Fabrication of new type of barium ferrite/copper oxide composite nanoparticles blended polyvinylchloride based heterogeneous ion exchange membrane

S.M. Hosseini; N. Rafiei; A. Salabat; A. Ahmadi

doi:10.1016/j.arabjc.2018.06.001

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Original article

13 (

); 2470-2482

doi:

10.1016/j.arabjc.2018.06.001

Fabrication of new type of barium ferrite/copper oxide composite nanoparticles blended polyvinylchloride based heterogeneous ion exchange membrane

S.M. Hosseini^{^a,⁎}, N. Rafiei^{^a}, A. Salabat^{^b}, A. Ahmadi^{^c}

a Department of Chemical Engineering, Faculty of Engineering, Arak University, Arak 38156-8-8349, Iran

b Department of Chemistry, Faculty of Sciences, Arak University, Arak 38156-8-8349, Iran

c Department of Physics, Faculty of Sciences, Arak University, Arak 38156-8-8349, Iran

⁎Corresponding author. S-Hosseini@Araku.ac.ir (S.M. Hosseini)

Received: 2018-3-22, Accepted: 2018-6-3, Published: 2018-01-01

Disclaimer:
This article was originally published by Elsevier and was migrated to Scientific Scholar after the change of Publisher.

Peer review under responsibility of King Saud University.

Abstract

The current study focuses on the electrochemical, morphological and antibacterial characteristics of a new type of polyvinylchloride based cation exchange membrane modified by BaFe₁₂O₁₉/CuO composite nanoparticles. The used BaFe₁₂O₁₉/CuO composite nanoparticles were synthesized by chemical precipitation technique. The formation of BaFe₁₂O₁₉/CuO was characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and X-ray diffraction (XRD). SEM and scanning optical microscopy (SOM) images also showed relatively uniform structure for the prepared membranes. The membrane water uptake was enhanced up to 14.5% in presence of BaFe₁₂O₁₉/CuO composite nanoparticles. The membrane ion exchange capacity, membrane potential, transport number, surface charge density, permselectivity and ion permeability/flux were also improved sharply by increase of additive concentration up to 2 wt% and then showed decreasing trend by more BaFe₁₂O₁₉/CuO content ratio from 2 to 8 wt%. The membrane areal electrical resistance were decreased significantly from ∼24 to ∼5 (Ω cm²) by using of BaFe₁₂O₁₉/CuO nanoparticles. Moreover, modified membranes demonstrated good ability to removal of E-coli bacteria.

Keywords

Cation exchange membrane

BaFe12O19/CuO nanoparticles

Chemical precipitation

Electrochemical properties

Antibacterial characteristic

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1 Introduction

Access to safe and potable water has become one of the serious issues of our age and requirement to clean water is growing every day. The water purification capability provides the possibility to obtain suitable sources for different utilization. Among the various separation processes, membrane processes due to low energy consumption, low harmful effects on the environment, low maintenance cost and easy conversion to industrial scale used in the water treatment industry (Thampy et al., 2011; Oren et al., 2010; Aryafard et al., 2016; Logan and Elimelech, 2012 ). With the development of ion exchange membranes (IEMs) during the past half century, the use of these membranes has risen dramatically in various processes such as environmental protection and treating industrial and biological effluents, production of organic acids, salt production, desalination of brackish water and also industrial separation processes such as industry chlor-alkali, electrodialysis, diffusion dialysis, etc. (Banasiak et al., 2011; Karimi et al., 2012; Strathmann, 2010; Xu and Fu, 2006 ). IEMs are classified according to the ionic charge groups attached to polymeric backbone into two groups of anion exchange membranes (AEMs) and cation exchange membranes (CEMs). In CEMs by binding the negatively charged groups to the polymeric backbone, the cations are able to cross of membrane. Similarly, in the AEMs, attached positively charged groups allow the transmission of anions but blocking transmission of cations (Vogel and Meier-Haack, 2014; Sata, 2004).

A lot of research has already been carried out to improve the IEMs properties. Variation of functional groups type, selection of different polymeric matrices, polymers blending, using of inorganic additives/filler, alteration of cross-link density and surface modification are the important techniques to obtain superior IEMs (Tong et al., 2016; Heydari et al., 2016; Hosseini et al., 2010; Hosseini et al., 2015; Nagarale et al., 2004 ).

Recently, inorganic-organic composite membranes gained considerable attention. The organic-inorganic composite membranes were developed to enhance the thermal, mechanical and chemical stability membrane matrix in severe conditions and also to increase the separation properties of them based on the synergism between organic-inorganic components properties (Hosseini et al., 2010; Hosseini et al., 2015). Among these, applying of nanomaterials in membranes’ structure has considered attractively (Heydari et al., 2016; Hosseini et al., 2010; Hosseini et al., 2015; Nagarale et al., 2004 ) which is assigned to high surface area, considerable level of mass unit and the quantum effect of them at this scale (Kojima and Wohlfarth, 1982; Kodama and Berkowitz, 1999).

An improvement of IEMs performance is a strategy for decreasing operating expenses and enhancing the process efficiency. Fabrication of favorable heterogeneous cation exchange membrane with improved physico-chemical and antibacterial characteristics for the application in electrodialysis processes related to water recovery and treatment in industrial plants was the primary target of the current research. This study focuses on the electrochemical, morphological and antibacterial characteristics of a new type of polyvinylchloride based cation exchange membrane modified by BaFe₁₂O₁₉/CuO composite nanoparticles. Currently no reports have considered incorporating BaFe₁₂O₁₉/CuO composite nanoparticles into heterogeneous IEMs and the literature is silent on the characteristics and functionality of electrodialysis of ion exchange membranes modified by BaFe₁₂O₁₉/CuO composite nanoparticles.

