1 s2.0 S0001868612001261 Main

Advances in Colloid and Interface Science 183184 (2012) 3045
Contents lists available at SciVerse ScienceDirect
Advances in Colloid and Interface Science

journal homepage: www.elsevier.com/locate/cis
Thermal properties of nanouids

John Philip , P.D. Shima 1
SMARTS, Metallurgy and Materials Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102, India
a r t i c l e
i n f o
Available online 7 August 2012

Keywords:
Nanouids
Dispersions
Thermal conductivity
Heat transfer
Agglomeration
a b s t r a c t
Colloidal suspensions of ne nanomaterials in the size range of 1100 nm in carrier uids are known as
nanouids. For the last one decade, nanouids have been a topic of intense research due to their enhanced
thermal properties and possible heat transfer applications. Miniaturization and increased operating speeds
of gadgets warranted the need for new and innovative cooling concepts for better performance. The low thermal conductivity of conventional heat transfer uid has been a serious impediment for improving the performance and compactness of engineering equipments. Initial studies on thermal conductivity of suspensions
with micrometer-sized particles encountered problems of rapid settling of particles, clogging of ow channels and increased pressure drop in the uid. These problems are resolved by using dispersions of ne
nanometer-sized particles. Despite numerous experimental and theoretical studies, it is still unclear whether
the thermal conductivity enhancement in nanouids is anomalous or within the predictions of effective medium theory. Further, many reports on thermal conductivity of nanouids are conicting due to the complex
issues associated with the surface chemistry of nanouids. This review provides an overview of recent advances in the eld of nanouids, especially the important material properties that affect the thermal properties of nanouids and novel approaches to achieve extremely high thermal conductivities. The background
information is also provided for beginners to better understand the subject.
2012 Elsevier B.V. All rights reserved.
Contents
1.
2.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Experimental ndings on factors affecting thermal conductivity(k) of nanouids
2.1.
Effect of particle volume fraction . . . . . . . . . . . . . . . . .
2.1.1.
Metal and metal oxide nanouids . . . . . . . . . . . .
2.1.2.
Carbon nanotube (CNT) nanouids . . . . . . . . . . .
2.2.
Effect of particle size . . . . . . . . . . . . . . . . . . . . . .
2.2.1.
Increase in k with decrease in nanoparticle size . . . . . .
2.2.2.
Decrease in k with decrease in nanoparticle size . . . . .
2.3.
Effect of temperature . . . . . . . . . . . . . . . . . . . . . .
2.3.1.
Enhancement in k and k/kf with temperature . . . . . . .
2.3.2.
Invariant k/kf with temperature . . . . . . . . . . . . .
2.3.3.
Decrease in k/kf with temperature . . . . . . . . . . . .
2.4.
Effect of particle shape/aspect ratio . . . . . . . . . . . . . . . .
2.5.
Effect of base uid material . . . . . . . . . . . . . . . . . . .
2.6.
Effect of nanoparticle material . . . . . . . . . . . . . . . . . .
2.7.
Effect of additives . . . . . . . . . . . . . . . . . . . . . . . .
2.8.
Effect of acidity (pH) . . . . . . . . . . . . . . . . . . . . . .
2.9.
Effect of sonication . . . . . . . . . . . . . . . . . . . . . . .
2.10. Effect of aggregation . . . . . . . . . . . . . . . . . . . . . . .
3.
Conclusions and future directions . . . . . . . . . . . . . . . . . . . .
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Corresponding author. Tel.: +91 94 431 51 536; fax: +91 44 27480356.

E-mail address: philip@igcar.gov.in (J. Philip).
1
Present address: Ecole Suprieure de Physique et de Chimie Industrielles de la ville de Paris (ESPCI), Paris.
0001-8686/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cis.2012.08.001
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J. Philip, P.D. Shima / Advances in Colloid and Interface Science 183184 (2012) 3045
1. Introduction
Advances in nanotechnology have led to miniaturization and increased operating speeds that warrant the need for new and innovative cooling concepts with improved performance [1]. The low
thermal conductivity (k) of conventional heat transfer uids is a serious limitation in improving the performance and compactness of engineering equipments. By considering the fact that metallic solids
possess higher k than uids, uids containing suspended solid particles are expected to exhibit signicantly higher k than that of
conventional heat transfer uids. Early studies on k of suspensions
with millimeter and micrometer-sized particles encountered problems of rapid settling of particles, clogging of ow channels and increased pressure drop in uids. Recently, colloidal dispersions of
nanometer-sized particles in traditional heat transfer uids, popularly
known as nanouids, have been attempted as a new class of engineering uids.
Advances in nanoscience during the past few decades made it possible to synthesize novel nanoparticles of desired size, morphology and
functionalization. Nanouids got intense scientic attention after the
rst report of unusually large k enhancement in copper (Cu) nanouids
at very low particle loading [2]. Subsequently, numerous theoretical and
experimental studies were done on the thermal conductivity of
nanouids [38]. Despite numerous experimental studies, it is still debated whether the k enhancement in nanouids are anomalous or within the predictions of effective medium theory (EMT) of Maxwell [9].
Many mechanisms are put forward to account for the k enhancement
of nanouids, which are liquid layering around nanoparticle surface,
ballistic phonon transport, Brownian motion induced microconvection
and the aggregation of nanoparticles [10]. Unfortunately, none of the
heat transport models could explain the wide spectrum of thermal
conductivity data reported in various nanouids. After detailed investigations and analysis, Brownian motion induced convection and effective conduction through percolating nanoparticle paths are considered
as the two most probable mechanisms responsible for the enhanced
heat conduction in nanouids [1113]. More recent systematic studies
reveal that the conduction path through agglomerates is one of the
most signicant factors responsible for the dramatic k enhancement in
nanouids [14,15].
The earlier reports showed an enhancement in thermal conductivity
ratio k/kf (kf is the base uid thermal conductivity) beyond EMT predictions [8,1636], whereas recent reports showed k/kf enhancement is
within the EMT predictions [4,14,21,3745]. Recent systematic studies,
by Buongiorno and his team in collaboration with thirty research
groups around the globe, on a series of stable nanouids produced by
the same production protocol (and same batch of samples) show
modest enhancement of k in polyalphaolen (PAO) lubricant based
alumina nanouids at low and high particle concentrations [4]. Also,
by analyzing large number of experimental data, Eapen et. al. have
elegantly demonstrated that almost all the reported thermal conductivity data are enveloped by the upper and lower Maxwell (H-S)
mean-eld bounds and the lack of consensus in nanouid k reports
arises mainly because of differences in the aggregation structures that
arise from colloidal chemistry, thermodynamic conditions and elds
[46]. There are also several computational analysis of factors inuencing
thermal conductivity of nanouids, which are not discussed in details
[4757]. Although there are several research articles on this relatively
new topics, there is no comprehensive review covering all aspects of
nanouids is available and this review is aimed at lling this gap. This
review starts with a brief outline of this topic covering all experimental
papers published so far on this topic. It later discusses the details of
various parameters inuencing the heat transport enhancement in
nanouids that includes those in metal, metal oxide, and carbon based
nanouids. As many of the researchers pursuing studies in this eld
are with engineering background and the above aspects would be
very benecial for them.
31
2. Experimental ndings on factors affecting thermal conductivity(k)

