International Communications in Heat and Mass Transfer 57 (2014) 128–131

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International Communications in Heat and Mass Transfer

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

Enhanced thermal conductivities of graphene oxide nanofluids☆

Zeinab Hajjar, Ali morad Rashidi ⁎, Ahmad Ghozatloo
Nanotechnology Research Center, Research Institute of Petroleum Industry (RIPI), West Blvd. Azadi Sport Complex, P.O. Box: 14665-1998, Tehran, Iran

a r t i c l e i n f o a b s t r a c t

Available online 17 July 2014 In this study, graphene oxide (GO) nanosheets were synthesized by the modified Hummers method. GO
structure was estimated by XRD, UV–vis-spectrophotometer and SEM imaging. Then homogeneous and stable
Keywords: GO/water nanofluid was prepared. The effects of GO concentration and temperature on the thermal conductivity
Graphene oxide were investigated.
Thermal conductivity The measurements of thermal conductivity indicate that the nanofluids have substantially higher thermal
Nanofluid
conductivities than the base fluid.
UV–vis
The thermal conductivity enhancement depends strongly on the concentration of GO and increases with the
increasing loading. When the nanosheet loading is 0.25 wt.%, the enhancement ratio is 33.9% at 20 °C and
when the temperature increased to 40 °C the enhancement is up to 47.5%. Therefore the level of enhancement
is dependent of temperature in the measured temperature range.
© 2014 Elsevier Ltd. All rights reserved.

1. Introduction
Most industries (power generation, automobiles, air conditioning, mi-
croelectronics and cooling systems) use conventional fluids like water,
ethylene glycol (EG) and transformer oil as heat transfer fluids [1]. Poor
thermal conductivity of these fluids greatly limits the cooling role in
heat exchangers [2]. Thus, improvement of the heat transfer capabilities
of fluids is an urgent need. The advances in nanotechnology have resulted
in the development of a class of fluids termed nanofluids (NFs). NFs,
which are suspensions prepared by dispersing nanoparticles, rods or
tubes in the base fluids with high stability have attracted much attention
due to the anomalous thermal conductivity enhancement [3] which
translates into lower operating costs, higher energy efficiency and better
performance [4–6].
Carbon nanostructures have higher thermal conductivity than other
nanoparticles because of their large intrinsic thermal conductivity and
low density compared with metals or metal oxides and also due to
strong C\C covalent bonds and phonon scattering [7]. The experimen-
tal results demonstrate that carbon materials, such as carbon nanotubes
[8–13], graphite nanoparticles [14,15], exfoliated graphite nanofibers
[16] and diamond nanoparticles [17,18], are good candidates for use in
NFs. For example, axial thermal conductivity of carbon nanotubes
(CNTs) is 3000 W/mK [19] and in-plane thermal conductivity of
single-layer graphene is 5000 W/mK [20]. Superb thermal conduction
property of graphene is beneficial for their application in NFs [21].
☆ Communicated by W.J. Minkowycz.
⁎ Corresponding author.
E-mail address: Rashidiam@ripi.ir (A. Rashidi).
Graphene has 2D structure, and the heat transfer properties and
mechanism are different from nanoparticles (NPs) and CNTs [22]. There-
fore it is very interesting to investigate the thermal properties of NFs.
Many methods have been applied to prepare graphene, such
as sonication in various solvents [23], solvothermal synthesis [24],
micromechanical methods [25] and chemical vapor deposition (CVD)
[26]. Among them, the chemical approach is suitable to produce
graphene nanosheets [27]. Graphite is a usual raw material for produc-
tion of graphene nanosheets (GNS) by the chemical methods. Therefore,
in this paper, graphite powder was applied to produce graphene oxide
nanosheets (GONs) which are the nanoparticles for water-based NFs.
Heat transfer by convection process depends in part upon thermal con-
ductivity of the fluid. Therefore in all of the physical properties of NFs,
thermal conductivity is the most complex and for many applications
the most important one.
2. Materials
Graphite powder (99.99%, 45 μm) was purchased from Bay Carbon,
Inc., USA. Nitric & sulfuric acids, potassium permanganate, sodium
nitrate and hydrogen peroxide were analytical grade. Deionized water
(DI) was used throughout the experiment.
Graphite oxide (GO) was prepared from graphite powder by the
modified Hummers method as described elsewhere [28]. Briefly, 2 g of
natural graphite powder was treated with 46 ml of mixed concentrated
nitric and sulfuric acids in an ice bath. 1 g of sodium nitrate was slowly
added to the above solution, followed by the addition of 6 g of potassi-
um permanganate.

