Thermal conductivity enhancement of suspensions containing nanosized

alumina particles
Huaqing Xie, Jinchang Wang, Tonggeng Xi, Yan Liu, Fei Ai et al.

Citation: J. Appl. Phys. 91, 4568 (2002); doi: 10.1063/1.1454184

View online: http://dx.doi.org/10.1063/1.1454184
View Table of Contents: http://jap.aip.org/resource/1/JAPIAU/v91/i7
Published by the American Institute of Physics.

Related Articles
Equilibrium molecular dynamics determination of thermal conductivity for multi-component systems
J. Appl. Phys. 112, 054310 (2012)
Nonequilibrium molecular dynamics simulations of the thermal conductivity of water: A systematic investigation of
the SPC/E and TIP4P/2005 models
J. Chem. Phys. 137, 074503 (2012)
Thermal rectification in a fluid reservoir
Appl. Phys. Lett. 100, 121901 (2012)
Anisotropic heat transport in nanoconfined polyamide-6,6 oligomers: Atomistic reverse nonequilibrium molecular
dynamics simulation
J. Chem. Phys. 136, 104901 (2012)
A 3-dimensional time-resolved photothermal deflection “Mirage” method
Appl. Phys. Lett. 100, 091908 (2012)

Additional information on J. Appl. Phys.

Journal Homepage: http://jap.aip.org/
Journal Information: http://jap.aip.org/about/about_the_journal
Top downloads: http://jap.aip.org/features/most_downloaded
Information for Authors: http://jap.aip.org/authors

Downloaded 22 Sep 2012 to 139.184.30.132. Redistribution subject to AIP license or copyright; see http://jap.aip.org/about/rights_and_permissions
JOURNAL OF APPLIED PHYSICS VOLUME 91, NUMBER 7 1 APRIL 2002

Thermal conductivity enhancement of suspensions containing nanosized

alumina particles
Huaqing Xie,a) Jinchang Wang, Tonggeng Xi, Yan Liu, and Fei Ai
Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
Qingren Wu
Department of Materials, South China University of Technology, Guangzhou 510641, China
共Received 10 October 2001; accepted for publication 4 January 2002兲
Various suspensions containing Al2 O3 nanoparticles with specific surface areas in a range of 5–124
m2 g⫺1 have been prepared and their thermal conductivities have been investigated using a transient
hot-wire method. Nanoparticle suspensions, containing a small amount of Al2 O3 , have substantially
higher thermal conductivity than the base fluid, with the enhancement increasing with the volume
fraction of Al2 O3 . The enhanced thermal conductivity increases with an increase in the difference
between the pH value of aqueous suspension and the isoelectric point of Al2 O3 particle. For the
suspensions using the same base fluid, the thermal conductivity enhancements are highly dependent
on specific surface area 共SSA兲 of nanoparticle, with an optimal SSA for the highest thermal
conductivity. For the suspensions containing the same nanoparticles, the enhanced thermal
conductivity ratio is reduced with the increasing thermal conductivity of the base fluid. The
crystalline phase of the nanoparticles appears to have no obvious effect on the thermal conductivity
of the suspensions. Comparison between the experiments and the theoretical model shows that the
measured thermal conductivity is much higher than the values calculated using theoretical
correlation, indicating new heat transport mechanisms included in nanoparticle suspensions.
© 2002 American Institute of Physics. 关DOI: 10.1063/1.1454184兴

