750 Materialwiss. Werkstofftech. 2022, 53, 750–761 doi.org/10.1002/mawe.

202100142

Influence of surface modification on droplet mobility

during dropwise condensation
Einfluss der Oberflächenmodifikation auf die
Tröpfchenbeweglichkeit während der tropfenweisen
Kondensation

J.A. Balbarona1, G.J.C. Denoga1, H.S. SalapareIII2, 3, 4

A two-step surface fabrication technique is used to modify the wetting character-

istics of copper sheets for heat transfer application. It consists of oxygen plasma
treatment that results in the formation of surface nanostructures, and a post-func-
tionalization process using self-assembled monolayers. The copper samples are
characterized by contact angle measurements, scanning electron microscopy, and
atomic force microscopy. Results show that surface roughness, described using
hybrid and functional roughness parameters, varies with irradiation power. The
plasma-treated copper samples become superhydrophobic with water contact an-
gles ranging from 150° to 160° after the post-functionalization. Condensation ex-
periments are conducted to explore the influence of surface wettability on con-
densate formation. Results show that droplets formed on the superhydrophobic
copper sheets are smaller and more mobile with sweep events that are 9x more
frequent compared to those on untreated copper sheets. Sweep events are shown
to be influenced by surface porosity, which is defined using standard roughness
parameters. It is demonstrated that higher surface porosity results to higher sweep
interval.

Keywords: superhydrophobic copper / dropwise condensation / surface porosity /

oxygen plasma / surface modification

Eine zweistufige Oberflächenherstellungstechnik wird verwendet, um die Benet-

zungseigenschaften von Kupferblechen für die Wärmeübertragungsanwendung zu
modifizieren. Sie besteht aus einer Sauerstoffplasmabehandlung, die zur Bildung
von Oberflächen-Nanostrukturen führt, und einem Nachfunktionalisierungsprozess
mit selbstorganisierten Monoschichten. Die Kupferproben werden durch Kontakt-
winkelmessungen, Rasterelektronenmikroskopie und Rasterkraftmikroskopie cha-
rakterisiert. Die Ergebnisse zeigen, dass die Oberflächenrauheit, beschrieben mit
hybriden und funktionellen Rauheitsparametern, mit der Bestrahlungsleistung vari-
iert. Die plasmabehandelten Kupferproben werden nach der Nachfunktionalisie-
rung superhydrophob mit Wasserkontaktwinkeln im Bereich von 150° bis 160°.
Kondensationsexperimente werden durchgeführt, um den Einfluss der Oberflä-
chenbenetzbarkeit auf die Kondensatbildung zu untersuchen. Die Ergebnisse zei-

1 University of the Philippines Diliman, Department of
Mechanical Engineering, College of Engineering,
Quezon City, Philippines
2 University of the Philippines Open University, Fac-
ulty of Education, Los Baños, Philippines
3 Université Côte d’Azur, Nice Lab, Nice, France
4 Air Link International Aviation College, Pasay City,
Philippines
Corresponding author: H.S. SalapareIII, University of
the Philippines Open University, Faculty of Education,
4030, Los Baños, Philippines,
E-Mail: hssalapare@up.edu.ph

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Materialwiss. Werkstofftech. 2022, 53, 750–761 Droplet mobility during dropwise condensation 751

gen, dass auf den superhydrophoben Kupferblechen gebildete Tröpfchen kleiner

und beweglicher sind, wobei Sweep-Ereignisse im Vergleich zu denen auf unbe-
handelten Kupferblechen 9x häufiger sind. Es wird gezeigt, dass Sweep-Ereignis-
se durch die Oberflächenporosität beeinflusst werden, die unter Verwendung von
Standardrauheitsparametern definiert wird. Es wird gezeigt, dass eine höhere
Oberflächenporosität zu einem höheren Sweep-Intervall führt.

