Particle size effects in the thermal conductivity enhancement of copper-based nanofluids
© Saterlie et al; licensee Springer. 2011
Received: 11 November 2010
Accepted: 14 March 2011
Published: 14 March 2011
We present an analysis of the dispersion characteristics and thermal conductivity performance of copper-based nanofluids. The copper nanoparticles were prepared using a chemical reduction methodology in the presence of a stabilizing surfactant, oleic acid or cetyl trimethylammonium bromide (CTAB). Nanofluids were prepared using water as the base fluid with copper nanoparticle concentrations of 0.55 and 1.0 vol.%. A dispersing agent, sodium dodecylbenzene sulfonate (SDBS), and subsequent ultrasonication was used to ensure homogenous dispersion of the copper nanopowders in water. Particle size distribution of the copper nanoparticles in the base fluid was determined by dynamic light scattering. We found that the 0.55 vol.% Cu nanofluids exhibited excellent dispersion in the presence of SDBS. In addition, a dynamic thermal conductivity setup was developed and used to measure the thermal conductivity performance of the nanofluids. The 0.55 vol.% Cu nanofluids exhibited a thermal conductivity enhancement of approximately 22%. In the case of the nanofluids prepared from the powders synthesized in the presence of CTAB, the enhancement was approximately 48% over the base fluid for the 1.0 vol.% Cu nanofluids, which is higher than the enhancement values found in the literature. These results can be directly related to the particle/agglomerate size of the copper nanoparticles in water, as determined from dynamic light scattering.
in which K, K1, and K2 are the thermal conductivities of the nanofluid, the dispersed phase, and the base fluid, respectively, n is an empirical shape factor dependent on the sphericity of the particles, and V2 is the volume fraction of the particles. This model includes the effect of particle shape and size and has been applied to a copper/water nanofluid system with three different sphericity factors, showing that the thermal conductivity of a nanofluid depends on both the particle volume fraction and the shape .
A comparison of particle shape in SiC nanofluids of water and ethylene glycol has been completed with powders of spherical morphology of 26-nm average crystallite size and cylindrical morphology of 600-nm average crystallite size along the fiber axis direction . It was concluded that because heat transfer occurs between the surface of the particles and the fluid, heat transfer is more efficient for a system with a larger interfacial area. Therefore, smaller crystallites will exhibit the greatest amount of thermal conductivity enhancement. However, this conclusion does not take into consideration the effect of agglomeration of the powders in the fluid. If the powders are heavily agglomerated, then heat transfer is possibly hindered, since transfer will only occur on the surfaces of the agglomerates, even if the powder crystallite sizes are in the nanometer range.
In nanofluids of Al2O3/water, an increase of 12% in thermal conductivity enhancement was observed with the addition of Al2O3 powders with crystallites of 28-nm average size at a particle volume fraction of 3% . Other studies of this same system, with powders of 13 and 38 nm Al2O3 average crystallite size exhibited a 20% and 8% thermal conductivity enhancement [5, 6]. The effect can be attributed to the phonon mean free path in the nanofluid  such that in a nanofluid containing nanoparticles of a crystallite size much different from the phonon mean free path, the thermal conductivity will increase with decreasing crystallite size, while in a nanofluid containing nanoparticles less than or equal to the mean free path, the thermal conductivity will be reduced with crystallite size reduction due to the scattering of phonons. None of these studies reported the level of agglomeration (i.e., the size of the particle/agglomerates) in the nanofluid. Since powders tend to heavily agglomerate in polar fluids, a comparison connected to the agglomeration of the particles and not just to crystallite size, cannot be ascertained without proper particle/agglomerate size distribution analysis [8–14].
Crystallite and particle size results in copper-based nanofluids
Crystallite size (nm)
Particle size (nm)
Cu prepared using oleic acid
Cu prepared using CTAB
Sinha et al. 
Wang et al. 
Liu et al. 
Eastman et al. 
Xuan and Li 
Velasco et al. 
Li et al. 
Yu et al. 
