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Synthesis and Reactivity in Inorganic, Metal-Organic,

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A Simple Solution Phase Synthesis of Copper Nanofluid

Using Single-step Glucose Reduction Method
a a
U. Sandhya Shenoy & A. Nityananda Shetty
a
Department of Chemistry, National Institute of Technology Karnataka, Surathkal,
Mangalore, Karnataka, India
Published online: 25 Jan 2013.

To cite this article: U. Sandhya Shenoy & A. Nityananda Shetty (2013): A Simple Solution Phase Synthesis of Copper Nanofluid
Using Single-step Glucose Reduction Method, Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry,
43:3, 343-348

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 Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 43:343–348, 2013
Copyright C Taylor & Francis Group, LLC

ISSN: 1553-3174 print / 1553-3182 online

DOI: 10.1080/15533174.2012.740758

A Simple Solution Phase Synthesis of Copper Nanofluid

Using Single-step Glucose Reduction Method
U. Sandhya Shenoy and A. Nityananda Shetty
Department of Chemistry, National Institute of Technology Karnataka, Surathkal, Mangalore,
Karnataka, India

submerged arc nanoparticle synthesis, laser ablation in liquids,

Synthesis of copper nanofluid by a one-step method involving arc spray nanofluid synthesis technique, or chemical methods
the reduction of copper sulfate by glucose in the presence of sodium such as polyol method, chemical reduction method, microwave
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lauryl sulfate has been reported. The method relies on the simulta- method.[1,5–9] Two-step methods as well as one-step physical
neous formation and dispersion of the copper nanoparticles in the
base fluid. Effects of various reaction parameters on the size and
methods have inherent limitations. There are only a few reports
reaction rate are investigated using different techniques. Thermal on the synthesis of nanofluids by single-step chemical method.
conductivity and viscosity measurements of the nanofluid are also Here in we report synthesis of copper nanofluids by single-
carried out. Sedimentation measurement reveals that the fluid is step chemical reduction method in the presence of sodium lauryl
stable for a minimum period of six weeks. The reported method is sulfate (SLS). The method is simple and allows easy variation
found to be rapid, simplistic, and cost effective.
of parameters to achieve the desired properties in the resulting
nanofluid. Since the application of the nanofluid is in the field of
Keywords copper, nanofluid, nanoparticles, thermal conductivity
cooling, thermal conductivity and viscosity measurements are
carried out along with the sedimentation measurements. The
fluid shows promising results.
INTRODUCTION
Cooling has become one of the most crucial technical chal-
lenges with advancement of device miniaturization and escalat- EXPERIMENTAL
ing need for improvement of heat transfer. Heat dissipation could
Synthesis of Copper Nanofluids
be increased by increasing the area available for heat exchange
All the reagents used in the experiment were of analytical
to the surrounding but this will lead to the increase in the device
grade and were used without further purification. In a typi-
size as well as the cost of production. Alternative would be to
cal procedure, aqueous solution of copper sulfate pentahydrate
increase the effective thermal conductivity of the conventional
(20 mL, 0.1 M) was made sufficiently alkaline by adding am-
base fluids, which basically have a lower magnitude, by the ad-
monium hydroxide. Further to this deep blue solution, solution
dition of particles with higher thermal conductivity.[1] Addition
of SLS in ethylene glycol (20 mL, 0.01 M) was added and
of metal and metal oxide nanoparticles would be a proficient
stirred for 15 min. Later glucose (3 g) was added and stirred at
way to bring about dramatic improvements in the heat transfer
70◦ C. During heating the color changes from blue to greenish
characteristics of the base fluid.
to golden yellow. At this point the pH of the reaction mixture
Synthesis of nanofluids could be done by a two-step method
was brought down to 3 by addition of sulfuric acid. The heat-
in which the nanoparticles are first prepared by inert gas con-
ing was continued until the color changed to reddish brown
densation, mechanical alloying, solvothermal synthesis, or other
color. On cooling copper nanofluid was obtained. The synthe-
techniques.[2–4] In the second step these particles are dispersed
sis was also carried out at varying concentration of reducing
into the base fluid and several methods such as ultrasonic ag-
agent, surfactant, and overall dilution of the reaction mixture.
itation, adjustment of pH, or addition of surfactant are used
Similar reactions were carried out by subjecting the mixtures to
to bring about uniform dispersion and prevent agglomeration.
microwave radiation. The solution was irradiated for 5 min with
One-step nanofluid synthesis could be done by either physi-
50% power. Several parameters such as ratio of the reactants,
cal methods such as direct evaporation condensation technique,
reaction time, and power of microwave radiation were varied
and its effect on particle size was studied.
Received 9 June 2012; accepted 11 June 2012.
Address correspondence to A. Nityananda Shetty, Department of
Characterization
Chemistry, National Institute of Technology Karnataka, Surathkal, Ma- The nanofluid was diluted with absolute ethanol and cen-
ngalore – 575025, Karnataka, India. E-mail: nityashreya@gmail.com trifuged for 1 h. The settled particles were given repeated wash

