International Journal of Heat and Mass Transfer 54 (2011) 2459–2466

Contents lists available at ScienceDirect

International Journal of Heat and Mass Transfer

journal homepage: www.elsevier.com/locate/ijhmt

Surface tension of evaporating nanofluid droplets

Ruey-Hung Chen a,⇑, Tran X. Phuoc b, Donald Martello b
a
Department of Mechanical, Materials and Aerospace Engineering, University of Central Florida, 4000 Central Florida Boulevard, Orlando, FL 32816-2450, USA
b
National Energy Technology Laboratory, Department of Energy, P.O. Box 10940, MS 84-340, Pittsburgh, PA 15261, USA

a r t i c l e i n f o a b s t r a c t

Article history: Measurements of nanofluid surface tension were made using the pendant droplet method. Three differ-
Received 1 July 2010 ent types of nanoparticles were used – laponite, silver and Fe2O3 – with de-ionized water (DW) as the
Received in revised form 21 January 2011 base fluid. The reported results focus on the following categories: (1) because some nanoparticles require
Accepted 21 January 2011
surfactants to form stable colloids, the individual effects of the surfactant and the particles were inves-
Available online 25 February 2011
tigated; (2) due to evaporation of the pendant droplet, the particle concentration increases, affecting
the apparent surface tension; (3) because of the evaporation process, a hysteresis was found where
Keywords:
the evaporating droplet can only achieve lower values of surface tension than that of nanofluids at the
Nanofluids
Surface tension
same prepared concentrations; and (4) the Stefan equation relating the apparent surface tension and heat
Evaporating droplet of evaporation was found to be inapplicable for nanofluids investigated. Comparisons with findings for
Stefan’s formula sessile droplets are also discussed, pointing to additional effects of nanoparticles other than the non-equi-
librium evaporation process.
Ó 2011 Elsevier Ltd. All rights reserved.

1. Introduction
Surface tension of a liquid can be reduced by adding either sur-
face active agents or nanoparticles [1]. The capability of manipulat-
ing surface tension of a liquid has a wide range of useful
applications including enhanced boiling heat transfer, oil recovery
efficiency, and the capability of cleaning oil spills. A nanofluid is
one in which nanosized particles remain stably suspended to form
a colloidal solution. In this study, three different types of nanopar-
ticles were added so as to alter surface tension of de-ionized water
(DW). They are laponite (a clay), Ag (metal silver) and Fe2O3 (a me-
tal oxide).
Liquid surface tension (r) plays an important role in boiling
heat transfer. Relevant pool boiling heat transfer parameters in-
clude the bubble departure diameter (dd), departure frequency
(f), nucleation site density (n), and boiling inception temperature
DTe (where the subscript signifies the inception or embryonic
stage). These nucleation and bubble parameters are related to fluid
surface tension r (see for example Ref. [2] for a comprehensive re-
view). Classical analyses and heat transfer correlations for pool
boiling indicate effects of surface tension in the following: (1)
dd / r1/2 [3,4], (2) f / r1/2 [5], (3) n decreases and DTe increases
with decreasing r [6], and (4) the heat flux q_00 / r1=2 [7–11]. Once
the nucleate boiling is established (i.e., n > 0 and DTe is surpassed)
nucleate boiling is enhanced by reducing the surface tension: early
bubble departure at higher frequencies (i.e. more effective vapor
⇑ Corresponding author. Tel.: +1 407 823 3402.
E-mail address: chenrh@mail.ucf.edu (R.-H. Chen).
and thus heat removal), resulting in higher values of q_ 00 . Such ef-
fects of nanoparticles on enhancing nucleate heat transfer has been
well documented (see for example [12–16] and a recent review by
Choi [17]).
Nanofluids made from metal nanoparticles and water, ethylene
glycol, or engine oil at concentrations as low as 1% can improve
thermal conductivity and single-phase heat transport up to 40%
[18–23]. Some studies reported increments to more than 250%
when carbon nanotubes (mean diameter of 25 nm and a length
of 50 lm) were used [24,25]. An increase in thermal conductivity
by more than 100% was also reported when Al2O3 nanoparticles
were added to deionized water (DIW), while the increase is further
enhanced by decreasing the particle size [26].
Besides the bubble parameters in boiling heat transfer correla-
tions, microlayer evaporation plays an important role in the mech-
anism of nucleate heat transfer [27–30]. The microlayer is the
liquid layer trapped between the heated surface and the growing
bubble. The thinner the microlayer is, the faster the evaporation
of the liquid would be to feed the bubble growth and thus the high-
er heat transfer rate. An extended microlayer is therefore beneficial
for heat transfer enhancement. This can be achieved by increasing
the disjoining pressure or by decreasing the surface tension (with
the later being associated with a small contact angle h). In nanofl-
uids, the orderly packing of nanoparticles in the meniscus region
[31–34] helps to increase the disjoining pressure that extends
the thin microlayer (i.e. the liquid wettability). A reduced surface
tension also leads to wettability enhancement of the fluid on a gi-
ven solid surface (i.e., ‘‘detergency’’). Because particles can act as
surfactants [1], they may thus enhance wettability of the base fluid

