International Journal of Heat and Mass Transfer 55 (2012) 2151–2159

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International Journal of Heat and Mass Transfer

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

Water droplet evaporation on Cu-based hydrophobic surfaces with nano-

and micro-structures
Chi Young Lee a,b,⇑, Bong June Zhang b, Jiyeon Park b, Kwang J. Kim b
a
KAERI (Korea Atomic Energy Research Institute), 989-111 Daedeok-daero, Yuseong-gu, Daejeon 305-353, Republic of Korea
b
Low Carbon Green Technology Laboratory, Department of Mechanical Engineering, University of Nevada-Reno, Reno, NV 89557, USA

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

Article history: The characteristics of water droplet evaporation on three different hydrophobic surfaces, PCu (Plain Cop-
Received 28 January 2011 per, h = 115°), MSCu (Micro-Structured Copper, h = 126°) and NSCuO (Nano-Structured Copper Oxide,
Received in revised form 30 November 2011 h = 159°) with coating of the same SAM (Self-Assembled Monolayer) material, were experimentally inves-
Accepted 30 November 2011
tigated. For industrial heat transfer applications, copper material was used as the substrate, and the simple
Available online 11 January 2012
and cost-effective fabrication technique to prepare the superhydrophobic surface, NSCuO, was introduced.
Based on the observations, the behavior of droplet evaporation was divided into three stages: Stage I
Keywords:
(constant contact area stage), Stage II (constant contact angle stage) and Stage III (mixed stage). When
Droplet evaporation
Surface structure
studying the PCu surface, the Stages I, II, and III were observed, consistent with previous reports. For the
(Super)hydrophobic surface MSCu surface, Stages I and III appeared without Stage II, and the pinning period of contact line was the
longest among the test samples due to the formation of Wenzel state droplet. In the case of the superhy-
drophobic NSCuO surface, only Stage III occurred, and the contact line moved freely during the entire
evaporation time because of the formation of Cassie state droplet. The total evaporation time of the NSCuO
was the longest out of all the samples tested. At the last stage of evaporation, the edge of the droplet shrank
at a much faster rate in all surfaces. On the other hand, the shrinking velocity of the droplet height drasti-
cally increased only on the NSCuO, which was considered as the unique behavior of superhydrophobic
surface. In this experiment, it was found that the surface structure determines the motion of the contact
line on the surface, which, in turn, strongly influences the characteristics of the droplet evaporation.
Ó 2011 Elsevier Ltd. All rights reserved.

1. Introduction
The natural evaporation of a droplet on various surfaces is a
fundamental problem and has been studied intensively for a wide
range of industrial and biological applications; e.g., inkjet printing,
spray painting, DNA chip fabrication, and cell patterning. In gen-
eral, the surface wettability is divided into two groups: the hydro-
philic surface which is the surface with a water contact angle below
90°, and the hydrophobic surface when the contact angle is above
90°. The characteristics of droplet evaporation on a hydrophobic
surface are more complicated than those on a hydrophilic surface.
Picknett and Bexon [1] reported that droplet evaporation on the
hydrophobic surface occurs in three distinct stages as shown in
Fig. 1. The first stage is the ‘‘constant contact area stage,’’ also
known as the pinned contact line stage (Stage I). As the droplet
evaporates, the contact angle decreases, while the contact area
radius remains constant. The second stage is the ‘‘constant contact
⇑ Corresponding author at: KAERI (Korea Atomic Energy Research Institute), 989-
111 Daedeok-daero, Yuseong-gu, Daejeon 305-353, Republic of Korea. Tel.: +82 42
868 4587; fax: +82 42 8630565.
E-mail address: chiyounglee@kaeri.re.kr (C.Y. Lee).
angle stage’’ also known as the moving contact line stage. As op-
posed to Stage I, the contact area radius recedes in Stage II and
the contact angle remains constant. The third stage is the ‘‘mixed
stage’’ (Stage III), an unpinned contact line stage where both the
contact angle and contact area radius decrease. Birdi and Vu [2]
and Birdi et al. [3] investigated the evaporation behavior of water
and n-octane droplets on smooth glass and Teflon surfaces. Both
studies reported that the evaporation of a water droplet on a glass
surface and n-octane on a Teflon surface were stationary processes
each with a constant contact radius and linear evaporation rates.
However, when the contact angle was over 90°, a constant contact
angle with a decreasing contact radius and a non-linear evapora-
tion rate was observed. None of these studies [1–3] considered
the effect of the surface morphology on the behavior of droplet
evaporation, and mentioned the behavior of droplet evaporation
on a superhydrophobic surface.
Recently, studies on superhydrophobic surfaces, which exhibit a
water contact angle larger than 150° [4], have been extensively
performed. A superhydrophobic surface is notable as it has the fea-
tures of water repellency and low surface energy. These two attri-
butes have vast potential in various industrial applications such as
anti-sticking, self-cleaning, anti-fouling, anti-corrosion, friction