http://dx.doi.org/10.1016/j.icheatmasstransfer.2014.07.018
0735-1933/© 2014 Elsevier Ltd. All rights reserved.
 Z. Hajjar et al. / International Communications in Heat and Mass Transfer 57 (2014) 128–131
Fig. 1. Schematic of experimental set-up for measuring thermal conductivity of the NFs.
During the reaction of natural graphite flakes with concentrated ni-
tric and sulfuric acids, water molecules, NO− 3 and SO4
−2
cations were
inserted into the graphene layers and expanded the interlayer spacing
in the graphite crystal structure. 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. The
graphite oxide can be effectively exfoliated via ultrasonic vibration to
generate GO. Finally the filter cake was washed with copious quantity
of DI water. At last, the suspension was filtered and dried in a vacuum
oven at 40 °C for 8 h. The product was a loose brown powder, and it
could be dispersed well in water.
2.1. Characterization techniques
The size and morphological characterization of the GONs were ex-
amined by using scanning electron microscopy (SEM, Hitachi S-4200
scanning electron microscope). The SEM samples were prepared by
dispersing the powder products in alcohol by ultrasonic treatment,
dropping the suspension onto a holey carbon film supported on a
copper grid and dried in air [22].
The UV–vis spectrum (PerkinElmer Lambda 900 spectrometer oper-
ating between 200 and 1100 nm) was used. The samples were diluted
up to the extent that they were suitable for UV–vis measurements.
One hour before the measurement, the UV spectrometer was turned
on to be warmed up. The GO/water NFs were filled in a 1 cm quartz
cuvette. When filling the cuvettes, care was taken to avoid bubbles,
while visually inspected for bubbles [29]. Each measurement was
repeated for three times to achieve a better accuracy.
Fig. 2. XRD patterns of GO.
129
Fig. 3. UV–vis spectra of GO dispersed in water.
A transient short hot-wire technique was applied to measure ther-
mal conductivities of NFs from 10 to 40 °C [30] by a KD2 Prothermal
properties analyzer (Decagon devices, Inc., USA). Fig. 1 illustrates the
experimental set-up for measuring thermal conductivity.
The instrument had a probe of 60 mm length and 1.3 mm diameter, a
thermoresistor and a microprocessor to control and measure the
conduction in the probe. The instrument had a specified accuracy of
5%. In order to obtain precise results, the sample and the probe were
maintained at constant temperature for about 15 min.
A temperature-controlled bath (Ningbo Scientz Co., Ltd.) was used
to maintain different temperatures of NFs during the measurement
process. After the sample temperature reached the bath temperature,
sample was kept at temperature for a further 30 min to ensure temper-
ature equilibrium before a measurement was taken. Numbers of
thermal conductivity measurements were taken for each sample and
only a mean value of those with correlation coefficient greater than
0.99 was considered.
2.2. Graphene oxide structure
The crystal structure of GONs was investigated by an XRD diffractom-
eter (X-pert Philips, pw 3040/60, Cu, λ = 1/54,056, β = 0/1 or 10%, on a
2100 series). The XRD pattern of GO was shown in Fig. 2.
As shown in Fig. 2, one high-intensity broad peak appeared about
2θ = 12.5 corresponding to (002) diffraction line (d-space 3.4 Å) plane
of graphite. The GO structure was proved [32].
UV–vis spectroscopy analysis is a convenient way to characterize
the structure of carbon allotropes [31]. It is known that GO is active in
the UV–vis region and exhibit characteristic bands corresponding to
Fig. 4. SEM image of GO.
130 Z. Hajjar et al. / International Communications in Heat and Mass Transfer 57 (2014) 128–131

Table 1
Specification of the samples (GO/water NFs).

Name of sample (#) Weight percentage (%)

Graphene oxide Deionized water

GO-1 0.05 99.95

GO-2 0.10 99.90
GO-3 0.15 99.85
GO-4 0.20 99.80
GO-5 0.25 99.75

additional absorption due to Van Hove singularities [32]. GO bundles,

however, are hardly active in the wavelength region of 230, where
their photoluminescence is quenched [33]. Fig. 3 illustrates the UV–vis
spectra of GO structure solutions, obtained one week after dispersion.
According to Fig. 3 the typical UV–vis absorption peak of GO appears
at 227 nm. Therefore it was found that GO structure was prepared. Fig. 6. Thermal conductivity of the samples versus temperature.

