RESTORING UNDERWATER SUPERHYDROPHOBICITY

WITH SELF-REGULATED GAS GENERATION

Choongyeop Lee and Chang-Jin “CJ” Kim
University of California, Los Angeles, California (UCLA), U.S.A.

ABSTRACT
We report an approach to restore a gas layer on
superhydrophobic surfaces by (i) implementing
self-regulating gas generation and (ii) designing surface
structures that allow the gas propagation along the surface.
Restoration of a gas layer is successfully demonstrated on
two surface patterns – mico posts and grates. The present
approach is shown to work even under harsh conditions such
as a high liquid pressure and defective surfaces.
gas pressure the liquid-gas interfaces can sustain against the
vertical direction should be larger than that against the
lateral direction. In both directions, the movement of the
interfaces is impeded by the surface tension acting on the
perimeter of surface structures. Meanwhile, the second
condition is satisfied when the liquid-gas meniscus can be
prevented from touching the bottom surface after the stable
gas formation on the surface structures.

INTRODUCTION
Superhydrophobic surfaces have been receiving great
attention in recent years for their water repellency,
self-cleaning ability, and the potential to reduce drag for
1,2
vessels and pipelines . While a giant slip (needed for the
above macroscale applications) has recently been Figure 1: Proposed approach to maintain
3,4
obtained , so far all the slip tests have been limited to superhydrophobicity. When a surface is impregnated with
“laboratory” conditions due to one unanswered question – the liquid, the gas produced from the bottom surface
how to retain the gas on superhydrophobic surfaces under displaces the liquid out of surface structures. Energy
“realistic” conditions. When a superhydrophobic surface is consumption is minimal if the gas is generated only when
impregnated somewhere by the surrounding liquid for any the liquid contacts the bottom surface.
3
reason, such as a high liquid pressure or diffusion of the gas
5
into the liquid – destined to occur in most applications, the MICROPOSTS: For a square array of microposts as shown
drag reduction is lost immediately. Recently, several in Fig. 2(a), the maximum sustainable pressure against the
methods have been devised to address this fundamental vertical direction is given by
problem by providing some stability of a gas layer against
the liquid pressure. For example, a gas layer was γπ D sin θ p , rec
6 7 ΔP = ,
pneumatically pressurized either actively or passively so Lφ
2

that it can withstand a liquid pressure. Alternatively,

hierarchically structures were employed to make
superhydrophobic surfaces more resistant to the liquid
4
pressure . However, the previous methods do not work
unless the liquid pressure is relatively small (e.g., even 0.5
atm is too high). Furthermore, they are only preventive
measures; they are ineffective once the gas layer is lost.
Here, we propose a new approach to preserve underwater
superhydrophobicty using the scheme illustrated in Fig. 1.
When the liquid impregnates surface structures, a gas
generated from the bottom surface displaces the
impregnating liquid out of the structures. We report a
success for the first time by (i) implementing a
self-regulated gas generation and (ii) designing surface
structures that restore a stable film using the generated gas.
DESIGN OF SURFACE STRUCTURES
We have started by reasoning that a gas may grow to
form a film on a structured surface if two criteria are met:
(1) The generated gas should propagate along the surface
rather than leaving off the surface. (2) The structures should
be tall enough to avoid premature wetting under a slight
liquid pressure. To satisfy the first condition, the maximum
while the pressure against the lateral direction is given by
L cos θ b, rec + 2H sin θ p , rec
ΔP = .
HL
Here, φ , H , L , θ are the gas fraction, height and pitch
(center-to-center distance between posts) of the posts, and
contact angle (CA), respectively. For the CA θ, the subscript
adv and rec mean advancing and receding, and subscript p
and b mean on the surface of the posts and on the bottom
surface between the posts, all respectively. Therefore, the
first criteria on posts can be expressed as the maximum
required height-to-pitch ratio of posts like as follows:
− cos θ b, rec
H /L< .
[2 sin θ p , rec (1 − π (1 − φ ) / φ )]

978-1-4244-9633-4/11/$26.00 ©2011 IEEE 1185 MEMS 2011, Cancun, MEXICO, January 23-27, 2011

