Journal of Colloid and Interface Science 277 (2004) 100103 www.elsevier.

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A novel one-step chemical method for preparation of copper nanouids

Hai-tao Zhu a,b, , Yu-sheng Lin b , Yan-sheng Yin a,
a Key Laboratory of Engineering Ceramics, Shandong University, Jinan 250061, Peoples Republic of China b Institute of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, Peoples Republic of China

Received 16 October 2003; accepted 16 April 2004

Abstract This paper presents a novel one-step method for preparing of copper nanouids by reducing CuSO4 5H2 O with NaH2 PO2 H2 O in ethylene glycol under microwave irradiation. Nonagglomerated and stably suspended Cu nanouids are obtained. The inuences of CuSO4 concentration, addition of NaH2 PO2 , and microwave irradiation on the reaction rate and the properties of Cu nanouids were investigated by transmission electron microscopy, infrared analysis, and sedimentation measurements. It is found to be a fast, efcient one-step chemical method to prepare Cu nanouids. 2004 Elsevier Inc. All rights reserved.
Keywords: Copper; Nanouids; Nanoparticles; One-step chemical method; Microwave irradiation

1. Introduction There is a strong need in many industrial elds to develop heat transfer uids with signicantly high thermal conductivity. It is well known that crystalline solids have higher thermal conductivities than traditional uids (such as water, ethylene glycol, and oil) by 13 orders of magnitude. Therefore, uids containing suspended solid particles can be reasonably expected to have higher thermal conductivities than pure uids. Nanouids [1] consisting of metallic or nonmetallic nanoparticles have attracted research attention. Several groups have obtained nanouids containing a small amount of Cu [2], Al2 O3 [3], CuO [3], or SiC [4] nanoparticles or nanotubes (CNTs) [5]. It has been found that the thermal conductivity of a nanouid consisting of ethylene glycol and only 0.3 vol% Cu nanoparticles increased by up to 40% over that of pure ethylene glycol [6]. At present, Cu nanouids are prepared by dispersing Cu nanoparticles into base liquids [2]. This is a step-by-step method that isolates the preparation of the nanouid from the preparation of Cu nanoparticles. As a result, agglomeration of nanoparticles may take place in both steps, especially in
* Corresponding authors. Fax: +86-531-839-2439.

E-mail addresses: zhuihaitao9211@sina.com (H.-t. Zhu), yin_yansheng@yahoo.com.cn (Y.-s. Yin). 0021-9797/$ see front matter 2004 Elsevier Inc. All rights reserved. doi:10.1016/j.jcis.2004.04.026

the process of drying, storage, and transportation of nanoparticles. The agglomeration will not only result in the settlement and clogging of microchannels, but also decrease the thermal conductivity. So it is necessary to develop one-step methods that combine the preparation of nanoparticles with the preparation of nanouids, so that the processes of drying, storage, transportation, and redispersion of Cu nanoparticles are avoided. One-step methods can also reduce production costs. Choi has developed a one-step physical method [6,7], in which Cu vapor is directly condensed into nanoparticles by contact with a owing low-vapor-pressure liquid (ethylene glycol). To our knowledge, one-step chemical methods have not been applied to the preparation of nanouids. Different methods have been used for the preparation of copper nanoparticles (not nanouids), such as microemulsions [8], reverse micelles [9], reduction of aqueous copper salts [10], -irradiation [11], UV light irradiation [12], and the polyol process [1315]. Among these, the polyol process is a successful method for preparing monodispersed, nonagglomerated copper nanoparticles, in which heating a suitable inorganic/organic metallic salt in polyol gives rise to metal particles, and polyol act as a solvent and reducing agent [13]. But the solution of the copper salt should be heated to its boiling point and kept under reuxing conditions for a long time. The present investigation was performed to prepare Cu nanouids of metallic Cu nanoparticles dispersed in

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ethylene glycol by one-step chemical methods, in which NaH2 PO2 H2 O was added as a reducing agent and microwave irradiation was used for heating.

