Arabian Journal of Chemistry (2020) 13, 1763–1802

King Saud University

Arabian Journal of Chemistry

www.ksu.edu.sa
www.sciencedirect.com

REVIEW ARTICLE

Science and Engineering of Superhydrophobic

Surfaces: Review of Corrosion Resistance,
Chemical and Mechanical Stability
Gh. Barati Darband a, M. Aliofkhazraei a,*, S. Khorsand b, S. Sokhanvar a,
A. Kaboli a

a
Department of Materials Engineering, Tarbiat Modares University, P.O. Box: 14115-143, Tehran, Iran
b
Brunel Centre for Advanced Solidification Technology (BCAST), Brunel University London, Uxbridge, Middlesex UB8 3PH, UK

Received 26 October 2017; accepted 23 January 2018

Available online 17 February 2018

KEYWORDS Abstract Investigations on superhydrophobic surfaces (SHS) are very interesting because of their
Chemical durability; importance in many applications. One of the major applications of these SHS is to increase the cor-
Corrosion resistance; rosion resistance of surfaces exposed to corrosive environments as well as their long-term chemical
Mechanical stability; stability and maintaining the superhydrophobic characteristics. Deep understanding of how to
Superhydrophobic surfaces increase the corrosion resistance by SHS has a significant effect on the development of strategies
to improve corrosion resistance and long-term chemical stability of these surfaces. Other important
properties that limited the real use of superhydrophobic surfaces are mechanical stability. In this
review article, an overview of SHS is provided, and then their fabrication methods discussed.
Moreover, the corrosion resistance of these SHS fabricated by various methods and their chemical
stability and mechanical stability are reviewed. -In the following, recent strategies for improvement
of corrosion resistance, chemical and mechanical stability are reviewed.
Ó 2018 Production and hosting by Elsevier B.V. on behalf of King Saud University. This is an open access
article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1765
2. Wetting phenomena. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1765
2.1. Wettability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1765
* Corresponding author.
E-mail addresses: maliofkh@gmail.com, khazraei@modares.ac.ir (M. Aliofkhazraei).
Peer review under responsibility of King Saud University.

Production and hosting by Elsevier

https://doi.org/10.1016/j.arabjc.2018.01.013
1878-5352 Ó 2018 Production and hosting by Elsevier B.V. on behalf of King Saud University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
1764 Gh. Barati Darband et al.

2.2. Requirements for fabrication of SHS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1765

2.2.1. Surface energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1766
2.2.2. Surface roughness . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1766
2.3. Wetting models. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1766
2.4. Rolling angle and the wetting angle hysteresis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1767
3. Application of superhydrophobic surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1767
3.1. Increase of corrosion resistance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1767
3.2. Anti-fogging surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1767
3.3. Anti-bacterial surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1767
3.4. Anti-icing surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1768
3.5. Oil and water separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1768
3.6. Self-cleaning surfaces. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1768
3.7. Drag reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1768
3.8. Battery manufacture technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1768
3.9. Sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1769
3.10. Water purification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1769
3.11. Optical devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1769
3.12. Membrane distillation and water desalination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1769
3.13. Microfluidic devices. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1769
3.14. Other applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1770
4. Fabrication of SHS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1770
4.1. Sol-gel method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1770
4.2. Electrospinning. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1770
4.3. Electrochemical methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1770
4.4. Layer-by-layer method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1771
4.5. Plasma techniques. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1771
4.6. Other important methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1771
5. Corrosion resistance of SHS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1771
5.1. Electrodeposition method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1772
5.2. Chemical fabrication methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1774
5.3. Sol-gel fabrication method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1777
5.4. Spray coating fabrication method. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1779
5.5. Hydrothermal synthesis fabrication method. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1780
5.6. Electrospinning fabrication method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1782
5.7. Laser operations fabrication method. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1782
5.8. Methods based on anodic oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1783
5.8.1. PEO and MAO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1783
5.8.2. Anodizing method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1785
5.9. Plasma techniques. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1785
5.10. Other fabrication methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1785
6. Chemical stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1786
6.1. The necessity of chemical stability investigation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1786
6.2. Chemical stability fading mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1786
6.2.1. Loss of roughness . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1786
6.2.2. Dissolution of surface layer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1786
6.3. Chemical stability evaluation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1786
6.3.1. Contact angle versus pH variations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1786
6.3.2. Contact angle versus immersion time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1788
6.3.3. Acid rain test . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1790
6.3.4. Droplet test in vapor-saturated atmosphere . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1790
6.4. Chemical stability improvement approaches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1791
7. Mechanical stability. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1791
7.1. Necessity of mechanical stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1791
7.2. Fading mechanism of superhydrophobicity due to mechanical contacts . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1792
7.3. Important approaches for improvement of mechanical stability. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1792
8. Concluding remarks and future trends. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1793
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1793
Science and Engineering of Superhydrophobic Surfaces
1. Introduction
Wettability of solid surfaces attracts many attentions both in
research and practical applications. Studies conducted on the
superhydrophobic surfaces have grown dramatically since
2004 and several review articles have been published about dif-
ferent aspects of superhydrophobic surfaces (Chu and Seeger,
2014; Ragesh et al., 2014; Bagheri et al., 2018; Shin et al., 2016;
Simpson et al., 2015; Su et al., 2016; Tam et al., 2016). Basi-
cally, superhydrophobic surfaces are described by static con-
tact angles higher than 150° and sliding angle less than 10°.
It is well known that the wettability of a solid surface is a func-
tion of two primary factors including surface roughness and
surface chemistry. The chemical composition of the surface
determines the surface energy, which has a great effect on its
wettability. However, only changing the surface chemistry
cannot determine the superhydrophobic state, and these two
factors must exist simultaneously (Woodward et al., 2000).
The surface topology also has a significant effect on the super-
hydrophobic nature of the surface. Surface roughening by
increasing the solid-liquid interface also increases the superhy-
drophobic state. By controlling these two parameters,
numerous methods were developed to fabricate SHS including
template based (Barshilia et al., 2012; Victor et al., 2012),
electrospinning (Gu et al., 2010), sol-gel (Lakshmi et al.,
2011), layer by layer (Zhao et al., 2012), etching (Yin et al.,
2012b), and electrochemical deposition (Crick et al., 2013)
methods, etc.
Superhydrophobic coatings have found many applications
in industry including anti-fog coating, anti-freeze surfaces,
oil and water separation, anti-bacterial surfaces, and medical
applications. Improving corrosion resistance is one of the most
important current problems of society causing large damages
(Bagheri et al., 2017; Forooshani et al., 2017). In general, cor-
rosion damage cannot be stopped completely, but there are
many methods for decreasing it; e.g., cathodic and anodic pro-
tection, using protective coating to reduce the corrosion rate.
One of the important coating methods to reduce the corrosion
rate of surfaces is to use superhydrophobic coatings. Basically,
it is believed that by creating an air layer between the surface
and corrosive environment, SHS prevent contact between the
corrosive ions and surface. In addition, these surfaces, reduce
the portion of real contact between the corrosive electrolyte
and surface, and thereby increase the corrosion resistance.
However, most of the superhydrophobic surfaces lose their
superhydrophobic characteristics once exposed to chemical
environment and they do not have enough long term stability.
Another factor that makes it difficult to use SHS is the long-
term chemical stability. Most of the superhydrophobic
surfaces once exposed to the chemical environment lose their
Fig. 1 Illustration of contact angles formed by sessile liquid drops on a smooth homogeneous solid surface (Yuan and Lee, 2013).
1765
superhydrophobic characteristics. Thus, nowadays, the strate-
gies for improving the long-term chemical stability are among
the most important challenges. Moreover, when the SHS influ-
enced by abrading forces, the wetting model is changed from
Cassie-Baxter to Wenzel, thus the liquid will penetrate inside
the surface pores and cracks and superhydrophobicity with
low hysteresis angle is destroyed. Therefore, mechanical dura-
bility is one of the other important factors which cause the
limitation of real use of SHS.
Based on mentioned difficulties with the real use of super-
hydrophobic surfaces, the corrosion resistance of SHS fabri-
cated by different methods, long-term chemical stability,
mechanical durability and recent developments in techniques
developed for improving corrosion resistance, chemical stabil-
ity and mechanical durability are reviewed in this paper.
2. Wetting phenomena
2.1. Wettability
Wetting of solid surfaces by liquid materials is an important
aspect of materials science and surface chemistry, and in clues
in practical applications in everyday life and industry. Ideally,
once a drop is placed on a surface, it forms a sphere or wets the
surface completely. The first and second cases are called anti-
wetting and super wetting, respectively (Durand et al., 2011).
In wetting studies, usually the contact angle is one of the
most important data showing the amount of the wetting value
when a liquid and solid are in contact with each other. Con-
sider a drop of liquid placed on a horizontal surface (Fig. 1).
The contact angle is defined as the angle formed by the inter-
section of the solid, liquid, and solid-gas interface. Fig. 1 shows
that the small contact angle is formed when the liquid is dis-
tributed on the surface, while large contact angles are formed
when there is lower contact area between solid and liquid
(Yuan and Lee, 2013).
2.2. Requirements for fabrication of SHS
SHS have been considered as important subjects in recent dec-
ades. These coatings can be applied on any surface, and this is
one of the features that made them attractive. For the first
time, SHS were widely industrially applied in highway speed
cameras in Germany (Kavale et al., 2011; Mohammadi
et al., 2004). Surface free energy, surface roughness, and
homogeneity are three important factors in controlling the
wettability, where the impact of the first two factors is more
important. Surface structures/roughness able to trap a high
amount of air in order to stabilize the Cassie-Baxter state.
The maximum wettability angle obtained for water on a flat
1766
surface by reducing the surface energy was about 120°. Fabri-
cation of uneven structure is necessary to reach higher angles.
By taking various approaches, we can fabricate rough surfaces
with low surface energy as their wettability angle is reported up
to 170° (Ma and Hill, 2006; Onda et al., 1996; Shibuichi et al.,
1996).
2.2.1. Surface energy
The decrease in surface energy is very common to achieve the
superhydrophobic surfaces. Surfactants are used for lowering
the surface energy. These compounds have a variety of differ-
ent types and applications. Silane groups are greatly consid-
ered for reducing the surface energy. In silane groups,
fluoroalkylsilanes are paid most attention, because, among
the identified compounds, it has the greatest impact on reduc-
ing the surface energy. Due to the simultaneous presence of
CF2 and CF3 groups, these compounds are very efficient.
On the other hand, due to their high cost and hazards bringing
to the environment by the presence of fluorine, researchers are
looking for alternative substances (substances such as stearic
acid and polymers) (Genzer and Efimenko, 2006; Yao and
He, 2014).
2.2.2. Surface roughness
An uneven surface is imperative to achieve superhydrophobic
property. Since in such surfaces, air bubbles are caught in the
ups and downs of the surface, when water is put on the surface,
it does not contact with all surface points. Due to low energy
of surface and the presence of air, water does not penetrate
into the valley and consequently, the surface area is reduced
which results in a reduction of friction (Fig. 2). As a result,
droplets slip on the surface easily (Onda et al., 1996;
Shibuichi et al., 1996). Methods for fabrication unevenness
Fig. 2 Trapped air between liquid and solid phases.
Fig. 3 Different wetting models.
Gh. Barati Darband et al.
can be divided into two bottom-up and top-down classifica-
tions. In the bottom-up approach, usually, nanoparticles are
used as the main constituents. In the top-down approach,
some methods such as etching and lithography with or without
a mask are used to fabricate the cover. Recently, processes
which considered combining these two methods are receiving
more interest (Yao and He, 2014).
2.3. Wetting models
Before discussing the SHS, firstly wetting and different theo-
retical models are described. Here, the original models for wet-
ting are presented and simple principles of each model are
discussed. The first model was introduced in 1805 by Young
