Fabrication of nonaging superhydrophobic surfaces by packing flowerlike hematite

particles
Anmin Cao, Liangliang Cao, and Di Gao

Citation: Applied Physics Letters 91, 034102 (2007); doi: 10.1063/1.2766697

View online: http://dx.doi.org/10.1063/1.2766697
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 APPLIED PHYSICS LETTERS 91, 034102 共2007兲

Fabrication of nonaging superhydrophobic surfaces by packing flowerlike

hematite particles
Anmin Cao, Liangliang Cao, and Di Gaoa兲
Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, Pennsylvania
15261
共Received 4 June 2007; accepted 5 July 2007; published online 19 July 2007兲
The authors demonstrate the fabrication of nonaging superhydrophobic surfaces by packing
flowerlike micrometer-sized hematite 共␣-Fe2O3兲 particles. Although hematite is intrinsically
hydrophilic, the nanometer-sized protrusions on the particles form textures with overhanging
structures that prevent water from entering into the textures and induce a macroscopic
superhydrophobic phenomenon. These superhydrophobic surfaces do not age even in extremely
oxidative environments—they retain the superhydrophobicity after being stored in ambient
laboratory air for 4 months, heated to 800 ° C in air for 10 h, and exposed to ultraviolet ozone for
10 h. © 2007 American Institute of Physics. 关DOI: 10.1063/1.2766697兴
Superhydrophobic surfaces are often found on plant not age even in extremely oxidative environments—they re-
leaves.1 Water on these surfaces beads up with a contact tain the superhydrophobicity after being stored in ambient
angle of greater than 150° and drips off rapidly when the laboratory air for 4 months, heated to 800 ° C in air for 10 h,
surfaces are slightly inclined, while taking away powderlike and exposed to ultraviolet ozone for 10 h.
contaminations. This phenomenon renders materials with The flowerlike ␣-Fe2O3 particles were synthesized by
such surfaces water repellent 共or nonwetting兲 and self- using an ethylene glycol 共EG兲-mediated reaction. The syn-
cleaning. As a result, there have been extensive research ef- thesis process was adopted from Zhong et al.12 with the fol-
forts to understand the fundamental mechanisms underlying lowing modifications: 共i兲 the surfactant was removed from
the behavior of liquid on such surfaces2–5 as well as to fab- the previously used reaction system and 共ii兲 iron nitrate
ricate artificial superhydrophobic surfaces for applications in 关Fe共NO3兲3兴 was used to replace the previously used iron
self-cleaning products.6–9 Recently, superhydrophobic sur- chloride. In a typical synthesis process, 0.7 g Fe共NO3兲3
faces have also been found to exhibit reduced viscous drag 共Fisher Scientific兲 and 0.7 g urea 关CO共NH2兲2, Sigmar-
due to slip associated with a layer of air trapped at the water- Aldrich兴 were added into 60 ml ethylene glycol 共C2H6O2兲
solid interface.10 Therefore, much interest has been attracted 共J.T. Baker兲 to form a cloudy mixture. The mixture was then
to use superhydrophobic surfaces on hulls of ships and pipes stirred with a magnetic stirrer bar and heated to 170 ° C. The
for hydrodynamic drag reduction.10,11 cloudy mixture turned clear in 10 min and became opaque
Artificial superhydrophobic surfaces have been made by again after 20 min, indicating the formation of iron oxide
either creating a rough topography on a hydrophobic surface precursor. The products were collected by centrifugation-
or modifying a rough surface by chemical compositions with redispersion cycles with alcohol. The collected products
a low surface free energy.6–9 Typically, a material with a were then calcined in air at 450 ° C for 3 h in a tube furnace
water contact angle of greater than 90° on its flat surface is 共Lindberg兲 to obtain ␣-Fe2O3 particles.
needed in order to enhance its hydrophobicity by increasing The ␣-Fe2O3 particles were characterized by x-ray dif-
the surface roughness. Unfortunately, many materials do not fractometry 共XRD兲 共Rigaku Dmax兲, transmission electron
possess this property without special surface treatments. microscopy 共TEM兲 共Philips TECNAI-20兲, and scanning elec-
