Junghyun Park1,2, Donghyun Kim2, Hyunsik Kim2, Woon Ik Park3, Junghoon Lee4, Wonsub Chung1. 1. Department of Materials Science and Engineering, Pusan National University, Busandaehak-ro 63 beon-gil, Geumjeong-gu, Busan 46241, Republic of Korea. 2. Korea Institute of Ceramic Engineering and Technology, Soho-ro 101, Jinju, Gyeongsangnam-do 52851, Republic of Korea. 3. Department of Materials Science and Engineering, Pukyoung National University, Yongso-ro 45, Nam-gu, Busan 48513, Republic of Korea. 4. Department of Metallurgical Engineering, Pukyong National University, Yongso-ro 45, Nam-gu, Busan 48513, Republic of Korea.
Abstract
Superhydrophobic surfaces have great potential for various applications owing to their superior dewetting and mobility of water droplets. However, the physical robustness of nano/microscale rough surface structures supporting superhydrophobicity is critical in real applications. In this study, to create a superhydrophobic surface on copper, we employed copper electrodeposition to create a nano/microscale rough surface structure as an alternative to the nanoneedle CuO structure. The rough electrodeposited copper surface with a thin Teflon coating shows superhydrophobicity. The enhancement of dewetting and mobility of water droplets on copper surfaces by electrodeposition and hydrophobization significantly improved the condensation heat transfer by up to approximately 78% compared to that of copper substrates. Moreover, the nano/microscale rough surface structure of the electrodeposited copper surface exhibits better tolerance to physical rubbing, which destroys the nanoneedle-structured CuO surface. Therefore, the condensation heat transfer of the superhydrophobic electrodeposited copper surface decreased by only less than 10%, while that of the nanoneedle-structured CuO surface decreased by approximately 40%. This suggests that an electrodeposited copper surface can lead to the stable performance of superhydrophobicity for real applications.
Superhydrophobic surfaces have great potential for various applications owing to their superior dewetting and mobility of water droplets. However, the physical robustness of nano/microscale rough surface structures supporting superhydrophobicity is critical in real applications. In this study, to create a superhydrophobic surface on copper, we employed copper electrodeposition to create a nano/microscale rough surface structure as an alternative to the nanoneedle CuO structure. The rough electrodeposited copper surface with a thin Teflon coating shows superhydrophobicity. The enhancement of dewetting and mobility of water droplets on copper surfaces by electrodeposition and hydrophobization significantly improved the condensation heat transfer by up to approximately 78% compared to that of copper substrates. Moreover, the nano/microscale rough surface structure of the electrodeposited copper surface exhibits better tolerance to physical rubbing, which destroys the nanoneedle-structured CuO surface. Therefore, the condensation heat transfer of the superhydrophobic electrodeposited copper surface decreased by only less than 10%, while that of the nanoneedle-structured CuO surface decreased by approximately 40%. This suggests that an electrodeposited copper surface can lead to the stable performance of superhydrophobicity for real applications.
Condensation is a ubiquitous
phenomenon in the natural environment
and is applied to various engineering systems, such as water harvesting,
energy conversion, and heat management systems.[1−3] In particular,
the condensation heat transfer caused by the release of latent heat
to the surface of the condenser at a lower temperature than that of
vapor, where the phase change from vapor to liquid occurs, is significant
in heat-exchange systems. The condensed liquid water forms a film
or droplet depending on the wettability of the cold surface. Condensed
water forms a film on a highly wettable (hydrophilic) surface, while
water droplets are formed on a dewettable (hydrophobic) surface.[4−7] Condensed water easily spreads to form a liquid film on the hydrophilic
cold surface, which can act as a thermal barrier to inhibit the heat
transfer between the ambient and cold solid surfaces.[8,9] Moreover, the unremovable water film causes local accumulation of
