A simple fabrication method for mechanically robust

superhydrophobic surface by hierarchical aluminum hydroxide

structures
Handong Cho
a
, Dongseob Kim
b
, Changwoo Lee
a
, Woonbong Hwang
a, b,
*
a
Department of Mechanical Engineering, Pohang University of Science and Technology, San 31, Pohang, Kyungbuk 790-784, Republic of Korea
b
Graduate School of Engineering Masterships, Pohang University of Science and Technology, San 31, Pohang, Kyungbuk 790-784, Republic of Korea
a r t i c l e i n f o
Article history:
Received 9 August 2012
Received in revised form
27 November 2012
Accepted 28 November 2012
Available online 17 December 2012
Keywords:
Superhydrophobicity
Aluminum hydroxide
Sandblasting
Hierarchical structure
a b s t r a c t
Superhydrophobic surfaces with uniformly superhydrophobic surface where nano-scale structures were
fabricated by alkali surface modication method and self-assembled monolayer coating. To enhance
mechanical durability of the superhydrophobicity, we propose the fabrication process for dual-scale
hierarchical structures combining both microstructure via sandblasting techniques and the nano-
structured aluminum hydroxide layer. The superhydrophobic surfaces fabricated by both methods
exhibited a high water contact angle and very low contact angle hysteresis. By forming the hierarchical
structure, the mechanical durability of superhydrophobic aluminumhydroxide surface was improved. The
resulting hierarchical structures are suitable for diverse applications of aluminum in various industrial
areas, including self-cleaning, anti-frosting, and microuidic devices for rigorous environments.
2012 Elsevier B.V. All rights reserved.
1. Introduction
Surfaces with a very high water contact angle larger than 150

and a low contact angle hysteresis of less than 10

are generally
known as superhydrophobic surfaces. These surfaces have attracted
much interest in industry, because many studies have shown that
these surfaces have properties such as self-cleaning [1e3], anti-
corrosion [4e6], anti-frosting [7e9], uid drag reduction [10e12],
non-sticky to oil andinks [13,14]. Asuperhydrophobic surface canbe
attained by forming a hierarchical roughness structure, that is,
a nanometer-sized structure superimposed over a micrometer-
structure, similar to those of the lotus leaf. Moreover, many recent
studies have reported that a hierarchical roughness ensures super-
hydrophobicity even after the surfaces are worn away [15e17].
Aluminum is widely used in various industrial elds as a basic
material for numerous mechanical components. For this reason,
making an aluminum surface superhydrophobic has many appli-
cation possibilities. However, only a few methods for fabricating
superhydrophobic aluminum surfaces have been reported. Qian
et al. reported a dislocation-selective chemical etching technique
for superhydrophobic aluminum surfaces with contact angles
larger than 150

[18]. Guo et al. fabricated a superhydrophobic

surface using chemical etching by immersing aluminum in sodium
hydroxide (NaOH) and then decorating with peruorononane [19].
On the other hand, anodization combined with a low-temperature
plasma treatment was used to form hierarchical structures on
aluminum surfaces [20]. Wu et al. realized a superhydrophobic
aluminum surface by forming alumina nanowire forests via high
eld anodization [21]. Kim et al. [22] and Jeong et al. [23] reported
a self-aggregation phenomenon for alumina nanowires by the
anodization of aluminum. However, chemical etching induces
serious problems such as damage to the aluminum substrate and
a non-uniformly etched site. The anodization method consumes
a large amount of electricity and causes defects in the alumina layer
from a failure to control the current.
Recently, Seo et al. reported a fabrication method for an
aluminum hydroxide layer that uses alkali surface modication
[24,25]. The fabricated aluminum hydroxide layer is composed of
gibbsite (g-Al(OH)
3
) and has a ake-like nanostructure. By means
of this method, uniformly distributed nanostructures on an
aluminum surface can be obtained quickly and simply. They
demonstrated that the wettability of the fabricated surface is
superhydrophilic.
Herein, we report uniformly superhydrophobic surface where
nano-scale structures were fabricated by alkali surface modication
* Corresponding author. Department of Mechanical Engineering, Pohang
University of Science and Technology, San 31, Pohang, Kyungbuk 790-784, Republic
of Korea. Tel.: 82 54 279 2174; fax: 82 54 279 5899.
E-mail address: whwang@postech.ac.kr (W. Hwang).
Contents lists available at SciVerse ScienceDirect
Current Applied Physics
j ournal homepage: www. el sevi er. com/ l ocat e/ cap
1567-1739/$ e see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cap.2012.11.021
Current Applied Physics 13 (2013) 762e767
method and self-assembled monolayer coating. And, we propose
the fabrication process for dual-scale hierarchical structures
combining both microstructure via sandblasting techniques and
the nanostructured aluminum hydroxide layer to enhance
mechanical durability of the superhydrophobicity.
This process has the following key advantages: industry
compatibility, robustness, and a uniformsuperhydrophobic surface.
We particularly investigated the wetting characteristics by
measuring the water contact angle and the improvement in the
mechanical robustness by an abrasion test.
2. Experimental details
The fabrication process for superhydrophobic nanostructured
and hierarchical aluminum hydroxide surfaces are shown sche-
matically in Fig. 1. Industrial grade aluminum sheets (99.5%,
50 mm 40 mm 1 mm) were used in all of the experiments. The
formation of nanostructured aluminum hydroxide was carried out
in a 0.05 M NaOH solution at 80

