rsif.royalsocietypublishing.org Review Cite this article: Xu Q, Zhang W, Dong C, Sreeprasad TS, Xia Z. 2016 Biomimetic self- cleaning surfaces: synthesis, mechanism and applications. J. R. Soc. Interface 13: 20160300. http://dx.doi.org/10.1098/rsif.2016.0300 Received: 18 April 2016 Accepted: 18 August 2016 Subject Category: Reviews Subject Areas: biomimetics, nanotechnology Keywords: self-cleaning, biomimetic, nanostructure, gecko, lotus effect, adhesion Authors for correspondence: Quan Xu e-mail: [email protected]Zhenhai Xia e-mail: [email protected]Biomimetic self-cleaning surfaces: synthesis, mechanism and applications Quan Xu 1 , Wenwen Zhang 2 , Chenbo Dong 3 , Theruvakkattil Sreenivasan Sreeprasad 3 and Zhenhai Xia 4 1 State Key Laboratory of Heavy Oil Processing, China University of Petroleum (Beijing), Beijing 102249, People’s Republic of China 2 College of Textile, North Carolina State University, Raleigh, NC 27607, USA 3 Department of Civil and Environmental Engineering, Rice University, Houston, TX 77005, USA 4 Department of Materials Science and Engineering, University of North Texas, Denton, TX 76203, USA QX, 0000-0003-2195-2513; ZX, 0000-0002-0881-2906 With millions of years of natural evolution, organisms have achieved sophisticated structures, patterns or textures with complex, spontaneous multifunctionality. Among all the fascinating characteristics observed in biosystems, self-cleaning ability is regarded as one of the most interesting topics in biomimicry because of its potential applications in various fields such as aerospace, energy conversion and biomedical and environmental protection. Recently, in-depth studies have been carried out on various compelling biostructures including lotus leaves, shark skins, butterfly wings and gecko feet. To understand and mimic their self-cleaning mechan- isms in artificial structures, in this article, recent progress in self-cleaning techniques is discussed and summarized. Based on the underlying self- cleaning mechanisms, the methods are classified into two categories: self-cleaning with water and without water. The review gives a succinct account of the detailed mechanisms and biomimetic processes applied to create artificial self-cleaning materials and surfaces, and provides some examples of cutting-edge applications such as anti-reflection, water repellence, self-healing, anti-fogging and micro-manipulators. The prospectives and directions of future development are also briefly proposed. 1. Introduction Regular cleaning involving sanitizing materials and solutions is necessary to maintain freshness on the routine surfaces that we encounter in our day-to-day life. In addition to the economic burden, extensive cleaning potentially introduces hazardous substances to the environment and ecosystem. By contrast, various sur- faces in Nature exhibit a high intrinsic ability to clean themselves without any external aid. This phenomenon, due to its unique mechanism and high adapta- bility, has attracted tremendous research curiosity in past decades [1–10]. The concept of self-cleaning was initially unveiled based on the superhydrophobic nature of certain plant leaves. Among them, the most well-known example is the lotus leaf, which could make water droplets roll off the leaf surface quickly to achieve surface cleaning. Lotus leaves exhibit a contact angle . 1508 and a small sliding angle , 28. The high surface tension of water will assemble the dro- plets into spheres that drive the droplets to roll off the surface together with embedded dirt from the surface. On the contrary, on superhydrophilic surfaces such as Tillandsia usneoides and sphagnum moss [11], the dirt components on surfaces can be detached using only water. Here, the extremely small or even zero contact angle at the interface between the surface and the water droplets makes the dirt components movable along with the water flow on the surface. Hence, both hydrophobic and hydrophilic surfaces can be efficiently cleaned with the aid of water [12–23]. In general, removing surface-coated/adhered contaminants is difficult because it is hard to dissolve them without the help of high surface energy, solubility and mobility of water. However, intelligent, intricate architectures developed in Nature present remarkable examples of & 2016 The Author(s) Published by the Royal Society. All rights reserved. on July 6, 2018 http://rsif.royalsocietypublishing.org/ Downloaded from
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& 2016 The Author(s) Published by the Royal Society. All rights reserved.