I. INTRODUCTION tional fluidic media and the suspensions containing coarse-

Much effort has been dedicated to more efficient heat
transfer systems.1,2 Among various heat transfer enhance-
ment techniques, an innovative way of improving the ther-
mal conductivities of working media is to suspend ultrafine
metallic or nonmetallic solid powders in traditional fluids
since the thermal conductivities of most solid materials are
higher than those of liquids. Some approaches for the aug-
mentation of the heat transport by utilizing solid particle sus-
pensions as heat transfer fluids were introduced.3,4 However,
the solid phases were limited to those with densities very
close to the base fluids, e.g., polystyrene particles, to keep
the suspension stable, whereas the intrinsic thermal conduc-
tivity of those solids is always very low. If a solid with high
thermal conductivity, e.g., metal or some metal oxide is dis-
persed into a fluid, the stability of the suspension is very
poor because of the great difference of density between the
solid and the fluid. The coarse-grained particles involved in
the suspensions settle out eventually. Early attempts at utiliz-
ing the solid particle suspensions for enhancing heat transfer
also were beset with some severe problems such as abrasion
and clogging in small passages caused by the suspended par-
ticles of ␮m or even mm dimensions.
Extensive research conducted on nanosized powder
preparation and processing technology in recent years has
provided an opportunity to apply this emerging nanotechnol-
ogy to thermal engineering. Nanoparticle suspensions are ex-
pected to exhibit excellence properties which the conven-
a兲
Electronic mail: huaqing_xie@hotmail.com
grained solid particles do not have. Because of the large
specific surface area 共SSA兲 and enhanced specific heat for
nanocrystalline materials,5–7 nanoparticle suspensions can be
expected to possess higher heat transfer capacities. Also,
nanoparticle suspensions can exhibits kinetic stability be-
cause of Brownian motion of the particles in a fluid.8 Fur-
thermore, nanoparticles may act as a lubricating medium be-
cause of their small sizes.9
Suspensions containing a small amount of metal 共e.g.,
Cu兲 or nonmetal 共e.g., SiC, Al2 O3 , and CuO兲 nanoparticles
have been reported to have substantially higher thermal con-
ductivities than those of the base fluids.10–17 Anomalously,
for a suspension consisting of ethylene glycol 共EG兲 and only
0.3 vol % Cu nanoparticles, the thermal conductivity was
shown to be increased by up to 40%.16 The enhanced thermal
conductivity of nanoparticle suspension appears highly de-
pendent on the morphologies 共the SSA and shape兲 of the
particle and the thermal conductivity of the base fluid.13,14,17
As a first try in practical application, nanosized metal par-
ticle suspension was used as a different coolant in the micro-
channel heat exchanger and it offered significant benefits.18
However, more experiments are needed for understanding
the mechanisms of the thermal conductivity behavior of
nanoparticle suspension.
In the present study we measured the thermal conduc-
tivities of the Al2 O3 nanoparticle suspensions. The effects of
the pH value of the aqueous suspension, the SSA of the
dispersed Al2 O3 particles, the crystalline phase of the solid
phase, and the thermal conductivity of the base fluid on the

0021-8979/2002/91(7)/4568/5/$19.00 4568 © 2002 American Institute of Physics

Downloaded 22 Sep 2012 to 139.184.30.132. Redistribution subject to AIP license or copyright; see http://jap.aip.org/about/rights_and_permissions
J. Appl. Phys., Vol. 91, No. 7, 1 April 2002 Xie et al. 4569

TABLE I. Properties of nanosized Al2 O3 particles.

Sample symbol ␣A-5 ␣A-25 ␣A-58 ␥A-58 ␣A-101 ␥A-122 ␥A-124

2 ⫺1
Specific area, (m g ) 5 25 58 58 101 122 124
Particle size, 共nm兲 302 60.4 26.0 26.0 15.0 12.4 12.2
Crystalline phase ␣ ␣ ␣ ␥ ␣ ␥ ␥

