Applied Surface Science 255 (2008) 21252128

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Surface treatment of CoFe2O4 nanoparticles to improve their dispersibility in aqueous phase with new uorine-contain polymers
Zhaobin Tang, Peng Liu, Jinshan Guo *, Zhixing Su *, Chao Yang
Institute of polymer Science and Engineering, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, Gansu 730000, PR China

A R T I C L E I N F O

A B S T R A C T

Article history: Received 1 May 2008 Received in revised form 30 June 2008 Accepted 30 June 2008 Available online 9 July 2008 Keywords: Magnetite CoFe2O4 nanoparticles Surface treatment Zeta potential

Magnetite CoFe2O4 nanoparticles were modied by a new series of uorine-containing polymeric dispersants. The Fourier transform infrared spectroscopy (FTIR) and element analysis showed that the polymer chains have been successfully adsorbed onto the surfaces of the CoFe2O4 nanoparticles. The inuence of the content of uoroalkyl groups on the surface tension and the dispersing properties were also investigated and the results showed that the modied CoFe2O4 nanoparticles exhibit excellent surface active properties and the nanoparticles can be dispersed very well in the aqueous phase. Zeta potential and the average diameter of the nanoparticles can reach to 68 mV and 42 nm with the increasing of the content of uoroalkyl groups of the polymeric dispersant, respectively. 2008 Elsevier B.V. All rights reserved.

1. Introduction Recently, polymeric dispersants attract more and more attention in the coatings, ceramics, nanoparticles and other industrial elds because of their versatility, low cost and technological advantages [15]. In all these applications, surface modication of the nanoparticles is strongly desired to improve their dispersibilities in polymer matrices and to tailor the interface interaction. The surfaces grafting of inorganic particles with polymers have been widely investigated to improve surface properties of inorganic particles. In the past reports, there are different approaches to graft the polymers onto the inorganic particles to improve their surface properties [68]. In aqueous phases, the charged polyelectrolytes are used as dispersants to enhance suspension stability and to impede particle occulation, thus leading to both high solid loadings and low viscosities. The adsorption technique is also used to improve dispersibility of the inorganic powders. The adsorption of polyelectrolytes onto the surfaces of the powder results in the formation of a double electrostatic layer that surrounds each particle and leads to the electrostatic repulsive forces between the particles [910]. Fluorinated surfactants containing a uoroalkyl chain have a number of special properties such as chemical and biological inertness, thermal stability, etc. [11]. Partially uorinated surfactants are now also attracting increasing interest. Oda et al. reported

that the combination of characteristics with the high hydrophobicity of the uoroalkyl groups led to very low surface tension and rendered the excellent dispersibility in water [1214]. In this paper, we describe that surface treatment of CoFe2O4 nanoparticles to improve their dispersibility in aqueous phases by a new uorine-contain polymeric dispersant. The dispersant was characterized by FT-IR, EA, TEM, and the surface tension, zetapotential and dispersing characteristics of the modied CoFe2O4 nanoparticles were also discussed. 2. Materials and methods 2.1. Materials The monomers of hexauorobutyl acrylate (FBA) and dodecauoroheptyl methacrylate (MFHA) were purchased from XEOGIA Fluorine-Silicon Chemical Co. Ltd. (Harbin, China) and used without any treatment. The other chemicals were purchased from Tianjin Chemicals Co. Ltd. (Tianjin, China) as reagent grade and used without further purication including methyl methacrylate (MMA), acrylic acid (AA), sodium hydroxide (NaOH), azodiisobutyronitrile (AIBN) and isopropanol. 2.2. Preparation of the CoFe2O4 nanoparticles The CoFe2O4 nanoparticles were prepared according to reference [15]. 70 ml deionizated water was charged into a bottom round ask. It was deoxygenated by bubbling N2 gas for 30 min. Then 10 ml CoCl2 (0.1 M) and 20 ml FeCl3 (0.1 M) aqueous

* Corresponding authors. E-mail addresses: gjs@lzu.edu.cn (J. Guo), suzx@lzu.edu.cn (Z. Su). 0169-4332/$ see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.apsusc.2008.06.196