Schlüsselwörter: Superhydrophobes Kupfer / tropfenweise Kondensation /

Oberflächenporosität / Sauerstoffplasma / Oberflächenmodifikation

1 Introduction tures that alter surface roughness. Extensive liter-

Surface wetting characteristics is important in vari-
ous fields of application such as biomedical pros-
thetics, food and liquid packaging, water harvest-
ing, microfluidics, oil-water separation, bio-fouling
control and energy systems [1–19]. Various techni-
ques may be used to achieve the desired wetting
behavior of a surface that is suitable for a specific
application. In thermal systems application, surface
wettability is found to significantly modify the
phase transition mechanism during condensation,
boiling, and sublimation on surfaces [20–22]. These
can either enhance or deteriorate the heat transfer
process. Heat transfer during condensation depends
on the rate of condensate formation on a surface
and the rate at which the condensate is drained
from the surface [23, 24]. This is because the con-
densate forms a thermal barrier between the surface
and the vapor, and this impedes thermal energy ex-
change. In filmwise condensation where the con-
densate forms a liquid layer over the surface, ther-
mal resistance increases with condensate thickness.
In dropwise condensation, the condensate forms
droplets on the surface, and the corresponding ther-
mal resistance depends on the size of these drops.
These drops are generally more mobile with higher
drain rate compared to liquid film layer. As such,
dropwise condensation has been shown to yield
higher heat transfer rate than filmwise con-
densation. For materials used in heat transfer appli-
cations such as metals and alloys, dropwise con-
densation is achieved by altering the wettability of
the surface by means of micro machining, laser tex-
turing, etching, deposition, or plasma treatment
[25–48]. This may then be followed by a mod-
ification procedure using a material of low surface
energy. These fabrication processes are usually ac-
companied by formation of micro and nano struc-
ature on fabrication of superhydrophobic materials
highlights the importance of surface roughness on
contact angle, contact angle hysteresis, sliding an-
gle, three phase contact line, and wetting modes
[49–51]. Theoretical studies use interfacial free en-
ergy to model the interaction between surface
roughness and changes in droplet surface area.
These studies explore the effect of different geo-
metric parameters such as aspect ratio and geo-
metric spacing on the degree of wetting [52–55].
Experimental studies have also demonstrated the
influence of surface topography on dropwise con-
densation. One study has shown that droplets on
flat surface slide while droplets on micro structured
surface roll down [35]. Another study has demon-
strated how the size, shape, and distribution of mi-
cro features and trapezoidal grooves and ridges en-
hanced droplet transition from Wenzel to Cassie
state during dropwise condensation [56]. Con-
densation on one-tier and two-tier micro/nano
roughness structures and on micro/nano-scale po-
rous surfaces, as well as on pyramid-shaped hier-
archical structures have been also been explored
[57–59]. Several studies had also shown how the
dynamics of the condensation of water droplets are
affected depending on the types of surface structure
and surface wettability, for example, surfaces that
are superhydrophobic with spike surface structures
demonstrated a three-step dynamics of water drop-
lets condensation, while a different type of water
droplets growth dynamics were observed from
square patterned rough hydrophobic surfaces [60–
64]. These and other studies highlight the bigger
role of surface topography and microstructures on
the wettability of surfaces, and its direct impact on
dropwise condensation [65–68].
In this study, a two-step process is employed to
alter the surface wetting characteristics of the sam-