Nowadays, magnetic nanoparticles are highly regarded due to their specific features (Martínez-Cabanas et al., 2016; Ahmadi Golsefidi et al., 2016; Saffari et al., 2015; BurakKaynar et al., 2015 ). The magnetic barium ferrite nanoparticles are new class of advanced nanomaterials with very interesting characteristics such as superior adsorption property, high surface area and favorable thermal and chemical stabilities which make it applicable in different processes such as water purification and treatment (Heydari et al., 2016; BurakKaynar et al., 2015; Mosleh et al., 2014; Molaei et al., 2012 ).

Moreover, the metal oxide nanostructures have gained more attention due to their favorable properties like chemical stability, unique adsorption property, good catalytic activity and electrical property, environmental friendliness, antibacterial characteristic, easy production and low cost (Chen and Mao, 2007; Wang, 2004; Gupta et al., 2016 ). The CuO nanoparticles are well known metal oxide nanomaterials which utilized in an extensive range of processes such as super capacitors, lithium-ion batteries, industrial wastewater treatment, microorganisms/microbial contamination and bacteria’s removal from water, gas sensors, photocatalytic reactions, catalysts and solar cells (Gupta et al., 2016; Guan et al., 2011; Bu and Huang, 2017; Lupan et al., 2016; Zhou et al., 2006; Kislyuk and Dimitriev, 2008; Akhavan et al., 2010; Cioffi et al., 2005; Baghbanzadeh et al., 2015 ).

Utilizing of BaFe₁₂O₁₉/CuO composite nanoparticles as filler additive in membrane matrix can provide favorable electrochemical and antibacterial characteristics for the prepared membranes with respect to combined components properties. The used BaFe₁₂O₁₉/CuO composite nanoparticles were synthesized by chemical precipitation technique. The effect of the concentration of composite nanoparticles in the casting solution on the physico-chemical properties of membranes was studied. The results are valuable for electro membrane processes especially in electrodialysis process for water recovery and waste water treatment.

2 Materials and methods

2.1

2.1 Materials

Polyvinyl chloride (PVC, grade S-7054, 490 g/lit) from Bandar Imam Petrochemical Company (BIPC), Iran, was used as membrane binder. Tetrahydrofuran (THF, molar mass: 72.11 g/Mol, density: 0.89 g/cm³) was utilized as the solvent. Cation exchange resin (Ion exchanger Amberlyst®¹⁵, strongly acidic cation exchanger, H⁺ form - more than 1.7 milli equivalent/g dry) was purchased from Merck Inc., Germany was employed in production of membrane. ${Fe ({NO}_{3})}_{3} \cdot 9 H_{2} O$ , $NaOH$ , ${Ba ({NO}_{3})}_{3}$ and ${CuCl}_{2} \cdot 2 H_{2} O$ were provided by Merck. Also during the experiment, distilled water was utilized.

2.2

2.2 Synthesis of BaFe₁₂O₁₉ nanoparticles

BaFe₁₂O₁₉ nanoparticles were synthesized by chemical precipitation method (Heydari et al., 2016; Martínez-Cabanas et al., 2016; Nabiyouni et al., 2016; Rahimi-Nasrabadi et al., 2017; Rahimi-Nasrabadi et al., 2017 ). For the purpose, the aqueous solution was prepared via dispersing 1.85 g of ${Fe ({NO}_{3})}_{3} \cdot 9 H_{2} O$ and 0.1 g of ${Ba ({NO}_{3})}_{3}$ into deionized water and under magnetically stirring. Then, 19 ml of $NaOH$ solution 1 M was slowly poured to the above solution during 30 min to reaching the solution pH to 10. Then the obtained brown precipitate was separated by centrifuge from the product mixture and washed with distilled water and was calcinated at 850 °C in an oven for 2 h. Finally the nanoparticles were collected by a simple magnet. A schematic diagram for synthesis of BaFe nanoparticles is shown in Fig. 1(a).

Schematic diagram for synthesis of (a) BaFe12O19 nanoparticles and (b) BaFe12O19/CuO composite nanoparticles.

2.3

2.3 Synthesis of BaFe₁₂O₁₉/CuO (70%/30%) nanocomposite

For the synthesis of BaFe₁₂O₁₉/CuO nanocomposite, 0.4 g of synthesized BaFe₁₂O₁₉ nanoparticles was dispersed in 30 ml distilled water under ultrasound for 15 min and then 0.17 g of ${CuCl}_{2} \cdot 2 H_{2} O$ was added in the solution. Slowly, 2.5 ml of $NaOH$ (1 M) was added into the aqueous solution for pH adjustment to 10 and the new solution was sonicated for 1 h. The black BaFe/CuO precipitate obtained was collected and washed with distilled water several times and calcinated at 400 °C for 2 h. Fig. 1(b) shows the schematic illustration of the preparation of BaFe₁₂O₁₉/CuO composite nanoparticles.

2.4

2.4 Preparation of cation exchange membrane

The CEMs employed in this experiment were synthesized via solution casting method as described elsewhere (Hosseini et al., 2010; Hosseini et al., 2015). In order to membranes preparation, resin particles were dried in oven at 30 °C for 48 h and then pulverized into fine particles in a ball mill and sieved to desired mesh size (−300 + 400 mesh). The membranes were prepared by dissolving the polymer binder (PVC) in THF solvent in a glass reactor equipped with a mechanical stirrer for more than 3 h. This was followed by dispersing a specific quantity of grinded resin particle as ion exchange functional groups and BaFe/CuO composite nanoparticles as filler additives in above mixture, respectively. In order to reach a better distribution of particles and the equilibrium between mechanical characteristic and electrochemical properties was employed sonication for 4 h. The mixing process was used again for 1 h via a magnetic stirrer. The composition of casting solution and chemical structures of used materials are given Tables 1 and 2 respectively. The mixture was then casted on a dry and clean glass plate and placed exposed to the ambient air to evaporate the solvent and membrane formation. Dry membranes were cut to the desired dimensions and placed in deionized water, respectively. Finally, the CEMs were treated by immersion in NaCl (0.5 M) for 48 h. The membrane thickness was measured around 95 µm by a digital caliper device (Electronic outside Micrometer, IP54 model OLR). The preparation of membranes is shown in Fig. 2.

