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Mechanisms of Enhanced

Heat Transfer in Nanofluids

J.A. Eastman,
Materials Science Division, Argonne National
Laboratory
jeastman@anl.gov

Fluctuations and Noise in Out of Equilibrium Systems, Sep 14-16, 2005

Supported by U.S. Department of Energy,


Office of Science, Office of Basic Energy
Office of Science
U.S. Department of Energy Sciences, under contract W-31-109-Eng-38
Motivation for improved heat transfer fluids
● Thermal loads are increasing in a
wide variety of applications
➤ Microelectronics: smaller features
and faster operating speeds
➤ Transportation: higher power
engines; lighter radiators for fuel
economy
➤ Lighting: brighter optical devices
➤ Utilization of solar energy for power
generation

● Conventional approach to increasing


heat dissipation is to increase heat
exchanger size
➤ Produces an undesired increase in
Macintosh G5 uses combination of fans and
thermal management system size liquid cooling to enable fast processor speed
➤ New approach is needed

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Nanofluids Motivation

● Fluids have low k compared to most solids


Material Room Temperature
Thermal
Conductivity
(W/m-K)
Metallic Solids: Silver 429
Copper 401
Aluminum 237
Nonmetallic Solids: Diamond 3300
Silicon 148
Alumina (Al2O3) 40
Metallic Liquids: Sodium @ 644K 72.3 ➪ Goal is to enhance
Nonmetallic Water 0.613 effective fluid thermal
Liquids: conductivity and heat
Ethylene Glycol 0.253 transfer coefficient by
Engine Oil 0.145 suspending solid
nanoparticles
U.S. Choi and J.A. Eastman, “Enhanced Heat Transfer
Using Nanofluids,” U.S. Patent #6,221,275
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Nanofluids motivation

Heat transfer
fluid in a pipe

Nanoparticles flow Nanoparticles


• Better dispersion
Surface
behavior
Microparticles sink
atoms
• Less clogging and
Heat transfer abrasion
fluid in a pipe
• Much larger
surface area-to-
volume ratio

The relative large mass of microparticles can


damage the pipe’s wall

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Outline

● Synthesis
● Thermal conductivity in stationary fluids
● Flow convection and boiling

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Synthesis of Nanofluids

● Nanofluids are produced by several techniques:


➪ Direct evaporation (1 step)
➪ Gas condensation (IGC)/dispersion (2 step)
➪ Chemical vapor condensation (1 step)
➪ Chemical precipitation (1 step)

● Gas condensation advantages:


➪ Wide variety of nanopowders can be
produced
➪ Powder production process has already been
commercialized

● Gas condensation disadvantages:


➪ Agglomeration
➪ Often poor dispersion properties

~30 nm diameter CuO produced by IGC


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Direct evaporation

● Less agglomeration than gas-


condensation
● Restricted to low vapor pressure
liquids and materials that can be
vaporized at low to moderate T Resistively Heated
Crucible

● Small particle size, but little Cooling System


Liquid

control over size


● Small sample sizes; slow
production rate; scalable?

~10 nm diameter Cu in ethylene glycol


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Chemical Vapor Condensation Synthesis
N2 Carrier Gas
O2 Inlet

3 Zone
Furnace

Nanoparticles

Particle 50 nm
Collector ~10 nm diameter Fe2O3 in H2O
Collection Precursor ~10 nm diameter TiO2 in H2O
Chamber
Pump

● powder can be directly deposited into liquids (less agglomeration than IGC,
but more than direct evaporation)
● size control is possible
● scale-up should be straight-forward (but hasn’t been done)
● layered oxide nanoparticles can be produced (e.g., for biomed. applications)
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Chemical synthesis

● Chemical synthesis techniques


can produce small,
~monodisperse nanoparticles
with no agglomeration
● Effect of surface molecules on
thermal properties?
● Few existing nanofluid thermal
properties studies have used this
type of particle 10 nm diameter thiol-stabilized
AuPd nanoparticles produced by co-
reduction of PdCl2 and HAuCl4

O.M. Wilson et al., Phys. Rev. B, 66,


224301 (2002)

M. Brust et al., J. Chem. Soc. Chem.


Commun., 801 (1994)