of nanouids
One of the earlier reports showed 40% enhancement in k for
ethylene glycol (EG) based Cu nanouids with mean diameter of
10 nm at a particle loading of 0.3 vol.% [2]. Abnormal k enhancement
was reported for oil based multi-walled carbon nanotube (MWCNT)
nanouids, with k/kf exceeding 2.5(>150% k enhancement) at a particle loading of 1 vol.% [58]. Later, many experimental studies have
been carried out on thermal conductivity of nanouids using a variety
of nanomaterials like:
Oxide ceramics: alumina (Al2O3) [5965,4,7,14,66,67], copper oxide
(CuO) [22,60,61,66,6872], magnetite (Fe3O4) [13,15,19,7382],
zinc oxide (ZnO) [64,83,84] and ceria (CeO2) [85]
Nitride/carbide ceramics: aluminium nitride (AlN) [63] and silicon
carbide (SiC) [38,45,8688]
Metals: copper (Cu) [2,35,69,8991], silver (Ag),[16,9294] gold
(Au) [16,37,66], iron (Fe) [17,25,35,9597] and aluminum (Al) [69]
Semiconductors: titania (TiO2) [20,66,95,97101], silica (SiO2)
[59,102,103] and tin oxide (SnO2) [104]
Metal alloys: aluminum copper (Al2Cu) [28,105] and silver aluminum (Ag2Al) [29,105]
Single and multi-walled carbon nanotubes (SWCNTs, MWCNTs)
[106121]
Graphene [122,123] and graphene oxide nanosheets [122,124126]
Reports show that the k of nanouids depend on factors like volume fraction (), nanoparticle size (d), morphology, additives, pH,
temperature, nature of base uid, nanoparticle material etc. Studies
on each of these factors are discussed briey.
2.1. Effect of particle volume fraction
Studies on thermal conductivity of nanouids at different shows
conicting reports of k enhancement. Enhancement within and beyond the EMT predictions is reported.
2.1.1. Metal and metal oxide nanouids
Studies on water and EG based Cu (80 nm) nanouids show k/kf
enhancement beyond EMT predictions [35,69]. In another report, relative increase in k was found to be twice that of the EMT predictions in
EG based Cu nanouids [89]. A linear increase in k with particle loading
is observed in water based Cu nanouids with a maximum k increment
of 74% at a nanoparticle loading of 0.3 vol.% [91]. In water based Cu
nanouids, the k/kf increases from 1.24 to 1.78 when the volume fraction of particles is increased from 2.5 to 7.5% [90]. Thermal conductivity
enhancement beyond EMT predictions is observed in EG based Fe
nanouids as well [35]. EG based Fe nanouid (10 nm) showed 16.5 %
enhancement in k at a particle loading of 0.3 vol.% [95]. A nonlinear enhancement in k with observed in EG based Fe ( 11 nm) nanouids
was attributed to rapid clustering of the nanoparticles at higher concentrations [17,96,97]. A k enhancement of 14.9% is observed in Fe
nanouids at a particle loading 5.0 vol.%, which was within the predictions of EMT [25]. Anomalous k was reported in EG based Ag nanouids
at very low particle loading, with a k increment of 1018%, corresponding to Ag nanoparticle concentration of 100010000 ppm [92]. Water
and transformer oil based Al (80 nm) nanouids also exhibited k/kf beyond EMT predictions [69]. However, toluene based Au (1.65 nm)
nanouid showed no anomalous k enhancements and the results
were within the predictions of Hamilton and Crosser for the spherical
nanoparticles [66]. A 1.4% enhancement in k was reported for 40 nm
sized Au nanoparticles suspended in water at a particle loading of
0.11 vol.%, which was within the predictions of EMT [37].
Monoethylene glycol and parafn liquid based CuO nanouids at
two different nominal particle size of 30 and 40 nm showed very
high k enhancement with particle loading [68]. Transformer oil
32
based CuO (31 nm) nanouids also exhibited k/kf beyond EMT predictions [69]. An enhanced k was observed for EG and water based
CuO nanouids [60,61,70]. k enhancements of 18, 28 and 31% was
reported for water based CuO nanouids at volume fractions of 1, 3
and 5% respectively [22]. EG based CuO (1030 nm) nanouids
showed 2.6% increase in k at a very low nanoparticle concentration
of 0.001 [71]. Also, higher thermal conductivities were reported for
EG based CuO nanouids with a maximum k enhancement > 20% at
a particle loading of 4 vol.% [72]. Another report shows no anomalous
k enhancement in water based CuO nanouids [66].
Thermal conductivity within and beyond EMT predictions were
observed in Al2O3 nanouids. Reports show high k/kf with for
water based Al2O3 nanouids [6062]. Al2O3 (53 nm) nanoparticles
dispersed in 60:40 EGWater mixture [64] and transformer oil
based Al2O3 (13 nm) nanouids [63] showed high k enhancement
with . Water based Al2O3 nanouids containing a small amount of
nanoparticles, have been reported to have substantially higher thermal conductivities than that of the same baseuids [72]. Hexadecane
based Al2O3 (70 nm) nanouids exhibited anomalous k enhancement
beyond the EMT predictions [14]. However, the recent benchmark exercise on Al2O3 nanoparticles and nanorods in water and PAO show
good agreement with EMT for well dispersed particles, thus,
suggesting no anomalous k enhancement for the nanouids [4]. No
k deviation from the Maxwell's model was observed for water based
Al2O3 (42 nm) nanouids [7]. In another report, no anomalous k
enhancements was observed for water based Al2O3 (20 nm)
nanouids and the experimental data was within the predictions of
Hamilton and Crosser model [66]. Car engine coolant based Al2O3
(50 nm) nanouids [65], water and EG based Al2O3 nanouids [67]
also showed k enhancement within EMT predictions.
Water and EG based spherical TiO2 and titanate tubes [99], water
based TiO2 (21 nm) [98] and EG based TiO2 (15 nm) nanouids
[100] showed large k enhancement. A maximum k enhancement of
14.4% is observed in EG based TiO2 (15 nm) nanouids, at a nanoparticle loading of 1 vol.% which was much above the EMT predictions
[95]. Rod shaped (10 nm 40 nm diameter by length) and spherical
(15 nm) TiO2 nanoparticles dispersed in water showed a k enhancement beyond the EMT predictions [20]. The maximum k enhancement observed was 29.7 and 32.8% for a particle loading of 5 vol.%
for spherical and rod shaped nanoparticles respectively. EG based
TiO2 (25 nm) nanouids exhibited 14 % enhancement in k at a particle loading of 1 vol.% that was above the EMT predictions [97]. Water
based titanate nanotubes with an aspect ratio of ~ 10 showed high k
enhancements even at low particle loading [101]. Another study reports no anomalous enhancement of k for water based TiO2
nanouids [66].
Kerosene [79] and water [19] based Fe3O4 nanouids showed
large k enhancement with . At a particle loading of 4 vol.%, water
based Fe3O4 (10 nm) nanouids exhibited a 38% enhancement in k
and the observed abnormal k enhancement was attributed to the
nanoparticle clustering and alignment [19]. However, the recent report shows a k enhancement within the predictions of EMT for kerosene based Fe3O4 nanouids [80]. Fe2O3 nanoparticles dispersed in a
mixture of water and EG showed no abnormal k enhancement beyond the predictions of EMT [82]. A very recent report showed the
thermal conductivity within the predictions of EMT in EG based
Fe2O3 and Fe3O4 nanouids [81].
Water based CaCO3 nanouids [127] and EG based ZnO
nanouids [128] showed k/kf enhancement beyond EMT predictions.
EG based WO3 (38 nm) nanouids [95] and transformer oil based
AlN nanouids also showed a large k enhancement at low particle
loading [63]. EG/water based Al2Cu and Ag2Al nanouids showed
very high k enhancement beyond EMT predictions [28,29,105]. A
16% enhancement in k was observed for EG based Al95Zn05
nanouids at a particle concentration of 0.1 vol.% where the level
of k enhancement was orders of magnitude higher than the EMT
predictions [129]. Water and EG based SiC nanouids [45] and

water based diamond nanouids [130] also exhibited high k enhancement with . For EG based SiC spherical particles and whisker
based nanouids, the k enhancement was in good agreement with
Maxwell model [131]. Water based SiC nanouids was reported to
have k enhancements within the Maxwell's prediction at lower volume fractions; however, at higher particle loadings (> 4 vol.%), enhancements were beyond Maxwell's prediction [38]. A maximum k
enhancement of 20% is observed in water based plasma treated diamond nanouids at a particle loading of 0.15 vol.%, which was much
higher than the EMT predictions [132]. For iron based
magnetorheological suspension, at low volume fractions, the k
values were in good agreement with Maxwell and Bruggeman
models and at higher volume fractions, the k values were signicantly higher than that of Maxwell predictions and the data was better
tted with Bruggeman model that accounts for thermal interactions
between particles [133]. Magnetorheological uids of 13 m diameter carbonyl iron particles dispersed in silicone oil showed good
agreement with Bruggeman's model at low particle concentrations
and the model underpredicted the k at high concentrations [134].
Thermal conductivity within EMT predictions is reported for water
based SiO2 nanouids [102]. The recent benchmark exercise on Au/
water, SiO2/water and MnZn ferrite/water nanouids also show
no anomalous enhancement in k [4].
A very recent study in nanouids containing graphene oxide
(GON) nanosheets shows signicantly higher thermal conductivities
than the base uids [125]. The k enhancement at a particle loading
of 5.0 vol.% were 30.2, 62.3 and 76.8%, for the base uids of distilled
water, propyl glycol and liquid parafn respectively. The same
group has reported k/kf beyond EMT predictions in EG based GON
nanouids, where a maximum k enhancement of 61% was observed
at a particle loading of 5.0 vol.% [124]. Another very recent study
shows a signicant k enhancement in nanouids containing graphene
nanosheets in EG i.e. 86% increase in k for 5.0 vol.% of graphene
nanosheets [122].
Interestingly, water and EG based Al2O3 nanouids at three different nominal particle size of 11, 20 and 40 nm showed a lower k enhancement than the EMT predictions for spherical particles [44]. In
magnetic microencapsulated phase change material (MMPCM) suspension, the observed k enhancement was below EMT predictions
[135] i.e. 812 % k enhancement with 5.129.21 vol.% of the particles. Recent report showed k/kf lower than the prediction of EMT
for water and EG based alumina nanouids [67]. Also, a negative k enhancement is reported for 2 nm sized TiO2 nanoparticles dispersed in
50:50 waterEG mixture recently [136].
Our thermal property studies in Fe3O4 (9 nm), CuO (9 nm) and Ag
(7 nm) nanoparticles in kerosene, ethylene glycol and hexadecane
base uids respectively show that the k enhancement is within the
EMT prediction for Fe3O4 and Ag nanouid while the enhancement
is beyond EMT prediction for CuO nanouid (Fig. 1) [13,15,73,
75,76,78]. Both Fe3O4 and Ag nanouids used were extremely stable
(stable for more than 4 years) due to proper steric stabilization
using surfactant moieties, which form a monolayer on each particles
thereby preventing the agglomeration of particles and subsequent
settling. However, no surfactant was used in CuO nanouids and
hence the dispersion stability was poor. On ultrasound sonication,
the CuO dispersions remain stable for several hours to a few days
depending upon the particle concentration. The conclusion drawn
from the above study was the thermal conductivity enhancement
was within the prediction of Maxwell's theory for stable dispersions
where the particles remain well suspended without any agglomeration. In agglomerating nanouids, the enhancement was beyond
EMT predictions as the agglomerating particles form a space lling
fractal network along the heat ow direction. However, the thermal
conductivity of such unstable nanouids decrease with time due to
the compaction of fractal network or settling of larger agglomerates.
33
of 34% at 0.6 vol.% of nanotube loading [145]. CNTs/ethylene glycol