Biomimetic self-cleaning surfaces:synthesis, mechanism and applications
Quan Xu1, Wenwen Zhang2, Chenbo Dong3, TheruvakkattilSreenivasan Sreeprasad3 and Zhenhai Xia4
1State Key Laboratory of Heavy Oil Processing, China University of Petroleum (Beijing), Beijing 102249,People’s Republic of China2College of Textile, North Carolina State University, Raleigh, NC 27607, USA3Department of Civil and Environmental Engineering, Rice University, Houston, TX 77005, USA4Department of Materials Science and Engineering, University of North Texas, Denton, TX 76203, USA
QX, 0000-0003-2195-2513; ZX, 0000-0002-0881-2906
With millions of years of natural evolution, organisms have achieved
sophisticated structures, patterns or textures with complex, spontaneous
multifunctionality. Among all the fascinating characteristics observed in
biosystems, self-cleaning ability is regarded as one of the most interesting
topics in biomimicry because of its potential applications in various fields
such as aerospace, energy conversion and biomedical and environmental
protection. Recently, in-depth studies have been carried out on various
compelling biostructures including lotus leaves, shark skins, butterfly
wings and gecko feet. To understand and mimic their self-cleaning mechan-
isms in artificial structures, in this article, recent progress in self-cleaning
techniques is discussed and summarized. Based on the underlying self-
cleaning mechanisms, the methods are classified into two categories:
self-cleaning with water and without water. The review gives a succinct
account of the detailed mechanisms and biomimetic processes applied to
create artificial self-cleaning materials and surfaces, and provides some
examples of cutting-edge applications such as anti-reflection, water repellence,
self-healing, anti-fogging and micro-manipulators. The prospectives and
directions of future development are also briefly proposed.
1. IntroductionRegular cleaning involving sanitizing materials and solutions is necessary to
maintain freshness on the routine surfaces that we encounter in our day-to-day
life. In addition to the economic burden, extensive cleaning potentially introduces
hazardous substances to the environment and ecosystem. By contrast, various sur-
faces in Nature exhibit a high intrinsic ability to clean themselves without any
external aid. This phenomenon, due to its unique mechanism and high adapta-
bility, has attracted tremendous research curiosity in past decades [1–10]. The
concept of self-cleaning was initially unveiled based on the superhydrophobic
nature of certain plant leaves. Among them, the most well-known example is
the lotus leaf, which could make water droplets roll off the leaf surface quickly
to achieve surface cleaning. Lotus leaves exhibit a contact angle . 1508 and a
small sliding angle , 28. The high surface tension of water will assemble the dro-
plets into spheres that drive the droplets to roll off the surface together with
embedded dirt from the surface. On the contrary, on superhydrophilic surfaces
such as Tillandsia usneoides and sphagnum moss [11], the dirt components on
surfaces can be detached using only water. Here, the extremely small or even
zero contact angle at the interface between the surface and the water droplets
makes the dirt components movable along with the water flow on the surface.
Hence, both hydrophobic and hydrophilic surfaces can be efficiently cleaned
with the aid of water [12–23]. In general, removing surface-coated/adhered
contaminants is difficult because it is hard to dissolve them without the help of
high surface energy, solubility and mobility of water. However, intelligent,
intricate architectures developed in Nature present remarkable examples of
superhydrophobic surface superhydrophilic surfacehorizontal line
10 mm
20 mm
(b)(a)
(c) (d )
(e)
Figure 1. Natural plants and their surface morphology. (a) Lotus leaf. (Reproduced from [35] with permission of The Royal Society of Chemistry.) (b) Scanningelectron microscopy (SEM) picture of lotus leaves. (Reproduced from [35] with permission of The Royal Society of Chemistry.) (c) Anubias leaves. (d ) SEM picture ofAnubias leaves. (Reproduced from [2] with permission of The Royal Society.) (e) Demonstration of self-cleaning on a superhydrophobic surface and a superhydrophilicsurface. For the superhydrophobic case, the particles on the surface can be removed by the rolling off of water droplets due to the high contact angle (usuallygreater than 1508) between the surface and the droplet. For the superhydrophilic surfaces, the particles on the surface can be easily separated by the small contactangle between the droplet and the surface and then taken away due to the good contact between the surface and the droplet.
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self-cleaning even without the aid of water. For example,
geckos can keep their feet clean through the unique, complex
structure of their foot skin. Pitcher plants have highly wetting
surfaces, which can cause water droplets to spread rapidly
across the surfaces. Wetting can enhance the slipperiness and
increase the capture rate of small insects as they slip off from
its rims [24,25]. Such self-evolved structures give inspiration
to researchers around the world to develop artificial materials
with self-cleaning capabilities by mimicking natural systems.
