APPLIED PHYSICS LETTERS VOLUME 78, NUMBER 6 5 FEBRUARY 2001

Anomalously increased effective thermal conductivities of ethylene

glycol-based nanofluids containing copper nanoparticles
J. A. Eastmana)
Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439
S. U. S. Choi
Energy Technology Division, Argonne National Laboratory, Argonne, Illinois 60439
S. Lib)
Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439
W. Yu
Energy Technology Division, Argonne National Laboratory, Argonne, Illinois 60439
L. J. Thompson
Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439
共Received 21 September 2000; accepted for publication 21 November 2000兲
It is shown that a ‘‘nanofluid’’ consisting of copper nanometer-sized particles dispersed in ethylene
glycol has a much higher effective thermal conductivity than either pure ethylene glycol or ethylene
glycol containing the same volume fraction of dispersed oxide nanoparticles. The effective thermal
conductivity of ethylene glycol is shown to be increased by up to 40% for a nanofluid consisting of
ethylene glycol containing approximately 0.3 vol % Cu nanoparticles of mean diameter ⬍10 nm.
The results are anomalous based on previous theoretical calculations that had predicted a strong
effect of particle shape on effective nanofluid thermal conductivity, but no effect of either particle
size or particle thermal conductivity. © 2001 American Institute of Physics.
关DOI: 10.1063/1.1341218兴

Heating or cooling fluids are of major importance to
many industrial sectors, including transportation, energy sup-
ply and production, and electronics. The thermal conductiv-
ity of these fluids plays a vital role in the development of
energy-efficient heat transfer equipment. However, conven-
tional heat transfer fluids have poor heat transfer properties
compared to most solids. Despite considerable previous re-
search and development focusing on industrial heat transfer
requirements, major improvements in heat transfer capabili-
ties have been lacking. As a result, a clear need exists to
develop new strategies for improving the effective heat trans-
fer behavior of conventional heat transfer fluids.
Crystalline solids have thermal conductivities that are
typically larger than those of fluids by 1–3 orders of magni-
tude. Therefore, fluids containing suspended solid particles
can reasonably be expected to display significantly enhanced
thermal conductivities relative to those of pure fluids. Nu-
merous theoretical and experimental studies of the effective
thermal conductivity of liquids containing suspended solid
particles have been conducted since Maxwell’s theoretical
work1 was first published more than 100 years ago.2–8 How-
ever, with very few exceptions, previous studies of the ther-
mal conductivity of suspensions have been confined to those
containing millimeter- or micrometer-sized particles.
Maxwell’s model1 predicts that the effective thermal
conductivity of suspensions containing spherical particles in-
creases with the volume fraction of the solid particles. Be-
cause heat transfer takes place at the surface of the particle, it
a兲
Electronic mail: jeastman@anl.gov
b兲
Present address: Seagate Technology, Bloomington, MN.
is desirable to use particles with a large surface area-to-
volume ratio. Hamilton and Crosser2 focused on the possible
effects of increasing particle surface area by controlling par-
ticle shapes to be nonspherical and modified Maxwell’s
model for spherical particles. However, typically less than an
order-of-magnitude improvement in surface area per particle
volume is attainable experimentally by this strategy alone.
On the basis of this historical background, it was pro-
posed that if nanometer-sized particles could be suspended in
traditional heat transfer fluids, a new class of engineered flu-
ids with high thermal conductivity could be produced.9
These so-called ‘‘nanofluids’’ are expected to exhibit supe-
rior properties relative to those not only of conventional heat
transfer fluids, but also of fluids containing micrometer-sized
metallic particles. Since the surface-area-to-volume ratio is
1000 times larger for particles with a 10 nm diameter than
for particles with a 10 ␮m diameter, a much more dramatic
improvement in effective thermal conductivity is expected as
a result of decreasing the particle size in a suspension than
can be obtained by altering the shapes of larger particles.
Recently, we demonstrated that nanofluids consisting of
CuO or Al2O3 nanoparticles in water or ethylene glycol ex-
hibit enhanced thermal conductivity.10 A maximum increase
in thermal conductivity of approximately 20% was observed
in that study for 4 vol % CuO nanoparticles with average
diameter 35 nm dispersed in ethylene glycol. Similar behav-
ior was observed in another recent study of Al2O3 nanopar-
ticles dispersed in water by Masuda and co-workers.11 The
present work demonstrates that significantly larger improve-
ments in effective thermal conductivity are obtained for
nanofluids containing smaller sized and higher conductivity