and CNTs/synthetic engine oil nanouids were reported to have k enhancement of 12.4 and 30% at particle loadings of 1 and 2 vol.% respectively [114]. A thermal conductivity enhancement of 19.6% was
observed for CNT loading at 1.0 vol.% in decene [108]. In general,
most of the reports on CNT based nanouids shows anomalous k
enhancement.
2.2. Effect of particle size
Fig. 1. The variation of k/kf and the percentage (%) of k enhancement as a function of
for kerosene based Fe3O4 nanouids (d = 6 nm), ethylene glycol based CuO nanouids
(d = 8 nm) and hexadecane based Ag nanouids (d = 7 nm), together with Maxwell's
t.
2.1.2. Carbon nanotube (CNT) nanouids

All the thermal conductivity studies in CNT nanouids show k enhancement beyond the predictions of EMT. The rst report showed an
abnormal k enhancement (150%) even at very low nanotube loading
(~ 1 vol.%). MWCNTs with a mean diameter of ~ 25 nm and a length of
~ 50 m dispersed in a synthetic polyalphaolen oil was used for the
above study [58]. Very recent report also shows a k/kf beyond the predictions of EMT in water based plasma treated MWCNTs nanouids,
i.e. 23% k enhancement at a particle loading of 0.01 vol.%. A nonlinear
dependence of k on enhancement is reported in MWCNT nanouids
[115]. Water and EG based metal dispersed MWCNT (Pd-MWNTs,
Au-MWNTs, and Ag-MWNTs) show a high k enhancement with
[116]. For CNT nanorefrigerants with 1.0 vol.% of CNTs, the enhancement in k were 82 , 104, 43 and 50% when the CNT aspect ratio
were 100, 666, 18 and 125 respectively [137]. For water and EG
based MWCNT nanouids, a considerable increase in thermal conductivity was observed with i.e. 17.5% k enhancement for a nanotube
loading of 1.0 vol.% in EG [138]. In EG based CNT nanouids, the
experimental k values were well above the predictions of EMT i.e.
20% increase in k at 2.5 vol.% of carbon nanotubes [118]. For water
based MWCNT nanouids, an abnormal k enhancement (64%) was
observed at a nanotube loading of 3 wt.% [117]. For SWCNT
nanouids, at a particle loading of 1.1 vol.%, the enhancement in k
was 35% [112]. Water based CNT nanouid shows nonlinear dependence of k on , with a maximum k enhancement of 34% at a particle
loading of 0.8 vol.% [91]. In plasma treated carbon nanober (average
diameter 10, 20 and 40 nm) based nanouids, k values were found to
increase with decrease in nanober diameter and the k enhancement
was approximately 16% at 0.5 vol.% of carbon nanobers of diameter
10 nm [139]. For hybrid sphere/CNT, consisting of CNTs attached to
an alumina/iron oxide sphere dispersed in PAO, the effective k of
the uids increased by about 21% for a particle loading of 0.2 vol.%
[140]. Study of k of PAO oil based nanouids made of three types of
nanomaterials CNTs, exfoliated graphite (EXG) and heat treated
nanobers (HTT) showed a maximum k enhancement of ~ 161%
for the CNTPAO oil suspension. The overall percent k enhancements
for different volume fractions of the nanoparticles were highest for
the CNT based nanouid, followed by the EXG and the HTT [141].
Oil based MWCNTs nanouids exhibited a large k enhancement
with [142]. MWCNTs/PAO nanouids were reported to have an abnormal k/kf of 3% for a particle loading of 0.35 vol.% [107]. CNTs/engine oil nanouids [100] also shows a large k enhancement. For
water based MWCNTs nanouid, the k enhancement was 11.3% for
a volume fraction of 0.01 which was much above the EMT predictions
[143]. A maximum k enhancement of 21% was observed in water
based MWCNTs nanouids for a volume fraction of 0.6 vol.% [144].
Water based CNTs nanouids exhibited a maximum k enhancement
There are conicting reports on the effect of nanoparticle size on thermal conductivity of nanouids. Few reports show an enhancement in k/kf
with decrease in particle size [26,2830,64,69,83,84,105,146149],
whereas other reports show a decrease in k/kf with decrease in particle
size [37,44,78,85,88,150,151]. An overview of experimental investigations
on the effect of particle size on the thermal conductivity for metal and ceramic nanouids is given below.
2.2.1. Increase in k with decrease in nanoparticle size
A study in water based Al2O3 nanouids with 3 different nominal
diameters of 20, 50, and 100 nm shows an enhancement in k/kf with
decrease in nanoparticle size [146]. In another study, the thermal conductivity of water and EG based Al2O3 nanouids was reported to increase with decrease in nanoparticle size [69]. No considerable
difference in k was observed for water based Al2O3 nanouids having
two nominal nanoparticle size of 36 and 47 nm at room temperature.
However, at elevated temperatures, particle size was shown to have
an inuence on k, i.e. for the same vol.%, nanouid with small particle
size yield greater k values [147]. Studies on water based Al2O3
nanouids with two different particle size of 45 and 150 nm show an
enhancement in k with reduced particle size [148]. ZnO (29 and
77 nm) dispersed in 60:40 of EGwater mixture showed higher k
ratio for smaller size nanoparticles [64]. Water and EG based Al2Cu
and Ag2Al nanouids were reported to exhibit an enhancement in k/kf
with decrease in particle size [28,29,105]. The k enhancement ratio relative to the base uid is found to increase linearly with decrease in particle size for water and EG based TiO2 (10, 34 and 70 nm) and ZnO (10,
30 and 60 nm) nanouids [83]. Water based Al2O3 nanouids with
nanoparticle diameters of 36 and 47 nm show a higher k enhancement
for 36 nm diameter nanouids than the 47 nm diameter Al2O3
nanouids at different volume fractions and temperature [30]. It has
been shown that a high power laser irradiation results in the fragmentation of suspended particles with a signicant increase in the effective
k for water based ZnO nanouids [84]. The effective k has been found to
decrease with increase in particle size for water based TiO2 nanouids
[149]. The thermal conductivity studies on Al2O3 nanouids as a function of nanoparticle size (ranging from 11150 nm nominal diameters)
over a wide range of temperature (from 2171 C) show an enhancement in k with decrease in nanoparticle size [26]. In a recent study, an
increase in k ratio with the decrease in crystallite size has been observed
for EG based Al95Zn05 nanouids [129].
2.2.2. Decrease in k with decrease in nanoparticle size
A very recent report in water based SiC nanouids with 4 different
nominal diameters of 16, 29, 66 and 90 nm show higher k values for
nanouids with larger particles [88]. Water based gold nanouids
shows a decrease in k with decrease in particle size in the range of
240 nm [37]. The k enhancement in aqueous alumina nanouids
at room temperature has been found to decrease as the particle size
decreases below 50 nm [150]. Water based ceria (CeO2) nanouids
also show an increase in k/kf with increase in nanoparticle size [85].
For water and EG based alumina nanouids with seven different particle sizes ranging from 8282 nm, the k enhancement has been
found to decrease with decreasing particle size [151]. An enhancement in k with increasing particles size is reported for SiC nanouids
[38,45,87]. Water based SiO2 nanouids also show an enhancement in
34
k with increase in nanoparticle size [103]. Very recent reports show

