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Paper Thermalconduc PDF
Paper Thermalconduc PDF
Lee
Department of Mechanical Engineering,
Kyonggi University,
Suwon, Kyonggi-Do Korea Measuring Thermal Conductivity
e-mail: shinpyo@kuic.kyonggi.ackr
of Fluids Containing Oxide
S. U.-S. Choi
Energy Technology Division,
e-mail: choi@anl.gov
Nanoparticles
Mem. ASME
Oxide nanofluids were produced and their thermal conductivities were measured by a
transient hot-wire method. The experimental results show that these nanofluids, contain-
S. Li ing a small amount of nanoparticles, have substantially higher thermal conductivities than
Materials Science Division the same liquids without nanoparticles. Comparisons between experiments and the Ham-
ilton and Crosser model show that the model can predict the thermal conductivity of
nanofluids containing large agglomerated Al203 particles. However, the model appears to
J. A. Eastman be inadequate for nanofluids containing CuO particles. This suggests that not only
Materials Science Division particle shape but size is considered to be dominant in enhancing the thermal conductivity
of nanofluids.
Argonne National Laboratory,
Argonne, IL 60439
280 / Vol. 121, MAY 1999 Copyright © 1999 by ASME Transactions of the ASME
Nomenclature
a = radius R = resistance Subscripts
g = Euler's constant t = time p = particle
k = thermal conductivity T = temperature
o = base fluid
K = thermal diffusivity a = particle volume fraction
ref = reference temperature
n = shape factor 8T = temperature difference
q = electric power i/; = sphericity
where T(t) is the temperature of the wire in the fluid at time t, TKf
is the temperature of the cell, q is the applied electric power, k is
the thermal conductivity, K is the thermal diffusivity of the fluid,
a is the radius of the wire, and In C = g, where g is Euler's
constant.
The relationship given by Eq. (1) implies a straight line for a
plot of 8T versus In (t). In practice, systematic deviations occur at
both short and long times. However, for each experimental mea-
surement, there is a range of times over which Eq. (1) is valid, that
is, the relationship between ST and In (0 is linear. The slope of the
ST versus In (i) relationship is obtained over the valid range, i.e.,
between times /, and t2, and, using the applied power, we calcu-
lated thermal conductivity from
diameters available are 25.4 (xm, 50.8 /xm, and 76.2 ftm. A water and ethylene glycol in the temperature range of 290 K to 310
76.2-/xm diameter Pt wire was used because the other two wires K and at atmospheric pressure.
were too fragile to be coated with electrical insulation, and we Typical temperature rises of the wire in water or ethylene glycol
believed that the ratios of wire diameter to thickness of the insu- are shown in Fig. 3. Thirty data points from 3 to 6 s were used to
lation layer were too low for the other two wires. The wire was calculate the slope of the temperature rise. We can see that while
welded to rigid copper supporters, with one side of a supporter the electric power applied to the wire for water and ethylene glycol
connected to a rubber string so the wire tension could be adjusted is the same, the slopes of the temperature rises are different, which
to hold the wire straight. means that the thermal conductivities of water and ethylene glycol
The wire and welded spots were coated with an epoxy adhesive are different, as expected. Because the thermal conductivity of
which has excellent electrical insulation and heat conduction. The water is greater than that of ethylene glycol, the slope for water is
thickness of the coating on the wire is estimated to be less than 10 lower than that for ethylene glycol.
/xm. Because the specific resistance of the 76.2 /xm wire is low, a Figure 4 shows the measured thermal conductivities derived
very long wire (the length is 180 mm, and the resistance at 20°C from Fig. (3) using Eq. (2), along with literature data for water and
is 4.594 Cl) was used to provide the high resistance required for a ethylene glycol (Touloukian and Ho, 1970). To determine the
hot-wire sensor. We did not use a two-wire compensation system uncertainty in the thermal conductivity measurement, we used Eq.
(Roder, 1981) to eliminate effects due to axial conduction at both (2) as the data reduction equation and performed an uncertainty
ends of the wire because identical geometry of the welded points analysis based on the presentations of Abernethy et al. (1985) and
and diameter of the coated hot wires cannot be guaranteed. Instead, Coleman and Steele (1989). The applied electric power was mea-
the long hot wire (wire length-to-diameter ratio is ^2300) was sured with an uncertainty of 0.26 percent and the wire temperature
used as a hot-wire sensor to minimize end conduction loss. A 500 variation with time was measured with an uncertainty of 1.4
mL polypropylene cylinder with inner diameter of 50 mm and percent. The uncertainty in the thermal conductivity for water at
length of 340 mm was used as the nanofluid container; the outside 304 K was 1.43 percent. The calibration data in Fig. 4 show that
of the cylinder is thermally insulated with glass fiber. The hot-wire our thermal conductivity measurement system and procedure is
sensor system is located at the center of the cylinder and the accurate to 1.5 percent in the temperature range tested, which is in
alignment to the direction of gravity is adjusted by the string excellent agreement with the results of the uncertainty analysis.
