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Droplet Evaporation Dynamics on Hydrophobic Network Surfaces

Minghao He, Yinchuang Yang, Mei Mei, and Huihe Qiu*
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sı Supporting Information

ABSTRACT: Surface modification, such as hydrophobic network modification,

is very promising technology to control droplet dynamics, heat transfer, and
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evaporation. However, fundamental mechanisms of how these chemically

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patterned surfaces affect the droplet evaporation dynamics and predictions of

evaporation rates are still lacking. In the present work, we systematically
investigated the full process of droplet evaporation dynamics on hydrophobic
network surfaces and distinguished four different stages: constant contact line
(CCL) stage, constant contact angle (CCA) stage, pattern-pinning (PP) stage,
and moving contact line (MCL) stage. We further developed a general model
considering the pinning and depinning forces to accurately predict the
evaporation transition from PP to MCL stages (i.e., critical receding contact
angle, θcr). As for the influence of the chemically patterned surface on the evaporation rate, a corrected contact line length was
considered and combined with the well-known Rowan and Erbil’s models. Finally, a general model was thus proposed and showed
successful predictions for the evaporation durations of each stage.

1. INTRODUCTION critical receding contact angle θcr then switching to the CCA
Evaporation of a droplet on a surface is a fundamental mode. The “stick-slide” process could repeat for several cycles
phenomenon and crucially important for numerous applica- until the drop disappeared. Additionally, the droplet
tions ranging from the macroscale to nanoscale: thermal evaporation evolutions on homogeneous substrates were also
management, spray cooling, inkjet printing, and DNA chips, theoretically studied by researchers. Rowan et al.24 introduced
an evaporation model for droplets under CCL mode. Later, by
etc.1−5 For over a century, researchers have developed many
incorporating a modification for a decrease effect of
theoretical models, simulations, and experimental studies6−13
evaporation, which results from the homogeneous surface
to describe the evaporation behavior, e.g., the evolution of
beneath the droplet, Erbil et al.25 introduced the CCA model
droplet volume, contact angle, contact radius, evaporation
and successfully predicted the evolution of droplets under
duration, etc., during the droplet evaporation. Due to the
CCA mode evaporation.
coupled internal liquid motion, heat transfer between three
As the techniques of surface modification developed over the
phases (solid−liquid−gas), and mass flux of the vapor phase,
past few decades, studies focused more on heterogeneous,
the sessile droplet evaporation is a complex and non-
patterned, or textured surfaces, which present distinct
equilibrium problem. The droplet evaporation dynamics are
evaporation behaviors compared to homogeneous surfa-
affected by many factors: droplet physicochemical properties
ces,17,26−35 and promising improvements for applications,
(single or multiple components),14 substrate thermophysical
such as anti-icing36 and droplet control/transportation,37 and
properties,15 substrate wettability16 and roughness proper-
controllable evaporation modes.38 More recently, chemically
ties,17 external excitations/vibrations,18 and inclination of the
patterned surfaces combining hydrophobic and hydrophilic
substrate,19,20 etc.
patterns were found enabling the manipulation of droplet
There are extensive studies of sessile droplet evaporation on
dynamics and intensification of droplet evaporation attributed
homogeneous surfaces. Picknett and Bexon21 conducted the
to enhanced diffusion with increased contact-line lengths.39,40
pioneering work of the sessile droplet’s evaporation on a
However, although a chemically patterned surface is promising
smooth homogeneous surface (PTFE) and identified three
because of less cost and an easier fabrication process than a
major evaporation mechanisms: (1) the constant contact line
(CCL) stage with pinned contact line and decreasing contact
angles, (2) constant contact angle (CCA) stage with constant Received: February 25, 2022
contact angle and diminishing contact radius, and (3) a mixed Revised: April 29, 2022
mode of CCL and CCA with both contact radius and contact Published: May 11, 2022
angles decreasing at the end of the evaporation process. Some
researchers22,23 described a “stick-slide/slip” mode: droplet
evaporation first experienced the CCL mode until reaching a

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Figure 1. (a−c) Microscopic images of hydrophobic network surfaces with hydrophobic substrates (i.e., Teflon, dark green) and hydrophilic
patterns (i.e., ITO glass, green) of 100 μm (ps100), 50 μm (ps50), and 25 μm (ps25); (d) ps100 profile of hydrophobic network surface measured
by AFM.

