Enhanced convective heat transfer using graphene dispersed nanofluids
© Baby and Ramaprabhu; licensee Springer. 2011
Received: 2 October 2010
Accepted: 4 April 2011
Published: 4 April 2011
Nanofluids are having wide area of application in electronic and cooling industry. In the present work, hydrogen exfoliated graphene (HEG) dispersed deionized (DI) water, and ethylene glycol (EG) based nanofluids were developed. Further, thermal conductivity and heat transfer properties of these nanofluids were systematically investigated. HEG was synthesized by exfoliating graphite oxide in H2 atmosphere at 200°C. The nanofluids were prepared by dispersing functionalized HEG (f-HEG) in DI water and EG without the use of any surfactant. HEG and f-HEG were characterized by powder X-ray diffractometry, electron microscopy, Raman and FTIR spectroscopy. Thermal and electrical conductivities of f-HEG dispersed DI water and EG based nanofluids were measured for different volume fractions and at different temperatures. A 0.05% volume fraction of f-HEG dispersed DI water based nanofluid shows an enhancement in thermal conductivity of about 16% at 25°C and 75% at 50°C. The enhancement in Nusselts number for these nanofluids is more than that of thermal conductivity.
Most industries use conventional fluids like deionized (DI) water, ethylene glycol (EG), transformer oil, etc., as heat transfer fluids. The efficiency of the heat transfer fluid determines the productivity and lifetime of the equipments, electronic circuits, machines, etc. The efficiency of the heat transfer fluids can be increased by enhancing the thermal conductivity and heat transfer properties. Conventional fluids have low thermal conductivity compared to solid counter parts. Therefore, solid particles with high thermal conductivity are generally added to these fluids to enhance their thermal conductivity. However, the addition of macro- and micro-sized particles can create problems like agglomeration and sedimentation. To avoid these problems Choi, Eastman, and co-workers [1, 2] introduced a new type of fluid called nanofluid wherein nanomaterials are dispersed in base fluids like water or EG. Subsequently many research groups have worked on the thermal conductivity and heat transfer mechanism of different nanomaterials dispersed nanofluids. Several groups have shown enhancement in thermal conductivity with Al2O3 and CuO nanoparticles dispersed water and EG based nanofluids [3–5]. The enhancement in thermal conductivity depends on several parameters like, size and shape of the nanomaterials, pH of the base fluid, temperature of the fluid, presence of additives, volume fraction of the nanomaterials, etc.
Similar to thermal conductivity, heat transfer mechanism also plays a crucial role in nanofluids. The use of nanofluids having good heat transfer properties reduces the size of the entire unit thereby increases the efficiency of the unit. Hence, it is necessary to determine the heat transfer performance of various nanofluids under dynamic flow conditions apart from steady state thermal conductivity measurements. The heat transfer measurements have been carried out for different flow conditions, laminar flow, and turbulent flow by several groups. Yang et al.  studied the heat transfer performance of several nanofluids under laminar conditions in a horizontal tube heat exchanger. Heris et al.  found heat transfer enhancement as high as 40% with Al2O3 particles. However, there is not much work on the heat transfer mechanism of carbon based nanofluids except a few on carbon nanotubes (CNTs) .
Recently, the two-dimensional one carbon atom thick graphene was found to exhibit high crystal quality and ballistic electron transport at room temperature. Theoretical study of thermal conductivity on graphene suggests that it is having unusual thermal conductivity [9, 10]. Following this, Balandin et al.  measured experimentally the thermal conductivity of about 5300 W/mK for a single layer graphene from the dependence of the Raman G peak frequency on the excitation laser power. The thermal conductivity of single layer graphene is higher than that of CNTs.
To our knowledge, there is no work on the heat transfer properties of graphene based nanofluids. In the present work, we have synthesized graphene dispersed nanofluids and studied its thermal conductivity and heat transfer properties. The nanofluids were prepared by taking DI water and EG as base fluids.
Graphite (99.99%, 45 μm) was purchased from Bay Carbon, Inc, USA. All other reagents like sulfuric acid, nitric acid, sodium nitrate, potassium permanganate, hydrogen peroxide, and ethylene glycol were analytical grade. DI water was used throughout the experiment. Graphite oxide (GO) was prepared from graphite using Hummers method . Briefly, 2 g of graphite was treated with 46 ml of sulphuric acid in an ice bath. One gram of sodium nitrate was added to the above solution slowly, followed by the addition of 6 g of potassium permanganate. At room temperature, specific quantity of water was added to the above mixture. After 15 min the suspension was further treated with hydrogen peroxide and was filtered. Finally the filter cake was washed with copious quantity of DI water. At last, the suspension was filtered and dried in vacuum oven at 40°C for 8 h. The dried GO was used for synthesizing hydrogen exfoliated graphene (HEG). Exfoliation of GO was done in hydrogen atmosphere at 200°C as reported previously . Functionalization of HEG was done by treating as synthesized HEG with conc. H2SO4:HNO3 in the ratio 3:1. The acid-HEG mixture was ultrasonicated for about 3 h at room temperature. After 3 h the sample was washed several times with DI water, filtered and dried in vacuum.