(Good, 1952; Young, 1805; Zhao et al., 2005a,b). For a drop
of liquid on an ideal flat surface (Fig. 3a), in this model, wet-
ting is defined by the surface free energy of a solid and derived
by Eq. (1) according to Young’s equation:
c  csl
cos h ¼ sv ð1Þ
clv
where, c is the surface tension, which represents energy per
unit area. As shown in this equation, the surface energy is pro-
portional to the contact angle. It can be said that Young angle
is fabricated by thermodynamic equilibrium of free energy sur-
faces at the solid-liquid-gas interface. Since the actual surfaces
usually have different surface conditions and surface rough-
ness of solid plays a significant role in determining the wetta-
bility, most of the contact angle states, in practice, cannot be
fully explained by Young’s equation. In 1936, Wenzel
suggested an equation where the surface roughness and surface
energy are associated with the contact angle according to
Eq. (2) (Wenzel, 1936).
rðcsv  csl Þ ¼ clv cos hw ð2Þ
where hw
is Wenzel’s contact angel affected by surface rough-
ness and r is a roughness parameter. Modified Wenzel’s equa-
tion is:
cos hw ¼ r cos h ð3Þ
In Wenzel equation, it is assumed that the liquid passes into
the grooves of the surface roughness (Fig. 3b), so the Wenzel’s
equation is related to the homogeneous wetting regime
(Marmur, 2003). The Wenzel equation cannot also explain
the possibility to obtain superhydrophobic properties from
hydrophilic materials or even superoleophobic properties from
oleophilic materials. Wenzel equation represents that rough-
ness modifies the wettability and anti-wettability, depending
on the nature of the surface. Therefore, when the contact angle
Science and Engineering of Superhydrophobic Surfaces
of the flat surface is greater than 90°, the surface roughness
increases the contact angle and if the h angle is less than 90°,
the increase in surface roughness reduces the contact angle
(Blossey, 2003). Wenzel model is only practical and workable
for the homogenous interfacial areas, and cannot be applied
to the non-homogeneous surfaces. In this regard, Cassie and
Baxter in 1944 provided another model for heterogeneous sur-
faces (Fig. 3c). Their model consists of two parts. The first part
includes surface fraction, f1, and contact angle of h1 and the
other part includes f2 and h2 (Cassie and Baxter, 1944). Hence,
in Cassie and Baxter’s equation, the contact angle is defined as
Eq. (4):
cos h ¼ f1 cos h1 þ f2 cos h2 ð4Þ
where h is the contact angle in the model of Cassie and Baxter
and fi is the fraction of surface area with contact angle hi
(f1 + f2 = 1). In Cassie and Baxter’s model, it is assumed that
the liquid is in contact with the solid only at the roughness tips
and it is assumed that air pockets are trapped below the liquid.
In this case, it can be considered that a part of the surface
where the air is trapped in, is not wetted by the liquid. If only
air is present between solid and liquid, h2 will be 180°. There-
fore, Eq. (4) can be written as Eq. (5):
cos hCB ¼ fs ðcos hs þ 1Þ  1 ð5Þ
where fs is the fractional solid surface with a contact angle of
hs. In addition to the models listed, more improved models
have been provided in references to predict the specific modes
of wetting (Erbil and Cansoy, 2009; Jung and Bhushan, 2009;
Koishi et al., 2009; Lundgren et al., 2007; Reyssat et al., 2007;
Vrancken et al., 2009).
2.4. Rolling angle and the wetting angle hysteresis
Rolling angle is the lowest horizontal angle to the in which the
droplet began to move on the surface and rolls on it. For SHS,
this angle should be less than 10° as well as hysteresis less than
10°. For studying the behavior of surfaces, in addition to the
measurement of contact angle and rolling angle, determining
the wetting angle hysteresis is also important, which is the dif-
ference between the advancing angel and receding angel. As
shown in Fig. 4, while rolling, the contact angle in front of
the drop is larger than behind. Difference between the advanc-
ing and receding angles of drop is introduced as hysteresis of
contact angle.
Fig. 4 (a) Schematic illustration of contact angle hysteresis on a tilted surface, (b) advancing and receding contact angles on a flat
surface via increasing and decreasing the volume of droplet, respectively (Yao and He, 2014).
1767
3. Application of superhydrophobic surfaces
Up to now, many SHS with proposed applications have been
fabricated by different methods. In this part, the main applica-
tions of these surfaces are discussed briefly. A schematic of the
main applications of SHS is shown in Fig. 5. In the next part,
the corrosion resistance of surfaces, chemical and mechanical
stability of SHS which is the main subject of this study will
be discussed in more details.
3.1. Increase of corrosion resistance
Corrosion is known as one of the most important problems in
our societies. Since this phenomenon brings about large dam-
ages, the increase of surface corrosion resistance has attracted
so much attention. Numerous methods have been applied to
prevent or reduce the corrosion rate of surfaces. But, recently
superhydrophobic coatings are introduced to prevent corro-
sion rate by applying on the whole range of metals such as alu-
minum (Barkhudarov et al., 2008; Hintze and Calle, 2006;
Skorb et al., 2010), copper (Cui et al., 2009; Zhang et al.,
2008b), magnesium (Ishizaki and Saito, 2010), steel (Luo
et al., 2008), titanium (Zhang et al., 2011), and zinc
(Hermelin et al., 2008; Ning et al., 2011).
3.2. Anti-fogging surfaces
Generally, the vapor is created on different substrates such as
mirrors, glass, and other substrates, which would cause
unknown risks and problems in daily life and industrial appli-
cations. This problem can be resolved by controlling the reac-
tion between the substrate and liquids. Briefly, these strategies
include superhydrophilic layers (with zero contact angle)
(Dong et al., 2010; Lu et al., 2011; Luo et al., 2008; You
et al., 2011), SHS with contact angle higher than 150°, and
hydrophilic/oleophobic layers (Howarter and Youngblood,
2007, 2008).
3.3. Anti-bacterial surfaces
One of the main concerns in many industries including the med-
ical industry is the environmental pollution of materials and
equipment. The growth of biofilms as a natural spontaneous
phenomenon can become a problem in the case of hospital
1768
Fig. 5 Schematic of important applications of superhydrophobic surfaces.
infections. To kill the biofilm or reduce their adhesion, two
strategies of bactericidal surfaces and anti-bioadhesion surfaces
are considered; and the SHS are also used for this purpose.
3.4. Anti-icing surfaces
Formation of ice on the substrates exposed to the environment
can interfere the functioning of many industries, such as high-
ways, aircraft, shipping, and the communications equipment.
Many of the strategies for elimination of this problem involves
removal of ice in the physical or chemical form which causes
damage and consumes so much energy. Recently, SHS on sub-
strates of aluminum (Jung et al., 2012; Kulinich et al., 2010;
Kulinich and Farzaneh, 2009a, 2009b), copper (Tourkine
et al., 2009), and steel (Meuler et al., 2010) have been used
to fix the problem. Due to the extraordinary properties of
SHS, they can prevent the formation and accumulation of
ice on the surfaces.
3.5. Oil and water separation
Due to the increase in industrial water laden with oil, separa-
tion of oil and water mixture has become one of the global
challenges. The combination of superhydrophobic and super-
oleophilic (Gui et al., 2011; Pan et al., 2008; Wang et al.,
2009, 2006c), superhydrophilic and under water superoleopho-
bic (Liu et al., 2009b; Tian et al., 2012; Wen et al., 2013), and
superhydrophilic and superoleophobic (Darmanin et al.,
2014a, 2014b; Kota et al., 2012) are used to separate oil and
water. By the use of different strategies, a series of materials
Gh. Barati Darband et al.
such as membranes, tissues, foams, and sorbents have been
developed for separating water and oil.
3.6. Self-cleaning surfaces
Self-cleaning surfaces have a large number of applications in
everyday life, agriculture, industry, and military industries.
Recently, many methods and strategies have been used to fab-
ricate self-cleaning surfaces (Blossey, 2003; Liu and Jiang,
2011; Parkin and Palgrave, 2005; Sanchez et al., 2005). Many
of the self-cleaning coatings such as glasses, tiles, and tissues
have been industrialized. Self-cleaning surfaces could be made
using the superhydrophobic surfaces.
3.7. Drag reduction
Drag is one of the main obstacles for aircraft, submarines, and
shipping equipment. Inspired by nature, we can find several
ways to reduce and optimize drag value. Basically, methods
for fabrication of drag-reducing coatings are inspired by lotus
plant’s leaves (Rothstein, 2010; Truesdell et al., 2006). At the
SHS, drag reduction can be connected to the water-repellent
properties, where a gas film is formed between the water and
the surface which reduces the contact between water and the
solid substrate.
3.8. Battery manufacture technology
Battery manufacture technology is a major research challenge
in electronics due to insufficient capacity and lifetime of
Science and Engineering of Superhydrophobic Surfaces
batteries in pursuit of the achieved advances in semi-
conductors technology (Lifton et al., 2005). A battery may
supply the required amount of energy and have an acceptable
performance when it is able to endure long capacitation peri-
ods. A simple mechanical separator is used in common batter-
ies for separation of the electrolyte and electrode which leads
to increase in excessive size of batteries.
3.9. Sensors
Due to their specific chemical composition, superhydrophobic
films may have various types of interactions with different
materials in liquid and gas media. Additionally, sensors
equipped with superhydrophobic properties are highly accu-
rate because of their roughness. This feature was investigated
in many cases (Andreeva et al., 2012; Cho et al., 2013; Lv
et al., 2012). For instance, Saito et al. employed a superhy-
drophobic quartz crystal balance for identification of volatile
organic compounds (Wang et al., 2011b). Several organic sub-
stances such as toluene and formaldehyde with van der Waals
interactions lead to increase in weight through SHS made of
trimethylmethoxysilane by means of superhydrophobic CVD
coating. Other research groups have also investigated SHS
produced by amine agents incorporating carbon dioxide
(Hassan et al., 2012). In metallic nanostructures, coherent fluc-
tuations in electrons conduction band may lead to extreme
plasmon resonance in the local electromagnetic field. This
effect, called surface enhanced raman scattering (SERC), is
used for identification of metallic particles in a solution
(Wang et al., 2011b). Lee et al. (Xu et al., 2011a), studied
the effect of increase in SERS in SHS made of ZnO nano-
bars and coated with silver nanoparticles. Signal increase
was observed to be three times more than a normal surface.
Most of biological systems are known to have complicated
bonds such as specific hydrogen bonds. For instance, protein-
carbohydrate interaction is a significant challenge in many
vital biological processes such as signaling, recognition and
decomposition (Williams and Davies, 2001) On the other
hand, development of sensors based on carbohydrate testing
is of great importance in medical, diagnosis and treatment
applications. Lee et al. (Qing and Sun, 2011) reported the fea-
sibility of acquiring SHS with variable wettability in presence
of saccharide. The implemented co-polymer comprised N-
isopropylacrylamide and a phenyl acid derivation. Polymeriza-
tion caused the micro and nano-structures obtain superhy-
drophobic properties. Wetting properties changed with
immersion in glucose from super hydrophobicity to superhy-
drophobocity due to interaction between the polymer and glu-
cose. The role of superhydrophobic surfaces in performance
improvement of different types of sensors has been widely
studied.
3.10. Water purification
In recent years, photocatalytic approaches were used for
removal soluble pollutants in water by means of optical energy
(Zhu et al., 2017; Zou et al., 2016) Superhydrophobic sub-
stances, made of titania nanoparticles and semi-conductive
ceramic materials possess photocatalytic properties were used
for removal of soluble pollutants in water (Darmanin and
Guittard, 2014; Cao et al., 2009) produced superhydrophobic
1769
In(OH)3 nano-cubes by hydrothermal procedure. They
reported that these nano-cubes demonstrated excellent photo-
catalytic activity under ultraviolet beams. Destruction rate of
rhodamine B (RhB) reached 93.25% after 16 h when In
(OH)3 nanocubes were introduced. In addition, Wang et al.
(2011c) reported photocatalytic activity by Cu/PANI superhy-
drophobic nanocomposites under ultraviolet beams. After
addition of Cu/PANI, destruction rate of RhB reached 97%
only in 35 min.
3.11. Optical devices
A surface structure is required to achieve superhydrophobic
films. Optical properties depend on the surface structure.
Superhydrophobic films and surfaces possess various struc-
tures and other features including self-cleaning, anti-dust,
anti-mist, etc. have also been studied in different terms of opti-
cal properties (Lin et al., 2017; Lomga et al., 2017; Martin and
Bhushan, 2017; Nakate et al., 2016). Depending on roughness
and light scattering, surface structure may reduce clarity;
while, this feature is necessary in several applications such as
glasses, optics, and cameras (Rahmawan et al., 2013). For
superhydrophobic film required along with clarity, surface
roughness has to be less than visual light wavelength. Hence,
most of superhydrophobic films with high clarity are produced
using nanoparticles (SiO2, TiO2, zinc oxide, C, polymer)
through electrospinning, sol-gel process, vapor deposition or
cloud lithography (Bravo et al., 2007; Zhu et al., 2014).
Superhydrophobic films are used for performance improve-
ment in other optical applications like light luminance (Nakate
et al., 2016; Tarwal et al., 2013), photon crystals (Bao et al.,
2016; Goodwyn et al., 2009) and solar cells (Xu et al., 2016b).
3.12. Membrane distillation and water desalination
Seawater desalination systems are used all over the world par-
ticularly in countries that suffer deficiency of drinkable water.
There are several industrial techniques for water desalination
including flash distillation, reverse osmosis and membrane dis-
tillation. In the latter, a hot mass of vapor with non-volatile
species is passed through a suprhydrophobic membrane. A
cooling flow is placed on the other side of the membrane. This
method is usually carried out by low flux in limited membrane
and precipitants which both depend on the microstructure and
constituents of the membrane. If the porous membrane is
made with superhydrophobic surfaces, the allowed pores size
may be increased so that the passing flux is escalated (Fan
et al., 2017; Ma et al., 2009). Superhydrophobic membranes
have been created using various materials and techniques to
improve the performance of water desalination systems (Fan
et al., 2016a; Ren et al., 2017). Generally, it may be concluded
that application of superhydrophobic properties in water
desalination systems is a promising technique leading to per-
formance improvement and reduction of consumed energy
which consequently will make these systems more environmen-
tally compatible.
3.13. Microfluidic devices
Liquid flow and penetration control is highly important in
microfluidic devices. Most of studies were conducted on trans-
1770 Gh. Barati Darband et al.