C for 5 min. After this, the spec-
imen was immediately immersed in 100

C deionized water for the
subsequent stabilization process. A microroughness structure was
prepared by sandblasting the aluminum sheet with sand particles.
The size of the sand particle was 500 mesh, and the particles were
ejected from a nozzle using compressed air at a pressure of
6 kgf cm
2
. After sandblasting, the aluminum sheet was cleaned
with deionized water. The hierarchical surface was fabricated by
forming aluminum hydroxide layer on the microroughened
aluminum specimen. Finally, superhydrophobic nanostructured
and hierarchical surfaces were obtained after self-assembled
monolayer coating with heptadecauoro-1,1,2,2-tetrahydrodecyl-
trichlorosilane (HDFS, Gelest) was applied on the specimen. The
specimen was dipped in a mixture of n-hexane and HDFS (volu-
metric ratio 1000:1) for 10 min. They were then washed with
distilled water and dried in the oven (105

C) for 1 h.
The static contact angle, contact angle hysteresis, and sliding
angle on the fabricated surface were measured using a drop shape
analysis system (DSA-100, Kruss). The contact angle hysteresis was
obtained by measuring the advancing contact angle and receding
contact angle at the maximum sliding angle by which the drop
would move by gravity. A 5-ml droplet of distilled water was used
for this purpose. The contact angle results were averaged over at
least ten measurements on different areas of each specimen at
roomtemperature. Scanning electron microscopy (SEM; JSM-7401F
FE-SEM, JEOL) images were obtained to investigate the surface
morphology.
In order to evaluate the robustness of the superhydrophobic
surface, abrasion test illustrated in Fig. 2 was performed. The
fabricated superhydrophobic surface was tested facing an abrasive
lm (1 micron grade Imperial lapping lm, 3 M). Applying
weights to the specimen, the surface was moved in one direction
with 5 mm/s at a stroke of 15 cm. The preload was applied on each
specimen and increased up to 1000 g. The static contact angles and
hysteresis changes of the superhydrophobic surface were measured
after abrasion test.
3. Results and discussion
The surface morphologies of several specimens were examined
using SEM, as shown in Fig. 3. Fig. 3(a) shows the surface of
industrial grade normal aluminum. Fig. 3(b) shows that the
aluminum surface had microscale unevenness and its morphol-
ogies changed signicantly after sandblasting. Fig. 3(c) shows that
the surface of the aluminum was covered with a ake-like
aluminum hydroxide layer. The thickness of this aluminum
hydroxide layer was around 500 nm with a nanoscale surface
morphology. Fig. 3(d) reveals that the hierarchical structure
included the microscale structure formed by sandblasting and
nanoscale aluminum hydroxide structures over the micro-
roughened structure.
The wettabilities of several specimens were characterized in
detail using contact angle measurements, as shown in Fig. 4(a). The
normal aluminum specimen exhibited slight hydrophilicity. For
a droplet in contact with a rough surface, the contact angle was
explained by the Wenzel state [26]. According to the Wenzel state,
the contact angle of the aluminum surface became more hydro-
philic because of the increase in its roughness after sandblasting.
Fig. 1. Steps in the fabrication of superhydrophobic nanostructured and hierarchical aluminum hydroxide surfaces.
Fig. 2. Schematic of abrasion test. (Inset: SEM image of abrasive lm). The abrasion
tests were conducted by changing applied weights from 10 g to 1000 g.
H. Cho et al. / Current Applied Physics 13 (2013) 762e767 763
Under this situation, the hydrophilic nature of the aluminum
hydroxide containing the hydroxyl group (eOH) [25] and the
increased roughness caused by the ake-like morphology played
important roles in the wettability. Therefore, both the aluminum
hydroxide nanostructure and the hierarchical structure showed the
superhydrophilic property.
After the SAM coating with HDFS, the wettabilities of the
specimens changed to hydrophobic. In the case of a rough hydro-
phobic surface, a water droplet cannot penetrate into a structural
groove because of the air pocket present between the water and the
surface, which is described as the Cassie state [27]. With the
exception of normal aluminum, the specimens had high static
Fig. 3. SEM images of (a) industrial grade normal aluminum, (b) sandblasted aluminum, (c) aluminum hydroxide layer on aluminum, and (d) aluminum hydroxide layer on
sandblasted aluminum. The thickness of the aluminum hydroxide layer was about 500 nm.
H. Cho et al. / Current Applied Physics 13 (2013) 762e767 764
contact angles, as shown in Fig. 4(b). Clearly, both the aluminum
hydroxide nanostructure and the hierarchical structure showed
superhydrophobic properties, with a high static contact angle of
160