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752 H.S. Salapare
ples. The chosen surface fabrication technique sig-
nificantly reduced the surface energy of the copper
samples, making them superhydrophobic. Ex-
perimentally, it was demonstrated that dropwise
condensation can be initiated simply by modifying
the surface characteristics of the copper samples.
More importantly, this study shows that the mobi-
lity of drops during condensation was influenced by
surface topography and surface porosity, obtained
from a two-step process of surface structuration by
plasma treatment followed by post-functionaliza-
tion to obtain self-assembled monolayers, which, in
this study, is defined using standard surface rough-
ness parameters.
2 Materials and experimental details
2.1 Fabrication of hydrophobic surface
Industrial grade copper sheets were obtained from
Hi-Top Merchandising, Inc. The samples were
0.9 mm in thickness and were cut into 50.8 mm ×
25.4 mm sizes. The samples were washed in soapy
water to remove dirt and grease, and then rinsed
thoroughly with tap water. The samples were soni-
cated in ethanol bath for 20 min, then triple rinsed
with demineralized water (Milli-Q), and then soni-
cated in demineralized water for 15 min. The clean
samples are placed in a drying oven until they are
completely dried. The cleaned and dried samples
were irradiated with oxygen plasma using a P300
plasma device (Alliance Concept, Cran-Gevrier,
France), Figure 1. The P300 plasma device has a
vacuum chamber of 300 mm × 300 mm × 300 mm
dimension and an electrode with a diameter of
Figure 1. Surface fabrication process a) schematic of the
overall process b) diagram of the plasma device.
© 2022 Wiley-VCH GmbH
Materialwiss. Werkstofftech. 2022, 53, 750–761
10 cm. The chamber was first evacuated using a
20 m3/h rotary vane pump until a base pressure of
8 · 10 2 mbar was achieved. Oxygen gas was fed
into the chamber at a rate of 20 sccm. Plasma treat-
ment was done using pulsed RF plasma source at
an excitation frequency of 13.56 MHz and 80 %
duty cycle. Irradiation power was varied from
300 W to 600 W at a fixed irradiation time of 10
minutes. Additional details of the plasma device
may be found in [69]. Formation of self-assembled
monolayers (SAM) is achieved by immersing the
plasma treated samples in a 2.5 mM solution of n-
octadecyl mercaptan (Sigma Aldrich) in ethanol for
15 h. The samples were then washed with ethanol
and allowed to dry in air.
2.2 Characterizations
2.2.1 Water contact angle measurements
The wettability of the samples before and after
plasma treatment are measured using DSA-30 goni-
ometer (Krüss GmbH) equipped with a drop shape
analysis (DSA4) software. Sessile drop method is
used to measure the apparent contact angle, using
2 μl of Milli-Q deionized water. For each sample,
water contact angles at three different sites are
measured, and standard deviations are recorded.
Contact angle measurements are taken at the same
humidity and temperature conditions.
2.2.2 Atomic force microscopy
Surface roughness of all the samples is charac-
terized using atomic force microscopy at scan size
of 5 micron × 5 micron and scan rate of 0.4 Hz. The
resulting images are analyzed using software pack-
age Scanning Probe Image Processor (SPIPTM). At
least 10 different locations are analyzed to assess
the surface roughness of the samples.
2.2.3 Scanning electron microscopy
Surface morphology of the untreated, plasma-treat-
ed, and post-functionalized substrates are obtained
using a Phenom ProX scanning electron micro-
scopy (Phenom World, B.V., France Scientifique,
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Materialwiss. Werkstofftech. 2022, 53, 750–761