3D-structured surface,11 the fundamental understanding of into the air, which was slow. Additionally, the evaporation was mainly
how it affects the droplet evaporation dynamics and affected by the wettability.
evaporation rate remains elusive.41 Therefore, it is necessary The wettability data of hydrophobic (Teflon), hydrophilic (ITO),
to propose the theoretical prediction for the droplet and hydrophobic network surfaces were measured by the snake-based
method of Stalder et al.42 to fit the morphology of the droplet and
evaporation behavior and duration on chemically patterned obtain the apparent contact angle, and compared to the theoretical
surfaces, which can give insightful information for surface results obtained by Cassie’s law,43 as reported in Table 1. The
designs.
To fill the research gaps, we systematically studied the full Table 1. Measured and Theoretical Wettability Data of
process of evaporation dynamics of droplets on chemically Heterogeneous (i.e., Hydrophobic Network) and
patterned (heterogeneous hydrophobic network) and homo- Homogeneous (Hydrophobic or Hydrophilic) Wettability
geneous (hydrophobic) surfaces and found that the dynamics Surfaces
and evaporation duration are remarkably influenced by the
arrangement of patterns on the surfaces. To understand the experimental apparent receding
phenomena, we also developed general models for analysis and apparent contact angle contact advancing
contact angle from Cassie’s angle contact
accurate predictions of the evaporation stage transitions and surfaces (°) law (°) θrec(°) angles (°)
evaporation durations on the chemically patterned surfaces. hydrophobic 124.6 N/A 70.6 128.2
hydrophilic 65.2 26.5 74.9
2. EXPERIMENTAL SETUP ps25 117.3 117.9 N/A
The droplet evaporation dynamics was studied with an experimental ps50 119.5 117.9
setup similar to our previous study40 (see Figure S1 in Section 1 of ps100 118.8 117.9
the Supporting Information). The tested chemically patterned
surfaces were hydrophobic network surfaces, shown in Figure 1a−c.
These surfaces consisted of the hydrophobic Teflon surfaces with theoretical static contact angle of the hydrophobic network surface of
hydrophilic Indium tin oxide (ITO) square patterns, keeping a a constant pattern fraction f p (ratio between the hydrophilic and
constant pattern area fraction f p (ratio between the hydrophilic area hydrophobic area) at 0.1 shows agreement with the experimental
and the total area) at 0.1 (see Supporting Information S2). The results with an error of ±2°.
pattern lengths (D) and pattern distances (L) thus ranged from 25 to Deionized water droplets with a volume of 0.45 ± 0.025 μL were
100 μm and from 80 to 316 μm, respectively. For convenience, we generated by a Hamilton microliter syringe and gently deposited on
denote these surfaces as ps25, ps50, and ps100, respectively. The the tested hydrophobic network surface. This droplet volume was
patterned surfaces were fabricated by the standard microfabrication small enough that surface tension dominates over gravity.25
processes: i.e., the photolithography and dry etching methodologies Therefore, the gravity can be neglected in the present study. The
(see Figure S2 in Section 2 of the Supporting Information). The experiments were conducted in the laboratory of the Center for
thickness and roughness of Teflon measured by an atomic force Energy and Thermal Systems at the Hong Kong University of Science
microscope (AFM) are as low as 45 and 8 nm, respectively, as shown and Technology. The laboratory environment is controlled by central
in Figure 1d. Thus, we can assume that the pattern height of the air-conditioning systems. During the evaporation experiments, the
Teflon layer and its thermal conduction resistance were negligible. room temperature was monitored and recorded by a TSI 982 probe
Droplet was almost isothermal on these surfaces and droplet connected to a Q-Trak Indoor Air Quality Monitor 7575. The
evaporation rate was mainly controlled by the diffusion of vapor experimental condition was at 23.5 ± 0.5°C and the room relative

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humidity was at 53 ± 0.5% according to TSI982’s readings.