0017-9310/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijheatmasstransfer.2011.12.019
2152 C.Y. Lee et al. / International Journal of Heat and Mass Transfer 55 (2012) 2151–2159

Nomenclature

A surface area [m2] Subscripts

Bo Bond number [–] A apparent contact angle
F force per unit length [N/m] a advancing contact angle
f fractional flat geometrical area [–] D dynamic contact angle
g gravitational acceleration constant [m/s2] E equilibrium (intrinsic) contact angle
H Height of structure [m] e total evaporation time
h droplet height [m] f roughness factor
Dh droplet height change [m] g gas
P pressure [Pa] h height
DP pressure difference [Pa] i initial
R roughness factor [–] l liquid
r contact area radius [m] lg liquid–gas
Dr contact area radius change [m] p projected surface area
s spacing between structures [m] r radius
t time [s] sg solid–gas
Dt time difference [s] sl solid–liquid
V shrinking velocity [m/s] t total (rough) surface area
UY unbalanced Young force
Greek letters
a a half of nano-structure cone angle [°] Superscript
⁄
h contact angle [°] normalized
Dq density difference [kg/m3]
r interfacial tension [N/m]

reduction, and heat transfer enhancement [5–9]. Additionally,
researchers [10–14] have investigated the droplet evaporation on
the (super)hydrophobic surfaces with structures. Shin et al. [10]
examined the evaporation characteristics of a water droplet on
hydrophilic, hydrophobic, and superhydrophobic surfaces. They
used glass (h = 58.64°), OTS (octadecyltricholorosilane,
h = 122.52°), and AKD (alkylketene dimmer, h = 160.59°) surfaces
as test samples. On the hydrophilic surface, the contact angle, cen-
ter-height and volume of droplet decreased linearly over the entire
evaporation time. The long pinning time – which is defined as the
total time that the contact area radius remains fixed during the
evaporation – was distinct and predictable. As a droplet evaporated
on the hydrophobic surface, typically three distinct stages (see
Fig. 1) were observed, but there was no pinning period for an evap-
orating droplet on the superhydrophobic surface. This study con-
cluded that as the hydrophobicity of a surface became stronger,
the pinning time became shorter and the total evaporation time
lasted longer. In a later study, Shin et al. [11] examined the evap-
oration of a sessile water droplet using non-patterned PDMS (poly-
dimethylsiloxane) and submicron sized post array silicon surfaces,
each with the same hydrophobic contact angle. On the non-pat-
terned PDMS surface, the contact angle showed the three noted,
distinct stages during evaporation (see Fig. 1). On the patterned sil-
icon post array surface, however, the contact angle decreased line-
arly while the contact area remained constant until the droplet
completely evaporated. Zhang et al. [12] investigated the droplet
evaporation on superhydrophobic lotus leaf and on biomimetic
polymer surfaces. Both hierarchically structured surfaces appeared
to maintain almost a constant contact radius stage during the
evaporation. Choi and Kim [13] studied on the evaporative process
of sessile droplets on superhydrophobic surfaces of the sharp-tip
post structures with three kinds of heights (i.e., 100, 300 and
500 nm) and a given constant pitch of 230 nm. A pure water
and a protein solution were used for testing. They concluded that
the superhydrophobicity of surface and the behavior of droplet
evaporation are strongly influenced by the three-dimensional
nano-structured morphology and the surface fouling such as pro-
tein adsorption. McHale et al. [14] reported the water droplet
evaporation process on the superhydrophobic SU-8 patterned
polymer surfaces. Based on the diffusion model of water vapor into
the surrounding atmosphere, they performed the quantitative
analysis of initial pinned contact line phase of evaporation, and
estimated the diffusion coefficient and the concentration differ-
ence. Currently, for the fabrication of well-ordered nano-structure,
the silicon substrate and MEMS technique are widely used
[4,7,8,11,13,14], but they are expensive. For industrial applications,
the fabrication technique of a nano-structure should be convenient
and cost-effective, and should have the ability to be applied to
large surface areas of a conventional metal substrate (e.g., copper).
Our group has tried to apply the nano-structured surfaces we