Table 1 The composition of casting solution used in membrane preparation.

Membrane^a	BaFe/CuO nanoparticle (additive: Total solid) (w/w)
Sample 1 (S1)	0.0:100
Sample 2 (S2)	1.0:100
Sample 3 (S3)	2.0:100
Sample 4 (S4)	4.0:100
Sample 5 (S5)	8.0:100

a Polymer binder (PVC): solvent (THF)) (w/v), (1:20); ((resin particle: polymer binder) (w/w), (1:1).

2.5

2.5 Test cell

The membranes’ electrochemical properties measurements were carried out using the test cell Fig. 3). The cell consists of two cylindrical compartments made of Pyrex glass which are separated by the membrane. One side of each vessel was closed by Pt electrode supported with Teflon and the other side was equipped with membrane. The membrane area was 19.63 cm². During the experiment, both sections were recirculated and stirred vigorously to minimize the effect of boundary layers.

Schematic diagram of test cell; (1) Pt electrode, (2) Magnetic bar, (3) Stirrer, (4) Orifice, (5) Rubber ring, (6) Membrane.

2.6

2.6 Characterization of synthesized nanoparticles

The phase purity and crystalline structure of BaFe and BaFe/CuO nanoparticles were investigated by using X-ray diffractometer (model X′ Pert Pw 3373, $λ_{Cr} = 2.289$ °A, Philips, Holland). The crystalline sizes were calculated by using the Debye-Scherrer equation (Eckertova, 1986).

(1)

D = \frac{K λ}{β \cos θ}

where θ is the diffraction angle in radian, λ is the X-ray wavelength, β is the width of the observed diffraction peak at its half maximum intensity (FWHM), K is equation constant (K = 0.95). Also the Fourier transform infrared spectroscopy (FTIR) analysis was used for evaluation of synthesis nanoparticles. Moreover, scanning electron microscopy (SEM, EM-3200, model KYKY) was employed in order to evaluate the particle shape and size of BaFe and BaFe/CuO composite nanoparticles.

2.7

2.7 Membrane characterization

2.7.1

2.7.1 Morphological studies

Surface morphology and structural homogeneity/uniformity of prepared membranes were studied by scanning optical microscopy (SOM Olympus, model IX 70) and scanning electron microscopy (SEM, EM-3200, model KYKY).

2.7.2

2.7.2 Antibacterial characteristic

Antibacterial properties of prepared membranes were studied by optical density technique and by employing a single beam spectrometer within a cell including 1000 CFU/ml of E-Coli (Zarrinkhameh et al., 2014). Also, a cell was used as control unit without any membrane, which gives growth rate of E-Coli with time. During the testing, all test cells were stirred via stirrers.

2.7.3

2.7.3 Water content

Water content is expressed as the weight difference between dry and wet membrane. To calculate the water uptake of prepared membranes, firstly the membranes were immersed in deionized water for 24 h. Then the excess water of membranes was taken by filter paper and wet membranes were weighed ( $W_{wet}$ ). Membranes were placed in oven at 65 °C for 4 h and weighed again ( $W_{d ry}$ ). Finally, water content will be calculated, through following equation (Sata, 2004; Hosseini et al., 2015; Shahi et al., 2003 ).

(2)

Water content % = (\frac{W_{wet - W_{dry}}}{W_{dry}}) \times 100

2.7.4

2.7.4 Ion exchange capacity (IEC)

For measuring ion exchange capacity by the classical back titration method, operation is as follows: (1) The membranes were soaked in 1 M HCl solution; (2) Then membranes removed from the solution and to wipe of excess acid, were rinsed by distilled water and again was placed in distilled water for 24 h; (3) To release $H^{+}$ ions by ${Na}^{+}$ ions, the samples were submerged in 1 M NaCl solution; (4) Solution containing $H^{+}$ ions were titrated by 0.01 M NaOH solution and phenolphthalein as indicator to achieve the content of HCl (milli-equivalent); (5) Membranes were dried at temperature of 50 °C, until constant weight ( $W_{dry}$ ) was reached. Ion exchange capacity (IEC) is number of ion exchangeable sites (meq) per mass of dry membrane (g) and will be evaluated according to the following equation (Sata, 2004; Hosseini et al., 2015; Gohil et al., 2006 ).

(3)

IEC = (\frac{a}{W_{dry}})

2.7.5

2.7.5 Membrane potential, transport number and permselectivity

Membrane potential is algebraic sum of Donnan and diffusion potential. It can be measured directly in the test cell Fig. 3 with an electrolyte solution with different concentrations (C₁ = 0.1 M, C₂ = 0.01 M) which its procedure described elsewhere (Hosseini et al., 2010; Hosseini et al., 2015).

The transport number is also described as the fraction of total current taken by opposite ions going past, through the membrane. According to the Nernst equation, calculate the transport number of membrane ( $t_{i}^{m}$ ) is as follows (Hosseini et al., 2010; Hosseini et al., 2015; Shahi et al., 2003; Gohil et al., 2006 ):

(4)

E_{m} = (2 t_{i}^{m} - 1) (\frac{RT}{n F}) \ln (\frac{a_{1}}{a_{2}})

where

E_{m}

is membrane potential (V), n is electrovalence of counter ion, F is Faraday constant, R is the gas constant, T is temperature (K) and

a_{1}

a_{2}

are activities of electrolyte solutions which were determined by Debye-Huckel limiting law (Stumm and Morgan, 1996).