The samples were characterized with different characterization techniques. Powder X-ray diffraction (XRD) studies were carried out using a PANalytical X'PERT Pro X-ray diffractometer with Nickel-filtered Cu Kα radiation as the X-ray source. The pattern was recorded in the 2θ range of 5° to 90° with a step size of 0.016°. The Raman spectra were obtained with a WITEC alpha 300 Confocal Raman spectrometer equipped with Nd:YAG laser (532 nm) as the excitation source. Identification and characterization of functional groups were carried out using PerkinElmer FT-IR spectrometer in the range 500-4000 cm-1. Digital photograph has been taken with a Canon Power Shot A590 IS 8 Megapixel camera with 4 × optical zooming. Field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) images were obtained using, FEI QUANTA and JEOL TEM-2010F instruments, respectively. Nanofluid was prepared by dispersing a known amount of f-HEG in the base fluid by ultrasonication (30-45 min). Thermal conductivity of the suspension was measured using KD2 pro thermal property analyzer (Decagon, Canada). The probe sensor used for these measurements were of 6 cm in length and 1.3 mm in diameter. In order to study the temperature effect on thermal conductivity of nanofluid a thermostat was used. Electrical conductivity of the nanofluid was measured using ELICO Ltd CM 183, EC-TDS meter.
Results and discussion
XRD and Raman analysis
FTIR study and digital photograph
Morphology of graphene sheet
Thermal conductivity study of graphene nanofluid
Figure 5b shows the normalized thermal conductivity of f-HEG dispersed EG based nanofluids with varying temperatures and volume fractions. The thermal conductivity of EG based nanofluids did not show much enhancement for low volume fractions. Till around 0.05% volume fraction there was no enhancement in thermal conductivity. Thermal conductivity started increasing from 0.05% volume fraction onwards. For 0.08% the enhancement was about 1% at 25°C and about 5% at 50°C. This low enhancement in thermal conductivity may be due to the high viscosity of EG. Even though the enhancement in thermal conductivity of EG based nanofluids with f-HEG is low, it is slightly higher than that of CNT dispersed EG .
Electrical conductivity of f-HEG dispersed nanofluids
Convective heat transfer
where u is the velocity of flow, A is the area of cross-section, and ρ is the density of fluid. Reynolds number is defined as Re = ρuD/μ and the Prandtl number is defined as Pr = ν/α, where μ is the fluid dynamic viscosity, ν is the fluid kinematic viscosity, and α is the fluid thermal diffusivity.
Validity of the experimental setup with DI water
As shown in Figure 8b, the good coincidence between the experimental results and the calculated values for water reveals that the precision of the experimental system is considerably good. The uncertainty of the experimental system is less than 8%.
Convective heat transfer of graphene nanofluids
Both the DI water and EG based nanofluids results suggests that the presence of nanomaterials dispersed nanofluids increases the Nusselts number significantly, and the increase is considerably more at high volume fractions and high Reynolds numbers. From Figure 9 it is clear that for a given f-HEG volume fraction, the Nusselts number decreases with axial distance. This is as expected for heat transfer in the entrance region. The percentage enhancement in heat transfer is calculated using the relation [hn(x) - hf(x)] × 100/hf(x), where hf(x) and hn(x) are the heat transfer coefficient for the base fluid and nanofluid at distance x, respectively. The enhancement in heat transfer for Re = 4500 at the tube entrance is about 64 and 76% for 0.005 and 0.01% volume fractions, respectively. At the outlet, the value decreases to about 21 and 57%, respectively, for 0.005 and 0.01%. When the Reynolds number increases (Re = 15,500) the enhancement also increases and it is about 108 for 0.005% and 171 for 0.01% at the entrance. At the end, the values change to about 92 for 0.005% and 141 for 0.01%, respectively.
Similar trend is observed in the case of EG based nanofluid also. Figure 10 shows the variation of Nusselts number for 0.005 and 0.01% f-HEG dispersed EG based nanofluids. From graph it is clear that heat transfer increases with volume fraction. The enhancement in heat transfer for Re = 250 at the tube entrance is about 100 and 172% for 0.005 and 0.01%, respectively. At the exit, the value decreases to about 59 and 140%, respectively, for 0.005 and 0.01%. Like water based nanofluids, here also the Nusselts number increases with increase in Reynolds number and it is around 130 and 219% for 0.005 and 0.01% volume fractions, respectively, at the entrance for Re = 1000. At the tube exit, the values change to about 69% for 0.005% and 183% for 0.01%. The enhancement in Nusselts number for EG based nanofluids are higher than that of DI water based nanofluids.