Fig. 1. Typical droplet evaporation stages on smooth hydrophobic surface: (a) Constant contact area (Stage I), (b) constant contact angle (Stage II) and (c) mixed (Stage III)
stages.
 C.Y. Lee et al. / International Journal of Heat and Mass Transfer 55 (2012) 2151–2159
introduced for heat transfer applications such as the nucleate boil-
ing heat transfer, and achieved some successful and meaningful re-
sults [15,16]. Meanwhile, in order to understand how the liquid
droplet evaporation can be influenced by the surface material
(chemical heterogeneity) and surface structure (roughness), both
effects need to be separately examined. It is believed that a com-
parative study of droplet evaporation between the plain and vari-
ous structured surfaces under the similar conditions (e.g., contact
angle and surface material) is one effective way to understand
the interaction of the surface structure on droplet evaporation.
The objective of this study is to experimentally investigate the
effect of a surface structure on the evaporation characteristics of a
water droplet using plain, micro-, and nano-structured hydrophobic
surfaces. Copper, a popular metal substrate in industrial heat trans-
fer applications, is used as the test sample. For a superhydrophobic
surface (Nano-Structured Copper Oxide: NSCuO), a convenient and
cost-effective technique that creates a well-ordered nano-structure
on a large surface area is introduced. In order to examine the effect
of the surface structure on droplet evaporation, (i) the same hydro-
phobic SAM (Self-Assembled Monolayer) coating is applied on all
the sample surfaces, removing the effect of a surface material
(chemical heterogeneity) during evaporation; and (ii) the plain
and structured surfaces with a similar contact angle are prepared.
The characteristics of an evaporating droplet (i.e., contact angle,
contact area radius, droplet height, shrinking velocities of droplet
height and contact radius) are measured on each surface and are re-
ported on utilizing the droplet imaging measurement technique.
Based on the experimental results and the analysis of the surface
structures, the relationship between the droplet evaporation and
the surface structure is able to be reviewed and discussed in detail.
2. Experiment
2.1. Preparation of test samples
The following three test specimens were prepared: PCu, indicat-
ing a Plain (non-structured) Copper surface; MSCu, a Micro-Struc-
tured Copper surface ground by power tool; and, NSCuO, Nano-
Structured Copper Oxide surface, whose fabrication procedure is
described presently.
For NSCuO, the initial surface treatment of the copper foil, ob-
tained from Alfa Aesar (99.98%, thickness 500 lm), power tool
grinding (Grit-120) is used. A specimen, then, is cleaned in acid
(HCl:HNO3 = 1:1 by volume) to remove organic residues. The spec-
imen is placed under ultra-sonication for 10 min and thoroughly
rinsed with DI water several times. Next, the specimen is cleaned
in acetone for 10 min under ultra-sonication. Subsequently, the
specimen is immersed in NH4OH solution (0.05 M) for a day at
55 °C. The self-assembled copper oxide black coating is then homo-
geneously applied to the surface. Thorough DI water rinsing is car-
ried out several times. The specimen is dried in the oven at 90 °C. In
order to remove the chemical heterogeneity on the surface and
achieve the hydrophobicity, all the samples are coated by SAM in
a process of immersion in 1.1 mM dodecanethiol for 1 h. By devel-
oping these surfaces and coating the samples, only surface struc-
tures influence the behavior of droplet evaporation.
The initial contact angles of all samples and the FESEM (Field
Emission Scanning Electron Microscopy) images of the MSCu and
NSCuO surfaces are shown in Figs. 2 and 3, respectively. The PCu
and MSCu had the initial contact angles of 115° and 126°, respec-
tively. Both are hydrophobic surfaces that have similar initial con-
tact angles (the contact angle difference is approximately 11°). It
should be noted that NSCuO has the well-ordered nano-structure
(see Fig. 3(b)) and becomes a superhydrophobic surface with the
initial contact angle of 159°.
2153
2.2. Experimental set-up and details
Using a syringe, a pre-measured de-ionized water sessile drop-
let was placed on test specimens. All droplets were of equal weight.
Contact angles that changed due to natural evaporation were mea-
sured using a CAM-100 (KSV Instruments Ltd., Finland as shown in
Fig. 4). The temperature and relative humidity of the environment
were maintained at 23.5 °C and 18%.
In order to determine if the shape of a sessile droplet on test
surfaces has a spherical cap, the Bond number, which is a dimen-
sionless number defined as the ratio of gravitational force to sur-
face tension force, is calculated using Eq. (1).
Dqrgh
Bo ¼ ð1Þ
rlg
Here, Dq is the density difference between air and water, g is the
gravitational acceleration constant, r is the contact line radius, h is
the droplet height, and rlg is the water surface tension [17]. The
Bond numbers calculated in the present experiments are in a range
of 0.011–0.38 for PCu, 0.024–0.36 for MSCu, and 0.005–0.33 for
NSCuO. As all Bond numbers are much less than unity, the surface
tension force dominates the gravitational force.
During evaporation, the images of a droplet are recorded every
1 min on a computer system. From the recorded images of the
water droplet on the surfaces (as shown in Fig. 5), the contact angle
(h), droplet height (h) and contact area radius (r) are measured
using an image processing technique.
3. Results and discussion
3.1. General trends of water droplet evaporation on PCu, MSCu, and
NSCuO
In Figs. 6 and 7, the images and contours of a droplet evaporated
on PCu, MSCu, and NSCuO surfaces are shown, respectively. In
Fig. 7, the numbers on contours indicate time in second.
The changes in the contact angle, the contact area radius and
the droplet height measured on PCu, MSCu, and NSCuO surfaces
during the water droplet evaporation are shown in Fig. 8(a)–(c),
respectively.
Fig. 9(a)–(c) show the trends of normalized contact angle, con-
tact area radius and droplet height with normalized evaporation
time, respectively. The normalized parameters are defined in Eq.
(2).
hðtÞ rðtÞ hðtÞ t