contaminants and corrosion, which degrades heat transfer. In contrast,
condensed water forms droplets on the hydrophobic surface so that
the dewetted cold solid surface remains heat-transferred from the
ambient.[10,11] In addition, because the contact area of
a water droplet on a hydrophobic surface depends on the surface physical
morphology, the mobility of water droplets on the surface can be enhanced.[12,13] Therefore, it is possible to remove condensed water droplets by
gravital sliding or rolling along the surface, thereby exposing the
dewetted cold solid surface to ambient conditions for continuous condensation.[14,15] Such effects enable hydrophobic surfaces to show a more enhanced
condensation heat transfer than that of hydrophilic water-wettable
surfaces. Therefore, the hydrophobization treatments of metallic materials
can enhance the efficiency of heat exchangers, water harvesting and
desalination, environmental control, and power generation.[16]Copper and its alloys are among the most
promising metallic materials
in applications related to heat transfer because of their high thermal
conductivity, ductility, and weldability.[17,18] Therefore, surface treatment and hydrophobization techniques that
enhance condensation heat transfer have significant potential for
various applications of copper. In addition, various strategies realizing
hydrophobicity on copper surfaces have been widely explored because
the dewetting surface provides anticontamination and anticorrosion.[19,20] A coating with low-surface energy materials and control of the surface
morphology of copper are required to create a superhydrophobic surface
on copper. Thin layers of fluorocarbon materials (for example, Teflon,
FDTS, and calcium stearate), which have a negligible effect on the
surface morphology, are used to reduce the surface energy of copper.[21−23] According to the Cassie–Baxter rendering, sharp micro/nanoscale
surface morphologies were created on copper for extremely high contact
angles and mobility of water droplets.[24,25] Various techniques,
including anodizing, chemical etching, thermal oxidation, and photolithography,
have been applied to build nano- and microscale porous surface structures
supporting superhydrophobicity.[26−28] In particular, a sharp nanoneedle
CuO formed by simple chemical and thermal treatments has been widely
applied to realize superhydrophobicity and enhance condensation heat
transfer of copper and its alloys.[29,30] However, the
nanoneedle CuO structure weakly adheres to copper and is brittle;
thus, the surface structure is easily destroyed by slight physical
damage, such as smooth rubbing with a finger. Therefore, the nanoneedle-structured
CuO surface is unsuitable for real applications, such as condensation
heat transfer, where long-term operation and maintenance are critical.
For better durability, multistep electrodeposition of copper or electrodeposition
in ionic liquids is introduced to create the superhydrophobic surface,
but the fabrication processes are not suitable for practical applications
with scalability.[31−33]In this study, we employed a single-step electrodeposition
of copper
to create a nano/microsharp morphology on a copper substrate (CS)
for the fabrication of durable superhydrophobic surfaces with enhanced
condensation heat transfer. Copper is one of the most widely used
metals for electrodeposition in practical fields. The physical morphology
of the copper substrate can be controlled by a simple modification
of processing parameters, such as the chemical composition of the
electrolyte, current density, temperature, agitation, and additive.
We adopted an electrodeposition condition to create a rough surface
morphology of the copper layer, which was subsequently hydrophobized
with a thin layer of poly(tetrafluoroethylene). Such a rough copper
surface structure is expected to show better tolerance against physical
damage than that of the nanoneedle CuO surface. In addition, the hydrophobized
copper layer formed by electrodeposition had a lower thermal resistance
than that of the nanoneedle CuO surface. The condensation heat transfer
of the fabricated hydrophobic rough copper surface was evaluated and
compared with that of the nanoneedle CuO surface. Moreover, we tested
its tolerance against physical damage to maintain stable condensation
heat transfer.