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Thermal Conductivity

● Most studies of nanofluids thermal properties have focused on thermal


conductivity

➯ Thermal conductivity = k T heat


source
➯ Heat flux = q
➯ Temperature gradient, dT/dx x

"T
q = !k ● Fourier’s Law
"x

● Heat transfer behavior also depends on other properties (specific heat,


density, viscosity)

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Thermal conductivity measurement

S. Choi

● Many studies have used transient hot-wire technique


➤ Thin Pt wire suspended in fluid is heated resistively
➤ k is calculated from time-temperature profile
➤ For electrically conducting fluids, wire must be coated
● Other techniques (e.g., 3-ω) have also been used

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Thermal conductivity of oxide nanofluids

H. Masuda, 1993
● Measured k/ko for 3 different
oxides in H2O

● Enhancement depended on
material; at 4 vol.% loading:
➤ ~30% for Al2O3
➤ ~10% for TiO2
➤ ~1% for SiO2

● Adjusted pH to create stable


dispersions
➤ pH =3 for Al2O3; pH=10 for
TiO2 and SiO2

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Oxide nanofluids

S. Lee, U.-S. Choi, S. Li, J.A. Eastman


ASME Journal of Heat Transfer 121, pp. 280-289 (1999)
● Saw smaller enhancement
1.25
water + Al2 O3 for Al2O3-in-H2O than
Masuda
Thermal conductivity ratio (k/k0)

water + CuO
1.20 ethylene glycol + Al2 O3
ethylene glycol + CuO ● Nanoparticles produced
1.15
by IGC; dispersed in H2O
ultrasonically, but no pH
adjustment
1.10
● Larger effect for ethylene
1.05
glycol than for water-
based nanofluids

1.00 ● Larger improvement for


0 0.01 0.02 0.03 0.04 0.05 0.06 CuO than Al2O3 is
Volume fraction surprising

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Other studies of oxide nanofluids
● Wang et al. observed 17%
improvement in k/ko for just 0.4
vol.% CuO in H2O
➤ >5x effect Masuda observed!
➤ 50 nm particle size
?

0.25 vol.%

L.-P. Zhou, B.-X. Wang, Ann. Proc.


● Surfactant used to improve Chinese Eng. Thermophysics, 889 (2002)

dispersion B.-X. Wang et al., proceedings of the


➤ But, agglomeration still 15th Symp. on Thermophysical
Properties (2003)
observed

➪ Other studies have seen enhancement intermediate to observations of Masuda and


Lee et al. (e.g., H. Xie et al., J. Appl. Phys., 91, 4568 (2002))
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Copper-containing nanofluids

Do metal nanoparticles behave like oxides?

J.A. Eastman et al., Appl. Phys. Lett., 78, 718 (2001)

● 10 nm diameter Cu
nanoparticles produce
much larger increase in k
than 30 nm diameter oxide
nanoparticles
● thioglycolic acid improves
dispersion behavior (but
adding acid alone does not
affect k)
● Is larger k enhancement
due to smaller particle size
or larger particle
conductivity?

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Iron-containing nanofluids

T.-K. Hong, H-S. Yang, J. Appl. Phys., 97, 064311, (2005)

● Behavior is similar to Cu
(without added surfactant)
● Fe nanoparticles produced by
chemical vapor condensation
● k/ko appears to be non-linear
with vol. %

0.55 vol.% Fe

● k/ko increases with sonication time


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Au-containing nanofluids
H.G. Patel et al., Appl. Phys. Lett., 83, 2931 (2003)
● Au-thiolate nanoparticles in toluene exhibit
➤ k/ko ~7% @ 0.011 vol.%
➤ ~5x larger enhancement than enhancement
seen for Cu-in-ethylene glycol
● Even larger improvement seen for very dilute
Au-citrate in H2O nanofluids Au-citrate
10-20 nm dia.
➤ 5% enhancement for 0.00026 vol.%
● Also see a strong T-effect

Au-thiolate
3-4 nm dia.

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Another look at Au-containing nanofluids
S.A. Putnam, D.G. Cahill, et al., submitted (2005)

● Investigated 2 types of
chemically-synthesized Au
nanoparticles
➤ 4 nm diameter alkanethiolate-
protected Au in ethanol
➤ 2 nm dodecanethiol
functionalized Au in toluene
● Maximum enhancement
1.3±0.8% @ ~0.02 vol.%
➤ ~2 orders-of-magnitude less
increase than seen by Patel et al.