Considering that TSI 982 probe’s accuracies are ±0.3 °C and ±3%
RH for temperature and relative humidity, respectively, the overall
uncertainty of temperature and relative humidity can be estimated at
±0.58 °C and ±3.04% RH. With the help of a high-resolution CCD
camera and a long zoom lens, the resolution for the contact angle and
the base diameter were at 0.5° and 1.4 μm, respectively. Taking
advantage of the transparent substrate (i.e., glass), we also investigated
the contact line movement under an inverted microscope. The
droplet evaporation experiment on each different surface was repeated
at least 8 times to ensure the reproducibility.

3. RESULTS AND DISCUSSION

3.1. Droplet Evaporation Dynamics on Hydrophobic
Network Surfaces. The droplet evaporation dynamics on the
hydrophobic (i.e., homogeneous wettability) and chemically
patterned hydrophobic network (i.e., heterogeneous wett-
ability) surfaces were investigated to distinguish different
evaporation modes during the entire droplet evaporation
process and the effects of wettability pattern on the
evaporation dynamics. The contact angle and contact base
radius of the droplet were measured through the image
processing, and the effect of the hydrophilic pattern size on the
droplet evaporation process was discussed here.
The homogeneous hydrophobic surface (i.e., Teflon) was
first investigated as a reference. As shown in Figure 2, the

Figure 2. Time evolutions of the contact angles and contact base Figure 3. Time evolutions of the contact base diameters and contact
diameters of a droplet on a homogeneous Teflon hydrophobic angles of a droplet on hydrophobic network surfaces including (a)
surface. ps25, (b) ps50, and (c) ps100.