Figure 2: Schematics of a gas spreading on (a) microposts
and (b) microgrates.
The second criteria can be satisfied when the maximum
sagging of meniscus is smaller than the height of posts as
shown in Fig. 3(a), leading us to the minimum
height-to-pitch of posts as follows:
2 − 2 (1 − φ ) / π )(−1 + sin θ p , adv )
H /L>
2 cos θ p , adv
Figure 3: Sagging of liquid-gas meniscus by liquid pressure
on (a) microposts and (b) microgrates. The sagging needs to
be smaller than the height of surface structures to maintain
a stable gas film.
MICROGRATES: The overall approach can also be
applied to microgrates as shown in Fig. 2(b). On
microgrates, the maximum sustainable pressure against the
vertical direction is given by
2γ sin θ g , rec
ΔP = ,
Lφ
while the pressure against the lateral direction is given by
1 cos θ b, rec 2 cos θ g , rec
ΔP = γ ( + + ).
H H Lφ
Here, θg,rec is a receding contact angle on the side surface of
grates. Therefore, the first criteria on posts can be expressed
as the minimum required height-to-pitch ratio of grates like
the following,
−(1 + cos θ b, rec )φ
H /L> .
2 cos θ b, rec − 2 sin θ g , rec
The second criteria can be satisfied when the maximum
sagging of meniscus is smaller than the height of grates as
shown in Fig. 3(b), leading us to the minimum
height-to-pitch of posts like the below.
φ (1 − sin θ g , adv )
H /L>
2
Combining all the resulting equations for posts and
grates, Fig. 4 graphically presents the conditions that allow
the formation of a stable gas film (“Acceptable zone”). For
microposts (Fig. 4a), there is only a limited acceptable zone
when the bottom is a smooth hydrophobic surface (i.e.,
CAb,rec = 110˚). To expand the acceptable zone, we
nanostructured the bottom surface (i.e., CAb,rec = 173.4˚),
which increases the required maximum height-to-pitch ratio
of the posts. For microgrates (Fig. 4b), the acceptable zone
is reasonably large even for a smooth bottom.
. Nanostructuring the bottom expands the acceptable zone
further by lowering the required height-to-pitch ratio of the
grates, ultimately leaving the meniscus sagging (red line) as
the sole limit.
SAMPLE FABRICATION
To realize the superhydrophobic surfaces satisfying our
design criteria, first we nanostructured the silicon substrate
using black silicon method, as a gas fraction over 0.99 has
been reported on similar nanostructures in the previous
study. Then, 200 nm / 20 nm thick Au/Cr was deposited
using e-beam evaporator and patterned as line electrodes for
electrolysis using a photolithography. Electrolysis was
deemed optimal for its simple implementation (vs.
8
pneumatic) and low energy consumption (vs. boiling).
Furthermore, electrolysis is compatible with water and the
generated gases by electrolysis last for several days.
Subsequently, 50 µm thick negative photoresist (KMPR
1050) was spin-coated and patterned to serve as microposts
or microgrates. To turn the sample hydrophobic, 2 wt%
Teflon solution in FC 40 was additionally spin-coated on
1186
the sample. Fig. 5 shows the SEM images of the fabricated
samples.
Figure 4: Geometric conditions of microposts (a) and
microgrates (b) that allow gas film formation underwater.
The “Acceptable zone” (between red and black lines for (a)
and above both red and black lines for (b)) increases when
the receding contact angle of the bottom surface increases
from 110˚ (smooth) to 173.4˚ (nanostructured).
Figure 5: Scanning electron microscopy of microposts on
nanostructured bottom surface and the embedded array of
electrodes for electrolysis.
EXPERIMENTAL RESULTS
Before testing, the proposed surfaces immersed under
the tap water were exposed to vacuum to induce the wetting
transition. Due to a high stability of nanostructures against
the wetting, nanostructures remained non-wetted even after
being exposed to vacuum, while microstructures were
observed to be wet. In the present experiment, the patterned
1187
lines on the bottom surface were used as cathode (H2
generation), while anode was placed above the tested
surface. The applied voltage across two electrodes was fixed
at 10 V, while the measured current was in the range of 1-10
mA. The gas generation process was recorded through a
microscope with X100-200 magnification.
Fig. 6 demonstrates the gas restoration on the proposed
surface. When the impregnating liquid closed the
electrochemical circuit, electrolysis was triggered. On
microposts with a smooth bottom (Fig. 6a), the generated
gas left the surface as bubbles of varying size and
non-uniform distribution, failing to restore any gas film. On
microposts with a nanostructured bottom (Fig. 6b), on the
other hand, the small patch of a gas film was formed on the
random location, and then it expanded laterally to form a
stable film, restoring the superhydrophobicity and finally
opening the circuit (i.e., self-regulated) for electrolysis.
Normally, it took about 1-2 min to restore a gas film on an
area of 2 cm by 2 cm. On the proposed surface, generated
gases are interconnected to each other through the residual
gas layer on nanostructures. Therefore, generated gas on a
nanostructured bottom is transported to the pre-formed gas
film on different locations by Laplace pressure difference,
leading to the continuous growth of the pre-formed gas film.
Figure 6: Gas generation and its fate on microstructures
(snapshots of videos recordings). (a) Microposts (100 µm
pitch; 95% gas fraction) on smooth bottom surface. (b)
Microposts (100 µm pitch; 95% gas fraction) on
nanostructured bottom surface. (c) Microgrates (50 µm
pitch; 80% gas fraction) on nanostructured bottom surface.
The generated gas leaves the surface as bubbles for (a) but
forms a stable film for (b) and (c), establishing
superhydrophobicity under water.
Using the reported scheme, we have verified a perfect
gas layer under water up to 700 kPa (vs. 0.1 kPa without the
scheme), as the pressure of newly generated gas
automatically adapted to the surrounding liquid pressure.
Moreover, nanostructures on the bottom surface enabled the
gas restoration on artificially defective surfaces by confining
the wetting only to the defected region without propagating
to the surrounding area. To prove drag-reduction, we further
confirmed the recovery of large slips underwater with flow
experiments; the fluid mechanical results have been
submitted elsewhere.
CONCLUSIONS
We have succeeded in restoring and/or maintaining
underwater superhydrophobicity by developing surface
structures allowing the formation of a stable gas layer and
implementing a self-limiting gas generation. By withstanding
a high liquid pressure and defects, our surfaces are expected
to open ways to implement superhydrophobic surfaces with a
large liquid slip for practical applications, at last.
ACKNOWLEDGEMENTS
This work has been supported by National Science
Foundation (NSF).
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