Experimental Methods
A polished pure copper plate (more than 99.9%, thickness: 0.45
mm) cut into 40 mm × 25 mm pieces were used as the substrate
for copper electrodeposition. The specimens were cleaned in ethanol
with ultrasonication for 5 min and then rinsed with deionized (DI)
water. The substrate was degreased in a 15 wt % sodium hydroxide (NaOH)
solution for 1 min and then activated in 15 wt % hydrochloric acid
(HCl) solution for 15 s. Copper was electrodeposited in an aqueous
solution with 0.25 M copper sulfate pentahydrate (CuSO4·5H2O), 0.5 M sulfuric acid (H2SO4), and 2.5 mM poly(ethylene glycol) (PEG, average molar weight
400) at 50 mA/cm2 for 10, 20, and 30 min. The electrolyte
was agitated with a stirring bar and maintained at 25 °C. The
electrodeposited sample was cleaned with ethanol and dried with compressed
air. The copper specimen activated in 0.08 M nitric acid was immersed
in a 2.5 M NaOH + 0.13 M (NH4)2S2O8 solution at 60 °C for 40 min to create the nanoneedle
CuO for comparison. After cleaning the surface with distilled water
and ethanol, the specimen was heat-treated in an electric box furnace
at 180 °C for 2 h. A thin layer of Teflon was coated with 0.2
wt % Teflon solution (a mixture of Teflon AF1600 powder (DuPont) and
perfluorocompound (FC-40) to realize hydrophobicity on the copper
surface).[34,35] A Teflon solution (20 μL/cm2) was dropped on the copper surface, and the solvent was evaporated
at 110 °C for 10 min; the Teflon film was baked at 250 °C
for 15 min.The surface morphology and topography were observed
using field
emission scanning electron microscopy (FE-SEM, Mira 3 LMH, Tescan)
and atomic force microscopy (AFM, XE-100, Park Systems). The static
contact angle and contact angle hysteresis were measured using a goniometer
system (SmartDrop, Femtobiomed) at room temperature with a 5 μL
water droplet. We fabricated a test setup to evaluate condensation
heat transfer (Figure ). Hot and humid conditions were formed using an acrylic box on an
electric water bath. In addition, a copper meter bar (25 mm ×
25 mm × 50 mm, more than 99.9%) cooled with circulating liquid
was inserted through the acrylic box. The copper meter bar was covered
with a Teflon insulator, and four T-type thermocouples were placed
from the top surface at the centerline of the meter bar with a spacing
of 10 mm. The sample was attached to the top surface of the copper
meter bar using thermal grease. The surface temperature of the sample
was controlled by varying the temperature of the circulating coolant.
The condensation heat transfer on the sample surface was estimated
from the heat flux calculated from the temperature gradient in the
meter bar and the thermal conductivity of the meter bar. The sample
surface was intentionally damaged to test the tolerance to mechanical
damage by a rubbing test (DIN EN ISO 11640). We used a rubber eraser
as a counterpart of the rubbing test. The rubbing load, speed, linear
distance, and total distance are 0.98 N, 20 cycle/min, and 0.5 and
20 cm, respectively.
Figure 1
Test setup for condensation heat transfer: (a) schematic
diagram
and (b) photo images ((i) front view, (ii) side view, and (iii) side
view of the meter bar with four thermocouples).
Test setup for condensation heat transfer: (a) schematic
diagram
and (b) photo images ((i) front view, (ii) side view, and (iii) side
view of the meter bar with four thermocouples).
Results and Discussion
Fabrication of the Superhydrophobic
Copper-Electrodeposited
Surface
The wettability of a hydrophobic surface depends
on the roughness with respect to Cassie–Baxter rendering.[36,37] The morphology and roughness of the sample surfaces with copper
electrodeposition and the Teflon coating were characterized using
SEM and AFM (Figure ). The copper substrate (CS) had linear grooves formed by mechanical
polishing. In addition, the Teflon coating used in this study only
has a thickness of a few nanometers, so the hydrophobizing coating
does not significantly affect the surface morphology.[38,39] In this study, we used a low-concentration electrolyte for copper
electrodeposition and PEG as an additive, causing film growth in the
preferred orientation of copper crystals.[27,40,41] Thus, randomly rough copper surface structures
(Figure a–d)
are created by electrodeposition, and the rough structure grows with
an increase in electrodeposition time. The formation and growth of
randomly rough surface structures contributed to the increase in surface
roughness. The average roughness (Ra)
increased from 90 ± 13 nm (for the copper substrate, CS) to 271
± 25 nm after 10 min of electrodeposition (ED10), which further
increased to 387 ± 31 and 845 ± 94 nm by copper electrodeposition
for 20 min (ED20) and 30 min (ED30), respectively.
Figure 2
Surface morphology of
(a) copper substrate and electrodeposited
copper surface for (b) 10, (c) 20, and (d) 30 min. (i) SEM and AFM
images from (ii) perspective view and (iii) top view. (e) Averaged
roughness from AFM images.