343
 344 U. SANDHYA SHENOY AND A. NITYANANDA SHETTY
with water and ethanol and finally dried at 80◦ C. These nanopar-
ticles were characterized by X-ray diffraction (XRD) technique,
field emission scanning electron microscopy (FESEM), and
energy-dispersive X-ray analysis (EDXA). The nanofluids as
such were characterized by transmission electron microscopy
(TEM), Fourier-transform infrared (FT-IR) spectroscopy, and
UV-visible spectroscopy. The thermal conductivity as well as
rheological measurements of the fluids were also done.
XRD patterns of the nanoparticles were taken on a JEOL X-
ray Diffractometer (Model DX GE 2P, NITK Surathkal) using
Ni-filtered Cu Kα radiation (λ = 1.54178 Å) with an operating
voltage of 30 kV and accelerating voltage was set at 0.06◦ /s in the
2θ range 35–85◦ . The FESEM images were taken on a Supra
40VP FESEM (IIT Kanpur) having a resolution up to 2 nm.
EDX Analysis was carried out on a JEOL JSM 6380LA model
analytical scanning electron microscope (NITK Surathkal).
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The TEM images of the nanofluids were recorded on a Philips
CM200 transmission electron microscope (IIT Mumbai) operat-
ing with an accelerating voltage of 20–200 kV with a resolution
of 2.4 Å. The samples for TEM were prepared by sonicating the
nanofluid and later placing it on carbon coated copper grid for
analysis.
The ingredients of the solution were identified using Nicolet
Avatar 330 FTIR spectrometer (NITK Surathkal). UV-visible
spectrum of the nanofluid was taken using an Ocean Optics
SD2000 fiber-optic spectrometer (NITK Surathkal) at room tem-
perature. The thermal conductivity of the nanofluid was mea-
sured using KD2 pro thermal property analyzer (Decagon De-
vices, USA). The measurements were made using KS-1 sensor
(Decagon Devices, USA) in low power mode with 1-min read
time. Rheological measurements were made using Brookfield
LV DV III ultra rheometer (NITK Surathkal).
RESULTS AND DISCUSSION
Results of XRD and EDX Analysis
The phase structure and the purity of the products were ex-
amined by XRD studies. The powder XRD pattern of the as ob-
FIG. 1. Powder XRD pattern of copper nanoparticles.
FIG. 2. EDX pattern of copper nanoparticles.
tained copper nanoparticles is shown in Figure 1. The diffraction
peaks could be indexed to the face centered cubic Cu [JCPDS
Card No. 04–0838, a = 3.6150 Å, Space group: Fm3m (225)].
The peaks correspond to (111), (200), and (220) planes, respec-
tively.
The average size of the particle was calculated using Scher-
rer’s formula.[10]
τ = K λ/Bcos θ [1]
where T is the thickness of the crystal (in Å), K is the shape
factor, λ is the X-ray wavelength, B is extra peak width, and θ is
the Bragg angle. No peaks of impurities such as those of cuprous
or cupric oxide were detected, suggesting the high purity of the
products.
The chemical composition and purity of the products were
also examined using EDX analysis. A typical EDX spectrum
of the copper nanoparticles is shown in the Figure 2. Only
copper is detected in the spectrum indicating that there is no
contamination.
Effect of Reaction Parameters
Effect of Ratio of Reactants
The effect of amount of glucose added on the size of the par-
ticle was studied both under thermal and microwave conditions
by varying the molar ratio of glucose to copper sulfate from 4.2
to 13.8. The results are as shown in the Table 1.
The results indicate that the size of the particles decrease
with increase in concentration of glucose, which is because of
the increase in the nucleation rate leading to formation of smaller
particles.
Glucose reduces copper ions as shown in Eq. 2.
Cu2+ + C6 H12 O6 + H2 O → Cu + C6 H12 O7 + 2H+ [2]
According to this equation rate and amount of electrons sup-
plied to copper ions is determined by concentration of glucose.
At lower concentration of reducing agent, the reduction rate of
 ONE-STEP SYNTHESIS OF NANOFLUID
copper precursor is slow and therefore only a few nuclei are
formed at the nucleation step. Precipitating copper atoms at the
later period of reactions are mostly involved in particle growth
by collision with already generated nuclei rather than forma-
tion of new particles. This leads to the formation of larger sized
particles. With increase in concentration of reducing agent, re-
duction rate is enhanced, leading to the formation of smaller
particles. At a higher reduction rate the number of precipitating
metallic clusters increases sharply and hence more nuclei are
formed during the nucleation period. Eventually the size of the
particles decreases because the amount of solute available for
particle growth per growing particle decreases with increasing
number of nuclei.[11]
Effect of Addition of Ammonia
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It was observed that when the reaction between copper sulfate
and glucose was carried out in neutral condition, the reaction
took place very fast and the product separated out as a brown
suspension of cuprous oxide. Since the Cu2+ ions exist as free
ions, the overall concentrations of the reactants are higher and
