Article

pubs.acs.org/JPCB

Evaporation of Sessile Droplets Affected by Graphite Nanoparticles

and Binary Base Fluids
Xin Zhong and Fei Duan*
School of Mechanical and Aerospace Engineering, Nanyang Technological University, Singapore 639798

ABSTRACT: The effects of ethanol component and nano-

particle concentration on evaporation dynamics of graphite−
water nanofluid droplets have been studied experimentally. The
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

results show that the formed deposition patterns vary greatly

with an increase in ethanol concentration from 0 to 50 vol %.
Downloaded via INDIAN INST OF TECH BHILAI on August 28, 2023 at 11:12:21 (UTC).

Nanoparticles have been observed to be carried to the droplet

surface and form a large piece of aggregate. The volume
evaporation rate on average increases as the ethanol
concentration increases from 0 to 50 vol % in the binary
mixture nanofluid droplets. The evaporation rate at the initial
stage is more rapid than that at the late stage to dry, revealing a deviation from a linear fitting line, standing for a constant
evaporation rate. The deviation is more intense with a higher ethanol concentration. The ethanol-induced smaller liquid−vapor
surface tension leads to higher wettability of the nanofluid droplets. The graphite nanoparticles in ethanol−water droplets
reinforce the pinning effect in the drying process, and the droplets with more ethanol demonstrate the depinning behavior only at
the late stage. The addition of graphite nanoparticles in water enhances a droplet baseline spreading at the beginning of
evaporation, a pinning effect during evaporation, and the evaporation rate. However, with a relatively high nanoparticle
concentration, the enhancement is attenuated.

■ INTRODUCTION
Nanofluids are kinds of fluids that normally contain insoluble
angle. It is attributed to the deposition of nanoparticles,
particularly the self-assembly near the three-phase line,13 which
nanosized particles. The evaporation of a nanofluid droplet on a modifies liquid−solid surface tension,14 and the interaction
solid substrate has attracted extensive interest as the self- with the solid substrate.15,16 Besides, nanoparticles have
assembly and deposition pattern forming after drying have influence on the evaporation rate of a droplet. Iron oxide
plenty of important applications, such as coating, inkjet (Fe2O3), zirconium dioxide (ZrO2), or nickel/iron (Ni/Fe)
printing,1 DNA molecular stretching,2 and micropatterning of nanoparticle addition into the droplets was observed to reduce
electronic devices. Controlling deposition patterns is useful in the evaporation rate, while the presence of clay nanoparticles
particular fields. A coffee-ring, for instance, is desirable in the increased evaporation.17 On one hand, the evaporation could
print of repetitive fine lines,3,4 while a uniform profile is be enhanced due to a prolonged pinning stage caused by
required in coating. The pattern formation is dependent on the nanoparticles; on the other hand, the aggregation of nano-
evaporation dynamics of the droplets. The prerequisite for particles at the three-phase line, and the increased fluid viscosity
forming a coffee-ring is a pinned contact line,3 while a uniform could attenuate evaporation. So far, the mechanism of the
pattern can be attained by driving particles to the liquid−vapor nanoparticle effect on evaporation is not fully understood, and
interface to achieve “skin formation”.5 The transition between further systemic exploration is necessary. Combined with the
the coffee-ring and uniform deposition can be managed by nanoparticles, the manipulation of base fluids has been made
changing the particle shapes6,7 and adding the surfactant.8,9 In with the employment of mixtures comprising liquids with
addition, the alteration of pinning and depinning of the contact different thermal and physical properties. Hitherto, some works
line can produce concentric rings, known as the stick−slip have been contributed to probe the complex flow regimes led
behavior.10 Thus, fully understanding the evaporation dynamics by the different volatility in the droplets of pure binary fluids
of nanofluid droplets makes it possible to meet the challenge of without nanoparticles.18−22 Sefiane et al. investigated the
producing desirable patterns. evaporation behavior of a pure ethanol−water sessile droplet
The evaporation process of a nanofluid droplet is a complex on a polytetrafluoroethylene (PTFE) substrate20 and found
process. The suspended nanoparticles cannot be simply treated three evaporation regions in terms of contact angle, base
as passively driven insoluble solutes, but they exert great impact diameter, and volume. They indicated that the ethanol, which is
on the wetting dynamics and evaporation of the droplet, more volatile, evaporated during the first phase, while the water
accordingly varying the profile of the deposition. The
nanoparticles can extend the pinning duration of a sessile Received: August 8, 2014
droplet and lead to more long-lasting radial outward flow.11,12 Revised: November 5, 2014
Nanoparticles have also been found to enlarge the contact Published: November 5, 2014

© 2014 American Chemical Society 13636 dx.doi.org/10.1021/jp508051y | J. Phys. Chem. B 2014, 118, 13636−13645
The Journal of Physical Chemistry B Article

evaporated at the third stage. In the second stage, the contact before the evaporation experiments. Clean silicon wafers
angle increased. Cheng et al. studied the evaporation of the (Bonda Technology Pte Ltd., hydrophilic) were used as
ethanol−water mixing droplets on the coated gold surface evaporation substrates.
under ambient conditions,21 and Liu et al. studied the Evaporation experiments were performed using a goniometer
evaporation of the sessile binary liquid droplets on an and a bright-field microscope to study the evaporation
oxygen-plasma-treated silicon plate without heating or cooling dynamics and the deposition patterns of the suspensions,
in a controlled chamber.22 They both verified the three respectively. For evaporation dynamics, the goniometer
evaporation regions in the binary liquid droplets before drying. employed to record the images of the evaporating droplets
Sefiane et al. and Cheng et al. indicated that the droplet was a “Wet Angle” Theta Optical Tensiometer, as shown in
baseline shrank at the very early stage.20,21 However, the Figure 1. A controlling dosing system was set to generate sessile
influence of nanoparticles on both droplet wettability and
evaporation still remains unsolved. In addition, the forming
process of a pattern affected by the complex flows in the
droplets containing nanoparticles has not been studied
extensively.
In this study, we quantitatively investigate the effect of
ethanol concentration in water for nanofluid droplets and the
graphite nanoparticle concentration for water-based droplets on
the wettability, evaporation rate, and deposition patterns. We
use a goniometer to study the evaporation dynamics and
microscopy to monitor the nanoparticle motion in the drying
nanofluid droplet. We provide a primarily direct glimpse of the
nanoparticle-modified evaporation dynamics in binary droplets, Figure 1. Schematic of the goniometer. The inset is the photo of the
the formation of the nanoparticle aggregation at the droplet test rig.
surface and the final deposition patterns affected by ethanol
concentration, and the initial spreading of the sessile water- droplets with a required volume of 2.09 ± 0.11 μL. The
based droplets due to graphite nanoparticle addition.