Although several reviews exist about self-cleaning [15,26–28],
rapid progress in this direction has led to the invention of
novel structures with enhanced properties, which closely
match nano/microstructures with their natural counterparts.
Hence, this mini-review focuses on recent developments
regarding different approaches for fabrication of biomimetic
self-cleaning surfaces with a particular emphasis on the
underlying mechanisms. A brief overview of some important
practical applications is also presented.
2. Self-cleaning with waterWater, the most abundant and freely available liquid system
with optimal density as well as polarity, is being used as an
essential medium to remove different types of contami-
nations on surfaces. In Nature, many ingenious designs
exist which combine surface properties and water energetics
to scour material surfaces. Lotus leaves, one of the earliest
discovered and investigated self-cleaning biosurfaces
[29,30], uses a specific water–surface interaction to clean
the surface of leaves. Young and co-workers [31–34]
proposed wetting models which can be used to explain the
self-cleaning mechanism of lotus leaves. Young’s equation
for the contact angle is given as
cos u0 ¼gSA � gSL
gLA
, ð2:1Þ
where u0 represents the contact angle of the liquid on the sur-
faces, and gSA and gSL are the surface energies of the solid
against air and liquid, respectively, and gLA is the surface
energy of liquid against air.
Young’s equation can successfully predict the contact
angle of a water droplet on a flat surface with a homogeneous
interface. If the surface is rough and the actual surface area is
larger than its flat projected area, the contact angle can be
Figure 2. Modelling of surface wetting. (a) The progress of wetting models for a droplet on a flat surface from Young’s model (flat surface) to the Cassie – Baxter model(with surface roughness). (b) Surface evolver of droplets, which is a calculation of the profile of the droplet with the minimal surface area, namely the minimal surfaceenergy. (Reproduced from [36] with permission of The Royal Society of Chemistry.) (c) Droplet profile on cones, which is a calculation of the droplet profile. (Reprintedwith permission from Michielsen S, Zhang J, Du J, Lee HJ. 2011 Gibbs free energy of liquid drops on conical fibres. Langmuir 27, 11 867 – 11 872. Copyright & 2011American Chemical Society.) (d ) Dynamic thermal simulation of droplets on a flat surface based on the chemistry interactions (this approach has requirement on dropletsize, which is limited by the computational capability). (Reproduced from [38] with permission of Nature Publishing Group.) (e) Schematics of configurations described bythe Wenzel equation (equation (2.2) for the homogeneous interface, Cassie equation equation (2.3) for the homogeneous interface and the Cassie – Baxter interface forthe composite interface with air pockets equation (2.4)). (Reprinted with permission from Bhushan B, Jung YC. 2011 Natural and biomimetic artificial surfaces forsuperhydrophobicity, selfcleaning, low adhesion, and drag reduction. Prog. Mater. Sci. 56, 1 – 108. Copyright & 2011 American Chemical Society.)
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where Rf represents the ratio of the actual surface area to its
flat projected area. As for a rough surface Rf . 1, which
means a hydrophobic surface becomes more hydrophobic
for rough surfaces and a hydrophilic surface becomes more
hydrophilic for rough surfaces. Similarly, for the hetero-
geneous surfaces composed of two fractions, the Cassie
equation can be derived
cos u ¼ f1 cos u1 þ f2 cos u2, ð2:3Þ
where f1 and f2 are the fractional area with contact angle u1
and u2, respectively.