system described above. Because the enhanced thermal conductivity of nanofluids is ex-
Switching the power supply from R4 to the Wheatstone bridge pected to be >1.5 percent of the base fluids at the minimum
initiates the voltage change in the hot wire, and this varying volume fraction of 0.01, this accuracy is considered adequate for
voltage over time is recorded by the A/D converter with resolution quantitatively determining the thermal conductivity of nanofluids.
of 1.53 mV at a sampling rate of ten times per second (compared
4.2 Measurement of Thermal Conductivity of A1203 and
to Nagasaka and Nagashima's six times per second for NaCl
CuO Nanofluids. The thermal conductivity measurements were
solution). From this measured voltage variation and Ohm's law
made at room temperature and no attempt was made to maintain
applied to the electric circuit shown in Fig. 2, the resistance change
the temperature of nanofluids at a constant temperature because the
of the wire and the heating current through the wire can be
fluctuations of the room temperature in the laboratory were very
calculated. Finally, the temperature variation of the wire can be
small.
calculated by the temperature-resistance relationship of the Pt
wire. A value of 0.0039092/°C (Bentley, 1984) has been used for Figure 5 shows the measured thermal conductivity of four oxide
the resistance temperature coefficient of the Pt wire. A linear nanofluids as a function of nanoparticle volume fraction. The
curve-fit of the experimental data in the log scale was performed results show that nanofluids, containing only a small amount of
by using a commercial software. nanoparticles, have substantially higher thermal conductivities
than the same liquids without nanoparticles. For the copper oxide/
ethylene glycol system, thermal conductivity can be enhanced by
4 Results and Discussion more than 20 percent at a volume fraction of 0.04 (4 vol.%).
Our experimental results clearly show that the thermal conduc-
4.1 Calibration With Base Fluids. The base fluids used in tivity ratios increase almost linearly with volume fraction, but with
this study as the suspending liquids are deionized water and different rates of increase for each system. The present experimen-
ethylene glycol. To establish the accuracy of our thermal conduc- tal data also show that the thermal conductivity of nanofluids
tivity measurements, calibration experiments were performed for depends on the thermal conductivities of both the base fluids and
u
3
2
I
10
Time, t (s)
particles. For nanofluids using the same nanoparticles, the conduc- tive thermal conductivity of suspensions containing spherical par-
tivity ratio increases of ethylene glycol nanofluid systems are ticles increases with the volume fraction of the solid particles. For
always higher than those of water nanofluid systems. For nanoflu- nonspherical particles, it is known that the thermal conductivity of
ids using the same liquid, the conductivity ratio of the CuO system suspensions depends not only on the volume fraction of the par-
is always higher than that of the A1203 system. We believe that ticles, but also on the shape of the dispersed particles.
CuO results in better thermal conductivity values than A1203 Hamilton and Crosser (1962) developed an elaborate model for
primarily because the CuO particles are smaller than the A1203 the effective thermal conductivity of two-component mixtures as a
particles as shown in Table 1. In addition, it is possible that the function of the conductivity of the pure materials, the composition
processing of the CuO nanoparticles could have resulted in incom- of the mixture, and the shape of the dispersed particles. The
plete oxidation, which would then be manifested by the presence conductivity of two-component mixtures can be calculated as
of a small amount of unreacted high thermal conductivity Cu being follows:
present in addition to the CuO.
4.3 Comparison With Hamilton and Crosser Model. Be- kp+ (n - l)k0 - (re - \)a(k0 - kp)
k = kQ (3)
cause of the absence of a theory for the thermal conductivity of k„ + (n - l)k0 + a(k0 - k„)
nanofluids, an existing model for the solid/liquid system has been
used to compare the predicted values with the measured thermal where k is the mixture thermal conductivity, kQ is the liquid
conductivity of nanofluids. Maxwell's model shows that the effec- thermal conductivity, kp is the thermal conductivity of solid par-
0.7
0.6
|
0.5 - water
ethylene glycol
o water: measured
0.4 • ethylene glycol: measured
13
0.3
0.2
290 295 300 305 310
Temperature, T (K)
1.30
•a
a 1.20
o
u
1.10
1.00
0 0.01 0.02 0.03 0.04 0.05 0.06
Volume fraction
tides, a is the particle volume fraction, and n is the empirical significant in enhancing the thermal conductivity of nanofluids, as
shape factor given by shown in Fig. 6(c-d) for CuO with krlka < 4.