■
evaporation process was recorded with a high-resolution digital
camera at a frequency of 1 frame per 5 s. Entire evaporation
EXPERIMENTAL METHODS times ranged from 20 to 30 min. Ball calibration was conducted
To investigate the effects of ethanol solvent and graphite before each experiment to minimize experimental error. After
nanoparticles on the droplet evaporation, a water-based the evaporation experiments, all of the images were
suspension of 1.5 g/L nanoparticles was selected as a reference. postprocessed by executing the graphic analysis function in
The ethanol concentration in the binary fluids and the the program, through which the contact angle, baseline length,
nanoparticle concentration are the two variables in the two and droplet volume were obtained and recorded. For part of
prepared batches of samples, respectively: (1) mixtures of 1.5 the deposition patterns, a microscopy system (LV100D-U from
g/L graphite nanoparticles and water-based binary fluids with 0, Nikon Inc.) with an objective lens at 2× magnification was
10, 25, 40, and 50 vol % ethanol; and (2) water-based employed to observe the transport of nanoparticles during
suspensions with graphite nanoparticle concentrations at 0, 0.5, evaporation and the formed patterns after evaporation. The
1.0, 1.5, and 2.0 g/L. The details are listed in Table 1. The droplets were evaporating under the open conditions with the
pressure at 1 atm, the temperate at 24 ± 1 °C, and the relative
Table 1. Experimental Conditions of Sessile Nanofluids for humidity at about 50 ± 5%.
Droplet Evaporation To ensure the repeatability of our experiments, at least three
tests were conducted for each set of experimental conditions in
ethanol concentration, vol % nanoparticle concentration, g/L
Table 1. The measurement accuracy of the contact angle or the
exp. no. 0 10 25 40 50 0.0 0.5 1.0 1.5 2.0 volume was ±0.1° or ±5%. The uncertainties of the
√ √ postprocessing were evaluated within ±5%.

■
N1
N2 √ √
N3 √ √ RESULTS AND DISCUSSION
N4 √ √ Effect of the Volume Concentration of Ethanol in the
N5 √ √ Binary Fluids. The role taken by ethanol in nanofluid droplet
N6 √ √ evaporation is examined by varying its concentration within the
N7 √ √ range from 0 to 50 vol %. The parameters examined here are
N8 √ √ droplet volume, baseline length, and contact angle. The visual
N9 √ √ changes of droplet drying sequences of experiments N1−N5
for the side view are in Figure 2a−e, while the resulting
nanofluids were prepared with graphite powders at 2−3 nm deposition patterns are shown in Figure 2f. Similar to the
from Skyspring Nanomaterial Inc., ethanol (C2H5OH, Reagent evaporation behavior of the pure liquid droplets on the no
ACS grade), and deionized water with the resistivity at 18.0 heating or cooling substrates reported by Sefiane et al.,20 Cheng
MΩ−cm. The surface tension of pure water was occasionally et al.,21 and Liu et al.,22 the droplets with graphite nanoparticles
measured as it was exposed in the laboratory environment for 1 evaporate faster with an increase in the ethanol concentration,
h, and no variation was observed. The samples were mixed first represented by the droplet volume, which decreases as the
and then kept in an ultrasonication bath (Fisher Scientific ethanol concentration increases at 400 s (Figure 2e). The initial
model 500) for 5 h to obtain well-distributed mixtures just droplet baseline is more extended with a higher ethanol
13637 dx.doi.org/10.1021/jp508051y | J. Phys. Chem. B 2014, 118, 13636−13645
The Journal of Physical Chemistry B Article

Figure 2. Drying sequences and patterns of 1.5 g/L nanofluid droplets with 0, 10, 25, 40, and 50 vol % ethanol concentrations at (a) 0, (b) 50, (c)
100, (d) 200, and (e) 400 s. The dotted−dashed lines show the edges of the droplets at 0 s. The dried patterns are shown in (f).

Figure 3. Drying sequence of a (a) 1.5 g/L nanofluid droplet with 10 vol % ethanol and (b) 1.5 g/L nanofluid droplet with 40 vol % ethanol. The
evaporation time is normalized with the entire evaporation lifetime for each experiment. For the 1.5 g/L nanofluid droplet with 10 vol % ethanol
(N2), the sporadic nanoparticle fragments were formed at 17% of the lifetime. The chaotic flows ended at around 25% of the lifetime, and the inward
flow to the centerline of the droplet, or Marangoni flow, was found; the Marangoni flow finished roughly at 70% of the lifetime. For the 1.5 g/L
nanofluid droplet with 40 vol % ethanol (N4), from the moment of 5 to 20 and 25% of the lifetime, the aggregate at the droplet interface grew
rapidly due to vortices; the aggregate fully covered the interface at about 55% of the lifetime, and the Marangoni flow started to act; it finished at
around 83% of the lifetime.