For a composite interface consisting of a solid–liquid frac-
tion ( f1 ¼ fSL and u1 ¼ u0) and liquid–air fraction ( f2 ¼ fLA
and cos u21 ¼ 21), the Cassie–Baxter equation can be derived
cos u ¼ Rf cos u0 � fLAðRf cos u0 þ 1Þ: ð2:4Þ
Based on these proposed models, it is possible for a surface
to achieve self-cleaning ability by controlling surface
Figure 3. Biomimetic self-cleaning surfaces. (a) Fabricated through soft-lithographic imprinting. (Reprinted with permission from [51]. Copyright & 2006 WILEY-VCH Verlag GmbH & Co. KGaA Weinheim.) (b) Fabricated through an electro-brush plating and blackening process. (Reprinted with permission from [52]. Copyright& 2015, Royal Society of Chemistry.) (c) Fabricated through aluminium oxide nanoparticles. (Reprinted with permission from Alexander S, Eastoe J, Lord AM,Guittard F, Barron AR. 2015 Branched hydrocarbon low surface energy materials for superhydrophobic nanoparticle derived surfaces. ACS. Appl. Mater. Interfaces8, 660 – 666. Copyright & 2016 American Chemical Society.) (d ) Fabricated through carbon nanotubes. (Reprinted with permission from Lau KK, Bico J, TeoKB, Chhowalla M, Amaratunga GA, Milne WI, McKinley GH, Gleason KK. 2003 Superhydrophobic carbon nanotube forests. Nano Lett. 3, 1701 – 1705. Copyright& 2003 American Chemical Society.) All these approaches increased the contact angles of droplets on them through an increase in the surface roughnessbased on the Cassie – Baxter model shown in figure 1a. (Online version in colour.)
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microstructures to promote free, spontaneous movement of a
liquid droplet on the surface, allowing it to extract contami-
nants from the surfaces. Therefore, for a surface to achieve
self-cleaning, the primary goal will be to ensure that droplets
can flow or roll off smoothly from the attached surface with-
out any resistance. Natural or biosurfaces principally
maximize or minimize the contact angles of the droplets to
facilitate free liquid droplet movement. This free movement
is achieved by modulating the surface energy of the three
phases including liquid, air and solid (on the surface).
When the contact angle of the droplets is approaching
1808, it is very easy for the droplets to roll off from the surface
(e.g. lotus leaves). Zhang et al. [35] studied this effect and
found that at this maximized contact angle droplets freely
move across the leaf’s surface and remove foreign bodies
(dirt components) by dissolving them in the liquid along
the direction of motion of the droplets (figure 1a,b). However,
several other natural systems apply the opposite approach,
e.g. pitcher plants have highly wettable surfaces, which can
minimize contact angles to form a water film. The wetting
surface is so slippery that prey slide off it [25]. When the con-
tact angle approaches zero (e.g. the smooth surface structure
of Anubias barteri in figure 1c or Heliamphora nutans), water
will flow more freely on it. In the presence of water, the
good solubility and high surface energy of water favourably
wash the contaminated area, taking out the dissolved con-
taminants. Moreover, the minuscule contact angle of water
droplets will serve as a sharp knife, which can scrape the
contaminants off the surface, separating the dirt that is
already stabilized via intramolecular forces, resulting in the
simple removal of the contaminants. The scanning electron
microscopy (SEM) pictures of the lotus leaf surface mentioned
above and A. barteri leaf surface studied by Koch & Barthlott
[2] are shown in figure 1b and 1d, respectively. The higher sur-
face roughness of lotus leaves compared with A. barteri leaves
is evident from the SEM images due to the protuberances on
lotus leaves being much smaller and denser.
In short, surfaces that apply the two opposite strategies
for maximizing and minimizing the contact angle of
droplets to promote free droplet fall-off are termed super-
hydrophobic and superhydrophilic surfaces, respectively.
Figure 1e illustrates the applied mechanism for each surface’s
self-cleaning process. Although the strategy typically requires
a large amount of water to clean the surface, water-assisted
self-cleaning is still attracting a high volume of attention
from scholars, as successful adaptation and development of
the strategies could lead to a considerable reduction in
efforts/costs in cleanliness and maintenance.
Inspired by the self-cleaning surfaces found in Nature,
many technological studies employing a variety of materials
and surface modification technologies have been conducted
to fabricate artificial superhydrophobic and superhydrophilic
surfaces with self-cleaning ability. Although significant pro-
gress has been achieved, the level of efficacy attained in
Nature is yet to be fully replicated. Figure 2 illustrates the
different models proposed to understand the surface-wetting
Figure 4. Structure hierarchy of the gecko adhesive system. (a) Macrostructure: ventral view of a tokay gecko climbing a vertical glass wall. (b) Mesostructure: ventralview of the foot. The visible overlapping pads are the adhesion lamellae (scansors). (c) Microstructure: a proximal portion of a single lamella, with a visible array ofindividual setae. (d and e) Nanostructure: the branched structure of a single seta at upper right, terminating in hundreds of spatula tips. (Reprinted with permissionfrom [69]. Copyright & 2005 National Academy of Sciences.)