h ¼ ; r ¼ ; h ¼ ; t ¼ ð2Þ
hi ri hi te
where h, r, h and t are contact angle, contact area radius, droplet
height and time, respectively. Subscripts of i and e indicate initial
value and total evaporation, respectively. A superscript of ⁄ signifies
a normalized value.
The initial contact angle of PCu is 115°. As shown in Fig. 8, until
1250 s, the contact angle steadily decreases to approximately 75°.
At this angle, the radius of the area between the water droplet and
the surface is almost the same as the initial value of 1.44 mm with
only a decrease in the droplet height. In this region, the change in
contact angle is about 40°. Although the droplet height continues
to decrease, the constant contact angle of approximately 75° is
maintained for about 1000 s. In this region, the contact area radius
does being to decrease. After 2250 s, the contact angle, the contact
area radius, and the droplet height all decrease. The total evapora-
tion time of PCu is 2541 s.
The present experimental data of PCu is in agreement with the
trend of previous research [1,10,11]: the behavior of droplet evap-
oration for 0–1250 s, 1250–2250 s and 2250–2541 s indicate the
2154 C.Y. Lee et al. / International Journal of Heat and Mass Transfer 55 (2012) 2151–2159

Fig. 2. Contact angle measurement of test specimens: (a) PCu, (b) MSCu and (c) NSCuO.

Fig. 3. FESEM image of test specimens: (a) MSCu and (b) NSCuO.

Fig. 4. CAM-100 contact angle measurement equipment. Fig. 5. Recorded image of water droplet on surface.

constant contact area, constant contact angle, and mixed stages,
respectively. Based on Fig. 9, approximately 50%, 40% and 10% in
total evaporation time occur in Stage I, II, and III, respectively.
In the MSCu study, the contact angle steadily decreases during
the entire evaporation time without having a region of a constant
contact angle (i.e., Stage II), as shown in Fig. 8(a). The contact area
radius remains constant until 2000 s (see in Fig. 8(b)); this behav-
ior corresponds to Stage I, and the change in contact angle is about
80°. Then, both the contact angle and the contact area radius de-
crease (i.e., Stage III). The droplet height decreases over the whole
evaporation period. Total evaporation time is 2388 s. As shown in
Fig. 9(a) and (b), the portions of Stage I and III are approximately
80% and 20% of the evaporation time. In other words, when the
water droplet on MSCu evaporates, the contact line – a perimeter
contacted between air, water droplet, and substrate – is pinned
over 80% of the time.
Although the initial contact angle of MSCu (126°) was similar to
that of PCu (115°), the detailed behavior of droplet evaporation on
both of MSCu and PCu surfaces differs greatly.
(i) Stage II, the constant contact angle stage, where the contact
area radius recedes and the contact angle remains constant,
does not occur in MSCu. Birdi and co-workers [2,3] reported
that the constant contact area stage for h < 90° and the con-
 C.Y. Lee et al. / International Journal of Heat and Mass Transfer 55 (2012) 2151–2159 2155

Fig. 7. Contours of droplet evaporated on (a) PCu, (b) MSCu, and (c) NSCuO.

ever, Stage II is observed on PCu, consistent with previous

(ii) Stage I of MSCu lasts longer than that of PCu. Shin et al. [10]
Fig. 6. Images of droplet evaporated on (a) PCu, (b) MSCu, and (c) NSCuO.
stant contact angle stage for h > 90° can dominate during the
process. Based on the present observations of MSCu, the con-
tact angle is 126° (>90°), and Stage II does not appear. How-
reports, implying that the surface structure is more impor-
tant than the initial contact angle when determining the
droplet evaporation process.
reported that, as the hydrophobicity of the surfaces became
stronger (as the contact angle became larger), the pinning
time became shorter. In this experiment, the MSCu has a
similar (or slightly larger) contact angle compared to PCu,
but the MSCu stays at Stage I much longer. Our belief is that
this difference is due to the effect of the surface structure on
droplet evaporation.
2156 C.Y. Lee et al. / International Journal of Heat and Mass Transfer 55 (2012) 2151–2159

(a) 180 (a) 1.2

150 1.0

Normalized Contact Angle

Contact Angle (deg.)