enhanced thermal conductivity ratio have been investigated. sent, respectively, the thermal conductivities of the suspen-
Possible mechanisms contributing to the enhancement of the sion and the base fluid and ␦ ␭⫽␭⫺␭ 0 . ⌽ is the volume
thermal conductivity of the suspension have been discussed. fraction of Al2 O3 . When the nanoparticles are dispersed into
water, the overall behavior of the particle–water interaction
II. EXPERIMENTAL DETAILS depends on the properties of the particle surface. For ␣A-25
particles, the isoelectric point (pHiep兲 is determined to be 9.2,
Al2 O3 nanoparticle suspensions were prepared by a two-
i.e., the repulsive forces among ␣A-25 particles is zero and
step method, in which Al2 O3 were first produced, followed
␣A-25 particles will coagulate together under this pH value.
by a second step in which the powers are dispersed into a
Therefore, when the pH value is equal to or close to 9.2,
base fluid in a mixing container. Solid particles were
␣A-25 particle suspension is unstable according to the
deagglomerated by intensive ultrasonication after mixed with
DLVO theory.20 The hydration forces among particles in-
base fluid, and then the suspensions were homogenized by
crease with the increasing difference of the pH value of a
magnetic force agitation. Various nanosized Al2 O3 powders
suspension from the pHiep , which results in the enhanced
were selected to produce the suspensions. The crystalline
mobility of nanoparticles in the suspension. The microscopic
phases of the powders were determined by x-ray diffraction
motions of the particles cause microconvection that enhances
patterns obtained on an automated diffractometer RAX-10.
the heat transport process.
The SSAs of the nanosized powders were measured by
Figure 3 shows the enhanced thermal conductivity ratios
Brunnauer–Emmett–Teller methods using a micromeritics
of the suspensions with Al2 O3 nanoparticles at different vol-
ASAP 2010 nitrogen adsorption apparatus. The properties of
ume fraction dispersed in EG. The results show that nano-
the used Al2 O3 powders were summarized in Table I. De-
particle suspensions have noticeably higher thermal conduc-
ionized water 共H2O兲, EG, and pump oil 共PO兲 were used as
tivities than EG without nanoparticles. The thermal
base fluids, respectively.
conductivity enhancement increases almost linearly with the
Some samples measured in our experiments are electri-
volume fraction, but the rates of the enhanced ratios to the
cally conductive, so a transient hot-wire cell and an electrical
volume fraction depend on the dispersed nanoparticles. For
system were designed. According to the principle presented
the ␣A-25/EG suspension, the thermal conductivity can be
by Nagasaka and Nagashima,19 the thermal conductivities ␭
enhanced by more than 29% at a volume fraction of 0.05.
of measured fluids can be determined by the following for-
Figure 4 presents the thermal conductivity enhancement
mula
of the nanoparticle suspensions as a function of the SSA of
␭⫽ 冉 冊冒冉
q
4␲
d„␪ 共 ␶ 兲 …
d 共 ln␶ 兲 冊
, 共1兲
the suspended particles. The volume fractions of the solid
phase of the suspensions are 0.05. For Al2 O3 /PO and
Al2 O3 /EG suspension systems, the thermal conductivity ratio
where q is the applied heating power per unit length, ␶ the increases first, and then decreases with an increase in the
heating time, and ␪共␶兲 the temperature rise of the hot wire. In SSA, with the largest thermal conductivity at a particle SSA
order to minimize the temperature fluctuation, the hot-wire
cell containing the measured samples was placed in a ther-
mostatic air bath at controlled temperatures when the thermal
conductivity measurements were performed. The uncertainty
of our measurements is estimated to be less than ⫾0.5%.

III. RESULTS AND DISCUSSION

A. Enhancement of the thermal conductivity
As expected, the thermal conductivities of the suspen-
sions have been increased over those of the base fluids with
the addition of a small amount of Al2 O3 nanoparticles. Fig-
ure 1 depicts the thermal conductivities of ␣A-25/H2O sus-
pensions as a function of the volume fraction of Al2 O3 . It is
clearly shown that the thermal conductivities increase with
an increase in the volume fraction, but with different slope
for different pH values. The results presented in Fig. 2 indi-
cate that the enhanced thermal conductivity ratio decreases FIG. 1. Thermal conductivities of ␣A-25/H2 O suspensions as a function of
with an increase in pH value. In this article, ␭ and ␭ 0 repre- solid volume fraction.

Downloaded 22 Sep 2012 to 139.184.30.132. Redistribution subject to AIP license or copyright; see http://jap.aip.org/about/rights_and_permissions
4570 J. Appl. Phys., Vol. 91, No. 7, 1 April 2002 Xie et al.