= 3/^, (4) 4.4 Comparison With Experiments of Masuda et al. To
our knowledge no experimental studies have been carried out on
where ty is sphericity, defined as the ratio of the surface area of a the thermal conductivity of CuO nanofluids. Direct comparison
sphere (with a volume equal to that of the particle) to the surface between the present experimental data and those of other investi-
area of the particle. This model shows that nonspherical shapes gators is possible only for water/Al203 nanofluids. Recently, Ma-
will increase conductivity above that of spheres. suda et al. (1993) showed experimentally that A1203 particles at a
Although Eq. (3) is highly nonlinear, if the thermal conductivity volume fraction of 4.3 percent can increase the thermal conduc-
ratio of solid phase to liquid phase, kplkQ : » 1 and the volume tivity of water by 30 percent.
fraction is low, Eq. (3) can be linearized as follows: For comparison, their experimental data and present work for
k/k0" 1 + net. (5) water/Al203 nanofluids are shown in Fig. 7. The thermal conduc-
tivity ratios in our present experiments are lower than those of
Applying the Hamilton and Crosser model to aluminum oxide Masuda et al. by more than 20%. This is not surprising, since the
and copper oxide nanoparticles in water and ethylene glycol, we mean diameter of A1203 particles used in the experiments of
estimated the thermal conductivity ratios for two values of n (6 for Masuda et al. is 13 nm, which in the present experiments is 38 nm.
cylinders and 3 for spheres). The present experimental thermal Because surface-area-to-volume ratio is three times larger for
conductivities of oxide nanofluids are compared with the predicted particles with a 13-nm diameter than for particles with a 38 nm
results of Hamilton and Cross using Eq. (3). Comparisons of diameter, a greater improvement in effective thermal conductivity
increase of the thermal conductivity ratios predicted by the is expected.
Hamilton-Crosser model with results from the present experiments Another reason for the significant differences is that Masuda
are shown in Fig. 6(a) for water/Al203 nanofluids, Fig. 6(b) for et al. used the electrostatic repulsion technique and a high-
ethylene glycol/Al203 nanofluids, Fig. 6(c) for water/CuO speed shearing disperser (up to «*20,000 r/min). These tech-
nanofluids, and Fig. 6(d) for ethylene glycol/CuO nanofluids. niques might change the morphology of the nanoparticles,
For A1203 nanofluids, it is seen from Fig. 6(a) and Fig. 6(b) that which was emphasized in the Hamilton-Crosser model as a
the predicted thermal conductivity ratios for spheres (n = 3) are shape factor n. Mainly because we did not use such techniques,
in good agreement with the present experiments. This is consistent nanoparticles in our systems were agglomerated and thus be-
with the TEM micrographs which show that A1203 particles are came larger and more spherical than those used by Masuda et al.
quite close to perfect spheres. The thermal conductivity of A1203 In fact, Fig. 7 clearly shows that the measured data by Masuda
nanofluids can be predicted satisfactorily by the Hamilton-Cross et al. agree better with the estimated thermal conductivity from
model because these nanofluids contain large agglomerated spher- the Hamilton and Crosser model, assuming the shape factor of
ical particles. n = 6 (cylinders), and that our data agree better with the model
Figures 6(c) and 6(0^ show the measured thermal conductivity predictions with the shape factor of n = 3 (spheres). However,
of nanofluids containing CuO, along with the model predictions. It it is important to note that even the model profile for nonspheri-
is seen that the agreement between the present experiments and cal particles begins to diverge from the experimental data of
model predictions is not good. The measured thermal conductivity Masuda et al. at a very low volume fraction. This strongly
ratios for CuO nanofluids are substantially larger than the suggests that not only particle shape but also size is considered
Hamilton-Crosser model predictions. It is possible that a small to be dominant in enhancing the thermal conductivity of
quantity of metallic Cu in the CuO material used in these exper- nanofluids. Therefore, it is reasonable to expect that the model
iments increased the thermal conductivity of CuO nanofluids. will fail to predict the thermal conductivity of nanofluids con-
In the Hamilton-Crosser model, the thermal conductivity of taining particles smaller than 13 nm.