In this study, we prepared copper nanopowders and then incorporated these powders into water, with SDBS as a dispersant, for the formation of well-dispersed nanofluids. The copper nanoparticles were produced through the reduction of copper (II) chloride with sodium borohydride in the presence of a surfactant [i.e., oleic acid or cetyl trimethylammonium bromide (CTAB)]. After preparation of powders using various surfactant concentrations, the optimal samples were chosen based on phase and particle size criteria. The small agglomerate sizes for the 0.55 and 1.0 vol.% copper nanofluids exhibited thermal conductivity enhancements of up to 48% over the base fluid with a mean thermal conductivity of 0.89 W/m·K, higher than the enhancement values found in other studies, as will be discussed later. We conclude that minimization of agglomerate size in nanofluids is important in order to take full advantage of the presence of nanopowders in the base fluid.
The main experimental result and contribution of this work to the nanofluid field is that excessive aggregation of the dispersed phase reduces the effectiveness of the produced nanofluid through the settling of particles and disruption of nanofluid flow during thermal conductivity testing. While this has been hypothesized extensively, our work shows definite experimental results to support this. When testing the thermal conductivity of the nanofluids, the increase in particle loading for the oleic acid powders from 0.55 to 1.0 vol.%, results in rapid settling due to increased agglomeration, as carefully determined by dynamic light scattering measurements.
Due to the rapid release of hydrogen during the reaction and the presence of bubbling nitrogen gas, significant foam was formed upon reduction of the copper salt/surfactant solution. To counteract this foaming, octyl aldehyde (98%, Sigma Aldrich, St. Louis, MO, USA), a known de-foaming agent, was added as needed throughout the process.
Once the reaction was complete, the fluid was removed from the reactor, emptied into 50-mL centrifuge tubes, and centrifuged using an Eppendorf Centrifuge 5810 (Eppendorf, Hamburg, Germany 22339) for 10 min at 11,000 rpm. The clear supernatant liquid was discarded and a solution of 50/50 semiconductor grade methanol (99.9%, Alfa Aesar, Ward Hill, MA 01835, USA) and de-ionized water was added to the centrifuge tubes in order to remove sodium chloride and the surfactant from the surfaces of the particles. These tubes were shaken vigorously for 5 min. A second methanol/water wash and a final methanol wash were applied on the powders while decanting the supernatant after each centrifugation. The copper powders were then placed in a vacuum dessicator for 2 to 3 days. Once dry, the powders were ground by hand using a mortar and pestle.
In later experiments, the batch sizes were increased. This required one solution to contain 67.08 g of CuCl2 in 200 mL of de-ionized water and a separate solution of 148.86 g of sodium borohydride in 300 mL of de-ionized water. The same molar ratios for the surfactants were used for the production of the larger batch sizes, resulting in amounts of 6.94 g of oleic acid and 1.29 g of CTAB.
Two different nanofluids, of 0.55 and 1.0 vol.% copper concentrations in water, were prepared. For preparation of the 0.55 vol.% copper nanofluid with 15 wt.% dispersant, 2.61 g of SDBS (Sigma Aldrich, St. Louis, MO, USA) was added to 296 mL of de-ionized water and allowed to stir at a slow speed, so that a high shearing force did not result in bubbles on the surface. A mass of 14.78 g of copper powder was then slowly added to the dispersant solution under slow stirring and allowed to mix for 1 h. The 1.0 vol.% copper nanofluid contained 4.74 g of SDBS and 26.88 g of copper powder in 292 mL of de-ionized water. The fluid was transferred to a jacketed reaction vessel and then ultrasonicated using an Ultrasonic Processor (Ace Glass, Vineland, NJ, USA) for 50 min with amplitude of 70%, pulsed on for 3 s, then off for 3 s.
