrane applications because of its excellent mechanical strength, outstanding flexibility, good hydrophilicity, as well as its cost effective and scalable production [10], [11], [12]. However, traditional blending modification could cause plenty of GO, as well as other nanoparticles, buried within the polymer matrix during the blending process, leading to low modification efficiency [13], [14].
Recently researchers have managed to fabricate magnetic nanoparticles by a coprecipitation method and they have been proven to possess excellent adsorption capacity to eliminate many kinds of organic pollutants, high magnetostriction, anisotropic magnetoelectric magnetic sensing capability and good linearity for polymer-based magnetic sensor devices, actuators and in the biomedical field, and in the field of cancer nanotheranostics owing to their intrinsic magnetic property [15], [16], [17], [18]. Several reported studies, has employed an external force (such as electric field or magnetic field) during the membrane preparation processes to enrich the anchoring of nanoparticles on the membrane surface to that can truly exploit the modification efficiency and thus to promote membranes’ flux and antifouling property [5], [19], [20] Magnetic Fe3O4 nanoparticles have been used in the magnetic liquid, magnetic memorizing material, magnetic polymer microspheres and so on, for its super-paramagnetism and it could be magnetized and arrange along the magnetic line of force in magnetic field [21], [22]. The use of such superparamagnetic and super hydrophilic nanoparticles in membrane modification is barely reported
In the present work, magnetic Fe3O4/GO (MGO) particles were synthesized by a facile one-step chemical coprecipitation method with a slight modification [22], [23], [24]. The directional migration and ordered arrangement of MGO sheets in magnetic field was investigated. Also, the preparation of multilayer composite membrane is in the form of functional layer and support substrate in series. The functional layer was prepared via magnetic field which induced the migration of MGO sheets to the membrane surface during the phase inversion process. With this method, MGO sheets migrated to the membranes’ top surface and orderly arranged into membranes’ surface along the magnetic field direction rather than embedding GO or Fe3O4 within the polymer matrix.
Section snippets
Materials
PVDF (Solef 6010) was purchased from Solvay Chemical Industry Co., Ltd. GO (1–5 layers, sheet size: 10–50 µm) prepared according to modified Hummers’ method was purchased from Suzhou TANFENG graphene Tech Co., Ltd. The polyester (PET) nonwoven (E74) was purchased from Suzhou Holykem Automatic Technology Co., Ltd and used as received. N,N-dimethylacetamide (DMAc) were purchased from Tianjin Kermel Chemical Reagents Co., Ltd (Tianjin, China). All the reagents were used without further purification.
Characterization of MGO particles
The morphology of Fe3O4, GO and MGO particles were illustrated respectively by TEM and SEM, as shown in Fig. 2. The typical TEM images of Fe3O4 nanoparticles (Fig. 2a) revealed that the sizes of Fe3O4 nanoparticles were almost uniform and most of the Fe3O4 nanoparticles were approximately spherical with the average diameters of 9.5 nm. For GO sheets (Fig. 2b and d), the transparency of GO exhibited layered structure and a transparent clean surface with a few thin ripples. As shown in Fig. 2c and
Conclusion
In this study, the superparamagnetic and hydrophilic MGO particles with Fe3O4 nanoparticles uniformly distributed on the surface of GO nanosheets were synthesized according to a facile one-step chemical coprecipitation method with a slight modification. The functional layer with MGO orderly embedded into the membrane surface was prepared via magnetic field induced MGO sheets to the membrane surface during the phase inversion process. This affected the pure water flux, hydrophilicity and
Acknowledgments
The authors gratefully acknowledge the research funding provided by the National Natural Science Foundation of China (51673149 and 51603146), the Science and Technology Plans of Tianjin (No. 15PTSYJC00240), and the Young Elite Scientists Sponsorship Program by CAST (2016QNRC001).
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