evaporation process of a deionized droplet on the Teflon
surface could be divided into three stages: constant contact line
(CCL), constant contact angle (CCA), and a mixed mode
according to a definition from a previous study.21
The evaporation time evolution of a contact angle and
contact line were similar to previous studies of water droplet
evaporation on a homogeneous Teflon substrate.44,45 The
evaporation of droplet on a Teflon surface started with the
CCL stage, in which the contact area between the droplet and
surface was pinned and maintained constant, leading to a
constant contact base radius and diminishing contact angles.
After the CCL stage, evaporation entered into the CCA stage,
in which the contact angle was almost constant, and the
contact base radius decreased apparently. Lastly, the
evaporation changed to the mixed stage, and both the contact
angle and the contact base radius decreased simultaneously.
Normally, the mixed mode is short.
For the hydrophobic network surfaces (i.e., ps25, ps50, and
ps100), droplet evaporation processes presented more complex
evaporation modes, as shown in Figure 3. Droplets on the ps50
and ps100 surfaces underwent four distinctive stages: constant
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contact line (CCL) stage, constant contact angle (CCA) stage,
pattern-pinning (PP) stage, and the final moving contact line
(MCL) stage. In the PP stage (or stick mode mentions in the
literature22) followed by the CCA stage, the contact line was
pinned by hydrophilic patterns, resulting in a constant contact
base radius again. During the MCL stage (or called stick-slide/
slip mode at the end of the evaporation process), the contact
line receded stepwise and the instantaneous contact angle
changed significantly after each jump (the contact base radius
and the contact angles changed46 in turn). The schematics of
representative evaporation stages (CCL, CCA, PP, and MCL)
on a chemically patterned surface are indicated in Figure 4, and
corresponding characteristics (i.e., contact base diameter and
contact angle) are also illustrated. For the ps25 surface, the
CCA after the CCL stage was identified and was shorter than
those of other patterned surfaces (ps50 and ps100), as shown
in Figure 3.
The CCL stages took a long time for all the surfaces until a
steep decrease of the contact base radius was achieved at a
critical contact angle θcca, which indicated the beginning of the
CCA stage. The CCL stages of hydrophobic network surfaces
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Figure 4. Schematics of (a) constant contact line (CCL), (b)
constant contact angle (CCA), (c) pattern-pinning (PP), and (d)
moving contact line (MCL) for an evaporating droplet on a
chemically patterned surface.
could be attributed to the hydrophobic area between the
hydrophilic patterns. The critical contact angles θcca (around
93°) for the hydrophobic network surfaces (i.e., ps25, ps50,
and ps100) were almost the same as the θcca (95°) for the
Teflon hydrophobic surface (see Figure 2), and this similarity
of θcca suggests that droplet evaporation at the CCL stage on a
hydrophobic network surface was dominated by the same
mechanism as that for a homogeneous hydrophobic surface.
The durations of the CCL stage for ps25, ps50, and ps100
surfaces were 359, 412, and 396 s, respectively.
After the CCL stage, the CCA stage appeared and was
maintained with a constant contact angle and moving contact
line. The CCA stage ended when the contact line was pinned
again (a constant contact base diameter), which also indicated
the start of the PP stage. During the PP stage, the contact line
was actually pinned at its nearest hydrophilic pattern from their
initial contact diameter, e.g., around 790 μm (5 times the
pattern lengths, i.e., 5L) for ps50 and around 850 μm (∼3L −
D) for ps100 (see Figure 3b,c). Finally, the last stage of the
evaporation process (i.e., MCL stage) began, in which the
contact line receded stepwise in a jumping behavior as
illustrated in Figure 5a. The contact line moving direction is
also illustrated from top view in Figure 5b. During the MCL
stage, the contact line will move from the present pinned ITO
pattern dot to the next neighboring ITO pattern dot. The
jumping distance, d, is related to the length of the hydrophobic
area between neighboring hydrophilic patterns (i.e., d = L −
D). Therefore, d values are 55, 108, and 216 μm for ps25, ps50,
and ps100 surfaces, respectively, giving reasonable matches
with the experimental data in Figure 3a−c. The distinctions of
the evaporation dynamics for various hydrophobic network
surfaces suggested the effects of the surface patterns’ scale and
structure, which will be modeled in subsection 3.2.
3.2. Theoretical Prediction of Droplet Evaporation
Duration on Hydrophobic Network Surfaces. To under-
stand how the hydrophobic network surface affects evaporation
dynamics and evaporation processes, we first evaluated the
duration of each evaporation stage. Based on the θcca, which
indicated the transition from CCL to the CCA stage, we can
theoretically predict the duration of the CCL stage for our
tested surfaces in subsection 3.1. In the present study, the
droplet evaporated on the unheated substrate with hydro-
phobic patterns of nanometer thickness (i.e., negligible
conduction resistance), and the diffusion of vapor into the
air was thus dominated by the droplet evaporation rate. This
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Figure 5. (a) Side view of a typical jumping behavior of a droplet on
the ps25 surface during the MCL stage. (b) Top view of the
representative contact line moving on the ps25 surface during the
MCL stage.
clarification is valid to the following theoretical prediction of
droplet evaporation at different stages (i.e., CCL, CCA, PP,
and MCL). Therefore, in this study, we adopted the
evaporation model derived by Rowan et al.,24 which predicted
the spherical droplet evaporation time during the CCL stage
(tccl). tccl is governed by the equations below:
r0 2
tccl = [F(θcca) − F(θc)]
2λ (1)
where θc is the apparent contact angle when the droplet was
initially deposited (refer to Table 1) on the surface, θcca is 93°
obtained from experimental measurements (see Figure 3), r0 is
the initial base radius of the droplet, F(θ) is an angular
function defined in eq 2, and λ is expressed in eq 3.
i θy
F(θ ) = lnjjjtan zzz +
k 2 { 1 + cos θ
1
(2)
2Df (Cinf − CS)
λ=
ρ (3)
where Df is the diffusion coefficient of water vapor (1.83 ×
10−5 m2 s−1 ).24 For the present experimental conditions
(room temperature: 23.5 ± 0.5 °C; atmosphere pressure:
1.013 × 105 Pa, relative humidity: 53 ± 0.5%). CS and Cinf are
the saturated water vapor concentrations at the droplet
interface and at infinity, which are 0.021 kg m−3 and 0.011
kg m−3, respectively. ρ is the water density (998 kg/m3). r0
values were calculated by the spherical cap approximation
given experimental θc and found to be 426, 454, 451, and 462
μm for the hydrophobic, ps25, ps50, and ps100 surfaces,
respectively. The durations of patterned surfaces were various
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because the droplet with same volume had different apparent

contact angles θc and base radii r0. Although their difference on
patterned surfaces was not large, they would still change the
F(θ) value in eq 2 and lead to different results of the duration
of the surface. As shown in Figure 6, the CCL times predicted

Figure 7. CCA stage durations of experimental measurements (black

squares) and theoretical predictions by Erbil’s model (blue
rhombuses).

