Colloids and Surfaces A: Physicochem. Eng.

Aspects 367 (2010) 60–64

Contents lists available at ScienceDirect

Colloids and Surfaces A: Physicochemical and
Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

A simple approach to fabricate regenerable superhydrophobic coatings
Jin Yang a,b , Zhaozhu Zhang a,∗ , Xuehu Men a , Xianghui Xu a,b , Xiaotao Zhu a,b
a
b

State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Tianshui Road 18th, Lanzhou 730000, PR China
Graduate School, Chinese Academy of Sciences, Beijing 100039, PR China

a r t i c l e

i n f o

Article history:
Received 24 March 2010
Received in revised form 17 June 2010
Accepted 18 June 2010
Available online 1 July 2010
Keywords:
Superhydrophobic coating
Spray
Regenerable
Metal alkylcarboxylate

a b s t r a c t
A simple approach is proposed to fabricate a regenerable superhydrophobic coating constructed by spraying metal alkylcarboxylate dispersion on any substrates. This dispersion is prepared by the reaction of
metal salt and alkylcarboxyl acid in ethanol solution. The sprayed coating with the flowerlike hierarchical structures shows stable super-repellent behavior for several oily liquids such as ethylene glycol
and benzyl alcohol. The advantage of the present approach is that the superhydrophobic performance
can be easily repaired by spraying the dispersion again when the coating surfaces are damaged, and the
cheap coating materials and simple fabrication approach allow the local repair at anytime and almost
anywhere.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction
In nature, many plant leaves exhibit an unusual superhydrophobicity and self-cleaning property, called “lotus-effect”, resulting
from the cooperative effect of special micro/nanostructures and
low-surface-energy materials on these surfaces [1]. To mimic the
effect, enormous contributions have been made to the design
and fabrication of superhydrophobic surfaces via two kinds of
approaches: either creating rough structures on low-surfaceenergy substrates or chemically modifying rough substrates with
low-surface-energy materials [2]. Meanwhile, many artificial surfaces with both water and oil super-repellent behavior can also
be fabricated according to the above design principle [3–8]. These
superhydrophobic surfaces are expected to have broad practical
applications such as self-cleaning products, drag free liquid transportation in microfluidic systems, water–oil repellent fabrics, and
biological applications [9–11]. However, in the practical applications of superhydrophobic surfaces, they are very weak to resist
mechanical contact on their surfaces, which makes the artificial surfaces lose their superhydrophobicity easily. Especially, unlike the
plant leaves, the destroyed surfaces cannot be repaired automatically. Therefore, we may need to change train of thought to develop
superhydrophobic surfaces. The cheap materials, simple fabrication
approach, and easy regeneration would be the alternative way.
Materials contain long-chain alkyl groups that have lower
surface free energy, which is favorable to create superhy-

∗ Corresponding author. Tel.: +86 931 4968098; fax: +86 931 4968098.
E-mail address: zzzhang@licp.cas.cn (Z. Zhang).
0927-7757/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfa.2010.06.016

drophobic surfaces [12–14]. There are some reports on making
superhydrophobic surfaces on metal substrates using in situ generated metal alkanoates [15] or metal alkyl phosphonates [16].
However, these surfaces are limited to certain substrates and timeconsuming, making it difficult to regenerate the superhydrophobic
performance of these surfaces after being mechanically damaged.
In this paper, we report a real simple, low-cost, and nontoxic
method to prepare superhydrophobic coatings made by spraying an
alkylcarboxylate dispersion on virtually any substrates. The alkylcarboxylate dispersion is prepared by the reaction of metal salt
and alkylcarboxyl acid in ethanol solution. After spraying on the
substrates it can form the flowerlike hierarchical structures and
hence allows the tethered alkyl groups to create superhydrophobic surfaces in situ. The contact angle (CA) for water and ethylene
glycol is 160◦ and 156◦ with sliding angle (SA) of about 5◦ and 10◦ .
Even benzyl alcohol has a large CA of about 151◦ . Importantly, once
the flowerlike nanostructures are scratched, the superhydrophobic
performance can be regenerated by spraying the dispersion again.

2. Experiment and characterization
2.1. Experiment
Copper acetate (0.1 g) was dissolved in ethanol (20 mL), and then
a palmitic acid (0.25 g) ethanol solution (20 mL) was added dropwise under stirring at ambient temperature. A slurry was generated
immediately due to the formation of the Cu(CH3 (CH2 )14 COO)2 , and
the reaction mixture was kept stirring for 2 h to form dispersion.
Then the as-prepared dispersion was sprayed onto glass, metal, or
other substrates with nitrogen gas and dried under room temper-

J. Yang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 367 (2010) 60–64

61

Fig. 1. (a and b) FESEM images of the as-prepared Cu(CH3 (CH2 )14 COO)2 flowerlike coatings at low and high magnifications. (c) FESEM image of the pure palmitic acid crystal
structures.

ature for 2 h until ethanol gradually evaporated. The thickness of
the coatings was estimated in the range of 40–60 ␮m.

droplets using a KRÜSS DSA 100 (KRÜSS Company, Ltd., Germany)
apparatus.