FIG. 2. Thermal conductivity enhancement ratios of ␣A-25/H2 O suspen-

sions at different pH values. FIG. 4. Enhanced thermal conductivity ratios as a function of the SSAs
共note: ⌽⫽0.05兲.

of 25 m2 g⫺1 . We ascribe the thermal conductivity change

To investigate the effect of the thermal conductivity of
behavior to two factors. First, as particle size decreases, the
the base fluid, the enhanced thermal conductivity ratios of
SSA of the particle increases proportionally. Heat transfer
␣A-25 suspensions as a function of ␭ 0 is shown in Fig. 5. At
between the particle and the fluid takes place at the particle–
all the selected volume fractions, the thermal conductivity
fluid interface. Therefore, a dramatic enhancement in thermal
augmentation ratio decreases with an increase in ␭ 0 , which
conductivity is expected because a reduction in particle size
indicates a much more dramatic improvement in the thermal
can result in a large interfacial area. Second, the phonon
conductivity of the suspension for a fluid with lower thermal
mean free path in polycrystalline Al2 O3 is estimated to be
conductivity, e.g., PO. The results shown in Fig. 5 are con-
around 35 nm,21 which is comparable to the size of the par-
sistent with the data presented in Ref. 13, in which it is
ticle we used. The intrinsic thermal conductivity of the nano-
shown that the thermal conductivity ratio of EG-based sus-
sized Al2 O3 particle may be reduced compared to that of
pension is higher than that of water-based suspension. How-
bulk Al2 O3 due to the scattering of the primary carriers of
ever, Wang et al.14 reported that the thermal conductivity ra-
energy 共phonon兲 at the particle boundary. It is expected that
tio of PO-based suspension is lower than that of EG-based
the suspension’s thermal conductivity is reduced with an in-
suspension. The discrepancy might be due to the difference
crease in the SSA. Therefore, for a suspension containing
in the interaction between the particle and the liquid caused
nanoparticles at a particle size different much from the mean
by the difference of the surface status of the nanoparticles
free path, the thermal conductivity increases when the par-
used. Further investigation is needed to reveal the detailed
ticle size decreases because the first factor is dominant. How-
mechanism.
ever, when the size of the dispersed nanoparticles is close to
The crystalline phase of Al2 O3 particles seems to have
or smaller than the mean free path, the second factor will
no obvious effect on the thermal conductivity enhancement
govern the mechanism of the thermal conductivity behavior
of the suspensions. It is seen from Fig. 6 that the enhanced
of the suspension.

FIG. 3. Enhanced thermal conductivity ratios of the suspensions with nano- FIG. 5. Thermal conductivity enhancement ratios as a function of the ther-
particles in EG. mal conductivities of the base fluids 共note: Solid phase is ␣A-25兲.