Figure 9b shows the effect of the Reynolds number on heat transfer. Figure clearly shows that the Nusselts number increases with increasing Reynolds number. There is a large difference in the Nusselts number at Re = 4500 and that at Re = 15,500 for DI water based nanofluids. Similar will be the case for EG based nanofluids also (figure not given). This suggests that Reynolds number has a significant effect on the heat transfer mechanism. The enhancement in heat transfer is very drastic compared to the enhancement in thermal conductivity. Another important observation is that even though enhancement in thermal conductivity is very low, enhancement in heat transfer is high for EG based nanofluid.
The reason for decrease in heat transfer from entrance to exit of the tube is due to the variation of thermal boundary layer. In a simple way heat transfer can be written as k/δ with δ the thickness of thermal boundary layer. At the entrance (x = 0), the theoretical boundary layer thickness is zero, hence the heat transfer coefficient approaches infinity. The boundary layer increases with axial distance until fully developed after which the boundary layer thickness and hence the convective heat transfer coefficient is constant . Since there is not much enhancement in thermal conductivity, the effect of thickness of thermal boundary may be the reason for this huge enhancement in heat transfer.
Ding et al.  also showed that for nanofluids containing 0.5 wt% CNT, the maximum enhancement reaches over 350% at Re = 800 and showed that enhancement is a function of the axial distance from the inlet of the test section. Similar observations but with less significant enhancement was observed by Xuan and Li  in the turbulent flow regime. Wen and Ding  also showed similar features at the entrance region in the laminar flow regime when they investigated heat transfer of aqueous c-alumina nanofluids. They have observed around 47% increase in the convective heat transfer coefficient for 1.6 vol.% nanoparticles loading and Re = 1600, which is much greater than that due to the enhancement of thermal conduction (<~10%).
According to the Brownian theory , the smaller the sizes of the colloid particles, the faster the particles move, so that energy transport inside the liquid becomes stronger. The clustering or restacking of graphene is very less in solution. Each sheet will be separated out during ultrasonication and was well dispersed which helps for fast heat transfer. Another factor which helps in the enhancement of thermal conductivity as well as heat transfer is surface area of the material. The surface area of hydrogen exfoliated graphene is approximately 450 m2/g . Other factors which affect the thermal conductivity and heat transfer of nanofluids are size and shape of the nanomaterials, the material (test section) in which nanofluid is flowing, temperature of the test section as well as the surrounding, viscosity of the fluid, etc. Further studies are being carried out for deeper understanding of the mechanism.
Graphene was synthesized by hydrogen induced exfoliation of graphite oxide. Further we effectively dispersed f-HEG in the base fluids without any surfactant or additives by using ultrasonication. Systematic characterization and experiments were carried out for the sample preparation as well as the thermal conductivity and heat transfer measurements. The results suggest that there was considerable enhancement in thermal conductivity and heat transfer for f-HEG dispersed fluid compared to its base fluid. The Nusselts number increases with increase in volume fraction and Reynolds number of f-HEG. Similarly, the thermal conductivity of f-HEG increases due to the increase in volume fraction and temperature. Electrical conductivity of f-HEG dispersed base fluids was also showing enhancement compared to the base fluid.
field emission scanning electron microscopy
hydrogen exfoliated grapheme
transmission electron microscopy
The authors like to thank Indian Institute of Technology Madras, India for giving the financial support for the present work.