that k of EG based Ag nanouids decreases with decreasing particle
size [94]. The k values of the SiCEG/water and SiC/water nanouids
has been reported to increase with increased nanoparticle sizes (16,
28, 66 and 90 nm) [86].
Our studies on the effect of particle size on k in model nanouids
(with long term stability) containing oleic acid coated magnetite
nanoparticles of average diameters 2.89.5 nm dispersed in kerosene
show an increase in k with increase in particle size. Thermal conductivity is measured as a function of particle size at two different volume
fractions of = 0.01 and 0.055 (Fig. 2). No enhancement in k has been
observed at a low particle loading of = 0.01. For = 0.055, the enhancement in k is about 5 and 25%, respectively, for 2.8 and 9.5 nm
sized nanouids. The experimental data shows a power law scaling
(k/kf ~ d x) where the exponent is found to be 1.24. The best t is
shown by the solid line in Fig 2. According to microconvection model,
the local convection is caused by Brownian motion of the nanoparticles
in the base uid. The Reynolds number (Re) for Brownian motion
is inversely proportional to square root of the particle size. Therefore,
an increase in k with decrease in particle size is predicted by
microconvection model. However, the observed results are contrary to
the above predictions and hence it is concluded that microconvection
is not the key mechanism responsible for k enhancements in nanouids.
It is believed that the observed increase in k may be originating from the
kinetic growth of small particles into fractal like aggregates in the suspensions where the process can be diffusion or reaction limited [152].
2.3. Effect of temperature
Few reports show an enhancement in k/kf with increase in
temperature [69,153,16,26,30,31,6062,64,69,100,101,104,106,109,
116,118,130,132,140,146,147,154159], whereas other reports show
least effect of temperature on k/kf of nanouids [14,37,38,44,65,
66,79,80,117,124,125,128,138,150,160,161]. There are also few reports
of reduction in k/kf with increase in temperature [98,162]. An overview
of experimental investigations on effect of temperature on nanouid
thermal conductivity is given below.
2.3.1. Enhancement in k and k/kf with temperature
2.3.1.1. Metal nanouids. Water and EG based Cu nanouids with a
particle size of 80 nm was reported to exhibit an enhancement in k/
kf with temperature [69]. Another report shows that the % of k enhancement in EG based Cu nanouids varies from 8 to 46% as the
temperature increased from 10 to 50 C at a particle loading of
0.5 vol.% [153]. Water and transformer oil based Al (80 nm)
nanouids [69] and engine oil based Al (80 nm) nanouids [100]
Fig. 2. The k/kf and the % of k enhancement of kerosene based magnetite nanouids
having two different volume fractions = 0.01 and = 0.055 as a function of nanoparticle size. Best t is shown by the solid line.
also exhibit an enhancement in k/kf with temperature. Water based

Ag (6080 nm) nanouids have shown k increments of 3.2% at
30 C and 4.5% at 60 C at a particle loading of 0.001 vol.%. Toluene
based Au (34 nm) nanouids exhibited k increments of 7 and 14%
at 30 and at 60 C respectively for a particle loading of 0.011 vol.%
[16].
2.3.1.2. Metal oxide nanouids. A recent study in water based Al2O3
nanouids of three different nominal diameters of 20, 50, and
100 nm have shown an enhancement in k/kf with increase in temperature [146]. EG based Al2O3 nanouids with two different nominal
particle size of 11 and 150 nm also exhibited an enhancement in k/
kf with temperature [69]. Transformer oil based CuO nanouids
exhibited an enhancement in k/kf with temperature [69]. An enhancement in k with temperature was observed in water based
Al2O3 nanouids [62] and Al2O3 nanoparticles in parafn emulsions
[154]. For water based Al2O3 and CuO nanouids (47 and 36 nm for
the Al2O3 nanouid and 29 nm for the CuO nanouid), the relative increase in k was found to be more at higher temperatures [147]. Thermal conductivity of aqueous amorphous carbonic (20 nm) and
alumina (2050 nm) nanouids was reported to increase with increase in temperature (2252C) [155]. Al2O3 (53 nm), ZnO (29
and 77 nm) and CuO (29 nm) nanoparticles dispersed in 60:40 EG
water mixture have shown an enhancement in k with increase in temperature [64]. Thermal conductivity of lubricant (R-134a refrigeration
system) containing Al2O3 nanoparticles increases from 1.5 to 4.6%
when the sample temperatures increased from 20 C to 40 C at a particle loading of 1.5 wt.% [156]. Water based Al2O3 (36 nm) nanouids
have shown an enhancement in k with temperature (250C) [157].
For water based Al2O3 nanouids, at 0.2 vol.%, the enhancement in k
was 3.26% at room temperature (30 C) and at 60 C the enhancement
was 10.76%. For CuO nanouids, k enhancement increased from 6.52 to
23.98% as the temperature was increased from 30 to 60 C [60,61]. EG
and water based Al2O3 (80 and 150 nm) nanouids exhibited an
enhancement in k/kf with temperature [100]. Thermal conductivity
enhancement was found to increase with increase in temperature
(2737C) in water based Al2O3 (36 and 47 nm) nanouids [30]. For
water based Al2O3 (36 nm) and CuO (29 nm) nanouids, the k/kf was
reported to increase with temperature in the range of 27.5 to 34.7C
[31]. The k studies on Al2O3 nanouids as a function of nanoparticle
size (ranging from 11150 nm diameters) over a wide range of temperature (from 21 to 71 C), show an increase in k with increase in temperature [26]. An enhancement in k with temperature (2055 C) was
reported for water based Al2O3 nanouids [158]. Water based SnO2
nanouids also showed an enhancement in k/kf with temperature
[104]. By increasing the temperature, a pronounced increase in the thermal conductivity of the nanouid was observed for water based diamond nanouids [130]. In water based titanate nanotubes with an
aspect ratio of ~10, k enhancement was~ 3 and 5% at 25 and 40 C
respectively at a nanotube loading of 2.5 wt.% [101]. Plasma treated
diamond nanoparticles in water have shown an enhancement in k/kf
with temperature from 20 to 50 C [132]. A linear increase in k with
temperature was observed in EG based Al95Zn05 nanouid over the
temperature range of 30 to 70 C [129].
2.3.1.3. CNT nanouids. The k/kf of EG based CNT nanouids was found
to increase with increase in temperature [109]. Water and EG based
metal dispersed MWCNTs (Pd-MWNTs, Au-MWNTs, and Ag-MWNTs)
also exhibited an enhancement in k/kf with temperature [116]. For
water based MWCNTs nanouids, k increase was nonlinear with temperature from 15 to 35 C [159]. For EG based CNT nanouids, k/kf increases with increase in temperature [118]. PAO based hybrid sphere/
CNT nanouids, consisting of CNTs (length up to 2 m) attached to an
alumina/iron oxide sphere (d=70 nm) exhibited enhancement in k
with increase in temperature i.e. about 20.5% at 10C and 23.6% at
90C for 0.2 vol% [140]. For water based MWCNT nanouids, k/kf is
found to increase with increase in temperature in the range of 20 to

30C [106]. The increase in temperature leads to k enhancement for
water based CNT nanouids over a temperature range of 10 to 50C
[163].
2.3.2. Invariant k/kf with temperature
2.3.2.1. Metal nanouids and metal oxide nanouids. Water based Au
nanouids showed a temperature independent behavior on k enhancement [37]. Temperature dependent k behavior of 10 and 50 nm sized
alumina nanoparticles dispersed in water, ethylene glycol, and ethylene
glycol + water mixture was found to follow the behavior of the base
uids [150]. An invariant k/kf with temperature was observed for kerosene based Fe3O4 nanouids [80]. Studies on car engine oil based Al2O3
(d= 50 nm) nanouids showed that the temperature dependence of
nanouid k originates from that of the base uid and the observed increase in k with rise in temperature is manifested from the base uid
rather than the behavior associated with Al2O3 nanoparticles. Thus it
was concluded that the k enhancement in nanouids relative to the
base uid is essentially temperature independent [65]. Temperature dependent k studies in kerosene based Fe3O4 nanouids showed that the
absolute k increases with the temperature, while the k ratios were almost constant [79]. For EG based ZnO nanouids, absolute k was
found to increase with increasing temperature, while the ratios were almost constant, therefore, the k of the nanouids simply track the k of
the base liquid [128]. Hexadecane based Al2O3 (70 nm) nanouids
also showed constant k/kf in the temperature range of 25 to 50 C
[14]. Temperature dependent k studies in water and EG nanouids
with 5 vol.% of 40 nm size alumina particles showed an enhancement
in absolute k in the temperature range of 10 to 65 C. However, this
temperature dependence of k in nanouids simply track the k of the
base uid [44]. In water based Al2O3 (20 nm) nanouids, the effective
k of nanouids increases with increase in temperature. However, the
temperature dependent k of nanouids were the same as that of base
uid [66]. For transformer oil based Fe3O4 nanouids, a decrease in k
with rise in temperature was observed both for nanouid and for base
uid over the temperature range of 20 to 80 C [160]. Very recent
study in nanouids containing graphene oxide nanosheets showed
that the k of the nanouids simply track the k of the base uid, and
the k enhancement ratios were almost constant in the temperature
range of 1060 C for the three nanouids where the base uids were
water, propyl glycol and liquid parafn [125]. An invariant k/kf with
temperature was observed in EG based nanouids [124]. For water
based SiC nanouids, enhancement in the k was temperature independent for all the nanoparticle loadings investigated [38]. The k studies of
epoxy-resin polymer and glass ber reinforced epoxy resin as a function
of the temperature showed less effect on temperature [161]. Recent
studies in EG based graphene nanouids show little inuence of temperature on the k enhancement of nanouids and the enhancement ratios were almost constant in the tested temperature range of 10 to 60C
[122]. Very recently, nearly temperature independent k behavior was
reported for EG based Fe2O3 and Fe3O4 nanouids [81]. Recent reports
in EG based Al2O3 nanouid also showed a nearly temperature independent k enhancement [164].
Our studies show a temperature independent k for both aqueous
and non-aqueous stable magnetite nanouids with average particle
size of 6 nm over the temperature range of 25 to 50 C. The thermal
conductivity of aqueous nanouids increases with temperature while
it shows a decrease in non-aqueous (kerosene and hexadecane based)
nanouids. Interestingly, the ratio of thermal conductivity (k/kf) of
kerosene [Fig. 3(a)], hexadecane [Fig. 3(b)] and aqueous [Fig. 3(c)]
nanouids remains constant with increase in temperature, irrespective
of the nature of the base uid. According to microconvection model,
the root-mean-square velocity (N) of a Brownian particle increases
linearly with the square root of temperature T. Thus, the k is also
expected to increase in the same manner irrespective of the uid
35
used. From the observed invariant k/kf with temperature we conclude