● Measured k using optical


technique
● Importance of different fluid,
loading %, measurement
technique?

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Macroscopic theory predictions

k 1 + 2Vp
!
ko 1 " Vp
● Macroscopic theory based on R. Hamilton and O. Crosser, I&EC
Fundamentals, 1, 187 (1962)
Maxwell’s predictions for
dielectric behavior of composites

● Predicts increase in conductivity


in nanofluids is approximately
independent of particle size and
particle conductivity

● Other versions of effective


media theory give similar
predictions

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Comparison with macroscopic theory
● Some data are in good
agreement with effective
media theory while other
studies show anomalous
behavior

Al2O3

P. Keblinski, J.A. Eastman, D.G. Cahill


Materials Today, pp. 36-44, June 2005

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Possible mechanisms
● Possible microscopic mechanisms:
(P. Keblinski et al., ASME Journal of Heat Transfer 45,
pp. 855-863 (2002))

➨ Brownian motion (but thermal motion is


expected to be faster than expected
particle motion)

➨ Effect of particles on liquid local ordering


(effectively decreases average spacing
between particles)

➨ Ballistic rather than diffusive thermal


transport in the particles (but isn’t Copper (bulk
amorphous)
Al (liquid)

expected to affect transport between


particles)

➨ Nanoparticle clustering (would probably P. Geysermans et al., Jn. Chem. Phys.,


lead to poor dispersion properties) 113, 6382, 2000.

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Effect of temperature on k/ko

S.K. Das, N. Putra, P. Theisen, W. Roetzel,


ASME J. Heat Transfer, 125, no. 4, 567 (2003)

H. Patel, S.K. Das et al., Appl. Phys. Lett, 83,


2931 (2003)

● Observed a large increase


in conductivity with
increasing temperature

● Concluded that particle


motion is important

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Another observation of T-dependence
J. Wu, J.A. Eastman, (2005)

1.4
0.5 % TiO2 / water • Linear relationship for
Thermal conductivity ratio (k/ko)

1 % TiO2 / water
2 % TiO2 / water
low particle loadings
1.3
4 % TiO2 / water
• smaller T-dependence
for lower loadings
1.2
• Saturation occurs when
temperature is high
1.1 enough for extensive
inter-particle interaction?

1.0
20 25 30 35 40 45 50 55

Temperature (°C)

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Importance of controlling interparticle interactions?

pH value of
nanofluid
As-processed
High Low surface Zero surface
surface charges charge
charges

Well-dispersed “Weakly attracted” agglomerated

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pH-dependent thermal conductivity of Al2O3/water
J. Wu, J.A. Eastman, (2005)

2.0

● Increased thermal conductivity


,!/!
Thermal Conductivity Ratio
0

1.8 at low pH
● Extremely increased thermal
1.6
conductivity at high pH

1.4
● Increased thermal conductivity
near PZC (similar to
enhancement seen previously
1.2
for Cu-in-ethylene glycol)

1.0

4 5 6 7 8 9 10 11 12 • 0.5 vol%Al2O3/water
pH Value
• Al2O3: 48 nm

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pH-dependent thermal conductivity of TiO2/water
J. Wu, J.A. Eastman, (2005)

1.6
,!/!
0
Thermal Conductivity Ratio

1.5
• Increased thermal conductivity
1.4 at low pH
1.3 • Extremely increased thermal
conductivity at high pH
1.2
• Increased thermal conductivity
1.1 near PZC

1.0

2 4 6 8 10 12
pH Value • 0.5 vol%TiO2/water
• TiO2: anatase, 10 nm

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Another view of pH-dependence
pp. 4568-72

● Xie et al. investigated


effect of pH on k of Al2O3-
containing nanofluids
● Concluded that k/ko
increases with difference
from ZPC pH
● Avoided region near ZPC
(pH~9)

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Carbon-nanotube nanofluids

S. Choi et al., Appl. Phys. Lett., 79, 2252 (2001)


● Carbon nanotubes in oil show
the largest enhancement in k to-
date (25 nm diameter x 50 µm
length)

● Is increased enhancement due


to higher conductivity of the
nanotubes or to their length?

200 nm 1 µm

P.M. Ajayan, RPI

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Other views of C-nanotubes

● Enhancements in k observed to
depend on fluid

● Smaller enhancement than seen by


Choi et al.