2. Experimental 2.1. Preparation of Cu nanouids All the reagents used in our experiments were of analytical purity and were used without further purication. In a typical procedure, 25 ml ethylene glycol solution (0.1 M) of copper sulfate pentahydrate (CuSO4 5H2 O) was mixed with 5 ml of ethylene glycol solution (0.01 M) of polyvinylpyrrolidone (PVP-K30) in a 100-ml beaker, followed by magnetic stirring for 30 min. Then 25 ml of ethylene glycol solution (0.25 M) of sodium hypophosphite (NaH2 PO2 H2 O) was added and stirred for another 15 min. The mixture was put into a microwave oven (700 W, Galanz Microwaves Oven Corp., Shunde, China) to react for 5 min under medium power. The color of the mixture turned from blue to dark red after the reaction. After being cooled to room temperature, Cu nanouid was obtained. For comparison, some syntheses were carried out without NaH2 PO2 H2 O, or microwave irradiation, or changing concentration of CuSO4 . 2.2. Characterization Transmission electron microscope (TEM) images were recorded on a JEOL JEM-2000EX transmission electron microscope. The samples used for TEM observations were prepared by diluting the Cu nanouids with ethylene glycol, followed by ultrasonic vibration for 10 min. Cu nanouid was also diluted with absolute ethanol, followed by centrifuging at 4000 rpm for 60 min, and then washed with absolute ethanol, and acetone and vacuum dried at 80 C for 2 h. X-ray diffraction (XRD) of the obtained powder was performed on a D/Max-rA diffractometer using nickel-ltered CuK radiation. A 510P FT-IR spectrometer was used to identify the ingredients of the reaction solution. The nanouids were centrifuged at 16,000 rpm for 60 min. The supernatant was used for FT-IR analysis. Sedimentation measurements under different conditions were used to evaluate the stabilization of the nanouids. The transient hot-wire method [16,17] is used in this study to measure uid thermal conductivity. The thermal conductivity, , is calculated by the formula = q t2 , ln 4(T2 T1) t1 (1)

Fig. 1. X-ray diffraction pattern of the as-prepared typical sample.

Fig. 2. TEM image (a) and corresponding SAED pattern (b) of a Cu nanouid prepared under a typical procedure.

3. Results and discussion The XRD pattern of a typical sample is shown in Fig. 1. The diffraction peaks can be indexed to those of pure facecentered cubic (FCC) Cu (JCPDS, File No. 04-0838), corresponding to the (111), (200), (220), and (311) planes, respectively. Figs. 2a and 2b depict a TEM image and the corresponding selected area electron diffraction (SAED) pattern of the as-prepared product, respectively. The micrograph reveals that the product consists of spherical particles. The diffraction pattern further proves a FCC structure. Most of the Cu particles are about 10 nm in diameter, a few are between 10 and 20 nm in diameter. It can also be noted that all Cu nanoparticles are dispersed very well. The stabilization of nanouid is very important for industrial application. It has been tested that at room temperature, the obtained nanouid is stable for more than 3 weeks in the stationary state and more than 8 h under centrifugation at 4000 rpm without sedimentation. And it also could be stably suspended for more than 2 weeks in the stationary state at 120 C. The stabilization of the obtained Cu nanouid is better than that of the one prepared by a step-by-step method [2], in which the nanouid only lasted 1 week in the stationary state at room temperature. Two factors may con-

where q is the applied electric power and T1 and T2 are the temperatures at times t1 and t2 , respectively. The uncertainty of our measurement is estimated to be less than 1.5%.

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Table 1 The inuence of NaH2 PO2 H2 O and microwave irradiation on the reaction rate and properties of obtained Cu nanouids Samples 1 2 3 4 [15] in TEM. The molar ratio of NaH2 PO2 to CuSO4 2.5 0 2.5 0 Heating methods Microwave irradiation Microwave irradiation Conventional heating Conventional heating Reaction condition Medium power, 5 min Medium power, 5 min 120 C, 1 h 190 C, 4 h Particles size (nm) <20 No particlesa 3080 90 The stabilization of nanouids 3 weeks in stationary conditions at room temperature 1 week in stationary conditions at room temperature not mentioned

a Without NaH PO H O (samples 2), the mixed solution only turned to dark green under microwave irradiation for 5 min, and no particles were observed 2 2 2