that microconvection has a less dominant role on thermal conductivity
enhancement of nanouids.
2.3.2.2. CNT nanouids. Temperature independent k enhancement ratios were reported over the temperature range of 5 to 65 C in
EG based MWCNTs nanouids [138]. For water based MWCNTs
nanouids, the k enhancement was found to be temperature independent at low nanotube loading [117].
2.3.3. Decrease in k/kf with temperature
For water based TiO2 (21 nm) nanouids, over the temperature
range of 1535 C, relative k was found to decrease with increase
in temperature [98]. For Bi2Te3 nanorods of average diameter 20 nm
and length 170 nm, dispersed in peruoron hexane and hexadecane
oil, the k enhancement was found to decrease with increase in temperature, in contrast to the trend observed in nanouids containing
spherical nanoparticles. The observed trend of k/kf with temperature
was attributed to the particle aspect ratio [162].
2.4. Effect of particle shape/aspect ratio
Most of the studies showed an enhancement in k with increase in
particle aspect ratio [4,20,45,107,117,119,131,137,139,145,165]. The
thermal conductivity studies in alumina nanouids with different
particle shapes of platelets, blades, cylinders and bricks showed that
the k enhancement coefcients follow the sequence platelets ~
blades b bricks b cylinders, indicating the effect of particle shape on k
[165]. Recent benchmark exercise on Al2O3 nanoparticles and
nanorods dispersed in PAO showed that k enhancement was more
for the nanorods [4]. For CNT nanorefrigerants, the CNTs with an aspect ratio of 18.8 have shown a k ratio of 1.43 where as CNTs with
an aspect ratio of 666.7 have shown k/kf of 2.04 for a particle loading
of 1.0 vol.% [137]. For EG based SiC nanouids, at a xed volume
Fig. 3. The variation of k/kf with temperature for (a): Kerosene based Fe3O4 nanouids
with = 0.008, 0.027, 0.05, 0.078 and 0.095 (d = 6 nm); (b): Hexadecane based Fe3O4
nanouids with = 0.0165 and 0.0608 (d = 6 nm) and (c): Water based Fe3O4
nanouids with = 0.0102 (d = 6 nm).
36
fraction, the k enhancement was found to vary from 16.5 to 39.5%

when the volume averaged aspect ratio increased from 4.8 to 9.6
[131]. In water based MWCNTs nanouids, the k enhancement increased with increase in nanotube length. For the shortest nanotubes
(~ 0.5 m), the relative increase in k was ~ 14%, while an increase of
18% was observed for a nanotube length of 1 m, 38% for 1.7 m,
and around 45% for the longest nanotubes tested with a mean length
of about 5 m [117]. For plasma treated carbon nanober (average diameter 10, 20 and 40 nm) based nanouids, the k values was found to
increase with decrease in carbon nanober diameter [139]. PAO
based MWCNTs have shown an enhancement in k with increase in aspect ratio of nanotubes [107]. At a particle loading of 5 vol.%, rod
shaped TiO2 nanoparticles (10 nm 40 nm diameter by length) and
spherical TiO2 nanoparticles (15 nm) showed a maximum k enhancement of 29.7 % and 32.80% respectively, compared to the base uid
(water) [20]. The enhancement in k was found to increase with increase in the aspect ratio for water based CNTs nanouids [145]. An
enhancement in k/kf with increase in aspect ratio was reported for
water based CNTs nanouids [119]. The k enhancement ratio of
spherical SiC nanouids with 26 nm particle size was reported to be
lower than those of cylindrical SiC nanoparticles with size 600 nm
[45]. However, least variation in k with aspect ratio was also reported
in EG based TiO2 nanouids. Thermal conductivity studies in water
and EG based titania spheres and nanotubes have shown almost the
same k values. TiO2 nanoparticles were of 25 nm size and titanate
nanotubes had a diameter of 10 nm and a length of 100 nm [99].
2.5. Effect of base uid material
Most of the studies have shown a decreased thermal conductivity
ratio with increase in k of the base uid [4,67,72,108,114,
125,135,138,143,166]. Very recent study in nanouids containing
graphene oxide nanosheets (GON) dispersed in water, propyl glycol
and liquid parafn showed a dramatic improvement in k of GON suspension for a base uid with lower k [125]. The k studies in water and
EG based Al2O3 nanouids have shown higher k/kf in EG than that in
water based alumina nanouids for the same concentrations [67].
Recent benchmark exercise on Al2O3 nanouid has reported an increase in nanouid k with decrease in base uid k [4]. For magnetic
microencapsulated phase change material (MMPCM) suspension,
variation of the k ratio with parafn content inside MMPCM particles
showed a decrease in k ratio with increase in parafn content inside
the MMPCM particles. The k/kf varied from 1.057 to 1.015 when the
parafn content was increased from 30 to 70 wt% and such degradation was resulted from the smaller k of parafn compared to the base
uid [135]. Decreases in the k ratio with an increase in k of the base
uid were reported in alumina nanouids [166]. Thermal conductivity studies in water and EG based MWCNTs nanouids have shown a
lower k enhancement ratio for water based nanouids as compared
to EG based nanouids. Much more dramatic improvement in k of
nanotube suspension was reported for a base uid with lower thermal conductivity. At 1.0 vol.%, the k enhancements were 17.5, 16
and 12% for CNT nanouids in EG, glycerol, and water respectively
[138]. In case of CuO (33 nm) nanouids, the k enhancement of EG
based nanouid was higher than that of water based nanouid
[143]. For CNT nanouids, the observed increase of k in mineral oil
was substantially smaller than for the ones in polar uids, such as
ethylene glycol or water [144]. The synthetic engine oil based CNT
nanouid was reported to have a much higher enhanced k ratio
than the EG based CNT nanouids [114]. For CNTs nanouids, much
more dramatic improvement in k was observed in base uid with
lower k. At 1 vol.%, the k enhancements were 19.6, 12.7, and 7% for
CNT suspension in decene, EG, and water respectively [108]. For the
suspensions containing the same nanoparticles, the enhanced k
ratio was reduced with increasing k of the base uid for Al2O3
nanouids. For water, EG, and pump oil based nanouids, more
dramatic improvement in the k was observed for the suspension