0017-9310/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijheatmasstransfer.2011.02.016
2460 R.-H. Chen et al. / International Journal of Heat and Mass Transfer 54 (2011) 2459–2466
Nomenclature
C concentration (%)
D droplet diameter (m)
dd bubble departure diameter (m)
f frequency (s1)
hfg heat of vaporization (J/kg)
K evaporation rate constant (m2/s)
M molar mass (grams)
NA Avagadro number (6.02  1023)
n number density (1/m3)
q_00 heat flux (W/m2)
t time (s)
T temperature (K)
and boiling heat transfer. During nucleate boiling, the contact re-
gion recedes causing the microlayer evaporation and thinning. This
may lead to further increases in local concentration of particles,
further enhancing contact region recession [35]. It is of interest
to determine the surface tension of a nanofluid with simultaneous
evaporation.
In the practice of oil recovery, it is desirable to manipulate the
surface tension and wettability of water, so that the surfaces in
the oil reservoir are preferentially wet by water [36]. If water is
treated with heating or surfactants, the rock surface will become
more water-wet than oil-wet, which is desirable because the pres-
sure applied to the waterflood for oil recovery can be reduced [36],
due to the associated increase in permeability and decrease in cap-
illary pressure. Lower water surface tension also helps water to fill
the smaller pores and wet their surface in the rock matrix and to
form oil-in-water emulsions, thus also enhancing secondary oil
recovery and the overall efficiency of oil recovery [36,37]. The
change of a rock surface from oil-wet to water-wet is called ‘‘wet-
tability reversal.’’ Adding nanoparticles can facilitate such a rever-
sal. The potential effects of nanoparticles to enhance detergency
and to act as emulsifiers are also useful for clean-up of oil-spills.
The wetting ability of a liquid manifests itself through the equi-
librium contact angle (h), which in turns can be related to surface
tension through the Young’s equation:
rv s  rls ¼ rv l cos h
where rvs, rls, and rvl are the surface tensions at the interfaces of
vapor–solid, liquid–solid, and vapor–liquid interfaces, respectively.
The values of rvs and rls are not easily known because of the tem-
poral and morphological characteristics of the surface. For example,
the surface might have been contaminated and might possess vary-
ing roughness [38]. However, for a given liquid–solid pair, Eq. (1)
suggest that rvlcos h is only a function of rvl and, for example, a de-
crease in h (i.e. increased wettability and extended microlayer) is
accompanied by a decrease in rvl. Determining rvl helps ascertain
whether the modified liquid has the potential benefits for the afore-
mentioned applications, including heat pipes, where wetting phe-
nomenon plays a key role [39]. The surface tension (r) used in
the afore-mentioned boiling heat transfer analyses and correlations
is in fact rvl. As detailed in [40], the wettability of a liquid relative to
a solid only depends on the properties of the solid. Therefore, with-
out specifying particular solids, it is desirable to determine r of
nanofluids for potential uses on a variety of solid surfaces. This
can conveniently performed using the pendant droplet method.
Because surfactants are sometimes used for stabilizing the
nanofluids both the surfactant and nanoparticles can contribute
to the enhanced boiling [14,16]. This leads to a competitive effect
between the surfactant and the particles. Optimal ratios between
the particle and surfactant might be achieved for maximizing the
Zs/Z steric factor (1)
Greek symbols
q density (kg/m3)
h contact angle (°)
r surface tension (mN/m)
Subscripts
o initial condition at t = 0
v vapor
l liquid
s surface
enhancement [14]. In this study, individual effects of nanoparticles
are revealed by laponite and Ag, which can be stabilized without
the aid of any surfactants. Combined effects of nanoparticles and
surfactant were investigated by adding a surfactant to the Ag nano-
fluid. Fe2O3 particles require a surfactant for stability in the
nanofluid.
A wide variety of thermal and transport properties of nanofluids
are functions of nanoparticle concentration, and so is the surface
tension. As the pendant droplet evaporates, the concentration
dependence of the surface tension can be determined. Fast-time
(or ‘‘frozen,’’ usually within a few seconds of forming the pendant
droplet) measurements of the surface tension were also carried out
before significant evaporation took place; such surface tension
should resemble that of the bulk nanofluid (i.e., for convenience,
it is called the static value in this report). Differences between
the fast-time results and those obtained during droplet evapora-
tion (hereafter called the apparent surface tension, analogous to
the dynamic contact angle when a sessile droplet evaporates) can
thus be attributed to the increasing particle concentration. As will
be shown in the following, the apparent value differs from the sta-
tic value with the same particle concentration. Because of the
time-dependent nature of the particle concentration, the heat of
vaporization (hfg) was known to vary [41]. According to the Stefan
equation, which relates the heat of vaporization and the surface
tension in thermodynamic equilibrium, surface tension might be
ð1Þ
expected to vary as the pendant droplet evaporates. Discussion
and comparison based on the Stefan equation and results on
evaporating sessile droplets published will be discussed to address
the role of nanoparticles. To the authors’ best knowledge, no sim-
ilar results are available in the literature regarding surface tension
of evaporating pendant droplets.
2. Experiment
The base fluid used in this study is de-ionized water (DW). The
nanoparticles used are laponite, iron oxide (Fe2O3) and silver (Ag).
The laponite and Ag nanofluids were stable for months without the
aid of a surfactant, while 1%PVP (polyvinylpyrrolidone) was used
to stabilize the Fe2O3 nanofluid. For the procedures for preparing
these nanofluids and the SEM images of the in-house Ag particles,
produced using laser ablation in liquid (LAL), the reader is referred
to [41,42]. The size and concentration of these particles in the
nanofluids investigated are listed in Table 1.
A Rame-Hart Model 250 Standard goniometer, with data pro-
cessing software, was used for measuring both the surface tension
and the droplet volume, as functions of time. The concentration (C)
of nanoparticles was determined then also as a function of time by
the measured droplet volume. The data were acquired with equal
 R.-H. Chen et al. / International Journal of Heat and Mass Transfer 54 (2011) 2459–2466 2461

Table 1 80 16
Properties of prepared nanofluids (all percentage by weight).