Surface morphology of
(a) copper substrate and electrodeposited
copper surface for (b) 10, (c) 20, and (d) 30 min. (i) SEM and AFM
images from (ii) perspective view and (iii) top view. (e) Averaged
roughness from AFM images.According to the Cassie–Baxter state, roughness is critical
for improving the dewetting of hydrophobic surfaces formed by the
Teflon coating with stability under hot and humid conditions.[42,43] Therefore, the Teflon coating on electrodeposited copper surfaces
with different average roughness values results in varying wettability
and mobility of water droplets. The apparent contact angle and contact
angle hysteresis (advancing contact angle–receding contact
angle) were measured to estimate the wettability and mobility of water
droplets, respectively (Figure ). In addition, water droplets mixed with a blue dye on the
sample are shown in Figure . The apparent contact angle and contact angle hysteresis
of the water droplet on the copper substrate were 87.4 ± 3.5
and 73.3 ± 12.9°, respectively. The copper electrodeposition
creating a randomly rough surface structure reduces the contact area
of the water droplet on the solid surface, which significantly increases
the contact angle with an increase in the surface roughness, such
as 142.4 ± 2.3, 154.2 ± 4.2, and 168.4 ± 3.7°
for 10, 20, and 30 min of copper electrodeposition, respectively.
The contact line of the three-phase interface (solid/air/liquid) also
affects the adhesion between the two phases (water and solid surface);
thus, the mobility of water droplets is enhanced on a rough hydrophobic
surface.[44,45] Therefore, the contact angle hysteresis
decreases with an increase in the average roughness, such as 18.9
± 1.4, 6.3 ± 3.1, and 2.3 ± 0.8° for 10, 20, and
30 min of copper electrodeposition, respectively. In particular, the
surface fabricated by 30 min of copper electrodeposition and its Teflon
coating exhibited superhydrophobicity with extremely low wettability
and high mobility of water droplets. These results suggest that superhydrophobicity
can be realized on copper using electrodeposition without surface
oxidation of copper-forming nanoneedle-structured CuO, which is generally
used to fabricate superhydrophobic surfaces on copper.[29,46]
Figure 3
Image
of water droplets on (a) copper substrate and hydrophobic
copper surface electrodeposited for (b) 10 (ED10), (c) 20 (ED20),
and (d) 30 (ED30) min. CA, CA_adv, and CA_rec indicate the static
contact angle, advancing contact angle, and receding contact angle,
respectively. (e) Averaged static contact angle and contact angle
hysteresis.
Image
of water droplets on (a) copper substrate and hydrophobic
copper surface electrodeposited for (b) 10 (ED10), (c) 20 (ED20),
and (d) 30 (ED30) min. CA, CA_adv, and CA_rec indicate the static
contact angle, advancing contact angle, and receding contact angle,
respectively. (e) Averaged static contact angle and contact angle
hysteresis.
Condensation
Heat Transfer
The condensation
heat transfer of four types of samples (CS, ED10, ED20, and ED30)
was tested using the setup shown in Figure with changing coolant temperature. The coolant
temperature controlled the temperature of the surface, and the condition
of the chamber was maintained at 90 °C with hot water at the
bottom. We measured the stabilized temperature of each location in
the meter bar (Figure ), and Figure shows
the temperature profile in the meter bar. The temperature gradient
(slope of temperature vs. distance in Figure ) was estimated by linear fitting and is
summarized in Table .[47] The sample surface temperature was
calculated considering the linear relationship between the temperature
and location in the meter bar (Table ). Even though the thermal conductivity of Teflon (poly(tetrafluoroethylene))
is 0.25 W/m·K, which is relatively very lower than that of copper,
the Teflon layer shows negligible thermal resistance on the copper
surface, due to its extremely low thickness (∼2 nm).[48] The sample surface had a lower temperature with
a decrease in the coolant temperature; thus, the temperature difference
between the vapor and sample surface increases, thereby enhancing
water condensation. In addition, the decrease in the coolant temperature
contributed to an increase in the temperature gradient in the meter
bar. When the coolant temperature was 70 °C, the temperature
gradients were −0.23, −0.30, −0.30, and −0.35
for CS, ED10, ED20, and ED30, respectively, showing no significant
difference. However, the hydrophobic surface with improved mobility
(low contact angle hysteresis) of the water droplet shows a significantly
enhanced temperature gradient with a decrease in the coolant temperature.
In particular, the temperature gradient of ED30 was higher than that
of CS by approximately 1.78-fold at a coolant temperature of 10 °C,
while ED30 shows approximately 1.55-fold higher temperature gradient
than that of CS at a coolant temperature of 50 °C. Hydrophobized
copper electrodeposition with high mobility of water droplets also
increases the surface temperature (Table ) for coolant temperatures below 50 °C.
