materials

Article
A Superhydrophilic Aluminum Surface with Fast
Water Evaporation Based on Anodic Alumina Bundle
Structures via Anodizing in Pyrophosphoric Acid
Daiki Nakajima 1 , Tatsuya Kikuchi 1, * , Taiki Yoshioka 1 , Hisayoshi Matsushima 1 ,
Mikito Ueda 1 , Ryosuke O. Suzuki 1 and Shungo Natsui 2
1 Faculty of Engineering, Hokkaido University, N13-W8, Kita-ku, Sapporo, Hokkaido 060-8628, Japan;
d.nakajima@eng.hokudai.ac.jp (D.N.); tysok0520@gmail.com (T.Y.); matsushima@eng.hokudai.ac.jp (H.M.);
mikito@eng.hokudai.ac.jp (M.U.); rsuzuki@eng.hokudai.ac.jp (R.O.S.)
2 Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Katahira 2-1-1, Aoba-ku,
Sendai, Miyagi 980-8577, Japan; shungo.natsui.b7@tohoku.ac.jp
* Correspondence: kiku@eng.hokudai.ac.jp




Received: 25 September 2019; Accepted: 23 October 2019; Published: 25 October 2019


Abstract: A superhydrophilic aluminum surface with fast water evaporation based on nanostructured
aluminum oxide was fabricated via anodizing in pyrophosphoric acid. Anodizing aluminum in
pyrophosphoric acid caused the successive formation of a barrier oxide film, a porous oxide film,
pyramidal bundle structures with alumina nanofibers, and completely bent nanofibers. During the
water contact angle measurements at 1 s after the water droplet was placed on the anodized surface,
the contact angle rapidly decreased to less than 10◦ , and superhydrophilic behavior with the lowest
contact angle measuring 2.0◦ was exhibited on the surface covered with the pyramidal bundle
structures. As the measurement time of the contact angle decreased to 200–33 ms after the water
placement, although the contact angle slightly increased in the initial stage due to the formation
of porous alumina, at 33 ms after the water placement, the contact angle was 9.8◦ , indicating that
superhydrophilicity with fast water evaporation was successfully obtained on the surface covered
with the pyramidal bundle structures. We found that the shape of the pyramidal bundle structures was
maintained in water without separation by in situ high-speed atomic force microscopy measurements.

Keywords: aluminum; anodizing; pyrophosphoric acid; superhydrophilicity; alumina nanofiber

1. Introduction
Aluminum possesses many attractive mechanical and physical properties, such as high
strength-to-weight ratio, heat conductivity, electrical conductivity, and reflectivity; thus, aluminum
alloys have been used for various industrial applications. Recently, wettability control on aluminum
surfaces has been an important strategy for corrosion protection, heat exchange devices, and anti-icing
surfaces [1–13]. For example, a superhydrophilic aluminum surface with a water contact angle
(θWCA ) measuring less than 10◦ exhibits rapid spreading of a water droplet, and such aluminum
substrates have potential as high-efficiency plate-fin heat exchangers and antifouling materials [14,15].
Conversely, superhydrophobic aluminum surfaces measuring more than θWCA = 150◦ with a low
contact angle hysteresis exhibit excellent water-sliding behavior and have potential for self-cleaning
materials and highly corrosion-resistant surfaces. Therefore, many surface finishing processes including
painting [14], plasma treatment [16,17], colloidal coating [18], and carbon nanoparticle deposition [19]
have been widely investigated for the fabrication of superhydrophilic and superhydrophobic
aluminum surfaces.

Materials 2019, 12, 3497; doi:10.3390/ma12213497 www.mdpi.com/journal/materials

Materials 2019, 12, 3497 2 of 12

Electrochemical anodizing is one of the most important surface finishing processes for aluminum and
its alloys and is widely employed for dielectric film coating [20–22], coloring [23–25], hardening [26–28],
corrosion resistance improvements [29–31], and novel nanomaterial fabrication [32–43]. So far, processes
combining traditional anodizing in sulfuric, oxalic, and phosphoric acids with self-assembled monolayer
(SAM) coatings have been reported by several research groups for superhydrophilic and superhydrophobic
aluminum surfaces [44,45]. In this technique, anodic alumina nanofibers are formed on the surface via
long-term anodizing and chemical dissolution of the upper part of porous alumina, and their nanostructure
exhibits superhydrophilic behavior. In addition, subsequent hydrophobic SAM modification causes
superhydrophobicity on the surface. However, it is difficult to accurately control the morphology of
alumina nanofibers during anodizing due to the uneven chemical dissolution. Very recently, we have
found the formation of alumina nanofibers formed by anodizing in a novel electrolyte, pyrophosphoric
acid. Pyrophosphoric acid anodizing improves the controllability of the morphology of the alumina
nanofibers due to the rapid dissolution of the anodic oxide and subsequent growth of the nanofibers
during the initial stage of anodizing. Thus, highly ordered nanofiber arrays can be easily fabricated
on the aluminum surface [46–48]. Superhydrophobic aluminum surfaces are successfully fabricated
by anodizing in pyrophosphoric acid and with SAM modification [49]. Moreover, the fabrication of
highly slippery and sticky superhydrophobic aluminum surfaces is easily achieved via the nanostructure
control of alumina nanofibers [50]. On the other hand, the nanofiber-covered aluminum surface without
SAM modification exhibits superhydrophilic behavior [51–53]. The contact angle measured on the
superhydrophilic aluminum surface greatly changed with the anodizing time. In addition, it was observed
that water evaporated quickly from the superhydrophilic surface. However, the effect of the morphology
of the alumina nanofibers on the superhydrophilicity and corresponding fast water evaporation is
still unclear.
In the present investigation, we describe the superhydrophilicity on the aluminum surfaces
covered with anodic alumina nanofibers and subsequent alumina bundle structures by anodizing in
pyrophosphoric acid under the optimum operating condition. The superhydrophilic behavior was
investigated by water contact angle investigation using a high-speed camera and water evaporation
rate measurements. The morphology of the alumina nanofibers was examined by scanning electron
microscopy and in situ high-speed atomic force microscopy, and a contact angle measuring less than
10◦ within 33 ms indicated that superhydrophilicity with fast water evaporation was successfully
achieved by the formation of pyramidal alumina bundle structures on the surface.

2. Experimental
First, 99.99 wt % aluminum plates (thickness: 400 µm, Nippon Light Metal, Tokyo, Japan)
were cut into rectangular pieces (width: 20 mm × height: 40 mm), which then were degreased in
ethanol for 10 min using an ultrasonic cleaner (US-1R, AS ONE, Osaka, Japan) The specimens were
electrochemically polished in 22 vol% 70%-HClO4 /78 vol% CH3 COOH solution at 280 K and a constant
voltage of 28 V for 1 min.
The specimens were anodized in a 74.0% pyrophosphoric acid solution (Kanto Chemical, Tokyo,
Japan) under constant voltage conditions for the fabrication of anodic alumina nanofibers. During this
process, an electrochemical cell with an inner diameter of 55 mm was filled with 100 mL pyrophosphoric
acid solution, and the aluminum specimen as an anode and a platinum plate as a cathode (99.95 wt %,
width: 16 mm × height: 28 mm × thickness: 100 µm, Furuya Metal, Tokyo, Japan) were immersed in
the electrolyte solution. The distance of the aluminum anode and the platinum cathode was adjusted
to 20 mm in the electrochemical cell. The temperature of the electrolyte solution was maintained at
283 K in a large-scale water bath (UCT-1000, AS ONE), and the pyrophosphoric acid was stirred at
a rate of 1 s−1 with a magnetic stirrer (MS-101, AS ONE). The aluminum specimens were anodized
at constant cell voltages of V = 75–80 V for up to 180 min using a DC power supply (PWR-400H,
Kikusui, Yokohama, Japan). This experimental condition was chosen for the formation of typical
anodic alumina nanofibers during pyrophosphoric acid anodizing [47]. After the electrochemical
Materials 2019, 12, 3497 3 of 12

