Eastman

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
Pioneering Office of Science

Science and U.S. Department
Technology of Energy
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
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

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

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

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

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)
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)

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)

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

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

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

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))
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?

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

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.

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?

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

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

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.

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

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)

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

pH-dependent thermal conductivity of Al2O3/water
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

pH-dependent thermal conductivity of TiO2/water
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

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)

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

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

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

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

Science and
Technology S.M. You, J.H. Kim, K.H. Kim, Appl. Phys. Lett., 83, 3374 (2003) U.S. Department
of Energy
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

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

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)
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

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


Eastman

Uploaded by

Document Information

Original Description:

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Eastman

Uploaded by

Copyright:

Available Formats

Mechanisms of Enhanced

Heat Transfer in Nanofluids

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

Supported by U.S. Department of Energy,

● Conventional approach to increasing

Pioneering Office of Science

● Fluids have low k compared to most solids

Nanoparticles flow Nanoparticles

The relative large mass of microparticles can

Pioneering Office of Science

Pioneering Office of Science

● Nanofluids are produced by several techniques:

● Gas condensation advantages:

● Gas condensation disadvantages:

~30 nm diameter CuO produced by IGC

● Less agglomeration than gas-

● Small particle size, but little Cooling System

control over size

~10 nm diameter Cu in ethylene glycol

● Chemical synthesis techniques

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

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

Pioneering Office of Science

● Most studies of nanofluids thermal properties have focused on thermal

➯ Thermal conductivity = k T heat

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

Pioneering Office of Science

● Many studies have used transient hot-wire technique

Pioneering Office of Science

● Adjusted pH to create stable

Pioneering Office of Science

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

1.00 ● Larger improvement for

Pioneering Office of Science

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

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

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

Do metal nanoparticles behave like oxides?

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

Pioneering Office of Science

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

● k/ko increases with sonication time

Pioneering Office of Science

● Measured k using optical

Pioneering Office of Science

● Predicts increase in conductivity

● Other versions of effective

Pioneering Office of Science

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

Pioneering Office of Science

➨ Brownian motion (but thermal motion is

➨ Effect of particles on liquid local ordering

➨ Ballistic rather than diffusive thermal

expected to affect transport between

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

Pioneering Office of Science

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

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

● Observed a large increase

● Concluded that particle

Pioneering Office of Science

Pioneering Office of Science

Well-dispersed “Weakly attracted” agglomerated