Therefore, it has been a common approach to treat materials tron microscopy 共SEM兲 共Hitachi S-4300F兲. The SEM and
by wet or dry 共plasma兲 chemistries7–9 for fabrication of su- TEM images of the synthesized particles were shown in
perhydrophobic surfaces. However, it is known that the su- Figs. 1共a兲 and 1共b兲, respectively. These particles are spheres
perhydrophobic properties of these chemically treated sur- of 1 – 2 ␮m in diameter. They have a rough surface consist-
faces deteriorate over time, which brings major problems to ing of 40– 60 nm thick distorted plates, which resemble the
the practical application of superhydrophobic surfaces— shape of petals of a flower. Figure 1共c兲 shows a TEM image
aging and decay.6 In addition, chemical treatments of these taken at the edge of a plate on the surface of the particle. It is
materials increase the cost of the products and produce seen that the thin plate is composed of interconnected crys-
chemical waste and pollution. tals of about 5 nm in diameter. Figure 1共d兲 shows the x-ray
A question of significant interest is whether one is able diffraction pattern of the synthesized particles, indicating that
to make intrinsically hydrophilic materials superhydrophobic the particles consist of crystalline Fe2O3 with a rhombohe-
without chemical modifications of their surfaces, because it dral symmetry.
may reduce the manufacturing cost, and more importantly, We fabricated superhydrophobic surfaces by packing
such surfaces may not age. In this letter, we demonstrate the these particles through three approaches: 共i兲 particles were
fabrication of such superhydrophobic surfaces by packing dispersed in ethanol, and the mixture was drop cast onto a
flowerlike particles of hematite 共␣-Fe2O3兲, an intrinsically double-sided tape adhered to a glass slide, followed by bak-
hydrophilic material. These superhydrophobic surfaces do ing in air at 80 ° C for an hour; 共ii兲 a multipurpose glue 共3M兲
was first sprayed on a piece of stainless steel, then the par-
a兲
Electronic mail: gaod@engr.pitt.edu ticles 共dispersed in ethanol兲 were sprayed onto the glue using
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0003-6951/2007/91共3兲/034102/3/$23.00 91, 034102-1 © 2007 American Institute of Physics
155.33.120.209 On: Mon, 24 Nov 2014 01:38:56
 034102-2 Cao, Cao, and Gao
FIG. 1. Flower-like ␣-Fe2O3 particles. 共a兲 An SEM image of a particle,
showing its flowerlike morphology. 共b兲 A TEM image of two ␣-Fe2O3 par-
ticles, showing that they are spheres of 1 – 2 ␮m in diameter with 40– 60 nm
thick distorted plates on the surface. 共c兲 TEM image taken at the edge of a
plate, showing that the thin plate is composed of interconnected crystals of
about 5 nm in diameter. 共d兲 XRD pattern of the synthesized particles, indi-
cating that the particles consist of ␣-Fe2O3 crystals.
an airbrush 共Iwata兲, followed by baking in air at 80 ° C for an
hour; and 共iii兲 the particles were compressed into a tablet
using a pellet die 共Sigma Aldrich兲. Figure 2共a兲 showed a
typical SEM image of the surfaces made by packing the
flowerlike ␣-Fe2O3 particles. It was observed that the par-
ticles retained their flowerlike morphology after they were
packed by any of the above three approaches. The topogra-
phy of these surfaces consisted of structures in multiple
length scales—the roughness caused by the thin plates, or
“petals,” on each particle was superimposed onto a larger
scale roughness formed by packing the particles.
The water contact angle 共WCA兲 was measured using a
VCA-OPTIMA drop shape analysis system 共AST Products,
Inc.兲 with a computer-controlled liquid dispensing system
and a motorized tilting stage. Water droplets with a volume
of 4 ␮l were used to measure the static WCA. The advancing
and receding angles were recorded during expansion and
contraction of the droplets induced by placing a needle in the
water droplets and continuously supplying and withdrawing
water through the needle. The sliding angle was measured by
tilting the stage and recorded when the droplet began to
move in the downhill direction. The experiments were per-