concentration. With time going, the evaporating droplets with relatively uniform distribution. With only 10 vol % ethanol
relatively low ethanol concentrations remain pinned, while concentration, however, most nanoparticle residuals stay at the
those at 40 and 50 vol % of ethanol exhibit a depinning central area and detach from the outer ring. As the ethanol
behavior at the late stage. Different from the observation of the concentration continues to increase to 25 vol %, the deposit
fast shrinkage of the baseline at the first stage for the pure approaches uniformity again. However, the detachment
ethanol−water droplets,20,21 the added graphite nanoparticles between the interior deposit and the outer ring emerges and
in the binary mixtures are seen to prolong the pinning duration intensifies with the ethanol concentration increasing to 40 and
for the nanofluid droplets. To quantify the evaporation 50 vol %. Even though we cannot measure the flowing in the
behavior shown qualitatively in Figure 2a−e, we plot the nanofluid droplet with particle image velocimetry now, we can
contact angle, baseline length, and volume as a function of time, refer to the findings by Christy et al.18 in explaining the flow
which are discussed further. regimes in a pure water−ethanol droplet. They classified three
The dried patterns in Figure 2f are sensitive to the variation regimes in evaporation: (1) the ethanol-dominated stage full of
of ethanol. The pattern from the water-based suspension shows chaotic flows and vortices; (2) the transient stage of Marangoni
13638 dx.doi.org/10.1021/jp508051y | J. Phys. Chem. B 2014, 118, 13636−13645
The Journal of Physical Chemistry B Article

flow led by the nonuniform distribution of ethanol on the of the graphite aggregates at the liquid−vapor interface could
liquid−vapor interface; and (3) the water-dominated radial modify the liquid−vapor surface tension, resulting in a modified
flow. These combined flow regimes can result in our observed gradient of surface tension and a subsequent fluid circulation
patterns. The deposition patterns in Figure 2f are distinctively even when less ethanol was left. However, in order to clarify the
varied by a small change in ethanol, particularly from 0 to 10 mechanism and to quantify the influence of ethanol
vol %, from 10 to 25 vol %, and from 40 to 50 vol %. It implies concentration on the flow regimes and the drying patterns of
that the component of ethanol exerts high influence in the the nanofluid droplets, further detailed visualization inves-
relative weight of the three regimes discussed by Christy et al.,18 tigation would help.
and the presence of nanoparticles may modify the flow regimes. Figure 4a shows the trend of the volume of the sessile
To confirm it, we employed the microscopy to record the droplets containing an ethanol component. The starting
evaporating graphite−ethanol−water droplets. On the top view,
we can observe the flow pattern on the basis of the motion and
assembly of the nanoparticles at the droplet surface. At the
initial time, strong vortices were observed to carry nanoparticles
to the liquid−vapor interface and make them form aggregates.
The flow in this stage was intense and rapid. Then, the flow
slowed down gradually, and the formed aggregates along the
liquid−vapor interface started to move to the droplet
centerline. This is seen to be generated by the Marangoni
flow, originating from the surface tension variation that is
induced by the nonuniform local evaporation flux with the
maximum value at the three-phase line.23,24 Ultimately, the
aggregates stopped moving inward but descended toward the
substrate. However, we found that both the duration for each
flow regime and the intensity of the fluid flow depend
significantly on the ethanol concentration. The top views of the
drying sequences of the nanofluid droplets with 10 and 40 vol
% ethanol concentrations are demonstrated in Figure 3.
Because the evaporation lifetimes for both of the droplets are
different, we normalized the evaporation time with the whole
drying time for each nanofluid droplet. As shown in Figure 3a
for 10 vol % ethanol (experiment N2), the regime of vortices
due to chaotic flows ended at around 25% of the lifetime,
during which the intense flow moved the nanoparticles and the
sporadic aggregate to the droplet surface. Afterward, the
fragments were transported to the centerline with the flow at
the liquid−vapor interface until 70% of the lifetime. With a
higher ethanol at 40 vol % (N4), the finishing moment of the
vortices and chaotic flow was roughly at 55%, and the flow Figure 4. (a) Droplet volume change with time of 1.5 g/L nanofluid
toward the centerline was almost gone at 83% of the lifetime. droplets with 0, 10, 25, 40, and 50 vol % ethanol concentrations; below
The detaching gap of the nanoparticle deposition in Figure 2f the dashed line, the evaporation stage is dominated by the less volatile
was a result of depinning at the last stage. The distinction component. (b) The averaged evaporation rate of 1.5 g/L nanofluid
between the patterns from these two droplets is attributed to droplets as a function of ethanol concentration and the comparison
with the pure water−ethanol sessile droplets,20−22 in which the
the concentration of ethanol. The induced vortices in
substrates were not heated and cooled. The inset is the comparison
experiment N2 were not as strong as those in experiment between the average evaporation rate at the late stage (0.7 μL before
N4; thus, the speed for the formation of the aggregates was low. dry-out) and the overall average rate of the graphite−ethanol−water
Moreover, the much stronger chaotic flows lasting for a longer droplets.
time in the droplet of 40 vol % ethanol led to more rapid
formation of the aggregates.
One noticeable difference in the observation of the surface volume for each evaporating droplet is about 2.09 μL. As
flow is that the nanoparticles prolonged the flow toward the ethanol is more volatile than deionized water, the droplet with a
centerline, or the Marangoni flow, in the water−ethanol-based higher concentration of ethanol is expected to evaporate faster,
nanofluid droplet in comparison with the pure liquid water− consistent with the steeper trend of the volume change at a
ethanol droplet. In the study of Christy et al.,18 the Marangoni higher ethanol concentration (Figure 4a). The droplet volume
flow in the transient stage occupied only 8% of the entire time, of the suspension without ethanol (experiment N1) declines
while in our observation, the slow inward movement of the almost linearly, suggesting an approximately constant evapo-
aggregate took over about 30% of the lifetime. Although the ration rate. With the addition of ethanol, the reducing rate of
mechanism underlying is still unclear at present, there are two the volume at the initial stage is more rapid than that at the late
possible reasons for the longer-lasting Marangoni flow in the stage, representing a deviation of the evaporation rate from a
nanofluid droplet: (1) A number of nanoparticles were seen to constant value. The deviation is more intensified with a higher
accumulate at the droplet rim in the experiments; therefore, the ethanol concentration, resulting from the fact that a relatively
pinning effect was enhanced and could maintain the nonuni- larger amount of ethanol that evaporates initially induces a
form local evaporation at droplet surface; and (2) the coverage greater difference between the initial stage with fast evaporation
13639 dx.doi.org/10.1021/jp508051y | J. Phys. Chem. B 2014, 118, 13636−13645
The Journal of Physical Chemistry B Article