120 0.8

90 0.6

60 0.4

NSCuO NSCuO
30 0.2
MSCu MSCu
PCu PCu
0 0.0
0 500 1000 1500 2000 2500 3000 3500 0.0 0.2 0.4 0.6 0.8 1.0 1.2
Time (sec) Normalized Time

(b) 2.0 (b) 1.2

NSCuO
MSCu 1.0

Normalized Contact Area Radius

PCu
Contact Area Radius (mm)

1.5
0.8

1.0 0.6

0.4
0.5
NSCuO
0.2
MSCu
PCu
0.0 0.0
0 500 1000 1500 2000 2500 3000 3500 0.0 0.2 0.4 0.6 0.8 1.0 1.2
Time (sec) Normalized Time

(c) 3.0 (c) 1.2

NSCuO NSCuO
2.5 MSCu 1.0 MSCu
PCu PCu
Normalized Droplet Height
Droplet Height (mm)

2.0 0.8

1.5 0.6

1.0 0.4

0.5 0.2

0.0 0.0
0 500 1000 1500 2000 2500 3000 3500 0.0 0.2 0.4 0.6 0.8 1.0 1.2
Time (sec) Normalized Time

Fig. 8. Changes in (a) contact angle, (b) contact area radius and (c) droplet height. Fig. 9. Normalized time vs. (a) normalized contact angle, (b) normalized contact
area radius and (c) normalized droplet height.

The droplet evaporation behaviors of the superhydrophobic
NSCuO are vastly different from those of the PCu and MSCu. The
contact angle of the NSCuO gradually reduces due to evaporation
with a decreasing contact area radius and droplet height until
3250 s. Then, the contact angle, the contact area radius, and the
droplet height all decrease dramatically. The droplet completely
evaporates at 3450 s, which is the longest period of evaporation
time among the samples tested in the present study. The slow
evaporation is because the droplet maintains its spherical shape
during the entire evaporation period. The spherical shape of the
water droplet can prevent the thin liquid film near the edge of
droplet from being formed, which leads to a suppression of the
evaporation [10]. In the evaporation process of NSCuO, only Stage
III is observed and can be further divided into two sub-stages: Slow
and Fast. Until 3250 s (about 95% of total evaporation time), the
contact angle and contact area radius slowly and steadily decrease
(referred to as Slow Stage III), then, both the angle and the radius
drastically shrink (Fast Stage III). The contact line on NSCuO is
 C.Y. Lee et al. / International Journal of Heat and Mass Transfer 55 (2012) 2151–2159 2157

(a) 0.012 surface structures. In the following section, this will be discussed
in detail.
NSCuO
0.010 MSCu
Radius Shrinking Velocity (mm/s)

PCu 3.2. Effect of surface structure on water droplet evaporation

0.008
In PCu, the Stages I, II, and III are observed, and the contact line
is pinned during 50% of the total evaporation time. In MSCu, the
0.006
Stages I and III occur, and the contact line is pinned during 80%
of the total evaporation time. In NSCuO, only Stage III appears,
0.004 and the contact line moves freely during the whole evaporation
time. Observing the results, it can be determined that the behavior
0.002 of droplet evaporation is closely related to the motion of the con-
tact line, which, in turn, is influenced by the surface structure.
0.000 When a droplet is placed on the surface, the equilibrium contact
angle is determined by Young’s equation, Eq. (4), which is derived
-0.002 from the force balance acting on the contact line, as shown in
0.0 0.2 0.4 0.6 0.8 1.0 1.2 Fig. 11.
Normalized Time ðrsg  rsl Þ
coshE ¼ ð4Þ
rlg
(b) 0.012
NSCuO Here, rsg, rsl and rlg are interfacial tensions of solid–gas, solid–li-
0.010 MSCu quid, and liquid–gas, respectively. At the initial moment of wetting,
Height Shrinking Velocity (mm/s)

PCu the droplet appears to be at or near the equilibrium contact angle.