and low contact angle hysteresis of 2

at a low sliding angle.

Thus, a superhydrophobic surface was successfully fabricated with
aluminum hydroxide and HDFS coating. However, the sandblasted
aluminum had a static contact angle of around 150

, while a water
drop on the surface was attached even at a sliding angle of 90

. This
was because increased surface roughness by sandblasting rein-
forced the hydrophobic characteristics but also amplied the
amount of pinning defect. These led to high contact angle and
sticky behavior at the same time [28]. Whereas the contact area was
reduced in the nanostructured surfaces and minimized in the
hierarchical-structured surfaces due to the presence of the air
pockets inside the grooves [29], so they had high contact angle and
slippery behavior.
According to Xiu et al., the superhydrophobicity of a hierarchical
structure is more robust than that of a single nanoscale structure
[16]. In this study, the abrasion resistance of the super-
hydrophobicities of the aluminum hydroxide nanostructure and
aluminum hydroxide hierarchical structure was evaluated, and the
robustness values of these superhydrophobic structures were
compared. Fig. 5(a) shows that the aluminum hydroxide nano-
structures were crushed and changed into a smooth surface after
abrasion. In the case of the aluminum hydroxide hierarchical
structure, however, only the hydroxide layer on the ridge was worn
away after the abrasion test, as shown in Fig. 5(b). The nano-
structures on the grooves remained unchanged because the peaks
of the microstructures helped the structures retain their shape
during the abrasion test.
Fig. 6(a) shows the effect of abrasion on the wetting proper-
ties of the superhydrophobic aluminum hydroxide structures.
Fig. 4. (a) Water contact angles of normal aluminum (S1), sandblasted aluminum (S2), aluminum hydroxide nanostructure (S3), and aluminum hydroxide hierarchical structure
(S4). (b) Water contact angles and contact angle hysteresis of these four specimens after application of HDFS coating.
Fig. 5. (a) SEM images of nanostructures and (b) hierarchical structures after abrasion tests with a weight of 100 g.
H. Cho et al. / Current Applied Physics 13 (2013) 762e767 765
After the abrasion test, the static contact angle of the hierarchical
structure changed slightly, from 159

to 151

. The contact angle of

the nanoroughness structure declined with an increase in the
applied load of the abrasion test, but the angle was also high
above 140