- Choi SUS, Zhang ZG, Yu W, Lockwood F, Grulke EA: Anomalous thermal conductivity enhancement in nanotube suspensions. Appl Phys Lett 2001, 79: 2252. 10.1063/1.1408272View Article
- 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. 10.1063/1.1341218View Article
- Lee S, Choi SUS, Li S, Eastman JA: Measuring thermal conductivity of fluids containing oxide nanoparticles. J Heat Transfer 1999, 121: 280. 10.1115/1.2825978View Article
- Das SK, Putra N, Thiesen P, Roetzel W: Temperature dependence of thermal conductivity enhancement for nanofluids. J Heat transfer 2003, 125: 567. 10.1115/1.1571080View Article
- Wang X, Xu X, Choi SUS: Thermal conductivity of nanoparticle fluid mixture. J Thermophys Heat Transfer 1999, 13: 474. 10.2514/2.6486View Article
- Yang Y, Zhang ZG, Grulke EA, Anderson WB, Wu G: Heat transfer properties of nanoparticle-in-fluid dispersions (nanofluids) in larninar flow. Int J Heat Mass Transfer 2005, 48: 1107. 10.1016/j.ijheatmasstransfer.2004.09.038View Article
- Heris SZ, Etemad G, Esfahany MN: Experimental investigation of oxide nanofluids laminar flow convective heat transfer. Int Commun Heat Mass Transfer 2006, 33: 529. 10.1016/j.icheatmasstransfer.2006.01.005View Article
- Ding Y, Alias H, Wen D, Williams RA: Heat transfer of aqueous suspensions of carbon nanotubes (CNT nanofluids). Int J Heat Mass Transfer 2006, 49: 240. 10.1016/j.ijheatmasstransfer.2005.07.009View Article
- Mingo N, Broido DA: Carbon Nanotube Ballistic Thermal Conductance and Its Limits. Phys Rev Lett 2005, 95: 096105. 10.1103/PhysRevLett.95.096105View Article
- Saito K, Nakamura J, Natori A: Ballistic thermal conductance of a graphene sheet. Phys Rev B: Condens Matter 2007, 76: 115409. 10.1103/PhysRevB.76.115409View Article
- Balandin AA, Ghosh S, Bao W, Calizo I, Teweldebrhan D, Miao F, Lau CN: Superior Thermal Conductivity of Single-Layer Graphene. Nano Lett 2008, 8: 902. 10.1021/nl0731872View Article
- Hummers WS, Offeman RE: Preparation of Graphitic Oxide. J Am Chem Soc 1958, 80: 1339. 10.1021/ja01539a017View Article
- Kaniyoor A, Baby TT, Ramaprabhu S: Graphene synthesis via hydrogen induced low temperature exfoliation of graphite oxide. J Mater Chem 2010, 20: 8467. 10.1039/c0jm01876gView Article
- Si Y, Samulski ET: Exfoliated Graphene Separated by Platinum Nanoparticles. Chem Mater 2008, 20: 6792. 10.1021/cm801356aView Article
- Wei L, Ming TD, Bing HY, Hui YC, Qiang SZ, Cheng CX, Meng CC, Xiang HP, Chang L, Hong YQ: Low-Temperature Exfoliated Graphenes: Vacuum-Promoted Exfoliation and Electrochemical Energy Storage. ACS Nano 2009, 3: 3730. 10.1021/nn900933uView Article
- Li ZQ, Lu CJ, Xia ZP, Zhou Y, Luo Z: X-ray diffraction patterns of graphite and turbostratic carbon. Carbon 2007, 45: 1686. 10.1016/j.carbon.2007.03.038View Article
- Wu H-L, Yang Y-T, Ma C-CM, Kuan H-C: Molecular Mobility of Free-Radical-Functionalized Carbon-Nanotube/Siloxane/Poly(urea urethane) Nanocomposites. J Polym Sci A: Polym Chem 2005, 43: 6084. 10.1002/pola.21121View Article
- Liu M-S, Lin MC-C, Huang I-T, Wang C-C: Enhancement of thermal conductivity with carbon nanotubes for nanofluids. Int Commun Heat Mass Transfer 2005, 32: 1202. 10.1016/j.icheatmasstransfer.2005.05.005View Article
- Maxwell JC: A Treatise on Electricity and Magnetism. Volume 1. Oxford: Pergamon; 1904.
- Hamilton RL, Crosser OK: Thermal conductivity of heterogeneous two-component systems. Ind Eng Chem Fundam 1962, 1: 187. 10.1021/i160003a005View Article
- Hasselman DPH, Johnson LF: Effective thermal conductivity of composites with interfacial thermal barrier resistance. J Compos Mater 1987, 21: 508. 10.1177/002199838702100602View Article
- Shah RK: Thermal Entry Length Solutions for the Circular Tube and Parallel Plates. In Proceedings of the 3rd National Heat Mass Transfer Conference. Volume 1. Indian Institute of Technology, Bombay; 1975. Paper no. HMT-11–75 Paper no. HMT-11-75
- Dittus FW, Boelter LMK: Heat Transfer in Automobile Radiators of the Tubular Type. University of California Publications in English 1930, 2: 443–461.
- Xuan YM, Li Q: Investigation on convective heat transfer and flow features of nanofluids. J Heat Transfer 2003, 125: 151. 10.1115/1.1532008View Article
- Wen DS, Ding YL: Convective heat transfer of nanofluids at the entrance region under laminar flow conditions. Int J Heat Mass Transfer 2004, 47: 5181. 10.1016/j.ijheatmasstransfer.2004.07.012View Article
- Xuan Y, Li Q, Hu W: Aggregation structure and thermal conductivity of nanofluids. AIChE J 2003, 49: 1038. 10.1002/aic.690490420View Article
This article is published under license to BioMed Central Ltd. This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.