0003-6951/2001/78(6)/718/3/$18.00 718 © 2001 American Institute of Physics

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Appl. Phys. Lett., Vol. 78, No. 6, 5 February 2001
FIG. 1. Bright-field transmission electron micrograph of Cu nanoparticles
produced by direct evaporation into ethylene glycol. Very little agglomera-
tion occurs using this processing method.
copper nanoparticles. As will be described, this is a surpris-
ing result based on theoretical predictions.
A one-step procedure for producing nanofluids contain-
ing metallic particles was used to disperse nanocrystalline
copper particles into ethylene glycol with little agglomera-
tion. Briefly, this technique, invented by Akoh and
co-workers,12 involves the direct condensation of metallic
vapor into nanoparticles by contact with a flowing low vapor
pressure liquid. A modification of the direct-condensation
process developed by Wagener et al.13 was used in the cur-
rent experiments 共see Ref. 14 for further details兲. As seen in
Fig. 1, Cu nanoparticles with little agglomeration and an
average diameter of less than 10 nm were produced. Load-
ings of up to approximately 0.5 vol % were produced and
tested. Particle loadings were estimated by weighing the re-
sistive evaporation source before and after the nanofluid
preparation. For some samples, a small amount of thiogly-
colic acid 共⬍1 vol %兲 was added to the nanofluid to improve
the particle dispersion behavior.
The transient hot-wire 共THW兲 method15–17 was used in
this study to measure fluid thermal conductivity. A THW
system involves a wire 共typically platinum兲 suspended sym-
metrically in a liquid in a vertical cylindrical container. Na-
gasaka and Nagashima’s method,18 in which the wire is
coated with a thin electrical insulation layer, was used in the
current experiment to avoid problems associated with the
measurement of electrically conducting fluids. Briefly, the
THW technique works by measuring the temperature/time
response of the wire to an abrupt electrical pulse. The wire is
used as both heater and thermometer and the thermal con-
ductivity, k is calculated from a derivation of Fourier’s Law
k⫽
q
4 ␲ 共 T 2 ⫺T 1 兲 冉冊
ln
t2
t1
, 共1兲
where q is the applied electric power and T 1 and T 2 are the
temperatures at times t 1 and t 2 . From the temperature coef-
ficient of the wire’s resistance, the temperature rise of the
wire can be determined by the change in its electrical resis-
tance with time. Calibration experiments were performed for
ethylene glycol in the temperature range of 290–310 K and
at atmospheric pressure. Literature values19 were reproduced
with an error of ⬍1.5%.
Figure 2 shows the thermal conductivity of Cu nanoflu-
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Eastman et al. 719
FIG. 2. The effective thermal conductivity of ethylene glycol is seen to be
improved by up to 40% through the dispersion of 0.3 vol % Cu nanopar-
ticles. Linear fits to the data are shown as a guide to the eye. The largest
increase in conductivity was seen for a nanofluid that also contained a small
quantity of thioglycolic acid to improve the stability of the metal particles
against settling. A small effect of sample age on thermal conductivity was
also observed. Samples without thioglycolic acid tested within two days of
preparation are denoted ‘‘fresh,’’ while those stored up to two months prior
to testing are denoted ‘‘old.’’
ids as a function of nanoparticle volume fraction. Data are
plotted normalized to the conductivity of nonparticle-
containing ethylene glycol. Several important points can be
noted. First, very significant increases in thermal conductiv-
ity are seen for all measured nanofluids, with conductivity
enhancements of up to 40% observed for particle loadings
well below one volume per cent. Second, nanofluids contain-
ing thioglycolic acid as a stabilizing agent show improved
behavior compared to nonacid-containing nanofluids. It
should be noted that fluids containing thioglycolic acid, but
no particles, showed no improvement in thermal conductiv-
ity. Third, fresh nanofluids tested within two days of prepa-
ration exhibited slightly higher conductivities than fluids that
were stored up to two months prior to measurement.
Figure 3 shows comparisons between metallic and oxide
nanofluids. All nanofluids containing Cu nanoparticles di-
rectly dispersed in ethylene glycol show significantly larger
increases in thermal conductivity than nanofluids containing
oxide particles produced by a two-step process involving
gas-condensation processing of powders followed by disper-
sion into the fluid.10,11 The conductivity enhancements for
both metallic and oxide nanofluids are approximately linear
with particle volume %. Compared to previous studies of