with a uid of lower k, i.e. pump oil [166]. For water and EG based
Al2O3 and CuO nanouids, with the same nanoparticles, the thermal
conductivity ratio enhancement of ethylene glycol nanouid was
higher than that of water based nanouids [72]. A recent report
showed a signicantly high k for SiC nanoparticles dispersed in EG
water mixture, compared to the analogous suspensions in water
for four sizes of SiC particles (1690 nm) [86]. This base uid effect
was attributed to the lower value of the interfacial thermal resistance
of the EGwater nanouids.
For water and EG based SiC nanouids, k ratio showed no signicant difference [45]. There are few reports on the effect of viscosity of
the base uid on k of nanouid [167,168]. The effect of viscosity of the
base uid on the k of nanouids was studied for Fe3O4 nanoparticles
suspended in the base uid composed of diesel oil and polydimethylsiloxane. Viscosity of the nanouid is varied by changing the volume
fractions. The measured k of nanouids gradually approached the
value predicted by the Maxwell equation by increasing the viscosity.
The highest enhancement of k is 18.85% at 4.48 vol.% of Fe3O4
nanoparticles [168]. Investigations on the thermal conductivities of
Fe3O4 and Al2O3 nanouids with the viscous base uid composed by
various uids showed that the values of k of nanouids gradually approaches the values predicted by Maxwell equation with increase in
the base uid viscosity [167]. In a recent study, different k values
were reported for Fe3O4 nanoparticles dispersed in different apolar
base uids. It was concluded that the difference in the effective k
for different base uids is attributed to the inherent k difference of
the base uids, but more likely to the compatibility of the base uid
with a specic particle type where the solvation of the stabilizing
layer may play a determining role [169]. Fig. 4 shows the variation
of k/kf as a function of for Fe3O4 nanouids with particle size
6 nm in different base uids of kerosene, hexadecane and water.
Our results show that the k enhancement has least dependence on
base uid materials.
2.6. Effect of nanoparticle material
Many reports show that the k enhancement of nanouid is higher
when the suspended nanoparticles have higher k [67,69,95,143,170],
whereas some reports show that the k of nanoparticles is not a principal factor related to k of nanouids [17,19,31,72,9597].
Thermal conductivity studies done on water, EG and transformer
oil based Cu, CuO, Al and Al2O3 nanouids show high k enhancements
for metallic nanouids compared to oxide nanouids [69]. In a recent
report the effect of nanoparticle species on k was studied by using
alumina, copper oxide, and a 1:1 mixture of alumina and copper
oxide nanoparticles dispersed in ethylene glycol. The results show a
high k for CuO nanouids compared to alumina nanouid, which
has a lower k. In addition, the k of 1:1 mixture of alumina and copper
Fig. 4. The variation of k/kf as a function of for Fe3O4 nanouids with particle size
6 nm in different base uids of kerosene, hexadecane and water.
Oxide in EG lies in between those two nanouids at higher concentrations [67]. For 1.0 vol.% Cu (20 nm) nanouids, the k enhancement
was in the range 4870%, while it was around 2133% for 1.0 vol.%
of Fe (10 nm) nanouids [35]. Studies on Al2O3 and Cu nanouids
show a high k enhancement for water based Cu nanouids compared
to water based Al2O3 nanouids, which was attributed to the higher k
of copper nanoparticles [170]. For a particle loading of 0.3 vol.%, Fe
nanouid showed 16.5% k enhancement whereas WO3 nanouid
showed only 13.8% k enhancement [95]. Among water based CuO,
SiO2 and MWCNT nanouids, MWCNT nanouid showed the highest
k and SiO2 nanouid showed the lowest k. These results show that the
k enhancement of nanouid was higher when the suspended
nanoparticles have higher k [143].
Water based TiO2 nanouid showed a higher enhancement of k
compared with Al2O3 nanouids even though bulk TiO2 crystal
showed lower k than Al2O3 crystal. While there was only 4% enhancement of k with 1 vol.% of Al2O3 nanoparticles, 14.4% k enhancement
was observed with 1 vol.% of TiO2 nanoparticles. This study concludes
that the k of nanoparticles is not the principal factor that decides the k
of nanouids [95]. For water based Al2O3 (36 nm) and CuO (29 nm)
nanouids, of loading of 10 and 6 vol.% show a k enhancement of
1.3 and 1.52% respectively [31]. The comparison of thermal conductivities of water based Fe3O4 (10 nm) nanouids with other oxides
show that the k of Fe3O4 nanouids are larger than those of
nanouids containing the same volume fractions of Al2O3, CuO, and
TiO2. At a particle loading of 4 vol.%, Fe3O4 nanouids exhibited 38%
k enhancement, while nanouids containing TiO2 or Al2O3
nanoparticles show 30% enhancement even though bulk Fe3O4 crystal
has a lower k than Al2O3, CuO, and TiO2 crystals [19]. Comparison of k
of EG based Fe and Cu nanouids shows that the highly thermal conductive material is not always the best candidate for thermal transport property of uids [17,96]. The study of k in Fe and TiO2
nanouids with Cu and Al2O3 nanouids also support the above ndings [97]. For water and EG based Al2O3 and CuO nanouids, the conductivity ratio of the CuO system was higher than that of the A12O3
system [72].
Our thermal conductivity studies in Fe3O4, CuO and Ag nanoparticle show that the k enhancement in Ag nanouid is almost the same
as that of Fe3O4 nanouids but was less than that of CuO of similar
size. This indicates that the k of solid particles in the dispersion
does not dictate the k enhancement in nanouids (Fig. 1). However,
we must admit that in the above studies the particle size and the
base uids used were slightly different and the CuO particles are
not functionalized.
2.7. Effect of additives
EG based Cu (b 10 nm) nanouids containing thioglycolic acid
as a stabilizing agent showed improved k enhancement compared
to nonacid-containing nanouids [2]. However uids containing
thioglycolic acid, without particles, showed no improvement in k.
The k ratio of nano-suspensions and the base uid as the function of
the SDBS dispersant for water based Cu and Al2O3 nanouids showed
an optimal SDBS concentration is attributed to the higher thermal
conductivity of the nanouids [170]. Studies in water based Al2O3
nanouids showed an optimum SDBS concentration is ideal for k enhancement [171]. For MWCNT/PAO nanouids with polyisobutene
succinimide (PIBSI) as the dispersant, the k/kf is found to be a minimum at 3 wt.% PIBSI [107]. Adsorption of the dispersant molecules
to the carbon nanotube surfaces creates steric hindrance that prevents agglomeration. At lower dispersant levels, less polymer molecules are adsorbed on the carbon surface. At higher dispersant
levels, bridging occulation can occur between polymer chains. For
EG and water based CNT nanouids, the SDS concentration is found
to have no apparent signicance for the k of the suspension
[119,144]. In water based CNTs nanouids, it was reported that
37
CTAB concentration has minor effects on the k of the suspension