In contrast, no significant difference was observed in the surface
temperature at a coolant temperature of 70 °C.
Figure 4
Temperature profile in
the meter bar during the condensation test
for (a) copper substrate and hydrophobic copper surface electrodeposited
for (b) 10 (ED10), (c) 20 (ED20), and (d) 30 (ED30) min with a coolant
temperature of 10 (CT10), 30 (CT30), 50 (CT50), and 70 (CT70) °C.
Table 1
Measured and Estimated Data from the
Condensation Heat Transfer Test for the Copper Substrate (CP) and
Hydrophobic Copper Surface Electrodeposited for 10 (ED10), 20 (ED20),
and 30 (ED30) min
coolant
temp
10 °C
30 °C
50 °C
70 °C
sample
CP
ED10
ED20
ED30
CP
ED10
ED20
ED30
CP
ED10
ED20
ED30
CP
ED10
ED20
ED30
temp gradient (°C/cm)
–0.97
–1.30
–1.47
–1.73
–0.67
–0.93
–1.03
–1.31
–0.47
–0.53
–0.68
–0.73
–0.23
–0.30
–0.30
–0.35
surface temp (°C)
15.9 ± 1.0
16.9 ± 0.9
17.3 ± 1.0
18.0
± 0.9
34.6 ± 0.8
35.8 ±
1.1
35.9 ± 1.1
36.2 ± 0.8
52.5 ± 1.0
52.8 ± 1.1
53.2 ± 0.9
53.3 ± 0.7
71.1
± 1.0
70.9 ± 1.0
71.2 ±
0.8
70.8 ± 1.2
Temperature profile in
the meter bar during the condensation test
for (a) copper substrate and hydrophobic copper surface electrodeposited
for (b) 10 (ED10), (c) 20 (ED20), and (d) 30 (ED30) min with a coolant
temperature of 10 (CT10), 30 (CT30), 50 (CT50), and 70 (CT70) °C.The increased temperature gradient in the meter bar
and surface
temperature of the sample due to the enhanced dewetting and mobility
of water droplets on the hydrophobized copper electrodeposition indicates
a change in the heat transfer in the copper meter bar. The transferred
heat (Q) from the sample surface to the coolant through
the meter bar can be calculated using the following equation[49,50]where λ, ΔT,
and d are the thermal conductivity of the copper
meter bar (391.1 W/(m·K)), temperature difference, and distance
between thermocouples, respectively.[17] The
temperature gradient summarized in Table corresponds to ΔT/d; thus, the heat flux through the copper meter
bar can be calculated.[51,52]Figure shows the calculated heat flux (condensation
heat transfer) as a function of the temperature difference between
the water vapor and the sample surface. The surface appearances of
the sample with condensed water droplets are shown in Figure .
Figure 5
Condensation heat transfer;
(a) estimated heat flux and appearance
of condensed water on (b) copper substrate and hydrophobic copper
surface electrodeposited for (c) 10 (ED10), (d) 20 (ED20), and (e)
30 (ED30) min.
Condensation heat transfer;
(a) estimated heat flux and appearance
of condensed water on (b) copper substrate and hydrophobic copper
surface electrodeposited for (c) 10 (ED10), (d) 20 (ED20), and (e)
30 (ED30) min.A lower temperature of the sample
surface than that of water vapor
causes the condensation of water on the surface. Thus, the latent
heat of condensation is released on the surface, which is transferred
to the meter bar and then to the coolant to condense more water on
the sample surface, producing a greater heat flux with a higher temperature
gradient in the meter bar. In addition, the higher the latent heat
by condensation, the higher the surface temperature of the sample.
For the coolant temperature of 70 °C, because the temperature
gradients of the samples did not show any significant difference,
the heat flux by condensation heat transfer showed a similar value
for each sample. However, with a decrease in the coolant temperature
from 70 to 10 °C, the heat flux on the CS increases by more than
4.2-fold. Nevertheless, the hydrophobized copper-electrodeposited
surfaces (ED10, ED20, and ED30) showed a more significant increase
in heat flux than for the CS. The decrease in the coolant temperature
from 70 to 10 °C increases the condensation heat flux by more
than 4.3-, 4.9-, and 5.5-fold for ED10, ED20, and ED30, respectively.
