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1 A New Method For Producing Lotus Effect'' On A Biomimetic Shark Skin
1 A New Method For Producing Lotus Effect'' On A Biomimetic Shark Skin
a r t i c l e
i n f o
Article history:
Received 14 April 2012
Accepted 14 August 2012
Available online 27 August 2012
Keywords:
Biomimetic surface
Shark skin
Microreplication
Lotus effect
Superhydrophobicity
a b s t r a c t
Nature has long been an important source of inspiration for mankind to develop articial ways to mimic
the remarkable properties of biological systems. In this work, a new method was explored to fabricate a
superhydrophobic dual-biomimetic surface comprising both the shark-skin surface morphology and the
lotus leaf-like hierarchical micro/nano-structures. The biomimetic surface possessing shark-skin pattern
microstructure was rst fabricated by microreplication of shark-skin surface based on PDMS; and then it
was treated by ame to form hierarchical micro/nano-structures that can produce lotus effect. The fabricated biomimetic surfaces were characterized with scanning electron microscopy (SEM), water contact
angle measurements and liquid drop impact experiments. The results show that the fabricated dual-biomimetic surface possesses both the vivid shark-skin surface morphology and the lotus leaf-like hierarchical micro/nano-structures. It can exhibit excellent superhydrophobicity that the contact angle is as high
as 160 and maintain its robustness of the superhydrophobicity during the droplet impact process at a
relatively high Weber number. The mechanism of the micromorphology evolution and microstructural
changes on the biomimetic shark-skin surface was also discussed here in the process of ame treatment.
This method is expected to be developed into a novel and feasible biomimetic surface manufacturing
technique.
2012 Elsevier Inc. All rights reserved.
1. Introduction
Nature provides abundant examples of structures, materials
and surfaces which can be investigated to understand the basic
principle and subsequently developed into fascinating technical
applications [1]. The term biomimetic, which means learning from
nature as an impulse for an independent technical design [2] is already popular in the eld of materials science and engineering.
There are many examples of biomimetic design originated from
the investigation and copy of the special properties and mechanisms of natural plants and animals [3,4].
Such an example is the shark skin effect, which is dened as a
mechanism of wall friction reduction of a uid resulted from a riblet structured surface similar to that of shark skin [5]. Shark skin
has been widely studied for decades due to its drag reduction
and antifouling properties [68]. Micron-sized grooved scales
growing on shark skin, which are called dermal denticles, are interlocked to form a natural non-smooth surface; and the grooves between adjacent riblets on the scales are directed almost parallel to
the longitudinal body axis of the shark. It has been reported that
the grooved scales can reduce vortice formation or lift the vortice
off the surface, so resulting in water moving easily over the skin
Corresponding author. Fax: +86 20 87113949.
E-mail addresses: liuyunhong_9@163.com (Y. Liu), gjli@scut.edu.cn (G. Li).
0021-9797/$ - see front matter 2012 Elsevier Inc. All rights reserved.
http://dx.doi.org/10.1016/j.jcis.2012.08.033
surface [911]. Besides, the rough texture formed by dermal denticles can reduce the adhesion area available to aquatic organisms
and keep the surface clean. It is exciting that the principle has been
adapted to aeroplane surfaces and achieved fuel-saving by about
1.5% [12]. Speedo invented the full-body swimsuit called Fastskin for elite swimming, which mimicked the shark-skin V-shape
ridges [13]. Sharklet is another commercial product inspired by
the overlapping, ridged platelet structures of shark scales. It can
display excellent microbe resistant properties, which is very
encouraging results to date [14,15].