Particle size measurements were performed on a Microtrac Nanotrac Ultra dynamic light scattering system (Microtrac Inc., Montgomeryville, PA, USA). The Microtrac Nanotrac Ultra instrument measures the particle size distribution in solution, with measurement capability from 0.8 nm to 6.5 μm. Multiple measurements were done on each sample, using the appropriate parameters determined by the estimated particle size range and fluid viscosity. With these parameters, the measurements were taken at a run time of 30 s. At least five measurements were taken for each sample and then averaged to produce accurate particle size distribution analysis for each sample as is recommended by the instrument manufacturer and in conjunction with ASTM standard E2490-09.
Results and discussion
There are several accepted measurement methodologies for thermal conductivity of a nanofluid. In this study, a flow cell experimental setup (Figure 1) was used for the evaluation of dynamic thermal conductivity of the nanofluids. This experimental setup allows for the continuous flow of the nanofluid between an insulated heating element and a cooling fan. Two thermoelectric modules were affixed to both walls of the heating channel and connected to a power supply. The power supply created an electric current which increased the temperature of the walls in the heating channel. A dc pump supplied the circulation of the nanofluid within the closed loop under laminar flow conditions, Re < 2,300. When the nanofluid was passed through the heating channel, it absorbed some of the heat, increasing the temperature of the nanofluid, and then was subsequently cooled back to room temperature by the cooling fan. The temperature of the nanofluid and the walls were monitored by four thermocouples located at the walls and at the inlet and outlet channels of the heating channel. By comparing the steady-state channel wall temperature, the effectiveness of a nanofluid was evaluated.
where, ΔQ is the heat input, A is the heat transfer surface area, and ΔT is the temperature difference between the solid surface and the surrounding fluid. The Nusselt number (Nu) is the ratio of convective to conductive heat transfer across the wall within the channel and is directly proportional to the convective heat transfer coefficient and the hydraulic diameter of the tube, while indirectly proportional to the thermal conductivity of the fluid. Calibration of the experimental setup was validated by testing the system with pure de-ionized water using a Nu of 5.9 for the calculations. A Nusselt number of 5.9 provides a reasonable estimate of k for pure water, but it may not be as accurate for nanofluids . Thus, there is likely some error in the determination of the nanofluid thermal conductivities. The thermal conductivity values of de-ionized water for three independent measurements were 0.61, 0.58, and 0.63 W/m·K, with errors of 1.67%, -3.33%, and 5.00%, respectively. For the case of the nanofluid thermal conductivities, the experimental errors are likely slightly greater than 5%, although the exact magnitude of these errors is not known.
More importantly, we observe that our nanofluid of 1.0 vol.% CTAB-prepared copper powders exhibits comparable or greater enhancement than some nanofluids with much greater particle loadings. For example, the water-based nanofluids prepared by Xuan and Li  have particle loadings greater than 30 wt.%, but exhibit almost the same (in fact, slightly lower) thermal conductivity enhancement as our own nanofluids, which have modest particle loadings of 1 vol.% (8.3 wt.%). We attribute this directly to our smaller particle/agglomerate size and possibly our lower viscosity, which plays an important role in dynamic heat transfer applications. An efficient nanofluid involves the greatest thermal conductivity enhancement, with the least amount of particle loading, and therefore, a low viscosity. Thus, we propose that determination of particle/agglomerate size in nanofluids is an important variable that should be determined in order to obtain a complete picture of the characteristics and behavior of nanofluids. An appropriate technique for these measurements is dynamic light scattering.
Copper nanopowders were successfully synthesized using a chemical precipitation method in the presence of two surfactants, oleic acid and CTAB. This study has explored the importance of particle size distribution analysis in the reporting of nanofluid results. The particle sizes of the powders produced in this study were successfully reduced from approximately 1 μm to 120 and 80 nm for the oleic acid- and CTAB-prepared powders, respectively, upon addition of a dispersant in water. Two particle loadings were used for producing the copper-based nanofluids, 0.55 and 1.0 vol.%. A dynamic thermal conductivity test setup was devised and thermal conductivity measurements were performed on both nanofluids. A thermal conductivity enhancement of 22% over water was observed for the 0.55 vol.% Cu nanofluids. When the particle loading was increased to 1.0 vol.%, the nanofluids of oleic acid-prepared Cu powders settled and clogged the test setup. The nanofluids of CTAB-prepared copper powders remained well dispersed, allowing for a successful thermal conductivity measurement. A maximum increase of 48% was observed for the 1.0 vol.% copper nanofluid from the CTAB-prepared Cu powders. The thermal conductivity enhancement in these latter fluids is directly attributable to the excellent dispersion of the nanoparticles in the fluid.