. However, with respect to the contact angle hysteresis

and the sliding angle, the difference between these values of the
nanostructure and the hierarchical structure increased after
abrasion, as shown in Fig. 6(b). The contact angle hysteresis and
sliding angle of the hierarchical structure were 8.8

and 9.6

respectively. These values accorded with the criteria for the

superhydrophobicity, and therefore the superhydrophobicity
characteristic was preserved until a weight of 100 g was applied.
The nanostructure, on the contrary, lost its superhydrophobicity
after the application of a weight heavier than 10 g. The contact
angle hysteresis and sliding angle of the nanostructure increased
to more than 10

, a water drop nally adhered to the surface of

the nanostructure at a sliding angle of 90

when more than 300 g

was applied.
In the case of the hierarchical structure, the microstructures
protected the nanostructures, which formed air pockets inside the
grooves under a water droplet. These reduced the contact area and
adhesiveness between the droplet and the surface, as shown in
Fig. 6(c). Therefore, low contact angle hysteresis and small sliding
angle were maintained to some extent external load, and the Cassie
state was stabilized by the dual scale structures [15]. On the other
hand, in the case of the nanostructure, the increase in the contact
angle hysteresis originated from the destruction of the nano-
structure that increased the contact area, as shown in Fig. 6(d).
Meanwhile, the contact angle hysteresis values of both structures
increased with an increase in the weights used for the abrasion
test. This was because the actual contact area between the
superhydrophobic surface and the abrasive lm increased when
heavier weights were applied, and surfaces of the structures
were subjected to a large amount of wear. Also, some regions
became more hydrophilic due to the loss of hydrophobic coating
and the exposure of hydrophilic aluminum hydroxide layer and
aluminum surface. Thus, mechanical durability of superhydro-
phobic aluminumhydroxide surface was improved by forming such
a hierarchical structure.
The proposed method for fabricating a hierarchical super-
hydrophobic aluminumhydroxide structure could be easily applied
to an aluminum structure with a complex geometry or large size.
Fig. 7 shows that aluminum letters with a superhydrophobic hier-
archical surface structure were immersed in colored water. The
micro- and nano-structures maintained a microscopic air layer on
the surface even when submerged in water. This super-
hydrophobicity amplied the effect of surface tension, and a wall of
water formed around the specimens.
Fig. 6. Changes in (a) contact angle and (b) contact angle hysteresis after abrasion test. (c) As to the hierarchical structure, the contact area between droplet and surface increased
slightly. But air pockets in the groove were maintained. (d) After abrasion, the contact area of nanostructure increased sharply and air layers disappeared.
Fig. 7. Superhydrophobic aluminum letters fabricated using sandblasting and aluminum hydroxide were immersed in colored water. The proposed method can be applied to
aluminum structures of any shape and size.
H. Cho et al. / Current Applied Physics 13 (2013) 762e767 766
4. Conclusions
In conclusion, we successfully fabricated a superhydrophobic
surface with uniform superhydrophobicity by nanostructured
aluminumhydroxide andSAMcoating. Andwe developedthe simple
andcost-effective methodtofabricate superhydrophobic hierarchical
surface composed of microstructures by sandblasting and nano-
structured aluminumhydroxide lm. These fabricated surfaces show
very low contact angle hysteresis less than 10

