Powder Technology 197 (2010) 218221

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Powder Technology
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / p ow t e c

Investigation on the thermal transport properties of ethylene glycol-based nanouids containing copper nanoparticles
Wei Yu, Huaqing Xie , Lifei Chen, Yang Li
School of Urban Development and Environmental Engineering, Shanghai Second Polytechnic University, Shanghai 201209, China

a r t i c l e

i n f o

a b s t r a c t
Stable ethylene glycol based copper nanouids were prepared through a two-step method, using polyvinyl pyrrolidone as dispersant, which was vital for the long-term stability of nanouids. The substantial thermal conductivity enhancements were seen for the obtained nanouids. For ethylene glycol based copper nanouids with 0.5 vol.% at 50 C, the enhancement ratio was up to 46%. The thermal conductivities depended strongly on the temperature of uid, and the enhancement ratios increased along with the increasing temperatures. Brownian motions of Cu nanoparticles would play the key role on determining the effects of the temperature on thermal conductivity enhancement of nanouids. The measured apparent thermal conductivity showed the time-dependent characteristic within 15 min. It indicated that the measurement should be made after 15 min at least to obtain the true thermal conductivities of ethylene glycol based copper nanouids. 2009 Elsevier B.V. All rights reserved.

Article history: Received 12 November 2008 Received in revised form 20 August 2009 Accepted 19 September 2009 Available online 29 September 2009 Keywords: Nanouid Heat transfer Copper nanoparticle Viscosity

1. Introduction Nanouids, produced by dispersing nanoparticles into conventional heat transfer uids, are proposed as the next generation heat transfer uids due to the fact that their thermal conductivities are signicantly higher than those of the base liquids [1]. Subsequently more than 16 laboratories worldwide have published experimental data on the thermal conductivity of nanouids. The colloidal uidic systems show unusually high thermal conductivity provided they are prepared in a suitable stable manner. At present the thermal conductivity data measured by different groups are scattered. Even for the same nanouids, different groups reported different enhancements [2]. For instance, Lee et al. [3] reported an increase in thermal conductivity ratio of 14% compared to pure water with 3.5 vol.% CuO particles, while Eastman et al. [4] obtained a 40% increase at the same volume fraction. Masuda et al. [5] published results on the thermal conductivity of Al2O3water nanouid as early as 1993. The average size of their Al2O 3 nanoparticles used is about 13 nm. Their measurements gave a 30% increase at the particle loading of 4.3 vol.%, which was more than 20% higher than that reported by Lee et al. [3]. Some researchers' results [6,7] showed that the thermal conductivities of nanouids were strongly dependent on the size of the suspended particles, with the conductivities decreasing with nanoparticle sizes. While Xie's results [8] showed that the 60 nm particles gave about twice the enhancement as compared to the 15 nm particles, which was contrary to the former stated inuence of the particle size. Hong's conclusion [9] was
Corresponding author. Tel./fax: +86 21 50217331. E-mail address: hqxie@eed.sspu.cn (H. Xie). 0032-5910/$ see front matter 2009 Elsevier B.V. All rights reserved. doi:10.1016/j.powtec.2009.09.016

similar to that of Xie's [8]. In Hong's opinion suspensions containing small nanoparticle clusters are more effective in improving thermal conductivity than that of individual dispersed nanoparticles because the clustered nanoparticles may provide a long path for heat transfer. Similar scattered phenomena occur in the study of the mechanisms of the thermal conductivity enhancements in nanouids. The above facts demonstrate that several factors affect the measured thermal conductivity values, such as the temperature of uid, particle size, the settlement time after nanouid preparation and the stability of nanouid. It should be noted that the stability of nanouid is vital, because it not only affects the accuracy of measurement for the thermal conductivity of nanouid, but also affects its application in heat transfer systems when nanouid is used as the substitute for conventional thermal uid. In the present paper, we prepared stable nanouids containing copper nanoparticles through a two-step method using polyvinyl pyrrolidone as surfactants. The thermal transport properties including thermal conductivity and viscosity were measured. The effects of the particle volume fraction, dispersants, measured temperature, settlement time on the thermal conductivity were further investigated in detail. 2. Experimental 2.1. Reagents CuSO45H2O, NaH2PO2H2O, polyvinyl pyrrolidone (PVP, weightaverage molecular weight of 40,000), and ethylene glycol were of analytical reagent (AR) grade, and were obtained from Shanghai Chemical Reagents Company. All the reagents were used as received.