fer properties of microfluidic devices based on application of

liquid penetration in microfluidic systems. Hence, there have
been many studies on reduction of flow drag on a surface,
bar or canal which affects the required energy and flow rate.
The drag force is caused by the shear stress between the flow
and surface (Darmanin and Guittard, 2014). Superhydropho-
bic properties may help in reduction of the drag force through
capabilities such as entrainment of air on surface (cassie-baxter
state) so that liquid transfer and penetration control is facili-
tated in microfluidic systems (Abramov et al., 2012; McHale
et al., 2011).

3.14. Other applications

In addition to these main applications of SHS, regarding the

industrial development and the emergence of new methods
for fabrication SHS, other applications will already be found
for the SHS. Some of other applications can be noted in med-
ical sciences (Bormashenko and Bormashenko, 2011; Song
et al., 2010; Yohe et al., 2012). Moreover, water shortage on
the earth and the unavailability of healthy drinking water is
one of the today’s challenges. Again inspired by nature, we
can fabricate alternative methods to directly withdraw water
from the atmosphere and resolve water scarcity in many
regions of the world. This goal is achievable by using a differ-
ent surface with various wettability (Choi et al., 2009; Garrod
et al., 2007; Zhai et al., 2006). Furthermore, using the technol-
ogy of SHS allows applying the printing and reprography.
Since wettability of surface plays a major role in this industry,
extensive studies have been conducted on this topic (Cui et al.,
2009; Zhao et al., 2009).
4. Fabrication of SHS
Generally, as noted earlier, methods for fabrication SHS are
inspired by nature. To achieve SHS, we should increase the
surface roughness and reduce the surface energy. Thus, it
can be concluded that trend of fabrication of SHS can be
achieved by either roughening the surface of a material with
low surface energy or reducing the surface energy of a rough
material or both of them. Therefore, methods that have been
created for fabrication of superhydrophobic surfaces can be
divided as follows. Schematic figure showing general methods
of fabrication SHS are shown in Fig. 6. In this section, these
methods are briefly discussed.
4.1. Sol-gel method
Sol-gel is one of the most popular methods for applying min-
eral coatings with the benefits such as low-temperature pro-
cess, the simplicity of the technique, low cost, and simple
control of the process (Hench and West, 1990). This method
is used to fabricate SHS on various oxides such as silica, alu-
mina, and titania based on theories of Wenzel and Cassi Bax-
ter (Hikita et al., 2005; Jitianu et al., 2010; Mahltig and
Böttcher, 2003; Pilotek and Schmidt, 2003; Wu et al., 2005;
Yu et al., 2007). By controlling sol-gel variables such as com-
position of precursor’s solutions, hydrolysis, and polyconden-
sation processes, the films would have different morphologies
and surface energies. Since this method is compatible with
glass, it is used for fabrication of transparent superhydropho-
Fig. 6 Schematic of different methods of fabrication superhy-
drophobic surfaces.
bic coatings on the glass (Rao et al., 2009; Shang et al., 2005;
Tadanaga et al., 2000).
4.2. Electrospinning
Electrospinning is a simple and versatile method to fabricate
continuous polymer fibers in micro or nanometer sizes (Ma
et al., 2005a; Wang et al., 2008). Using this method and rough-
ening approach, it is possible to fabricate the SHS (Tuteja
et al., 2007). By adding polymer to the precursor’s solution,
it is also possible to fabricate inorganic fibers using electrospin-
ning method. The existence of polymer can change the viscos-
ity, surface tension, conductivity, and other properties of
electrospinning as these cases are essential for electrospinning
process. In order fabricate uniform fibers, polymer molecular
weight and solution concentration should be selected properly
(Ma et al., 2005b).
4.3. Electrochemical methods
Many processes have been used to control surface roughness
and surface morphology. But, comparing with other methods,
electrochemical deposition process offers a feasible way to con-
trol growth kinetics of deposits and also allows to simply
obtaining large surfaces with different morphologies. In fact,
electrochemical methods are simple, rapid, and highly repeat-
able. In addition, unlike many other techniques, using electro-
chemical methods, it is possible to fabricate different
morphologies such as needles, fibers, tubes, dendrites, and
sheets (Darmanin et al., 2013). Electrochemical methods
include electrochemical deposition, anodic oxidation
(Shibuichi et al., 1998; Tsujii et al., 1997), and polymerization
reactions (Li and Shi, 2005; Nicolas et al., 2006; Yan et al.,
2005), and the reaction of galvanic cells (Shi et al., 2006;
Wang et al., 2006a) are used frequently to fabricate superhy-
drophobic surfaces (Jiang et al., 2005; Yu et al., 2005; Yu
Science and Engineering of Superhydrophobic Surfaces
et al., 2006). Jiaming et al. (Ye et al., 2009) investigated the
relationship between different structures and wetting proper-
ties on the aluminum substrates using electrochemical anodic
oxidation method. The relationship between the honeycomb
the bird’s nest structures and superhydrophobicity was also
reviewed, where the results showed that fabrication of the
bird’s nest structure is essential for fabrication of superhy-
drophobic surface. Oikawa et al. (2009), fabricated superhy-
drophobic porous anodic layer with porosity dimensions
around 10 nm by anodic oxidation method with a wetting
angle of 158° on niobium.
4.4. Layer-by-layer method
The layer-by-layer technique is widely used for fabricate of
various nano- and microstructures as well as fabricating super-
hydrophobic surfaces (Han et al., 2005; Shi et al., 2005; Zhao
et al., 2005a,b). The main principle of this method is changing
the substrate surface charge that leads to the fabrication of
multi-layer films (Chen and McCarthy, 1997). In this method,
in order to improve the wettability of fabricated films, nano or
microparticles are added to increase the surface roughness of
the film. One advantage of this method is the precise control
of the thickness of the coating, so it is the perfect method to
fabricate transparent surfaces. Moreover, this method is used
to fabricate superhydrophobic surfaces on non-flat surfaces
(Zhang et al., 2008c).
4.5. Plasma techniques
Plasma is a simple and effective technique to fabricate
hydrophobic surfaces. Using this method, it is possible to
reduce surface energy and increase the roughness of the surface
at the same time. Superhydrophobic surfaces can be easily
achieved using oxygen plasma. However, ageing is the main
problem of superhydrophobic surfaces fabricated by plasma
technique. Since the roughness of surfaces fabricated by the
plasma can be easily adjusted, this method is appropriate
way to fabricate superhydrophobic coatings with special opti-
cal properties, where the surface roughness of these coatings is
the most important factor (Zhang et al., 2008c). Up to now, a
plenty of works have been reported to fabricate superhy-
drophobic coating of fluorine using plasma techniques
(Coulson et al., 2000; Morra et al., 1989; Woodward et al.,
2003; Youngblood and McCarthy, 1999).
4.6. Other important methods
In addition to the mentioned methods for fabrication of super-
hydrophobic surfaces, there are also many other methods
applicable. These methods include vapor deposition techniques
such as physical vapor deposition (PVD) and chemical deposi-
tion which allows creating highly controlled regular nanostruc-
tures (Akram Raza et al., 2010; Du and He, 2011; Xu et al.,
2009). In this regard, spray technique is another technique
which is frequently used to fabricate superhydrophobic sur-
faces. Furthermore, spin-coating method is another method
for fabrication superhydrophobic surfaces that allow prepar-
ing uniform film with hierarchical nanostructures and
microstructures (Liu et al., 2008). Also, various structural pat-
terns can be used as a template to obtain surface roughness
1771
and superhydrophobic surfaces, that are known by the name
of the template (Feng et al., 2002). Using the instability of
multi-component mixtures, especially in the case of polymers
and using phase separation method, also makes it possible to
fabricate superhydrophobic surfaces.
5. Corrosion resistance of SHS
Generally, it is believed that fabrication of superhydrophobic
coating on the surfaces protects them from environmental
moisture and inhibits the electrochemical reactions. This can
improve the corrosion resistance of the surface in highly
aggressive media. In other words, superhydrophobic surfaces
can be used as a solution to decrease the corrosion of the metal
substrates, such as magnesium, aluminum, copper, zinc, nickel
and steel alloys. The anticorrosion mechanism of the superhy-
drophobic surfaces is considered in this section. Many tech-
niques of fabrication superhydrophobic surfaces, as well as
various methods of characterization and analysis were applied
in literature, but their conclusion was the same; superhy-
drophobic coatings prevent metallic substrates from corrosion
attacks (Ishizaki et al., 2010). As mentioned in Section 2.2, the
requirements for fabrication superhydrophobic surfaces are
preparing micro and nano-roughness on the surface and
decrease of surface energy. When the surface is roughened,
large peaks are formed on the surface associated with numer-
ous valleys placed between them. The inhomogeneity of the
superhydrophobic coatings allows air to be trapped easily
within the valleys between the peaks of the rough surface. Con-
sequently, the aggressive ion species such as Cl in the elec-
trolyte or corrosive environments can rarely attack the
underlying surface owing to the obstructive influence of
trapped air. In fact, the air trapped on the superhydrophobic
surface acts as a passivation layer and prevents substrate from
corrosive processes. When smooth metals are exposed directly
to the environment containing corrosive species, the aggressive
ions can easily corrode the surface. While, in superhydropho-
bic surfaces, the air trapped in the surface grooves can hinder
direct contact between the corrosive media and the material.
The superhydrophobic structure would permit an enhance-
ment of the surface air fraction in the valleys and also decrease
the actual area of rough surface in contact with aggressive
solution (Ishizaki et al., 2010, Radwan et al., 2015;
Boinovich and Emelyanenko, 2012).
Capillarity is another important factor that explains why
super-hydrophobic surface can improve the corrosion resis-
tance of metals and was introduced by Liu et al. (Liu et al.,
2007a). The height (h) of the water column within the tube
can be calculated by the following equation:
2c cos h
h¼ ð6Þ
qgR
where c is the surface tension, h is the contact angle, q is the
density of the liquid, g is the gravity acceleration and R is
the radius of a cylindrical tube. SHS is considered as a vertical
cylindrical tube dumped in the liquid. The water contact angle
of the super-hydrophobic surface is higher than 150° and the
pore diameter is very small. As a result, the corrosive liquid
can be forced out of the pores of superhydrophobic surface
by the Laplace pressure and thus, the substrate could be per-
fectly protected from corrosion in the aggressive environment.
1772
Schematic of the mechanism of increasing resistance to cor-
rosion of fabricated superhydrophobic surfaces is shown in
Fig. 7. In this section, the corrosion resistance of fabricated
superhydrophobic surface by different methods will be
reviewed to compare the corrosion resistance. Several works
have been carried out in order to study the corrosion resistance
of superhydrophobic surfaces. In the next sections, some of the
results obtained by different methods will be discussed.
5.1. Electrodeposition method
Firstly, the corrosion resistance of fabricated superhydropho-
bic coating using electrodeposition method will be studied.
Compared to many other methods, electrodeposition do not
require long-term conditions such as exhausting chemical
treatment, expensive materials, complex multi-stage proce-
dures, and expensive equipment (Chen et al., 2012; Liu et al.,
2014b, 2014c; She et al., 2012).
Wang et al. (Wang et al., 2011a), prepared superhydropho-
bic coating as a corrosion barrier using an single-stage elec-
trodeposition method. In their study, zinc tetradecanoate
film was formed on the substrate by two-electrodes arrange-
ment, with the zinc sample used as the anode and platinum
serve as the cathode. Film was formed on the surface by elec-
trochemical method at potential of 30 V for 2 h at room tem-
perature by direct current power supply. The corrosion
resistance of fabricated coating was studied and corrosion test
results demonstrated that form of superhydrophobic coating
on the surface significantly increased the corrosion resistance
of the substrate. In addition, the trapped air acted as dielectric
film as a pure capacitor with parallel plates that would prevent
the transfer of electrons between the substrate and the
electrolyte and as a result improve the corrosion resistance
of the substrate. In another study (Wang et al., 2013), the
zinc-laurylamine complex film was applied with superhy-
drophobic properties on a zinc substrate via the electrodeposi-
tion method and the corrosion resistance of the fabricated film
in the marine atmosphere simulated environment was
investigated. Results of this study indicated that the fabricated
superhydrophobic coating possesses significant corrosion
resistant, with the corrosion inhibition efficiency reaching
more than 99%.
Fig. 7 Schematic of corrosion resistance improvement by superhydrophobicity.
Gh. Barati Darband et al.
Wu et al. (Wu et al., 2014b) fabricated the superhydropho-
bic silica film on the steel surface using the electrical deposition
method, resulting in simultaneous fabrication of low energy
and rough surface for improving the corrosion resistance prop-
erties. Corrosion resistance of the surface was studied by elec-
trochemical impedance spectroscopy (EIS) method and a
significant improvement in corrosion resistance was found
because of the fabrication of superhydrophobic surfaces on
the substrate.
Liu et al. (Liu et al., 2015a, 2015c) fabricated a superhy-
drophobic coating to improve the corrosion behavior on the
copper substrate using an electrochemical method. Corrosion
behavior of fabricated coating was studied using polarization
and EIS methods. Results of polarization and EIS studies
showed a significant improvement in corrosion resistance by
applying the above hydrophobic film on the surface of the cop-
per substrate. Mechanism of protection against corrosion by
the superhydrophobic film was presented in Fig. 8. As shown
in this figure, the unique SHS entraps a considerable amount
of air, thus, it would prevent the wettability of the surface
and significantly reduce the actual contact area between the
liquid and the surface. Consequently, the air layer fabricated
on the surface prevents the formation of a closed circuit and
significantly improves the corrosion behavior.
Fabrication of SHS leads to uniform corrosion and reduces
the corrosion rate of the substrate. Fig. 9 shows the potentio-
dynamic polarization curves of samples of uncoated copper
(BS) copper samples with the SHS (SS) and deaerated SS
(DS) sample. The superhydrophobic coating was created on
a copper substrate using the electrochemical method. As it
could be seen, in the copper substrate without coating, the
anodic branch can be divided into three distinct zones. In
the first area increase in the current can be taken up to the
maximum current density due to the dissolution of copper to
Cu+ according to the Eq. (6). Then in the second area, current
density would be decreased until the minimum value, caused
by the formation of CuCl according to the Eq. (7) and in the
third area, increase of current density was happened according
to the Eq. (8) (Zhang et al., 2009).
Cu ! Cuþ þ e ð7Þ
Cuþ þ Cl ! CuCl ð8Þ
Science and Engineering of Superhydrophobic Surfaces
Fig. 8 Schematic illustrations of a water droplet on the super-
hydrophobic film: (a) the model of a water droplet on the surface
and (b) a drop of water in contact with the surface with
electrodeposition 30 min at 20 V DC voltage (Liu et al., 2015c).
Fig. 9 Polarization curves of BS, SS and DS in 3.5 wt% NaCl
solution (Wang et al., 2010b).
CuCl þ Cl ! CuCl
2 ð9Þ
By applying the superhydrophobic coating on the surface,
corrosion resistance was increased while the anodic and catho-
dic polarization currents decreased. The important point noted
after the test was about the durability of the superhydrophobic
1773
state after applying polarization test, which reflects the high
stability of the coating in the presence of chlorine ions. It
was seen that corrosion resistance of DS sample was slightly
increased, suggesting that the presence of the air layer is essen-
tial to improve the corrosion resistance of the coating (Wang
et al., 2010b).
Most of the studies conducted on the corrosion resistance
of the superhydrophobic surfaces were taken regardless of
the type of contact between the electrolyte and the hydropho-
bic surface, while the type of contact is also important and
should be considered. In this regard, Wang et al. (Wang
et al., 2012a) used the synthesized 3-undecyl-4-amino-
5-mercapto-1,2,4-triazole (UAMT) for fabrication the
superhydrophobic coating on the copper. They fabricated
superhydrophobic coatings using the single-step electrodeposi-
tion method and studied the corrosion resistance of coating
under different modes (Cassie and Wenzel). Based on the
results of their study, depending on the depth of immersion
in the electrolyte, the fabricated superhydrophobic film can
contact the NaCl solution in two cases: Cassie and Wenzel.
Such contact mode leads to different mechanisms of corrosion
protection. It was concluded that superhydrophobic film fabri-
cated in the Cassie condition shows better corrosion resistance
properties, because of the trapped air.
One of the main problems of fabricated superhydrophobic
coatings on surfaces is about their low mechanical durability.
Although numerous superhydrophobic surfaces were made
using different methods, few studies reported the applications
of these coatings in the industry due to their poor wear prop-
erties and low chemical stability of these coatings.
Thus, obtaining excellent mechanical properties and excel-
lent chemical stability is the main requirement for application
of these surfaces (it will be discussed in detail in Sections 6 and
7). In this regard, few studies have been conducted for investi-
gating the mechanical stability (Lee et al., 2012; Zhu et al.,
2011, 2012), chemical stability (Boinovich and Emelyanenko,
2012), and long-term stability (Hao et al., 2012) of these sur-
faces. Accordingly, abrasion resistance and excellent corrosion
resistance are among the main requirements for resolving this
solution and fabrication the superhydrophobic coatings with
proper abrasion and corrosion resistance properties, in this
regard, Su et al. (Su and Yao, 2014) developed superhydropho-
bic coatings with high wear resistance and excellent corrosion
resistance on a copper substrate using two-step procedure
including electrodeposition in the Watts bath and then thermal
treatment in the presence of the AC-FAS. This case removed
many practical limitations in the application of superhy-
drophobic surfaces. Fig. 10 shows the polarization curve of
uncoated samples, samples electrodeposited by Ni, and SHS.
As can be seen, the corrosion resistance of superhydrophobic
surface is greater than that of the other ones. The microstruc-
ture of the fabricated superhydrophobic coating shows that,
according to the Cassie-Baxter relationship, air can be trapped
in surface lines, leading to the improved corrosion resistance of
superhydrophobic surfaces.
Magnesium and its alloys are used extensively in the indus-
try because of their good properties, but one of the limitations
of using magnesium is their low corrosion resistance. It is indi-
cated that, by applying the superhydrophobic coating on the
surface of magnesium, it possesses very high resistance to
corrosion. There are some reports about the fabrication of
superhydrophobic coating on the surface of magnesium
1774
Fig. 10 Potentiodynamic polarizaiton curves measured in 3.5 wt%
NaCl solution for the bare Cu substrate (Cu-I), electrodeposited
Ni (Ni-I), and superhydrohobic surface (Ni-III) (Su and Yao,
2014).
(Gao et al., 2014; Wang et al., 2010c), but most of the applied
methods require special conditions and are expensive, as toxic
substances should be used in many methods. Recently, the
single-stage electrochemical method was introduced for apply-
ing hydrophobic coatings with high corrosion resistance on
magnesium (Liu et al., 2015b). This method is simple, low-
cost and nature-friendly and is believed to facilitate the opera-
tional applications of magnesium alloys.
Nickel is one of the engineering materials with desirable
properties such as high corrosion resistance, hardness, and
good magnetic properties, which can protect the copper sub-
strate. Even more satisfactory properties can be obtained by
combining these properties with superhydrophobic properties.
Study on the fabrication of nickel superhydrophobic surfaces
using a single-step electrodeposition without using the surface
energy reducing materials and evaluation of the corrosion
resistance of these coatings were done by Khorsand et al.
(Esmailzadeh et al., 2015; Hashemzadeh et al., 2015;
Khorsand et al., 2014; Khorsand et al., 2016). The corrosion
resistance of coatings was studied by EIS and potentiodynamic
polarization methods. The results showed the improvement in
corrosion resistance of the substrate, caused by fabrication of
SHS on the surface. In another study conducted by this group,
effect of NH4Cl on the microstructure and corrosion resistance
of Ni coating fabricated by electrodeposition was studied
(Hashemzadeh et al., 2015). The results indicated that NH4Cl
was significantly effective on the microstructure of the coating
and as a result on the final corrosion resistance of created coat-
ing. Corrosion resistance of nickel-cobalt alloy superhy-
drophobic coating fabricated by electrodeposition was also
investigated (Khorsand et al., 2016). These authors studied
the long-term stability of these coatings and reported that
improvement of corrosion resistance was affected by fabrica-
tion of superhydrophobic coating on the surface. Moreover,
by increasing the time after fabrication of superhydrophobic
coating, the corrosion resistance of the coating was improved
by adsorption of a carbon layer on the surface.
Iron is one of the other engineering materials with numer-
ous applications, but one of its disadvantages that caused lots
Gh. Barati Darband et al.
of limitations in the industries is its low corrosion resistance
(Cote et al., 2015; Fan et al., 2013). It has been shown that,
fabrication of superhydrophobic coatings on the iron is one
of the most important and applicable methods to improve its
corrosion resistance. Many methods have been applied for fab-
rication the superhydrophobic coating on the substrate of iron
(Gao et al., 2015a; Li et al., 2015b; Zhang et al., 2015c, 2015d).
However, most of the proposed methods suffer from many
constraints such as time-consuming, being complicated, requir-
ing special equipment as well as the raw materials and being
expensive. Fabrication of superhydrophobic coating on the
iron using a simple and low-cost approach is very effective.
Black chrome is one of the coatings with very good corrosion
resistance (Sheu et al., 2015), as its deposition on iron and
applying superhydrophobic coating operation can be very use-
ful. In this regard, Zhang et al. (Zhang et al., 2016a, 2016b,
2016c) fabricated chromium coating on iron via electrodeposi-
tion method and then taking the stearic acid modification.
They investigated the corrosion resistance of superhydropho-
bic coating by EIS and their results showed improved corro-
sion resistance by applying the superhydrophobic coating on
the surface. Equivalent-circuits proposed by the electrochemi-
cal impedance curves for different samples are shown in
Fig. 11. As shown in this figure, in the deposited and
superhydrophobic-treated sample (Iron-BC-SA) with the most
resistant to corrosion, air bubbles are trapped in the nanopores
of the surface film that improved the corrosion resistance of
the surface. Since the trapped air prevents the transformation
between the electrolyte and the electrodes surface, electrons
tend to pass through the limited points subject to the elec-
trolyte. Thus, the effective conductive area is significantly
decreased. In addition, due to the very high corrosion resis-
tance of chromium layer, by applying a hydrophobic layer of
stearic acid on a layer of chromium, electron transfer in this
system is very difficult and corrosion resistance is significantly
increased. The summary of other researches about corrosion
resistance of superhydrophobic coating fabricated by electro-
chemical methods are represented in Table 1.
5.2. Chemical fabrication methods
Immersion in organic acids solutions is among the applicable
methods which have been used to obtain a surface roughness
as well as fabrication a surface with low surface energy. Hence,
this method can be regarded among the one-step methods for
creating superhydrophobic coatings (Wang et al., 2006b).
Tetra decanoic acid is one of these organic acids that, because
of its long fatty acid chains, can be noted as a nature-friendly
materials for fabricating the superhydrophobic coatings
(Richard et al., 2012). Coatings fabricated by this method
can improve the corrosion resistance of the surface. Fig. 12
shows the polarization curves of magnesium uncoated samples
after 2 h immersion in a solution of 3.5% NaCl in addition to
the superhydrophobic surface fabricated on magnesium in dif-
ferent times. As shown, in the polarization curves, fabrication
of superhydrophobic surface on magnesium surface signifi-
cantly improves the corrosion resistance. (Zhao et al., 2014).
This result was also reported in the other studies
(Barkhudarov et al., 2008; Ishizaki and Saito, 2010).
In another study, the corrosion resistance of the fabricated
superhydrophobic coating via chemicals method and soaking
Science and Engineering of Superhydrophobic Surfaces 1775