[145].
2.8. Effect of acidity (pH)
A recent systematic study on pH inuences of zeta potential, particle size distribution, rheology, viscosity, and stability on heat transfer nanouids show signicant enhancement of thermal conductivity
in 3 wt % zirconium dioxide and titanium dioxide near the isoelectric
point, which indicate that the stability of nanouids are inuenced by
pH values [172]. The same group has studied the effects of alignment,
pH, surfactant and solvent on heat transfer nanouids containing
Fe2O3 and CuO nanoparticles where they found the surfactants prevent agglomeration of particles [173]. The aggregation kinetics was
controlled by adjusting pH of dispersed SiO2 sols in water where the
clustering did not show any discernable enhancement in the thermal
conductivity even at high particle loading (23.3 vol.%) [102]. For
water based Cu and Al2O3 nanouids, at lower pH, the thermal conductivity ratio was found to increases with pH for different weight
fractions of nanoparticles, whereas at higher pH, the thermal conductivity ratio decreases. It was concluded that an optimal pH value can
result in the highest thermal conductivity of the nanouids [170]. In
water based SnO2 nanouids, the pH value far from the isoelectric
point (IEP) enhanced the dispersion stability and thermal conductivity of the nanouids [104]. Measurement of k ratio for water based
Al2O3 nanouids with SDBS dispersant as a function of pH showed
an increase in k ratio when pH was increased from 3 to 8.09.0
[171]. The stability and k enhancements of water based Al2O3 (15
50 nm) nanouids were highly dependent on pH values, with an optimal pH value for the best dispersion behavior and high k [171]. For
water based Cu nanouids, k was enhanced by 10.7%, with an optimal
pH value [174]. The effect of pH value on k of water based alumina
(4050 nm) nanouids showed a lower pH results in less aggregation, better dispersion stability and higher effective k [67]. In water
based CuO (25 nm) nanouids, as the pH of the solution varied far
from the isoelectric point of particles, the colloidal particles become
more stable and eventually alter the k of the uid [175]. For water
based Al2O3 nanouids, k was reported to increase with an increase
in the pH value [166].
2.9. Effect of sonication
In a recent study, different sonication power was used to probe
the effect of sonication on effective k of nanouids [67]. For both alumina and copper oxide nanouids, 450 W sonication power gave the
smallest nanoparticle cluster size and the highest effective k enhancement. Ultrasonication has found to have twofold effect on the water
based MWCNT nanouids. Below the optimum processing time, the
ultrasonication aids in forming better dispersion, however, beyond
optimum ultrasonication results in an increased breakage of
nanotubes and a reduction in the aspect ratio of CNTs [159]. Studies
on water based SWCNTs and MWCNTs nanouids showed that k of
nanouid is time dependent immediately after ultrasonication and
time independent after longer time [113]. k was reported to increase
with ultrasonication time in EG based CNTs nanouids [118]. For
water based CuO nanouids, it was observed that the k decreases
with elapsed time after sonication due to particle agglomeration
that was conrmed microscopically [70]. In PAO based MWCNT
nanouid, the aspect ratio decreases with increase in dispersing energy and dispersing time and a decrease in k with increase in dispersing
energy was observed [107]. Water based Cu nanouids, without the
addition of surfactant showed a time-dependent k characteristic
[176]. In EG based CNT nanouids, k enhancement decreased with
the duration of ultrasonic homogenization due to the reduction of
the nanotube length which was conrmed by SEM [144]. EG based
Fe (11 nm) nanouids showed an enhanced k after sonication. The
38
k of 0.2 vol.% nanouid exhibits 18% enhancement with a 30 min sonication and was saturated after 30 min. Measurement of the cluster
size revealed that ultrasonication broke the nanoclusters into smaller
clusters. From the variations of the cluster size and k as a function of
time, it was found that the k of nanouids was related closely to the
clustering of nanoparticles. There was 14.2% k enhancement right
after the sonication and then the enhancement reduces to 8.5% in
an hour [17,96,97]. In water based CNTs nanouids, increased
homogenization time reduced the k of the suspension due to the
breakage and reduction in the length of the nanotubes that was conrmed by SEM [119].
We have measured the time dependant k, average particle size, microstructure and viscosity of a stable (non-aggregating) and
unstable (aggregating) nanouid after sonication [70,76]. The aggregating EG based CuO nanouids (d=10 nm) showed a time dependent
k behaviors after sonication. The highest value of k/kf was observed immediately after sonication, which was found to decrease with elapsed
time and nally reaches an equilibrium value after a time interval of
about 45 min (Fig. 5). The average cluster size increases with time after
sonication in the above nanouids. The average cluster size grown
from 23 to 95 nm for the lowest concentration while its value exceeded
300 nm for =0.0131 (Fig. 6). In CuO nanouids, due to the absence of
stabilizers, the aggregation and the subsequent settling of agglomerates
leads to a decrease in k with elapsed time. The stable nanouids showed
time independent k after sonication. Oleic acid coated kerosene based
Fe3O4 (d=8 nm) nanouids [Fig. 7(a)], oleylamine coated hexadecane
based Ag (d=7 nm) nanouids [Fig. 7(b)], oleic acid coated hexadecane
based Fe3O4 (d=8 nm) nanouids [Fig. 7(c)] and TMAOH coated water
based Fe3O4 (d=8 nm) nanouids [Fig. 7(d)] show invariant k/kf with
time after sonication. The particle size remains constant with time for
the above nanouids as observed in the DLS studies (Fig. 8), which is
consistent with the primary crystallite size obtained from XRD results.
The microscopy images of EG based CuO nanouids taken at three different time intervals (t=0, 30, and 60 min) after sonication for different
values of 0.0054 [Fig. 9(a1a3)], 0.0092 [Fig. 9(b1b3)] and 0.0131
[Fig. 9(c1c3)] respectively, show cluster formation in nanouids with
elapsed time where the cluster size is found to increase with time.
Fig. 9(c1c3) shows the micrograph of oleic acid coated kerosene
based Fe3O4 (d=8 nm) nanouid with =0.05. The micrograph show
no aggregation (with cluster size>200 nm) with elapsed time after sonication, due to sufcient repulsion through steric hindrance.
2.10. Effect of aggregation
It was reported that linear and fractal nanoparticles congurations
provide extra conduction paths which enhances the effective k of
nanouids [13,25,80,110,111,135,177], whereas large aggregates and
clumps sediment in base uids, resulting in a lower k [91,115,132].
Fig. 5. The variation of k/kf and % of k enhancement with time after sonication for ethylene glycol based CuO nanouids with = 0.0018, 0.0054, 0.0092 and 0.0131 (d =
10 nm).
Fig. 6. The plot of mean number percentage as a function of cluster size at different
time intervals after sonication of 5, 20, 40, and 60 min for ethylene glycol based CuO
nanouids (d = 10 nm) with (a): = 0.0018 and (b): = 0.0131.
High speed microscopy allowed real time visualization of the movement of single walled carbon nanotubes with magnetic nanoparticles in
presence of a stabilizer in water [178]. This study demonstrated the
alignment of nanotubes in presence of magnetic eld. It has also been
shown that the thermal conductivity of magnetic-metal-coated carbon
nanotubes can signicantly enhance under applied magnetic eld
[179]. Studies showed an enhancement of k/kf in magnetic nanouids
in presence of an external magnetic eld due to controlled aggregation
of nanoparticles along the eld direction [13]. Fe nanoparticles (26 nm)
suspended in water show an enhancement in the k under applied
magnetic eld [25]. Magnetic eld induced k enhancement is also
reported in Ni and Fe2O3 incorporated SWCNTs dispersed in water
[110,111,177]. Magnetic microencapsulated phase change material
(MMPCM) suspension show an enhancement in k/kf in presence of external magnetic eld. A recent report showed an enhancement in k/kf
under the inuence of transverse magnetic eld in kerosene based
Fe3O4 nanouids [80]. In this paper, we report the observed real images
of Ni-coated single wall carbon nanotubes in water and oils
(polyalphaolen, polyol ester) under magnetic eld by high speed microscopy, and correlate them with TC measurements. Initially, the
nanotubes are randomly dispersed in the uid, however, on longer
holding in magnetic eld the nanotubes gradually stretch and are nally
aligned.
Unstable nanouids exhibited a decrease k with sedimentation
time. A decrease in k with sedimentation time was reported in
water based Cu and CNT nanouids. The stability studies in
nanouids show a decrease in supernatant particle concentration
with sedimentation time [91]. Nanouids of untreated diamond
nanoparticles in water showed a decrease in k with settling time,
whereas plasma treated stable diamond nanouids show very stable
k with little change with settling time over a week [132]. The
untreated CNT nanouids initially show a little increase in k, which
decreased rapidly and similar trends were also observed for plasma
treated CNT nanouids [115]. A reduction in k with time is observed
in water based CNT nanouids due to agglomeration [163]. However,
some reports show aggregation in water based Al2O3 nanouids signicantly increases the k of the uid [36,180]. For water based
Al2O3 nanouids, evolution in k with time (aging effect) was observed especially in suspensions with higher concentrations of nominally smaller (1120 nm) nanoparticles. These studies concluded that
the formation of larger agglomerates upon aging lead to larger k [44].
Stable nanouids showed no variation in k with time. The k of EG
based ZnO nanouids [128] and kerosene based Fe3O4 nanouids
39
Fig. 7. The variation of k/kf with time after sonication for (a): Kerosene based Fe3O4 nanouids (d = 8 nm) with = 0.0171, 0.05 and 0.082; (b): Hexadecane based Ag nanouid
(d = 7 nm) with = 0.0116; (c): Hexadecane based Fe3O4 nanouids (d = 8 nm) with = 0.0164 and 0.0608 and (d): Water based Fe3O4 nanouids (d= 8 nm) with = 0.0102
and 0.0213.
[79] were independent of time. Car engine coolant based Al2O3

nanouid exhibited no degradation of k with time [65]. Thermal conductivity of EG based graphene oxide nanosheets was almost invariant for 7 days [124].
We observed a dramatic enhancement in k under controlled aggregation in magnetically polarizable nanouids [13,15,73]. Stable
nanouids of oleic acid coated magnetite nanoparticles of average diameter of 9 nm dispersed in kerosene are used. Thermal conductivity
is measured under the inuence of an applied magnetic eld. The advantage of this system was that one can achieve controlled aggregation with different chain lengths. As the particles are sterically
stabilized, no permanent aggregation due to van der Waals attraction

occurs. Due to superparamagnetic nature of particles, the aggregation
phenomenon was perfectly reversible. Fig. 10 shows the k/kf and the
percentage of enhancement of k without and with magnetic eld of
different strengths for kerosene based Fe3O4 nanouids. The Maxwell
upper, lower bounds, series and parallel bound ts are also shown in
Fig. 10. In the lower HS limit, nanoparticles were well suspended and
conduction was through series modes whereas in the upper HS limit,
the conduction path was through dispersed particles. In the absence
of magnetic eld, the particles were well dispersed and hence the
nanouids exhibit series mode conduction and the observed variation
Fig. 8. The plot of mean number percentage as a function of particles size at different time intervals after sonication of 5 and 60 min for (a): (a): Kerosene based Fe3O4 (d= 8 nm)
nanouids with = 0.0171; (b): Hexadecane based Ag nanouid (d = 7 nm) with = 0.0116; (c): Hexadecane based Fe3O4 nanouids (d = 8 nm) with = 0.0164 and (d): Water
based Fe3O4 nanouids (d = 8 nm) with = 0.0102.
40
Fig. 9. The phase contrast microscopy images taken immediately after sonication, after 30 and 60 min of sonication for ethylene glycol based CuO nanouids (d = 10 nm) with =
0.0054 (a1a3), = 0.0092 (b1b3), = 0.0131 (c1c3) and Fe3O4 nanouids with = 0.05 (d1d3).
of k/kf with is well within the lower Maxwell limit. In the limit
(kp/kf) >>1, (kp and kf are thermal conductivities of particles and
uid respectively) the predicted values of k/kf for the upper HS and
parallel modes were (2/3)kp/kf and kp/kf respectively. As the magnetic eld strength is increased progressively, continuous conduction
paths emerge along the nanoparticle chains that results from series to
parallel mode of conduction. At a magnetic eld strength of 315 G,
the k/kf data ts fairly well with the parallel mode conduction.
Fig. 11 shows the variation of k/kf as a function of applied magnetic
eld, for kerosene based Fe3O4 nanouids with =0.063. Here, the
thermal conductivity increases with increase in applied eld strength.
The highest value of k/kf observed is 4 for a magnetic eld strength of
82 G, above which the k/kf decreases. After the formation of linear
chains, they come together to form denser chains due to interaction between uctuations in the shape of the adjacent columns. The decrease
in thermal conductivity observed above a critical magnetic eld
strength is expected to be due to zippering of chains [181].
To conrm the lateral overlap (zippering) of chains, phase contrast microscopic studies under external magnetic eld is carried
out at sufciently high magnetic eld strengths. Fig. 12(a) show the
micrograph of kerosene based magnetite nanouids with = 0.05
in the absence of external magnetic eld, where no aggregates were
visible. Fig. 12(be) shows the micrograph of the nanouid in presence of increasing magnetic strengths. At low magnetic eld strength
(Fig. 12b), there is a formation of small dipolar chains, whose length
increases with increasing magnetic eld strength (Fig. 12c), resulting
in an evenly spaced single nanoparticle chains throughout the
nanouid volume. At very high magnetic eld strength (Fig. 12(d
e)), zippering of the dipolar chain is evident in the microscopic images. The Fig. 12(f) shows the image after switching off the magnetic
eld where no permanent aggregates are visible. This conrms the
perfect reversibility of the dipolar chains formed in the uid.
Recent studies on thermal properties of nanouids show a prominent role of aggregation on k enhancements of nanouids. Stable
nanouids exhibit moderate k enhancement within the EMT predictions [76]. However, aggregating nanouids show enhancement in
thermal conductivity beyond EMT predictions. The aggregating
Fig. 10. The variation of k/kf with volume fraction in absence and in presence of
different magnetic eld strengths of 126, 189, 252 and 315 G for kerosene based
Fe3O4 (d = 9 nm)nanouids tted with Maxwell upper and lower, HS upper and
lower bounds.
Fig. 11. The k/kf and % of enhancement in k as a function of external magnetic eld
strength for kerosene based Fe3O4 nanouids (d = 6 nm) with = 0.049 and 0.063.
The applied magnetic eld is parallel to temperature gradient here.
nanouids show a time dependent variation in k with elapsed time