Table 2. Critical Receding Contact Angle θcr of

Hydrophobic Network Surface (ps25, ps50, and ps100)
Figure 6. CCL stage durations of the experimental measurements hydrophobic pattern critical receding contact error of 95%
(black squares) and the theoretical predictions (blue rhombuses) by network surfaces fraction angle, θcr (°) confidence (°)
Rowan’s model. The pattern size 0 represents the Teflon hydrophobic ps100 0.1 56.3 1.1
surface. ps50 0.1 57.6 1.6
ps25 0.1 57.5 1.3
by Rowan’s model were 457, 346, 384, and 391 s for the
hydrophobic, ps25, ps50, and ps100 surfaces, which shows
good agreement with our experimental measurements (i.e.,
468, 359, 412, and 396 s, respectively).
Quantitatively, the duration of the CCA stage tcca can be
predicted by the model proposed by Erbil et al.25,47 as
following:
r0 2 − rcca 2
tcca = −
2λφ(θcca) (4)
where rcca are 440,425, and 400 μm for ps25, ps50, and ps100,
respectively. φ(θ) is defined in eq 5. λ is calculated according
to eq 3
sin 2 θ Figure 8. PP stage durations of experimental measurements (black
φ (θ ) = squares), theoretical predictions by Rowan’s model (blue rhombuses),
(1 − cos θ )(2 + cos θ ) (5) and our model (red rhombuses).
In Figure 7, the theoretical time prediction of tcca (35, 122,
and 92 s) for all patterned surfaces (ps25, ps50, and ps100) hydrophilic pattern during the PP stage (unlike the previous
presents good agreement with experimental data (39, 124, and CCL stage), leading to the failure of applying Rowan’s model.
106 s). The failure of Rowan’s model implied modification induced by
The duration of the PP stage was further studied. Like the the hydrophobic network surfaces should be established to the
CCL stage, Rowan’s model was first applied as the contact line PP stage.
ÄÅ ÉÑ−1/2 + θ / π
Å x 2Ñ
was also pinned by the hydrophilic patterns. PP stage duration The vapor mass flux j from the drop can be calculated by

j(x) = j0 ÅÅÅÅ1 − r ÑÑÑÑ

tpp is thus expressed as below:

rcca 2
t pp = [F(θcr) − F(θcca)]
2λ
where θcr is the critical receding contact angle summarized in
Table 2 and θcca is 93°. Interestingly, θcr values are almost the
same for these surfaces (around 56∼57°, see Figure 3a−c) and
we adopted θcr = 57° for calculation. However, as seen in
Figure 8, Rowan’s model presents an overestimation for the
duration of the PP stage compared with the experimental ones.
Those huge variations suggested that we could not simply
apply this model for hydrophobic network surfaces. We
noticed that the contact line was highly distorted due to the
ÇÅ ÖÑ
() ,48 where θ (0 < θ < π/2) is the
(6) contact angle during evaporation, r and x are the droplet base
radius and the distance from the centroid of the droplet to
edge of contact line, and the prefactor j0 is affected by the
vapor diffusivity, saturation pressure, and the far-field
1
concentration. As 0 < θ < π/2, the exponent − 2 + θ /π will
always be smaller than 0, and the j(x) will increase with x and
reach its maximum when x approaches droplet base radius r.
The vapor mass flux is the largest at the contact line when the
droplet contact angle is below 90°, which was proven by Hu
and Larson9 theoretically and experimentally. This also means
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a longer contact line will lead to higher evaporation flux. In
addition, recalling some previous studies10 either investigated
by molecular dynamics simulation39 or experiments,40 it is also
shown that increasing the contact line induced by hydro-
philic−hydrophobic patterns can enhance the droplet evapo-
ration rate. This enhancement of the droplet evaporation rate
compared to the homogeneous hydrophobic surfaces is caused
by a large number of water molecules diffusing from the
contact line to air. Since hydrophilic patterns on the present
tested surface can also elongate the contact line, Rowan’s
model should be modified with a new factor relative to the
increasing contact line for our case. The enhancement of the
droplet evaporation rate was also observed in our experiments.
To determine the contact line factor, we recorded the
contact line movement by an inverted microscope and
analyzed for the PP and MCL stage. During the experiment,
we found that the MCL stage was repetition of several PP
stages: during evaporating in the MCL stage, once the contact
line de-pinned the hydrophilic pattern, it “jumped” and tried to
pin to the nearest hydrophilic pattern along the shrinking
direction of the base contact diameter, which was similar to the
contact line movement of the PP stage. Figure 9 shows the
Figure 9. Movement of the contact line from pinning to depinning
during the MCL stage, showing a constant receding rate of the
contact line.
contact line movement and elongated contact line during the
MCL stages. Roughly, in our observation, the contact line
between two hydrophilic patterns receded with almost a
constant speed from pinning to depinning conditions. In
addition, the contact line would soon pin on the nearest
hydrophilic pattern along the receding direction. Assuming
contact line pinning at the hydrophilic pattern at the beginning
of PP or each contact line jump interval of the MCL stage (like
0 s in Figure 9) and depinning at the hydrophilic pattern (like
16 s in Figure 9), we can have the average contact line length
on the hydrophobic network surface, which can be estimated
as L + (2D + L) , where L represents the contact line length at the
2
beginning while 2D + L represents the length at the end of PP
or each contact line jump interval of the MCL stage.
Therefore, we could establish the ratio (ω) of the average
contact line length with and without pattern pinning as
L + (2D + L)
2 L+D
ω= L
= L
= 1.32 for the PP stage and MCL stage.
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Accordingly, inspired by previous molecular dynamics
simulation39 that showed that the evaporation flux was
proportional to liquid boundary length, we try to modify
Rowan’s model by considering the contact line effects as
below:
(rcca /ω)2
t pp, m = [F(θcr) − F(θcca)]
2λ (7)
where rcca/ω represents a corrected contact line length since
we assumed that j is proportional to the contact line length.
Applying eq 7, we can see good agreement in Figure 8
between the theoretical and experimental results of tpp for all
tested hydrophobic network surfaces: experimental average of
151, 126, and 142 s and theoretical average of 160, 132, and
154 s for ps25, ps50, and ps100 surfaces, respectively. This
good agreement between experimental and theoretical
predictions indicated that our assumption of the proportional
relationship between mass flux and contact line length is
reasonable.
In addition, although these hydrophobic network surfaces
exhibited different evaporation stages, the critical receding
contact angles θcr were surprisingly constant (around 56∼59°)
for them (see Table 2). A similar phenomenon in the
experiments of multicomponent droplets on a hydrophilic
network surface was also observed in He et al.’s work,40 which