2.2. Characterization

3. Results and discussion

Scanning electron microscopy images were obtained on a
JSM-6701F field-emission scanning electron microscope (FESEM).
Fourier transform infrared (FTIR) spectra were collected on a
Bruker IFS66 V/S spectrometer. X-ray photoelectron spectroscopy
(XPS) analysis of the sample was performed on a PHI-5702 electron spectrometer using an Al K␣ line excitation source with the
reference of C 1s at 285.0 eV. The CA and SA for liquids with
surface tension  ranging from water ( = 72.8 mN/m) to hexadecane ( = 27.5 mN/m) was measured with approximately 5 ␮L

The surface morphology of the as-prepared coating is clearly
shown by the FESEM images in Fig. 1. Fig. 1a illustrates the rough
coating surface with the packed flowerlike clusters. The magnified
image in Fig. 1b shows a typical single flowerlike microcluster that
is composed of a number of distorted nanosheets. The thickness of
the nanosheet is about 50–150 nm. In addition, the edges of these
nanosheets are irregular, and a large fraction of air can be trapped
in the troughs between interconnected nanosheets. Therefore, this
morphology is thought to give rise to the super-repellent behavior.

Fig. 2. Schematic illustration of the structure of Cu(CH3 (CH2 )14 COO)2 .

Fig. 3. FTIR spectra of palmitic acid (a) and Cu(CH3 (CH2 )14 COO)2 (b).

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J. Yang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 367 (2010) 60–64

Fig. 6. Snapshots of a water droplet of 10 ␮L vertically hitting the slightly tilted
Cu(CH3 (CH2 )14 COO)2 coating.

Fig. 4. XPS spectra (a) and the C 1s peaks (b) of Cu(CH3 (CH2 )14 COO)2 coatings.

Fig. 1c is a FESEM image of pure palmitic acid crystal structures.
As seen in Fig. 1c, the morphology of palmitic acid is similar to
that of the product as-prepared, indicating that the structure of
Cu(CH3 (CH2 )14 COO)2 is related to the original structure of palmitic
acid. According to previous report [17], the possible structure of
Cu(CH3 (CH2 )14 COO)2 is presented in Fig. 2. The model is comprised
of parallel slabs of connected Cu and O atoms and there is stacking of
layers between the distal atoms of the alkanoate substituents. Each
layer of Cu(CH3 (CH2 )14 COO)2 is separated from the neighboring
layer by twice the length of the alkyl chain. The intralayer structure provides the packing characteristics of the organic as well as
the inorganic slabs [13]. In particular, it leads to films with preferential orientation, which is favorable for the subsequent growth of
nanosheets. This result also indicates that the Cu(CH3 (CH2 )14 COO)2
particles stack together to form the flowerlike structures.

The chemical composition of the as-prepared surface is studied
by FTIR technique and XPS. As shown in Fig. 3, FTIR spectra indicate that the free COO band from palmitic acid at 1702 cm−1 is no
longer present. A new band appears at 1587 cm−1 , corresponding to
coordinated COO moieties. But the bands standing for the methylene and methyl group have unobvious change. The XPS spectrum
in Fig. 4a demonstrates that the elements of the prepared coating
are C, O, and Cu. In Fig. 4b the C 1s signal can be deconvoluted into
two peaks at 288.8 and 285.0 eV. The 288.8 eV signal is assigned
to the carbon of coordinated COO group, and the 285.0 eV signal
is assigned to the carbon of the alkyl group. Importantly, the atom
ratio between copper and carbon (coordinated COO) is about 1:2
according to the calculation from the areas of their peaks. Thus, we
conclude that the packed flowerlike nanostructure of this coating
is composed of Cu(CH3 (CH2 )14 COO)2 .
The CA for the sample was measured with water, ethylene glycol, and benzyl alcohol. The surface tension of the above mentioned
liquids are 72.8, 48.4, and 38.0 mN/m, respectively. Fig. 5 shows the
photographs of these liquid droplets on the as-prepared sample,
and the insets are the CA images. As shown in Fig. 5, the droplets
of water, ethylene glycol, and benzyl alcohol exhibit the spherical shapes on the coating surfaces with the CAs of 160◦ , 156◦ ,
and 151◦ , indicating that the sprayed Cu(CH3 (CH2 )14 COO)2 coatings are superhydrophobic. Other metal alkanoates have also been
synthesized such as Zn(CH3 (CH2 )14 COO)2 or Cd(CH3 (CH2 )14 COO)2 .
All of these metal alkanoate coatings on various substrates exhibit
good superhydrophobicity. However, when we used hexadecane
( = 27.5 mN/m) to measure the CA, hexadecane droplet can spread
out thoroughly on the surface with the CA of 0◦ , that is, the coating
surface for hexadecane is superoleophilic. This superoleophilicity
is possible due to the similar chemical composition between hexadecane and metal alkanoate.