Fig. 11 Electrical equivalent circuits for EIS of (a) Bare iron; (b) Iron-SA; (c) Iron-BC; (d) Iron-BC-SA (Zhang et al., 2016a, 2016b,
2016c).

Table 1 Summary of research about corrosion resistance of superhydrophobic coating fabricated by electrochemical methods.
Substrate Method Surface energy reducer Contact icorr before icorr after Corrosion Reference
agent angle treatment treatment protection
(A/cm2) (A/cm2) efficiency (%)
Mild steel Electrodeposition Dodecyltrimethoxysilane 155 1.5  105 2.5  107 98 Zhou et al. (2016)
Mg Electrodeposition Perfluorocaprylic acid 160.2 26.4  106 7.61  106 71 Liu et al. (2016b, 2016c)
carbon steel Electrodeposition Palmitic acid 160.5 16.70  106 0.85  106 95 Fan et al. (2016b)
Iron Electrodeposition Ethanolic stearic acid 158.8 21.90  106 1.34  108 99.99 Zhang et al. (2016a,
2016b, 2016c)
Al Electrodeposition Stearic acid 160 16.06  106 108 99.99 Xu et al. (2016a)
Cu Electrodeposition Cerium myristate 161.5 7.096  106 4  107 94 Liu et al. (2015b)
Cu Electrodeposition Triethoxysilane 162 5.99  104 4.51  106 99.2 Su and Yao (2014)
Cu Electrodeposition – 155.7 3.2  106 5  109 99.99 Khorsand et al. (2014)
Cu Electrodeposition – 155 4.30  106 26  108 99.39 Esmailzadeh et al. (2015)
Cu Electrodeposition – 158 1.5  105 8  108 99.46 Khorsand et al. (2016)
Cu Electrodeposition 1-dodecanethiol 154 9.33  106 108 99.89 Liu et al. (2016b, 2016c)
Cu Electrodeposition Myristic acid 160 7.84  106 4.08  107 95 Su et al. (2013)
Al Electrodeposition Myristic acid 162.1 7.16  108 8.76  1011 99.99 Zhang et al. (2015a)
Mg Electrodeposition Myristic acid 159.8 2.48  105 1.42  107 99.43 Liu and Kang (2014)
Al Electrodeposition Hexadecanoic acid 167.4 9.64  108 2.86  1010 99.7 Zhang et al. (2016a,
2016b, 2016c)
Steel Electrodeposition Flour 157 7.27  106 4.12  106 43 Peng et al. (2016)

in the solution of n-tetradecanoic acid and sea water on the
copper substrate was studied (Liu et al., 2007a). Fig. 13 shows
the potentiodynamic polarization curves of different samples.
Obviously, the fabrication of the superhydrophobic coating
on the surface reduces the corrosion current density and
changes of corrosion potential toward more positive values.
It can be seen that the current of the anodic branch was signif-
icantly decreased. In addition, it could be seen that the severe
increase of the current in the anodic branch was removed in
the presence of the superhydrophobic film, which confirms that
the dissolution of copper and penetration of chlorine ion was
severely restricted by the superhydrophobic film. Mechanism
of corrosion resistance increase caused by the superhydropho-
bic film can be ascribe to air pocket phenomena in which, the
superhydrophobic coating includes valleys and hills with
entrapped gasses; therefore, chlorine ion hardly can reach
the uncoated surface and hence corrosion resistance is
increased.
1776
Fig. 12 Potentiodynamic curves of the untreated AZ31 magne-
sium alloy and superhydrophobic surface formed on magnesium
alloy after immersion in 3.5 wt% NaCl aqueous solution for (a
and e) 2, (b) 6, (c) 12 and (d) 24 h and enlarged the anodic curves
(Zhao et al., 2014).
Fig. 13 Potentiodynamic polarization curves of the copper
electrodes with and without the super-hydrophobic film for 1
day in sterile seawater at 2 mV s1 (Liu et al., 2007a).
Fabrication of superhydrophobic coatings without organic
modification operation has been the subject of many investiga-
tions (Liu et al., 2014c; Ning et al., 2011; Xu et al., 2011b,
2011c). Cheng et al. (Cheng et al., 2015) fabricated the super-
hydrophobic coatings of Au-AlAu4-Al2O3 on aluminum sub-
strates without any organic modification operation and then
examined the corrosion resistance of the created coating. Eval-
uation of corrosion resistance using potentiodynamic polariza-
tion method indicates the improved corrosion resistance of the
superhydrophobic film formed on the surface. The mechanism
of electrochemical corrosion of the created superhydrophobic
coatings is shown schematically in Fig. 14. When the alloy is
placed in the aqueous solution, corrosion starts by releasing
Gh. Barati Darband et al.
the Al3+ ions, which lead to the formation of corrosion prod-
ucts in the form of Al(OH)3 at the interface of the alloy and the
substrate (Fig. 14a). Meanwhile, the cathodic reaction of
hydrogen evolution ions occurs. As the chlorine ions penetrate
to the alloy via tiny imperfections, they make small channels,
which create pores on the surface (Fig. 14b). Then these pores
join together, leading to the destroyed superhydrophobic sur-
face of Au-AlAu4-Al2O3 and hydrophobicity. Compared to
the uncoated substrate, the substrate is removed more quickly
by NaCl solution. Therefore, the SHS of Au-AlAu4-Al2O3
provides better corrosion resistance to the substrate.
Although the surface energy can be reduced by absorbing
components with a low surface energy such as fluoroalkylsi-
lanes (FAS) (Fadeev et al., 2002; McArthur et al., 2004), in
many cases, FAS physically is adsorbed on the surface. Thus,
it is expected that by chemical bonding of FAS to the surface,
the stability of the formed superhydrophobic surface increases,
leading to the improved corrosion resistance. Corrosion resis-
tance of the superhydrophobic coatings was investigated by
Ou et al. (Ou et al., 2012) by chemical adsorption of FAS on
Ti-6Al-4V. The samples were first etched in HF solution, fol-
lowed by performing the chemical adsorption of surface energy
reducing agents on it. Samples were named as Ti-HF, Ti-HF/
H2O2, Ti-HF-PFOTS, and Ti-HF/H2O2, where two samples of
reducing agents were adsorbed on the surface and adsorption
did not happen in the other two samples for which only chem-
ical etching occurred. The exact mechanism of samples corro-
sion also can be attributed to air pocket which trapped in
superhydrophobic surface. Due to the minute pore structures
and large WCA, water can even push out of the pores of the
SHS against the gravity force. Therefore, the surface is signif-
icantly protected.
Liu et al. (Liu et al., 2007b) synthesized the superhydropho-
bic coating on copper substrate using chemical etching by n-
tetradecanoic acid (CH3 [CH2]12COOH) and studied its corro-
sion resistance against seawater using EIS method. The
Nyquist plot of uncoated and modified copper substrate is
shown in Fig. 15. It could be seen that by deposition of n-
tetradecanoic molecules on copper, charge transfer resistance
increases, implying the increase in corrosion resistance. The
Nyquist plot of modified copper suggests the presence of War-
burg impedance which can be attributed to the cooperative
binary structure at the superoleophobic surface.
Few studies have been conducted on fabrication of super-
hydrophobic surfaces resistant to corrosion on the magnesium
alloys. Zhang et al. (Zhang et al., 2008a) created the superhy-
drophobic film of hierarchical micro/nanostructure on the
PAO/Al substrate, which had a high level of corrosion resis-
tance. In addition, Yin et al. (Yin et al., 2012b) fabricated
the superhydrophobic coating on aluminum using chemical
etching method as well as the modification operation, which
also showed a good corrosion resistance.
Feng et al. (Feng et al., 2013) created the superhydrophobic
surfaces on an aluminum substrate using an environmentally-
friendly approach which showed a high corrosion resistance.
To fabrication the SHS, after preparation of the surface, alu-
minum samples were placed in boiling water and finally sam-
ples were immersed in the solution of ethanol-water
containing 10 mmol/l of stearic acid (STA) at 60 °C. Boiling
water operation created a porous structure on the surface
Science and Engineering of Superhydrophobic Surfaces
Fig. 14 Schematic illustration of electrochemical corrosion mechanism of superhydrophobic surface in NaCl solution (Cheng et al.,
2015).
Fig. 15 Nyquist plot of Cu immersed in seawater for 1 day
(25 °C) (Liu et al., 2007b).
while in STA modification operation, hydrophobic alkyl
chains were absorbed on the alloy. Therefore, it can be con-
cluded that the fabrication of a superhydrophobic state
depends on the geometry and surface energy. A schematic of
the superhydrophobic coating formation is shown in Fig. 16.
The corrosion resistance test was conducted using polariza-
tion and indicated the improved corrosion protection because
of the fabrication of a SHS. Fig. 17 shows the surface
microstructure and STA layer at the interface of solid/air in
addition to the micromodel of a water droplet in contact with
Fig. 16 The fabrication procedure of the superhydrophobic aluminum alloy surface (Feng et al., 2014).
1777
the aluminum substrate. As shown in this schematic diagram,
the surface of aluminum has a hierarchical structure in micro
and nano-dimensions and also hydrophobic alkyl chains are
adsorbed on the aluminum surface. Complex interfaces
between liquids and solids cause the contact area between
water drop and the solid surface become minimal and drop
contact angle increase. By combining the chemical and physi-
cal effects, it can be realized that such a superhydrophobic sur-
face can repel any hydrophilic molecules that move toward it.
Thus, it can be concluded that the surface prevents the
entrance of corrosive ions of the solution to an aluminum sub-
strate and this leads to the improved corrosion resistance. The
summary of other researches about corrosion resistance of
superhydrophobic coatings fabricated by chemical methods
are represented in Table 2.
5.3. Sol-gel fabrication method
Alkylsilane is among the most important materials used for the
preparation of superhydrophobic films for practical applica-
tions. The main reason for the widespread applications of this
material is its high mechanical and chemical stability because
of strong immobilization via siloxane bond (Rao et al.,
2011). Alkylsilane sol-gel technique is an important single-
step strategy to fabricate a superhydrophobic coating on engi-
neering materials. This method allows to create rough struc-
tures and also reduce surface energy by hydrolysis and
condensation of alkylsilane, simultaneously (Deng et al.,
2011; Wen et al., 2011; Xue et al., 2009; Yang et al., 2010).
Corrosion resistance and also stability of the silica-based
1778 Gh. Barati Darband et al.