The permselectivity of IEMs is resulting, exclusion of co ions from the membrane phase. Indeed, IEM must pass the upper limit of counter ions, and prevented from passing of co ions. The permselectivity is expressed based on the migration of counter ion through the ion-exchange membrane and can be calculated form the following equation (Zarrinkhameh et al., 2014; Shahi et al., 2003; Gohil et al., 2006 ):

(5)

P_{s} = \frac{t_{i}^{m} - t_{0}}{1 - t_{0}}

where

t_{0}

is the transport number of counter ions in solution (Lide and Handbook, 2006–2007).

2.7.6

2.7.6 Concentration of fixed charge on membrane surface

Based on permselectivity of membrane is estimated the concentration of fixed charge on the membrane surface (Y, mol/l) which is given below (Hosseini et al., 2010; Hosseini et al., 2015; Shahi et al., 2003 ).

(6)

Y = \frac{2 c_{mean P_{s}}}{\sqrt{1 - P_{s}^{2}}}

Here, $C_{mean}$ (M) is the average concentration of electrolytes. The presence of more conducting areas, decreased concentration polarization phenomenon, and consequently improves the intensity of uniform electrical field around the membrane (Hosseini et al., 2010; Kang et al., 2003).

2.7.7

2.7.7 Ionic permeability and flux

The ionic permeability and flux were measured using the test cell Fig. 3. A 0.1 M solution (NaCl) was placed on one side of the cell and a 0.01 M solution on its other side. A DC electrical potential with an optimal constant voltage was applied across the cell with stable platinum electrodes. During the experiment, both sections were stirred vigorously. The cations pass through the membrane to cathodic section. Also, according to anodic and cathodic reactions, the produced hydroxide ions remain in cathodic section and increase the pH of this region. ${2 Cl}^{-} \Rightarrow {Cl}_{2} ↑ + {2 e}^{-} (Anodic reaction)$ ${2 H}_{2} O + {2 e}^{-} \Rightarrow H_{2} ↑ + {2 OH}^{-} (Cathodic reaction)$

According to Fick's law, flux of ions (N) through the membrane can be expressed as follows (Hosseini et al., 2010; Kerres et al., 1998; Berezina et al., 2008 ).

(7)

N = - P \frac{dC}{dx} = P \frac{C_{1 - C_{2}}}{d}

where P is the permeability coefficient of ions, C is the concentration of cations in the compartments and d is membrane thickness.

The boundary conditions were:

(8)

C_{1}^{0} = 0.1 M, C_{2}^{0} = 0.01 M, {C_{1} + C_{2} = C}_{1}^{0} + C_{2}^{0} = 0.11 M

(9)

N = - \frac{V}{A} \times \frac{d C_{1}}{dt} = P \frac{C_{1} - C_{2}}{d}

where A is the membrane surface area (m²), V is the volume of each compartment in the used test cell (m³) and t is the time (S). Integrating of Eq. (9) was as follows:

(10)

- \frac{V}{A} \times \frac{d (C_{1}^{0} + C_{2}^{0} - C_{2})}{dt} = P \frac{(C_{1}^{0} + C_{2}^{0} - 2 C_{2})}{d}

(11)

\int_{C_{2}^{0} = 0.01}^{C_{2}} - \frac{d (C_{1}^{0} + C_{2}^{0} - C_{2})}{(C_{1}^{0} + C_{2}^{0} - 2 C_{2})} = \int_{0}^{t} P \frac{A}{Vd} \times dt

(12)

\ln \frac{(C_{1}^{0} + C_{2}^{0} - 2 C_{2})}{(C_{1}^{0} - C_{2}^{0})} = - \frac{2 PAt}{Vd}

The cation flux was measured directly through considering pH changes in cathodic section (Digital pH-meter, Jenway, Model: 3510). The permeability coefficient (P) and the rate of ionic permeability ( $\frac{P}{d}$ ) in membrane phase are calculated from Eq. (12).

2.7.8

2.7.8 Electrical resistance

The membrane electrical resistance was measured by using of 0.5 M NaCl ionic solution and alternative current bridge as described earlier (Hosseini et al., 2015; Tanaka, 2007). An equilibrated membrane was incorporated into the cell containing of electrolyte solution and the electrical resistance (R₁) was measured with frequency of 1500 Hz (signal generator, Electronic Afzar Azma Co. P.J.S). Then, the membrane sample was taken and the apparatus integrated without membrane. The electrical resistance (R₂) was measured again. The membrane resistance is measured using the difference between the cell and solution resistances (R_m = R₁ − R₂).

Finally, membrane areal resistance is calculated as below:

(13)

r = (R_{m} A)

where

(

(Ω cm²) is areal resistance and A is the surface area of membrane (cm²).

3 Results and discussion

3.1

3.1 Characterization of BaFe and BaFe/CuO nanoparticles

X-ray analysis was performed on synthesized nanoparticles, to identify the phase type and crystal size of them. The XRD pattern of BaFe nanoparticles is shown in Fig. 4(a) which reveals a pure hexagonal phase with P63-mmc space group (JCPDS No. 70-1441). Fig. 4(b) also illustrated XRD pattern of BaFe/CuO nanocomposite. It can be observed hexagonal phase of BaFe (JCPDS No. 70-1441, space group: P63-mmc) and cubic phase of CuO (JCPDS No. 78-0428, space group, Fm-3m) in the pattern. The calculated crystalline size by Scherrer’s equation was about 54.9 and 43.2 nm for BaFe and BaFe/CuO, respectively which may be due to twice calcinations for the BaFe/CuO composite nanoparticles.

XRD pattern of (a) BaFe12O19 nanoparticles and (b) BaFe12O19/CuO composite nanoparticles.