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process of diverse surfaces. Figure 2a demonstrates a very
traditional wetting model reported by Young, Wenzel and
Cassie–Baxter. This model can be used to estimate the con-
tact angle of rough surfaces where air pockets exist,
providing a theoretical approach for the design of functional
surfaces with special wettability. However, the effect of
gravity is not considered in the model, which leads to an
imprecise estimation of contact angles of droplets on
surfaces compared with the ones simulated with gravity
considered, resulting in high variability [40]. Figure 2bshows a droplet profile study by Muller et al. [36] based on
surface evolvers. This surface evolver is a simulation tool
that can determine the profile of the droplet with minimal
surface area, namely minimal surface energy, which indicates
that attaining low surface energy is a fundamental property
of self-cleaning surfaces [36]. Michielsen et al. [37] considered
surfaces to be composed of cones, a very common shape in
Nature, and computed the wetting behaviour of such surfaces
(figure 2c). This study implied that barrel-shaped droplets
could move spontaneously to any location along the cone
axis where the defined systems, including the liquid, solid
and gas phases, achieve their lowest Gibbs free energy. For
a constant cone angle, as the contact angle between the
liquid and the cone increases, the drop will move towards
the apex of the cone. Likewise, for a constant contact angle,
as the cone angle increases, the drop moves toward the
apex. According to this theory, it is possible to make a droplet
move towards the apex and then roll away from the surface to
clean the surface by controlling the geometry and surface
energy of the cone. Shih et al. [38] simulated the wetting be-
haviour of various surfaces with small droplets, such as the
tiny droplets in fog that have a complicated intramolecular
interaction (figure 2d ). This unique approach is used to
understand the formation of contact angles by calculating
the molecular interaction at the liquid–solid interface. This
study indicated that the quantum effect or atomic-level inter-
actions between liquid and solid phases could be
quantitatively revealed. However, this study is limited only
to small droplets due to the limited capability of the compu-
ter processing regarding the volume of the droplets. In all the
above modelling approaches, parameters including the Gibbs
free energy, surface evolver, and dynamic thermal modelling
are widely used. All these models are useful to understand
the intricate parameters and factors that control the self-
cleaning behaviour of the surfaces (figure 2e).
Experimentally, surface modification [41], which only
requires limited material consumption, proves to be the most
effective and widely used method to create a surface with
unique wetting properties. Diverse approaches, including
the creation of the three-dimensional gradient porous
Figure 5. SEM images of a polypropylene (PP) fibrillary adhesive and conventional pressure-sensitive adhesives. (a) Fibrillar adhesive contaminated by gold microspheres.(Reprinted with permission from Lee J, Fearing RS. 2008 Contact self-cleaning of synthetic gecko adhesive from polymer microfibres. Langmuir 24, 10 587 – 10 591.Copyright & 2008 American Chemical Society.) (b) Fibrillar adhesive after 30 contacts (simulated steps) on a clean glass substrate. (Reprinted with permission from LeeJ, Fearing RS. 2008 Contact self-cleaning of synthetic gecko adhesive from polymer microfibres. Langmuir 24, 10 587 – 10 591. Copyright & 2008 American ChemicalSociety.) (c) PP fibres fouled with 3210 mm glass spheres, where some can be seen deeply embedded (EM) between fibres. (Reprinted with permission from Gillies AG,Puthoff J, Cohen MJ, Autumn K, Fearing RS. 2013 Dry self-cleaning properties of hard and soft fibrillar structures. ACS Appl. Mater. Interfaces 5, 6081 – 6088. Copyright& 2008 American Chemical Society.) (d ) Polydimethylsiloxane (PDMS) fibres contaminated with 40250 mm glass spheres after 40 recovery steps. Particles canbe readily seen embedded between the fibres (EM). (Reprinted with permission from Gillies AG, Puthoff J, Cohen MJ, Autumn K, Fearing RS. 2013 Dry self-cleaningproperties of hard and soft fibrillar structures. ACS Appl. Mater. Interfaces 5, 6081 – 6088. Copyright & 2008 American Chemical Society.)