formed under normal laboratory ambient conditions 共20 ° C
and 40% relative humidity兲. The WCA was measured five
times on each sample. Figure 2共b兲 showed a 4 ␮l water drop-
let on the surface with a WCA of 159± 2°, which moved
around rapidly when it was slightly disturbed, and dripped
off the substrate rapidly when the substrate was tilted less
than 2°. Despite the differences in the sample preparation
methods, a static WCA of greater than 150° and a
hysteresis—the difference between the advancing and reced-
ing WCA—of less than 3° were consistently obtained.
␣-Fe2O3 is one of the most stable metal oxides in
nature.13 We therefore anticipate that the fabricated surfaces
consisting of the flowerlike ␣-Fe2O3 particles cannot be fur-
ther oxidized and the superhydrophobicity of the surfaces
can be preserved for a long time in laboratory ambient con-
ditions. Indeed, these surfaces retained their superhydropho-
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bicity after being stored in ambient laboratory air 共20 ° C and
155.33.120.209 On: Mon, 24 Nov 2014 01:38:56
Appl. Phys. Lett. 91, 034102 共2007兲
FIG. 2. 共Color online兲 Superhydrophobic surfaces fabricated by packing the
flowerlike ␣-Fe2O3 particles. 共a兲 A typical SEM image of the surface. The
topography of the surface consists of structures in multiple length scales—
the roughness caused by the thin plates, or “petals,” on each particle is
superimposed onto a larger scale roughness induced by packing the par-
ticles. 共b兲 Optical image of a 4 ␮l water droplet on the surface with a WCA
of 159± 2°. Inset is an optical image of the water droplet during the WCA
measurement. 共c兲 Schematic cross-sectional profile of water in contact with
the flowerlike particles. 共d兲 Schematic cross-sectional profile of water in
contact with a solid indent consisting of overhanging structures.
40% relative humidity兲 for 4 months. We further carried out
aging tests by placing these samples in extremely oxidative
environments—they were heated in a tube furnace 共Lind-
berg兲 to 800 ° C in air for 10 h, and exposed to ultraviolet
ozone 共UVO兲 共Jelight Inc.兲 for 10 h. No significant changes
in the WCAs or hysteresis were observed after these treat-
ments 共Table I兲.
␣-Fe2O3 is an intrinsically hydrophilic material.13 Heat-
ing the samples to 800 ° C in air for 10 h and exposing them
to UVO for 10 h are sufficient to remove the possible or-
ganic residuals left on the surface of the particles after
the synthesis process. Therefore, the observed superhydro-
phobic phenomenon is induced on an intrinsically hydro-
philic material. The principle of inducing a superhydropho-
bic behavior on a hydrophilic material has been proposed by
Herminghaus4 and recently proved by experiments.14 This
principle may be applied here to explain the superhydropho-
bicity observed on these intrinsically hydrophilic flowerlike
particles.
Figure 2共c兲 schematically illustrates a possible cross-
sectional profile of water in contact with the flowerlike par-
ticles. The distorted plates, or petals, of the particles form
overhanging structures on the surface, which prevent water
from penetrating the textures and replacing the air trapped
inside. A more detailed profile for water in contact with a
solid indent consisting of overhanging structures is shown in
Fig. 2共d兲. Two critical parameters in this profile are the angle
共␪overhang兲 formed between the sidewalls of the indent and the
horizontal line, and the intrinsic WCA 共␪flat兲 of the solid
surface, defined as the WCA on a flat surface. When ␪overhang
is less than ␪flat as the case shown in Fig. 2共d兲, the water-air
interface 共or meniscus兲 inside the indent is convex when
viewed from the water side, and the capillary force generated
by the meniscus prevents water from entering into the indent.
Therefore, water is in contact with a composite surface of
solid and air. This state of water in contact with a solid rough
surface is typically referred to as Cassie state in literatures.3
In Cassie state, the apparent WCA 共␪rough兲 is related to the
 034102-3 Cao, Cao, and Gao Appl. Phys. Lett. 91, 034102 共2007兲