The FT-IR spectrum of the BaFe nanoparticles is shown in Fig. 5(a). Results indicated two absorption bands at 435 and 590 cm⁻¹ related to $Fe - O$ and $Ba - O$ (metal–oxygen) bonds. In Fig. 5(b), the FT-IR spectrum of BaFe/CuO nanocomposite clearly shows strong absorption band at 435 and 592 cm⁻¹ which relevant to phonon absorptions of the BaFe/CuO lattice.

FT-IR spectrum of (a) BaFe12O19 nanoparticles and (b) BaFe12O19/CuO nanoparticles.

The particle size and shape of nanoparticle powders were characterized by SEM. The image of BaFe and BaFe/CuO nanoparticles are illustrated in Fig. 6(a) and (b), respectively. The results confirm that BaFe and BaFe/CuO nanoparticles formed with average diameter size of 51.5 and 48.5 nm, respectively.

SEM images of (a) BaFe12O19 nanoparticles and (b) BaFe12O19/CuO nanoparticles.

3.2

3.2 Characterization of nanocomposite membranes

3.2.1

3.2.1 Morphological study

The structural homogeneity or uniformity of prepared membranes was studied by SOM. As shown in Fig. 7, the polymer binder and resin particles are clearly visible in the images. Images exhibit relatively uniform surface and also uniform distribution of particles in prepared membranes. It reveals that sonication was a critical step in the fabrication of membranes to reach uniform distribution of particles (Hosseini et al., 2010). Existence of more conducting regions in membrane surface strengthens the electrical field which leads to reduction of polarization phenomena (Hosseini et al., 2015; Kang et al., 2003). The SOM images indicate that the amount and size of dark spots are increased by increase of nanoparticles loading ratios which is due to tendency of particles to agglomeration at high concentration. Additionally, the SEM images of the fabricated nanocomposite membranes Fig. 8) confirm uniform dispersion of BaFe/CuO nanoparticles in the membrane matrix.

SOM images of prepared membranes with various ratios of BaFe12O19/CuO composite nanoparticles; (a) pristine membrane; (b) 1.0 wt%, (c) 2.0 wt%, (d) 4.0 wt%, (e) 8.0 wt%. (bright region: polymer binder, dark spot: resin/nanoparticles).

Surface SEM image of prepared nanocomposite membranes filled with BaFe12O19/CuO nanoparticles.

3.2.2

3.2.2 Antibacterial properties

The Escherichia-coli bacteria were applied as the target bacterium to investigate the antibacterial effects of the fabricated membranes. For this purpose three separate cells were prepared, which a cell was used as control unit and gives the growth rate of E-Coli. One of two other cells contains membrane without nanoparticles, and another has a membrane containing nanoparticles. Fig. 9 indicates the change of optical density with time in all cells. Results showed good ability to removal of Escherichia coli for the prepared membranes. This is assigned to chloride of polymer binder and copper oxide in used additives which attached to cell surface receptor and bacteria DNA and disturb the cell proliferation (Cioffi et al., 2005; Chang et al., 2012; Ojas et al., 2008 ).

Variation of optical density (O.D) with time in the cell containing of Escherichia coli (membrane ability in E-coli removal).

3.2.3

3.2.3 Water content

Water content is a fundamental parameter in describing the function of IEMs and has a considerable influence on the function of membrane separation, mechanical strength and dimensional stability of the polymeric chains. Moreover, the attendance of water molecules inside of membrane structure is too momentous for transfer of ions (Wang et al., 2013; Chakrabarty et al., 2012). Fig. 10 represents the water content of the prepared membranes. The findings indicate that with increasing content ratios of BaFe/CuO nanocomposite up 1 wt% in the membrane structure, the water content was sharply increased. This may be because of increase of membrane heterogeneity by use of additive particles which tends to voids formation/gap between the inorganic and organic (polymer chains) phases and so provides more spaces for water molecules embedding. With more adding nanoparticles from 1 to 8 wt% water content of membranes slowly decreased. This may be attributed to pores filling phenomenon at high filler concentration which provides a compact structure for the membranes and so restricts the water accommodation. The suitable amount of membrane water content has better control on the pathways of ion transport and improves the membrane permselectivity. Based on the Donnan theory, high percentage of water content by providing more and wider transfer channels, facilitates the co and counter ions transport through the membrane and decreases the ion selectivity (Geise et al., 2014).

The effect of BaFe12O19/CuO nanoparticles loading ratios (wt%) on water content and ion exchange capacity of prepared heterogeneous cation exchange membranes.

3.2.4

3.2.4 Ion exchange capacity (IEC)

Ion exchange capacity is other vital parameters of IEMs that depend on extant functional groups in the membrane matrices. This parameter plays important role in transport number, selectivity and ionic conductivity of membranes (Zhang et al., 2013). It was found that, IEC Fig. 10 sharply was improved by incorporation the BaFe/CuO composite nanoparticles up to 2 wt%. This may be assigned to adsorptive characteristic of composite nanoparticles. The surface sites binding, electrostatic interaction and ligand combination are main factors for this adsorptive behavior. This characteristic acts as a driving force for cations' transportation from solution into membrane matrix which can improve the ion exchange possibilities. Moreover, negative charge of nanoparticles (Tang et al., 2006) increases the electrostatic interactions between the used nanoparticles and cations which improves the probability of ${Na}^{+}$ ions transportation toward the membrane and consequently leads to enhancement in IEC. The membrane IEC showed a decreasing trend by more increase of composite nanoparticles concentration from 2 to 8 %wt. This happening can be explained with respect to occupied ionic channels by the composites nanoparticles which surround the resin particles and decreases the accessibility of ion exchange functional group by their isolation.