was well interpreted by the local force model at the contact
line. Therefore, the local force model was adopted here to
explain this phenomenon and test for validity in the case of the
hydrophobic network surface.
In the local force model, the depinning force Fd and pinning
force Fp at the contact line are considered. The depinning force
is calculated as
Fd = 2rσ(cos θ − cos θc) (8)
where r is the droplet base radius, σ is the surface tension of
the liquid (i.e., water), θ is the contact angle during the
evaporation, and θc is the apparent contact angle on the
patterned surface. Since Cassie’s law is verified on the
patterned surfaces (see Table 1), we can modify the pinning
force according to the previous research17,49,50 and establish a
new expression as below:
Fp = 2rσ[(cos θro philic − cos θao philic)fp +
(cos θro phobic − cos θao phobic)(1 − fp ) + Hr ] (9)
where θao philic and θro philic represent advancing and receding
contact angles on the hydrophilic surfaces, θao phobic and
θro phobic represent advancing and receding contact angles on
the hydrophobic surface, f p is the pattern fraction. Hr is the
proportion to the ratio (D2/L2) between the pattern length D
and pattern-to-pattern spacing L, representing the adhesive
force induced by the heterogeneity and microscale surface
roughness. Here, we adopted the Hr at 0.1. Hence, if the
driving ratio τ
Fd
τ=
Fp
= (cos θ − cos θc)/[(cos θro philic − cos θao philic)fp
+ (cos θro phibic − cos θao phobic)(1 − fp ) + Hr ] (10)
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is larger than or equal to 1, the contact line will start receding,
and the droplet evaporation stage will convert from the PP
stage to the MCL stage. Inserting the wettability data from
Table 1 and setting τ = 1, the theoretical critical receding
contact angle θcr can be calculated by eq 10. As can be seen in
Figure 10, the calculated θcr values of all patterned surfaces are
Figure 10. Comparison of the theoretical critical receding contact
angle (θcr) and the experimental measurements for different
hydrophobic network surfaces when driving ratio τ = 1.
constant and equal to 56.7°, which shows good agreement with
the experimental data. This agreement shows that the local
forces model for θcr prediction is valid for both the hydrophilic
network40 and the hydrophobic network surfaces in the
present study. In addition, the constant θcr value also implies
that θcr is mainly dominated by the pattern fraction of surfaces
and not affected by the pattern size.
The MCL stage can be regarded as a combination of several
PP stages connected by sudden jumps. We could thus apply
the similar equation of the PP stage to predict the MCL stage.
It is assumed that the time of sudden jumps was negligible, and
the droplet volume remained constant before and after each
jump. The jump distance (d) for patterned surfaces is
determined by the pattern size (D) and distance (L) and
equal to the difference between them, i.e., d = L − D (∼200,
∼110, and ∼55 μm for ps100, ps50, and ps25, respectively).
The contact line movement from one hydrophilic pattern to its
neighboring hydrophilic pattern is confirmed by Figure 3a−c.
With the above assumption, we can calculate the duration of
the MCL stage (tmcl, detail shown in S3 Supporting
Information).
The comparison of experimental and theoretical total
evaporation duration on hydrophobic network surfaces (ttot =
tccl + tcca + tpp, m + tmcl) is shown in Figure 11. The results
indicate that the proposed theoretical model could reasonably
predict the experimental data with an average 15% over-
estimation. It is also shown that when the pattern distance is
small, our model has better consistency with experiments. This
may be attributed to two reasons: (1) the droplet shape
distortion in ps100 surfaces was larger because of the higher
ratio of pattern size to droplet diameter, leading to deviations
between (I) the calculated contact angles (after jumps) using
the spherical cap approximation and the real ones and (II)
calculated droplet volumes (before jumps) using the spherical
cap approximation and the real ones, which can be seen from
calculation results in Supporting Information S3 and
experimental results from Figure 3a−c; (2) when the contact
line receded stepwise, the contact line decreased and the
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Figure 11. Total evaporation duration of experimental measurements
(black squares) and theoretical predictions (blue rhombuses) from
our model.
average ratio (ω) of the contact line length would also change
whether with or without pattern pinning. However, although
for ps25 and ps50 surfaces, the distortion also happened in the
PP and MCL stage, these surfaces have a smaller ratio of the
pattern size to the droplet diameter and, thus less droplet
distortion and better prediction of evaporation duration.
Despite the low deviations resulting from droplet shape
distortion, our model presented good consistency to predict
the droplet evaporation on the patterned hydrophobic network