This project was funded by the National Science Foundation under contract no. IIP 0823112.
- Hamilton RL, Crosser OK: Thermal conductivity of heterogeneous two-component systems. Ind Eng Chem Fundam 1962, 1: 187–91. 10.1021/i160003a005View ArticleGoogle Scholar
- Choi SUS: Enhancing thermal conductivity of fluids with nanoparticles. American Society of Mechanical Engineers, Fluids Engineering Division (Publication) FED 1995, 231: 99–105.Google Scholar
- Xie H, Wang J, Xi T, Liu Y: Thermal conductivity of suspensions containing nanosized SiC particles. Int J Thermophys 2002, 23: 571–80. 10.1023/A:1015121805842View ArticleGoogle Scholar
- Wang X, Xu X, Choi SUS: Thermal conductivity of nanoparticle-fluid mixture. J Thermophys Heat Transfer 1999, 13: 474–80. 10.2514/2.6486View ArticleGoogle Scholar
- Masuda H, Ebata A, Teramae K, Hishinuma H: Alteration of thermal conductivity and viscosity of liquid by dispersing ultra-fine particles (dispersion of γ-Al2O3, SiO2, and TiO2ultra-fine particles. Netsu Bussei 1993, 7: 227–33.View ArticleGoogle Scholar
- Lee S, Choi SUS, Li S, Eastman JA: Measuring thermal conductivity of fluids containing oxide nanoparticles. J Heat Transfer 1999, 121: 280–90. 10.1115/1.2825978View ArticleGoogle Scholar
- Xie H, Wang J, Xi T, Liu Y, Ai F, Wu Q: Thermal conductivity enhancement of suspensions containing nanosized alumina particles. J Appl Phys 2002, 91: 4568–72. 10.1063/1.1454184View ArticleGoogle Scholar
- Sinha K, Kavlicoglu B, Liu Y, Gordaninejad F, Graeve OA: A comparative study of thermal behavior of iron and copper nanofluids. J Appl Phys 2009, 106: 064307. 10.1063/1.3225574View ArticleGoogle Scholar
- Graeve OA, Kanakala R, Madadi A, Williams BC, Glass KC: Luminescence variations in hydroxyapatites doped with Eu2+and Eu3+ions. Biomaterials 2010, 31: 4259–67. 10.1016/j.biomaterials.2010.02.009View ArticleGoogle Scholar
- Kelly JP, Kanakala R, Graeve OA: A solvothermal approach for the preparation of nanostructured carbide and boride ultra-high temperature ceramics. J Am Ceram Soc 2010, 93: 3035–8. 10.1111/j.1551-2916.2010.04007.xView ArticleGoogle Scholar
- Graeve OA, Madadi A, Kanakala R, Sinha K: Analysis of particle and crystallite size in tungsten nanopowder synthesis. Metall Mater Trans A 2010, 41: 2691–7. 10.1007/s11661-010-0280-9View ArticleGoogle Scholar
- Sinha K, Pearson B, Casolco SR, Garay JE, Graeve OA: Synthesis and consolidation of BaAl2Si2O8:Eu. Development of an integrated process for luminescent smart ceramic materials. J Am Ceram Soc 2009, 92: 2504–11. 10.1111/j.1551-2916.2009.03242.xView ArticleGoogle Scholar
- Graeve OA, Varma S, Rojas-George G, Brown D, Lopez EA: Synthesis and characterization of luminescent yttrium oxide doped with Tm and Yb. J Am Ceram Soc 2006, 89: 926–31. 10.1111/j.1551-2916.2006.00845.xView ArticleGoogle Scholar
- Graeve OA, Sinha K: Dynamic light scattering study of reverse micellar systems for the synthesis of iron-based nanofluids. Int J Mod Phys B 2007, 21: 4774–81. 10.1142/S0217979207045657View ArticleGoogle Scholar
