Synthesis and characterization of alumina nano-particles polyamide membrane with enhanced flux rejection performance

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Abstract

This paper presents polyamide (PA) nanocomposite membrane containing alumina nanoparticles synthesized via in situ interfacial polymerization. Polymerization reaction occurred from the aqueous phase of m-phenylenediamine and the organic phase of trimesoyl chloride in which alumina nanoparticles were homogeneously dispersed. In the first part of the work, aluminum oxide (Al2O3) nanoparticles with average size of 14 nm, were synthesized by an aqueous sol–gel method using precursors of aluminum nitrate and citric acid mixed solution. The as-synthesized Al2O3 nanoparticles were characterized by X-ray diffractometer (XRD), scanning electron microscope (SEM), energy-dispersive X-ray spectroscope (EDX) and Fourier transform infrared spectrometer (FTIR). In the second part, the Al2O3 were used to prepare nanoparticles entrapped PA membrane via interfacial polymerization. SEM analysis demonstrated that nanoparticles were dispersed in the membrane and embedded in polyamide chains. Elemental analysis by EDX demonstrated the presence of nanoparticles on the membrane surface. The FTIR data confirm the formation of polyamide layer with Al2O3. The performance of the nanocomposite membrane, which was cured at 80 °C for 5 min, was observed to be better than pristine membrane. The existence of nanoparticles in the membrane improves the permeate flux and maintains the salt rejection. It also resulted in enhanced hydrophilicity of the membranes proved by decreased water contact angle.

Graphical abstract

Polyamide membrane embedded with aluminum oxide nano-particles.

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Highlights

► A polyamide-alumina (14 nm) nanocomposite membrane has been synthesized. ► The membrane was characterized by SEM, EDX and FTIR. ► The performance of nanocomposite membrane was enhanced.

Introduction

Water sustainable supplies are vital for agriculture, industry, recreation, energy production and domestic consumption. Thus, there is a need to improve the efficiency of water purification technology. Membrane technology is of a great potential for application in water treatment systems. It is used to remove fine particles from water with high separation efficiency [1]. Inorganic materials incorporation into the polymer matrix is being of great interest due to their completely hydrophilic characteristic and their certain functionality to benefit membrane properties of fouling reduction [2]. Therefore, extensive efforts are being devoted to incorporate inorganic nanoparticles into polymeric membrane. It was reported that inorganic materials could be incorporated into membranes by doping and coating technologies [3], [4]. However, the doping technology has the disadvantage that inorganic materials are buried in the polymer matrix and in turn rendered non-functional. On the other hand, the coating technology has the disadvantage of the instability of inorganic materials onto polymer surface, especially for those not subject to chemical bonds or physical restraints between the inorganic materials and membrane matrix. The concept for formation of mixed matrix reverse osmosis membranes, by interfacial polymerization of nanocomposite thin films on porous supports, has been reported [5]. The emergence of nano-technology in membrane materials science could offer an attractive alternative to polymeric materials [6].

Zeolite nano-particles have been used to prepare nanocomposite membrane where first zeolite nano-particles are synthesized via a template hydrothermal reaction followed by a series of complex processes involving template removal, carbonization, sodium exchange and calcination [7]. Titanium oxide nanoparticles have been incorporated into polyamide (PA) thin film membranes by applying an in situ interfacial polymerization procedure [8]. Polyethersulfone–TiO2 nanoparticle composite membranes made from casting solution consisting of various compositions of polymer solvents (DMF and EtOH) and TiO2 additive showed significant improvement in fouling resistance [9]. Silica oxide nanoparticles have been incorporated into PA thin film membrane via in situ interfacial polymerization process [10]. Zirconium oxide has been used as a bulk material in polyvinylidene fluoride membranes [11]. ZnO enhanced polyethersulfone membrane has been synthesized by diffusion induced phase inversion in N-methyl-pyrrolidone. It has reported that membrane materials embedded with ZnO nanoparticles have significantly improved membrane features. It showed lower flux decline and better permeability compared to neat polymeric membrane due to a higher hydrophilicity of the ZnO membranes. ZnO nanoparticles provide a remarkable improvement in the methylene blue rejection potential [12]. Aluminum oxide (Al2O3) nanoparticles were also incorporated into a membrane of polyvinylidene fluoride using dimethyl acetamide as solvent [13]. Same type of polymer was used to prepare a membrane by doping with anhydrous and hydrated aluminum oxide particles through in situ particle embedment and subsequent crystal growth under a hydrothermal environment [14].

Recently, an informative review on the use of nanoparticles in polymeric and ceramic membrane structures has been published [15]. Different strategies using a wide range of nanoparticles have been presented for the manufacturing of membrane materials with their potential applications in the field of water treatment. Despite the efforts, there is still a need for investigating different nanocomposite membranes with increased water permeability for energy savings and at the same time improved salt rejection for good water quality; along with long service life of the membrane that is resistant to fouling. Aluminum oxide (Al2O3) is one of the most stable inorganic materials, and thus it is used as ultra-filtration membranes [16]. In addition, it is inexpensive, non-toxic, highly abrasive and resistant. Remarkably, the use of alumina nanoparticles in membranes, especially in PA membrane synthesis by interfacial polymerization, has not yet been investigated to a large extent, in spite of their wide availability and applications in water treatment technology.

In this study, the Al2O3 nanoparticles were synthesized and characterized. Then, they were incorporated into a thin film polyamide membrane via interfacial polymerization process. The performance of the membrane was evaluated in terms of permeate flux and salt rejection.

Section snippets

Reagents and chemicals

Aluminum nitrate, citric acid, polysulfone (PS) m-phenylenediamine (MPD), trimesoyl chloride (TMC), n-hexane and N,N-dimethylformamide (DMF) were obtained from Sigma Aldrich and used as received. The water employed in the syntheses processes was double distilled. The other chemicals and reagents were of high analytical purity, obtained from Sigma Aldrich and used as received.

Synthesis of alumina nanoparticles

The nanoparticles of alumina were prepared by the following process. The aluminum nitrate and citric acid were dissolved

Characterization of the synthesized Al2O3 nanoparticles

The prepared alumina nanoparticles were characterized by EDX, SEM, XRD and FTIR. The EDX spectrum is presented in Fig. 1a. It shows two peaks reflecting the presence of aluminum and oxygen. The quantitative analysis is presented in the inset of Fig. 1a. The SEM image is presented in Fig. 1b. Field emission scanning electron microscope (FESEM) image of the alumina nanoparticles is depicted in Fig. 2. It shows the nanoparticle size of the synthesized alumina. An XRD pattern of alumina

Conclusions

Al2O3 nanoparticles were synthesized, via sol–gel method, and characterized via various characterization tools; X-ray diffractometer, scanning electron microscope and Fourier transform infrared spectroscope. The as synthesized Al2O3 nanoparticles were embedded into polyamide membrane via interfacial polymerization process. EDX, SEM and FTIR confirm the formation of polyamide membrane embedded with aluminum oxide nano-particles. EDX quantitative analysis confirms the presence of

Acknowledgement

Authors acknowledge the support of Chemistry department and King Fahd University of Petroleum and Minerals (KFUPM) Dhahran, Saudi Arabia for this work.

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