● Wen and Ding observed ~25%


enhancement @ 0.8 vol.% in H2O (J.
Thermophys. Heat Trans., 18, 481,
2004); Assael et al. observed 38%
enhancement @ 0.6 vol.% (proc. 27th
Int. Therm. Cond. Conf.,153, 2005)
TCNT = treated carbon nanotubes
● Effects of different fluids, different DW = distilled water
preparation techniques? EG = ethylene glycol
DE = decene
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Outline

● Synthesis
● Thermal conductivity in stationary fluids
● Flow convection and boiling

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Pool boiling heat transfer: background

S.M. You, J.H. Kim, K.H. Kim, Appl. Phys. Lett., 83, 3374 (2003)

● Pool boiling heat transfer (BHT) defined as “a process of vigorous heat transfer
occurring with a phase change from liquid to vapor in a pool of initially quiescent
liquid.”

● Nucleating small bubbles is desirable rather than coalescing large ones; critical
heat flux (CHF) is the maximum heat flux under which a boiling surface stays in
the nucleate boiling regime

● Film boiling due to CHF is undesirable because portions of the surface become
covered with vapor (lower k leads to increased T)

● Surface roughening is known to increase CHF (more nucleation sites)

● Increased k of nanofluids is not expected to increase BHT (depends on heat of


vaporization, density of vapor and liquid, and surface tension); nanoparticles may
have other effects

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Effect of nanofluids on boiling critical heat flux

● ≤0.05 g/l Al2O3 nanoparticles in deionized H2O

● Saw 200% increase in CHF; constant BHT coefficient; Vassalo et al. saw
similar behavior with SiO2 (Int. J. Heat Mass Trans., 47, 407 (2004)
● 30% larger bubbles; consistent with increased
surface tension
● Existing theories would predict only 15% increase
in CHF for observed bubble size increase

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Measurements under flow conditions

● heat transfer depends not only on k, but also on


parameters including specific heat, viscosity, flow rate,
and density
● For forced convection in tubes: h ∝ k2/3 * Cp1/3 * ρ 0.8 / η0.467

● Determine heat transfer coefficient from T-rise and


pressure drop across test section

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Heat transfer under forced convection

S.U.-S. Choi et al., Mater. Sci. Forum, 312-314, 629 (1999)

➪ ~15% increase in heat


transfer coefficient observed
for 1% CuO in water
➪ Larger increase than
expected based on k
enhancement

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Other heat transfer observations

● Cu nanoparticles in deionized H2O

● 2 vol.% Cu improved heat transfer Y. Xuan, Q. Li, J. Heat Trans., 125, 151 (2003)
coefficient >39%

● Friction factor unchanged at this loading

● In contrast, Pak and Cho (Exper.


Heat Trans., 11, 151, 1998) found
that 3 vol.% Al2O3 or TiO2 in H2O
decreased convective heat transfer
coefficient 12%

● Putra et al. (Heat Mass Trans.,


39, 775, 2003) saw a reduction
under natural convection of Al2O3-
and CuO-H2O nanofluids

● Wen and Ding (Int. J. Heat Fluid Flow, in press 2005) also saw a reduction under natural
convection of TiO2-H2O nanofluids; adjusted the pH to be far from ZPC (well dispersed,
but non-interacting nanofluids)
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Conclusions

● Many studies have observed significantly improved heat transfer


properties in nanofluids (thermal conductivity, pool boiling critical
heat flux, heat transfer coefficient)
● Many conflicts exist between different studies
● Different sample preparation techniques, particle size, surface
treatment, fluid and nanoparticle materials, measurement techniques
may be important
● Degree of interaction between particles appears to be important
(control with pH for H2O based nanofluids)
● Systematic studies are needed; improved synthesis techniques
would help (control of size, surface properties, dispersion behavior)
● New theories are needed that take into account all important
characteristics of nanofluids

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Collaborators

● Steve Choi
● Ho-Soon Yang
● Jie Anny Wu
● Loren Thompson
● Guo-Ren Bai
● Pawel Keblinski (RPI)
● Simon Phillpot (U. FL)

Supported by U.S. Department of Energy, Office of Science, Office of


Basic Energy Sciences, under contract W-31-109-Eng-38

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