Nanoparticle Size (nm) Particle PVP

(%wt) (%wt)
Laponite (disk) (25–30 nm dia. 0.5 0
Surface Tension of DW + 1%PVP
60 Run1 Surface Tension 12
1–2 nm thick)

Surface Tension (mN /m)

Ag 10–30 0.04 0 Run2 Surface Tension

Droplet Volume (mm 3 )

Ag 10–30 0.05 1.0 Run1 Volume
Run2 Volume
(Approximately spherical by
laser ablation in liquid)
Fe2O3 10–30 0.05 1.0 40 8
(Spheres)

temporal spacing, and the procedure is similar to that described in

20 4
Ref. [41]. It is noted that because no attempt was made for environ-
mental and climate control, the droplet evaporation rate varied
from run to run. For both DW and DW + 1%PVP, the surface tension
determined using the fast-time method did not depend on the
droplet size in the range of approximately 1–12 mm3 (i.e. 1– 0 0
12 lL). The nanofluid droplet investigated was allowed to 0 100 200 300 400 500

evaporate over similar size ranges. Therefore, the surface tension
variations during the evaporation of nanofluid droplet must not
be attributed to possible size dependence, but were due to the
presence of the nanoparticle and the increase in its concentration
resulting from water evaporation.
3. Results
3.1. Surface tension of DW and DW + 1%PVP
Values of static surface tension of the nanofluids investigated
are given in Table 2. It is noted that some of the particle concentra-
tions of laponite nanofluids shown in Table 2 are different from
(i.e., up to four times higher than) those in Table 1. These measure-
ments were carried out in anticipation for comparison of the static
values shown in Table 2 with the dynamic values obtained from
evaporating droplets with initial particle concentration (Co) shown
in Table 1. Similar measurements were not done for Ag and Fe, be-
cause of the excessive amount of time needed for LAL and of the
difficulty of stabilizing higher concentrations of Fe2O3,
respectively.
As shown in Table 2, the surface tension of DW + 1%PVP is only
approximately 4% lower than that of DW (73.60 mN/m without
PVP and 70.04 mN/m with 1%PVP), probably because of the low
concentration of PVP. The surface tension of DW was found to re-
main nearly constant over the droplet lifetime, suggesting that the
pendant method produced surface tension values that were rela-
tively independent of the size range in this study. Fig. 1 also dem-
onstrated that the ‘‘base’’ fluid for the Fe2O3 nanofluid,
DW + 1%PVP, also remained nearly constant over the droplet life-
time, where the droplet volume decreased by a factor of approxi-
Time (second)
Fig. 1. Surface tension and nanoparticle concentration of evaporating nanofluid
droplets of (DW + 1%PVP).
mately 3. Therefore, no ‘‘apparent’’ surface tension could be
determined of the evaporating DW + 1%PVP pendant droplet.
Although not presented, evaporating DW droplets also produced
nearly constant surface tension during the droplet lifetime, further
suggesting size independence and no effect due to evaporation
process.
As can be seen from Table 2, all additives appeared to reduce
the static surface tension value somewhat from that of pure DW.
It can be seen that PVP did not have a significant effect on the sur-
face tension of DW and of the Ag nanofluid fluid (72.95 mN/m
without PVP and 69.78 mN/m with 1%PVP), although the Ag con-
centrations differed slightly (0.04% and 0.05%). Increasing the lap-
onite concentration (C) by a 10-fold from 0.1% to 1% caused
approximately 30% reduction in r. Doubling the concentration of
laponite from 1% to 2% caused r to decrease from 52.31 to
40.97 mN/m, an approximately 25% reduction. An accelerated
reduction in r appeared by increasing the laponite concentration.
However, doubling the Fe2O3 concentration, from 0.05% to 0.1%
(note that this is the same ratio as discussed in the case of laponite,
but not the same absolute values), did not have an appreciable ef-
fect on r. The combination of PVP and Ag/Fe2O3 appeared to only
weakly affect the static surface tension, with values within 5% of
pure DW. Because r of DW + 1%PVP is relatively independent of
the droplet size over its lifetime, when Ag and Fe2O3 were added
to, the changes in r might be attributed to the effect of these
nanoparticles.

3.2. Effect of nanoparticle concentration on dynamic surface tension

Table 2
Static surface tension of DW and several nanofluids (percentage in weight). Because particles did not dissolve in DW, they do not evaporate.
Fluid Surface tension, r (mN/m) Consequently, as the droplet evaporates, the nanoparticle concen-
DW 73.60 tration increases. During the experiment, the initial droplet size
1%PVP in DW 70.04 was chosen (usually 8–10 mm3) so that the concentration would
0.1%Laponite in DW 72.84 increase by approximately an order of magnitude or more as the
1%Laponite in DW 52.31 droplet evaporated.
2%Laponite in DW 40.97
0.04%Ag in DW 72.95
3.2.1. Laponite nanofluid
0.05%Ag in (DW + 1%PVP) 69.78
Fig. 2 shows the results of the laponite nanofluid, with an initial
0.05%Fe2O3 in (DW + 1%PVP) 70.00
concentration (Co = 0.5%). For both Run 1 (denoted by diamonds)
0.1% Fe2O3 in (DW + 1%PVP) 71.20
and Run 2 (denoted by triangles), the surface tension remained
2462 R.-H. Chen et al. / International Journal of Heat and Mass Transfer 54 (2011) 2459–2466

80 8 80 1.6

0.5% Laponite in DW 0.04%Ag in DW

60 6 60 1.2
Run 1 Surface Tension
(mN/m)

Run 1 Surface Tension

Surface Tension (mN /m)

Run 2 Surface Tension Run 2 Surface Tension

Concentration, C (%)

Concentration (%)
Run 1 Concentration Run 1 Concentration
Run 2 Concentration Run 2 Concentration
Surface Tension,

40 4 40 0.8

20 2 20 0.4

0 0 0 0
0 400 800 1200 1600 2000 0 500 1000 1500
Time (second) Time (second)