In particular, ED30 with the lowest contact angle hysteresis showed
the most significant increase in the heat flux with the highest surface
temperature. Therefore, the temperature difference between the water
vapor and sample surface (Tvap – Tsurf) slightly decreases with the condensation
heat transfer.The shape and mobility of water droplets on a
superhydrophobic
copper surface enhance the condensation heat transfer. The CS surface,
easily wettable by water, shows widespread water droplets (Figure b) as a filmwise
condensation. Moreover, the water droplet is almost immobile on the
CS surface, and the water film wetting the copper surface is not easily
removed by gravity. However, the condensed water shows a spherical
shape on the hydrophobic copper surfaces (Figure c–e), indicating dropwise condensation
due to their dewetting property, which shows a high apparent contact
angle of the water droplet. Despite the spherical shape of the condensed
water droplets, the hydrophobic surfaces demonstrate different sizes
of water droplets. ED10 showed the largest number of water droplets
pinned on the surface. The size of the water droplets was smaller
on the ED20 surface than in the case of ED10. The gravity of a water
droplet on a vertically inclined hydrophobic surface provides a force
to roll off the droplet along the surface so that a small droplet
is easily mobile on the surface with high mobility of water droplets
(low contact angle hysteresis).[53,54] Therefore, the condensed
water droplet on the ED20 surface with a lower contact angle hysteresis
than that of ED10 cannot be grown up to the droplet size on the ED10
surface. In the case of ED30 with the lowest contact angle hysteresis,
a significant area of noncondensed copper surface is exposed to ambient
and smaller condensed water droplets than in the case of ED20. These
results are attributed to the frequent roll-off of the condensed water
droplet with a small size. A rolling condensed water droplet combines
with other droplets along the rolling path; thus, a larger area of
the cold copper surface can be exposed to humid conditions to initiate
the nucleation of water condensation. These results indicate that
coating with a thin hydrophobic material and controlling the surface
morphology enhance water mobility, significantly improving the condensation
heat transfer.To examine the stability of the Teflon layer,
the contact angle
of water droplets on ED30 is measured after testing condensation heat
transfer up to 7 days (Figure a) and exposing to air up to 24 days (Figure b). During the condensation heat transfer
testing, the contact angle of the water droplet on ED30 is consistently
maintained at 170–175°, showing the superhydrophobicity.
Moreover, the exposure of ED30 to air for a month does not affect
the contact angle of 170–175°. These results indicate
that the Teflon coating on roughly electrodeposited copper stably
shows superhydrophobicity both under humid and air conditions over
time.
Figure 6
Contact angle of water droplets on the ED30 surface after (a) condensation
heat transfer test up to 7 days and (b) exposure to air up to 24 days.
Contact angle of water droplets on the ED30 surface after (a) condensation
heat transfer test up to 7 days and (b) exposure to air up to 24 days.
Tolerance to Physical Damage
Nanoneedle
CuO (NNC) structures are generally used to fabricate superhydrophobic
surfaces on copper substrates. Moreover, the enhancement of condensation
heat transfer is achieved owing to its exceptional water droplet mobility.
We compared the condensation heat transfer of the superhydrophobic
copper-deposited surface with that of the NNC surface. In addition,
the tolerance of the superhydrophobic copper-electrodeposited and
NNC surfaces to mechanical damage was evaluated using a rubbing test
(DIN EN ISO 11640) with an elastomer. The changes in the surface morphology,
distribution of fluorine, and wettability by the rubbing test are
shown in Figure .
In the case of the superhydrophobic electrodeposited copper surface,
the rough-structured surface is stronger than the elastomer; thus,
no significant damage is found on the surface, and only worn elastomer
particles adhere to the rough structure. Moreover, no significant
change in fluorine distribution indicating the coated Teflon on the
surface is observed. Such elastomer particles adhered to the rough
structure inhibit the dewetting of the hydrophobic surface, so the
apparent contact angle of ED30 decreases from 168.4 ± 3.7 to
158.6 ± 3.9°, indicating that the surface is still superhydrophobic.
The superhydrophobic NNC surface showed a significant change in the
surface structure and wettability by the rubbing test. Owing to the
brittle nature of CuO, most of the sharp nanoneedle structure, which
effectively supports the Cassie–Baxter interface for superhydrophobicity,
is destroyed by rubbing, so the distribution of fluorine is significantly
decreased, indicating the removal of the coated Teflon layer. For
these reasons, the apparent contact angle of the water droplet on
the damaged NNC surface is significantly decreased from 174.2 ±
1.4 to 132.6 ± 3.3°. These results imply that a simple physical
contact can easily degrade the superhydrophobicity of the NNC-structured
surfaces.