process, the specimens were quickly removed from the electrolyte solution and then washed with
ultrapure water. Some anodized specimens were immersed in a 0.52 M phosphoric acid solution at
293 K for up to 20 min to dissolve the anodic oxide.
The nanostructured surface of the specimen was characterized by field-emission scanning electron
microscopy (FE-SEM, JSM-6500F, JEOL, Akishima, Japan) and atomic force microscopy (AFM, Nanocute,
Hitachi High-Technologies, Tokyo, Japan). Before SEM observations, the anodized specimens were
covered with a thin platinum electroconductive layer by sputter coating. The nanostructure of
the anodic oxide was quantified with a computerized image analysis software (Image-Pro, Media
Cybernetics, Rockville, MD, USA). The anodized specimens were also examined by high-speed AFM
(HS-AFM) with an imaging rate of 0.5 frames per second (fps) for in situ observation of anodic alumina
nanofibers in ultrapure water.
The contact angles of an ultrapure water droplet (specific resistance: 18.2 MΩ·cm) formed on
the aluminum specimen were measured by an optical contact angle meter (DM-501, Kyowa Interface
Science, Niiza, Japan). The water droplet adjusted to 0.5 µL in volume was placed on the surface of the
anodized specimens, and the water contact angles were continuously measured from 33 ms to 1 s just
after the water droplet was placed on the anodized surface. The contact angle investigations were
made at five different surfaces, and the obtained contact angles were averaged without the maximum
and minimum contact angles. Evaporation behavior of the water droplet was also investigated on the
anodized aluminum surface. A 0.5 µL water droplet was placed on the anodized specimens, and the
time required for the complete evaporation of the water droplet from the surface was measured by
a charge-coupled device (CCD) camera. During evaporation measurements, the temperature of the
anodized specimens was maintained at 313 K using a thermoelectric Peltier module (CP-085, Scinics,
Tokyo, Japan). The environment temperature and humidity were not controlled.

3. Results and Discussion

The pretreatment specimens were anodized in pyrophosphoric acid at 80 V and 283 K for up
to 180 min. Figure 1a shows the change in the water contact angle measured on the aluminum
specimen, θWCA , with the anodizing time, ta . Here, the θWCA values were measured at td = 1 s after
the 0.5 µL water droplet was placed on the surface. The electropolished aluminum surface exhibited
hydrophilicity measuring θWCA = 25.9◦ due to the formation of a hydrophilic, thin native oxide film
after electropolishing [54]. As the electropolished specimen was anodized for 5 min, a superhydrophilic
surface measuring θWCA = 9.8◦ was successfully obtained due to the formation of anodic aluminum
oxide. The θWCA then gradually decreased with increasing anodizing time, and lower contact angles
measuring 2◦ –4◦ were obtained after anodizing for 30–180 min. Notably, the minimum contact angle
measuring 2.0◦ was obtained on the surface anodized for 60 min, and it appears that the contact
angle very slightly increased with the anodizing time, although it is difficult to conclude a significant
difference based on these small values. Therefore, the contact angles were also measured at the early
stages after the droplet was placed on the surface using a high-speed CCD camera.
Figure 1b shows the θWCA − ta curves obtained at td = 200, 100, 66, and 33 ms after the 0.5 µL
water droplet was placed on the surface. Although similar tendencies were obtained at td = 200 ms
through 33 ms, the contact angles obtained at each anodizing time decreased with increasing td
value. The minimum contact angle was measured at ta = 60 min in either case except for 66 ms,
and superhydrophilicity, with a contact angle measuring θWCA = 9.2◦ , was exhibited on the surface
anodized for ta = 60 min within only 33 ms after the water placement.
was measured by a charge-coupled device (CCD) camera. During evaporation measurements, the
temperature of the anodized specimens was maintained at 313 K using a thermoelectric Peltier
module (CP-085, Scinics, Tokyo, Japan). The environment temperature and humidity were not
controlled.
Materials 2019, 12, 3497 4 of 12
3. Results and Discussion

Materials 2019, 12, x FOR PEER REVIEW 4 of 12

also measured at the early stages after the droplet was placed on the surface using a high-speed CCD
camera.
Figure 1b shows the θWCA – ta curves obtained at td = 200, 100, 66, and 33 ms after the 0.5 µL water
droplet was placed on the surface. Although similar tendencies were obtained at td = 200 ms through
33 ms, the contact angles obtained at each anodizing time decreased with increasing td value. The
Figure (a) Change
Figure contact
minimum 1.
1. (a) angle
Change in
in the
waswater
the contact
contact angle
measured
water at ta measured
angle = 60 min
measured on
on the
theanodized
in either
anodizedcase aluminum
aluminum for 66θθWCA
exceptsurface,
surface, ms, ,
WCA, and
with the anodizing
superhydrophilicity, time
with the anodizingwith t . The
time taa. The
a electropolished
contact specimens
angle measuring
electropolished were
θWCA
specimens anodized
were=anodized
9.2°, was in pyrophosphoric
exhibited on the
in pyrophosphoric acid at
acidsurface
at
283 K
anodized
283 and
andta80
Kfor VV for
= 60
80 min
for 1−180 min,only
within
1−180 min, and 33
and the contact
thems afterangles
contact were
the water
angles measured
measured at
wereplacement. at ttdd == 11 ss after
after aa 0.5
0.5 µL
µL water
water
droplet was
droplet was placed
placed on
on the
the surface. (b) The
surface. (b) θWCA
The θ tatcurves
WCA–− a curves obtained
obtained atat = 200,
td t=d 200, 100,
100, 66,66,
andand
33 33
ms.ms.

The pretreatment specimens were anodized in pyrophosphoric acid at 80 V and 283 K for up to
180 min. Figure 1a shows the change in the water contact angle measured on the aluminum specimen,
θWCA, with the anodizing time, ta. Here, the θWCA values were measured at td = 1 s after the 0.5 µL
water droplet was placed on the surface. The electropolished aluminum surface exhibited
hydrophilicity measuring θWCA = 25.9° due to the formation of a hydrophilic, thin native oxide film
after electropolishing [54]. As the electropolished specimen was anodized for 5 min, a
superhydrophilic surface measuring θWCA = 9.8° was successfully obtained due to the formation of
anodic aluminum oxide. The θWCA then gradually decreased with increasing anodizing time, and
lower contact angles measuring 2°–4° were obtained after anodizing for 30–180 min. Notably, the
minimum contact angle measuring 2.0° was obtained on the surface anodized for 60 min, and it
appears that the contact angle very slightly increased with the anodizing time, although it is difficult
to conclude a significant difference based on these small values. Therefore, the contact angles were

Figure 2. Change in the evaporation time of a 0.5 µL water droplet, t , with the anodizing time, ta ,
Figure 2. Change in the evaporation time of a 0.5 µL water droplet, teva
eva, with the anodizing time, ta,
on the aluminum specimen anodized at 283 K and 80 V. The temperature of the aluminum substrate
on the aluminum specimen anodized at 283 K and 80 V. The temperature of the aluminum substrate
was maintained at 313 K using a thermoelectric Peltier module.
was maintained at 313 K using a thermoelectric Peltier module.
As the water droplet was placed on the superhydrophilic surface, the droplet spread isotropically
As the water droplet was placed on the superhydrophilic surface, the droplet spread
and soon evaporated from the surface. Because the evaporation time of the water droplet strongly
isotropically and soon evaporated from the surface. Because the evaporation time of the water droplet
depends on the hydrophilicity of the surface, the evaporation time was investigated on the aluminum
strongly depends on the hydrophilicity of the surface, the evaporation time was investigated on the
surface anodized for various operating times. Figure 2 shows the change in the evaporation time
aluminum surface anodized for various operating times. Figure 2 shows the change in the
of a 0.5 µL water droplet on the specimen anodized under the same operating conditions shown in
evaporation time of a 0.5 µL water droplet on the specimen anodized under the same operating
Figure 1, teva , with the anodizing time, ta . Here, the temperature of the aluminum substrate was
conditions shown in Figure 1, teva, with the anodizing time, ta. Here, the temperature of the aluminum
maintained at 313 K using a thermoelectric Peltier module during the measurements. The time required
substrate was maintained at 313 K using a thermoelectric Peltier module during the measurements.
for the complete evaporation of the water droplet from the electropolished surface was measured
The time required for the complete evaporation of the water droplet from the electropolished surface
to be teva = 88.5 s. The evaporation time decreased with the increased anodizing time, and the
was measured to be teva = 88.5 s. The evaporation time decreased with the increased anodizing time,
minimum rapid evaporation time measuring teva = 26.3 s was obtained on the surface anodized for
and the minimum rapid evaporation time measuring teva = 26.3 s was obtained on the surface
ta = 60 min. However, excess anodizing for more than 90 min caused the evaporation time increase
anodized for ta = 60 min. However, excess anodizing for more than 90 min caused the evaporation
to teva = 29.2–41.6 s. Comparing Figure 2 with Figure 1, the shape of this teva − ta curve is in good
time increase to teva = 29.2–41.6 s. Comparing Figure 2 with Figure 1, the shape of this teva – ta curve is
agreement with the θWCA − ta curves shown in Figure 1. It is clear from Figures 1 and 2 that the highest
in good agreement with the θWCA – ta curves shown in Figure 1. It is clear from Figures. 1 and 2 that
superhydrophilicity can be obtained on the aluminum surface anodized for 60 min. To investigate
the highest superhydrophilicity can be obtained on the aluminum surface anodized for 60 min. To
investigate the effect of the morphology of the anodic oxide formed by pyrophosphoric acid
anodizing on the superhydrophilic behavior, the surface of the anodized specimens was
characterized by SEM.
Figure 3 shows SEM images of the aluminum specimen anodized in pyrophosphoric acid at 80
Materials 2019, 12, 3497 5 of 12