Fig. 2. Surface tension and nanoparticle concentration of evaporating nanofluid Fig. 3. Surface tension and nanoparticle concentration of evaporating nanofluid
droplets of (DW + 0.5%laponite). droplets of (DW + 0.04%Ag).

relatively constant (71–72 mN/m) until C > 1%. Toward the end of
the droplet lifetime (approximately 1800 s), r was reduced by a
factor as much as 2.7, to approximately 27 mN/m (Run 2 data in
Fig. 2).
For comparison between the static and dynamic values of r,
consider for example the static value of r at C = 1% is 52.31 mN/
m (Table 2). To achieve this value of r, the evaporating droplet
would need to have C  3.0% and 2.5%, respectively, for Run 1
and Run 2 (see Fig. 2). For the static value of r at C = 2%
(40.97 mN/m shown in Table 2), the droplet would have to evapo-
rate to achieve a concentration of approximately 3.2% (Run 2 in
Fig. 2) or higher (by extrapolating data from Run 1, although for
which 40.97 mN/m was not achieved). Because the surface tension
of evaporating DW droplet is independent of size, these results
suggest the ability of laponite nanoparticles to reduce surface ten-
sion of its base fluid (DW). There also is a hysteresis that the appar-
ent surface tension during evaporation was larger than that of its
static value at the same particle concentration level. For example
at 2% laponite during evaporation, values of r are approximately
65 and 60 mN/m for Run 1 and Run 2, respectively, compared to
the static value of 40.97 mN/m as shown in Table 2.
particles produced using the LAL technique serves the purpose
well, as the nanofluid remained stable for months without PVP.
To investigate the combined effect of Ag nanoparticles and PVP,
LAL was carried out with the silver target submerged in the
DW + 1%PVP liquid. The surface tension of droplets of this
DW + 0.05%Ag + 1%PVP nanofluid as a function of time (and of con-
centration) is shown in Fig. 4. At t = 0 and Co = 0.05%, r  70 mN/m,
similar to that of DW + 1%PVP shown in Table 2 and slightly lower
than that of Co = 0.04% without PVP at t = 0 (approximately 73 mN/
m; see Fig. 3). In contrast to Co = 0.04%Ag in DW without PVP, the
surface tension remained nearly constant over the lifetime of the
droplet, except toward the end r decreased to approximately
64 mN/m when C exceeded 0.6%. This result suggests that for more
than a approximately 10-fold increase in concentration the value
of r (from 0.05%Ag to approximately 0.5% in Fig. 4) for
DW + 0.05%Ag + 1%PVP does not change appreciably. A similar
80 0.8

60 0.05%Ag in DW + 1%PVP 0.6

3.2.2. Ag nanofluid Run1 Surface Tension
Surface Tension (mN /m)

The effect of silver (Ag) nanoparticles is shown in Fig. 3, where Run2 Surface Tension
Concentration (%)

Co = 0.04%. The value of r was nearly constant for C < 0.2%, approx- Run1 Concentration
Run2 Concentration
imately 70–73 mN/m. During the droplet lifetime, r decreased
from that value to approximately 25 and 20 mN/m for Run 1 and 40 0.4
Run 2, respectively, as the particle concentration increased to
approximately 1.0% and 0.4%. A more than three-fold reduction
in surface tension is possible from its base fluid (DW). It might
be noted that the concentrations at the end of measurements for
20 0.2
Run 1 and Run 2 differ (1.0% vs. 0.4%), possible resulting from no
environmental control, as described in the Experimental section.
Nonetheless, the qualitative trend of decreased surface tension
with increases in particle due to evaporation is clearly seen from
the results shown in Fig. 3. 0 0
Because surfactants were previously used by other researchers 0 100 200 300
Time (second)
for stabilizing the nanofluid [14,16], it is desirable to compare
the combined effects of the nanoparticle and the surfactant using Fig. 4. Surface tension and nanoparticle concentration of evaporating nanofluid
a nanoparticle that does not require stabilizing agents. Silver nano- droplets of (DW + 0.05%Ag + 1%PVP)
 R.-H. Chen et al. / International Journal of Heat and Mass Transfer 54 (2011) 2459–2466 2463

10-fold increase in Ag concentration in DW without PVP causes the 80 0.8

surface tension to decrease by a factor of three. PVP appeared to
cancel the effect of Ag nanoparticles even as the concentration in-
creased, as shown in Fig. 4. It might be said that PVP has a ‘‘pacify-
ing’’ effect on Ag, preventing the effect of Ag particle in reducing r, 0.1%Fe2O3 in DW + 1%PVP
60 0.6
as shown in Fig. 3. Although not known to these authors, it is spec- Run2 Surface Tension

Surface Tension (mN /m)

ulated that PVP is preferentially adsorbed onto the Ag particle sur- Run3 Surface Tension

Concentration (%)
face and the PVP-wrapped particle behave essentially like PVP Run2 Concentration
Run3 Concentration
itself. It is known that the surface coverage due to preferential
adsorption is always complete [43]. The fact that r of 40 0.4
DW + 0.05%Ag + 1%PVP did not change appreciably (Fig. 4) is simi-
lar to that observed for Fig. 1, where the results of DW + 1%PVP
(that is, without Ag nanoparticles) is shown.
As noted in the ‘‘Experiment’’ Section, no attempt was made for
20 0.2
environmental and climate control. Therefore, the droplet evapo-
rated with somewhat different rates from run to run. Conse-
quently, the results of Figs. 3 and 4 were obtained over different
time scales. However, the effect of particle concentration (i.e., as
a result of droplet evaporation in this study) is of the primary con- 0 0
cern when comparing the results of Figs. 3 and 4. Similar discus- 0 200 400 600
Time (second)
sion can be made for the results shown in Figs. 5 and 6 in the
following section. Fig. 6. Surface and nanoparticle concentration of evaporating nanofluid droplets of
(DW + 0.1%Fe2O3 + 1%PVP).