Fig. 18 Potentiodynamic polarization curves of (a) untreated

aluminum substrate; and superhydrophobic surfaces formed on
aluminum substrate after immersion in 3.5 wt% NaCl aqueous
solution for (b) 30, (c)120, (d)420 and (e) 1440 min (Liang et al.,
2014).

changes occurred on the surface morphology and the contact

Fig. 17 Schematic illustration of a water droplet in contact with
the superhydrophobic aluminum alloy surface (Feng et al., 2013).
coating created on the aluminum substrate in the corrosive
solution of NaCl was studied by Liang et al. (Liang et al.,
2014). In order to evaluate the corrosion resistance as well as
stability of the coating, the coatings were immersed for differ-
ent times in NaCl solution and polarization tests were applied
on them (Fig. 18). Microscopic results showed slight surface
change between 30 and 120 min of immersion. However, dur-
ing a longer time range between 420 and 1440 min, major
angle was decreased up to 138° at 1440 min of immersion, rep-
resenting the destruction of hierarchical microstructure on the
surface. Furthermore, the separation of hydrophobic agents
occurred by increasing the immersion times. Polarization
curves of different samples also show the reduction of corro-
sion resistance of coating as a result of increasing the immer-
sion time. A noteworthy point in this curve is the more
positive corrosion potential of coated and immersed samples
at different times than the uncoated samples. Such difference
can be attributed to the improved corrosion resistance of coat-
ing compared to uncoated sample. In general, the improved
corrosion protection can be attributed to the simultaneous
effect of superhydrophobic properties and also silica-based
oxide films as a corrosion barrier.
Superhydrophobic surfaces were also created by Fan et al.
(Fan et al., 2012) via sol-gel process using the hydrolysis

Table 2 Summary of research about corrosion resistance of superhydrophobic coatings fabricated by chemical methods.
Substrate Method Surface energy Contact icorr before icorr after Corrosion Reference
reducer agent angle treatment treatment protection
(A/cm2) (A/cm2) efficiency (%)
Mg Immersion Tetradecanoic acid 165 2.075  105 2.57  108 99.87 Zhao et al. (2014)
Mg Etching Dodecyl mercaptan 154 1.66  103 4.99  104 69.37 Feng et al. (2015)
Al Immersion HAuCl4 171 5.64  104 5.45  105 90.42 Cheng et al. (2015)
Al Chemical Flour 161.2 1.4  103 7.04  107 99.99 Yin et al. (2012a)
etching
Al Boiling water Stearic acid 155 1.25  104 1.65  105 86 Feng et al. (2013)
treatment
Al Boiling water Stearic acid 154.1 7.26  104 5.01  105 93.11 Feng et al. (2014)
treatment
Ti Etching PFOTS 152.1 2.51  107 3.9  109 98.44 Ou et al. (2012)
Stainless steel Etching Silane 164.3 4.7  103 2.86  106 99.81 Latthe et al. (2015)
Science and Engineering of Superhydrophobic Surfaces
reaction between the vinyl-terminated trimethoxylsilane
(VTMS) and wafer surfaces of copper substrate, where the sur-
face roughness and surface energy were low. The stability test
conducted in 3.5 wt% NaCl solution indicated that after 14
immersions, superhydrophobic state of this surface is main-
tained. However, after 14 days of immersion in a solution, it
was found that the contact angle reached less than 150°, sug-
gesting the decrease in superhydrophobic property of silica
film. Corrosion resistance of superhydrophobic membranes
in humidified atmosphere is new and ongoing investigations
are being conducted on it. Wang et al. (Gao et al., 2014) stud-
ied the corrosion resistance of superhydrophobic membranes
formed by sol-gel method and modified with hexade-
cyltrimethoxysilane (HDTMS), Tetraethyl orthosilicate
(TEOS), trimethylethoxysilane (TMES) and methyltri-
methoxysilane (MTMS) in a 3.5 wt% solution of NaCl and
the moist air. The results showed the improved corrosion resis-
tance by fabrication superhydrophobic surfaces on the surface
of the uncoated sample. Fig. 19 shows a schematic of surface
anti-corrosion mechanism created in corrosive environments.
Trapped air on the surface can cause air protection shield,
which significantly decreases the contact of corrosive ions with
the steel substrate (She et al., 2012). Furthermore, it was con-
cluded that in comparison with surface morphology, chemical
composition of surface plays a more important role in resis-
tance to corrosion in corrosive environment. Table 3 summa-
rizes the results of studies conducted on the corrosion
resistance of superhydrophobic surfaces created by the sol-
gel methods.
5.4. Spray coating fabrication method
Spray coating is a technique used for creating coatings in
industrial dimensions. The main characteristic of this method
is using inexpensive materials, simple manufacturing process,
and its availability in commercial form (Wu et al., 2009). This
method also can be used to fabrication of superhydrophobic
Fig. 19 Anti-corrosion mechanism of superhydrophobic mem-
branes in corrosive solution medium (Gao et al., 2014).
Table 3 Summary of research about corrosion resistance of superhydrophobic coatings fabricated by sol-gel method.
Substrate Method Surface energy Contact angle icorr before
reducer agent treatment (A/cm2)
Al Sol-gel – 154.9 4.08  107
Steel Sol-gel Flour 151.5 7.68  103
1779
substrates (Feng et al., 2004; Pan et al., 2008). Under such con-
ditions, the increase surface roughness and reduction of sur-
face energy is taken in one step by reacting alkanethiols salts
and metals salts, which involve groups of high and low energy
chains (Carotenuto et al., 2003). Superhydrophobic metal
meshes were created via spraying method by Xu et al. (Xu
et al., 2011d) through reducing the surface energy as well as
increasing the surface roughness in one step by the reaction
between the metals salt and alkanethiols. Stability and corro-
sion resistance of coated meshes were studied and the results
showed that by creating a superhydrophobic coating on the
surface, corrosion current density was decreased around two
decades. As stated earlier, one of the major problems that
cause functional limitations of superhydrophobic coatings is
the mechanical stability of the coatings. Therefore, fabrication
of coatings with high mechanical durability, and at the same
time superhydrophobicity, is one of the challenges we face
todays. In order to overcome this problem incorporating
nanoparticles and sticks in coatings were suggested. In this
regard, polydimethylsiloxane (PDMS) resin is frequently used
for its high mechanical stability, low surface energy, and super-
hydrophobic properties (Chakrabarty et al., 2012; Thanawala
and Chaudhury, 2000). Zhang et al. (Zhang et al., 2016g) used
the spraying method to create coatings with high corrosion
resistance and high mechanical stability. In this study, PDMS
and inorganic nanoparticles of fluorinated alkyl silane func-
tionalized silica were used in coatings. The results of the corro-
sion resistance evaluation by electrochemical impedance
spectroscopy and polarization tests showed that the fabrica-
tion of superhydrophobic coating caused a 315 times reduction
in corrosion current density. The researchers considered the
improved corrosion protection of coating because of two rea-
sons: the effect of capillary forces and the impact of air pockets
and barrier layer (Fig. 20). Under the superhydrophobic con-
dition, surface has a hierarchical structure, as such structure
can entrap the air between the created intervals, reduce the real
surface between the corrosive liquid and the substrate, and
improve the corrosion resistance. As noted above, stability
of hydrophobic coating under extreme conditions is one of
the big challenges of coatings. Polysulfone (PSU) is one of
the materials used to create superhydrophobic coatings
because of its unique properties such as excellent thermal sta-
bility, excellent mechanical properties and chemical inertness
(Yue et al., 2013). Nevertheless, brittleness is one of the main
disadvantages of this material which limits its application for
fabrication of abrasion resistant coatings. Polymers with excel-
lent ductility can be used to overcome this problem. PVDF
polymer is used for removing the PSU limitations
(Stoiljkovic and Agarwal, 2008). PVDF also has a very low
surface energy and is used to reduce the surface energy of
materials. It is also used for fabrication of hierarchical
microstructure in MMT covers. In the same way, composite
and superhydrophobic coatings of PSU/PVDF/MMT/PDMS
icorr after Corrosion protection Reference
treatment (A/cm2) efficiency (%)
2.79  109 99.31 Liang et al. (2014)
3.44  105 99.55 Mo et al. (2015)
1780 Gh. Barati Darband et al.

Fig. 20 Schematic illustration of the capillary effect (a) and coating-corrosion liquid interfaces (b) (Zhang et al., 2016f).

which was resistant to abrasion and corrosion were introduced
by Wang et al. (Zhang et al., 2016f) by a combination of chem-
ical modification and simple spray methods. The prepared
superhydrophobic coating showed excellent properties.
Besides, the hierarchical structure created by incorporation
of MMT to coating improved the mechanical properties of
the coating as 14.3%. Angular curve of the created coating
and immersion in different pH values are shown in Fig. 21.
As it could be seen, in different acidic or basic conditions
not much changes were observed in the coating contact angle;
implying that the corrosion resistance of coating in different
acidic and alkaline conditions was perfect.
Due to the potential applications of superhydrophobic sur-
faces, fabrication of colorful superhydrophobic surfaces was
always of great importance in academic and industrial sectors.
But up to now, fabrication of colorful SHS has rarely occurred
due to the difficulty in changing the color and appearance of
coatings. Recently researchers aimed to create colorful super-
hydrophobic surfaces (Ge et al., 2014; Ishizaki and
Sakamoto, 2011; Ogihara et al., 2011; Soler et al., 2011).
Colorful superhydrophobic coatings were created by Wu
et al. (Li et al., 2015a) using a simple and single step procedure
of spray-coating by spraying stearate particle ethanol suspen-
sions on stainless steel in order to study the corrosion resis-
tance of the created coatings. Test results showed that the
corrosion resistance of coating has been two or three times bet-
ter than that of uncoated substrate. Furthermore, results of
long-term immersion showed that the created coating has a
good long-term sustainability. In addition, results of the elec-
trochemical impedance curves showed that by increasing the
immersion time, slight changes occurred in diameter of capac-
itive loop, which in turn represents the high stability of the
coatings. Table 4 summarizes the results of studies on the cor-
rosion resistance of superhydrophobic surfaces created by the
spray methods.

5.5. Hydrothermal synthesis fabrication method

Regarding its high efficacy in fabrication of microstructures,

Fig. 21 The relationships between pH and WCA on the PSU/
PVDF/MMT–PDMS composite coating (Zhang et al., 2016f).
hydrothermal synthesis method is one of the best options for
creating superhydrophobic surfaces (Guo et al., 2012; Wang
et al., 2010a). Zhang et al. (Zhang et al., 2015b) applied a
superhydrophobic coating on magnesium substrate to improve
its corrosion resistance using a combination of simple
hydrothermal treatment and modification methods by stearic
acid. Based on this study, initially using the hydrothermal pro-
cess, a hierarchical structured oxide layer was deposited on a
substrate of magnesium hydroxide, which simplified the oper-
ation by stearic acid. The corrosion resistance of coatings and

Table 4 Summary of research about corrosion resistance of superhydrophobic coatings fabricated by spraying method.
Substrate Method Surface energy Contact icorr before icorr after Corrosion protection Reference
reducer agent angle treatment (A/cm2) treatment (A/cm2) efficiency (%)
Cu Spraying n-octadecanethiol 161 3.89  107 8.66  109 97.77 Xu et al. (2011d)
Cu Spraying Silane 156 5.75  105 1.82  107 99.68 Zhang et al. (2016g)
Al Spraying PVDF 159 100.9  106 103.6  106 29 Zhang et al. (2016f)
Al Spraying – 156 2.41  106 2.42  108 98.99 Cao et al. (2009)
Al Spraying Stearate particle 162.1 2.41  106 3.27  108 98.64 Li et al. (2015b)
Science and Engineering of Superhydrophobic Surfaces 1781

their long-term stability were also investigated. Results of the

corrosion resistance studies showed that the highest corrosion
resistance belongs to the coating created by hydrothermal
operation and then treated by corrective actions with stearic
acid. In order study the long-term sustainability, various sam-
ples were immersed in 3.5 wt% NaCl solution for 120 h.
Fig. 22 shows images of the immersion of samples. As could
be seen, a high local corrosion rate occurred on the surface
of uncoated sample, while in the case of the hydrothermal trea-
ted sample, local corrosion of the surface was reduced; imply-
ing that the hydrothermal treatment could improve the long-
term stability of the samples. But it is also observed that the
corrosion was lowered on the surface of superhydrophobic
coated sample, suggesting that the superhydrophobic opera-
tions have effectively improved the long-term stability.
Magnesium is one the low-density metals which has been a
great interest in many industries. One way to improve the cor-
rosion resistance of this metal is to create LDHs layer on it Fig. 23 Potentiodynamic polarization curves of the bare Mg
(Wu et al., 2014a; Zheludkevich et al., 2010). Among the exist- alloy substrate, Zn–Al LDHs coated Mg alloy and superhy-
ing methods to fabricate the layer, the hydrothermal synthesis drophobic Mg alloy surface. (Zhou et al., 2015).
has a high capacity of flexibility due to the control of surface
morphology. Zhou et al. (Zhou et al., 2015) created a superhy-
drophobic film of zinc-aluminum layered double hydroxides released surface energy by means of surface energy reducing
(Zn-Al LDHs) on the substrate of magnesium using a simple materials and examined the corrosion resistance behavior of
hydrothermal crystallization method followed by chemical the coating and its stability. Corrosion resistance studies
modification, and then investigate the corrosion resistance of showed the improved resistance to corrosion by creating a
created layer by polarization method. Fig. 23 shows the polar- superhydrophobic coating. To evaluate the long-term sustain-
ization curves of substrate, hydrothermal-treated, and super- ability, the created coatings were immersed in sodium chloride
hydrophobic samples. Accordingly, the superhydrophobic solution for different durations. It was observed that by
samples represent lowest corrosion current density, and most increasing the duration of immersion, the contact angle varied
positive corrosion potential, indicating the highest corrosion from more than 150° to less than 10° and SA increased from
resistance. less than 10° to 90°. Thus, it can be concluded that the super-
Oxide films formed on the metals act as the barrier layer to hydrophobic state was destructed by increasing the duration of
prevent corrosion. Although techniques such as plasma elec- immersion. In this study, two methods were used to create
trolytic oxidation are used to fabricate the layer superhydrophobic coatings including hydrothermal treatment
(Aliofkhazraei et al., 2010; Seyfoori et al., 2013), they involve and fabrication of superhydrophobic coating (HT-SHS) and
high complexities. Instead, using a simple hydrothermal chemical etching followed by the fabrication of superhy-
method, we can create a hydride or oxide layer on the light drophobic coating (CE-SHS). The results showed that the
metals with rough microstructure. For improving the corro- coating created by HT-SHS method had a longer durability
sion resistance as well as creating the superhydrophobic condi- than other coatings. The reason for such behavior is the gener-
tion, chemical treatment can be used after the hydrothermal ation of an oxide and hydroxide layer on the metals surface
treatment to reduce the surface energy. Ou et al. (Ou et al., acted as barrier layer. In addition, the layer of oxide and
2013b) used hydrothermal treatment to form the oxide or hydroxide increased the active sites of hydroxyl groups on
hydroxide barrier layer on the light alloy substrates. Then, the surface, which improved the adsorption of perfluoroalkyl-
for creating superhydrophobic conditions, they decreased the silane on the surface.