Fig. 5. Photographs of liquid droplets on the as-prepared sample: (a) water, (b) ethylene glycol, and (c) benzyl alcohol. The inset is the CA images of these liquid, respectively.

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63

Fig. 7. Photographs of the Cu(CH3 (CH2 )14 COO)2 coating partly destroyed by scratching (a) and water droplets on the reparative coating by spraying again (b).

The dynamic behavior of liquid droplets on superhydrophobic
surfaces is of great importance in practical applications. Therefore,
we investigated the SA and the impact effort of a water droplet on
the spray-coated surface. A water droplet of 5 ␮L can easily roll off
with the SA of about 5◦ on the Cu(CH3 (CH2 )14 COO)2 coating. Moreover, when a water droplet of 10 ␮L vertically hit the slightly tilted
coating, it can bounce away from the surface. Along the continuous
bounce on the surface, the water droplet moved from left to right
rapidly. This bouncing and rolling process is clearly shown in Fig. 6.
We also measured the SAs of ethylene glycol and benzyl alcohol.
Ethylene glycol can roll off with a tilting of the surface of about
10◦ ; however, benzyl alcohol droplet cannot move at any tilt angle,
even when the coating is turned upside down. Theoretically, two
contact models of liquid droplets on the rough surfaces were usually used to describe the wetting behavior of a surface, i.e., Wenzel’s
and Cassie’s models, respectively [18,19]. Both contact states can
bring about the superhydrophobic behavior. However, in Wenzel’s
model, the liquid droplets pin the surface in a wet-contact mode
and cannot slide on the surface. Conversely, in Cassie’s model, the
liquid droplets adopt a non-wet-contact mode on solid surface and
roll off easily owing to large trapped air between the liquid droplet
and the surface [20,21]. For the benzyl alcohol, the contact model is
apparently in the Wenzel’s model, liquid droplet can penetrate into
the cavities to direct contact with the surface, resulting in the suspended behavior. For the water and ethylene glycol, a considerable
amount of air was trapped on the surface, so that the liquid droplets
can roll off with the low SA, which indicates that the contact model
is the Cassie’s model.
There are some reports on making robust superhydrophobic
surfaces, which generally shows the high stability or strong adhesion to substrates [22,23]. However, regarding the real application,
their superhydrophobic properties are also fragile to mechanical scratch on the surfaces for their fine structures. Mechanical
durability is still the biggest problem to limit the applications of
superhydrophobic surface. In our method, the prepared coating
can also be easily scratched because there is no strong chemical
bonding to substrates. However, this problem is resolved by simple spraying the alkylcarboxylate dispersion again on the destroyed
coating, and the cheap coating materials and simple fabrication
approach allow the local repair at anytime and almost anywhere.
As shown in Fig. 7a, after the surface of the superhydrophobic
coating is scratched with a knife, the water CA decreases sharply
to about 100◦ . Water droplets cannot roll off the coating, even
when the surface is positioned vertically. To repair the destroyed
superhydrophobic coating, we only need to spray the alkylcarboxylate dispersion again on the substrate. The reparative coating can
restore its good superhydrophobicity with the CA of 160◦ (Fig. 7b),
and water droplets can roll off the surface at a tilt angle of about 5◦ .
Importantly, the time of regeneration is unlimited. The easy regen-

eration is expected to satisfy the future demands in the practical
application of superhydrophobicity.
4. Summary
We have demonstrated oil and water repellency of metal alkylcarboxylate coatings fabricated by spraying their dispersion on
various substrates. The sprayed coatings with the flowerlike hierarchical structures exhibit stable superhydrophobicity. The CA for
water and ethylene glycol is 160◦ and 156◦ with the SA of about 5◦
and 10◦ . Even benzyl alcohol has a large CA of about 151◦ . This fabrication technique could perhaps show the most promise for the
widest array of applications as it can be applied to large surface
areas, it do not typically require expensive materials and complicated application methods, and it can be easily used to repair the
damaged superhydrophobic coatings.
Acknowledgments
The authors acknowledge the financial support of the National
973 Project of China (Grant No. 2007CB607601) and the National
Science Foundation of China (Grant No. 50835009, Grant No.
50773089 and Grant No. 50721062).
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