surfaces considering the effects of the contact line through
introducing corrected contact line length (rcca/ω). Further-
more, the proposed model could provide some guidelines of
the surface wettability designs applied for the thermal
management and droplet manipulation.
In summary, this study investigated droplet evaporation on
hydrophobic network surfaces and tried different models for
prediction of all major stages. In CCL and CCA stages,
Rowan’s and Erbil’s models were introduced and showed
agreement with experimental results. In the PP stage, a
modified Rowan’s model with corrected contact line length
(rcca/ω) was applied and showed better consistency with
experiments. In the MCL stage, a combination of several PP
stages connected by sudden jumps, Rowan’s model with
corrected contact line length of the PP stage was applied but
the effectiveness was undermined due to the droplet shape
distortion in the MCL stage.
4. CONCLUSIONS
In the present work, the evaporation dynamics of the droplet
during the evaporation process was systematically investigated
on hydrophobic network surfaces, containing the constant
pattern fraction (f p = 0.1) and various pattern sizes. Analyzing
the time evolution of the contact angle and the contact base
diameter, four major evaporation stages (i.e., CCL, CCA, PP,
and MCL) and different time durations were distinguished,
which was largely dependent on the substrate patterns (i.e.,
surface patterns’ scale and structure). It should be worth
emphasizing again that current theoretical prediction of
different stages of evaporation was built on boundary
conditions that the droplet was almost isothermal and the
evaporation process was dominated by the vapor diffusion into
air. To interpret the distinguished evaporation stages on
different surfaces, some existing models (e.g., Rowan’s model,
Erbil’s model) presented good predictions for the CCL and
CCA stage. During the PP stage, a modified model considering
https://doi.org/10.1021/acs.langmuir.2c00479
Langmuir 2022, 38, 6395−6403
Langmuir
pubs.acs.org/Langmuir
the corrected contact line length (rcca/ω) was proposed, which
presented better prediction and consistency compared with
Rowan’s model. Furthermore, the critical receding contact
angles θcr were obtained experimentally and found constant for
all tested hydrophobic network surfaces. Theoretically, a local
force model originating from the hydrophilic network surfaces
was modified to predict θcr for hydrophobic network surfaces
and showed consistency with the experimental data.
This constant critical receding contact angles indicated that
it is determined mainly by the surface pattern fraction and
independent from the surface pattern size. Finally, the
proposed model for the total evaporation duration gave out
reasonable consistency to the experimental data. All these
findings could provide important insights to the functional
surface design for the evaporation enhancement and
evaporation control.
■
ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.langmuir.2c00479.
Experimental setup, sample fabrication process, and
prediction of evaporation duration of MCL stage (PDF)
■
AUTHOR INFORMATION
Corresponding Author
Huihe Qiu − Department of Mechanical and Aerospace
Engineering, The Hong Kong University of Science and
Technology, Hong Kong, SAR, China; orcid.org/0000-
0002-2135-9771; Email: meqiu@ust.hk
Authors
Minghao He − Department of Mechanical and Aerospace
Engineering, The Hong Kong University of Science and
Technology, Hong Kong, SAR, China
Yinchuang Yang − Department of Mechanical and Aerospace
Engineering, The Hong Kong University of Science and
Technology, Hong Kong, SAR, China
Mei Mei − Department of Mechanical and Aerospace
Engineering, The Hong Kong University of Science and
Technology, Hong Kong, SAR, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.langmuir.2c00479
Author Contributions
M. H. and H. Q. conceived the research. M. H. prepared the
samples and performed the experiments. M. H., Y. Y., M. M.,
and H. Q. discussed, interpreted, and explained the results with
theoretical models. M. H. drafted the manuscript. M. M., Y. Y.,
and H. Q. revised the manuscript. All authors have approved
the final version of the manuscript.
Funding
Research Grants Council of the Government of Hong Kong
Special Administrative Region (HKSAR) with RGC/GRF
Project Nos. 16205018 and the International Science and
Technology Project of Huangpu District of Guangzhou City
(2020GH08).
Notes
The authors declare no competing financial interest.
6402
■
Article
ACKNOWLEDGMENTS
We acknowledge assistance from the Nanosystem Fabrication
Facility (NFF) of HKUST for the device/system fabrication.
■
ABBREVIATIONS
AFM, atomic force microscope; CCA, constant contact angle;
CCL, constant contact line; ITO, indium tin oxide; MCL,
moving contact line; PP, pattern-pinning; ps25, patterned
surface with pattern length at 25 μm; ps50, patterned surface
with pattern length at 50 μm; ps100, patterned surface with
pattern length at 100 μm
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