France) at 15 kV accelerating voltage and at secon-
dary electron detector (SED) imaging mode. All
scanning electron microscopy micrographs are re-
ported at 10,000x magnifications.
2.2.4 Condensation experiment
The condensation experiment set up consists of
four major components: a custom-made steam gen-
erator for supplying steam, a cooling water line, a
test chamber, and an imaging system, Figure 2. The
test chamber houses the cooling block where the
cooling water line flows through. The copper sam-
ple is fixed vertically to the cooling block using
thermal grease and a custom-made clamp made of
acrylic. The clamp not only holds the sample in
place but also provides reference points which are
useful for the image-processing stage. The test
chamber also has a viewing port through which ac-
tual condensation on the samples are observed and
recorded. The viewing port is heated to steam tem-
perature throughout the experiment to ensure that
no condensate will form on the inside surface
which could block the view of the imaging system.
When the sample is secured in place, the steam
generator and cooling water pump are switched on
simultaneously. Steam enters the test chamber
through a 2-inch inlet port to ensure that the steam
coming in is laminar. A steam outlet is located at
the top part of the test chamber to purge the system
of any non-condensable gases, and to maintain at-
mospheric pressure throughout the experiment. Al-
though dropwise condensation is transient in na-
ture, droplet nucleation, growth, coalescence, and
departure for a generation of droplets may be con-
Figure 2. Diagram of the condensation experiment set up.
© 2022 Wiley-VCH GmbH
Droplet mobility during dropwise condensation 753
sidered steady provided that operating conditions
are maintained during the experiment. Thus, data
recording is started only when conditions of steady
state are met. Operating conditions such as cooling
water temperature and vapor temperature are re-
corded throughout the duration of the experiment.
Only the cooling water temperature is varied from
30 °C to 50 °C at increments of 5 °C. In situ droplet
formation during condensation is recorded using a
micro four thirds mirrorless camera (Panasonic Lu-
mix GH5) that can take still photos at a rate of 30
frames per seconds at 18-megapixel resolution.
3 Results and discussion
3.1 Surface wettability
All copper samples exhibited enhanced wetting
properties based on their contact angle, θ, after
plasma treatment, Table 1. The samples became hy-
drophilic, and further increase in irradiation power
resulted to lower water contact angle compared to
the untreated, cleaned sample which has θ = 84°.
This may be attributed to the increase in interaction
of the different plasma species with the samples
which lead to the increase in surface roughness that
simultaneously occurs as the oxide layer is formed.
This is corroborated by the findings of [69] where
they found that at high irradiation power and duty
cycle, plasma treatment resulted to physical and
chemical change on the material. After, all the sam-
ples became superhydrophobic, with θ ranging
from 150° to 160°, Table 1. The differences in θ
may be due to the changes in roughness character-
istics resulting from varying the irradiation power
during plasma treatment. In comparison, the un-
treated, cleaned sample was also subjected to the
Table 1. Static water contact angle on copper surface
after plasma treatment and after SAM modification.
Power (W) θ after plasma θ after SAM
treatment (°) modification (°)
300 76 � 3 151 � 2
400 80 � 2 158 � 2
500 69 � 1 160 � 1
600 56 � 2 159 � 2
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754 H.S. Salapare Materialwiss. Werkstofftech. 2022, 53, 750–761