3.2.3. Fe2O3 nanofluid

Figs. 5 and 6 show the results of Co = 0.05% and 0.1%Fe2O3 in
DW + 1%PVP, respectively. For both cases, the value of r remained
relatively constant throughout the lifetime of the droplet, over
which the nanoparticle concentration increased up to nearly 10-
fold. These results are similar to those shown in Fig. 4
(DW + 0.05%Ag + 1%PVP). The effect of Fe2O3 alone on DW cannot
be known, as without PVP, the Fe2O3–DW solution was not stable
and sedimentation occurred within minutes even after being son-
icated for more than 15 min. Measurements of r for such a hypo-
thetical Fe2O3–DW nanofluid were not possible. Therefore, the
pacifying effect of PVP on Fe2O3 nanoparticle cannot be confirmed.
A recent study [44] of aluminum–ethanol nanofluid revealed that
the surface tension was relatively independent of particle concen-
tration up to 6% (also by weight). The pendant droplet method was
also used in that study, where the TEM image indicated a particle
size in the range around 50 nm and no surfactant was used. It is be-
80
0.05%Fe2O3 in DW + 1%PVP
60
Run1 Surface Tension
Surface Tension (mN /m)
lieved that Al2O3 forms on aluminum surface when exposed in air,
which is invariably the case unless the particles are processed and
sealed in vacuum.
4. Discussion
Questions arise regarding the hysteresis phenomena and the ef-
fects of nanoparticles and PVP shown in this study. Although the
real reason is not yet known to these authors, such a ‘‘hysteresis’’
might be due to the thermocapillary stresses resulting from evap-
oration. In this study, no effort was made to observe particle or
fluid motion within the droplet during the evaporation process
(i.e. possible Marangoni–Bernard convection). Therefore, it was
not known whether stratification of particle concentration took
place within the droplet. All these possibilities result from evapo-
ration, which deviates from the underlying equilibrium assump-
tion of Young’s equation. It is useful then to examine the
behavior of the surface tension reported in this study, by incorpo-
0.4
rating the effects of evaporation. Since it is difficult to quantify the
degree of departure from equilibrium, another equilibrium rela-
tionship is employed – Stefan’s formula – which relates the surface
tension and heat of vaporization for pure, molecular fluids [45] as
0.3 follows:

Run2 Surface Tension 2

Run1 Concentration hfg q3 Z s
Concentration (%)

r¼ 1
ð2Þ
M3 N2 Z
Run2 Concentration 2

40 0.2 where hfg, q, M, NA, and Zs/Z are, respectively, the heat of vaporiza-
tion, fluid density, molar mass, Avogadro’s number, and the steric
coefficient. It indicates that surface tension is linearly proportional
to the heat of vaporization under thermodynamic equilibrium,
20 0.1
which implies no evaporation.
The apparent heats of vaporization (hfg) of droplets of the nano-
fluids used here have been reported in a separate paper [41]. It was
shown that, depending on the type of the nanoparticles added, the
droplet evaporation rate and hfg might not remain constant
0 0 throughout the droplet lifetime [41]. In that paper, the evaporation
0 400 800 1200 1600 2000
rate and the values of hfg of DW, DW + 1%PVP, and DW + 0.5%lapo-
Time (second)
nite did not change during the lifetime of the droplet. On the other
Fig. 5. Surface and nanoparticle concentration of evaporating nanofluid droplets of hand, the evaporation rates of DW + 0.04%Ag, DW + 1%PVP +
(DW + 0.05%Fe2O3 + 1%PVP). 0.05%Ag, and DW + 1%PVP + 0.05%Fe2O3 droplets decreased as they
2464 R.-H. Chen et al. / International Journal of Heat and Mass Transfer 54 (2011) 2459–2466

vaporized. The evaporation rate constant K is defined in the

following:

D2 ¼ D2o  Kt ð3Þ
where D and t are, respectively, the droplet diameter and time,
while the subscript o represents the initial value. Because K / 1/
hfg [41], a decrease in K represents an increase in hfg. For conve-
nience, a representative case of changing value of K is reproduced
from Ref. [41] for the droplet of DW + 0.04%Ag nanofluid, shown
in Fig. 7. According to Stefan’s equation, one would expect the value
of r to increase as the droplet evaporates. However, the opposite
trend (i.e., decreasing r with an increasing hfg) is seen from the re-
sults of Figs. 3 and 7 at t  900 s. It appears that the combined effect
of nanoparticles and the non-equilibrium evaporation process ren-
ders the Stefan’s formula inapplicable to the DW + 0.04%Ag
nanofluid.
For the DW + 1%PVP + 0.05%Ag nanofluid, the value of hfg at
t  100 s also increased as the droplet evaporated (shown in
Fig. 8, which is also taken from [41]). Cross-examination of results
shown in Fig. 4 reveals the insensitivity of r to hfg over the droplet Fig. 8. D2 as a function of time for DW + 1%PVP + 0.05%Ag (data are taken from Ref.
lifetime and thus the ‘‘pacifying’’ effect of PVP mentioned earlier. [41]). K is the evaporation rate constant as defined in Eq. (3). Purple and blue
Results of r of the two DW + PVP + Fe2O3 nanofluids (Figs. 5 and symbols correspond to Run 1 and Run 2 data in Fig. 4, respectively. (For
interpretation of the references to colour in this figure legend, the reader is
6) also point to the pacifying effect of PVP. Although PVP appeared
referred to the web version of this article.)
to have reversed the effect of Ag nanoparticles on DW, the reversal
does not appear capable of forcing the DW + 1%PVP + 0.05%Ag
nanofluid to follow Stefan’s formula.
For the case of DW + 0.5%laponite nanofluid (Fig. 2), the value of
r during the later part of the droplet lifetime was seen to decrease
from its initial value, as the evaporation process increased the par-
ticle concentration. However, the value of hfg did not change over
the same period of time (see Fig. 9, using the technique described
in Ref. [41]). These results suggest that the Stefan’s formula inap-
plicable to the DW + 0.5%laponite nanofluid.
The apparent value of hfg of the DW + 0.1%PVP + 0.05%Fe2O3
nanofluid also increased as the droplet evaporated (qualitatively
similar to the results of DW + 0.04%Ag and DW + 1%PVP + 0.05%Ag
nanofluids; but not shown here – see Ref. [41]). However, the sur-
face tension during evaporation remained relatively constant
(Fig. 5), much like the case of DW + 1%PVP + 0.05%Ag. Stefan
formula is therefore not applicable for the DW + 0.1%PVP +
0.05%Fe2O3 nanofluids as r did not vary with hfg according to
Fig. 9. D2 as a function of time for DW + 0.5%laponite (data are taken from [40]). K is
Eq. (2). One might only speculate for the Fe2O3 nanofluids the
the evaporation rate constant as defined in Eq. (3). Purple and blue symbols
similar reversing effect of PVP on Ag nanoparticles, because the correspond to Run 1 and Run 2 data in Fig. 2, respectively. (For interpretation of the
hypothetical DW + Fe2O3 nanofluids were not stable. references to colour in this figure legend, the reader is referred to the web version of
There has been limited literature on the effect of evaporation on this article.)
surface tension of pure, molecular liquids. Several articles ad-
dressed the contact angle of water and organic liquid sessile drops evaporating on various substrates [46–48], where values of the
contact angle were compared with and without evaporation. The
onset of evaporation was allowed by decreasing the vapor pressure
in a controlled environment from the saturation value and thereaf-
ter the evaporation rate was controlled by diffusion and could be
expected to be governed by an equation similar to Eq. (3). One ex-
pect from Eq. (1) that for a given pair of liquid–solid substrate, h
decreases as r decreases. The effect of evaporation on r in the
study of Bourges-Monnier et al. [46] can then be inferred from h
of the sessile drop when it was allowed to evaporate. These authors
found that for a given volume of a given liquid, the sessile drops
forming smaller/larger initial value of h (i.e. smaller/larger r
according to Eq. (1)), has a higher/lower evaporation rate (smal-
ler/larger apparent heat of vaporization, hfg). These observations
were consistent with theoretical analysis based on diffusion-con-
trolled evaporation put forward in Ref. [47]. These findings indicate
Fig. 7. D2 as a function of time for DW + 0.04%Ag (data are taken from Ref. [41]). K is that for pure fluids r decreases/increases with decreasing/increas-
the evaporation rate constant as defined in Eq. (3). Purple and blue symbols
correspond to Runs 1 and 2 data in Fig. 3, respectively. (For interpretation of the
ing hfg, which qualitatively agrees with Stefan’s formula, even
references to colour in this figure legend, the reader is referred to the web version of though the evaporation process implies no thermodynamic
this article.) equilibrium.
 R.-H. Chen et al. / International Journal of Heat and Mass Transfer 54 (2011) 2459–2466
Differences between the present experimental conditions and
those for the aforementioned sessile droplets are: (1) nanofluids
vs. pure fluids and (2) pendant vs. sessile droplets, where heat
transfer at the solid–liquid interface may play a role on evapora-
tion rates. While Stefan’s formula helps to qualitatively explain
the dependence of surface tension on the evaporation rate for pure
fluid sessile drops, the present nanofluid results demonstrated
either no or weak dependence of r on hfg, or simply opposite
trends (i.e. r decreases while hfg increases).
One recent study by Vafaei et al. [48] related to sessile droplet
contact angles on glass and silicon wafers used deionized water
with bismuth telluride (Bi2Te3) nanoparticles (nominal diameters