. The mechanical
durability of the fabricated surfaces has been evaluated using abra-
sive test and the result shows that the superhydrophobicity of
aluminum hydroxide structure becomes more robust by forming
hierarchical roughened structures. The proposed fabrication process
has the advantages of simplicity, industry compatibility, and easy
scale-up. We believe that proposed method would be favorable for
aluminum devices having self-cleaning, anti-frosting and anti-
corrosion properties in rigorous environments.
Acknowledgments
This researchwas supportedby theMinistryof Education, Science
Technology(MEST) andNational ResearchFoundationof Korea (NRF)
through the Human Resource Training Project for Regional Innova-
tion and Do-yak research program (No. 2011-0018645).
References
[1] B. Bhushan, Y.C. Jung, K. Koch, Langmuir 25 (2009) 3240e3248.
[2] T.-I. Kim, D. Tahk, H.H. Lee, Langmuir 25 (2009) 6576e6579.
[3] K. Lee, S. Lyu, S. Lee, Y.S. Kim, W. Hwang, Appl. Surf. Sci. 256 (2010)
6729e6735.
[4] B. Grignard, A. Vaillant, J. de Coninck, M. Piens, A.M. Jonas, C. Detrembleur,
C. Jerome, Langmuir 27 (2010) 335e342.
[5] T. Ishizaki, Y. Masuda, M. Sakamoto, Langmuir 27 (2011) 4780e4788.
[6] K. Liu, M. Zhang, J. Zhai, J. Wang, L. Jiang, Appl. Phys. Lett. 92 (2008) 183103.
[7] A.J. Meuler, G.H. McKinley, R.E. Cohen, ACS Nano 4 (2010) 7048e7052.
[8] K.K. Varanasi, T. Deng, J.D. Smith, M. Hsu, N. Bhate, Appl. Phys. Lett. 97 (2010)
234102e234103.
[9] M.A. Sarshar, C. Swarctz, S. Hunter, J. Simpson, C.H. Choi, Colloid Polym. Sci.
(2012).
[10] S. Lee, J.H. Kang, S.J. Lee, W. Hwang, Lab Chip 9 (2009) 2234e2237.
[11] C.-H. Choi, C.J. Kim, Phys. Rev. Lett. 96 (2006) 066001.
[12] C. Lee, C.H. Choi, C.J. Kim, Phys. Rev. Lett. 101 (2008) 064501.
[13] K. Ellinas, A. Tserepi, E. Gogolides, Langmuir 27 (2011) 3960e3969.
[14] S.M. Kang, S.M. Kim, H.N. Kim, M.K. Kwak, D.H. Tahk, K.Y. Suh, Soft Matter 8
(2012) 8663e8668.
[15] T. Verho, C. Bower, P. Andrew, S. Franssila, O. Ikkala, R.H.A. Ras, Adv. Mater. 23
(2011) 673e678.
[16] Y. Xiu, Y. Liu, D.W. Hess, C.P. Wong, Nanotechnology 21 (2010) 155705.
[17] W.G. Bae, K.Y. Song, Y. Rahmawan, C.N. Chu, D. Kim, D.K. Chung, K.Y. Suh, ACS
Appl. Mater. Interfaces 4 (2012) 3685e3691.
[18] B. Qian, Z. Shen, Langmuir 21 (2005) 9007e9009.
[19] Z. Guo, F. Zhou, J. Hao, W. Liu, J. Am. Chem. Soc. 127 (2005) 15670e15671.
[20] H. Wang, D. Dai, X. Wu, Appl. Surf. Sci. 254 (2008) 5599e5601.
[21] W. Wu, X. Wang, D. Wang, M. Chen, F. Zhou, W. Liu, Q. Xue, Chem. Commun.
(2009) 1043e1045.
[22] D.-H. Kim, Y. Kim, B.M. Kim, J.S. Ko, C.-R. Cho, J.-M. Kim, J. Micromech.
Microeng. 21 (2011) 045003.
[23] C. Jeong, C.-H. Choi, ACS Appl. Mater. Interfaces 4 (2012) 842e848.
[24] Y.I. Seo, Y.J. Lee, D.-G. Kim, K.H. Lee, Y.D. Kim, Appl. Surf. Sci. 256 (2010)
4434e4437.
[25] Y.I. Seo, D.-G. Kim, Y.D. Kim, B.J. Lee, K.H. Lee, Scr. Mater. 59 (2008) 889e892.
[26] D. Kim, S. Lee, W. Hwang, Curr. Appl. Phys. 12 (2012) 219e224.
[27] B. Bhushan, Y.C. Jung, K. Koch, Philos. Trans. R. Soc. A 367 (2009) 1631e1672.
[28] K. Koch, B. Bhushan, Y.C. Jung, W. Barthlott, Soft Matter 5 (2009) 1386e1393.
[29] D. Qur, A. Lafuma, J. Bico, Nanotechnology 14 (2003) 1109e1112.
H. Cho et al. / Current Applied Physics 13 (2013) 762e767 767