same post functionalization method and the result- Table 2. Surface roughness analysis.
ing water contact angle is 133°. This proves that the
Roughness parameter Power (Watts) Mean (nm)
oxygen plasma treatment was a necessary step in
the surface fabrication process which resulted in the Sk 300 13.7 � 0.84
improvement of the surface hydrophobicity by
400 10.5 � 1.54
12 % to 17 %.
500 8.6 � 0.65
600 5.9 � 0.61
3.2 Surface morphology
Sdq 300 0.063 � 0.005
Standard surface roughness parameters are classi- 400 0.039 � 0.004
fied as either amplitude, hybrid, or functional pa-
500 0.038 � 0.001
rameters and are used in this study to characterize
surface roughness as influenced by plasma power. 600 0.035 � 0.002
Amplitude parameters such as arithmetic mean
height (Sa), root mean square height (Sq), and max- Sdr 300 0.196 � 0.029
imum height (Sz) are observed to decrease as the 400 0.077 � 0.014
irradiation power is increased. However, these am- 500 0.074 � 0.006
plitude parameters are determined solely by height
information and its distribution over the sampling 600 0.062 � 0.006
area and use maximum and minimum values which
Vv 300 12.7 � 3.84
are sensitive to outliers and noise. These are also
insensitive in distinguishing between peaks and 400 7.5 � 1.18
valleys and do not account for the spatial frequency 500 6.4 � 1.43
of the texture features [70–71]. The result of sur-
600 4.5 � 0.6
face roughness analysis suggests that Sk, Sdq, Sdr,
and Vv are the more appropriate roughness parame- Vvc 300 0.882 � 0.263
ters that distinguish the influence of irradiation
power on the copper surface, Table 2. Sk is a func- 400 0.678 � 0.255
tional parameter that indicates of the core rough- 500 0.697 � 0.26
ness of the surface after eliminating predominant 600 0.712 � 0.238
peaks and valleys. Alternatively, it may be consid-
ered as a measure of nominal height of roughness
features [72]. Sdq and Sdr, are hybrid parameters
that are based on a combination of frequency and These relative flattening may be due to the in-
height and are affected by both texture amplitude creased plasma power that interacts with the sur-
and spacing [71]. Sdq is defined as the root mean face. At 300 W, plasma interaction modifies the
square surface slope of the roughness structures and surface chemically and physically which results in
indicates local gradients or steepness. Sdr is the de- the thermal oxidation of copper and formation of
veloped interfacial area ratio defined as the percent- nanostructures. But at 600 W, and at the same 80 %
age of additional surface area due to surface texture duty cycle, more dissociated plasmas interact with
as compared to the projected area of the sampling the surface causing amplified physical con-
region [72]. These two parameters represent the de- sequences. Another possible mechanism is that at
gree of fineness or coarseness of the slopes and 600 W, less time is required before formation of
spacing of roughness features. At low irradiation distinct nanostructures is observed. And that with
power, Sk, Sdq and Sdr are high implying fine continued exposure, the nanostructures formed are
spacing of roughness feature with high peaks and further bombarded with plasma species resulting to
steep gradients. As irradiation power in increased, the apparent flattening.
these parameters are reduced suggesting relative Physical interpretation of these parameters may
flattening of peaks and wider spacing of features. be further illustrated by using four surface rough-