Cu2+ ions rapidly get reduced to Cu2 O rather than Cu. When
the reaction was carried out in the presence of ammonia, copper
nanofluid was obtained.
The standard half cell potential for the reduction of copper
ion (Eq. 3) is 0.34 V.
Cu2+ + 2e− → Cu
The standard half-cell potential for the redox equilibrium of
glucose is 0.050 V.
C6 H12 O7 + 2H+ + 2e− → C6 H12 O6 + H2 O
FIG. 3. A typical FESEM (a) and TEM (b) image of the product obtained.
345
The overall standard state cell potential for the reaction given
in Eq. 2 is 0.29 V and hence favorable. However the reaction
is not run under standard state conditions. It takes place in
a solution to which aqueous ammonia has been added. Most
of the copper ion is therefore present as Cu(NH3 )4 2+ complex
ion. The half-cell potential for the reduction of this complex is
considerably smaller than that for reduction of Cu2+ ion. This
leads to a significant decrease in the overall cell potential for the
reaction because the complex ion is a much weaker oxidizing
agent than the Cu2+ ion.
The fact that the reaction is run in an aqueous ammonia
solution has an effect on the electrode potential of the glucose
system also because of a pair of H+ ions involved. The half-
cell potential for the reaction given in Eq. 4 therefore depends
on the pH of the solution. Because two H+ ions are given off
when glucose is oxidized, the reaction quotient for this reaction
depends on the square of H+ ion concentration. A change in
solution pH from standard state conditions to pH of 11, therefore
results in a decrease of half-cell potential for this reaction and
increase in the reducing strength of glucose. The increase in
the reducing strength of glucose when the reaction is run at
pH 11 more than compensates for the decrease in oxidizing
strength of Cu2+ in the presence of ammonia. Therefore the
overall cell potential for the reduction of copper ions to copper
metal is actually more favorable in aqueous ammonia than under
standard state conditions.
[3]
Effect of Dilution
The reaction mixtures were diluted with varying amount of
water. It was seen that with dilution the size of the particle
decreased. The particle size ranged between 32 nm for zero
[4] dilution to 21 nm for 50 mL dilution. It further decreased to
 346 U. SANDHYA SHENOY AND A. NITYANANDA SHETTY
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FIG. 4. UV-vis spectrum of copper nanofluid. The adsorption edge at 545 nm
shows the presence of copper particles.
16 nm for 100 mL dilution. The observed trend can be explained
as follows, with increase in the overall dilution the proximity
between the precipitating metal atoms decreases and hence the
collision between them is reduced preventing the particle growth
and hence resulting in smaller size of the nanoparticles formed.
Effect of Surfactant
The effect of surfactant concentration on particle size is as
shown in the Table 2. It was observed that the addition of SLS
as a surfactant decreases the size of the copper nanoparticles.
This could be attributed to the capping effect of SLS resulting in
restriction on growth of particles and controlling the size of cop-
FIG. 5. FTIR spectra of (a) pure ethylene glycol and (b) copper nanofluid.
per particles. With increase in concentration of SLS the capping
action increases and hence size of the particles decreases.
SLS not only controlled the size of particles but also provided
the required stability to the fluid. In the absence of surfactant
the fluid was highly unstable and the particles started settling
as soon as they were formed. In the presence of surfactant, the
fluid was stable for a minimum period of six weeks at room
temperature under stationary conditions.
The stability of the as-synthesized fluid is better than the one
achieved by the two-step method wherein they could achieve it
for one week in the case of copper–transformer oil system and
30 h for copper–water system and in the case of the one-step
chemical method where the copper nanofluid stayed stable for
a duration of three weeks.[12,13] The stability of the fluid could
be ascribed to the small size of the particles and their uniform
distribution.
Effect of Microwave Irradiation
The reaction was carried out at varying power and reaction
time. Irradiation for 5 min with 30% power yielded particles of
13 nm but the reaction was not complete. At 50% irradiation
the reaction proceeded towards completion. For 50%, 70%, and
90% the size of the particles was 33, 28, and 19 nm, respectively.
The irradiation duration also had an effect on size as well as
progress of reaction. For 2.5-min irradiation, particles formed
had a size of 30 nm but the reaction was incomplete. For 5-, 7.5-,
and 10-min irradiation the sizes obtained were 33, 28, and 17 nm
respectively. The observed trend is attributed to the fact that
microwave irradiation causes increased friction and collision of
molecules, causing increase in nucleation rate. With increase
in the power and irradiation duration these effects increase and
hence reduction in growth of particles is seen.
 ONE-STEP SYNTHESIS OF NANOFLUID 347