suspensions depends strongly on particle shape when the ratio of Because heat transfer between the particles and the fluid takes
the conductivities of the two phases kp/k0 is high as shown in Fig. place at the particle-fluid interface, our expectation is that if we
6(a-b) for alumina. When kp/k0 = 0(1), particle shape is not have more interfacial area, then we would expect heat transfer to
1.30
1.20
1.10 O O
1.00
0.01 0.02 0.03 0.04 0.05 0.06
Volume fraction
Fig. 6(a)
1.50
O present experiments
Hamilton-Crosser model: spheres
1.40 • — - Hamilton-Crosser model: cylinders
1.30
1.20
1.10
H
1.00
0.01 0.02 0.03 0.04 0.05 0.06
Volume fraction
Fig. 6(b)
Fig. 6 Comparison of increase of thermal conductivity ratio between Hamilton-Crosser model and present experiment (a) water/AI2Oa nanofluids, (b)
ethylene glycol/AI 2 0 3 nanofluids, (c) water/CuO nanofluids, and (d) ethylene glycol/CuO nanofluids
be more efficient and thus quicker. If the behavior was just a interest in the present study, the phonon mean-free path can be
simple rule of mixtures, where all that matter is the volume of estimated using an equation that Debye derived (Geiger and
particles, then particle surface area wouldn't matter. However, our Poirier, 1973). Calculations show that for oxides such as A1203,
thermal conductivity data indicate this not to be the case. There- the estimated phonon mean-free path is comparable to the particle
fore, it is desirable to use particles with a large-surface-area-to- sizes we used. Therefore, the intrinsic thermal conductivity of
volume ratio. Previous theoretical work by Hamilton and Crasser oxide nanoparticles may be reduced compared to bulk oxides due
(1962) focused on the possible effects of increasing particle sur- to the size effect. Supporting this idea, the thermal conductivity of
face area by controlling particle shapes to be nonspherical. How- yttria-stabilized zirconia (YSZ) thin films with controlled nanoc-
ever, improvement in surface area per particle volume attainable rystalline grain sizes was recently measured (Soyez et al., 1998).
by this strategy is limited. As particle size decreases, the surface At room temperature, approximately a factor of two reduction in
area of the particle decreases as the square of the length dimension, thermal conductivity of 10-nm grain-sized YSZ compared to that
while the volume decreases as the cube of the length dimension. of the bulk material is seen.
Because of this "square/cube law," the surface-area-to-volume All existing theories, models, and correlations for thermal
ratio of nanoparticles is three orders of magnitude greater than that conductivity (Maxwell, 1873; Hamilton and Crosser, 1962;
of microparticles. Therefore, a much more dramatic improvement Hashin and Shtrikman, 1962; Jeffrey, 1973; Jackson, 1975;
in effective thermal conductivity is expected as a result of decreas- Davis, 1986; Bonnecaze and Brady, 1991; Lu and Lin, 1996)
ing the particle size than can be obtained by altering the particle were developed for fluids with relatively large particles and are
shapes of larger particles. Because all previous studies of the very limited and often contradictory when applied to fluids
thermal conductivity of suspensions have been confined to those containing nanoparticles because, in these theories, the effec-
containing millimeter or micrometer-sized particles, existing mod- tive thermal conductivity of liquid/particle suspensions depends
els appear to be inadequate for nanofluids containing particles as only on the volume fraction and shape of the suspended parti-
small as 10 nm. cles, not on particle size.
It is well known that, in the microscale regime, the thermal There is a large body of literature that addresses the effect of
conductivity of a thin film material is much less than its bulk value, the boundary resistance between the particle and the fluid on the
due to the scattering of the primary carriers of energy (phonon thermal conductivity of composites and suspensions (Ben-
and/or electron) at its boundary (Flik and Tien, 1990; Majumdar, veniste, 1987; Chiew and Glandt, 1987; Concalves and Kolodz-
1998). For electrical insulators such as the oxide materials of iej, 1993; Auriault and Ene, 1994; Ni et al., 1997). However,
1.30
a 1.20
o
O
1.10 O
S o °
0
1.00 O '" ' ' '
0.01 0.02 0.03 0.04 0.05 0.06
Volume fraction
Fig. 6(c)
1.50
O present experiments
Hamilton-Crosser model: spheres
1.40 Hamilton-Crosser model: cylinders
1.30
1.20
1.10
1.00
0.01 0.02 0.03 0.04 0.05 0.06
Volume fraction
Fig. 6(d)
these models predict decreased thermal conductivity of nanoflu- size, in contrast to the predictions based on boundary resistance.
ids due to increased surface boundary resistance when particle Also, these models are confined to conventional suspensions
size decreases. Comparison of our A1203 in water results with containing millimeter or micrometer-sized particles. Nanofluids
those of Masuda et al. (1993) clearly indicate that the effective appear to be quite different from conventional suspensions. The
conductivity for this system increases with decreasing particle much larger surface areas of nanophase powders relative to
O present experiments
• Masuda et al.
1.40 Hamilton-Crosser model: cylinders
o
•a
•
1.30
y
y
S*
D
1.20
*****-" ^^-—*"
D ** ^ "^
1.10 ^"" ^^^To
• " "
** ' ^-r-"""*^°
. - — - ^ - — " * ^ - - '
•*"* _ - — P T " ^ ^
LOOP
0.01 0.02 0.03 0.04 0.05 0.06
Volume fraction