Another well-known example is to design and fabricate biomimetic surface possessing Lotus Effect, which is dened as the
self-cleaning properties (phenomenon) and highly superhydrophobic surface like a lotus leaf [16]. It has been reported that the surface of a lotus leaf is covered with wax and has an intrinsic
microscale and nanoscale hierarchical structures, providing superhydrophobicity, self cleaning, low adhesion and drag reduction
[1719]. Model proposed to interpret superhydrophobic phenomena was published by Cassie and Baxter [20], as well as Wenzel
[21,22]. In the past decades, designing articial superhydrophobic
surfaces has become one of the top issues due to their potential
applications in different realms, and numerous techniques have
been developed to mimic lotus effect, including electrospinning
[23], plasma treatment [24,25], chemical vapor deposition [26],
molding [27] and phase separation [28,29]. However, there is still
236
2. Experimental
2.1. Materials
Fresh shark skin from a great white shark (Carcharodon carcharias), which is one of the fastest swimming sharks, was purchased
from a sherman. The subcutaneous fat was removed from fresh
shark skin rst. The shark skin was then washed several times with
deionized water, carefully attened, cut into the required shape
and dried. The treated shark skin was stored in a refrigerator before
use. A two-component room temperature vulcanizable liquid silicone rubber including precursor of PDMS and curing agent, which
were purchased from Zhejiang Runhe Silicone New Material Co.,
Ltd., was used as received. The low viscosity precursor is composed
of vinyl-polydimethylsiloxane (PDMS), which contains 25 wt.% of
fumed silica (300 m2/g) ller treated with Si(Me)2-O-oligomers.
237
Fig. 2. The SEM images of the shark-skin surface and the surfaces of PDMS sheets prepared via microreplication.
p
2gh
238
Fig. 4. (a) The SEM images (shown at four magnications (I)(IV)) of the ame-treated SSR sample and (b) image of a water droplet sitting on the ame-treated SSR surface.
239
Fig. 5. The comparison of the SEM images of the SSR surfaces treated by ame for [(a) and (b)] 0 s; [(c) and (d)] 10 s; [(e) and (f)] 20 s; and [(g) and (h)] 30 s, respectively.
240
Fig. 6. The CA of water droplet on the surfaces of PDMS sheets fabricated via different routes and the corresponding schematic diagrams.
Table 1
Water contact angle and sliding angle measured on the various surfaces.
Sample
CA ()
SA
F-PDMS
SSR
The ame-treated F-PDMS
The ame-treated SSR
103
120
153
160
90
Stick to the surface
<1
<1
can roll back and forth with no visible distortion, exhibiting ultralow adhesion to the superhydrophobic surfaces.
In addition, as shown in Table 1, the water droplet on the FPDMS surface does not move when the slide angle is smaller than
90; and the water droplet on the SSR surface can stick to it even
though the surface is turned upside down. However, the SA for
water droplet on the superhydrophobic surfaces having nanostructures or hierarchical micro/nano-structures merely reaches a
limiting value of 1. This result suggests that the lotus leaf-like
hierarchical structured surfaces can be created through a simple
ame treatment on the biomimetic shark-skin surface made of
polymeric materials. And what is more important, just 20 s of
ame treatment on the biomimetic shark-skin surface can make
it exhibit superhydrophobicity.
The high contact angles on the hierarchical structured surface
can be easily interpreted by the Cassies theory [20] which has
been widely used to study liquid drops in contact with microstructured surfaces. Two different wetting states can be observed on
microstructured surfaces: (i) Wenzel state: the liquid droplet retains contact at all points with the solid surface below it and (ii)
Cassie state: the liquid drop sits on the highest parts of the rough
solid with trapped air underneath. The prepared dual-biomimetic
surface possessing both the vivid shark-skin surface morphology
and the lotus leaf-like hierarchical micro/nano-structures in this
work can be considered as a typical airsolid composite surface,
and the wetting behavior can be determined using the following
Eq. (2) derived by Cassie and Baxter [20]:
cos h fS cos hS fG
contact the very top of the surface and does not penetrate the interspaces among the microstructures. These results indicate that the
surface morphology plays an important role in the formation of a
superhydrophobic surface.
To investigate the durability of the biomimetic superhydrophobic surface, the ame-treated SSR sample with superhydrophobicity was either immersed in water for 2 month or continuously
exposed to the water ow from the laboratory faucet at 1.0 m/s
for 2 h and then the contact angle was measured. The test results
show that the sample surface still maintains almost the same
hydrophobicity. That is to say, there is little damage of the hierarchical structures on the surface and the dual-biomimetic surface
can exhibit excellent long-term stability. The reason for it is partly
due to the strong bonding of nano-silica particles with the PDMS
substrate.
3.3. Liquid drop impact on various surfaces
From the energy considerations [3335] for both the wetting
states, Wenzel state and Cassie state, the former is stable and the
latter is metastable. It means that the water droplet will remain
in Cassie state only if it is not subjected to external disturbances.
There exists a free-energy barrier DG for the transition from the
metastable Cassie state to the stable Wenzel state, as shown in
Fig. 7 [36,37]. So it is quite necessary to consider this transition
when the superhydrophobic surface possessing special surface
Fig. 7. Schematic view of the free-energy barrier DG separating the Wenzel and
Cassie state.