of 2.5–10 nm) with no surfactants for stabilization [48]. The value
of h was determined before visible droplet volume change (i.e.,
evaporation) took place. As a consequence, equilibrium values of
h were believed to have been measured, although it might very
well be a receding contact angle [46]. Adding Bi2Te3 nanoparticles
to DW was shown to increase h (and therefore in r) from that of
pure DW. According Eq. (2) for a given liquid–solid pair, r of the
DW + Bi2Te3 nanofluid increased as a consequence. This result is
in qualitative disagreement with the present results for the
DW + 0.04%Ag and DW + 0.5%laponite nanofluids. In that study
[48], effect of evaporation (i.e. of hfg) was not reported (it was con-
ducted in the ‘‘open’’ laboratory environment). However, if Bi2Te3
behaved like most of the nanofluids reported in [41] where hfg in-
creased with evaporation and, therefore, with the particle concen-
tration, then the results of [48] are in qualitative agreement with
Stefan’s formula.
When studying sessile droplet evaporation, the evaporation rate
has been shown to depend on the stages before and after the
depinning of the contact line. In one study using CuO and Al2O3
nanoparticles in water, while varying particle size and concentra-
tion, demonstrated that he evaporation process was dominated
by the fluid and particle, respectively, before and after the depin-
ning occurred [49]. Such result suggests a change in hfg following
depinning and is expected to affect h and r as evaporation pro-
ceeds. It can therefore be said that the apparent hfg affects the sur-
face tension, while the qualitative and quantitative effects for
sessile droplets are at the present time not clear yet.
5. Conclusion
Three different types of nanoparticles were investigated for
their effects on the surface tension of the nanofluids: laponite, Ag
and Fe2O3. The pendant droplet method was used. Both laponite
and Ag solutions did not require the surfactant PVP for stabiliza-
tion, while 1%PVP was sufficient for stabilizing both Fe2O3–DW
nanofluids. To delineate the combined effects of nanoparticles
and the surfactant, 1%PVP was also added to an Ag–DW nanofluid.
During the droplet evaporation, the particle concentration in-
creased, resulting in concentration-dependent surface tension.
The following results were obtained.
1. Laponite and Ag nanoparticles are capable of reducing the
apparent surface tension by a factor of approximately 3, when
the particle concentration increases by a factor of approxi-
mately 10 as the droplet evaporates toward the end of their life-
time. For the case of laponite nanofluid a hysteresis was
observed, in which the evaporating droplet could not produce
the static surface tension when reaching the same particle con-
centration. Further evaporation for higher particle concentra-
tions is necessary for the same static value.
2. The apparent surface tension of the laponite and Ag nanofluids
during evaporation decreases while the apparent heat of vapor-
ization increases, opposite to the trend predicted by the Stefan
2465
formula. This result suggests that Stefan’s formula is not appli-
cable to these two nanofluids due to the presence of
nanoparticles.
3. Adding a surfactant (1%PVP in this study) appears to partially
cancel (or pacify) the effect of Ag, resulting in approximately
constant surface tension throughout the droplet lifetime. How-
ever, this combined effect still cannot be predicted by the Stefan
formula.
4. The Fe2O3–(DW + 1%PVP) nanofluid surface tension remains
constant during the lifetime of the evaporating droplet. This
result is similar to that of the Ag–(DW + 1%PVP) nanofluid.
Because a hypothetical Fe2O3–DW nanofluid does not exist (in
that it does not maintain its stability for more than a few min-
utes) no conclusion can be made as to whether the surfactant
cancels the effect of Fe2O3 nanoparticles. On the other hand,
the apparent heat of vaporization increased with time, suggest-
ing that Stefan’s formula is not applicable.
5. Although Stefan’s formula may help to qualitatively explain the
sessile droplet surface tension during evaporation, it fails to
explain the present results of pendant droplets where an
increase in the heat of vaporization have led to decreases of
or nearly no change in the surface tension. The existence of
nanoparticles appears to have effects in addition to the non-
equilibrium evaporation process.
Acknowledgment
One of the authors (RHC) is supported by DOE’s Faculty Re-
search Participation Program to conduct work at NETL-Pittsburgh.
References
[1] B.P. Binks, Particles as surfactants – similarities and differences, Current Opin.
Colloid Interface Sci. 7 (2002) 21–41.
[2] V.P. Carey, Liquid-Vapor Phase-Change Phenomena, 2nd ed., Taylor and Francis,
New York, 2008.
[3] R. Cole, Bubble frequencies and departure volume at subatmospheric
pressures, AIChE J. 13 (1967) 779–783.
[4] W. Fritz, Maximum volume of vapor bubble, Phys. Zeitung 36 (1935) 379–384.
[5] B.B. Mikic, W.M. Rohsenow, Bubble growth rate in nonuniform temperature
fields, Progr. Heat Mass Transfer II (1969) 283–292.
[6] Y.Y. Hsu, On the size range of active nucleation cavities on a heating surface, J.
Heat Transfer 84 (1962) 207–213.
[7] W.M. Rohsenow, A method of correlating heat transfer data for surface boiling
of liquids, Trans. ASME 74 (1952) 969–975.
[8] H.K. Forster, N. Zuber, Dynamics of vapor bubbles and boiling heat transfer,
AIChE J. 1 (1955) 531–535.
[9] K. Stephan, M. Abdelsalam, Heat transfer correlations for natural convection
boiling, Int. J. Heat Mass Transfer 23 (1980) 73–87.
[10] R.I. Vachon, G.H. Nix, G.E. Tanger, Evaluation of constants for the Rohsenow
pool boiling correlation, J. Heat Transfer 90 (1968) 239–247.
[11] B.B. Mikic, W.M. Rohsenow, A new correlation of pool boiling data including
the effect of heating surface characteristics, J. Heat Transfer 91 (1969) 245–
250.