and the late stage of the water-dominated evaporation with a

relatively low rate.
The data are summarized and plotted in Figure 4b to show
the average volume evaporation rates of the graphite−ethanol−
water droplets as a function of ethanol concentration in the
binary mixtures. The evaporation rate of the nanofluid droplets
increases approximately linearly with the loading of ethanol
from 0 to 40 vol %, but at 50 vol % of ethanol, the evaporation
rate exhibits a remarkable increase. The average evaporation
rate for the water-based nanofluid droplet (N1) is roughly 1.53
× 10−3 μL/s, almost half of that of the droplet with 40 vol %
ethanol (N4) and about one-fifth of that for the droplet with 50
vol % ethanol (N5). The results are compared with the
evaporation rates of the pure ethanol−water droplets without
any particles20−22 in Figure 4b. The ethanol−water droplets
were evaporating on a PTFE surface at 1 atm in the
investigation of Sefiane et al.20 As the ethanol concentration
is at 0, 25, and 50%, the evaporation rates of the pure binary
droplets20 are all below those of the binary fluids containing 1.5
g/L graphite nanoparticles in this study. Further comparisons
are made with the evaporation experiments of the pure
ethanol−water droplets on the monolayer-coated gold surface
at the temperature of 23 °C with the relative humidity of 40−
50%21 and on the no heating or cooling silicon plate with the
relative humidity of 47−64%.22 The evaporation rates with the
nanoparticles are higher than those of the pure binary liquid
droplets. It could be a result of the enhanced thermal
conductivity of the nanofluids. Another reason is related to Figure 5. (a) Contact angle change with time in droplets with 0, 10,
the enhanced pinning effect led by nanoparticles. 25, 40, and 50 vol % ethanol concentrations in 1.5 g/L nanofluids. (b)
Moreover, we investigate the average evaporation rate at the The relative contact angle change with time. The initial contact angle
late stage of the binary nanofluid droplets. The data of the last of 1.5 g/L nanofluid droplets as a function of ethanol is in the inset.
0.7 μL (under the dashed line in Figure 4a) are selected,
plotted, and illustrated in the inset of Figure 4b. The average
evaporation rate at the late stage is much lower than the related
overall rate, and it still increases with the ethanol loading and
stays higher than that of the pure water droplet with 1.5 g/L
graphite nanoparticles (N1). One possible factor is that the left
solvents still have ethanol; the other, more important, factor is
the enhanced pinning effect of the three-phase line led by the
nanoparticles. The baseline length is found to be extended with
the higher loading of ethanol; therefore, the nanofluid droplet
with a higher ethanol concentration has a larger contact area
with the substrate, leading to a more rapid evaporation.14
Besides, the nanoparticle deposit at the contact line helps
pinning of the contact line. Even though the ethanol loss in the
binary mixtures becomes higher with the proceeding of
evaporation, the deposited particles retard the contact line
shrinkage; thus, the droplet can maintain a relatively large
contact area. We can see that the last-stage baseline of the
nanofluid droplet with 50 vol % ethanol (N5) is still way longer
than that of the pure water-based nanofluid droplet (N1).
On the basis of the above discussion, we measure the contact
angle and the baseline to reveal the role taken by ethanol in
evaporation. Figure 5a is for the raw data of the contact angle,
and Figure 5b is for the normalized data with a reference to the
initial contact angle. Figure 6a,b illustrates the raw data of the
baseline length as a function of time and the relative values with
a reference to the initial baseline, respectively. As the droplets
maintain pinned for most of the lifetime, the evaporation-
Figure 6. (a) Baseline length change as a function of time of droplets
induced reduction of volume is primarily reflected in the with 0, 10, 25, 40, and 50 vol % ethanol−water binary nanofluids. (b)
decrease of the contact angle. Similar to the trend of volume, The relative baseline length change with time.
the contact angle shows a faster reducing rate with a higher
ethanol component in the nanofluid droplets in Figure 5. The
13640 dx.doi.org/10.1021/jp508051y | J. Phys. Chem. B 2014, 118, 13636−13645
The Journal of Physical Chemistry B Article

Figure 7. Drying sequences of droplets with 0, 0.5, 1, 1.5, and 2 g/L nanoparticle concentrations at (a) 0, (b) 20, (c) 100, (d) 500, and (e) 1100s.
The dotted−dashed lines show the edges of the droplets at 0 s. The dried patterns are shown in (f).