0.008 As the droplet begins to evaporate, the droplet height and contact
angle decrease. Therefore, it is no longer the initial equilibrium con-
0.006 dition and the unbalanced Young force can be expressed as below.
F UY ¼ rlg ðcoshD  coshE Þ ð5Þ
0.004
where, hD is the dynamic contact angle by evaporation. According to
Eq. (5), the contact line tends to recede, and the unbalanced Young
0.002
force makes the contact line pinned or de-pinned. An opposing fric-
tional force between the liquid and the solid surface, which leads to
0.000
the pinning of the contact line, is induced by the surface roughness,
and chemical heterogeneities of the solid surface. Whether the con-
-0.002
0.0 0.2 0.4 0.6 0.8 1.0 1.2
tact line is pinning or de-pinning is determined by the competition
between the unbalanced Young force and frictional forces. When
Normalized Time
the unbalanced Young force overcomes the frictional force, the con-
Fig. 10. Normalized time vs. shrinking velocities of (a) radius and (b) height of tact line can be de-pinned [18].
droplet. In general, when a water droplet resides on a rough surface, (i)
the liquid can completely wet the cavities of rough surface or (ii)
the liquid cannot penetrate into the cavities.
not pinned over the entire evaporation time. This trend may be If the droplet wets the surface structure (without an air-pocket
considered as a unique behavior of the superhydrophobic surface. inside the cavity), its apparent contact angle is given by Wenzel’s
In Fig. 10, the shrinking velocities of contact area radius (Vr) and model [19]. Wenzel [19] proposed the relationship between the
height (Vh) of droplet on PCu, MSCu and NSCuO are shown. Vr and apparent (hA) and the intrinsic (hE) contact angles through the
Vh are defined as Eq. (3) modification of Young’s equation to utilize a roughness factor (Rf)
that is defined as a ratio of projection and total surface areas, as
Dr Dh
Vr ¼ ; Vh ¼ ð3Þ follows.
Dt Dt  
The shrinking radius velocities of all the samples are drastically
At rsg  rsl
cos hA ¼ ¼ Rf cos hE ð6Þ
increased at the last stage of droplet evaporation as shown in
Ap rlg
Fig. 10(a). Based on the measurements, the edge of droplets shrink
very fast for the last 10% period of the total evaporation time. How-
ever, the trend of the shrinking droplet height velocity seems to
vary from that of the shrinking radius velocity. At the last evapora-
tion stage, the shrinking velocity of the droplet height in NSCuO
rises more sharply than that of PCu and MSCu, as shown in
Fig. 10(b). This difference is due to the droplet on NSCuO maintain-
ing a spherical shape during the entire evaporation time. This
spherical formation is owing to the low surface energy and the free
moving contact line on the superhydrophobic surface, which is dif-
ferent from that on PCu and MSCu (see Figs. 6 and 7). This peculiar
behavior of water droplet evaporation on the superhydrophobic
surface is unique.
Based on the present observations, the evaporation characteris-
tics of a water droplet on a surface are significantly influenced by Fig. 11. Force balance at contact line during the evaporation [18].
2158 C.Y. Lee et al. / International Journal of Heat and Mass Transfer 55 (2012) 2151–2159
where, At and Ap are the total surface and projection areas, respec-
tively, and, therefore, the value of Rf is greater than unity. Wenzel’s
equation in Eq. (6) implies that the free energy of the liquid–solid
interface on the rough surface is Rf times larger than that on the
perfectly smooth surface. The Wenzel’s model of Eq. (6) predicts
that, if the intrinsic contact angle is larger than 90°, the apparent
contact angle increases with an increase in the roughness factor.
If the intrinsic contact angle is less than 90°, the roughness factor
leads to a decrease in the apparent contact angle.
On the other hand, the droplet can sit on the peaks of the sur-
face roughness (with an air-pocket inside the cavity). In this case,
a liquid–solid–gas interface is formed, and Wenzel’s model [19]
can be modified by considering the fractional areas of wetted
and non-wetted surfaces. The apparent contact angle is given by
Cassie and Baxter’s model [20].
cos hA ¼ Rf  flg ðRf cos hE þ 1Þ
Here, flg is the fractional flat geometrical area of the liquid–gas
interface under the droplet.
Two different droplet states, Wenzel and Cassie, can be deter-
mined by the surface structures and may be related to the detailed
behavior of the droplet evaporation. Therefore, it is worthwhile to