the effect of the morphology of the anodic oxide formed by pyrophosphoric acid anodizing on the
superhydrophilic behavior, the surface of the anodized specimens was characterized by SEM.
Figure 3 shows SEM images of the aluminum specimen anodized in pyrophosphoric acid at 80 V
and 283 K for (a) 20 min, (b) 30 min, (c) 60 min, and (d) 180 min. As the electropolished aluminum
specimen was anodized for 20 min (Figure 3a), a porous oxide film with numerous pores measuring
Materials 2019, 12, x FOR PEER REVIEW 5 of 12
87 nm in average pore diameter was formed on the aluminum surface. Increasing the anodizing time
to 30 min (Figure 3b) led to the growth of alumina nanofibers at the triple points of the honeycomb
structure due to the chemical dissolution of anodic oxide during anodizing, and small pyramidal
structure due to the chemical dissolution of anodic oxide during anodizing, and small pyramidal bundle
bundle structures consisting of several nanofibers were formed on the surface because of the bending
structures consisting of several nanofibers were formed on the surface because of the bending and
and subsequent tangling of the alumina nanofibers. The number of alumina nanofibers contained in
subsequent tangling of the alumina nanofibers. The number of alumina nanofibers contained in each
each bundle structure increased with the anodizing time due to the growth of the alumina nanofibers,
bundle structure increased with the anodizing time due to the growth of the alumina nanofibers, and
and larger bundle structures were formed by anodizing for 60 min (Figure 3c). Further anodizing
larger bundle structures were formed by anodizing for 60 min (Figure 3c). Further anodizing caused
caused the formation of longer alumina nanofibers and subsequent complete bending due to their
the formation of longer alumina nanofibers and subsequent complete bending due to their own weight,
own weight, and the surface was covered with the bent alumina nanofibers (Figure 3d). Comparing
and the surface was covered with the bent alumina nanofibers (Figure 3d). Comparing the SEM images
the SEM images with the contact angle measurements and the evaporation behaviors, the following
with the contact angle measurements and the evaporation behaviors, the following results are obtained:
results are obtained: a) Superhydrophilicity can be obtained on the porous alumina- and nanofiber-
(a) Superhydrophilicity can be obtained on the porous alumina- and nanofiber-covered aluminum
covered aluminum surface formed by anodizing in pyrophosphoric acid. b) In particular, the highest
surface formed by anodizing in pyrophosphoric acid. (b) In particular, the highest superhydrophilicity
superhydrophilicity is exhibited on the surface covered with the large pyramidal bundle structures
is exhibited on the surface covered with the large pyramidal bundle structures after anodizing for
after anodizing for 60 min.
60 min.

Figure 3. SEM (scanning electron microscopy) images of the aluminum specimen anodized at 283 K
Figure 3. SEM (scanning electron microscopy) images of the aluminum specimen anodized at 283 K
and 80 V. ta = (a) 20 min, (b) 30 min, (c) 60 min, (d) 180 min.
and 80 V. ta = (a) 20 min, (b) 30 min, (c) 60 min, (d) 180 min.
When the water droplet is placed on the aluminum surface covered with the pyramidal alumina
When
bundle the water
structures, onedroplet is placed
question on theor
is whether aluminum surface
not the shape ofcovered with is
the bundles themaintained
pyramidal in alumina
water.
bundle structures, one question is whether or not the shape of the bundles is maintained
To reveal the morphology of the alumina bundle structures in ultrapure water, the specimen anodized in water. To
reveal the morphology of the alumina bundle structures in ultrapure water,
for 60 min was examined by in situ HS-AFM. Figure 4a shows a HS-AFM image of a bundle structure the specimen anodized
for 60 min
formed bywas examined
anodizing in by in situ HS-AFM.
pyrophosphoric Figure
acid 4a shows
at 293 K and a75 HS-AFM
V for 15 image
min.ofIta bundle
is clearstructure
that the
bundle structures consisting of many alumina nanofibers maintained their shape in ultrapurebundle
formed by anodizing in pyrophosphoric acid at 293 K and 75 V for 15 min. It is clear that the water;
structures
the alumina consisting
nanofibers of were
manynot alumina
separatednanofibers maintained
and fluttered their shape in
in the underwater ultrapureFigure
conditions. water;4b,c
the
alumina nanofibers were not separated and fluttered in the underwater conditions.
show HS-AFM images of the bundle structure at 10 s and 20 s after starting the observation, respectively.Figures 4b,c show
HS-AFM images
Although severalofnanofibers
the bundlewerestructure at 10
slightly s andby
moved 20 the
s after startingofthe
scanning theobservation,
cantilever, therespectively.
shape of
Although several nanofibers were slightly moved by the scanning
the bundle structure and the alumina nanofibers was largely maintained during in situof the cantilever, the shape of the
HS-AFM
bundle structure and the alumina nanofibers was largely maintained during in
observation for 20 s. Therefore, it is expected that the bundle structures maintained their shapes in water situ HS-AFM
observation
when the waterfor droplet
20 s. Therefore, it ison
was placed expected that the
the anodized bundle
surface structures
during maintained
the contact their shapes in
angle measurements.
water when the water droplet was placed on the anodized surface during the contact angle
measurements. The reason that the bundle structures were unchanged in water may be due to the
van der Waals forces between the alumina nanofibers [55].
Materials 2019, 12, 3497 6 of 12

The reason that the bundle structures were unchanged in water may be due to the van der Waals forces
Materials 2019, 12, x FOR PEER REVIEW 6 of 12
between the 12,
Materials 2019, alumina nanofibers
x FOR PEER REVIEW[55]. 6 of 12