3.2.5

3.2.5 Transport number, membrane potential, charge density and permselectivity

The results Figs. 11 and 12) indicated that membrane potential, transport number and permselectivity were enhanced initially by growing the additive concentration up to 2 wt%. This is attributed to increase of membrane surface charge density and IEC which improve the exclusion of co ions. Moreover, narrowing the transfer channels by the used additives leads to a better control for ionic sites on the passage of ions which improves the membrane selectivity. The increase of Donnan exclusion is responsible for enhancement in membrane potential, transport number and permselectivity (Zarrinkhameh et al., 2014; Shahi et al., 2003; Gohil et al., 2006 ). By increase of BaFe/CuO nanoparticles loading ratios, selectivity, transport number and membrane potential showed a decreasing trend. This is due to accumulation of nanoparticles at high concentration which decreases the membrane charge density/IEC and so makes facile the co ions percolation through the membrane matrix. In addition, increase of structural heterogeneity at high additive ratios propagated the cracks in membrane body which declines the ionic site dominations on ions transport.

The effect of BaFe12O19/CuO concentration on membrane potential (E) and surface charge density (Y) of prepared membranes.

Permselectivity and transport number of nanocomposite membranes at various BaFe12O19/CuO concentration (wt%).

3.2.6

3.2.6 Ionic permeability and flux

Fig. 13 shows that increasing the concentration of barium ferrite/copper oxide composite nanoparticles up 2 wt% in the membrane body leads to increase of ionic flux and permeability. Generally, this phenomenon has three main reasons: (1) increase of the membrane IEC and water content lead to creating suitable ionic pathways in membrane matrices; (2) adsorption feature of used nanoparticles increases the interaction between ${Na}^{+}$ ions and membrane surface (3) increase of membrane heterogeneity by incorporating of additive nanoparticles propagates the cracks in membrane matrix and makes facile the ions transportation through them. Moreover, change of fixed-charge distribution inside the membrane matrix due to variation in membrane heterogeneity affects on ions transport (Moya and Moleón, 2010; Moleón and Moya, 2008). The permeability and flux of ions were decreased again by more increase of nanocomposite concentration from 2 to 8 wt%. This may be due agglomeration of nanoparticles at high concentration which decreases the membrane charge density. Also occupation of transfer channels by the additive particles makes narrow the ionic pathways and restricts the ions transport. The current density for unmodified membrane and the modified ones (S3) during the process was also measured (16.5–19.6) mA and (17.2–20.5) mA respectively. Results showed higher current density for the modified membrane which is directly related with the energy consumption in the process.

Ionic permeability and flux of ions for the prepared membranes at various blend ratios of BaFe12O19/CuO composite nanoparticles.

3.2.7

3.2.7 Electrical resistance

The amount of energy consumed in the process of electrodialysis, has direct relation with electrical resistance of IEMs. According to the association among energy consumption and operating costs, membranes with less resistance are chosen for employed in electrodialysis. The electrical resistance of pristine sample ( $S_{1}$ ), superior sample ( $S_{2}$ ) and sample 3 ( $S_{3}$ ) was evaluated by a 0.5 M NaCl solution. Results Fig. 14 indicate lower electrical resistance for the modified membranes containing of barium ferrite/copper oxide nanocomposite compared to pristine ones obviously. This can be explained with respect to higher IEC and water content for the modified membranes. In addition, adsorption characteristic of used additives increase the intensity of electric field around the membrane and improves ions interaction with membrane surface. The growth of conductivity is also due to the elevated concentration of counter ions in the nanoparticles electrical double layer (Porozhnyy et al., 2016). In order to minimize the experimental errors and investigate the stability of prepared membranes, all measurements were carried out three times for each samples and the average reported. Tables 3 and 4 compare the electrochemical properties of prepared membranes in this study with some commercial membranes and current state-of-the-art membranes. The obtained results show that the modified membrane (S3) containing of 2 wt% nanoparticles with ∼99% selectivity and ∼5 (Ω cm²) areal electrical resistance is comparable with other reported ones. Also modified membrane demonstrated good ability to removal of E-coli bacteria.

The areal electrical resistance of prepared membranes with various ratios of BaFe12O19/CuO composite nanoparticles.

Table 3 Comparison between the selectivity and areal electrical resistance of fabricated membranes in this study and some commercial membranes (Nagarale et al., 2006; Dlugolecki et al., 2008; Xu, 2005 ).

Membrane	Permselectivity^a (%)	Electrical resistance^b (Ω cm²)
Un-modified membrane (S1) (HCEM)^c	>92	<24
Modified membrane (S3) (HCEM)	>99	<5
Ralex® CMH-PES (HCEM)	>92	<10.0
Ionics Inc., USA, CR61-CMP (HCEM)	–	11
CSMCRI, India (HCEM)	87	4.0–6.0
Ionics Inc., USA (61CZL386) (HCEM)	–	9
RAI Research Corp., USA R-5010-H	95	8–12
Tokuyama Soda Co. Ltd. Japan (Neosepta CMX)	97	1.8–3.8
FuMA-Tech GmbH, Germany FKB	–	5–10
Fumasep® FKD	>95	<3

a (Measured in 0.1/ 0.01 M NaCl solution).

b (Measured in 0.5 M NaCl solution).

c (Heterogeneous cation exchange membrane).

Table 4 Comparison of the performance characteristics of modified ion exchange membrane in this paper with that of the some earlier reported studies (Hosseini et al., 2017; Hosseini et al., 2014; Hosseini et al., 2012; Nemati et al., 2017; Hosseini et al., 2014; Nemati and Hosseini, 2016 ).