2126 Table 1 Recipes of uorine-containing polymer dispersant Sample FBA/g BA/g MMA/g MFHA/g

Z. Tang et al. / Applied Surface Science 255 (2008) 21252128

AA/g

AIBN/g

Fluorine content (%) 2.42 4.83 18.47 27.29 36.10

1 2 3 4 5

2 4 8 8 8

6 4 0 0 0

18 18 12 6 0

0 0 6 12 18

14 14 14 14 14

1.2 1.2 1.2 1.2 1.2

solutions were added. The solution was heated at 80 8C for 1 h while being stirred. Afterwards, 5 ml NH4OH (25%, w/w) solution was added rapidly to it under vigorous stir and a black precipitate appeared immediately. The resulting suspension is vigorously stirred for another 1 h and then cooled to the room temperature. The precipitated particles are washed ve times with water and alcohol, respectively. 2.3. Preparation of the uorine-containing polymeric dispersants The dispersants were prepared by radical copolymerization of hexauorobutyl acrylate, dodecauoroheptyl methacrylate, methyl methacrylate and acrylic acid. Detailed recipes were given in Table 1. The copolymerization was carried out in 36 g isopropanol in the presence of azodiisobutyronitrile as initiator for 1.5 h at 80 8C. Then the mixture was reuxed for another 1.5 h. Finally, the pH value of the mixture was adjusted to 88.5 by adding sodium hydroxide solution. 2.4. Surface modication of the CoFe2O4 nanoparticles Experiments concerning the surface modication of the CoFe2O4 nanoparticles were performed by adding given amounts of the copolymer solution. Then suspensions containing the nanoparticles and dispersants were irradiated ultrasonically for 15 min under an output power of 200 W and shaken for 24 h to reach equilibrium. Then the nanoparticles were separated by being centrifuged at 3000 rpm for 30 min. 2.5. Measurement and analysis Bruker IFS 66 V/s infrared spectrometer was used for the Fourier transform infrared (FTIR) analysis. Elemental analysis (EA) of carbon and hydrogen was performed with an Elementar vario EL instrument. Surface tension was determined at room temperature with a Japan Kaimenkaguka CBVP-A3 surface tensiometer. The particle size of the nanoparticles was determined by light scattering method with MALVERN 4700 using a suspension containing 20 mg nanoparticles and 50 mg dispersant in 100 ml water. The zeta potential measurements were made on a Colloidal Dynamics Acoustosizer where ionic strength adjustments were made using sodium chloride as necessary. The dispersing property of the nanoparticles in aqueous suspensions was performed on H600 transmission electron microscope (TEM). The CoFe2O4 nanoparticles was dispersed in aqueous system phase in an ultrasonic bath for 15 min, and then deposited on a copper grid covered with a perforated carbon lm. 3. Results and discussion 3.1. FTIR analysis In the IR spectra of the uorine-containing polymeric dispersant (Fig. 1a), the absorbance peak around 3430 cm1 was attributed to stretching vibration of OH. The absorbance peaks around 2937 cm1 and 2850 cm1 were attributed to the asymmetric and symmetric stretching vibration of CH, respectively. The absorbance peaks around 1744 cm1 was attributed to vibration of C O. The absorbance peaks around 1577 cm1 was attributed to the stretching vibration of COO. The absorbance peaks around 1109 cm1 was attributed to the stretching vibration of CF [16]. The absorbance peak around 1247 cm1 was attributed to the stretching vibration of COC. These bands were the characteristics of the desired compounds. Fig. 1b and c are the FT-IR spectra of the blank CoFe2O4 nanoparticles and the modied CoFe2O4 nanoparticles, respectively. The absorbance peaks at 2931 cm1 and 1632 cm1 of the CH stretching vibration and C O stretching mode appeared in the FTIR spectrum of the modied nanoparticles (Fig. 1c), respectively. 3.2. Adsorption At pH 8.5, the uoroalkyl groups of uorine-containing polymeric dispersants were adsorbed onto the surfaces of the CoFe2O4 nanoparticle which led to the repulsion among the CoFe2O4 nanoparticles. For the ve synthesized copolymers, the adsorbed amount onto the surfaces of the CoFe2O4 nanoparticles increased with the increasing of the uoroalkyl groups in the

Fig. 1. FTIR spectra of (a) uorine-containing polymer dispersant, (b) nano-CoFe2O4 nanoparticles and (c) nano-CoFe2O4/polymer nanoparticles.