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2.2. Instruments The size and morphology of the Cu nanoparticles were examined by using transmission electron microscopy (TEM, JEOL 2100F). The TEM samples were prepared by dispersing the powder products in alcohol by ultrasonic treatment, dropping the suspension onto a holey carbon lm supported on a copper grid, and drying it in air. XRD measurements were recorded using a (D8-Advance, Germany) X-ray diffractometer equipped with a back monochromator operating at 40 kV and a copper cathode as the X-ray source ( = 0.154 nm). XRD patterns were recorded from 30 to 80 (2) with a scanning step of 0.01. The viscosities of the uid were measured as a function of temperature using a NXE-1B viscometers (Chengdu Instrument Factory, China, Measurable scope 0.51000 mPa s), and 1.3 ml sample was needed. In order to obtain precise experimental data high rotation speed was employed as possible. A transient short hot wire (SHW) technique was applied to measure the thermal conductivities of the nanouids [10], and the accuracy of these measurements was estimated to be within 1%. The thermal conductivity of the uid was measured after the nanouid was settled for more than 30 min to eliminate the effects caused by ultrasonic oscillation. 2.3. Synthesis of copper nanoparticles and preparation of nanouids Most of the nanouids were prepared by physical method, and nanouids formed by wet chemistry were fewer relatively [11]. In the present work, chemical reduction method was used to synthesize copper nanoparticles, and stable nanouids containing copper nanoparticles were obtained with the addition of polyvinyl pyrrolidone (PVP) as surfactants. In a typical synthesis, 50 ml aqueous solution of 0.04 mol NaH2PO2H2O was directly mixed with another 50 ml aqueous solution of 0.01 mol CuSO45H2O and 0.5 g PVP under stirring. The mixture was kept at 90 C without any inert gas protection. After 20 min the precursor solution with blue color changed into buff, khaki, and ultimately into red, indicating the formation of Cu nanoparticles. After 1 h, Cu nanoparticles were collected via centrifuge (15,000 rpm for 20 min) of the mixture. Stable ethylene glycol based copper nanouids (Cu-EG nanouids) were obtained through a two-step method, by dispersing the copper nanoparticles into 30 ml ethylene glycol with 1.5 g PVP as dispersant under ultrasonic oscillation for 30 min. 3. Results and discussion Fig. 1 depicts the XRD pattern and all the peaks can be readily indexed to pure copper (JCPDS le No. 04-0836), indicating the copper powder is stable in air with no clear oxidation. Fig. 2 presents the TEM image of a typical sample of the copper particles. It appears

Fig. 2. Typical TEM image of the as prepared Cu nanoparticles.

that the product consists of spherical particles with a narrow size distribution. All the nanoparticles are dispersed very well with no clear aggregation. The diameters estimated from the TEM image are in the range of 510 nm. Fig. 3 represents the thermal conductivity enhancement ratios ((k k0/k0)) for Cu nanouids. In this article, k and k0 represent the thermal conductivities of the nanouid and base uid, respectively. The addition of PVP improves the stability of the nanouids signicantly, and the nanouids show no precipitation in two months. However, negative effects of the surfactant addition on the thermal conductivity might be brought about. When adding 5 wt.% PVP, the thermal conductivity of EG-surfactant mixture lowers by about 2% compared to that of pure EG. The addition of Cu nanoparticles in EG enhances the thermal conductivity substantially. The enhancement ratios of the Cu nanouids with the volume fractions of 0.3% and 0.5% are 11% and 16% at room temperature (25 C), respectively. The values are a little larger than the corresponding values reported by Eastman et al. [12]. Fluid temperature may play an important role in enhancing the effective thermal conductivity of nanouids, and some researchers have investigated the temperature effect on the effective thermal conductivity of nanouids [1315]. Fig. 3 demonstrates that the thermal conductivities are dependent on the temperatures, with the thermal conductivity enhancement ratios increasing along with the temperature. The enhancement ratios are 5% and 8% for the nanouids with volume fractions of 0.3% and 0.5% at 10 C, respectively. However, the values are enlarged up to 33% and 46%, respectively

Fig. 1. XRD pattern of the as prepared copper nanoparticles.

Fig. 3. Thermal conductivity enhancement ratios as a function of temperature.