Fig. 22 Photographs of various samples after 120 h immersion in 3.5 wt% NaCl solution: (a) bare AZ31 substrate, (b) the hydrothermal
treated sample, and (c) the superhydrophobic sample (Zhang et al., 2015b).
1782 Gh. Barati Darband et al.

5.6. Electrospinning fabrication method Fig. 25. As could be seen in the images, the highest corrosion
resistance was for the coating with higher thickness.
Electrospinning is a very powerful technique to synthesize fine
fibers in the view of many scholars. This technique is useful to 5.7. Laser operations fabrication method
generate the required roughness for fabricating the superhy-
drophobic mode. Surface roughness and surface microstruc- Laser marking is one of the simple, straightforward affordable
ture of the fabricated coating can be controlled by many operations with many applications (Tang et al., 2015). By
parameters such as concentrations of polymer or polymer type, adjusting the operating parameters such as laser processing
electrospinning parameters such as applied potential and flow textures spacing and laser scanning speed, it can be precisely
rate (Acatay et al., 2004; Peng et al., 2005). As noted before, control the surface morphology. Tang et al. (Tang et al.,
PVDF has a low surface energy and it can be used to reduce 2016) created the superhydrophobic coating on an aluminum
the surface energy of materials. In many investigations, nano- substrate using laser marking method with an array of
materials such as zirconia, alumina, silica, titania, and ZnO micro-orifices and evaluated the corrosion resistance of created
were mixed with PVDF (Hashim et al., 2011; Mohamed coating in corrosive environments such as seawater and acidic
et al., 2014). Radwan et al. (Radwan et al., 2015) created the and alkaline solutions. In addition, the mechanical and chem-
PVDF-ZnO coating on aluminum using the electrospinning ical stability of created surface were also studied. The results of
technique for corrosion protection. The results of corrosion the corrosion resistance evaluation showed that the corrosion
resistance survey showed that polarization resistance of Al- resistance of the superhydrophobic coating was about 1.7%
PVDF-ZnO coating was more than Al-PVDF alone. The pri-
mary cause for the improved corrosion resistance by incorpo-
rating ZnO nanoparticles into the coating is the formed pores
on the surface. These pores prevent the diffusion of corrosive
ions into the nanocomposite coating, because of the existence
of trapped air. When there is only Al-PVDF in the coating,
large pores are created; which cannot prevent the penetration
of corrosive ions to the surface of the coating. Images of Al-
PVDF-ZnO and Al-PVDF samples after polarization tests
are shown in Fig. 24. Accordingly, at the surface of the sample
whit out ZnO nanoparticles, there are many corrosion pores,
while on the surface of the sample including ZnO nanoparticles
the coating has fully covered the surface and no significant cor-
rosion occurred.
Superhydrophobic coatings have been successfully fabri-
cated by Grignard et al. (Grignard et al., 2010) on aluminum
with excellent corrosion resistance using the electrospinning Fig. 25 Corrosion test of aluminum plate covered by pure P
of new solution of the fluorinated diblock copolymer. In this (FDA-co-AA)-b-PAN diblock copolymer exposed to acetic acid
study, the accelerated acetic acid salt spray test was used for salt spray test (5% NaCl, 1–3% HAc, pH 3.1–3.3, 35 (1C): (A)
studying the corrosion resistance of created coating. After Neat aluminum plate. (B) Surface coated by a coating of 3.1 (2.5
placement of various samples for 100 and 200 h in corrosive lm thickness, after exposure for 200 h, black spots = corrosion.
environments, their corrosion resistance was monitored. (C) Surface coated by a coating of 23.2 (8.2 lm thickness after
Images of the samples after salt spray tests are shown in exposure for 200 h (Grignard et al., 2010).

Fig. 24 SEM micrographs for (A) pure PVDF and (B) PVDF–ZnO composite after Tafel polarization in 3.5 wt% NaCl using a scan rate
of 0.167 mV s1 (Radwan et al., 2015).
Science and Engineering of Superhydrophobic Surfaces 1783

of the uncoated substrate. Moreover, variation of the contact
angle with pH values in immersion environment showed that
no considerable change occurred in contact angle, implying
the significant corrosion resistant of the created coating. The
mechanism of corrosion resistance of the superhydrophobic
coating can be explained based on Fig. 26. When the laser-
treated sample is immersed in a modification solution, perflu-
orosilane self-assembled monolayers could be created on the
surface. Also, because of the high polarity and the electron
withdrawing effect of fluorine atoms, C-F bond has a very
strong chemical inertness. Thus, the created perfluorosilane
has very low surface energy and can prevent the electron trans-
mission which passes the corrosive solution. In addition, based
on the conducted calculations, about 92% of the created rough
surface is covered by the air and just 8% is in contact with a
corrosive environment that also improves the corrosion resis-
tance of the surface.
increased by increasing the immersion time. The maximum
angle was 151.1° obtained by immersion for 10 h. Corrosion
resistance was studied by potentiodynamic polarization curves
(PDP), EIS, and long-term immersion test, which showed that
fabrication of superhydrophobic surface improved the corro-
sion resistance of MAO coatings and therefore the AZ31 alloy.
This mechanism was proposed for the fabrication of a
hydrophobic surface (Fig. 27). As shown in this figure, MAO
method was applied to create a microporous surface. The
outer layer was porous and hydrophilic, while the inner layer
was dense. By immersion of the MAO-treated sample in etha-
nol stearic acid solution, due to the low surface energy of the
liquid, it penetrated through porous layers, which is associated
with self-assembly process (b–c). The porous surface of the

5.8. Methods based on anodic oxidation

5.8.1. PEO and MAO

Through the methods of creating oxide layer such as plasma
electrolytic oxidation (Darband et al., 2017; Farhadi et al.,
2017b; Farhadi, 2014; Gnedenkov et al., 2011) method and
anodizing (Liu et al., 2013), it is possible to create a rough sur-
face, with at the micro/nanoscale roughened. Superhydropho-
bic surfaces can be made by reducing the surface energy of the
coatings.
Cui et al. (Cui et al., 2015) created a superhydrophobic
coating on the surface of AZ31 alloy to improve the corrosion
resistance of magnesium created by MAO two-step procedure.
In this research, in order to create a hydrophobic surface,
MAO coated samples were immersed at different times in the
stearic acid solution, where the surface contact angle was

Fig. 27 Schematic representation of the formation of a H-MAO

coating on AZ31 Mg alloy: (a) formation of a MAO coating, (b)
Fig. 26 Schematic illustration of effect of the hydrophobic hydrophobic modification of the MAO coating, and (c) the
modification and specific roughness structure of the surface to the formation of a H-MAO coating by increasing the micro-pores
improvement of corrosion resistance (Tang et al., 2016). (Cui et al., 2015).
1784
layer was coated by oxide and hydroxide to promote a chem-
ical reaction of stearic acid as a monolayer on the surface of
MAO coating. The stearic acid reaction causes the formation
of symmetric and asymmetric sediments and the sediments
remain in the pores of a single weak layer, which consequently
increases the capacitance 2 of MAO coating. Results presented
in Fig. 27c show the formation of a hydrophobic layer on the
MAO coating, where both single-layers and sediments resulted
in the sealing of coating, and as a result improved the corro-
sion resistance. It is well known that the cathodic reaction of
hydrogen gas occurs at the cathodic polarization curve while
the anodic reaction is related to the dissolution of coating/
metal. As shown in Fig. 28, the cathodic polarization for sam-
ples with MAO coating and hydrophobic samples was similar
to the uncoated alloy. The cathodic reaction of the substrate
was less affected by MAO coating and the hydrophobic mod-
ification. However, evidence suggests that the polarization
curve of coated alloy has the passive area. Results showed that
the corrosion resistance of MAO coatings is significantly
increased after modification by stearic acid. It also means that
the hydrophobicity created by bonding of the carboxyl group
of stearic acid on the surface can effectively reduce the surface
contact with the corrosive solution, which will further improve
the corrosion resistance.
Gnedenkov et al. (Egorkin et al., 2016; Egorkin et al., 2015)
created the superhydrophobic coatings on aluminum alloys by
two-stage PEO method. For generating the hydrophobic coat-
ing, first PEO method was used for creating a rough and por-
ous surface and then the coated samples were immersed in a
solution containing ethanol and a hydrophobic agent. For cre-
ating the chemically active surface, samples were treated in two
different ways including washing by ethanol and irradiated by
UV in the presence of the ozone plasma and then their effect
on corrosion resistance were also examined. Corrosion testing
results showed that the superhydrophobic coating improved
the corrosion resistance of the alloy. Furthermore, the
hydrophobic coating had the highest contact angle and maxi-
mum corrosion resistance under UV radiation.
Guo et al. (Guo et al., 2009) fabricated the hydrophobic
nanocomposite coating on magnesium alloy using single-
stage PEO treatment. In this regard, Polytetrafluoroethylene
Fig. 28 PDP curves of AZ31 Mg alloy in an uncoated state, and
with MAO coatings modified for different times in a 3.5 wt%
NaCl aqueous solution (Cui et al., 2015).
Gh. Barati Darband et al.
(PTFE) was used as nanoparticle in the structure of hydropho-
bic nanocomposite nanoparticles because of its hydrophobic
properties, chemical stability, and high corrosion resistance
in the coating structure. The size of the drop contact angle
obtained for the PEO nanocomposite coating was 101°. Corro-
sion resistance evaluation showed that the PEO nanocompos-
ite coating had lower corrosion current density and more
positive corrosion potential than pure PEO coating, indicating
the improved corrosion properties.
Jiang et al. (Jiang et al., 2015) fabricated a superhydropho-
bic coating on Ti-6Al-4V alloy using two-stage MAO method.
To obtain a superhydrophobic coating, the MAO coated alloy
was immersed in an organic solution containing 2H-perfluor
ooctyl-trichlorosilane (PFOTS) for 12 h. The contact angle
of the superhydrophobic coating of MAO was 153°. The
results of corrosion resistance studies showed that the superhy-
drophobic coatings had a more positive corrosion potential
and lower corrosion current density than the specific alloy
and MAO coating, which causes higher corrosion resistance
as shown in Fig. 29. The increase in corrosion resistance due
to the loss of contact surface of corrosion solution with the
superhydrophobic surface is justified because of the existence
of air in the pores and surface roughness.
Wang et al. (Wang et al., 2012b) created a superhydropho-
bic coating on the Mn-Li alloy using a two-step MAO-sol-gel
method. MAO layer was used as the middle layer of superhy-
drophobic coatings because of very rough surface, high corro-
sion resistance, as well as high cohesion to the outer layer or
the hydrophobic layer. Also, a layer of silica, as a hydrophobic
layer film was coated on MAO layer by sol-gel method.
According to Fig. 30, corrosion current density of superhy-
drophobic coating has the lowest value for the uncoated alloy
and the alloy coated by MAO. In addition, it should be noted
that the superhydrophobic silica film showed a better perfor-
mance than pure silica provides in the case of corrosion protec-
tion. Such a higher performance means that, regarding the
linked the presence of functional groups methyl on its surface,
superhydrophobic coatings can effectively reduce the contact
area and thus increase the corrosion resistance.
Fig. 29 Potentiodynamic polarization curves of Ti-6Al-4 V,
MAO and MAO + TFOS samples in Hank’s solution (Jiang
et al., 2015).
Science and Engineering of Superhydrophobic Surfaces 1785

slippery coating fabricated on the surface of pure aluminum

and super-slippery coating fabricated on the surface of ano-
dized aluminum were compared (EIS). As shown in Fig. 31,
the results showed that the coating fabricated on the anodized
surface had higher corrosion resistance than the one fabricated
on pure aluminum, which is not due to lack of porous surface
on the non-anodized aluminum. Porous surface creates the
super-slippery stable coating without pores and gaps; thus, it
improves the resistance to corrosion (Song et al., 2015). Table 5
shows a summary of study results on the corrosion resistance
of superhydrophobic surfaces created by the anodic
oxidation-based methods.

5.9. Plasma techniques

In the recent years, some works have been reported using

plasma techniques to approach superhydrophobic surfaces.
Fig. 30 Potentiodynamic polarization curves of various samples One of the beneficial factors in this technique is the ability of
in 3.5 wt% NaCl solution (Wang et al., 2012b). utilizing different gases for plasma treatments. Yung et al.
found that the use of O2 and/or CF4 plasma on vertically
aligned carbon nanotubes (VACNTs) could lead to obtain
5.8.2. Anodizing method
highly efficient superhydrophobic surfaces by changing the
Anodizing is another electrochemical method that can be used morphology of VACNTs (Yung et al., 2018). Also, usage of
to fabricate rough surface to obtaining superhydrophobic sur- Argon and Oxygen gases in plasma treatment on polytetraflu-
face. He et al. (He et al., 2009) fabricated a superhydrophobic oroethylene (PTFE) was investigated. They achieved a great
coating on aluminum by two-stage method of anodizing- change in contact angle (up to 178°) via a single step treatment
chemical approach. Once, the first anodizing operation was of the as-mentioned substrate (Ryu et al., 2017). In addition,
performed on metal, and then superhydrophobic surface was suspension plasma spraying (SPS) in another branch of plasma
created on the metal using chemical methods. The contact techniques used to approach superhydrophobic surfaces for
angle of droplet on surface was reported to be 154°. Also, the future applications in the engineering field. Sharifi et al.
the corrosion resistance of coatings was investigated. The (Sharifi et al., 2017), prepared surfaces with significant super-
results showed that corrosion resistance was significantly hydrophobicity by controlling of coating parameters and
increased due to the reduced contact surface of metal and sea- obtaining dual-scale surface textured coatings.
water solution.
Yin et al. (Yin et al., 2011) proposed a simple and efficient 5.10. Other fabrication methods
method for fabrication industrial scale superhydrophobic coat-
ings on aluminum alloy. Through this procedure, first, the
many other methods have been used to create superhydropho-
metal was coated by the anodizing method and then the super-
hydrophobic surface was generated on this layer via chemical bic surfaces and their corrosion resistance was also investi-
etching. Corrosion resistance of superhydrophobic coatings gated. A summary of all of these methods, as well as the
improved corrosion resistance of the substrate because of the
was evaluated as the corrosion resistance was increased. Also,
fabrication of superhydrophobic layer, is presented in Table 6.
the stability of the superhydrophobic coatings was investi-
gated, for which the results showed that the coating had a
chemical stability in sea water solution.
Superhydrophobic coatings were created on aluminum via
two-stage anodizing-chemical approaches, where the corrosion
resistance increased. Chemical and mechanical stability and
weathering superhydrophobic coatings were also examined.
The results showed that superhydrophobic coatings were
almost stable in acidic and alkaline environments and the coat-
ing possessing mechanical stability has been tested by sand-
blasts system. Results for sustainability erosion (for 7 days)
superhydrophobic coating does not cover significant changes
in the contact angle is stable erosion. Results for erosion sus-
tainability (for 7 days) of superhydrophobic coating did not
show any significant change in contact angle while the coating
showed high erosion stability (Zheng et al., 2016).
The superslippery coating was fabricated on aluminum
alloy using anodizing and immersion methods, which
improved the corrosion resistance of the aluminum alloy. Fig. 31 Nyquist plots of Co3O4 grown AAO and pure aluminum
The effect of the anodizing process on the corrosion resistance super slippery surfaces after immersion for 16 h in 3.5% NaCl
was also evaluated, so the corrosion resistance of these super- solution (Song et al., 2015).
1786 Gh. Barati Darband et al.