Typical FESEM and TEM image is shown in Figure 3. The

structure is somewhat irregular.

RESULTS AND DISCUSSION

Results of UV-Vis and FTIR Analysis
Figure 4 shows the UV-vis spectrum of the as-synthesized
nanofluid. The absorption edge at 545 nm confirms the presence
of copper nanoparticles.[14] Figure 5 shows the FTIR spectra of
pure ethylene glycol (a) and copper nanofluid (b). The oxidized
products of ethylene glycol are not detectable in Figure 5, indi-
cating that the copper ions are reduced by glucose and not ethy-
lene glycol. This method preserves the advantages of chemical
reduction method as well as polyol method.

Results of Thermal Conductivity and Rheological

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Measurements
FIG. 6. Variation of thermal conductivity ratio (Kf /Kb ) with nanoparticle The nanofluid showed a thermal conductivity of 0.812
weight fraction (Fw ). Wm−1K−1 for particle weight fraction of 0.3%. With decrease

FIG. 7. Viscosity measurements. (a) Shear stress (τ ) versus shear rate (γ ) at 30◦ C for particle loading of 0.3%. (b) Viscosity (η) as a function of shear rate (γ )
for particle loading of 0.3% at different temperatures. 20◦ C, 25◦ C, 30◦ C, •35◦ C, 40◦ C, 45◦ C, and 50◦ C. (c) Viscosity (η) as a function of temperature
(T) for particle loading of 0.3%. (d) Variation of relative viscosity (ηf /ηb ) of nanofluid with particle weight fraction (Fw ).
 348 U. SANDHYA SHENOY AND A. NITYANANDA SHETTY
in the weight fraction up to 0.15%, the thermal conductiv-
ity increased and showed a maximum conductivity of 0.979
Wm−1K−1. With further decrease, the thermal conductivity de-
creased. Figure 6 shows the variation of thermal conductiv-
ity ratio with particle weight fraction. Kf and Kb represent the
thermal conductivity of the nanofluid and the base fluid, re-
spectively. Fw indicates the nanoparticle weight fraction. The
thermal conductivity ratio increases almost linearly with the
weight fraction of copper nanoparticles. The initial increase in
the thermal conductivity ratio with increase in particle weight
fraction could be accredited to the higher thermal conductiv-
ity of the copper nanoparticles and their uniform distribution.
The thermal conductivity of the synthesized copper nanofluid
is found to be significantly higher than the reported value
of 0.279 Wm−1K−1 and 0.6 Wm−1K−1 for copper nanofluid
(0.1%) synthesized by sodium hypophosphite reduction tech-
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nique and 0.259 Wm−1K−1 for copper nanofluid (0.5%) syn-
thesized by single-step physical method of direct evaporation
technique.[1,13,15]
Establishment of the rheological behavior of the nanofluids
becomes an important aspect during its application as coolant.
The variation of shear stress (τ ) with shear rate (γ ) at 30◦ C
is as shown in Figure 7a. The linear relation between shear
stress and shear rate demonstrates the Newtonian behavior of
the nanofluid.[15] Figure 7b demonstrates that the viscosity (η) of
the fluid is independent of shear rate (γ ) at different temperatures
from 20–50◦ C. The viscosity (η) of the fluid was measured at
different particle weight fraction (Fw ) and temperature (T). It is
seen that the viscosity increases with increase in particle concen-
tration and decreases with temperature. Figure 7c shows varia-
tion of viscosity with temperature and Figure 7d shows the varia-
tion of relative viscosity with particle weight fraction. The trend