Downloaded 22 Sep 2012 to 139.184.30.132. Redistribution subject to AIP license or copyright; see http://jap.aip.org/about/rights_and_permissions
J. Appl. Phys., Vol. 91, No. 7, 1 April 2002
FIG. 6. Enhanced thermal conductivity ratios of suspensions with different
crystalline phase nanosized Al2 O3 .
thermal conductivity difference between ␣A-58/EG suspen-
sion and ␥A-58/EG suspension is smaller than the measure-
ment uncertainty at the same volume fraction.
B. Comparison with the calculated values
Various theories have been developed to compute the
thermal conductivity of solid particle suspensions based on
the thermal conductivity of the solid and the liquid and their
relative volume fraction.22–26 Most of these models have
been successfully verified by experimental data for suspen-
sions with large particles at low concentrations. The differ-
ence between the measured data and the prediction is less
than a few percent when the volume fraction is less than
20%. In the present investigation, Davis’ correlation is em-
ployed, which has the form,24
␭ 3 共 a⫺1 兲
⫽1⫹ 兵 ⌽⫹ f 共 a 兲 ⌽ 2 ⫹0 共 ⌽ 3 兲 其 , 共2兲
␭0 关 a⫹2⫺ 共 a⫺1 兲 ⌽ 兴
where a is the ratio of the thermal conductivity of solid par-
ticle to ␭ 0 and the function f (a) is presented in Ref. 24.
Comparisons of the results of the enhanced thermal conduc-
tivity calculated by Davis’ model with the present experi-
ments are shown in Fig. 7. In the calculation, the thermal
conductivities of the base fluids were taken as 0.141 for PO,
0.258 for EG, and 0.604 W m⫺1 K⫺1 for water, respectively.
A bulk value of 46.0 W m⫺1 K⫺1 for the Al2 O3 particle was
used due to no available data for nanoparticles. In Fig. 7 a
⫽76.3, 178.3, and 325.3 correspond to ␣A-25/water, ␣A-25/
EG, and ␣A-25/PO suspensions, respectively. The perdicted
values are very close for these three suspension systems.
However, the experimetal results indicate that the thermal
conductivity enhancements are different for the different
base fluids. The enhancement in PO is the highest, whereas
that in water is the lowest, about half of that in PO. The
measured thermal conductivities of the suspensions with
␣A-25 nanoparticles dispersed in all three fluids are much
higher than those of the perdicted. For a volume fraction of
0.05, the perdicted enhanced thermal conductivity ratio is
Downloaded 22 Sep 2012 to 139.184.30.132. Redistribution subject to AIP license or copyright; see http://jap.aip.org/about/rights_and_permissions
Xie et al. 4571
FIG. 7. Comparison between the predicted values and the experimental
results.
about 0.15, while the experiments result in 0.384 for ␣A-25/
PO, 0.294 for ␣A-25/EG, and 0.210 for ␣A-25/water, respec-
tively.
When the dimension of a material is reduced to the
nanoscale regime, the thermal conductivity of the material
will decrease because of the boundary scattering of the pho-
non and/or electrons. A variety of experiments for nanosized
films have proved it.27,28 Due to size effect, it is expected that
the thermal conductivity of the nanopaticle may be reduced
compared to the bulk material. Therefore, the thermal con-
ductivity of the nanoparticle suspension should be lower than
that of the large particle suspension. However, as shown in
Fig. 7, the measured thermal conductivity enhanced ratios
for nanosized particle suspensions are greater 共5.5% for ␣A-
25/water, 13.5% for ␣A-25/EG, and 22.4% for ␣A-25/PO,
respectively兲 than the values calculated by theoretical corre-
lation even when the thermal conductivity of nanosized
Al2 O3 is taken as a bulk value. As discussed in Sec. III A, the
enlarged SSA of nanosized powder and the microscopic mo-
tions of nanoparticles in the fluids help to enhance heat trans-
fer. Also chain structures formed by the particles may con-
tribute to the thermal conductivity enhancement.14,22
Therefore, the existing theoretical models which successfully
predict the thermal conductivities of large-size particle sus-
pensions, cannot be used to calculate the effective thermal
conductivity of nanoparticle suspension. The mechanisms
may include Brownian motion of nanoparticles, molecular-
level layering of the liquid at the liquid/particle interface,
nonlocal heat transport in nanoparticles, and nanoparticle
clustering.21,29
IV. CONCLUSIONS
The themal conductivity behaviors of nanosized Al2 O3
suspensions have been investigated. The experimental results
show that the addition of nanoparticles into fluids leads to
increased thermal conductivities of the suspensions. The en-
hanced thermal conductivity ratios increase with the volume
fraction of nanoparticles. For the suspensions using the same
nanoparticles, the enhanced thermal conductivity ratio is re-
duced with increasing thermal conductivity of the base fluid.
4572 J. Appl. Phys., Vol. 91, No. 7, 1 April 2002 Xie et al.