Figure 4. In situ HS-AFM (high-speed atomic force microscopy) images of the pyramidal bundle
Figure
Figure 4. In
In situ
situ HS-AFM
4. consisting HS-AFM (high-speed
(high-speed atomic
atomic force
force microscopy)
microscopy) images
images of
of the
the pyramidal
pyramidal bundle
bundle
structure of anodic alumina nanofibers in ultrapure water: (a) when observation starts, (b)
structure
structure consisting
consisting of
of anodic
anodic alumina
alumina nanofibers
nanofibers inin ultrapure
ultrapure water:
water: (a)(a) when
when observation
observation starts,
starts, (b)
10 s after, and (c) 20 s after. The aluminum specimen anodized at 293 K and 75 V for 15 min.
(b)
10 s10after,
s after,
andand
(c) (c)
20 20 s after.
s after. TheThe aluminum
aluminum specimen
specimen anodized
anodized at 293
at 293 K and
K and 75 75 V for
V for 15 15 min.
min.
Figures5a–c
Figure 5a–cdepict
depictthree-dimensional
three-dimensionalAFM AFMimages
imagesof ofaaspecimen
specimen anodized
anodized in in pyrophosphoric
pyrophosphoric
acid Figures
at 283 K 5a–c
and depict
80 V forthree-dimensional
(a) t = 20 min, (b)AFM
60 images
min, and of a180
(c) specimen
min, anodized inAs
respectively. pyrophosphoric
the aluminum
aluminum
acid at 283 K and 80 V for (a) ta = 20 min, (b) 60 min, and (c) 180 min, respectively. As the
a
acid at 283
specimen was K and 80
was anodized V
anodized forfor (a)
for 20 t a = 20 min, (b) 60 min, and (c) 180 min, respectively. As the aluminum
20 min,
min, aa porous
porous oxide
oxide film
film was
was formed
formed on on the
the surface
surface (Figure
(Figure 3a),3a), and
and aa
specimen
specimen flat wassurface
anodized fornumerous
20 min, a porous oxide filmwas wasobserved
formed on the surface (Figure 3a), and a
relatively flat surface with numerous small nanopores was observed in the AFM image (Figure 5a).
relatively with small nanopores in the AFM image (Figure 5a).
relatively
As the flat
the anodizing surface
anodizing time with numerous small nanopores was observed in the AFM image (Figure 5a).
As time increased
increasedto to6060min,
min,many
manyconvex
convexbundle
bundlestructures
structures ofof
approximately
approximately 1 µm
1 µmin
As the anodizing
maximum height time
were increased
observed toto60 be
min, many convex
distributed on bundle
the structures
surface (Figures of approximately
3c and 5b). 1 µm in
However,
in maximum height were observed to be distributed on the surface (Figures 3c and 5b). However,
maximum
further height for
anodizing were
180observed
min caused
caused to the
be distributed
disappearance on of
thethe
surface
bundle(Figures
structures3c due
and to5b).theHowever,
complete
further anodizing for 180 min the disappearance of the bundle structures due to the complete
further
bending ofanodizing
of longer for 180
longer alumina min caused
alumina nanofibers, the disappearance of the bundle structures due to the complete
bending nanofibers, and and the
the surface
surface roughness
roughness decreased
decreased (Figures.
(Figures 3d 3d and
and 5c).
5c).
bending
Figure 5d of longer
summarizes alumina
the nanofibers,
change in the and the
arithmetic surface
mean roughness
roughness decreased
measured (Figures.
from the 3d
AFM and 5c).
image,
Figure 5d summarizes the change in the arithmetic mean roughness measured from the AFM image,
Figure
Ra, with 5dthe
summarizes
anodizingthe change
time. The in the arithmetic
roughness rapidlymean roughness
increased withmeasured
the anodizingfrom time
anodizing the AFM duringimage,
the
Ra, with the anodizing time. The roughness rapidly increased with the time during the
Ra, with
initial stagethe
stage due anodizing
due toto the time.
the formationThe
formation of roughness
of alumina rapidly
alumina nanofibers increased
nanofibers and with
and subsequent the anodizing
subsequent bundle time
bundle structures, during
structures, and andthe
initial aa
initial
maximum stage due to
roughness the formation
measuring of
Ra alumina
= 124 nm nanofibers
was and
obtained subsequent
by anodizing bundle
for 60structures,
min. With and
thisa
maximum roughness measuring Ra = 124 nm was obtained by anodizing for 60 min. With this
maximum
anodizing time, roughness measuring Ra = 124 nm was obtained by anodizing for 60 min. With this
anodizing time, the
thehighest
highestsuperhydrophilicity
superhydrophilicitywas wasexhibited
exhibitedonon the aluminum
the aluminum surface
surface (Figures 1,2).
(Figures 1
anodizing
The time, the
roughness, then, highest superhydrophilicity
gradually decreased to was exhibited50
approximately onnmthe due
aluminum
to the surface
bending (Figures
of 1,2).
alumina
and 2). The roughness, then, gradually decreased to approximately 50 nm due to the bending of
The roughness,
nanofibers then, anodizing.
by excess gradually decreased
The water to approximately
contact 50 nm at due tostage
the bending of with
alumina
alumina nanofibers by excess anodizing. The waterangle measured
contact angle measuredthis increased
at this stage increased the
nanofibers
anodizing by excess
time. Astime. anodizing.
compared The
the contactwater contact angle
angle investigations measured
with theat this stage
surface increased
roughness, with the
the water
with the anodizing As compared the contact angle investigations with the surface roughness, the
anodizing
contact time.
angle angle As compared
and hydrophilic the contact
behavior angle investigations
clearlyclearly
depend on theon with
surfacethe surface
roughness. roughness, the water
water contact and hydrophilic behavior depend the surface roughness.
contact angle and hydrophilic behavior clearly depend on the surface roughness.

Figure
Figure 5. Three-dimensional AFM
5. Three-dimensional AFM images
images of
of the
the pyramidal
pyramidal bundle
bundle structure
structure consisting
consisting of
of anodic
anodic
alumina
Figure 5.nanofibers formed at 283
Three-dimensional t = (a)pyramidal
K and 80 V.of 20 min, (b) 60 min,structure
(c) 180 min. (d) Change in the
alumina nanofibers formed atAFM
283 Kimages
and 80 V.a the
ta = (a) 20 min, bundle
(b) 60 min, (c) 180consisting of anodic
min. (d) Change in
arithmetic
alumina mean roughness
nanofibers formedof
at the
283anodized
K and 80specimen,
V. t a = (a) R
20
a , min,
with (b)
the 60
anodizing
min, (c) time,
180 ta . (d) Change in
min.
the arithmetic mean roughness of the anodized specimen, Ra, with the anodizing time, ta.
the arithmetic mean roughness of the anodized specimen, Ra, with the anodizing time, ta.
The contact angle of the droplet formed on the rough surface can be described by Wenzel’s
The contact angle of the droplet formed on the rough surface can be described by Wenzel’s
equation
The as [56] angle of the droplet formed on the rough surface can be described by Wenzel’s
contact
equation as [56]
equation as [56] cos θW = R cos θ (1)
cos θW = R cos θ (1)
cos θW = R cos θ (1)
where R corresponds to the specific surface area, and θW and θ are the contact angles obtained on the
where Rsurface
rough corresponds to the
and the specific
flat surface
surface, area, and θThe
respectively. W and θ are the contact angles obtained on the
anodic alumina nanofibers formed by
pyrophosphoric acid anodizing consists of pure aluminum anodic
rough surface and the flat surface, respectively. The alumina
oxide without anynanofibers
electrolyteformed by
anion, and
pyrophosphoric acid anodizing consists of pure aluminum oxide without any electrolyte anion, and
Materials 2019, 12, 3497 7 of 12