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when the temperature is raised to 50 C. When the temperature is below 30 C, there is a nearly linear dependence between the thermal conductivity enhancement and the temperature. The slope of the enhancement ratio to the temperature becomes larger at temperatures higher than 30 C. The thermal conductivity dependence on the temperature has also been observed in the system of Al2O3water nanouids [16,17]. Various mechanisms and models have been proposed recently for explaining the unusually high thermal conductivity of nanouids using various assumptions [1820]. The size of nanoparticle has direct effect on the thermal conductivity of nanouid, because heat transfer takes place at the surface of the particles, it is desirable to use particles with larger surface area. The relatively larger surface areas of nanoparticles compared to microparticles, provide signicantly improved heat transfer capabilities. In addition, particles ner than 20 nm carry 20% of their atoms on their surface, making them instantaneously available for thermal interaction [21]. A few models correlate the thermal conductivity enhancements of nanouids to the temperatures. The particle size is important because shrinking it down to nanoscale not only increases the surface area relative to volume but also generates some nanoscale mechanisms in the suspensions. Theoretical evidence indicates that the effective thermal conductivity of nanouids increases with decreasing particle size [22]. Brownian motions of nanoparticles in the nanouids are conjectured to play key roles on determining the effects of the temperature on thermal conductivity enhancement of nanouids [7]. According to the Einstein diffusion theory [16], Brownian velocity of a nanoparticle increases greatly with the decrease of the diameter of the nanoparticle. The calculated results of Chon et al. show that the Brownian velocity increases with the temperature, but dramatically decreases with nanoparticle size in Al2O3H2O nanouid. For example, the dependence of the Brownian velocity on temperature becomes obvious for those nanoparticles with an average diameter of 11 nm [16]. For Cu-EG nanouid, the diameters of copper nanoparticles are in the range of 510 nm. It is expected that the dependence of the Brownian velocity on the temperature would be evident. Therefore, in our opinion, Brownian motions of Cu nanoparticles would play dominant roles on the thermal conductivity enhancement ratios of nanouids. The tendency is also conrmed by Jang's theoretical model [20] based on the Brownian motions of nanoparticles at the molecular and nanoscale level. The settlement time is a vital factor. Fig. 4 shows the thermal conductivity enhancement ratios as a function of settlement time after nanouid preparation. It is found that the conductivity decreases with elapsed time. Initially, the apparent thermal conductivity of EG based Cu nanouid with a volume fraction of 0.3 vol.% is 9.5% higher compared to the base uid. The value decreases monotonously until it

reaches a constant value of 7.5% when the time is over 15 min. The tendency of the settlement time dependence of thermal conductivity enhancements has also been observed in water based Cu nanouids and Fe nanouids [11,23,24]. Previous literatures proposed that the decrease was probably due to the appreciable particle agglomeration. When nanoparticles get agglomerated, the ratio of the effective area to the volume decreases. The effective area reduction of the thermal interaction of particles causes a decrease in the thermal conductivity of the uid [6,7]. However, for Cu-EG nanouid, the reduced ratio of thermal conductivity from 1 to 15 min is about 21%. It is unreasonable that the sedimentation of Cu nanoparticles amounts up to 21% in the rst 15 min, and then keeps stable ultimately. In our opinion, the unnished microoscillation after ultrasonic oscillation in nanouid preparation might be the key reason. When thermal conductivity is measured right after the ultrasonic oscillation, the unnished microoscillations of nanoparticles and uid molecules may contribute thermal energy transport, leading to the obtained higher apparent thermal conductivity enhancement. Obviously this does not reect the intrinsically physical features of nanouids in enhancing heat transfer. Kim et al. [6] found that the thermal conductivity decreased rapidly for nanouids without surfactants after preparation. But no obvious changes in the thermal conductivity of the nanouids with sodium dodecyl sulfate (SDS) as surfactant were observed even after 5 h settlement. It is clear that the stability of nanouid is vital for the reliability of thermal conductivity measurements. To eliminate the confusion caused by the measurements, all the thermal conductivity experiments were performed after the nanouids were settled for more than 30 min in this study. It is believed that viscosity is as critical as thermal conductivity in engineering systems that employ uid ow. Pumping power is proportional to the pressure drop, which in turn is related to uid viscosity. In laminar ow, the pressure drop is directly proportional to the viscosity [2527]. In general, the viscosities of nanouids are abnormally increased. Our measurements are in the temperature range from 10 to 50 C with an increment of 5 C. The measured viscosities are given in Fig. 5. It is shown that the addition of PVP makes the viscosity enhanced by about three times compared to the corresponding value of pure EG. For nanouids, the dispersed nanoparticles would further hinder the uid to ow. It is seen from Fig. 5 that at 10 C the viscosities of nanouids with volume fractions of 0.3% and 0.5% become larger, reaching about 3.5 and 4.2 times, respectively, compared with pure EG. In the temperature range from 10 to 30 C, the viscosity of a nanouid decreases rapidly with an increase in temperature. When the temperature is over 30 C, the slope of the viscosity to the temperature decreases. The decrease in the viscosity makes for an increase in the average velocity of Brownian motion of the nanoparticles.