evaluate the droplet state formed on the each structured surface
we used.
Choi et al. [8] proposed the criteria of structure spacing (s) and
height (H) for liquid meniscus to withstand the pressure of liquid
using a simple geometrical calculation and the Laplace–Young
equation, as follows:
pffiffiffi j cosðha  aÞj
s < 2 2rlg
DP
1  sinðha  aÞ
H > pffiffiffi s ð9Þ
2j cosðha  aÞj
The idealized surface structure in Fig. 12 is different from that in the
present surface structure, but Eqs. (8) and (9) may be a good indica-
tor when evaluating the spacing and height of structure for Cassie
drop. In order to estimate the drop states on the present structured
surfaces, the spacing and height of the structure were calculated at
the following condition [8]: rsl = 0.0727 N/m, ha  a = 120° and DP
(=Pl  Pg) = 1 atm. It is figured that the spacing between the struc-
tures is less than 1.0 lm, and the height of structures is larger than
0.2 lm. Based on Fig. 3(b), the NSCuO structure is satisfied with the
s < 1.0 lm and H > 0.2 lm proposed by Eqs. (8) and (9). However,
the MSCu structure does not seem to meet the criteria. The struc-
ture spacing in y-direction is above about tens of lm, and the inter-
face curvature of x-direction in Fig. 3(a) between liquid and gas is
Fig. 12. Gas–liquid interface on an idealized structured hydrophobic surface.
likely too large to be maintained. In this case, the liquid may touch
the bottom surface of the cavity, and the surface structures may
then be flooded. From these findings, we conclude that Cassie and
Wenzel state droplets are formed on the NSCuO and MSCu,
respectively.
Two different states of a droplet on the structured surface, the
Wenzel and the Cassie, can affect the behavior of the evaporation.
The stages of droplet evaporation are closely related to whether
the contact line is pinned or not. The motion of the contact line de-
pends on the droplet states on the structured surface and the dif-
ferent frictional forces of both drop states. In the droplet of
Cassie state on a superhydrophobic nano-structured surface, a slip
of liquid can occur due to the air trapped between the nano-struc-
tures [8]. In this case, the frictional force becomes smaller due to
the small shear stress and the small contact area on the surface
when compared to the droplet in Wenzel state. Moreover, in the
ð7Þ Wenzel droplet state, the surface structure may play a role as the
defect and severely prevents the contact line from moving. Conse-
quently, Cassie state droplet on the nano-structured surface ap-
pears to have a smaller contact angle hysteresis and a weaker
pinning of the contact line. In the NSCuO, which exhibits only Stage
III, the contact line is observed to move freely, and the shrinking
velocity of droplet height drastically increases at the last stage of
evaporation due to the formation of Cassie droplet state. The
MSCuO has the longest period of Stage I, where the contact line
is pinned in test samples due to the formation of the Wenzel drop-
let state.
In summary, the surface morphology has a great influence on
the behavior of droplet evaporation. The surface structure deter-
mines the state of the droplet placed on the surface, and this affects
ð8Þ
the motion of the contact line. The behavior of the contact line (i.e.,
whether it is pinned or de-pinned) results in a change of the details
in droplet evaporation, for example, a change of the contact angle,
contact area radius, droplet height, shrinking velocities of droplet
radius and height.
4. Conclusion
In the present experimental study, the characteristics of droplet
evaporation on three kinds of hydrophobic surfaces were investi-
gated utilizing PCu, MSCu and NSCuO surfaces, all coated by the
same hydrophobic SAM material.
In the PCu experiment, Stages I, II, and III were observed, which
was consistent with previous reports. In the MSCu experiment,
Stages I and III were observed without Stage II – in spite of a similar
contact angle to the PCu experiment. The pinning period of the
contact line was longest (80% of total evaporation time) in the
MSCu test sample. This was due to the Wenzel state droplet that
was formed on the MSCu surface which prevents the contact line
from moving due to the large frictional force. In the NSCuO exper-
iment, only Stage III occurred. During the total evaporation time,
the contact line was able to move freely due to the sliding effect
of the contact line caused by the formation of the Cassie state drop-
let. The total evaporation of NSCuO lasted the longest out of the