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Materialwiss. Werkstofftech. 2022, 53, 750–761
ness scenarios consisting of sinusoids, Figure 3. Y1
is the reference surface roughness. Y2, Y3, and Y4
are derived from Y1 by simply changing the ampli-
tude and frequency. For the same core roughness,
higher Sdq is achieved by reducing the spacing be-
tween peaks and consequently creating steeper
slopes as shown in Y3. For the same Sdq as the ref-
erence roughness, lower Sk pertains to roughness
with lower peak heights, as shown in Y2. Addition-
ally, for the same low Sk, such as in Y2 and Y4,
high Sdq refers to finely spaced peaks as compared
to that in Y2. Consequently, for the same Sk, the
higher the Sdq, the higher is the developed percent-
age area Sdr. These three parameters are considered
relevant in drop growth mechanism because they
can adequately describe the characteristics of
roughness structures in terms of spatial frequency
and height distribution.
Figure 3. Representative surface roughness with varying
Sk and Sdq, a.) y3, higher Sdq, same Sk, b) y4, lower Sk,
higher Sdq, c.) y1 as reference, d.) y2, lower Sk, same Sdq.
Figure 4. Scanning electron microscopy images of copper at different irradiation powers (x10.0 K magnification) a. 400 W,
b. 600 W.
© 2022 Wiley-VCH GmbH
Droplet mobility during dropwise condensation 755
The reported roughness values are 3D parame-
ters which are evaluated within a sampling area.
This provides better detail of the height and spatial
characteristic of the surface as opposed to 2D pa-
rameters which are evaluated over sampling
lengths. 3D parameters can easily be interpreted in
terms of the change of material and void volume at
various roughness levels. One such parameter is the
void volume, Vv, which is computed from the core
fluid retention index and the valley fluid retention
index. These two indices are functional parameters
that characterize surface zones that are relevant in
lubrication, contact phenomenon and tribology. Vv
indicates the void created by the roughness result-
ing from the formation of micro and nano struc-
tures post plasma treatment. Result of surface
anaylsis imply that irradiation power significantly
alters the roughness structure which consequently
changes the void volume. As irradiation power is
increased, relative “flattening” occurs as manifested
by the reduction in core roughness, coupled with
coarsening of roughness spacing and reduction in
void volume. These results are presented to empha-
size the fact that functional properties are influ-
enced by surface roughness, and that there are spe-
cific roughness parameters that best describe the
correlation [60, 61, 73].
All the measured roughness parameters are aver-
aged from 10 distinct points on each sample meas-
uring 1 μm × 1 μm. The measured change in surface
topography at different irradiation power is also
evident in the scanning electron microscopy micro-
graphs, Figure 4. Comparison of the scanning elec-
tron microscopy images show that formation of
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756 H.S. Salapare
structures that appear to resemble micro globules or
spheres are observed at 400 W. The structures ap-
pear to clump together resembling nano cauli-
flower-like structures when irradiation power is at
600 W. This suggests that irradiation power drasti-
cally alters the topography of the copper samples in
a very distinct fashion.
The scanning electron microscopy images of the
untreated copper immersed in a 2.5 mM solution of
n-octadecyl mercaptan compared to the 600 W
plasma-treated copper immersed in a 2.5 mM sol-
ution of n-octadecyl mercaptan with self-assembled
monolayer shows that the micro-structures ob-
served after post-functionalization resembles the
shape of the micro-structure observed after plasma
treatment, this indicate that the self-assembly of n-
octadecyl mercaptan had followed the initial pattern
produced by the oxygen plasma treatment, Fig-
ure 5. The self-assembled monolayer is mostly uni-
form in form and size, ranging from 2 μm to 3 μm
in sizes and covers mostly the surface of the sub-
strate. Comparing the untreated copper immersed in
a 2.5 mM solution of n-octadecyl mercaptan and
the 600 W plasma-treated copper immersed in a
2.5 mM solution of n-octadecyl mercaptan, the ini-
tial roughening of the surface by the oxygen plasma
treatment had contributed to the good adhesion of
the self-assembled monolayer on the copper sub-
strate.
Figure 5. Scanning electron microscopy images (x10.0 K magnification) of a. untreated copper immersed in a 2.5 mM solu-
tion of n-octadecyl mercaptan, b. 600 W plasma-treated copper immersed in a 2.5 mM solution of n-octadecyl mercaptan
showing self-assembled monolayer.
© 2022 Wiley-VCH GmbH
Materialwiss. Werkstofftech. 2022, 53, 750–761
3.3 Dropwise condensation
Visual inspection of the actual images of dropwise
condensation on the untreated copper sample, Fig-
ure 6, reveal that the drops are significantly larger
compared to the drops on the superhydrophobic
copper samples, Figure 7. Images in super-
hydrophobic copper samples are post processed to
enhance the contrast against the treated copper
sample which has turned reddish brown due to the
formation of oxide layer after plasma treatment,
Figure 7. Dropwise condensation was observed to
for all treated samples that became super-
hydrophobic after the two-step modification proc-
ess. This result supports previous studies that sur-
face wetting characteristics influence how
condensate forms on a heat transfer surface. Addi-
tionally, dropwise condensation was observed at
the different cooling water settings, even at 50 °C