where R corresponds to the specific surface area, and θW and θ are the contact angles obtained
on the rough surface and the flat surface, respectively. The anodic alumina nanofibers formed by
Materials 2019, 12, x FOR
pyrophosphoric acidPEER REVIEW consists of pure aluminum oxide without any electrolyte anion,
anodizing 7 of 12
and anodic aluminum oxide exhibits hydrophilicity due to the presence of the surface-bound hydroxyl
anodic
groups aluminum oxideWenzel’s
[51]. Therefore, exhibits equation
hydrophilicity duethat
indicates to the
thepresence of thedecreases
contact angle surface-bound hydroxyl
with increasing
groups
specific [51]. Therefore,
surface area on suchWenzel’s equationsurface.
a hydrophilic indicates that
The the contact
aluminum anglecovered
surface decreaseswithwiththe increasing
pyramidal
specific surface area on such a hydrophilic surface. The aluminum
bundle structures consisting of numerous alumina nanofibers possesses a higher surface roughness surface covered with the
pyramidal
(Figure 5d).bundle structures
In addition, SEMconsisting
observation of (Figure
numerous 3c) alumina
shows that nanofibers possesses
many nanoscale a higher
spaces surface
are formed
roughness (Figure 5d). In addition, SEM observation (Figure 3c) shows
under the pyramidal bundle structures. Moreover, strong capillary forces are induced by these alumina that many nanoscale spaces
are formed under the pyramidal bundle structures. Moreover, strong capillary
nanofibers. Therefore, the highest superhydrophilicity may be obtained on the surface covered with the forces are induced by
these alumina
pyramidal nanofibers.
bundle structures Therefore,
by anodizingthe highest
for 60 superhydrophilicity
min (Figures 1 and 2). mayOnbetheobtained
other hand, on the surface
long-term
covered with the pyramidal bundle structures by anodizing for 60
anodizing leads to the disappearance of the bundle structures due to the complete bending of min (Figures 1 and 2). On the other
the
hand, long-term anodizing leads to the disappearance of the bundle
long alumina nanofibers, and most of the aluminum surface is covered with the bent nanofibers structures due to the complete
bending 3d
(Figures of the
andlong
5c). alumina
Thus, thenanofibers,
contact angle andmaymostslightly
of the aluminum
increase bysurface is covered for
excess anodizing with the than
more bent
nanofibers (Figures
60 min (Figures 1 and 2). 3d and 5c). Thus, the contact angle may slightly increase by excess anodizing for
moreSummarizing
than 60 min (Figuresso far, 1the and 2).
pyramidal alumina bundles are important nanostructures for the
Summarizing so far, the pyramidal
fabrication of superhydrophilic surfaces with alumina bundles
fast water are important
evaporation, nanostructures
but excess anodizing for the
causes
fabrication of superhydrophilic surfaces with fast water evaporation, but
the hydrophilicity to decrease due to the disappearance of the bundle structures. On the other hand, excess anodizing causes the
hydrophilicity
short-term anodizing to decrease
for 10due mintocaused
the disappearance
a slight increase of the
in thebundle
contact structures.
angle duringOn thetheother hand,
high-speed
short-term anodizing for 10 min caused a slight increase in the contact
contact angle measurements for td = 33–200 ms (Figure 1b), although the anodic oxide grew on angle during the high-speed
contact angleTherefore,
the surface. measurements for td = 33–200
we demonstrate ms (Figure
further contact1b), although
angle the anodic
investigations oxide
in the grewstage
initial on theof
surface. Therefore, acidwe demonstrate further contact angle
the θinvestigations in the initial stage of
pyrophosphoric anodizing in detail. Figure 6 shows WCA − ta curves for the initial stage of
pyrophosphoric
anodizing on the acid anodizing
aluminum surfacein detail.
anodized Figure
at 806Vshows
and 283 theK.θAtWCA – ta curves for the initial stage of
td = 1 s after the droplet was placed
anodizing
on the surface, the contact angle rapidly decreased to θWCA = 9.8 asAtthe
on the aluminum surface anodized at 80 V and 283 K.
◦ td specimen
= 1 s afterwasthe anodized
droplet was for
placed
ta = 5 minon the
and surface, the contact
then slightly angle rapidly
decreased with the decreased
anodizing to θ WCA = 9.8° as the specimen was anodized
time. However, very little change in the
for ta = 5angle
contact min and
was then slightly
measured decreased
during the rangewithofthe
10 anodizing
min < ta < time.
20 min. However,
Based onvery little changecontact
the high-speed in the
contact angle was measured
angle investigations duringms,
at td = 33–200 theitrange of 10 minthat
is noteworthy < ta the
< 20contact
min. Based
angleon the high-speed
gradually increasedcontact
with
angle investigations at t d = 33–200 ms, it is noteworthy that the contact angle gradually increased with
the anodizing time from 10 min < ta < 20 min, although hydrophilic aluminum oxide was formed
the anodizing
surface time from 10 min < ta is
< 20 min,difference
although hydrophilic
in the θWCA aluminum
− ta curvesoxide wast formed on
on the via anodizing. There a clear between d = 1 s and
the surface
200–33 ms. via anodizing. There is a clear difference in the θWCA – ta curves between td = 1 s and 200–
33 ms.

Figure 6.
Figure Changeininthe
6. Change thewater
water contact
contact angle
angle measured
measured on on
thethe anodized
anodized aluminum
aluminum θWCAθ, WCA
surface,
surface, with,
with the anodizing time, t
the anodizing time, ta, during
a , during the initial stage of anodizing. The electropolished specimens
the initial stage of anodizing. The electropolished specimens were were
anodized in
anodized in pyrophosphoric
pyrophosphoric acid acid at
at 283
283 K
K and
and 80
80 V.
V.

Figure 77 shows
Figure showsSEMSEMimages
imagesofofthe
theanodized
anodized aluminum
aluminum surface
surfacein the initial
in the stage
initial of (a)
stage of1(a)
min and
1 min
(b)
and10(b)
min. A thinAbarrier
10 min. oxide film
thin barrier oxide with
filmnarrow stripes approximately
with narrow 100–150 nm
stripes approximately widenm
100–150 waswide
observed
was
on the surface anodized for 1 min (Figure 7a). This stripe pattern corresponds to the
observed on the surface anodized for 1 min (Figure 7a). This stripe pattern corresponds to the nanomorphology
of the electropolished
nanomorphology aluminum
of the surface aluminum
electropolished [57]. As thesurface
anodizing
[57].time increased
As the anodizing = 10increased
to tatime min, a porous
to ta
= 10 min, a porous alumina film with numerous nanopores measuring 52 nm in average diameter
was formed (Figure 7b). Further anodizing for ta = 20 min caused the pore diameter increase by
chemical dissolution of the anodic oxide (average pore diameter: 87 nm, Figure 3a). Therefore, the
period of the contact angle increase, ta = 10–20 min, corresponds to the expansion of the nanopores in
the porous alumina matrix.
Materials 2019, 12, 3497 8 of 12

alumina film with numerous nanopores measuring 52 nm in average diameter was formed (Figure 7b).
Further anodizing for ta = 20 min caused the pore diameter increase by chemical dissolution of the
Materials 2019, 12, x FOR PEER REVIEW 8 of 12
anodic oxide (average pore diameter: 87 nm, Figure 3a). Therefore, the period of the contact angle
Materials 2019, 12, x FOR PEER REVIEW 8 of 12
increase, ta = 10–20 min, corresponds to the expansion of the nanopores in the porous alumina matrix.

Figure 7. SEM images of the aluminum specimen anodized at 283 K and 80 V (a) ta = 1 min and (b) 10
Figure 7. SEM images of the aluminum specimen anodized at 283 K and 80 V (a) ta = 1 min and
min.
Figure 7. SEM images of the aluminum specimen anodized at 283 K and 80 V (a) ta = 1 min and (b) 10
(b) 10 min.
min.
To understand the
To understand the effect of pore
effect of pore diameter
diameter in in the
the porous
porous alumina
alumina film film on on the
the contact
contact angle,
angle,
contactTo angle measurements
understand the effectwere
of also
pore performed
diameter in using
the pore-widening
porous
contact angle measurements were also performed using pore-widening porous alumina specimens. alumina porous
film onalumina
the specimens.
contact angle,
Here,
Here, the
contact electropolished
angle
the measurements
electropolished aluminum
were also
aluminum specimens
performed
specimens were
were anodized
using in
in pyrophosphoric
pore-widening
anodized porous alumina
pyrophosphoric acid
acid at 283
283 K K and
atspecimens. and
80 V
Here, for 5 min to form a porous alumina film, and the anodized specimens
80 V for 5 min to form a porous alumina film, and the anodized specimens were then immersed and
the electropolished aluminum specimens were anodized in were
pyrophosphoric then immersed
acid at 283 K in
in aa
0.52
80
0.52VMM phosphoric
forphosphoric
5 min to form acidasolution
solution
porousat at 293
alumina Kfilm,
for
up upto tto
and tp =anodized
the 15 min for pore-widening.
specimens were then Figure 8a shows
immersed in a
acid 293 K for p = 15 min for pore-widening. Figure 8a shows SEM
SEM
0.52 Mimages of
phosphoricthe surface
acid of
solutionthe anodized
at 293 K forspecimen
up to t pafter
= 15 pore-widening.
min for Circular
pore-widening.
images of the surface of the anodized specimen after pore-widening. Circular pores and linear trenches pores
Figure and
8a linear
shows
trenches
SEM images
were wereof
formed onformed
the on the
thesurface
surface of
bysurface
the by pore-widening
anodized
pore-widening specimen
for 2 min, for
after 2 min, and the was
pore-widening.
and the porosity porosity
Circular was calculated
pores
calculated toand
be linear
22.8%to
be 22.8%
trenches
using imageusing
were imagesoftware.
formed
analysis analysis
on software.
the surface
Although Although
by pore-widening
the porosity theoffor
porosity
min,of
the2 porous andthe porous
the
alumina porosity
wasalumina was
was calculated
almost almost
unchanged to
unchanged
be 22.8% in
usinga short
image immersion
analysis time
software. for t p = 5 min,the
Although it gradually
porosity increased
of
in a short immersion time for tp = 5 min, it gradually increased with immersion time by long-term the porous with immersion
alumina was time
almostby
long-term
unchanged
pore-widening
pore-widening
in a (25.2% (25.2% for
short immersion
for 10 mintime
1031.4%
and for
min and
tp =for 31.4%
5 min, for 15 min).
it gradually
15 min). The porous
The
increased porous
alumina withfilm alumina
immersion film
timewas
was completely by
completely
long-term dissolved
pore-widening into the solution
(25.2% for by
10 immersion
min and for
31.4% 20
formin.
15 Figure
min).
dissolved into the solution by immersion for 20 min. Figure 8b shows the θWCA − tp curves obtained
8b
The shows
porous the θ WCA – film
alumina t p curves
was
obtained
completely ondissolved
the anodized
into the specimens
solution after
by pore-widening.
immersion At Figure
td = 1 8b s, the contact angle
– tpslightly
on the anodized specimens after pore-widening. At td for
= 1 20 min.
s, the contact angle shows thedecreased
slightly θWCA curves
during
decreased
obtained during the initialspecimens
stage of pore-widening and thenAtwas =almost unchanged during pore-
the initial on theofanodized
stage pore-widening and then after was pore-widening.
almost unchanged tdduring
1 s, pore-widening.
the contact angle slightly
Conversely,
widening.
decreased Conversely,
during the it is clear
initial stagethatof the contact angleand
pore-widening obtained
then at td =almost
was 33 ms unchanged
gradually increased
during with
pore-
it is clear that the contact angle obtained at td = 33 ms gradually increased with the pore-widening
the pore-widening
widening. timeitand corresponding the porosity. BasedatontdFigures 6gradually
and 8, the porosity—in
Conversely, is clear that the contact angle obtained
time and corresponding the porosity. Based on Figures 6 and 8, the porosity—in other words,with = 33 ms increased the
other
the words, the diameter
pore-widening time andof the pores formed
corresponding in the porous
the porosity. Based on alumina
Figures film—strongly
6 and 8, the affects the
porosity—in
diameter of the pores formed in the porous alumina film—strongly affects the contact angle obtained
contact
other angle obtained
words, the diameter at theofinitial stageformed
the pores after theindroplet
the porousis placed on the
alumina surface, and the
film—strongly contact
affects the
at the initial stage after the droplet is placed on the surface, and the contact angle increases with the
angle
contact increases with the pore diameter.
angle obtained at the initial stage after the droplet is placed on the surface, and the contact
pore diameter.
angle increases with the pore diameter.