- Wang XJ, Zhu DS, Yang S: Investigation of pH and SDBS on enhancements of thermal conductivity in nanofluids. Chem Phys Lett 2009, 470: 107–11. 10.1016/j.cplett.2009.01.035View ArticleGoogle Scholar
- Liu MS, Lin MCC, Tsai CY, Wang CC: Enhancement of thermal conductivity with Cu for nanofluids using chemical reduction method. I J Heat Mass Transfer 2006, 49: 3028–33. 10.1016/j.ijheatmasstransfer.2006.02.012View ArticleGoogle Scholar
- Eastman JA, Choi SUS, Li S, Yu W, Thompson LJ: Anomalously increased effective thermal conductivities of ethylene glycol-based nanofluids containing copper nanoparticles. Appl Phys Lett 2001, 78: 718–20. 10.1063/1.1341218View ArticleGoogle Scholar
- Xuan Y, Li Q: Heat transfer enhancement of nanofluids. Int J Heat Fluid Flow 2000, 21: 58–64. 10.1016/S0142-727X(99)00067-3View ArticleGoogle Scholar
- Velasco AF, Perales-Perez O, Gutierrez G: Synthesis of Cu nanoparticles for preparation of nanofluids. In Nanotechnology 2008: Materials, Fabrication, Particles and Characterization: 2008; Boston. Edited by: Laudon M, Romanowicz B. NSTI Nanotechnology Conference and Trade Show; 2008:424–7.Google Scholar
- Li XF, Zhu DS, Wang XJ, Wang N, Gao JW, Li H: Thermal conductivity enhancement dependent pH and chemical surfactant for Cu-H2O nanofluids. Thermochim Acta 2008, 469: 98–103. 10.1016/j.tca.2008.01.008View ArticleGoogle Scholar
- Yu W, Xie H, Chen L, Li Y: Investigation on thermal transport properties of ethylene glycol-based nanofluids containing copper nanoparticles. Powder Technol 2010, 197: 218–21. 10.1016/j.powtec.2009.09.016View ArticleGoogle Scholar
- Joshi SS, Patil SF, Iyer V, Mahumuni S: Radiation induced Synthesis and characterization of copper nanoparticles. Nanostruct Mater 1998, 10: 1135–44. 10.1016/S0965-9773(98)00153-6View ArticleGoogle Scholar
- Wu SH, Chen DH: Synthesis of high-concentration Cu nanoparticles in aqueous CTAB solutions. J Colloid Interface Sci 2004, 273: 165–9. 10.1016/j.jcis.2004.01.071View ArticleGoogle Scholar
- Athawale AA, Katre PP, Kumar M, Majumdar MB: Synthesis of CTAB-IPA reduced copper nanoparticles. Mater Chem Phys 2005, 91: 507–12. 10.1016/j.matchemphys.2004.12.017View ArticleGoogle Scholar
- Chen L, Zhang D, Chen J, Zhou H, Wan H: The use of CTAB to control the size of copper nanoparticles and the concentration of alkylthiols on their surface. Mater Sci Eng A 2006, 415: 156–61. 10.1016/j.msea.2005.09.060View ArticleGoogle Scholar
- Yang JG, Yang SH, Okamoto T, Bessho T, Satake S, Ichino R, Okido M: Synthesis of copper monolayer and particles at aqueous-organic interface. Surface Sci 2006, 600: L318–20. 10.1016/j.susc.2006.10.014View ArticleGoogle Scholar
- Li X, Zhu D, Wang X: Evaluation on dispersion behavior of the aqueous copper nano-suspensions. J Colloid Interface Sci 2007, 310: 456–63. 10.1016/j.jcis.2007.02.067View ArticleGoogle Scholar
- Yang JG, Zhou YL, Okamoto T, Ichino R, Okido M: A new method for preparing hydrophobic nano-copper powders. J Mater Sci 2007, 42: 7638–42. 10.1007/s10853-007-1899-9View ArticleGoogle Scholar