with no observable change in droplet behavior. The
recorded dropwise condensation at 30 frames per
seconds and 18-megapixel resolution sufficiently
captures droplet growth cycle at different location
within the 10 mm × 7.5 mm surface area of interest.
Simultaneous droplet growth cycles captured in the
recorded images correspond to roughly 15 seconds
of dropwise condensation. The number of drops at
different size range present on the surface vary with
time resulting from multiple coalescence events, re-
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Materialwiss. Werkstofftech. 2022, 53, 750–761
Figure 6. Actual images of dropwise condensation on untreated copper sheets.
Figure 7. Actual images of dropwise condensation on copper treated at 400 W of irradiation power.
generation, and sweeping events that occur simulta-
neously. Note that the objective of the study is to
present a controllable surface fabrication technique
and to show that the mobility of drops is influenced
by the presence of surface micro and nano scale
structures. As such, only the cooling water temper-
ature and the steam temperature are monitored, and
no heat transfer computations are presented.
Side by side comparison of still images of drop-
wise condensation on the untreated and the super-
hydrophobic copper also reveal the difference in
drop sizes throughout the duration of the experi-
ment. Maximum size of drops on untreated copper
is 3 times to 5 times the size of the maximum drops
on the superhydrophobic copper. At any given
time, there are comparatively smaller and more mo-
bile drops on the superhydrophobic copper. From a
heat transfer standpoint, drops that have a big foot-
print tend to retard heat transfer because it serves to
insulate the surface from the vapor. Heat transfer
during dropwise condensation is modelled by ac-
counting for all the resistances through a single
condensate drop. These resistances are namely: re-
sistance due to droplet curvature, resistance at the
liquid-vapor interface, conduction resistance
© 2022 Wiley-VCH GmbH
Droplet mobility during dropwise condensation 757
through the drop, and resistance due to the thermal
resistance of the coating material. These resistances
are dependent on the size and shape of the droplet,
such that during early stages, one resistance is more
dominant than the other, and overtime, the influ-
ence of one outweighs the other when a certain
drop size is reached. Additionally, further growth in
drop size results in higher total thermal resistance
which leads to heat flux degradation [74–75]. With
the drop growth, coalescence, departure, and re-
generation occurring simultaneously without delay,
small, mobile drops that are observed on the super-
hydrophobic copper, are more favorable from a
heat transfer perspective.
Sweep events are also monitored during the con-
densation experiments for both treated and un-
treated copper samples. As drops grow to a certain
size, the center-to-center distance between them de-
creases until such time that the drops coalesce.
Continuous growth via multiple coalescence and
vapor accretion on the surface of the drops even-
tually lead to the drops growing to such a size that
the effect of gravity outweighs the adhesive force
between the copper surface and the drops. The
drops detach from the surface and sweep all the
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758 H.S. Salapare
drops along the path. The sweeping action leaves a
swath of fresh surface area for the new generation
of drops. Using the recorded images, the interval
between sweep events were quantified. Results
showed that the average sweep interval of drops on
all treated samples were 0.94 seconds at cooling
water temperature of 40 °C. Whereas the sweep in-
terval on the untreated sample at the same cooling
water temperature is 3.5 seconds. This is com-
parable to the lowest sweep interval observed on
treated copper sample at the same cooling water
temperature, which is 0.37 seconds. This means
that sweep events are 9 times more frequent for the
superhydrophobic copper sample for the same oper-
ating condition. This also implies that the rate of
condensate formation on superhydrophobic copper
samples is much higher, and thus heat transfer rate
is also higher. Sweep events also reflect growth
rate of drops and the number of sites where these
drops nucleate. The higher the sites for drop nucle-
ation, the closely packed the drops are. Because
drops grow by accumulation of vapor on the liquid-
vapor interface and by coalescence, it may be in-
ferred that high sweep rate or lower sweep interval
is a consequence of faster droplet growth rate.
Sweep events on the treated copper samples are
also shown to be influenced by the roughness char-
acteristics of the surface. The presence of rough-
ness features on a surface that creates void volumes
can be described in terms of porosity. Porosity is
defined as the ratio of pore volume to the total vol-
ume [76]. Applying this definition, porosity can be
derived from standard roughness parameters as
porosity ¼ Vvc=Sk
where core void volume Vvc has units μm3/μm2
(volume per area) because it is normalized to the
measurement area which is 1 μm × 1 μm. Compar-
ison of porosity against sweep interval show that
the more porous the surface is, the higher is the
sweep interval, Figure 8. Conversely, the more po-
rous the surface is, the longer it takes for the drop
to depart from the surface. This is because porosity
enables the droplet to infiltrate the roughness struc-
ture, creating better solid-liquid contact. This in-
creased area of contact translates to higher adhesion
force which delays the detachment of drops from