Table 5 Summary of research about corrosion resistance of superhydrophobic coating fabricated by anodic oxidation based methods.
Substrate Method Surface energy Contact icorr before icor after Corrosion Reference
reducer agent angle treatment treatment protection
(A/cm2) (A/cm2) efficiency (%)
Titanium PEO Methoxy-silane 165.8 1:4  107 1:4  109 98.60 Gnedenkov et al. (2011)
Mg-Li MAO ATP 1:37  104 5:6  107 99.60 Hou and Kang (2013)
Mg–Mn–Ce PEO Methoxy-silane 166 6:6  106 1:5  109 99.97 Kang et al. (2011)
Aluminum Anodizing Stearic acid 160 2  107 88  109 95.60 Huang et al. (2016)
AZ31 Mg alloy MAO Stearic acid 151 16  107 14  109 99.91 Cui et al. (2015)
Aluminum PEO Methoxy-silane 157 6:1  107 4:8  1012 99.99 Egorkin et al. (2015)
Titanium PEO N,N,N-trimethyl-1-silane 165 1:4  107 1:4  109 – Gnedenkov et al. (2014)
Magnesium alloy 166 6:6  106 1:5  109
Low-carbon steel 161 2:1  109 3:3  109
Magnesium PEO Polytetrafluoroethylene 101 2:4  106 2:1  107 91.25 Guo et al. (2009)
Ti-6Al-4 V MAO PFOTS 153.3 2:2  107 1:4  108 93.63 Jiang et al. (2015)
Mg–Nd–Zn–Zr MAO Tetraethoxysilane 151 2:2  105 2:6  108 99.88 Wang et al. (2012b)
&methyltriethoxysilane
Aluminum Anodizing Fluorinated silane 163 5:6  106 1:5  108 99.73 Zhang et al. (2015c, 2015d)
Aluminum Anodizing Myristic acid 155.2 3  107 1:52  109 99.49 Zheng et al. (2016)
Aluminum alloy Anodizing Myristic acid 155.6 2:7  107 9:9  1011 99.63 Zheng et al. (2015)
Mg-Li-Ca alloy PEO Stearic acid 155.5 4.23  105 5.36  108 99.2 Zhao et al. (2017)

6. Chemical stability
6.1. The necessity of chemical stability investigation
A very influential parameter in evaluation of corrosion resis-
tance of superhydrophobic films is determination of their
chemical stability under various working conditions and solu-
tions. As chemical stability is a crucial variable in selection of
materials for duty in a specific environment, the process of
measurement and evaluation itself becomes considerably
important.
surrounding corrosive medium (Fig. 33). Thickness of the sur-
face layer which is responsible for low surface energy and
superhydrophobic properties reduces as the layer reacts with
the solution. In another scenario, chemical composition of
functional groups of the surfactant changes due to various pro-
cesses leading to a gradual increase in surface energy and fad-
ing of superhydrophobic properties (Farhadi et al., 2017a;
Guo et al. (2015a); Heinonen et al., 2014; Ishizaki et al.,
2010; Zhao et al., 2017).
6.3. Chemical stability evaluation

6.2. Chemical stability fading mechanisms
Considering the fact that fabrication of superhydrophobic
films requires two essential conditions which are surface
roughness and low surface energy, it may be deduced that a
film may lose its chemical stability due to following
mechanisms:
6.2.1. Loss of roughness
After being exposed to the chemical medium, the film may
undergo a chemical process. Hence, the rough materials that
constitute the film are dissolved according to their inherent
properties. The film, therefore, loses its primary rough mor-
phology over time (Fig. 32) and contact angle of droplet
reduces gradually. It is even possible that the film becomes
hydrophilic (Cai et al., 2015; Cui et al., 2017; Farhadi et al.,
2017a; Guo et al. (2015b)).
6.2.2. Dissolution of surface layer
Another proposed mechanism for chemical instability of a film
after immersion in the corrosive medium is removal or alter-
ation of the chemical composition of surface layer with mini-
mum surface tension due to chemical reaction with the
There are many methods for evaluation the chemical stability
of superhydrophobic coatings. In the following sections, we
will review recent studies on superhydrophobic films based
on the methods used for evaluation of chemical stability.
6.3.1. Contact angle versus pH variations
As it was mentioned earlier, it is highly frequent in experimen-
tal works to evaluate chemical stability by achieving contact
angle versus pH plots. Chemical stability of a superhydropho-
bic film is readily estimated with this method. It should be
noted that while investigating pH, the working environment
of a film is given attention rather than its lifetime. An example
for such studies is formation of thin superhydrophobic films
through chemical electrodeposition from reinforced vapor
phase with microwave plasma (MPECVD). Ishizaki et al.
(Ishizaki et al., 2010) deposited films on a magnesium substrate
and immersed them in different media. It was reported that
films were deteriorated in alkaline solutions and almost
became hydrophobic. It was revealed that SiOx which is the
functional group responsible for superhydrophobic properties
was dissolved at pH ranges above 10 and consequently the
film’s stability was lost. In addition, contact angle also
decreased, not as intensely as alkaline solutions though, in
Science and Engineering of Superhydrophobic Surfaces 1787

Table 6 Summary of research about corrosion resistance of superhydrophobic coating fabricated by other methods.
Substrate Method Surface energy Contact icorr before icorr after Corrosion Reference
reducer agent angle treatment treatment protection
(A/cm2) (A/cm2) efficiency (%)
Mg Phase separation – 155 1.73  105 9.17  109 99.46 Yang et al. (2016)
Cu Dip coating STA 162.3 6.7  105 6.2  106 90.74 Qing et al. (2015)
Cu Dip coating PVDF 160.1 6.7  105 1.1  106 98.35 Qing et al. (2016)
Cu Polymerisation HFBA 159 34  106 1.61  106 95.26 Yuan et al. (2011)
Cu Etching and calcination Stearic acid 157.6 4.31  106 2.35  108 98.90 Liu et al. (2016a)
ethanol solution
Cu Electroless and electro 153.2 10.37  106 0.85  106 91.80 Hu et al. (2015)
deposition
Stainless Flame spraying PU 151 2.21  10–3 1.87  10–4 91.53 Chen et al. (2014)
steel 316 l
Stainless Etching and oxidation – 158.2 3.35  107 1.08  107 67.76 Park and Hwang (2016)
steel
Al Spin coating – 161.2 0.19  106 0.008  106 95.87 Momen and Farzaneh
(2014)
Al Spin coating Graphene-E 153.7 7.19  104 2.54  107 99.64 Liu et al. (2014c)
Al Etching and spraying PVDF 164 106 108 99 Wang et al. (2015)
Al Anodization Myristic acid 155.2 3.06  107 1.52  1010 99.95 Zheng et al. (2016)
Al Boiling water treatment Stearic acid 156.6 1.54  105 2  107 98.70 Feng et al. (2016)
Al Chemical etching and FDTS 170 1.65  104 2.36  108 99.99 Wang et al. (2016)
anodization
Al Chemical etching and PTES 156 6.33  106 5.71  1010 99.99 Wu et al. (2016)
anodization
Mg Electrochemical FAS 165.2 9.96  105 9.68  108 99.90 Xu et al. (2011b, 2011c)
machining process
Cu Self-assembly PFDTS 152.5 180  106 5.3  106 97.05 Ou et al. (2013a)
Mg Microwave plasma- – 150 9.25  105 7.41  108 99.91 Ishizaki et al. (2010)
enhanced chemical
vapor deposition
Al Successive thermal – 169 1.06  104 1.84  106 98.26 Cheng et al. (2015)
treatment
Zn Immersion process PFTS 151 1.09  105 1.62  107 98.51 Liu et al. (2009a)
Zn Electroless deposition DDT 152 4.38  104 1.6  104 63.47 Shi et al. (2014)
Zn Etching in hydrochloric – 170 1.66  104 7.24  105 56.38 Zhang et al. (2016a,
acid, electrodeposition of 2016b, 2016c)
ZnO coatings, thermal
annealing
Carbon Electric corrosion Stearic acid 152 105 1.25  107 98.75 Sun et al. (2016)
steel ethanol solution
Brass Etching and heat Stearic acid 153.6 9.55  107 5.40  109 99.43 Jie et al. (2016)
treatment ethanol solution
Titanium Chemical etching Fluoroalkylsilane 160 1.46  10–7 1.69  1010 99.88 Lin et al. (2016)
Mg Co-precipitation method Stearic acid 153.5 4.7  105 3.4  1010 99.99 Zhang et al. (2016d)
and hydrothermal

Fig. 32 Fading of surface roughness as a result of exposure to a corrosive medium.

acidic solutions; hence, it may be deduced that the best stabil- cial baths designed for deposition of self-repairing coatings. It
ity may be expected in neutral solutions. Yang et al. (Yang was shown that contact angle reduced with increase in acidity;
et al. (2015)) investigated formation of self-repairing super yet, it remained above 150° and the medium did not affect sta-
hydrophobic films on Mg substrates through immersion in spe- bility of films.
1788
Fig. 33 Chemical instability of surface layer due to (a) dissolution of layer and (b) change of layer chemical composition.
Li et al. (Zhao et al., 2017) fabricated superhydrophobic
properties on steel pipelines through deposition of Cu-Zn films
with rough dandelion-like in a two-step procedure including
electroplating and chemical oxidation. The stability of such
films was reported excellent in all environments except harsh
alkaline solutions. This was due to removal of the acid mole-
cules adsorbed on surface by the alkaline medium. Carbon
and fluorine faded gradually indicating removal of the acid
layer.
Another application of superhydrophobic films is manufac-
ture of anti-rain surfaces which was discussed by Liu et al. (Cui
et al., 2017). They acquired contact angles above 170° through
calcination of polydimethylsiloxane on glass and modification
with CVD. It was observed that contact angle reduced over a
constant period of time in acidic and alkaline solutions. The
reduction, of course, was less intensely in acidic solutions
due to changes in morphology of roughness structure on sur-
face. The same morphology was entirely destructed in alkaline
solutions. Then, it may be concluded that these films had a
desirable performance in both acidic and neutral media.
Cai et al. (Cai et al., 2015) managed to form wooden super-
hydrophobic films through immersion in solution. They used
lauryl aldehyde and lauric acid for surface modification and
investigated adhesiveness and stability of films. It was observed
that the sample saturated with lauric acid lost superhydropho-
bic properties in all pH ranges except from 6 to 7 due to loss of
the adsorbed acid. In result, the air layer left the film and dro-
Fig. 34 SEM micrographs of the sample without silver after immersion for 8 weeks in (a) harsh acidic and (b) harsh alkaline media
(Heinonen et al., 2014)
Gh. Barati Darband et al.
plets could penetrate into the coating. However, regarding the
sample saturated with lauryl aldehyde, higher stability rates
were observed within all pH ranges.
Formation of antibacterial superhydrophobic films con-
taining Ag by means of sol-gel method was investigated by
Heinonen et al. (Heinonen et al., 2014). It was observed that
after immersion for 8 weeks, the highest concentrations of
Ag ions were found in extremely acidic and alkaline solutions.
In order to investigate the effect of silver, immersion test was
carried out on silver-free films under harsh conditions. As seen
in SEM micrographs in Fig. 34, The film was entirely dissolved
in acidic solutions and wetting angle plummeted to 100° at
alkaline pH ranges. Besides, contact angle did not vary notably
in neutral and mild alkaline media.
Also in Fig. 35, SEM micrographs of silver-containing
superhydrophobic samples shows that sample exposed to
highly acidic solution has been completely desolved. However,
the one immersed in sever alkaline media has shown a flaky
structure in comparison with the silver-free sample which has
no specific structure after exposure.
There have been many studies conducted on formation of
superhydrophobic films by this technique which are summa-
rized in Table 7.
6.3.2. Contact angle versus immersion time
Another highly employed technique for investigation of chem-
ical stability is evaluation of contact angle of a droplet on sur-
Science and Engineering of Superhydrophobic Surfaces 1789

Fig. 35 SEM micrographs of the sample with silver after immersion for 8 weeks in (a) harsh acidic and (b) harsh alkaline media
(Heinonen et al., 2014).

Table 7 Results of studies conducted based on contact angle versus pH variations.