contact angle displays a deviation as well in the nanofluid gradually decreases. The sessile droplets exhibit depinning
droplets comprising ethanol, in contrast to the linear reduction behavior at only the late stage of evaporation at 40 and 50 vol %
of the contact angle of the nanofluid droplet without ethanol of ethanol. As aforementioned, the ethanol addition leads to
addition. The reducing contact angle throughout the fluid circulation in the droplets; thus, the inward flow along the
evaporation is significantly different from the ones of pure liquid−vapor interface can move the nanoparticles toward the
ethanol−water mixtures, which increase in the stage of fast centerline of the droplet, while the outward flow, due to the
evaporation of ethanol,20−22 resulting from the enhanced higher evaporation loss at the contact line,8,23 transfers the
pinning effect of the three-phase contact line due to the nanoparticles to the three-phase line. More particle aggregation
nanoparticle deposition. reinforces the pinning effects. However, a higher inward flow
Due to the lower surface tension of ethanol, the droplet with from the contact line at a higher ethanol concentration can
a higher ethanol concentration exhibits a smaller contact angle reduce the pinning effect. The two mechanisms compete and
and stronger wettability. As shown in the inset of Figure 5, for result in the pinning behavior at most lifetimes in the series of
the water-based nanofluid droplet, the initial contact angle is experiments and the depinning behavior at the last period of
50.8°. With the ethanol increasing to 10, 25, 40, and 50 vol %, experiments N4 and N5.
the corresponding contact angle is 47.6, 41.2, 36.9, or 23.9°, The pinning three-phase line during evaporation in the
respectively. A higher ethanol concentration results in a nanofluid droplets is quite different from the experiments of
relatively lower apparent surface tension in the water−ethanol pure ethanol−water droplets.20,21 The droplets without
binary fluids. The force balance at the contact line can be particles were observed to shrink rapidly from the beginning
expressed in principle by the Young equation,25 γSV = γSL + γLV of evaporation, and then the retraction continued but with a
cos θ, in which γSV, γSL, γLV, and θ are the solid−vapor surface slower rate. The receding trend was seen more intense with a
tension, solid−liquid surface tension, liquid−vapor surface higher ethanol component. With the nanoparticle addition in
tension, and contact angle. As the droplets are added with more the binary fluids, the droplets containing ethanol maintain
ethanol, the γLV is found to reduce significantly;26 therefore, the pinned on the solid surface for most of the lifetime, as shown in
contact angle θ should decrease to maintain the balance while Figure 6. Even for the one with 50 vol % ethanol (N5), the
there is not much change in γSV and γSL. Thus, a higher ethanol pinning behavior can be seen in the first 50 s. Then, the droplet
concentration leads to a smaller initial contact angle for the is depinned. However, its baseline length at the late stage is still
nanofluid droplets in the inset of Figure 5 and a longer baseline much longer than that of the other droplets (N1−N4).
in Figure 6. Recalling Figure 4 for the average evaporation rate, we can
Corresponding to the reduced contact angle in experiments conclude that the pronounced evaporation in ethanol−water
N1−N5, the droplet baseline length at the beginning of nanofluid droplets in the last stage is mainly attributed to the
evaporation is evidently elongated with more addition of extended baseline by the ethanol and the long pinning stage by
ethanol. The pure water-based nanofluid droplet maintains the nanofluids. The large baseline length and the high ethanol
pinned on the substrate for almost the whole drying time in component make the nanofluid droplet with 50 vol % ethanol
experiment N1. As the ethanol concentration increases from 10 (N5) evaporate much more rapidly than the others in the series
(N2) to 50% (N5), the duration of the pinned baseline length of experiments.
13641 dx.doi.org/10.1021/jp508051y | J. Phys. Chem. B 2014, 118, 13636−13645
The Journal of Physical Chemistry B Article

In addition, we have noticed a repeatedly continuous

spreading phenomenon in the water-based nanofluid droplet
without ethanol (experiment N1) at the very beginning of the
evaporation stage, as shown in Figure 6b. It promotes us to
study the effect of nanoparticle concentration on evaporation
dynamics of nanofluid droplets.
Effect of Graphite Nanoparticle Concentration. In the
evaporation of sessile nanofluid droplets, both increased and
decreased evaporation rates were found to result from the
addition of nanoparticles.17 Although the nanoparticles have
been confirmed to enhance liquid film spreading by generating
the structural disjoining pressure,27,28 the enlarged contact
angle of the nanofluid droplet compared to that of a pure base
fluid droplet seems to contradict it. Thus, we investigate water-
based nanofluids with the addition of 0.0, 0.5, 1.0, 1.5, and 2.0
g/L graphite nanoparticles to examine the influence of
nanoparticles on sessile water droplet evaporation.
Figure 7 shows the drying sequences and the deposition
patterns of water droplets with the various concentrations of
graphite nanoparticles. At a first glance of Figure 7a−e, it is easy
to find out that the pure water droplet is flatter as compared to
the other nanofluid droplets. The water droplet retracts from its
initial position, different from the long-lasting pinning of the
droplets containing nanoparticles. The nanoparticle deposits
are shown in Figure 7f. Different from the coffee-ring
observation,23 the nanoparticle deposition covers almost the
area circumscribed by the initially formed ring mainly due to Figure 8. (a) Baseline length change as a function of time in the water-
the nanoparticle sticking to the agglomerate in drying.8,29 With based nanofluids with graphite nanoparticle concentrations at 0, 0.5,
the increasing concentration of graphite nanoparticles, both the 1.0, 1.5, and 2.0 g/L. (b) The maximum baseline spreading with
nanofluid concentrations.
interior residual and the coffee-ring are intensified, denoted by
the darker deposition color. Moreover, there are formed
aggregates as the nanoparticle concentration increases,
especially in the droplet with 2.0 g/L nanoparticle concen-
tration.
Interestingly, the droplet with the graphite nanoparticles
exhibits a fine but obvious behavior: the contact line spreads at
the very early stage of evaporation. The initial spreading is not
observed in the water droplet. It is suggested that the
nanoparticles are the inducement of the spreading. Wasan et
al.27,28 observed nanoparticle-induced slow spreading of the
nanofluid in a wedge film confined by a glass slide and an oil
droplet that was immersed in the nanofluids. The spreading of
sessile droplets led by the nanoparticles, however, has not been
observed extensively. Here, we provide both direct observation
and quantitative analysis for the initial spreading behavior.
To investigate the impact of nanoparticles on evaporation,
we plot Figures 8 and 9 to show the trend lines of the baseline
length and contact angle for experiments N1 and N6−N9.
Demonstrated in Figure 8a, the baseline of the deionized water
droplet initially is much longer than those of the nanofluid
droplets, suggesting that the initial wetting of the pure water
droplet (N6) is stronger. Due to the deposition of nano-
particles, the superficial structure and the roughness of the
wafer are modified.14 The nonuniform deposition of the
nanoparticles particularly near the three-phase line produces
inhomogeneity of the surface energy of the substrate, thus
attracting the three-phase line to attach to a new site13,14 and Figure 9. (a) Contact angle change as a function of time in water-
varying the contact angle. However, the spreading at the early based droplets with graphite nanoparticle concentrations at 0, 0.5, 1.0,
stage is found only in the nanofluid droplets but not in the pure 1.5, and 2.0 g/L. (b) The relative contact angle change with time. The
water droplet. It is sensitive to the graphite nanoparticle inset is the initial contact angle for droplets with various nanoparticle
loading. Figure 8b demonstrates the initial spreading behavior concentrations.
of each droplet by plotting the increase of a droplet maximum
baseline from its initial baseline. It can be found that the
13642 dx.doi.org/10.1021/jp508051y | J. Phys. Chem. B 2014, 118, 13636−13645
The Journal of Physical Chemistry B Article