Figure 7
Surface morphology of (a) hydrophobic copper surface electrodeposited
for 30 min (ED30) and (b) hydrophobic nanoneedle copper oxide surface
(i) before and (ii) after rubbing. (c) Averaged static contact angle
and contact angle hysteresis.
Surface morphology of (a) hydrophobic copper surface electrodeposited
for 30 min (ED30) and (b) hydrophobic nanoneedle copper oxide surface
(i) before and (ii) after rubbing. (c) Averaged static contact angle
and contact angle hysteresis.The degradation of hydrophobicity by damage to the micro/nanostructure
can also deteriorate the condensation heat transfer; thus, we measured
the condensation heat transfer of the superhydrophobic ED30 and NNC
surfaces with and without the rubbing test (Figure ). The temperature gradients and surface
temperatures are summarized in Table . The intact NNC demonstrated higher temperature gradients
(slope of temperature vs. distance in Figure ) and surface temperature than those of ED30
for each coolant temperature, indicating better condensation heat
transfer of the NNC surface than that of the ED30 surface. These results
are in good agreement with the NNC surface, showing better mobility
and dewetting of water droplets than those of the ED30 surface (Figure ). Despite such superior
hydrophobicity and condensation heat transfer, the damaged NNC showed
significantly reduced temperature gradients by more than 35% than
the entire surface because the physical damage to NNC by rubbing with
an elastomer significantly deteriorates the dewetting and mobility
of water droplets. However, regardless of the physical damage, the
ED30 surface showed a less-significant reduction in the temperature
gradient by less than 10% compared to that of the entire surface.
Moreover, the temperature gradients of the damaged ED30 were higher
than those of the NNC with damages for each coolant temperature.
Figure 9
Condensation
heat transfer of the damaged surface; (a) estimated
heat flux and appearance of condensed water on (b) hydrophobic copper
surface electrodeposited for 30 min and (c) hydrophobic nanoneedle
copper oxide surface (i) before and (ii) after rubbing.
Table 2
Measured and Estimated Data from the
Condensation Heat Transfer Test for the Hydrophobic Copper Surface
Electrodeposited for 30 min (ED30) and Hydrophobic Nanoneedle Copper
Oxide (NNC) with and without Surface Rubbing
coolant temp
10 °C
30 °C
50 °C
70 °C
ED30
NNC
ED30
NNC
ED30
NNC
ED30
NNC
sample
intact
damage
intact
damage
intact
damage
intact
damage
intact
damage
intact
damage
intact
damage
intact
damage
temp gradient (°C/cm)
–1.73
–1.57
–1.87
–1.03
–1.31
–1.2
–1.49
–0.93
–0.67
–0.66
–0.8
–0.5
–0.35
–0.32
–0.4
–0.26
surface temp (°C)
18.0 ± 0.9
16.9 ± 1.0
18.3 ± 0.7
15.7
± 1.0
36.2 ± 0.8
35.5 ±
1.3
37.3 ± 0.3
35.3 ± 0.9
53.1 ± 0.7
52.8 ± 1.1
53.7 ± 0.5
52.1 ± 1.0
70.8
± 1.2
70.9 ± 1.1
71.7 ±
0.6
70.6 ± 1.3
Figure 8
Temperature
profile in the meter bar during the condensation test
for (a) hydrophobic copper surface electrodeposited for 30 min and
(b) hydrophobic nanoneedle copper oxide surface (i) before and (ii)
after rubbing at a coolant temperature of 10 (CT10), 30 (CT30), 50
(CT50), and 70 (CT70) °C.
Temperature
profile in the meter bar during the condensation test
for (a) hydrophobic copper surface electrodeposited for 30 min and
(b) hydrophobic nanoneedle copper oxide surface (i) before and (ii)
after rubbing at a coolant temperature of 10 (CT10), 30 (CT30), 50
(CT50), and 70 (CT70) °C.Figure illustrates the condensation heat transfer
calculated
from the temperature gradients in Table and the surface appearance during condensation.