oxide-containing nanofluids there are two potentially impor-
tant differences: 共1兲 the Cu particles used in the current study
are expected to have a much higher intrinsic thermal conduc-
tivity than the oxide particles used previously, and 共2兲 the
average particle diameters in the present study are more than
four times smaller than for the oxide particles.
Hamilton and Crosser’s analysis predicts that the con-
ductivity of two-component mixtures can be described by
冋 册
k m ⫹ 共 n⫺1 兲 k 0 ⫺ 共 n⫺1 兲 ␣ 共 k 0 ⫺k m 兲
k⫽k 0 , 共2兲
k m ⫹ 共 n⫺1 兲 k 0 ⫹ ␣ 共 k 0 ⫺k m 兲
720 Appl. Phys. Lett., Vol. 78, No. 6, 5 February 2001
FIG. 3. Significantly greater enhancements are seen for nanofluids consist-
ing of ⬍10 nm diameter Cu nanoparticles dispersed into ethylene glycol
than for ethylene glycol-based nanofluids containing either CuO or Al2O3
nanoparticles of average diameter 35 nm. This is an unexpected result since
theoretical calculations had predicted no effect of either particle diameter or
particle conductivity on nanofluid conductivity.
where k is the mixture thermal conductivity, k 0 is the liquid
thermal conductivity, k m is the thermal conductivity of solid
particles, ␣ is the particle volume fraction, and n is an em-
pirical scaling factor that takes into account the effect on
thermal conductivity of different particle shapes.
Since the nanoparticles produced in this investigation are
approximately spherical, n⬇3 and Eq. 共2兲 thus predicts very
low enhancements in thermal conductivity compared to those
observed 共e.g., a conductivity ratio of approximately 1.015
would be predicted for a 0.5 vol % copper particles in ethyl-
ene glycol, which is a smaller enhancement than the ob-
served value by well over an order of magnitude兲. An obvi-
ous shortcoming in Hamilton and Crosser’s theory is the lack
of any predicted dependence of conductivity on particle size.
While the shape factor in the Hamilton and Crosser analysis
takes into account the increased surface area of nonspherical
particles, it does not account for the orders-of-magnitude in-
crease in surface-area-to-volume ratio that accompany de-
creasing particle size into the nanocrystalline regime.
A second possible weakness in the Hamilton–Crosser
analysis is that the thermal conductivity of the particles has
only a weak predicted effect on k in Eq. 共2兲. For example,
using quantities in Eq. 共2兲 that correspond to 0.5 vol % par-
ticles in ethylene glycol predicts less than 0.1% larger con-
ductivity ratio for Cu particles than for Al2O3 particles. Since
in our previous study10 nanofluids containing essentially
identically sized and shaped oxide particles of different com-
position were observed to exhibit conductivity ratios that
varied by almost 100%, this weak predicted effect of k m on k
appears unreasonable.
It was demonstrated that thermal conductivities pre-
dicted by theoretical models such as Hamilton and Crosser’s
are much lower than the measured data for oxide
nanofluids.18 The present study shows the discrepancy is
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Eastman et al.
even larger for metallic nanofluids than oxide nanofluids.
This suggests that current models, which account only for
the volume fraction and shape of the suspended particles and
the differences between the thermal conductivity of particles
and fluids, are insufficient to explain the energy transfer pro-
cesses in the nanofluid system. A more comprehensive
theory is needed to explain the behavior of nanofluids. Ad-
ditional studies are required before this theory can be devel-
oped and the mechanism共s兲 responsible for the observed en-
hancements in fluid thermal conductivity are understood.
These include planned experimental studies of samples with
varying particle sizes, but the same composition. Addition-
ally, more sophisticated theoretical treatments are needed.
Simulation studies have recently been initiated20 that hope-
fully will provide insight into the atomistic processes con-
trolling the thermal conductivity of nanofluids.
In summary, nanofluids consisting of Cu nanoparticles
directly dispersed in ethylene glycol have been observed to
exhibit significantly improved thermal conductivity enhance-
ments compared to nonparticle-containing fluids or nanoflu-
ids containing oxide particles. The large improvement in ef-
fective conductivity obtained for nanofluids containing
metallic particles holds significant potential for revolutioniz-
ing industries that are dependent on the performance of heat
transfer fluids.
This work was supported by the U.S. Department of En-
ergy, Office of Science and Office of Transportation Tech-
nologies, under Contract No. W-31-109-Eng-38.
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