Membrane	Permselectivity (%)	Electrical resistance (Ω cm²)
Modified membrane (S3)	>99	<5
HCEM (4.0 wt% - GONs) (Hosseini et al., 2017)	>89	6.5–7
HCEM (2.0 wt% - Zeolite NPs) (Hosseini et al., 2014)	>88	6–7
HCEM (0.5 wt% - Fe₂NiO₄ NPs) (Hosseini et al., 2012)	81	<9.5
HCEM (2.0 wt% - AMAH) (Nemati et al., 2017)	>95	14–15
HCEM (8.0 wt% - Al₂O₃ NPs) (Hosseini et al., 2014)	>80	6–7
HCEM (0.5 wt% - Fe₃O₄/PAA NPs) (Nemati and Hosseini, 2016)	>84	11–12

4 Conclusion

In this research, the effect of synthesized BaFe₁₂O₁₉/CuO composite nanoparticles on morphological, physico-chemical and antibacterial characteristics of CEM was studied. The synthesized BaFe₁₂O₁₉/CuO composite nanoparticles were characterized by SEM, FTIR and XRD. Results showed relatively uniform particle distribution for the synthesized BaFe₁₂O₁₉/CuO composite nanoparticles. SOM and SEM images indicated that produced membranes have relatively uniform dispersion of resin particles and additive fillers in a polymeric matrix. The membrane water uptake was also enhanced in presence of BaFe₁₂O₁₉/CuO composite nanoparticles. The results indicated that by incorporating of nanoparticles in polymeric structure up to 2 wt%, membrane IEC, membrane potential, selectivity and transport number, flux of ions and permeability were enhanced sharply and then showed decreasing trend by more BaFe₁₂O₁₉/CuO content ratios from 2 to 8 wt%. Furthermore, modified samples exhibited lower electrical resistance in comparison with virgin membrane. The results clearly exhibited that modified membrane containing of 2 wt% BaFe₁₂O₁₉/CuO nanoparticles illustrated superior specifications compared to other prepared membranes. The modified membranes comprising BaFe₁₂O₁₉/CuO nanoparticles showed good antibacterial activity to decline of E-coli growth rate.

Acknowledgment

The authors gratefully acknowledge Arak University for the financial support during this research.

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Introduction

Materials and methods

Materials
Synthesis of BaFe12O19 nanoparticles
Synthesis of BaFe12O19/CuO (70%/30%) nanocomposite
Preparation of cation exchange membrane
Test cell
Characterization of synthesized nanoparticles
Membrane characterization

Results and discussion

Characterization of BaFe and BaFe/CuO nanoparticles
Characterization of nanocomposite membranes

Conclusion

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[1] Ahmadi Golsefidi M., Abbasi F., Abrodi M., Abbasi Z., Yazarlou F., . Synthesis, characterization and photocatalytic activity of Fe2O3-TiO2 nanoparticles and nanocomposites. J. Nanostruct.. 2016;6(1):64-69.
[Google Scholar]

[2] Akhavan O., Ghaderi E., Akhavan O., Ghaderi E., . Cu and CuO nanoparticles immobilized by silica thin films as antibacterial materials and photo catalysts. Surf. Coat. Technol.. 2010;205:219-223.
[Google Scholar]

[3] Aryafard E., Farsi M., Rahimpour M.R., Raeissi S., . Modeling electrostatic separation for dehydration and desalination of crude oil in an industrial two-stage desalting plant. J. Taiwan Inst. Chem. Eng.. 2016;58:141-147.
[Google Scholar]

[4] Baghbanzadeh M., Rana D., Matsuura T., Lan C.Q., . Effects of hydrophilic CuO nanoparticles on properties and performance of PVDF VMD membranes. Desalination. 2015;369:75-84.
[Google Scholar]

[5] Banasiak L.J., Van der Bruggen B., Schafer A.I., . Sorption of pesticide endosulfan by electrodialysis membranes. Chem. Eng. J.. 2011;166:233-239.
[Google Scholar]

[6] Berezina N.P., Kononenko N.A., Dyomina O.A., Gnusin N.P., . Characterization of ion-exchange membrane materials: Properties vs structure. Adv. Colloid Interface Sci.. 2008;139:3-28.
[Google Scholar]

[7] Bu I.Y.Y., Huang R., . Fabrication of CuO-decorated reduced graphene oxide nano sheets for super capacitor applications. Ceram. Int.. 2017;43(1):45-50.
[Google Scholar]

[8] BurakKaynar M., Özcan S., IsmatShah S., . Synthesis and magnetic properties of nanocrystalline BaFe12O19. Ceram. Int.. 2015;l41:11257-11263.
[Google Scholar]

[9] Chakrabarty T., Singh A.K., Shahi V.K., . Zwitterionic silica copolymer based crosslinked organic-inorganic hybrid polymer electrolyte membranes for fuel cell applications. RSC Adv.. 2012;2:1949-1961.
[Google Scholar]

[10] Chang Y., Zhang M., Xia L., Zhang J., Xing G., . The Toxic Effects and Mechanisms of CuO and ZnO Nanoparticles. Materials. 2012;5:2850-3287.
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[11] Chen X., Mao S., . Titanium dioxide nanomaterials: synthesis, properties, modifications, and applications. Chem. Rev.. 2007;107:2891-2959.
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[12] Cioffi N., Torsi L., Ditaranto N., Tantillo G., Ghibelli L., Sabbatini L., . Copper nanoparticle/polymer composites with antifungal and bacteriostatic properties. Chem. Mater.. 2005;17:5255-5262.
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[13] Cioffi N., Torsi L., Ditaranto N., Tantillo G., Ghibelli L., Sabbatini L., . Copper nanoparticle/polymer composites with antifungal and bacteriostatic properties. Chem. Mater.. 2005;17:5255-5262.
[Google Scholar]

[14] Dlugolecki P., Nymeijer K., Metz S., Wessling M., . Current status of ion exchange membranes for power generation from salinity gradients. J. Membr. Sci.. 2008;319:214-222.
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[15] Eckertova L., . Physics of Thin Films (second ed.). Plenum Press; 1986.