Figure 8. (a) SEM images of the porous alumina film formed by pyrophosphoric acid anodizing after
Figure 8. (a) SEM images of the porous alumina film formed by pyrophosphoric acid anodizing after
pore-widening for tp = 2–15 min. (b) Changes in the water contact angle, θWCA , with the pore-widening
pore-widening
Figure for tp = 2–15 min.porous
(b) Changes in the water contact angle, θWCA, with the pore-widening
time, tp8., at(a)tdSEM
= 33images
ms andof 1 sthe alumina
after the water film
droplet formed
was by pyrophosphoric
placed on the surface. acid anodizing after
time, t , at t = 33 ms and 1 s after the water droplet was placed
pore-widening for tp = 2–15 min. (b) Changes in the water contact angle,
p d on the surface.
θWCA, with the pore-widening
Whentp,the
time, at twater
d = 33 ms and 1 is
droplet s after the on
placed water
thedroplet
porouswas placedfilm,
alumina on the surface.
water enters into the nanopores of
the hydrophilic aluminum oxide. However, because a repulsive force is generated by the air in the
 trenches were formed on the surface by pore-widening for 2 min, and the porosity was calculated to
be 22.8% using image analysis software. Although the porosity of the porous alumina was almost
unchanged in a short immersion time for tp = 5 min, it gradually increased with immersion time by
long-term pore-widening (25.2% for 10 min and 31.4% for 15 min). The porous alumina film was
completely
Materials dissolved
2019, 12, 3497 into the solution by immersion for 20 min. Figure 8b shows the θWCA – tp curves 9 of 12
obtained on the anodized specimens after pore-widening. At td = 1 s, the contact angle slightly
decreased during the initial stage of pore-widening and then was almost unchanged during pore-
pores, a composite
widening. Conversely,surface
it isconsisting of aluminum
clear that the oxide
contact angle and airatmay
obtained td = be
33 formed on theincreased
ms gradually surface inwith
the
initial stage after the water placement (Figure 9a). The Cassie–Baxter model is widely
the pore-widening time and corresponding the porosity. Based on Figures 6 and 8, the porosity—in employed to
consider the contact
other words, angle formed
the diameter of theon such formed
pores a composite surface,
in the porous and the contact
alumina angle obtained
film—strongly on the
affects the
solid–air composite surface, θ , can be described by the equation [56]
contact angle obtained at the initial stage after the droplet is placed on the surface, and the contact
c
angle increases with the pore diameter.
cos θc = f (1 + cos θ) − 1 (2)

where f is the area fraction of the projected contact area and θ is the contact angle obtained on the flat
surface. This equation indicates that a decrease in the solid area leads to an increase in the contact
angle. The reason why the θWCA obtained at td = 33–200 ms increases with the anodizing time in
the initial anodizing stage of ta = 10–20 min (Figure 6) may be due to this relation. The contact angle
increases with the anodizing time for up to 20 min because the diameter of the nanopores increases by
pore-widening (Figure 9b). However, water enters into the nanopores of the hydrophilic aluminum
oxide as the td value increases, and the composite surface disappears from the surface. Thus, the
contact angle slightly decreases with the anodizing time at td = 1 s. On the other hand, the contact
angles obtained at whole td values decreased after anodizing for 30 min (Figure 6). As described in
Figure 3, anodic alumina nanofibers and subsequent bundle structures were formed on the surface by
anodizing for 30 min. The water droplet can quickly spread on the nanofiber-covered surface without
closedFigure 8. (a) SEM
nanopores dueimages
to theofcapillary
the porous alumina
effect film
of the formed by(Figure
nanofibers pyrophosphoric acid
9c); thus, anodizing after
superhydrophilicity
pore-widening for t p = 2–15 min. (b) Changes in the water contact angle, θWCA, with the pore-widening
with fast water evaporation appears on the surface after the formation of alumina nanofibers. By in situ
time, tp, at td = 33 ms and 1 s after the water droplet was placed on the surface.
HS-AFM, the shape of the pyramidal bundle structures was maintained in water without separation.

Figure 9. Schematic illustrations of the cross-section of the anodized specimen after the water droplet
was placed on the surface: (a) porous alumina with narrow pores, (b) porous alumina with large-scale
pores, and (c) nanofiber-covered surface.

Although several research groups have reported that superhydrophilic aluminum could be
fabricated by anodizing, the time after the water droplet was placed on the surface during contact
angle investigations was unknown in many cases. Ye et al. reported that ‘bird’s nest’ surface fabricated
by typical anodizing in phosphoric acid exhibited superhydrophilicity measuring θWCA = 3◦ when a
water droplet was dropped on the surface after around 0.8 s [58]. In our investigation, the minimum
contact angles measuring θWCA = 2.0◦ at td = 1 s and 3.0◦ at td = 500 ms were obtained on the
surface anodized in pyrophosphoric acid for 60 min, and this result is lower than that obtained by the
previous investigation. Therefore, our anodizing technique using pyrophosphoric acid is useful for the
fabrication of superhydrophilic aluminum surface in the various engineering fields.

4. Conclusions
We investigated the superhydrophilicity of an aluminum surface anodized in pyrophosphoric
acid. Pyrophosphoric acid anodizing leads to the fabrication of thin uniform oxide, porous oxide,
pyramidal bundle structures consisting of many alumina nanofibers, and completely bent nanofibers.
The change in the water contact angle with the anodizing time exhibits different behaviors depending
on the measurement time after the water droplet is placed on the surface. During the measurement at
1 s after the water placement, the water contact angle greatly decreases to less than θWCA = 10◦ by
pyrophosphoric acid anodizing for up to 5 min, and a superhydrophilic aluminum surface is easily
obtained. On the other hand, the contact angle slightly increases in the initial stage of anodizing due to
the formation of porous alumina during the measurement at 200–33 ms after the water placement,
Materials 2019, 12, 3497 10 of 12

and then, superhydrophilic behavior is exhibited on the nanofiber-covered surface. In particular,

the value θWCA = 9.8◦ at 33 ms after the water placement indicates that superhydrophilicity with fast
water evaporation can be successfully achieved on the surface covered with the pyramidal alumina
bundle structures.