- Khanna PK, Kale TS, Shaikh M, Rao NK, Satyanarayana CVV: Synthesis of oleic acid capped copper nano-particles via reduction of copper salt by SFS. Mater Chem Phys 2008, 110: 21–5. 10.1016/j.matchemphys.2008.01.013View ArticleGoogle Scholar
- Kanninen P, Johans C, Merta J, Kontturi K: Influence of ligand structure on the stability and oxidation of copper nanoparticles. J Colloid Interface Sci 2008, 318: 88–95. 10.1016/j.jcis.2007.09.069View ArticleGoogle Scholar
- Liu L, Chen L, Wan H, Chen J, Zhou H: Study on the tribological behaviors of N , N -dioctyldithiocarbamate monolayer-stabilized copper nanoparticles in liquid paraffin. J Dispersion Sci Technol 2009, 30: 144–7. 10.1080/01932690802313147View ArticleGoogle Scholar
- Hwang KS, Jang SP, Choi SUS: Flow and convective heat transfer characteristics of water-based Al2O3nanofluids in fully developed laminar flow regime. Int J Heat Mass Transfer 2009, 52: 193–199. 10.1016/j.ijheatmasstransfer.2008.06.032View ArticleGoogle Scholar
- Xuan Y, Li Q: Investigation on convective heat transfer and flow features of nanofluids. J Heat Transfer 2003, 125: 151–5. 10.1115/1.1532008View ArticleGoogle Scholar
- Sohn CW, Chen MM: Microconvection thermal conductivity in disperse two phase mixture as observed in a low velocity couette flow experiment. J Heat Transfer 1981, 103: 47–51. 10.1115/1.3244428View ArticleGoogle Scholar
- Gupte SK, Advani SG, Huq P: Role of micro-convection due to non-affine motion of particles in a mono-disperse suspension. Int J Heat Mass Transfer 1995, 38: 2945–58. 10.1016/0017-9310(95)00060-MView ArticleGoogle Scholar
- Xuan Y, Roetzel W: Conceptions for heat transfer correlation of nanofluids. Int J Heat Mass Transfer 2000, 43: 3701–7. 10.1016/S0017-9310(99)00369-5View ArticleGoogle Scholar
- Keblinski P, Phillpot SR, Choi SUS, Eastman JA: Mechanisms of heat flow in suspensions of nano-sized particles (nanofluids). Int J Heat Mass Transfer 2002, 45: 855–63. 10.1016/S0017-9310(01)00175-2View ArticleGoogle Scholar
- Henderson JR, Van Swol F: On the interface between a fluid and a planar wall: theory and simulations of a hard sphere fluid at a hard wall. Mol Phys 1984, 51: 991–1010. 10.1080/00268978400100651View ArticleGoogle Scholar
- Yu CJ, Richter AG, Datta A, Durbin MK, Dutta P: Molecular layering in a liquid on a solid substrate: an X-ray reflectivity study. Physica B 2000, 283: 27–31. 10.1016/S0921-4526(99)01885-2View ArticleGoogle Scholar
- Joshi AA, Majumdar A: Transient ballistic and diffusive phonon heat transport in thin films. J Appl Phys 1993, 74: 31–9. 10.1063/1.354111View ArticleGoogle Scholar
- Eastman JA, Choi SUS, Li S, Soyez G, Thompson LJ, DiMelfi RJ: Novel thermal properties of nanostructured materials. Mater Sci Forum 1999, 312–314: 629–34. 10.4028/www.scientific.net/MSF.312-314.629View ArticleGoogle Scholar
- Xie H, Fujii M, Zhang Z: Effect of interfacial nanolayer on the effective thermal conductivity of nanoparticle-fluid mixture. Int J Heat Mass Transfer 2005, 48: 2926–32. 10.1016/j.ijheatmasstransfer.2004.10.040View ArticleGoogle Scholar
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