In the case of the NNC surface, the condensation heat transfer values
are 4.8 ± 0.6, 9.7 ± 1.2, 18.1 ± 0.8, and 2.3 ±
1.6 (kW/m2) for the coolant temperatures of 10, 30, 50,
and 70 °C, respectively, which are higher than those of the ED30
surface by less than 15%. In addition, the temperature difference
between the humid atmosphere and the sample surface of NNC is lower
than that of the ED30 surface. These results indicate that the superhydrophobic
NNC has superior condensation heat transfer compared to that of the
superhydrophobic electrodeposited copper surface. Nevertheless, a
physical rubbing test destroying the brittle nanoneedle CuO structure
diminishes the dewetting and mobility of water droplets; thus, the
size of the condensed water droplet pinned on the surface significantly
increases (Figure b). Such changes in the wetting of the condensed water decrease the
condensation heat transfer by more than 35%. Although the condensation
heat transfer of the entire ED30 surface is slightly lower than that
of the entire NNC surface, the dewetting and mobility of water droplets
on the damaged ED30 surface are better than those on the NNC surface.
Therefore, smaller condensed water droplets were pinned on the damaged
ED30 surface (Figure c) than on the damaged NNC surface (Figure b). These results indicate that the superhydrophobic
surface fabricated on an electrodeposited copper surface has superior
physical contact tolerance compared to that of the superhydrophobic
surface with a nanoneedle CuO structure. Owing to the robustness of
the rough structure by copper electrodeposition, a stable surface
with dewetting and mobility of water droplets can be enabled against
physical contacts, which may destroy the rough surface structure of
NNC, supporting the superhydrophobicity. Therefore, the condensation
heat transfer values of the damaged ED30 surface are higher than those
of the damaged NNC surface by more than 22%, such as 3.9 ± 1.0,
8.0 ± 1.2, 14.5 ± 0.6, and 19.0 ± 0.4 (kW/m2) for the coolant temperatures of 10, 30, 50, and 70 °C, respectively.
Stable performance against unwanted physical contacts and physical
robustness of the surface structure are two of the most important
characteristics for the practical application of hydrophobic surfaces.
Therefore, although the hydrophobic performance was slightly less
than that of the previous nanoneedle CuO structure, the physically
robust rough structure by copper electrodeposition can be a potential
candidate for practical applications of hydrophobic surfaces, including
condensation heat transfer. Moreover, since hydrophilic or hydrophilic/hydrophobic
hybrid surfaces provide benefits in boiling heat transfer, the application
of a durable rough electrodeposited copper surface with scalability
and practical feasibility can be extended to heat exchange using boiling
heat transfer.[55−60]Condensation
heat transfer of the damaged surface; (a) estimated
heat flux and appearance of condensed water on (b) hydrophobic copper
surface electrodeposited for 30 min and (c) hydrophobic nanoneedle
copper oxide surface (i) before and (ii) after rubbing.
Conclusions
A multifunctional superhydrophobic
surface can be fabricated using
a thin Teflon coating on an electrodeposited copper surface. The microscale
roughness of the copper deposit increases with an increase in the
electrodeposition duration, thereby enhancing the dewetting and mobility
of the water droplet. This enhancement contributes to the easy roll-off
of condensed water droplets on the cold surface; thus, the surface
of an electrodeposited copper layer with a Teflon coating shows a
significant improvement in the condensation heat transfer. Moreover,
the rough microscale structure fabricated by copper electrodeposition
has a better tolerance against physical contacts that destroy the
rough surface structure, such as rubbing, compared to that of the
nanoneedle CuO structure, which is generally used to fabricate superhydrophobic
surfaces on copper. Therefore, the superhydrophobic electrodeposited
copper surface shows stable condensation heat transfer. In contrast,
the superhydrophobic nanoneedle CuO surface is significantly damaged
by surface rubbing, which causes significant debilitation in condensation
heat transfer.
Authors: Nenad Miljkovic; Ryan Enright; Youngsuk Nam; Ken Lopez; Nicholas Dou; Jean Sack; Evelyn N Wang Journal: Nano Lett Date: 2012-12-17 Impact factor: 11.189
Authors: Yufen Zhang; Frank Feyerabend; Shawei Tang; Jin Hu; Xiaopeng Lu; Carsten Blawert; Tiegui Lin Journal: Mater Sci Eng C Mater Biol Appl Date: 2017-04-12 Impact factor: 7.328