11
For the suspensions using the same base fluid, the enhance- U. S. Choi, in Developments and Applications of Non-Newtonian Flows,
ments of the thermal conductivities are dependent on SSA, edited by D. A. Siginer and H. P. Wang 共ASME, New York, 1995兲, FED
Vol. 231, p. 99.
with an optimal SSA for the highest thermal conductivity. 12
J. A. Eastman, U. S. Choi, S. Li, L. J. Thompson, and S. Lee, Mater. Res.
Thoroughly different from the traditional suspensions with Soc. Symp. Proc. 457, 3 共1997兲.
␮m or mm size particles dispersed in a fluid, nanoparticle 13
S. Lee, U. S. Choi, S. Li, and J. A. Eastman, J. Heat Transfer 121, 280
suspensions have much higher thermal conductivity than the 共1999兲.
14
calculated values using theoretical correlations. The thermal X. Wang, X. Xu, and U. S. Choi, J. Thermophys. Heat Transfer 13, 474
共1999兲.
conductivity of the nanoparticle suspensions appears very 15
Y. Xuan and Q. Li, Int. J. Heat Fluid Flow 21, 58 共2000兲.
dependent on the size of the nanoparticles, the interaction 16
J. A. Eastman, U. S. Choi, S. Li, W. Yu, and L. J. Thompson, Appl. Phys.
between the particle and liquid, and the thermal conductivity Lett. 78, 718 共2001兲.
of the base fluid.
17
H. Xie, J. Wang, T. Xi, and Y. Liu, Int. J. Thermophys. 共to be published兲.
18
S. Lee and U. S. Choi, in Recent Advance in Solids/Structures and Appli-
cation of Metallic Materials, edited by Y. Kwon, D. Davis, and H. Chung
ACKNOWLEDGMENT 共ASME, New York, 1996兲, Vol. 72, pp. 227.
19
Y. Nagasaka and A. Nagashima, J. Phys. E 14, 1435 共1981兲.
This work was supported by the Natural Science Foun- 20
W. B. Russel, D. A. Saville, and W. R. Schowwalter, Colloidal Suspen-
dation of China 共Project No. 50006014兲. sions 共Cambridge University Press, Cambridge, UK, 1989兲, p. 259.
21
P. Keblinski, S. R. Phillpot, U. S. Choi, and J. A. Eastman, Int. J. Heat
1
A. E. Bergles, J. Heat Transfer 110, 1082 共1988兲. Mass Transf. 45, 855 共2002兲.
2
A. E. Bergles, Handbook of Heat Transfer Application 共McGraw–Hill,
22
R. L. Hamilton and O. K. Crosser, I & EC Fundamentals 1, 187 共1962兲.
New York, 1985兲, Sec. 3-1-80.
23
D. J. Jeffrey, Proc. R. Soc. London, Ser. A 335, 155 共1973兲.
3
A. S. Ahuja, J. Appl. Phys. 46, 3408 共1975兲.
24
R. H. Davis, Int. J. Thermophys. 7, 609 共1986兲.
25
4
A. S. Ahuja, Int. J. Heat Mass Transf. 25, 725 共1982兲. R. T. Bonnecaze and J. F. Brady, Proc. R. Soc. London, Ser. A 430, 1879
5
J. Rupp and R. Birringer, Phys. Rev. B 36, 7888 共1987兲. 共1990兲.
26
6
H. Gleiter, Prog. Mater. Sci. 33, 223 共1989兲. R. T. Bonnecaze and J. F. Brady, Proc. R. Soc. London, Ser. A 432, 1886
7
H. Zhang and J. F. Banfield, J. Mater. Chem. 8, 2073 共1998兲. 共1991兲.
27
8
L. Zhang and J. Mou, Nanoscale Material Sciences 共Liaoning Science & K. E. Goodson, M. I. Filk, L. T. Su, and D. A. Antoniadis, J. Heat Transfer
Technology, 1994兲, p. 73 共in Chinese兲. 116, 317 共1994兲.
9
Z. S. Hu and J. X. Dong, Wear 216, 92 共1998兲. 28
S. R. Mirmira and L. S. Fletcher, J. Thermophys. Heat Transfer 12, 121
10
H. Masuda, A. Ebata, K. Teramae, and N. Hishinuma, Netsu Bussei 7, 227 共1998兲.
共1993兲. 29
G. Chen, J. Heat Transfer 118, 539 共1996兲.

Downloaded 22 Sep 2012 to 139.184.30.132. Redistribution subject to AIP license or copyright; see http://jap.aip.org/about/rights_and_permissions