the surface. This results to higher sweep interval or
lesser sweep events. This corroborates the findings
© 2022 Wiley-VCH GmbH
Materialwiss. Werkstofftech. 2022, 53, 750–761
Figure 8. Plot of surface porosity against sweep interval.
of a study by [10] where the concept of porosity
may be applied to explain the drop mobility ob-
served on surfaces with microscale grates and mi-
croscale posts with varying structural parameters.
Surfaces with microscale grates have lower poros-
ity and consequently will exhibit higher drop mobi-
lity, as was observed. Conversely, surfaces with
microscale posts have higher porosity such that the
observed sliding condensate diameter were com-
parably larger. Similar result is observed in another
study [57] where parallel micro-groves exhibited
smaller droplet diameter compared with drops on
cross micro-grooves. In terms of porosity, the cross
micro-groove configuration is more porous, and as
observed in the study, creates larger liquid stem
that was responsible for stickier droplet and larger
droplet departure diameter. The concept of porosity
is also in agreement with the result of another study
where, using resistant energy, they showed that the
total resistance that the condensate drop needs to
overcome depends on pillar width and spacing [77].
Increase or decrease in pillar width and spacing
also translate to a change in porosity of the surface.
As the pillar width is increased for a given spacing,
thereby reducing surface porosity, resistant energy
is reduced which favors out of plane growth of
drops. Their study shows that an optimum pillar
width and spacing exists where the resistant energy
is a minimum. In relation to the present study, fur-
ther investigation is needed to determine how much
change in sweep interval will be observed for po-
rosity values beyond the scope of this study. It is
inferred that an optimum value of porosity exists
considering that the solid-liquid interface provides
www.wiley-vch.de/home/muw
Materialwiss. Werkstofftech. 2022, 53, 750–761
an avenue for thermal energy exchange between the
condensing surface and the droplet. However, the
micro and nano scale structures are also physical
barriers that drops need to overcome for them to
depart from the surface. Thus, while an increase in
available area for nucleation is favorable for drop
growth, a corresponding increase in adhesion en-
sues which impedes droplet mobility. The concept
of porosity unifies the result of other studies that at-
tempt to elucidate the dynamic interaction between
condensate drops and surfaces with micro and
nanoscale structures but using surface roughness
parameters that describe the functional nature of the
surface.
4 Summary
In this study, a two-step fabrication process is pre-
sented which successfully altered the wettability of
the copper samples. The oxygen plasma treatment
resulted in the simultaneous formation of nano-
scale surface structures and oxide layer. This sig-
nificantly altered the surface roughness of the cop-
per samples such that the samples became hydro-
philic after plasma treatment. The formation of
oxide layer also served to improve the bond be-
tween the surface and the self-assembled mono-
layer. Surface roughness parameters Sk, Sdq, Sdr,
and Vv were found to be the relevant parameters
that can sufficiently describe the changes in surface
structure with plasma power. The samples then be-
came superhydrophobic after subsequent post func-
tionalization with water contact angle ranging from
150° to 160° after modification. Condensation ex-
periments demonstrated the influence of surface
wettability on the formation of condensate on cop-
per sheets. Results showed that dropwise con-
densation ensues when the copper samples became
superhydrophobic. Dropwise condensation was also
observed on the untreated copper sample, but the
drops were less mobile and grew to sizes that are
3x to 5x that of the maximum drop size on the su-
perhydrophobic samples. Sweep events were also
more frequent on the superhydrophobic samples.
This suggests that droplet growth rate is higher on
the treated copper samples and departs from the
surface faster. This translates to higher con-
densation heat transfer, which when applied to ther-
mal systems can result to improvements in system
© 2022 Wiley-VCH GmbH
Droplet mobility during dropwise condensation 759
performance. Porosity defined in terms of standard
roughness parameters was introduced to further
elaborate the macroscopic influence of surface
roughness on droplet mobility. It was demonstrated
that the higher the surface porosity, the higher is
the sweep interval which suggests that the drops are
less mobile. This new insights on porosity and sur-
face roughness characteristics that are influenced
by fabrication parameters can be used to guide opti-
mization of textured surfaces for condensation heat
transfer enhancement. Further characterizations are
being conducted to determine the durability and ag-
ing behavior of the post-functionalized copper sur-
faces. Results of tests such as tensile surface test-
ing, coating adhesion testing, tearing resistance
testing, heat aging resistance, heat and humidity re-
sistance testing, resistance to hydrolysis testing,
and chemical resistance testing will be reported in
the future.
Acknowledgement
This research is funded by the Engineering Re-
search and Development for Technology (ERDT)
scholarship, Science Education Institute (SEI)-De-
partment of Science and Technology (DOST), Phil-
ippines.
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Received in final form: March 22nd 2022
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