addition of nanoparticles generally enlarges the baseline length Compared with the pure water droplet, the initial contact
at the early evaporation stage. With the graphite nanoparticle angle of the nanofluid droplets is apparently enlarged, as
concentration increasing from 0.0 to 0.5, 1.0, and 1.5 g/L, the illustrated in the inset of Figure 9. However, the initial contact
maximum spreading of the baseline increases to 0.018, 0.023, angle is not sensitive to the nanoparticle concentration. It
and 0.046 mm. Therefore, the spreading is proportional to the recalls our discussion in the enhanced pinning effect of
increase of the nanoparticles within the range between 0.0 and nanoparticles on the contact line. The deposition of nano-
1.5 g/L. The nanoparticles arriving at the three-phase line tend particles on the substrate would modify and roughen the solid
to self-assemble into the ordered structures, leading to an substrate surface, resulting in adsorption of the contact line to
excess energy in the wedge film, known as the structural new sites on the substrate.13,14 It was clarified by Blake and De
disjoining pressure, which can drive the three-phase line into Coninck that the advancement of liquid on a solid surface was a
motion.28 With the increasing concentration of the nano- successive-attaching process that liquid molecules were inclined
particle, more available nanoparticles can access the thin wedge to be absorbed on sites on the solid surface in a preferable
film and self-organize there; therefore, the baseline length is orientation.32 Therefore, the deposited nanoparticles create
elongated from 0.0 to 1.5 g/L. However, as the nanoparticle new sites for liquid molecules to be attracted and thus to
concentration increases from 1.5 to 2.0 g/L, the initial change the contact angle.14 The accumulated deposit at the
extension of the baseline is smaller. As stated by Vafaei et contact line helps anchoring of the three-phase line on the
al.,15 the structural disjoining pressure is more pronounced with substrate and prevents its macroscopic movement like the pure
smaller nanoparticles, and a larger number of nanoparticles water droplet.
would inhibit the film spreading due to a higher opportunity for Figure 10a demonstrates the change in droplet volume as a
them to agglomerate and to form clusters.30 The formed function of time at the particular nanoparticle concentrations
clusters (see Figure 7f) usually are unable to fit into the thin
film; thus, the total number of nanoparticles capable of
enhancing droplet spreading could be reduced. The nonun-
idirectional change of the spreading behavior with the
nanoparticle concentration is determined by the two competing
mechanisms, resulting in a peak of the baseline difference at 1.5
g/L of the nanoparticle concentration. The initial spreading by
the nanoparticles might also help extend the baseline for the
graphite−ethanol−water droplets (N2−N5), although it was
not easy to be separated from the overlapping function by
ethanol.
During evaporation, the wettability development of droplets
is expressed in both the baseline length in Figure 8a and the
contact angle in Figure 9. As seen in Figure 8a, the baseline of
the pure water droplet remains constant at the initial stage of
evaporation. Afterward, at about 400 s, the baseline begins to
reduce, and the shrinking is roughly constant until the
evaporation completion. The corresponding contact angle in
Figure 9a,b shows a quick and linear decrease until around 400
s, and from that moment, the decrease of the contact angle
almost stops. The behaviors of the contact angle and baseline of
the deionized water droplet suggest that the droplet goes
through a constant contact radius (CCR) mode at first and
then an approximate constant contact angle (CCA) mode on
our silicon substrate. It is seen from the normalized contact
angle curves in Figure 9b that the transition point occurs only Figure 10. (a) Droplet volume as a function of time for droplets with
in the pure water droplet. With the addition of 0.5, 1.0, 1.5, or 0, 0.5, 1.0, 1.5, and 2.0 g/L graphite nanoparticle concentrations. (b)
2.0 g/L graphite nanoparticles, the contact angle keeps The average evaporation rate of the nanofluid droplets with different
reducing at an approximately linear rate before the final drying, graphite nanoparticle concentrations. The data are compared with
and the change of contact angle as a function of time becomes those from the pure water experiments.21,22
faster as the nanoparticle concentration increases. In addition,
the baseline length of the nanofluid droplets on the substrate for experiments N1 and N6−N9. The volume change of the
remains similar during evaporation, although a small degree of deionized water droplet as a function of time is much slower,
spreading at the beginning stage has been observed. It is and the lifetime is longer compared to that of the droplets
indicated that the nanofluid droplet drying goes through the suspended with the graphite nanoparticles, implying that the
CCR mode. The considerably enhanced pinning effect relates pure water droplet has a lower average evaporation rate. The
to the forces acting on the contact line. The local forces at the steeper trend lines of the other nanofluid droplets suggest that
three-phase line include the depinning force responsible for the the evaporation is enhanced with a higher concentration of
retracting behavior and the pinning force, which are found graphite nanoparticles. Figure 10b presents the average
dependent on contact angle, roughness, and heterogeneity of evaporation rates of the droplets in the series of experiments.
the solid surface.31 The deposition of nanoparticles roughens The average evaporation rate of N6 is comparable with those of
the substrate and acts like an obstacle in the retracting path of the pure water droplets.21,22 The evaporation rate basically
the contact line. increases linearly with the graphite concentration ranging from
13643 dx.doi.org/10.1021/jp508051y | J. Phys. Chem. B 2014, 118, 13636−13645
The Journal of Physical Chemistry B