[16] Geise G.M., Paul D.R., Freeman B.D., . Fundamental water and salt transport properties of polymeric materials. Prog. Polym. Sci.. 2014;39:1-42.
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[17] Gohil G.S., Binsu V.V., Shahi V.K., . Preparation and characterization of mono-valent ion selective polypyrrole composite ion-exchange membranes. J. Membr. Sci.. 2006;280:210-218.
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[18] Guan X., Li L., Li G., Fu Z., Zheng J., Yan T., . Hierarchical CuO hollow microspheres: controlled synthesis for enhanced lithium storage performance. J. Alloy. Compd.. 2011;509:3367-3374.
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[19] Gupta V.K., Chandra R., Tyagi I., Verma M., . Removal of hexavalent chromium ions using CuO nanoparticles for water purification applications. J. Colloid Interface Sci.. 2016;478:54-62.
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[20] Heydari F., Nemati Kharat A., Khodabakhshi A.R., . Preparation, characterization and transport properties of novel cation-exchange nanocomposite membrane containing BaFe12O19 nanoparticles. J. Cluster Sci.. 2016;27(1):193-211.
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[21] Hosseini S.M., Madaeni S.S., Khodabakhshi A.R., . Preparation and characterization of PC/SBR heterogeneous cation exchange membrane filled with carbon nano-tubes. J. Membr. Sci.. 2010;362:550-559.
[Google Scholar]

[22] Hosseini S.M., Madaeni S.S., Heidari A.R., Amirimehr A., . Preparation and characterization of ion-selective polyvinyl chloride based heterogeneous cation exchange membrane modified by magnetic iron-nickel oxide nanoparticles. Desalination. 2012;284:191-199.
[Google Scholar]

[23] Hosseini S.M., Rafiei S., Hamidi A.R., Moghadassi A.R., Madaeni S.S., . Preparation and electrochemical characterization of mixed matrix heterogeneous cation exchange membranes filled with zeolite nanoparticles: ionic transsport property in desalination. Desalination. 2014;351:138-144.
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[24] Hosseini S.M., Gholami A., Koranian P., Nemati M., Madaeni S.S., Moghadassi A.R., . Electrochemical characterization of mixed matrix heterogeneous cation exchange membrane modified by aluminum oxide nanoparticles: mono/bivalent ionic transportaion. J. Taiwan instit. Chem. Eng.. 2014;45:1241-1248.
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[25] Hosseini S.M., Hamidi A.R., Moghadassi A.R., Koranian P., Madaeni S.S., . Fabrication of novel mixed matrix electrodialysis heterogeneous ion-exchange membranes modified by ilmenite (FeTiO3): electrochemical and ionic transport characteristics. Ionics. 2015;21:437-447.
[Google Scholar]

[26] Hosseini S.M., Jashni E., Habibi M., Nemati M., Van der Bruggen B., . Evaluating the ion transport characteristics of novel graphene oxide nanoplates entrapped mixed matrix cation exchange membranes in water deionization. J. Membr. Sci.. 2017;541:641-652.
[Google Scholar]

[27] Kang M.S., Choi Y.J., Choi I.J., Yoon T.H., Moon S.H., . Electrochemical characterization of sulfonated poly (arylene ether sulphone) (S-PES) cation-exchange membranes. J. Membr. Sci.. 2003;216:39-53.
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[28] Karimi F., Ashrafizadeh S.N., Mohammadi F., . Process parameter impacts on adiponitrile current efficiency and cell voltage of an electromembrane reactor using emulsion-type catholyte. Chem. Eng. J.. 2012;183:402-407.
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[33] Lide D.R., . CRC Handbook of Chemistry and Physics (87th edition). CRC press; 2006–2007.

[34] Logan B.E., Elimelech M., . Membrane-based processes for sustainable power generation using water. Nature. 2012;488:313-319.
[Google Scholar]

[35] Lupan O., Postica V., Ababii N., Hoppe M., Cretu V., Tiginyanu I., . Influence of CuO nanostructures morphology on hydrogen gas sensing performances. Microelectron. Eng.. 2016;164:63-70.
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Material	Chemical structure
Polyvinylchloride (PVC)
Cation exchange resin
Tetrahydrofuran (THF)
Barium ferrite (BaFe₁₂O₁₉) (Shepherd et al., 2007)
Cupper oxide (Zoolfakar et al., 2014)

Fabrication of new type of barium ferrite/copper oxide composite nanoparticles blended polyvinylchloride based heterogeneous ion exchange membrane

Abstract

Keywords

Cation exchange membrane

BaFe12O19/CuO nanoparticles

Chemical precipitation

Electrochemical properties

Antibacterial characteristic

1 Introduction

2 Materials and methods

2.1 Materials

2.2 Synthesis of BaFe12O19 nanoparticles

2.3 Synthesis of BaFe12O19/CuO (70%/30%) nanocomposite

2.4 Preparation of cation exchange membrane

2.5 Test cell

2.6 Characterization of synthesized nanoparticles

2.7 Membrane characterization

2.7.1 Morphological studies

2.7.2 Antibacterial characteristic

2.7.3 Water content

2.7.4 Ion exchange capacity (IEC)

2.7.5 Membrane potential, transport number and permselectivity

2.7.6 Concentration of fixed charge on membrane surface

2.7.7 Ionic permeability and flux

2.7.8 Electrical resistance

3 Results and discussion

3.1 Characterization of BaFe and BaFe/CuO nanoparticles

3.2 Characterization of nanocomposite membranes

3.2.1 Morphological study

3.2.2 Antibacterial properties

3.2.3 Water content

3.2.4 Ion exchange capacity (IEC)

3.2.5 Transport number, membrane potential, charge density and permselectivity

3.2.6 Ionic permeability and flux

3.2.7 Electrical resistance

4 Conclusion

Acknowledgment

References

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