Fig. 4. The time-dependent characteristic of Cu-EG nanouid at 15C.

Fig. 5. The viscosity data for the uids as a function of measured temperatures.

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According to the statistics and analysis of Murshed, all reported results show that the viscosity of nanouids is increased anomalously and cannot be predicted by classical models such as by Einstein, Krieger and Dougherty, Nielsen, and Batchelor [22]. No rm conclusion can be drawn from the above uctuating data of several nanouids. The facts illustrate that nanouid is a complicated twophase system, and several important factors such as volume fraction, particle size and shapes, clustering of particles, temperature of the uid, and the interface interaction between nanoparticles and uid, have great effect on the viscosity. For Cu-EG nanouid, PVP was used as dispersant, the viscosity behavior was more complicated due to the existence of PVP. The effects of particle surface chemistry and particles interaction for nanometer-sized particles could be signicant for the viscosity of nanouids. PVP is a common used polymeric surfactant. On one hand, the steric effect prevents the particles to form large aggregation; on the other hand, PVP has the structure of a polyvinyl skeleton with nitrogen and oxygen polar groups, and the polar group donates lone-pair electrons forming a coordinative interaction with copper [28]. More detailed investigations should be conducted to conrm the effects of these factors, especially the effects of particle surface chemistry on the viscosity of nanouids. Although the potentials for the applications of nanouids in a wide variety of elds are promising, some stumbling blocks seriously hinder the practical developments. The following considerations would be worthwhile. Firstly, the reliability of data of thermal conductivity should be ensured, which is the premise to give a sound basis for a systematic theoretical analysis. Some negligible details, such as settlement time, measured temperature, and surfactant should be studied intensively. Secondly, a challenge for the future is to improve existing synthesis techniques, that is, to develop novel cost-efcient one-step synthesis routes. To control the size as well as the shape of the nanoparticles is desirable. Thirdly, the stability of nanouids should be improved greatly, which is not only responsible for scattered data of thermal conductivity, but also an important aspect in the practical applications of nanouids. In order to reach the aim, more dispersion techniques should be developed, in which particle surface treatment is very important. Surfactants are often used to improve the dispersion properties and long-term stability of nanouids. However, the negative effects should not be neglected, such as foam formation, surface adhesion to nanoparticles, and rise in viscosity. Finally, the rheological behaviors of nanouids should be investigated because the viscosities of nanouids are system-depended. Conventional models might be incapable of predicting the viscosities of nanouids. 4. Conclusion Chemical reduction method has been used to synthesize well dispersed copper nanoparticles with a narrow size distribution of 5 10 nm diameters. Stable ethylene glycol-based copper nanouids were obtained with the addition of polyvinyl pyrrolidone (PVP) as surfactants. Detail experimental studies have been carried out to analyze the effective thermal conductivity of the nanouids. The results indicate that the thermal conductivities increase with the volume fraction and the temperature. Brownian motions of Cu nanoparticles are accounted for the increment of the thermal conductivity enhancement ratio with the temperature. The addition of PVP as surfactant signicantly improves the stability of copper nanouids, but the negative effects on thermal transport properties are nontrivial. For different nanouids, particle agglomeration, sedimentation, and microoscillation might play different roles on the time-dependent characteristic of the thermal conductivity of nanouids after preparation.

Acknowledgements The work was supported by the National Science Foundation of China (50876058), Shanghai Educational Development Foundation and Shanghai Municipal Education Commission (07SG56 & 08CG64), the Excellent Young Scholars Research Fund of Shanghai (No. RYQ307007) and the Program for Professor of Special Appointment (Eastern Scholar) at Shanghai Institutions of Higher Learning.

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