tribute to this improvement. One is that the smaller size and better dispersity of Cu nanoparticles in our case, compared with that of the literature [2], in which particle diameter was about 100 nm and there were some clusters of Cu particles. The other is the protective role of PVP. In the preparation of metal nanoparticles, PVP usually is added as a protective polymer; it retards the growth and agglomeration of metal nanoparticles by a steric effect [18]. Initial research also shows that thermal conductivities of these Cu nanouids are signicantly larger than that of pure ethylene glycol (0.256 W m1 K1 ). For example, when the volume fraction of Cu nanoparticles in nanouid is only 0.1%, the effective thermal conductivity increases 9%, up to 0.279 W m1 K1 . The value approaches that of a nanouid prepared by a one-step physical method [6]. However, our method is cheaper. Systematic studies on the thermal conductivity of these nanouids are still on the way. To understand the reaction mechanism, we have investigated the effects of NaH2 PO2 H2 O and microwave irradiation on the reaction rate and the properties of the obtained Cu nanouids. From Table 1, it can be seen that the addition of NaH2 PO2 and the exertion of microwave irradiation result in higher reaction rates, smaller particle size, and better stabilization of Cu nanouids. In the polyol process, polyol acts not only as a solvent and reducing agent, but also as a particle surface protective agent to prevent the agglomeration and the abnormal growth of particles [13]. The particle size is small and the size distribution is narrow. But the reaction rate of this system is slow; the mixed solution should be heated to its boiling point and kept under reuxing conditions for a long time. In the aqueous chemical reduction system for preparing Cu particles, NaH2 PO2 is usually used as a strong reducing agent; the reaction rate of this system is very fast. But the agglomeration of particles is often serious [19]. Our method was designed to preserve both the advantages of the polyol process and the aqueous chemical reduction method with added NaH2 PO2 as reducing agent. Fig. 3A and 3B are the IR spectra of the reaction solution and analytical pure ethylene glycol, respectively. It can be seen that both spectra are the same. All peaks can be indexed to ethylene glycol according to the SADTLER Standard Infrared Grating Spectra, File 299 K. There is no sign indicating oxidized products of ethylene glycol in Fig. 3A,

Fig. 3. FT-IR spectra of reaction solution (A) and pure ethylene glycol (B).

suggesting that it is NaH2 PO2 , not ethylene glycol, that acts as reducing agent. So this method preserves the respective advantages of the polyol process and the aqueous chemical reduction method. This is a fast and novel method for preparing Cu nanouids. Microwaves are electromagnetic waves containing electric and magnetic components. Recently, microwave irradiation has been widely applied to materials science due to its thermal and nonthermal effects [20]. As a heating method, compared with the conventional methods, it has the properties of being fast, simple, and energy-saving. Due to the intense friction and collision of the molecules created by microwave irradiation, microwave irradiation not only provides the energy for the heating, but also greatly accelerates the nucleation of Cu and depresses the straightforward growth of newly born Cu. With microwave irradiation of the reactant solution, temperature and concentration gradients can be avoided, leading to uniform nucleation [21]. Consequently, the as-prepared Cu nanoparticles are of small size and the obtained nanouids have good stabilization.

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of NaH2 PO2 H2 O and the adoption of microwave irradiation greatly affect the reaction rate and the properties of Cu nanouids. Further research on the purication and improvement of the effective thermal conductivity of Cu nanouids is on the way. It is expected that this method can be extended to synthesize other metallic nanouids or nanoparticles.

Acknowledgments We are grateful for the kind assistance from Dr. De-Bao Wang and Professor Xun Fu, Institute of Chemistry and Molecular Engineering, Qingdao University of Science and Technology.
Fig. 4. TEM photographs of Cu nanouids prepared with different CuSO4 concentration: (A) 0.2 M, (B) 0.5 M.

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The inuence of CuSO4 concentration on Cu nanoparticles is shown in Fig. 2a (0.1 M), Fig. 4A (0.2 M), and Fig. 4B (0.5 M). As shown in Fig. 4A, when CuSO4 concentration is 0.2 M, most of the Cu particles are about 10 nm in diameter, except some in the range 1020 nm. When CuSO4 concentration is increased to 0.5 M, the product is a mixture of Cu nanoparticles with bimodal size distribution (Fig. 4B): most of them are about 5 nm in diameter, while some of them are 2040 nm in diameter. It is clear that increasing the concentration of CuSO4 results in move broadly distributed Cu nanoparticles. This phenomenon can be explained by the inuence of concentration on nucleation and growth [2224]. When the concentration is low, the nucleation and growth stages are separated, so the distribution range of Cu nanoparticles is narrow. At higher concentrations, the nucleation and growth take place at the same time. Some large particles grow continually and some newly born particles appear, so the distribution of Cu nanoparticles is broadened. It should be also noted that the Cu nanoparticles prepared with 0.5 M CuSO4 still disperse very well in the ethylene glycol solution, and the sizes are less than 50 nm, suggesting that the new method is effective.

4. Conclusions In summary, a novel one-step method for preparing copper nanouids by reducing CuSO4 5H2 O with NaH2 PO2 H2 O in ethylene glycol under microwave irradiation has been developed. Nonagglomerated and stably suspended Cu nanouids are obtained. The results show that the addition