after sonication. The highest value of k/kf is observed immediately
after sonication, which decreases with elapsed time and nally
reaches an equilibrium value after a time interval of about 45 min
[182]. In the absence of stabilizers, the aggregation and the subsequent settling of agglomerates leads to a decrease in k with elapsed
time. The cluster size and /0 (where and 0 are the viscosity of
nanouid and base uid respectively) increases with elapsed time
after sonication in aggregating nanouids. Nanouids with low particle loading shows least enhancement in with time and the extent of
enhancement is high for nanouids with higher particle loading,
owing to the degree of aggregation. The optical micrographs conrm
cluster formation in unstable nanouids with elapsed time and an increase in cluster size with time. Stable nanouids with steric and electrostatic stabilization show time independent k with time. They
also show an invariant particle size distribution and with elapsed
time. Sterically stabilized Ag nanouids show no shift in plasmon resonance absorption with time indicating the absence of aggregation.
Microscopy studies in surface modied nanouids show no sign of
aggregation (with cluster size > 200 nm) with time. The k of aqueous
nanouids increase with temperature while it shows a decrease
in nonaqueous nanouids. The k/kf remains constant with an increase
in temperature, irrespective of the nature of base uids. These results
suggest that the k of the nanouids simply track the k of the base uid
41
and the enhancement in nanouids relative to base uids is

essentially temperature independent [75]. These results unambiguously conrm the less dominant role of microconvection on k
enhancement.
Dynamic light scattering studies show no aggregation of nanoparticles with temperature in stable water and oil based nanouids. The
present results show that the aggregation is essentially governed by
surface chemistry of nanoparticles and the stabilizing moieties used.
Nanoparticle aggregation is insignicant with the increase in temperature in properly functionalized nanouids. Such nanouids are ideal
for practical applications because of their long-term stability. For kerosene based magnetite nanouids having a = 0.055, k/kf increases
from 1.05 to 1.25 with increasing particle diameter. Upon increasing
the aspect ratio of the linear chains in nanouids, very large enhancement of k is observed [78]. The larger surface area of solid/liquid
interfaces and increased effective volume of solids together with the
surfactant contribution results in such variation in with nanoparticle size. Based on the present experimental results, it can be concluded that the particle size is a very important parameter for
thermal property management in nanouids.
A new approach to tune the thermal properties of magnetic
nanouids from low to very high values is demonstrated by varying
the magnetic eld strength and its orientation. This study reveals a
unique possibility of tuning the keff/eff ratio in magnetically controllable nanouids, making them superior to carbon nanotubes based
suspensions in terms of reversible tunability of k for heat transport
applications [77]. In the present study, dramatic k enhancement is observed in magnetite nanouids under the inuence of an applied
magnetic eld parallel to the temperature gradient. The higher the
of nanouids, the larger is the observed k increment. The maximum
k enhancement observed is 300% for nanouid with a particle loading
of = 0.063. As the magnetic eld strength is increased progressively, the continuous conduction paths along the nanoparticle chains result in a series to parallel mode of conduction [13]. The decrease in k
observed above a critical magnetic eld strength is due to zippering
of chains, which is conrmed by microscopy studies [15]. k measurements under different magnetic eld orientations with respect to the
thermal gradient show maximum k enhancement when the eld direction is exactly parallel to the thermal gradient. No enhancement
is observed when eld direction is perpendicular to the thermal gradient. A gradual reduction in the k enhancement is observed as the
eld direction is shifted from parallel to perpendicular direction
with respect to thermal gradient [74]. When nanoparticles starts to
Fig. 12. The phase contrast microscopy images of for kerosene based Fe3O4 nanouids (d = 9 nm) with = 0.05 (a) in the absence of external magnetic eld, (b) to (e) in presence
of increasing magnetic eld and (f) after removal of magnetic eld.
42
form aggregates of larger size or chains, the convection velocity drops

drastically due to the cubic dependence on the particle size and the
Brownian motion is severely reduced. The increase in k for magnetic
nanouids under external magnetic eld is attributed to the effective
conduction of heat through the chainlike structures formed under
magnetic eld when the dipolar interaction energy becomes greater
than the thermal energy. The k measurements in stable oil based
magnetite nanouids during rise and decay of magnetic eld strength
show that the k enhancement is reversible with a small hysteresis
under repeated magnetic cycling. The observed reversible tunable
thermal property of nanouid may nd many technological applications in NEMS and MEMs based devices [73]. Reversible eld induced
enhancement with a slight hysteresis is observed in stable oil based
magnetite nanouids during the rise and decay of magnetic eld
strength.
3. Conclusions and future directions
Although the topic of thermal property of nanouids is rich with
large data base, there are many conicting reports on thermal conductivity enhancements due to poor characterization of nanouids
and inaccuracies in the measurement techniques. It should be noted
that even small temperature gradients in the sample, during measurements, can lead to large errors in the thermal conductivity results. Further, nanouids are prone to agglomeration and settling,
which are not carefully looked at by researchers. Therefore, caution
should be adopted to ensure equilibrium sample temperature while
measurements are carried out and to avoid microstructural changes
in the samples during measurements. Contrary to the popular belief,
the latest systematic studies in well characterized nanouids, suggest
that microconvection has no major role in the thermal conductivity
enhancement in nanouids. The agglomerates, their conformation in
the base uids and the effective conduction of heat through such
agglomerates seems to dictate the percentage of enhancement in
nanouids. Though the modest thermal conductivity enhancement
in stable nanouids is a cause of concern for practical applications,
novel approaches to achieve thermal conductivity enhancement
close to parallel modes of conduction is very promising for innovative
cooling applications. Response stimuli nanouids [73,74,77,183185],
modied carbon nanotubes, graphene based nanouids etc are also
potential candidates for heat transfer and other applications. Novel
strategies to produce stable nanouids using cost effective techniques, adoption of response stimuli nanouids, carbon nantubes
and graphene for miniature cooling applications will have to be
developed.
Acknowledgements
J.P. thanks BRNS for funding of a perspective research grant on
advance nanouids. Authors thank Dr. T. Jayakumar and Shri. S. C.
Chetal, Director, IGCAR for fruitful discussions.
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Advances in Colloid and Interface Science 183184 (2012) 3045

Contents lists available at SciVerse ScienceDirect

Advances in Colloid and Interface Science

Thermal properties of nanouids

Available online 7 August 2012

Corresponding author. Tel.: +91 94 431 51 536; fax: +91 44 27480356.

2. Experimental ndings on factors affecting thermal conductivity(k)

predictions [129]. Water and EG based SiC nanouids [45] and

of 34% at 0.6 vol.% of nanotube loading [145]. CNTs/ethylene glycol

2.1.2. Carbon nanotube (CNT) nanouids

k with increase in nanoparticle size [103]. Very recent reports show

also exhibit an enhancement in k/kf with temperature. Water based

found to increase with increase in temperature in the range of 20 to

used. From the observed invariant k/kf with temperature we conclude

fraction, the k enhancement was found to vary from 16.5 to 39.5%

dramatic improvement in the k was observed for the suspension

CTAB concentration has minor effects on the k of the suspension

[79] were independent of time. Car engine coolant based Al2O3

stabilized, no permanent aggregation due to van der Waals attraction

nanouids show a time dependent variation in k with elapsed time

and the enhancement in nanouids relative to base uids is

form aggregates of larger size or chains, the convection velocity drops

[7] Gerardi C, Cory D, Buongiorno J, Hu LW, McKrell T. Nuclear magnetic

[144] Assael MJ, Metaxa IN, Kakosimos K, Constantinou D. Thermal Conductivity of

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