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Figure 6. (a) Model of interactions between N gecko spatulae of radius Rs, a spherical dirt particle of radius Rp and a planar wall. (Reprinted with permission from[69]. Copyright & 2005 National Academy of Sciences.) (b) One cycle of simulated steps, with contact with an initially clean glass slide: (i) applying normalcompressive force, (ii) shear load added to the compressive load by a hanging weight, (iii) removing the compressive load ( pure shear loading) and (iv) detachingthe sample. (Reprinted with permission from Lee J, Fearing RS. 2008 Contact self-cleaning of synthetic gecko adhesive from polymer microfibres. Langmuir 24, 10 587 –10 591. Copyright & 2008 American Chemical Society.) (c) Schematics of gecko toe peeling induced by digital hyperextension. (Reproduced from [71] with permission ofThe Royal Society.) (d ) Optical image of a gecko-like log constructed using SiO2 microparticles (size d ¼ 1 – 25 mm) via precisely assembling them on a glass slide witha biomimetic micromanipulator and using an atomic force microscope. (Reproduced from [88] with permission of Nature Publishing Group.)
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even smaller hairs, each of which ends in a flattened spatula
(figure 4a–e). The van der Waals (vdW) interaction between
the millions of spatulae and the surface after coming into inti-
mate contact is sufficient for the gecko to adhere to the surface
[70]. This highly evolved mechanism allows the gecko to
adhere to surfaces irrespective of whether they are hydro-
phobic or hydrophilic, dry or wet, rough or smooth. In 2005,
Hansen & Autumn [69] discovered that, in addition to this
high adhesion ability, the gecko toe pads have a unique self-
cleaning capability. Unlike the classic ‘lotus effect’, the
gecko’s self-cleaning ability does not demand the assistance
of water. This ability is regarded as a ‘dry self-cleaning’ prop-
erty because geckos can successfully dislodge most attached
contaminants simply by contacting with external surfaces
during their movement from one place to another [71,72].
Another interesting example is tree frogs. Although their
strong adhesion is aided by the secretion of mucus, the shear
movements and ‘flushing’ play an important role in shedding
particles/contaminants and keeping their feet from fouling
[73]. Mimicking these hierarchical fibrillary or thin soft film
adhesive structures, one can create the next generation of
Figure 7. Multifunctionality of self-cleaning surfaces and their applications. (a) Anti-icing surfaces obtained through increasing both the contact angle of water due to airpockets trapped in the rough surfaces and the heterogeneous nucleation energy barrier by reducing the size of particles on the surface. (Reprinted with permission fromCao L, Jones AK, Sikka VK, Wu J, Gao D. 2009 Anti-icing superhydrophobic coatings. Langmuir 25, 12 444 – 12 448. Copyright & 2009 American Chemical Society.)(b) Anti-fogging surfaces obtained through creating a superhydrophobic surface which can prevent the condensation of water. (Reprinted with permission from [93].Copyright & 2014, Royal Society of Chemistry.) (c) Water/oil separation based on the difference between the contact angles of water and oil on the same surfaces.(Reproduced from [94] with permission of The Royal Society.) (d ) Antimicrobial surface inspired by shark skin which uses a certain micro-sized pattern to resist bacteriaadhesion to the surface. (Reprinted with permission from [95]. Copyright & 2014 Springer International Publishing Switzerland.) (Online version in colour.)
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contamination. Followed by a load–drag–unload dry contact-
ing self-cleaning process, they discovered large particles rolling
during the drag process. If the particles are smaller than the
adjacent fibre distances, they may be embedded in between
those fibres. If the particles are far below the size of the
fibres, they may stay on the surfaces of those fibres and thus
be hard to remove.
The fundamental mechanism behind the self-cleaning
ability of gecko feet-like structures is also proposed. First,
Hansen & Autumn suggested that contact self-cleaning occurs
when a particle–substrate adhesive force (Fw2p) overcomes
the seta–particle adhesive forces (Fs2p), or simply Fw2p .
Fs2p (figure 6a) [69]. However, this model failed to give a com-
plete explanation of why certain particles demonstrate a
a continuous, sustained, rigorous study of different biosurfaces
present in Nature and construction of futuristic multifunctional
surfaces with unprecedented properties are expected.
Competing interests. We declare we have no competing interests.
Funding. We thank the National Nature Science Foundation of China(no. 51505501) and the National Key Research and DevelopmentPlan (no. 2016YFC0303700) for support.
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