Author Contributions: D.N. and T.K. designed and fabricated the superhydrophilic aluminum surfaces, analyzed
the data, and wrote the manuscript. T.Y., H.M., and M.U. performed the AFM measurements and contributed to
writing the manuscript. R.O.S. and S.N. contributed to the analysis and writing the manuscript.
Funding: This work was funded by the Japan Society for the Promotion of Science (JSPS), Japan, “KAKENHI”
(grant number: 16H04531, 19H02470).
Acknowledgments: The authors thank Nobuyuki Miyazaki and Takashi Endo for their support with SEM
observations based on the “Nanotechnology Platform” Program of the Ministry of Education, Culture, Sports,
Science, and Technology (MEXT), Japan.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Buijnsters, J.G.; Zhong, R.; Tsyntsaru, N.; Celis, J.P. Surface wettability of macroporous anodized aluminum
oxide. ACS Appl. Mater. Interfaces 2013, 5, 3224–3233. [CrossRef] [PubMed]
2. Feng, L.; Zhang, H.; Wang, Z.; Liu, Y. Superhydrophobic aluminum alloy surface: Fabrication, structure,
and corrosion resistance. Colloids Surf. A 2014, 441, 319–325. [CrossRef]
3. Cheng, Y.; Lu, S.; Xu, W. Controllable wettability of micro-and nano-dendritic structures formed on aluminum
substrates. New J. Chem. 2015, 39, 6602–6610. [CrossRef]
4. Li, X.; Zhang, Q.; Guo, Z.; Shi, T.; Yu, J.; Tang, M.; Huang, X. Fabrication of superhydrophobic surface with
improved corrosion inhibition on 6061 aluminum alloy substrate. Appl. Surf. Sci. 2015, 342, 76–83. [CrossRef]
5. Liu, T.; Dong, L.; Liu, T.; Yin, Y. Investigations on reducing microbiologically-influenced corrosion of
aluminum by using super-hydrophobic surfaces. Electrochim. Acta 2010, 55, 5281–5285. [CrossRef]
6. Li, X.W.; Zhang, Q.X.; Guo, Z.; Yu, J.G.; Tang, M.K.; Huang, X.J. Low-cost and large-scale fabrication of
a superhydrophobic 5052 aluminum alloy surface with enhanced corrosion resistance. RSC Adv. 2015, 5,
29639–29646. [CrossRef]
7. Sommers, A.D.; Jacobi, A.M. Creating micro-scale surface topology to achieve anisotropic wettability on an
aluminum surface. J. Micromech. Microeng. 2006, 16, 1571. [CrossRef]
8. Ngo, C.V.; Chun, D.M. Control of laser-ablated aluminum surface wettability to superhydrophobic or
superhydrophilic through simple heat treatment or water boiling post-processing. Appl. Surf. Sci. 2018, 435,
974–982. [CrossRef]
9. Kim, J.; Jun, S.; Lee, J.; Godinez, J.; You, S.M. Effect of surface roughness on pool boiling heat transfer of
water on a superhydrophilic aluminum surface. J. Heat Trans. 2017, 139, 101501. [CrossRef]
10. Song, M.; Liu, Y.; Cui, S.; Liu, L.; Yang, M. Fabrication and icing property of superhydrophilic and
superhydrophobic aluminum surfaces derived from anodizing aluminum foil in a sodium chloride aqueous
solution. Appl. Surf. Sci. 2013, 283, 19–24. [CrossRef]
11. Milles, S.; Soldera, M.; Voisiat, B.; Lasagni, A.F. Fabrication of superhydrophobic and ice-repellent surfaces on
pure aluminium using single and multiscaled periodic textures. Sci. Rep. 2019, 9, 13944. [CrossRef] [PubMed]
12. Peng, H.; Luo, Z.; Li, L.; Xia, Z.; Du, J.; Zheng, B. Facile fabrication of superhydrophobic aluminum surfaces by
chemical etching and its anti-icing/self-cleaning performances. Mater. Res. Express 2019, 6, 096586. [CrossRef]
13. Qiu, R.; Li, Z.; Wu, Z. Enhanced anti-icing and anti-corrosion properties of wear-resistant superhydrophobic
surfaces based on Al alloys. Mater. Res. Express 2019, 6, 045059. [CrossRef]
14. Hiromae, Y.; Kurata, M.; Kobayashi, M.; Saito, M. Wettability and corrosion resistance of prepainted
aluminum fins for heat exchangers. J. Surf. Fin. Soc. Jpn. 1990, 41, 1187–1191. [CrossRef]
15. Vatanpour, V.; Madaeni, S.S.; Rajabi, L.; Zinadini, S.; Derakhshan, A.A. Boehmite nanoparticles as a new
nanofiller for preparation of antifouling mixed matrix membranes. J. Membr. Sci. 2012, 401, 132–143. [CrossRef]
16. Takata, Y.; Hidaka, S.; Yamashita, A.; Yamamoto, H. Evaporation of water drop on a plasma-irradiated
hydrophilic surface. Int. J. Heat Fluid Flow 2004, 25, 320–328. [CrossRef]
Materials 2019, 12, 3497 11 of 12

17. Tsougeni, K.; Vourdas, N.; Tserepi, A.; Gogolides, E.; Cardinaud, C. Mechanisms of oxygen plasma
nanotexturing of organic polymer surfaces: From stable super hydrophilic to super hydrophobic surfaces.
Langmuir 2009, 25, 11748–11759. [CrossRef]
18. Lee, M.; Kwak, G.; Yong, K. Wettability control of ZnO nanoparticles for universal applications. ACS Appl.
Mater. Interfaces 2011, 3, 3350–3356. [CrossRef]
19. Esmeryan, K.D.; Castano, C.E.; Bressler, A.H.; Abolghasemibizaki, M.; Mohammadi, R. Rapid synthesis of
inherently robust and stable superhydrophobic carbon soot coatings. Appl. Surf. Sci. 2016, 369, 341–347.
[CrossRef]
20. Shimizu, K.; Kobayashi, K.; Thompson, G.E.; Wood, G.C. The nature and origin of defects in the barrier
oxide layers grown on etched aluminium foils for capacitor applications. J. Mater. Sci. Lett. 1992, 11, 281–283.
[CrossRef]
21. Mozalev, A.; Sakairi, M.; Takahashi, H.; Habazaki, H.; Hubálek, J. Nanostructured anodic-alumina-based
dielectrics for high-frequency integral capacitors. Thin Solid Film. 2014, 550, 486–494. [CrossRef]
22. Shimizu, K.; Brown, G.M.; Habazaki, H.; Kobayashi, K.; Skeldon, P.; Thompson, G.E.; Wood, G.C. Impurity
distributions in barrier anodic films on aluminium: A GDOES depth profiling study. Electrochim. Acta 1999,
44, 2297–2306. [CrossRef]
23. Asoh, H.; Ishino, M.; Hashimoto, H. AC-Bipolar anodization of aluminum: Effects of frequency on thickness
of porous alumina films. J. Electrochem. Soc. 2018, 165, C295–C301. [CrossRef]
24. Kikuchi, T.; Nishinaga, O.; Natsui, S.; Suzuki, R.O. Polymer nanoimprinting using an anodized aluminum
mold for structural coloration. Appl. Surf. Sci. 2015, 341, 19–27. [CrossRef]
25. Liu, Y.; Chang, Y.; Ling, Z.; Hu, X.; Li, Y. Structural coloring of aluminum. Electrochem. Commun. 2011, 13,
1336–1339. [CrossRef]
26. Fratila-Apachitei, L.E.; Duszczyk, J.; Katgerman, L. Vickers microhardness of AlSi (Cu) anodic oxide layers
formed in H2 SO4 at low temperature. Surf. Coat. Technol. 2003, 165, 309–315. [CrossRef]
27. Kikuchi, T.; Takenaga, A.; Natsui, S.; Suzuki, R.O. Advanced hard anodic alumina coatings via etidronic acid
anodizing. Surf. Coat. Technol. 2017, 326, 72–78. [CrossRef]
28. Tseng, C.C.; Lee, J.L.; Kuo, T.H.; Kuo, S.N.; Tseng, K.H. The influence of sodium tungstate concentration and
anodizing conditions on microarc oxidation (MAO) coatings for aluminum alloy. Surf. Coat. Technol. 2012,
206, 3437–3443. [CrossRef]
29. Thompson, G.E.; Zhang, L.; Smith, C.J.E.; Skeldon, P. Boric/sulfuric acid anodizing of aluminum alloys 2024
and 7075: Film growth and corrosion resistance. Corrosion 1999, 55, 1052–1061. [CrossRef]
30. Suzuki, Y.; Kawahara, K.; Kikuchi, T.; Suzuki, R.O.; Natsui, S. Corrosion-resistant porous alumina formed
via anodizing aluminum in etidronic acid and its pore-sealing behavior in boiling water. J. Electrochem. Soc.
2019, 166, C261–C269. [CrossRef]
31. Kikuchi, T.; Hara, Y.; Sakairi, M.; Yonezawa, T.; Yamauchi, A.; Takahashi, H. Corrosion of Al–Sn–Bi alloys in
alcohols at high temperatures. Part II: Effect of anodizing on corrosion. Corros. Sci. 2010, 52, 2525–2534.
[CrossRef]
32. St˛epniowski, W.J.; Bojar, Z. Synthesis of anodic aluminum oxide (AAO) at relatively high temperatures.
Study of the influence of anodization conditions on the alumina structural features. Surf. Coat. Technol. 2011,
206, 265–272. [CrossRef]
33. St˛epniowski, W.J.; Choi, J.; Yoo, H.; Oh, K.; Michalska-Domańska, M.; Chilimoniuk, P.; Czujko, T.;
Łyszkowski, R.; Jóźwiak, S.; Bojar, Z.; et al. Anodization of FeAl intermetallic alloys for bandgap tunable
nanoporous mixed aluminum-iron oxide. J. Electroanal. Chem. 2016, 771, 37–44. [CrossRef]
34. Wen, L.; Xu, R.; Mi, Y.; Lei, Y. Multiple nanostructures based on anodized aluminium oxide templates.
Nat. Nanotechnol. 2017, 12, 244–250. [CrossRef] [PubMed]
35. Kikuchi, T.; Nishinaga, O.; Natsui, S.; Suzuki, R.O. Fabrication of self-ordered porous alumina via etidronic
acid anodizing and structural color generation from submicrometer-scale dimple array. Electrochim. Acta
2015, 156, 235–243. [CrossRef]
36. Ozel, T.; Bourret, G.R.; Mirkin, C.A. Coaxial lithography. Nat. Nanotechnol. 2015, 10, 319–324. [CrossRef]
37. Yanagishita, T.; Masuda, H. High-throughput fabrication process for highly ordered through-hole porous
alumina membranes using two-layer anodization. Electrochim. Acta 2015, 184, 80–85. [CrossRef]
38. Jha, H.; Kikuchi, T.; Sakairi, M.; Takahashi, H. Area-selective microscale metallization on porous anodic
oxide film of aluminium. Electrochem. Commun. 2007, 9, 1596–1601. [CrossRef]
Materials 2019, 12, 3497 12 of 12