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Fig. 4. Zeta potential versus different uorine content of dispersants onto the surface of nano-CoFe2O4 nanoparticles. Fig. 2. Adsorption isotherms of the uorine-containing polymer dispersants onto CoFe2O4 nanoparticles.

polymeric dispersants (Fig. 2). It suggests an increase in the proportion of the uoroalkyl groups resulted in an increase of the adsorbed amount onto the surfaces of the CoFe2O4 nanoparticles. Such an observation indicates a rather high afnity type adsorption between the uorine-containing polymer dispersants and the CoFe2O4 nanoparticles. The lower of molecular surface energy can more easily be adsorbed by the high surface energy molecule to reduce superuous surface energy. So the adsorption of the uorine-containing polymer dispersants on the surfaces of the CoFe2O4 nanoparticles increases with the increased ratio of uoroalkyl groups in different polymer. This allows a denser packing of the macromolecular chains on the CoFe2O4 nanoparticles surfaces and an expected formation of loops in the adsorbed conguration as the fraction of uoroalkyl units increases. 3.3. Surface tension As shown in Fig. 3, the surface tension decreased in the aqueous solution with the increasing of the ratio of the uoroalkyl group in the different polymeric dispersants. It was attributed to the fact that the surface energy values of the uorinated polymers were

Fig. 3. Plots of surface tension against concentration of uorine-containing polymer dispersants: (a)(e): sample 1sample 5.

Fig. 5. Inuence of dispersed nano-CoFe2O4 nanoparticles examined by the TEM: (a) synthesized nano-CoFe2O4 nanoparticles (b) dispersed nano-CoFe2O4 nanoparticles by sample 5.

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Fig. 6 shows the correlation between the particle size and the proportion of the uoroalkyl groups in aqueous suspensions. Compared to the particle size of the raw CoFe2O4 nanoparticles, there was an obvious decrease in the particle size when an increase of the uoroalkyl groups which possibly due to the reason that the agglomeration state of particles was broken with the increase of the amount adsorbed onto the CoFe2O4 nanoparticles surface. 4. Conclusion A novel series of the uorine-containing polymeric dispersants with water-soluble properties were prepared by the copolymerization of hexauorobutyl acrylate, dodecauoroheptyl methacrylate, methyl methacrylate and acrylic acid. These novel polymeric dispersants exhibited good dispersing stability and surface activities including surface tension. They could prevent the reaggregation of the CoFe2O4 nanoparticles dispersed in aqueous suspensions. The decrease of the surface tension in the aqueous solution was observed when the concentration of uoroalkyl group in the solution was increased. References
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Fig. 6. Average diameter of disperse nano-CoFe2O4 nanoparticles versus different uorine content of dispersants.

considerably lower than those of the other polymers [17]. However, an abrupt inection in the curves, which corresponds to the critical micelle concentration in the case of traditional surfactants, was not observed. This might due to the presence of monomolecular micelles. 3.4. Zeta potential analysis The effect of dispersant on the dispersibility of the CoFe2O4 nanoparticles were investigated by measuring the zeta potential of the suspension. Zeta potential values of the uorine-containing polymeric dispersants as a function of the potential and the uoroalkyl group proportion are shown in Fig. 4. In general, the dispersibility of the CoFe2O4 nanoparticles in suspensions can be improved when the absolute value of the zeta potential is increased in the present of the dispersants. Due to the same ratio -COO in these anionic uorine-containing polymers, the absolute value of the zeta potential is increased with the increasing of the ratio of the uoroalkyl group in different polymers. The higher the charge density on surface of powders and the larger the repulsion among particles, the higher the absolute value of the zeta potential was achieved. 3.5. Effect of the dispersiant on the dispersibility of the nanoparticles Fig. 5a and b showed the morphologies of the nanoparticles before and after the surface treatment. Due to the serious aggregation resulting from the high-specic surface area, the raw CoFe2O4 nanoparticles aggregated severely. When the nanoparticles were treated by the synthesized dispersant, they could be well dispersed in the water and showed much better dispersibility. It demonstrated that after the surface of CoFe2O4 nanoparticles was treated by the synthesized dispersant, the aggregation of CoFe2O4 nanoparticles was greatly reduced, which would benet the subsequent composites manufacturing. The uorine-containing polymeric dispersants prepared in this study exhibited excellent dispersibility and prevented the reaggregation of the CoFe2O4 nanoparticles in aqueous suspensions.