Substrate Method SH agent CA° Immersion conditions Chemical Reference
stability
Polyester sponge Sol-gel PMHS-TEOS >150 1 < pH < 14 Good Guo et al.
(2015b)
Glass Phase separation BMA-BDO- 159.5 Acid, alkali, salt Good Liu et al. (2014a)
EDMA-NMP aqueous solution
Copper Electrolytic Ethanolic stearic 156– 1 < pH < 14 Good Tan et al. (2015)
acid 162
Wood Immersion TEOS >150 1 < pH < 14 Good Li et al. (2016)
AZ91D ED Stearic acid 167 1 < pH < 14 Good She et al. (2013b)
Copper Immersion Stearic acid 163 2 < pH < 12 Good Liu et al. (2014a)
Al alloy Anodization Myristic acid 155.6 DI water, ethanol Good Zheng et al.
(2015)
Al alloy Anodization Myristic acid 155.2 1 < pH < 12 Good Zheng et al.
(2016)
Zn Galvanic replacement reaction Ethanol-PFDT >150 1 < pH < 13 Good Xu et al. (2012)
Al alloy Laser marking Ethanol-PFDTCS 155.1 1 < pH < 14 Good Tang et al. (2016)
AZ91D Electrodeposition and chemical Stearic acid 158.5 1 < pH < 13 Good She et al. (2017b)
magnesium alloy modification
High-purity Versatile one step Stearic acid >155 1 < pH < 14 Good Guo et al.
aluminum foils electrodeposition (2015a)
Copper mesh Electrodeposition Lauric acid 155.5 1 < pH < 14 Good She et al. (2017a)
Carbon steel One-step electrodeposition Lanthanum nitrate 160 1 < pH < 13 Good Yang et al.
(2015)
Iron Phosphate, Cu co-deposition in FAS-17 160 1 < pH < 14 Good Zhang et al.
phosphating bath (2017b)
Various One-step sol–gel electrochemistry DTMS >150 4 < pH < 14 Good Wu et al.
route method HTMS (2014c,d)
Copper mesh Solution-immersion Triazinedithiolsilane >150 3 < pH < 13 Good Wang et al.
(2017b)
Wood Solution-immersion Stearic acid 155 1 < pH < 14 Good Gao et al.
(2015b)
Cotton Covalent deposition method Trimethoxysilane 158 1 < pH < 14 Good Zhang et al.
(2016e)
NMOF-1 Solution-immersion OPE-C18 >155 1 < pH < 14 Good Roy et al. (2016)
Aluminum Anodization FAS 156 0 < pH < 14 Good Wang et al.
(2017a)
AZ31 Solution-immersion Fluoroalkylsilane >142 1 < pH < 14 Good Ishizaki and
Saito (2010)
Copper Oxidation  reduction reaction – >160 1 < pH < 14 Good Lee et al. (2012)
Mg-Mn-Ce Electrodeposition Myristic acid 159.8 1 < pH < 14 Good Liu et al. (2014a)
magnesium plate
Various Anti-deposition route method Stearic acid >150 1 < pH < 13 Good Si et al. (2016)
Copper Electrodeposition and heat- AC-FAS 162 1 < pH < 13 Good Koishi et al.
treatment (2009)
1790
face as a function of immersion time in any sort of solution.
This approach may be used in a single solution to evaluate sta-
bility or in different media with various pH values in order to
compare the stability in different media. The obtained data are
eventually plotted on a curve whose abscissa is immersion time
and ordinate is contact angle or droplet sliding angle on the
surface. This technique has been used in many cases regarding
formation of superhydrophobic films. Wu et al. (Wu et al.
(2014c,d)) developed surfaces to separate water from organic
materials such as oil through applying superhydrophobic films
on polyester substrates by means of dip coating and saturation
with TOES and n-HDTOES. Through immersion in different
solutions after long periods, it was observed that immersion
time did not significantly affect superhydrophobic properties.
It seemed that the reason of desirable performance was strong
HD-silica/HD-polymer bonds with the substrate as well as sta-
bility of the nanocomposite in organic media such as crude oil.
Seeking to develop and apply superhydrophobic properties
in textile industries, Li et al. (Fang et al., 2017) produced
superhydrophobic cotton fabrics using copolymer materials
which maintained a high contact angle (above 147°) after
immersion in different pH solutions for 96 h. This can be real-
ized as fairly high stability in acidic, neutral and alkaline solu-
tions. The high lifetime is equivalent bonds between fluorine-
containing polymeric chains and the cotton fabrics. Yang
et al. (Yang et al., 2017) also improved stability in superhy-
drophobic epoxy films. They managed to keep contact angle
above 150° in neutral, harshly acidic and harshly alkaline solu-
tions for long exposure by random distribution of fluoro-
graphene nano-planes as could be seen in the micrographs pre-
sented in Fig. 36. This clearly indicated the favorable chemical
stability of films under the aforementioned conditions. Super-
hydrophobic films with adhesiveness control capability were
deposited on titanium substrates by Guo et al. (Guo et al.
(2015a)) via thermal oxidation and self-adjustment technique.
A rough, scaled oxide film was applied on surface by alterna-
tive heating and quenching cycles so that superhydrophobic
properties were obtained. Fig. 37 illustrates dual-scale rough-
ness of this structure.
After immersion in harshly corrosive media, contact angle
reduced over time which was due to a gradual decrease in sur-
face superhydrophobic groups (N-ODTCS and n-hexane) as
they have high affinity in reactions with extreme acidic solu-
tions. Hence, the film is much more destructible in acidic envi-
ronments. Within the first 5 days of immersion, contact angle
Fig. 36 FE-SEM micrographs of fluoro-graphene nano-planes randomly distributed on the surface (Yang et al., 2017).
Gh. Barati Darband et al.
remained above 150° in both types of solutions; however, this
parameter plummeted to 146° in acidic media in long term
while it yet remained above 150° in alkaline solutions.
The above technique may also be used in study of self-
cleaning surfaces. For instance, Zheng et al. (Zheng et al.
(2016, 2015)) investigated the stability of their films by pH
variations. Superhydrophobic properties were not consider-
ably affected after immersion in deionized water for 19 days.
As mentioned previously, this technique is well-known
broadly used approach in investigation of chemical stability.
The results obtained in several works conducted based on
pH versus contact angle variations technique are presented
in Table 8.
6.3.3. Acid rain test
Sometimes, working conditions decree that in addition to
mechanical stability, chemical stability against acid rain most
be studied. Here, sample is subjected to simulated acid rain
with different pH values. The pH of simulation solution is gen-
erally adjusted with various concentrations of sulfuric acid.
Due to complexity of simulation process, this technique is
rarely used by researchers in study of chemical stability of
coatings. For example, Zheng et al. (Zheng et al., 2016) con-
ducted acid rain test within a pH range of 1 to 4 and at a con-
trolled pH value of 5.6. The sample was exposed to simulated
rain for 12 h. Similar to the results of other experiments, the
film maintained superhydrophobic after 12 h of exposure to
acid rain.
6.3.4. Droplet test in vapor-saturated atmosphere
Instead of direct droplet test, sample is enclosed by an isolated
cell saturated with vapor of the intended vapor. The required
data including contact angle and droplet sliding threshold
angle are extracted after formation of droplets on surface. This
technique is also less frequently used for chemical stability
investigation due to complexity of the required data.
Emelyanenko et al. (Emelyanenko et al., 2015) formed
nano-texture superhydrophobic surfaces on stainless steel sub-
strates. They used laser and chemical adsorption of fluoro exi-
silane to achieve a contact angle above 170° after immersion
for 24 h. Xiao et al. (Xiao et al., 2016) reported that films pro-
duced on oxidized aluminum substrates had a contact angle
above 150° after exposure for 60 h in an atmosphere saturated
with NaCl vapor. This indicates high stability of coatings in
Science and Engineering of Superhydrophobic Surfaces 1791

Fig. 37 FE-SEM micrographs of thermally oxidized samples at 1100 °C for 15-min periods (M. Guo et al. (2015a)).

Table 8 Some of the works conducted based on pH versus contact variations technique.
Substrate Method SH agent CA° Immersion conditions Chemical Reference
stability
Hierarchical Acid etching and subsequent ABS-PC-PMMA- >150 pH = 1, 14 Good Long et al.
aluminum boiling water treatment PS-PU (2016)
Aluminum In-situ growth process Stearic acid 152.1 21–36 days in an specific Good Liang et al.
solution (2013)
Steel Etching and solution- Stearic acid 158 24 h in 3.5% NaCl sol. Good Zhang et al.
immersion (2017b)
Stainless steel One-step vapor deposition PDMS >160 40mins in NaOH and HCl Good Kim et al.
mesh (2016)
Cotton MWCNTs coating Nafion 154.6 96 h in water Good Zou et al.,
xxxx
Aluminum Etching with ferric chloride FDTS-PDMS- >150 72 h for alkali an acidic sol-48 h Good Maitra
MTS for ionic sol et al. (2014)
Cotton Single-pot coating solution Fluorinated alkyl 163 96 h in various organic solvents Good Zeng et al.
silane and aqueous solutions (2015)
Copper Electrodeposition 1-Dodecanethiol / 154 In 3.5 wt% NaCl solution for Good Liu et al.
polydopamine 35 days (2014a)
Various Surface-functionalized quartz Polyvinylchloride >150 In water for 30 days Good till the Qu et al.
sand nanoparticles 20th day (2016)
– Gel immersion Fluorosilane >150 In pH = 1,14 for 30 mins Good Zhang et al.
(2017a)
Alumina Onestep anodization process PDES - stearic >150 In diverse organic solvents Good Peng et al.
acid (2005)

saline corrosive media. However, droplet sliding angle
increased by 90° which cannot be acceptable. They explained
that this phenomenon is caused by facilitation of a continuous
contact line among solid, liquid and vapor phases through
integration of distilled water droplets. The droplets are mixed
with NaCl solution so that the locked air bags are isolated and
consequently more power is required to encounter the negative
pressure. Multiple degrees of drop in contact angle was
reported by She et al. (She et al. (2013b)) in Ni-Co films depos-
ited on magnesium after exposure to harsh acidic and alkaline
vapors for 36 h. Superhydrophobic properties were observed
to remain after the experiment.
6.4. Chemical stability improvement approaches
As it was observed previously, depending on the chemical com-
position, the deposited film may have various scales of lifetime
and stability in different media. According to the stated mech-
anisms for removal of chemical stability including application
of more stable functional groups to reduce surface energy or
use of self-repairing mechanism in coatings, there may be var-
ious approaches for improvement of lifetime of coatings.
7. Mechanical stability
7.1. Necessity of mechanical stability
Under various applications, superhydrophobic films are typi-
cally applied on to different surfaces so that wear processes
may be induced between layers. Being so fragile, superhy-
drophobic films will lose their superhydrophobic properties
as soon as they contact with an external surface. Thus, high
mechanical stability is a major requirement for industrial
applications of superhydrophobic films. In this section, several
1792
issues such as fading of superhydrophobic properties due to
mechanical loadings, mechanical stability evaluation tests
and recent developments in improving mechanical stability
are discussed.
7.2. Fading mechanism of superhydrophobicity due to
mechanical contacts
As mentioned earlier, it is necessary to create the cassie-baxter
state in which water cannot penetrate through rough surfaces
in order to achieve superhydrophobic properties with a high
contact angle and a low residual angle. In Wenzel’s wetting
state, water penetrates into a rough surface which results in
higher slide angles. In general, it may be stated that cassie-
baxter roughness state fades; water may penetrate into the
rough surfaces and extinguish superhydrophobic properties.
Mechanical fragility of superhydrophobic textures in surface
causes creation of the Wenzel’s state as soon as a contact is
made between internal and external surfaces. Therefore, the
droplet and surface are locked with each other and their adhe-
siveness improves leading to fading of superhydrophobic prop-
erties (see in Fig. 38). Then, it may be realized that
superhydrophobic properties reduce through two mechanisms:
first, decrease of surface roughness and transition to the Wen-
zel’s state increases the contact area between water and surface
and second, surface may lose its inherent hydrophobicity due
to contamination with hydrophilic species.
7.3. Important approaches for improvement of mechanical
stability
So far, great deals of studies have been conducted on improve-
ment of mechanical stability in superhydrophobic films. This
section is allocated to a review on the newest approaches for
improving the mechanical stability in superhydrophobic films.
As it was mentioned earlier, in order to achieve superhydropho-
bic properties, it is required to procure the cassie-baxter state.
Note that transition from cassie-baxter to the Wenzel’s state
fades superhydrophobic properties of the surface. An interest-
ing method to increase mechanical stability in superhydropho-
bic surfaces even after application of mechanical loads is
creation of dual scale surface roughness (Chen et al., 2016).
In this case, a stable cassie-baxter state is reached which does
not fade even after application of external loads. Xiu et al.
Fig. 38 Schematic of fading mechanism of superhydrophobicity due to mechanical contact.
Gh. Barati Darband et al.
(Xiu et al., 2010), investigated the effect of dual scale surface
roughness on mechanical stability of silicon superhydrophobic
films by means of wear tests and compared the results with sur-
face roughness and they observed that noticeable variations
occurred in increase of residual contact angle where the water
droplet causes mechanical destruction on the surface and pen-
etrates into the rough surface increasing the contact angle. It
was reported that silicon superhydrophobic films with dual
scale surface roughness showed an excellent mechanical stabil-
ity. SEM studies revealed that only cone peaks undergo
destruction in surfaces with dual scale roughness and the rough
parts in the valley remains intact. Hence, the contact angle still
has a large value. Using the same concept, there were other
researchers that attempted to improve mechanical stability of
superhydrophobic films (Zimmermann et al., 2008).
Since increase in inherent strength of a superhydrophobic
surface texture leads to maintenance of Cassie-Baxter state,
an important approach to enhance mechanical stability in a
superhydrophobic film appears to be increasing the inherent
strength in that superhydrophobic film. A practical technique
for this purpose is fabrication of nanocomposite films (Ebert
and Bhushan, 2012; Tadanaga et al., 2003; Zhu et al., 2011)
implementing hydrophobic nanoparticles where grain size
reduces and a new area is exposed as surface wearing process
continues. Another approach which is used to improve inher-
ent strength and consequently mechanical stability in superhy-
drophobic films is alloying of the surface texture through
electrodeposition processes.
Mechanical stability in superhydrophobic films can also be
improved by means of a hydrophobic bulk substance. Usually,
a typical rough film may be produced via any available tech-
nique; then, its surface is modified with chemical treatment
by applying a material with low surface energy (e.g. fatty acids)
on the surface so that the superhydrophobic film is obtained.
In this case, after the superhydrophobic film is worn, superhy-
drophobic properties are naturally lost. Thus, if the superhy-
drophobic film is produced totally with a hydrophobic
material, new superhydrophobic surface is constantly exposed
throughout the wearing process and mechanical stability
improves. The last method to improve mechanical stability in
superhydrophobic films discussed here is using self-repairing
films. Such surfaces are capable of repairing the worn surfaces
and maintain superhydrophobic properties (Ionov and
Synytska, 2012; Li et al., 2010). In this field many studies have
been done. For example, a micro-arc oxidation (MAO)/zinc
Science and Engineering of Superhydrophobic Surfaces
stearate (ZnSA) composite coating was fabricated on Mg-4Li-
1Ca alloy by means of MAO and subsequent sealing with elec-
trodeposition of a superhydrophobic ZnSA. Corrosion resis-
tance improvement of fabricated coating was attributed to
self-healing property (Cui et al., 2017). Also Superhydrophobic
Mg(OH)2/Mg-Al Layered Double Hydroxide coating was fab-
ricated on Mg alloys and high resistance improvement of
superhydrophobic coating was ascribed to self-healing prop-
erty (Zhang et al., 2016d).
8. Concluding remarks and future trends
In this work, a brief overview was conducted on methods of
creating superhydrophobic surfaces and also the application
of superhydrophobic surfaces was investigated. The main
focus of this article was on the corrosion behavior as well as
chemical and mechanical stability of developed superhy-
drophobic coatings. According to this study, it can be con-
cluded that superhydrophobic surfaces created by different
micro and nano surface roughness methods enhance the corro-
sion resistance of the substrate, as the air is trapped in them
and prevents the transmission of electron and ion between
the substrate and electrolyte. Moreover, the created Laplace
pressure prevents the entrance of electrolyte to the substrate,
which also improves the corrosion resistance of the surface.
In addition, based on the overall results of this study, it can
be found that the wetting angle is directly related to the corro-
sion resistance of surface; by increasing the wetting angle, cor-
relation of the substrate and the corrosive species is decreased;
which consequently increases the corrosion resistance. One of
the main drawbacks of using superhydrophobic surfaces is
their low mechanical and chemical stability when being
exposed to corrosive environments. Based on this, recent
advanced in chemical and mechanical stability enhancement
were discussed in this paper.
As noted earlier, most scholars believe that the Laplace
pressure and trapped air can improve the corrosion resistance
of these surfaces. But, it seems that more extensive studies are
required to understand the mechanism of enhanced corrosion
resistance of superhydrophobic surfaces. Further studies are
needed to increase the mechanical and chemical stability of
these surfaces. According to the most of the reviewed articles,
there is no comprehensive standard for assessing the mechan-
ical stability of these surfaces and more studies must be con-
ducted to standardize these cases. By reading this article and
other reviews it can be found that most studies conducted in
the case of corrosion resistance included corrosion resistance
studies of superhydrophobic surfaces fabricated by deposition
via electrical and chemical methods. Therefore, studying the
corrosion resistance of fabricated superhydrophobic surfaces
by other methods is also required. In addition, most studies
have been conducted in the laboratory and further examina-
tion for industrialization of these coatings is required.
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