39. Kondo, T.; Matsumoto, F.; Nishio, K.; Masuda, H. Surface-enhanced Raman scattering on ordered gold
nanodot arrays prepared from anodic porous alumina mask. Chem. Lett. 2008, 37, 466–467. [CrossRef]
40. Jha, H.; Kikuchi, T.; Sakairi, M.; Takahashi, H. Synthesis of aluminum oxy-hydroxide nanofibers from porous
anodic alumina. Nanotechnology 2008, 19, 395603. [CrossRef]
41. Kashi, M.A.; Ramazani, A.; Abbasian, H.; Khayyatian, A. Capacitive humidity sensors based on large
diameter porous alumina prepared by high current anodization. Sens. Actuators 2012, 174, 69–74. [CrossRef]
42. Kondo, T.; Miyazaki, H.; Yanagishita, T.; Masuda, H. Anodic porous alumina with elliptical apertures.
Electrochem. Commun. 2018, 96, 61–65. [CrossRef]
43. Abbasimofrad, S.; Kashi, M.A.; Noormohammadi, M.; Ramazani, A. Tuning the optical properties of
nanoporous anodic alumina photonic crystals by control of allowed voltage range via mixed acid concentration.
J. Phys. Chem. Solids 2018, 118, 221–231. [CrossRef]
44. Kim, Y.; Lee, S.; Cho, H.; Park, B.; Kim, D.; Hwang, W. Robust superhydrophilic/hydrophobic surface
based on self-aggregated Al2 O3 nanowires by single-step anodization and self-assembly method. ACS Appl.
Mater. Interfaces 2012, 4, 5074–5078. [CrossRef]
45. Jeong, C.; Choi, C.H. Single-step direct fabrication of pillar-on-pore hybrid nanostructures in anodizing
aluminum for superior superhydrophobic efficiency. ACS Appl. Mater. Interfaces 2012, 4, 842–848. [CrossRef]
46. Kikuchi, T.; Nishinaga, O.; Nakajima, D.; Kawashima, J.; Natsui, S.; Sakaguchi, N.; Suzuki, R.O. Ultra-high
density single nanometer-scale anodic alumina nanofibers fabricated by pyrophosphoric acid anodizing.
Sci. Rep. 2014, 4, 7411. [CrossRef]
47. Nakajima, D.; Kikuchi, T.; Natsui, S.; Sakaguchi, N.; Suzuki, R.O. Fabrication of a novel aluminum surface
covered by numerous high-aspect-ratio anodic alumina nanofibers. Appl. Surf. Sci. 2015, 356, 54–62. [CrossRef]
48. Nakajima, D.; Kikuchi, T.; Natsui, S.; Suzuki, R.O. Highly ordered anodic alumina nanofibers fabricated via
two distinct anodizing processes. ECS Electrochem. Lett. 2015, 4, H14–H17. [CrossRef]
49. Nakajima, D.; Kikuchi, T.; Natsui, S.; Suzuki, R.O. Mirror-finished superhydrophobic aluminum surfaces
modified by anodic alumina nanofibers and self-assembled monolayers. Appl. Surf. Sci. 2018, 440, 506–513.
[CrossRef]
50. Nakajima, D.; Kikuchi, T.; Natsui, S.; Suzuki, R.O. Advancing and receding contact angle investigations for
highly sticky and slippery aluminum surfaces fabricated from nanostructured anodic oxide. RSC Adv. 2018,
8, 37315–37323. [CrossRef]
51. Nakajima, D.; Kikuchi, T.; Natsui, S.; Suzuki, R.O. Superhydrophilicity of a nanofiber-covered aluminum
surface fabricated via pyrophosphoric acid anodizing. Appl. Surf. Sci. 2016, 389, 173–180. [CrossRef]
52. Kondo, R.; Nakajima, D.; Kikuchi, T.; Natsui, S.; Suzuki, R.O. Superhydrophilic and superhydrophobic
aluminum alloys fabricated via pyrophosphoric acid anodizing and fluorinated SAM modification.
J. Alloy. Compd. 2017, 725, 379–387. [CrossRef]
53. Peng, R.; Yang, W.; Fu, L.; Zhu, J.; Li, D.; Zhou, L. Superhydrophilicity of novel anodic alumina nanofibers
films and their formation mechanism. Mater. Res. Express 2017, 4, 065007. [CrossRef]
54. Shimizu, K.; Furneaux, R.C.; Thompson, G.E.; Wood, G.C.; Gotoh, A.; Kobayashi, K. On the nature of “easy
paths” for the diffusion of oxygen in thermal oxide films on aluminum. Oxid. Met. 1991, 35, 427–439. [CrossRef]
55. Hill, J.J.; Haller, K.; Gelfand, B.; Ziegler, K.J. Eliminating capillary coalescence of nanowire arrays with
applied electric fields. ACS Appl. Mater. Interfaces 2010, 2, 1992–1998. [CrossRef] [PubMed]
56. Murakami, D.; Jinnai, H.; Takahara, A. Wetting transition from the Cassie–Baxter state to the Wenzel state on
textured polymer surfaces. Langmuir 2014, 30, 2061–2067. [CrossRef]
57. Konovalov, V.V.; Zangari, G.; Metzger, R.M. Highly ordered nanotopographies on electropolished aluminum
single crystals. Chem. Mater. 1999, 11, 1949–1951. [CrossRef]
58. Ye, J.; Yin, Q.; Zhou, Y. Superhydrophilicity of anodic aluminum oxide film: From “honeycomb” to “bird’s
nest”. Thin Solid Film. 2009, 517, 6012–6015. [CrossRef]

© 2019 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).