2.3. SEM imaging
In theory, the single-layer graphene sheet is atomically flat with a
well-known van der Waals thickness of 0.34 nm [34], while GO sheets
are expected to be ‘thicker’ due to the presence of covalently bound ox-
ygen and the displacement of the sp3 hybridized carbon atoms slightly
above and below the original graphene plane [35].
Fig. 4 shows the typical SEM images of GO. The sizes of nanosheets
are in the range of 1–3 μm. GO tend to congregate together to form
multilayer agglomerates [22].
Most GONs exist in the form of thin few-layer graphene, and some of
them are folded at the edge of nanosheets [22].
2.4. Preparing nanofluids
A two-step method was used to prepare the GO/water NFs [36]. The
fixed quality of GO with different concentrations (0.05, 0.1, 0.15, 0.2 &
0.25 wt.%) was dispersed in water. The NF mixture was stirred and son-
icated (60 kHz, 200 W) using an ultrasonic washing machine (Shanghai
Shengpu Ultrasonic Equipment, SC-350). Specifications of the samples
were tabulated in Table 1.
Volume fraction of the powder could calculate from the weight
of dry powder using the density of graphite (2.62 g/cm3) and the total
volume of the suspension [37].
3. Results and discussion
3.1. Stability of nanofluids
GO has good hydrophilic nature and good compatibility with water
because the hydroxyl groups are bonded to the edges of the basal planes
of GONs, which are formed during the oxidation reaction. Therefore
GO/water NFs have long-term stability [22]. Fig. 5 illustrates the stability
of GO in water.
According to Fig. 5 dispersion was observed and no sedimentation of
GONs was observed in water. Consequently, GO has a good stability and
dispersion in base fluid.
3.2. Thermal conductivity of nanofluids
Thermal conductivity enhancement of the samples with different
concentrations and temperatures was investigated. Fig. 6 shows
the thermal conductivity of water as base fluid and 0.5 to 0.25 wt.%
GO/water NFs at different temperatures.
Thermal conductivity of the NFs increased notably with an increase
of the GO weight fraction (%) in water. For example thermal conductivity
of the NF with 0.05 wt.% of GO showed a 14.75% increase with respect to
water and with an increasing GO concentration up to 0.25 wt.%, thermal
conductivity increases up to 47.57%. Improvement of thermal conduc-
tivity of the samples in various concentrations and temperatures is
presented in Table 2.
From Fig. 3, it can be observed that there is an approximate linear
relationship between the enhancement ratios and weight fractions.
NFs may be used under various temperatures, and some researchers
have investigated the temperature effect on the thermal conductivity
of the nanofluids [1]. For sample GO-5 (when the loading is 0.25 wt.%),
the enhancement ratio is up to 31.03 at 10 °C and improved up to
47.5 by increasing of temperature up to 40 °C. Therefore the thermal

Table 2
Improvement of thermal conductivity of the samples in various concentrations (%).

Temp (°C) GO-1 GO-2 GO-3 GO-4 GO-5

(0.05 wt.%) (0.10 wt.%) (0.15 wt.%) (0.20 wt.%) (0.25 wt.%)

10 1.72 12.07 20.69 24.14 31.03

20 6.78 15.25 22.03 27.12 33.90
30 11.67 15.00 20.00 28.33 45.00
40 14.75 24.59 31.15 39.34 47.54
Fig. 5. Digital picture of GO dispersed in water.
 Z. Hajjar et al. / International Communications in Heat and Mass Transfer 57 (2014) 128–131
conductivity enhancement ratios increased by increasing of tempera-
ture which is similar to the conclusion of other researches [38–41].
4. Conclusion
Graphene oxide was synthesized by the modified Hummers method.
The hydrophilic surfaces let graphene oxide nanosheets have good com-
patibility with water. So GO was effectively dispersed in water without
any surfactant or additives just by using ultrasonication. The thermal
conductivity of suspensions of GO/water nanofluids at five different
concentrations and temperatures was investigated.
Key conclusions can be summarized as follows:
➣ Noticeable thermal conductivity enhancements were observed in all
types of GO/water nanofluids and it has been confirmed that GO
nanofluids have potential as heat transfer fluids.
➣ In comparison, thermal conductivity of nanofluids containing GO is
higher than the nanofluids containing spherical nanoparticles with
the same loading. The facts demonstrate that the heat transfer
mechanism may be different when the structure is different.
➣ Among all types of GO/water nanofluids, GO-5 showed the best
result in the case of thermal conductivity enhancement over the
base fluid (47.54% increasing than water at 40 °C).
➣ Heat transport in the GO/water NFs is one of the major contributions
to the increase in the effective thermal conductivity of nanofluids.
➣ The heat conduction along the length of the sheet direction plays an
important role for the high thermal conductivity of graphene oxide
composites.
➣ The increase of temperature in all the samples led to thermal con-
ductivity enhancement and a semi-linear relationship was obtained
between these two parameters in the range of 10 to 40 °C.
➣ The outstanding thermal properties of GO are favorable combination
of the high aspect ratio, two-dimensional geometry, stiffness and
low thermal interface resistance of graphene nanosheets.
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