■
Article

0.0 (N6) to 1.5 g/L (N8). However, the evaporation increasing AUTHOR INFORMATION
trend at 2.0 g/L (N9) is slowed down but still higher than the
Corresponding Author
water droplet. As illustrated by Figure 8a, the depinning
*E-mail: feiduan@ntu.edu.sg. Phone: +65 67905510. Fax: +65
behavior of the pure water droplet cannot be seen in the
67924062.
nanofluid droplets due to the greatly enhanced pinning effect
by nanoparticles. Evaporation is faster in those nanofluid Notes
droplets with a nearly pinned baseline. Furthermore, as the The authors declare no competing financial interest.
graphite nanoparticles have a higher thermal conductivity
compared to water, the high loading of graphite nanoparticles
can enhance heat conduction for phase change and lead to the
■ ACKNOWLEDGMENTS
The authors acknowledge the support of A*Star Public Sector
evaporation enhancement consequently. However, adding Funding (1121202010).
nanoparticles into base fluids leads to a higher fluid viscosity,30
which could inhibit the outward radial flow serving for the
replenishment of the high evaporation loss at the droplet edge.
More particle aggregation at the surface or in the vicinity of the
■ REFERENCES
(1) Zhang, L.; Liu, H.; Zhao, Y.; Sun, X.; Wen, Y.; Guo, Y.; Gao, X.;
contact line can also negatively influence the evaporation. The Di, C. A.; Yu, G.; Liu, Y. Inkjet Printing High-Resolution, Large-Area
Graphene Patterns by Coffee-Ring Lithography. Adv. Mater. 2012, 24,
combination of the reasons determines that the increase of the
436−440.
evaporation rate reduces as the nanoparticle concentration (2) Woolley, A. T.; Kelly, R. T. Deposition and Characterization of
reaches 2.0 g/L. Extended Single-Stranded DNA Molecules on Surfaces. Nano Lett.

■
2001, 1, 345−348.
CONCLUSION (3) Deegan, R.; Bakajin, O.; Dupont, T.; Huber, G.; Nagel, S.;
Witten, T. Capillary Flow as the Cause of Ring Stains from Dried
We provide direct observation and analysis of the effects of the Liquid Drops. Nature 1997, 389, 827−829.
ethanol concentration in the binary fluids and the nanoparticle (4) Xu, J.; Xia, J.; Lin, Z. Evaporation-Induced Self-Assembly of
concentration in water-based droplets on the evaporation Nanoparticles from a Sphere-on-Flat Geometry. Angew. Chem., Int. Ed.
dynamics and the deposition patterns in graphite nanofluid 2007, 46, 1860−1863.
droplets. The nanofluid droplet with a higher ethanol ratio has (5) Bigioni, T. P.; Lin, X. M.; Nguyen, T. T.; Corwin, E. I.; Witten, T.
A.; Jaeger, H. M. Kinetically Driven Self Assembly of Highly Ordered
a higher evaporation rate, and the evaporation rate at the initial
Nanoparticle Monolayers. Nat. Mater. 2006, 5, 265−270.
stage is more rapid than that at the late stage, revealing a (6) Yunker, P. J.; Still, T.; Lohr, M. A.; Yodh, A. G. Suppression of
deviation from a constant evaporation rate. This deviation is the Coffee-Ring Effect by Shape-Dependent Capillary Interactions.
more intensified with a higher ethanol concentration. The Nature 2011, 476, 308−311.
experiments demonstrate that nanoparticles are carried to the (7) Crivoi, A.; Duan, F. Elimination of the Coffee-Ring Effect by
interface and form aggregate at the droplet surface only in Promoting Particle Adsorption and Long-Range Interaction. Langmuir
droplets containing ethanol, revealing a strong fluid circulation 2013, 29, 12067−12074.
(8) Crivoi, A.; Duan, F. Effect of Surfactant on the Drying Patterns of
that is not observed in the water-based droplets. The formed
Graphite Nanofluid Droplets. J. Phys. Chem. B 2013, 117, 5932−5938.
drying pattern is sensitive to the ethanol concentration in the (9) Majumder, M.; Rendall, C. S.; Eukel, J. A.; Wang, J. Y. L.;
graphite−ethanol−water nanofluid droplets. In comparison Behabtu, N.; Pint, C. L.; Liu, T. Y.; Orbaek, A. W.; Mirri, F.; Nam, J.;
with the pure ethanol−water droplet, the graphite particles et al. Overcoming the “Coffee-Stain” Effect by Compositional
enhance the pinning effect and block the contact angle increase Marangoni-Flow-Assisted Drop-Drying. J. Phys. Chem. B 2012, 116,
and contact line shrinkage during the ethanol-dominated fast 6536−6542.
evaporation stage. The nanoparticle pinning effect reinforces a (10) Moffat, J. R.; Sefiane, K.; Shanahan, M. E. Effect of TiO2
high average evaporation rate with a high ethanol ratio in the Nanoparticles on Contact Line Stick−Slip Behavior of Volatile Drops.
J. Phys. Chem. B 2009, 113, 8860−8866.
nanofluid droplets. Moreover, we present an initial baseline (11) Sefiane, K.; Skilling, J.; MacGillivray, J. Contact Line Motion
spreading in the sessile graphite−water droplets. The initial and Dynamic Wetting of Nanofluid Solutions. Adv. Colloid Interface
spreading is intensified first and then attenuated with the Sci. 2008, 138, 101−120.
loading of graphite nanoparticles. In the drying process, the (12) Shanahan, M.; Sefiane, K.; Moffat, J. Dependence of Volatile
droplet with the graphite nanoparticles basically shows a Droplet Lifetime on the Hydrophobicity of the Substrate. Langmuir
stronger pinning effect and an enlarged initial contact angle in 2011, 27, 4572−4577.
comparison with the pure water droplet. The intensified (13) Radiom, M.; Yang, C.; Chan, W. K. Dynamic Contact Angle of
Water-Based Titanium Oxide Nanofluid. Nanoscale Res. Lett. 2013, 8,
evaporation is mainly due to a prolonged pinning stage and
282.
higher thermal conduction for phase change with more (14) Sefiane, K.; Bennacer, R. Nanofluids Droplets Evaporation
nanoparticles. However, the graphite nanoparticles with the Kinetics and Wetting Dynamics on Rough Heated Substrates. Adv.
concentration at 2.0 g/L attenuate the evaporation rate Colloid Interface Sci. 2009, 147−148, 263−271.
increasing trend. Evaporation of a nanofluid droplet is a (15) Vafaei, S.; Borca-Tasciuc, T.; Podowski, M. Z.; Purkayastha, A.;
complex process. The pining and depinning behaviors are Ramanath, G.; Ajayan, P. M. Effect of Nanoparticles on Sessile Droplet
affected by the base fluids and nanoparticles. The complexity Contact Angle. Nanotechnology 2006, 17, 2523−2527.
(16) Vafaei, S.; Wen, D.; Borca-Tasciuc, T. Nanofluid Surface
would pose a challenge for the prediction of droplet
Wettability Through Asymptotic Contact Angle. Langmuir 2011, 27,
evaporation from a simple model,3 and further modeling 2211−2218.
would help to explicate the phenomena. In addition, further (17) Moghiman, M.; Aslani, B. Influence of Nanoparticles on
detailed flow tracking would improve our understanding of the Reducing and Enhancing Evaporation Mass Transfer and Its
role of convection on nanofluid droplet evaporation. Efficiency. Int. J. Heat Mass Transfer 2003, 61, 114−118.