is similar to the one reported in Li et al.[16] ηf and ηb represent
the viscosity of the nanofluid and the base fluid, respectively.
CONCLUSIONS
A straightforward synthetic route for the preparation of cop-
per nanofluids using copper sulfate and glucose has been re-
ported. The addition of SLS led to the increase in stability of the
nanofluid up to a minimum period of six weeks. The characteri-
zation of the fluids confirmed the formation of copper nanoparti-
cles with size less than 50 nm. The nanofluid so formed showed
Newtonian behavior and enhanced thermal conductivity com-
pared with the base fluid. To conclude, the method is found to
be simple, efficient, and low cost.
REFERENCES
1. Eastman, J. A.; Choi, S. U. S.; Li, S.; Yu, W.; Thompson, L. J. Anomalously
increased effective thermal conductivities of ethylene glycol based nanoflu-
ids containing copper nanoparticles. Appl. Phys. Lett. 2001, 78, 718–720.
2. Wang, X.; Xu, X.; Choi, S. U. S. Thermal conductivity of nanoparticle fluid
mixture. J. Thermophys. Heat Transfer 1999, 13, 474–480.
3. Chopkar, M.; Das, P. K.; Manna, I. Synthesis and characterization of
nanofluid for advanced heat transfer applications. Scr. Mater. 2006, 55,
549–552.
4. Zhu, H.; Zhang, C.; Yin, Y. Rapid synthesis of copper nanoparticles by
sodium hypophosphite reduction in ethylene glycol under microwave irra-
diation. J. Cryst. Growth 2004, 270, 722–728.
5. Lo, C. H.; Tsung, T. T.; Chen, L. C.; Su, C. H.; Lin, H. M. Fabrication
of copper oxide nanofluid using Submerged Arc Nanoparticle Synthesis
System (SANSS). J. Nanopart. Res. 2005, 7, 313–320.
6. Phuoc, T. X.; Soong, Y.; Chyu, M. K. Synthesis of Ag-deionized water
nanofluids using multi-beam laser ablation in liquids. Opt. Lasers Eng.
2007, 45, 1099–1106.
7. Chang, H.; Tsung, T. T.; Chen, L. C.; Yang, Y. C.; Lin, H. M.; Lin, C. K.; Jwo,
C. S. Nanoparticle suspension preparation using the arc spray nanoparticle
synthesis system combined with ultrasonic vibration and rotating electrode.
Int. J. Adv. Manuf. Technol. 2005, 26, 552–558.
8. Zhao, T.; Sun, R.; Yu, S.; Zhang, Z.; Zhou, L.; Huang, H.; Du, R. Size
controlled preparation of silver nanoparticles by a modified polyol method.
Colloids Surf., A, 2010, 366, 197–202.
9. Zhu, H.; Lin, Y.; Yin, Y. A novel one-step chemical method for preparation
of copper nanofluids. J. Colloid Interface Sci. 2004, 277, 100–103.
10. West, A. R. Solid State Chemistry and Its Applications; Wiley, Singapore,
1989.
11. Park, B. K.; Jeong, S.; Kim, D.; Moon, J.; Lim, S.; Kim, J. S. Synthesis
and size control of monodisperse copper nanoparticles by polyol method.
J. Colloid Interface Sci. 2007, 311, 417–424.
12. Xuan, Y.; Li, Q. Heat transfer enhancement of nanofluids. Int. J. Heat Fluid
Flow 2000, 21, 58–64.
13. Kumar, A. S.; Meenakshi, K. S.; Narashimhan, B. R. V.; Srikanth, S.;
Arthanareeswaran, G. Synthesis and characterization of copper nanofluid
by a novel one-step method. Mater. Chem. Phys. 2009, 113, 57–62.
14. Bicer, M.; Sisman, I. Controlled synthesis of copper nano/microstructures
using ascorbic acid in aqueous CTAB solution. Powder Technol. 2010, 198,
279–284.
15. Yu, W.; Xie, H.; Chen, L.; Li, Y. Investigation of thermal conductivity and
viscosity of ethylene glycol based ZnO nanofluid. Thermochim. Acta 2009,
491, 92–96.
16. Li, D.; Xie, W.; Fang, W. Preparation and properties of copper oil based
nanofluids. Nanoscale Res. Lett. 2011, 373, 1–7.