[12] H. Kim, J. Kim, M.H. Kim, Effects of nanoparticles on CHF enhancement in pool
boiling of nano-fluids, Int. J. Heat Mass Transfer 49 (2006) 5070–5074.
[13] S.K. Das, N. Putra, W. Roetzel, Pool boiling characteristics of nano-fluids, Int. J.
Heat Mass Transfer 46 (2006) 851–862.
[14] R. Kumar, D. Milanova, Effect of surface tension on nanotube nanofluids, Appl.
Phys. Lett. 94 (2009) 073107.
[15] D. Wen, Mechanisms of thermal nanofluids on enhanced critical flux (CHF), Int.
J. Heat Mass Transfer 51 (2008) 4958–4965.
[16] Y.H. Jeong, W.J. Chang, S.H. Chang, Wettability of heated surface under pool
boiling using surfactant solutions and nano-fluids, Int. J. Heat Mass Transfer 51
(2008) 3025–3031.
[17] S.U.S. Choi, Nanofluids: from vision to reality through research, J. Heat Transfer
131 (3) (2009) 033106.
[18] S. Lee, SUS. Choi, S. Li, J.A. Eastman, Measuring thermal conductivity of fluids
containing oxide nanoparticles, J. Heat Transfer 121 (1999) 280–289.
[19] X. Wang, X. Xu, SUS. Choi, Thermal conductivity of nanoparticle–fluid mixture,
J. Thermophys. Heat Transfer 13 (4) (1999) 474–480.
[20] JA. Eastman, SUS Choi, S. Li, W. Yu, L.J. Thomson, Anomalously increased
effective thermal conductivities of ethylene glycol-based nanofluids
containing copper nanoparticles, Appl. Phys. Lett. 78 (2001) 718–720.
2466 R.-H. Chen et al. / International Journal of Heat and Mass Transfer 54 (2011) 2459–2466
[21] SK. Das, N. Putra, P. Thiesen, W. Roetzel, Temperature dynamics simulations to
determine dependence of thermal conductivity the effective thermal
conductivity of enhancement for nanofluids, J. Heat Transfer 125 (2003)
567–574.
[22] H.E. Patel, S.K. Das, T. Sundararajan, A.S. Nair, B. George, T. Pradeep, Thermal
conductivities of naked and monolayer protected metal nanoparticle based
nanofluids: manifestation of anomalous enhancement and chemical effects,
Appl. Phys. Lett. 91 (2003) 2931–2933.
[23] Y. Xuan, Q. Li, Heat transfer enhancement of nanofluids, Int. J. Heat Fluid Flow
21 (2000) 58–64.
[24] SUS. Choi, ZG. Zang, W. Yu, FE. Lookwood, EA. Grulke, Anomalous thermal
conductivity enhancement in nanotube suspension, Appl. Phys. Lett. 79 (2001)
2252–2254.
[25] H. Xie, H. Lee, W. Youn, M. Choi, Nanofluids containing multiwalled carbon
nanotubes and their enhanced thermal conductivities, J. Appl. Phys. 94 (8)
(2003) 4967–4971.
[26] C.H. Chon, K.D. Kihm, S.Y. Lee, S.U.S. Choi, Empirical correlation finding the role
of temperature and particle size for nanofluid (Al2O3) thermal conductivity
enhancement, Appl. Phys. Lett. 87 (2005) 153107.
[27] R.L. Judd, K.S. Hwang, A comprehensive model for nucleate boiling heat
transfer including microlayer evaporation, J. Heat Transfer 98 (1976) 623–629.
[28] M.G. Cooper, A.J.P. Lloyd, The microlayer in nucleate pool boiling, Int. J. Heat
Mass Transfer 12 (1969) 895–913.
[29] F.D. Moore, R. Mesler the measurement of rapid surface temperature
fluctuations during nucleate boiling of water, AIChE J. 7 (4) (1961) 620–624.
[30] T.F. Rogers, R. Mesler, An experimental study of surface cooling by bubbles
during nucleate boiling of water, AIChE J. 10 (5) (1964) 656–660.
[31] G.N. Sethumadhavan, A.D. Nokolov, D.T. Watson, Stability of liquid films
containing monodisperse colloidal particles, J. Colloid Interface Sci. 240 (2001)
105–112.
[32] D.T. Wasan, A.D. Nikolov, Spreading of nanofluid on solids, Nature 423 (8)
(2003) 156–159.
[33] J. Mitrovic, The flow and heat transfer in the wedge-shaped liquid film during
the growth of a vapor bubble, Int. J. Heat Mass Transfer 41 (2) (1998) 1771–
1785.
[34] P.C. Wayner, Intermolecular forces in phase-change heat transfer: 1998 Kern
Award Review, AIChE J. 45 (10) (1999) 2055–2068.
[35] A. Chengara, A.D. Nikolov, D.T. Wasan, A. Trokhymchuk, D. Henderson,
Spreading of nanofluids driven by the structural disjoining pressure
gradient, J. Colloid Interface Sci. 280 (2004) 192–201.
[36] E. Donaldson, W. Alam, Wettability, Chapter 1, ‘‘Wettability’’, Gulf Publishing
Co., Houston, 2008. pp. 1-55.
[37] Ibid, Chapter 4, Pore size effects and wettability alteration, pp. 173–238.
[38] F. Barberis, M. Capurro, Wetting in the nanoscale: a continuum approach, J.
Colloid Interface Sci. 326 (2008) 201–210.
[39] V.S. Ajaev, T. Tatiana-Roisman, P. Stephan, Static and dynamic contact angles
of evaporating liquid on heated surfaces, J. Colloid Interface Sci. 342 (2010)
550–558.
[40] P.G. de Gennes, Wetting: statics and dynamics, Rev. Mod. Phys. 57 (1985) 827–
863.
[41] R.-H. Chen, T.X. Phuoc, D. Martello, Effects of nanoparticles on nanofluid
droplet evaporation, Int. J. Heat Mass Transfer 53 (2010) 3677–3682.
[42] T.X. Phuoc, Y. Soong, M.-K. Chyu, Synthesis of Ag-deionized water nanofluids
using multi-bean laser ablation in liquids, Opt. Laser Eng. 45 (2007) 1099–
1106.
[43] R. Aveyard, D.A. Haydon, An Introduction to the Principle of Surface Chemistry,
Cambridge University Press, 1973. p. 200.
[44] K. Sefiane, J. Skilling, J. MacGillivray, Contact line motion and dynamic wetting
of nanofluid solutions, Adv. Colloid Interface Sci. 138 (2008) 01–120.
[45] A.A. Strechan, G.J. Kabo, Y.U. Paulechka, The correlations of the enthalpy of
vaporization and the surface tension of molecular liquids, Fluid Phase
Equilibria 250 (2006) 125–130.
[46] C. Bourges-Monnie, M.E.R. Shanahan, Influence of evaporation on contact
angle, Langmuir 11 (1995) 2820–2829.
[47] R.G. Picknett, R. Bexon, The evaporation of sessile and lendant drops in still air,
J. Colloid Interface Sci. 61 (1977) 336–350.
[48] S. Vafaei, T. Borca-Tasciuc, M.Z. Podowski, A. Purkayastha, G. Ramanath, P.M.
Ajayan, Effect of nanoparticles on sessile droplet contact angle,
Nanotechnology 17 (2006) 2523–2527.
[49] C.H. Chon, S. Paik, J.B. Tipton, K.D. Kihm, Effects of nanoparticle sizes and
number densities on the evaporation and dryour processes for strongly pinned
nanofluid droplets, Langmuir 23 (2007) 2953–2960.