13644 dx.doi.org/10.1021/jp508051y | J. Phys. Chem. B 2014, 118, 13636−13645

The Journal of Physical Chemistry B Article

(18) Christy, J. R. E.; Hamamoto, Y.; Sefiane, K. Flow Transition

within an Evaporating Binary Mixture Sessile Drop. Phys. Rev. Lett.
2011, 106, 205701.
(19) Christy, J. R. E.; Sefiane, K.; Munro, E. A Study of the Velocity
Field during Evaporation of Sessile Water and Water/Ethanol Drops. J.
Bionic. Eng. 2010, 7, 321−328.
(20) Sefiane, K.; Tadrist, L.; Douglas, M. Experimental Study of
Evaporating Water−Ethanol Mixture Sessile Drop: Influence of
Concentration. Int. J. Heat Mass Transfer 2003, 46, 4527−4534.
(21) Cheng, A. K. H.; Soolaman, D. M.; Yu, H. Z. Evaporation of
Microdroplets of Ethanol−Water Mixtures on Gold Surfaces Modified
with Self-Assembled Monolayers. J. Phys. Chem. B 2006, 110, 11267−
11271.
(22) Liu, C.; Bonaccurso, E.; Butt, H. Evaporation of Sessile Water/
Ethanol Drops in a Controlled Environment. Phys. Chem. Chem. Phys.
2008, 10, 7150−7157.
(23) Deegan, R. D. Pattern Formation in Drying Drops. Phys. Rev. E
2000, 61, 475−485.
(24) Duan, F.; Ward, C. A. Investigation of Local Evaporation Flux
and Vapor-Phase Pressure at an Evaporative Droplet Interface.
Langmuir 2009, 25, 7424−7431.
(25) Young, T. An Essay on the Cohesion of Fluids. Philos. Trans. R.
Soc. London 1805, 95, 65−87.
(26) Rilo, E.; Vila, J.; Pico, J.; Garcia-Garabal, S.; Segade, L.; Varela,
L. M.; Cabeza, O. Electrical Conductivity and Viscosity of Aqueous
Binary Mixtures of 1-Alkyl-3-methyl Imidazolium Tetrafluoroborate at
Four Temperatures. J. Chem. Eng. Data 2009, 55, 639.
(27) Wasan, D. T.; Nikolov, A. D. Spreading of Nanofluids on Solids.
Nature 2003, 423, 156−159.
(28) Nikolov, A.; Kondiparty, K.; Wasan, D. Nanoparticle Self-
Structuring in a Nanofluid Film Spreading on a Solid Surface.
Langmuir 2010, 26, 7665−7670.
(29) Crivoi, A.; Duan, F. Amplifying and Attenuating the Coffee-Ring
Effect in Drying Sessile Nanofluid Droplets. Phys. Rev. E 2013, 87,
042303.
(30) Duan, F.; Wong, T.; Crivoi, A. Dynamic Viscosity Measurement
in Non-Newtonian Graphite Nanofluids. Nanoscale Res. Lett. 2012, 7,
360.
(31) Chen, X.; Ma, R.; Li, J.; Hao, C.; Guo, W.; Luk, B. L.; Li, S. C.;
Yao, S.; Wang, Z. Evaporation of Droplets on Superhydrophobic
Surfaces: Surface Roughness and Small Droplet Size Effects. Phys. Rev.
Lett. 2012, 109, 116101.
(32) Blake, T. D.; Coninck, J. D. The Influence of Solid−Liquid
Interactions on Dynamic Wetting. Adv. Colloid Interface Sci. 2002, 96,
21−36.

13645 dx.doi.org/10.1021/jp508051y | J. Phys. Chem. B 2014, 118, 13636−13645