TABLE I. Results of WCA measurements on surfaces made by packing ␣-Fe2O3 particles with different morphologies before and after aging treatments.

WCA measured after ageing treatments 共deg兲

WCA measured Stored in ambient Heated in air Exposed to

on fresh sample laboratory air at 800 ° C for UVO for
Hematite particlesa 共deg兲 for 4 months 10 h 10 h

Synthesized flowerlike Static WCA 159± 2 157± 2 158± 2 157± 2

particles Hysteresis ⬃2 ⬃2 ⬃2 ⬃2
Sliding angle ⬍2 ⬍2 ⬍2 ⬍2

Synthesized particles after they

Static WCA 17± 3 16± 3 17± 3 17± 3
were mechanically ground into
irregular shapes Sliding angle ⬎90 ⬎90 ⬎90 ⬎90

Commercial particles of Static WCA 13± 3 12± 3 15± 3 12± 3

2 ␮m in average diameter Sliding angle ⬎90 ⬎90 ⬎90 ⬎90

Commercial particles of 50 nm Static WCA ⬍10 ⬍10 ⬍10 ⬍10

in average diameter Sliding angle ⬎90 ⬎90 ⬎90 ⬎90
a
All the samples are made by compressing particles into a tablet using a pellet die to remove the effect of any possible organic contaminations from the
adhesion layer that is needed when other approaches are used to pack the particles on the substrate.

intrinsic WCA 共␪flat兲 of the solid surface by the Cassie-
Baxter equation,15
cos ␪rough = ␾s cos ␪flat − 共1 − ␾s兲, 共1兲
where ␾s is the area fraction of the solid surface that contacts
water. From this equation, it is apparent that ␪rough is greater
than 90° 共or cos ␪rough ⬍ 0兲 if
1 is preserved. Because a variety of flowerlike structures have
␾s ⬍ . 共2兲
1 + cos ␪flat
If ␪flat for ␣-Fe2O3 is estimated to be 45°,13 ␾s needs to be
less than 0.59 to make ␪rough greater than 90°. This condition
can be easily satisfied by the surfaces shown in Fig. 2共a兲 with
a schematic cross-sectional profile shown in Fig. 2共c兲. In
addition, the indentation produced by the overhanging petals
of the particles bears larger indentations on a larger scale
produced by packing these particles. For surfaces with such
hierarchical structures, ␪rough increases monotonically as the
generation of the indentation hierarchy increases.4 Therefore,
the hierarchical topography of the surfaces consisting of
these flowerlike particles further increases ␪rough to over 150°
and induces the observed superhydrophobic phenomenon.
To prove the important role of the flowerlike morphol-
ogy of the synthesized Fe2O3 particles for inducing the su-
perhydrophobic behavior, we mechanically ground the par-
ticles using an agate mortar to destroy their flowerlike
morphology and repeated the experiment. We found that sur-
faces made by packing these ground particles were hydro-
philic with static WCAs of less than 20° and sliding angles
of greater than 90°, which was in an obvious contrast to the
results obtained from these particles before they were
ground. We also made surfaces by packing commercial
Fe2O3 particles in two different sizes 共2 ␮m and 50 nm in
diameter, respectively, purchased from Sigma Aldrich兲 that
did not have the flowerlike morphology, and found that the
samples made using these particles were also hydrophilic.
The results of the WCA measurements are summarized in
Table I.
It is evident that the flowerlike morphology of the syn-
thesized Fe2O3 particles—micrometer-sized spheres with
This article is copyrighted as indicated in the article. Reuse of AIP content is subject
nanometer-sized protrusions—is essential for making the
155.33.120.209 On: Mon, 24 Nov 2014 01:38:56
surfaces consisting of these particles superhydrophobic. Such
superhydrophobicity is induced by the overhanging struc-
tures present on the surface and does not require the material
to be intrinsically hydrophobic. After the aging tests, because
the ␣-Fe2O3 particles retain their flowerlike morphology 共as
confirmed by SEM and TEM characterizations兲, the superhy-
drophobicity of the surfaces made by packing these particles
been synthesized and reported in the literatures,16–18 we an-
ticipate that the demonstrated approach of packing flowerlike
structures could also be applied to many other materials for
fabrication of nonaging superhydrophobic surfaces. Such
surfaces may provide a solution to the aging and decay prob-
lems that currently hinder the practical applications of artifi-
cial superhydrophobic surfaces.
This work was supported by the National Science Foun-
dation and the University of Pittsburgh Mascaro Sustainabil-
ity Initiative.
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