three tested surfaces. While the shrinking velocity of the contact
area radius drastically increased for all surfaces at the last evapo-
ration stage, the droplet height shrunk sharply for only the NSCuO
surface, which was considered as one of the unique evaporation
behaviors of the superhydrophobic surface. These findings are pre-
sumed to be caused by the droplet on such a surface maintaining
its spherical shape.
In this study, the superhydrophobic surface can be fabricated
utilizing simple and cost-effective techniques to create well-con-
trolled nano-structures on a large surface area. It is found that
the surface structure is a more important factor than the initial
 C.Y. Lee et al. / International Journal of Heat and Mass Transfer 55 (2012) 2151–2159
contact angle when determining the characteristics of droplet
evaporation. This study implies that the modification of surface
structure is one of ways to control the evaporation rate in the heat
transfer application.
Acknowledgements
This material is based upon work partially supported by the Na-
tional Science Foundation under Grant No. (#0923869) via a STTR
Phase II program of Advanced Materials and Devices Inc. (AMAD),
Reno, NV (subcontracted to the University of Nevada, Reno; PI:
KJK). Special thanks go to Dr. Y. Liu of AMAD. Also, Nano-Struc-
tured Copper Oxide structures were developed under a DOE Grant
DE-EE0003231 to the University of Nevada, Reno (PI: KJK).
References
[1] R.G. Picknett, R. Bexon, The evaporation of sessile or pendant drops in still air, J.
Colloid Interface Sci. 61 (2) (1976) 336–350.
[2] K.S. Birdi, D.T. Vu, Wettability and the evaporation rates of fluids from solid
surface, J. Adhesion Sci. Technol. 7 (6) (1993) 485–493.
[3] K.S. Birdi, D.T. Vu, A. Winter, A study of the evaporation rates of small water
drops placed on a solid surface, J. Phys. Chem. 93 (9) (1989) 3702–3703.
[4] B. Bhushan, Y.C. Jung, Wetting study of patterned surfaces for
superhydrophobicity, Ultramicroscopy 107 (10–11) (2007) 1033–1041.
[5] H. Zhang, R. Lamb, J. Lewis, Engineering nanoscale roughness on hydrophobic
surface-preliminary assessment of fouling behaviour, Sci. Technol. Adv. Mater.
6 (3–4) (2005) 236–239.
[6] G.R.J. Artus, S. Jung, J. Zimmermann, H.P. Gautschi, K. Marquardt, S. Seeger,
Silicone nanofilaments and their application as superhydrophobic coatings,
Adv. Mater. 18 (20) (2006) 2758–2762.
2159
[7] David Qúeŕe, Non-sticking drops, Rep. Prog. Phys. 68 (11) (2005) 2495–2532.
[8] C.H. Choi, C.J. Kim, Large slip of aqueous liquid flow over a nanoengineered
superhydrophobic surface, Phys. Rev. Lett. 96 (2006) 066001.
[9] J.B. Boreyko, C.H. Chen, Self-propelled dropwise condensate on
superhydrophobic surfaces, Phys. Rev. Lett. 103 (2009) 184501.
[10] D.H. Shin, S.H. Lee, J.Y. Jung, J.Y. Yoo, Evaporating characteristics of sessile
droplet on hydrophobic and hydrophilic surfaces, Microelectron. Eng. 86 (4–6)
(2009) 1350–1353.
[11] D.H. Shin, S.H. Lee, C.K. Choi, S. Retterer, Evaporation and wetting dynamics of
sessile water droplets on submicron-scale patterned silicon hydrophobic
surfaces, J. Micromech. Microeng. 20 (5) (2010) 055021.
[12] X.Y. Zhang, S.X. Tan, N. Zhao, X.L. Guo, X.L. Zhang, Y.J. Zhang, J. Xu, Evaporation
of sessile water–droplet on natural lotus and biomimetic polymer surface with
superhydrophobicity, Chem. Phys. Chem. 7 (2006) 2067–2070.
[13] C.H. Choi, C.J. Kim, Droplet evaporation of pure water and protein solution on
nanostructured superhydrophobic surfaces of varying heights, Langmuir 25
(2009) 7561–7567.
[14] G. McHale, S. Aqil, N.J. Shirtcliffe, M.I. Newton, H.Y. Erbil, Analysis of droplet
evaporation on a superhydrophobic surface, Langmuir 21 (2005) 11053–
11060.
[15] C.Y. Lee, M.M.H. Bhuiya, K.J. Kim, Pool boiling heat transfer with nano-porous
surface, Int. J. Heat Mass Transfer 53 (19–20) (2010) 4274–4279.
[16] C.Y. Lee, B.J. Zhang, K.J. Kim, Morphological change of plain and nano-porous
surfaces during pool boiling and its effect on nucleate boiling heat transfer,
Exp. Therm. Fluid Sci. (Under review).
[17] H. Hu, R.G. Larson, Evaporation of a sessile droplet on a substrate, J. Phys.
Chem. B 106 (2002) 1334–1344.
[18] L. Shi, P. Shen, D. Zhang, Q. Lin, Q. Jiang, Wetting and evaporation behaviors of
water–ethanol sessile drops on PTFE surfaces, Surf. Interface Anal. 41 (2009)
951–955.
[19] R.N. Wenzel, Surface roughness and contact angle (letter), J. Phys. Coll. Chem.
53 (9) (1949) 1466.
[20] A. Cassie, S. Baxter, Wettability of porous surfaces, Trans. Faraday Soc. 40
(1944) 546–551.