We
qV 2 r
r
241
Fig. 8. The snapshots of a droplet with 1.1 mm radius hitting various surfaces.
242
on the hierarchical micro/nano-structured ame-treated SSR surface at the impact velocity of 0.5 m/s and 0.9 m/s, respectively,
whose corresponding Weber numbers are 3.8 and 12.2, respectively, the water droplet rst deforms followed by spreading and
retracting, and nally rebounds off the surface within 10.98 ms
and 10.54 ms. The Cassie model is usually used to explain this phenomenon. In the Cassie model, air can be trapped underneath the
droplet and in the interstices of the microstructures, so that the
droplet bounces off and cannot wet the surface.
However, when the impact velocity reaches 1.5 m/s or the corresponding Weber number is 34.0, the droplet rst deforms, then
develops outward to form water ring with wavy bumps, and
eventually merges together at the center to form an elongating
water fountain. The bottom of the elongated droplet irreversibly
adheres to the solid surface, which cause the droplet not to bounce
off completely and just to be pinned on the partly wetted surface
with maintaining small contact area after 3000 ms. The abovementioned results indicate that a transition from the composite
interface to the homogenous interface can occur as the kinetic energy overcomes the surface energy and the liquid surface tension.
For the ame-treated SSR sample, if the Weber number that depends on the features, size and impact velocity of liquid droplet
reaches 34 or high, the Cassie state is broken and the droplet turns
to the wetting Wenzel state, in which it is pinned on the surface.
4. Conclusion
A brand new method was successfully developed using PDMS
containing nano-silica as a substrate for producing a dual-biomimetic surface structure comprising both the shark-skin surface
morphology and the lotus leaf-like hierarchical micro/nano-structures. It involves the PDMS microreplication processes using shark
skin as a template and the subsequent ame treatment. The SEM
observations show that the biomimetic shark-skin surface fabricated by the way of microreplication possesses vivid shark-skin
surface morphology, or micron-sized shark-skin pattern structure;
and the subsequent ame treatment makes it possess hierarchical
micro/nano-structures with no damaging its shark-skin pattern
structure, thereby constructing the dual-biomimetic surface as expected. The duration of ame treatment is an important factor
affecting and controlling the hierarchical micro/nano-structures
of the treated surface. The dual-biomimetic surface or the ametreated biomimetic shark-skin surface exhibits excellent superhydrophobicity with a low SA. Its CA reaches 160, which increases
by 40 as compared with that of the untreated biomimetic sharkskin surface. This implies that the ame treatment producing hierarchical micro/nano-structures on PDMS surfaces is a key process
to fabricate superhydrophobic surface. According to the results of
liquid drop experiment and their analyses, the robustness of the
dual-biomimetic superhydrophobic surface is conrmed and the
transition from the Cassie state to the Wenzel state arises and
the phenomenon of pining a droplet on the surface occurs when
the impact velocity exceeds a threshold velocity (V 1.5 m/s), at
which the corresponding Weber number We reaches 34.0.
Summarily, the novel method developed in this study can not
only fabricate a superhydrophobic dual-biomimetic surface as expected, but also is characterized by simplicity, high efciency and
low cost. What is more signicant, combined with the other techniques for fabricating biomimetic surfaces, it is expected to be
developed into a novel and feasible biomimetic surface manufacturing technique, that can create multifunctional biomimetic
structured surfaces providing a better performance on self-cleaning, antifouling, drag reduction, antireection, and so forth, thereby
satisfying the requirements for practical applications in different
elds. The further study on the drag reduction and anti-bioadhesion of the fabricated dual-biomimetic surface is in progress and
will be reported in our future papers.
Acknowledgments
This work was nancially supported by the National Natural
Science Foundation of China (NSFC, Grant No. 50873039) and the
Foundation of Key Laboratory of Surface Functional Structure Manufacturing of Guangdong Higher Education Institutes, South China
University of Technology (SFS-KF201011). The authors would like
to thank Peng Xinyan, Su Dong, and Li Shuai of South China University of Technology. The authors also grateful acknowledge Mr. Wu
Chaomao and his fellow workers from Yuan Ao International Trade
Co., Ltd. (Hongkong) for the friendly supply of the high-speed
camera.
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