Applied Surface Science 351 (2015) 1161–1168

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

A two-step anodic method to fabricate self-organised nanopore arrays

on stainless steel
Bowei Zhang a,b , Hongwei Ni a,b,∗ , Rongsheng Chen a,b , Weiting Zhan a,b , Chao Zhang a,b ,
Rui Lei a,b , Yaxin Zha a,b
a
The State Key Laboratory of Refractories and Metallurgy, Wuhan University of Science and Technology, Wuhan 430081, China
b
Key Laboratory for Ferrous Metallurgy and Resource Utilization of Ministry of Education, Wuhan University of Science and Technology,
Wuhan 430081, China

a r t i c l e i n f o a b s t r a c t

Article history: We report a simple two-step anodic method to fabricate self-organized nanopore arrays on 316L stainless
Received 18 December 2014 steel surface, with the initial anodization in perchloric acid-based electrolyte followed by the second
Received in revised form 29 May 2015 anodization in sodium dihydrogen phosphate-based electrolyte. The morphology and chemical analysis
Accepted 16 June 2015
of anodic overlayers after the first and second anodizations were explored by AFM, SEM and XPS. The
Available online 22 June 2015
influence of various applied voltages, current density, various anodization times and temperatures on
nanoscaled morphology was investigated in the process of the second anodizing step. As a result, the
Keywords:
dimension of the nanopores depends linearly on the anodization time and was controlled by the applied
Two-step anodic method
Self-organization
voltage and current density in a certain range. At the premise of no appreciable expansion in the mean
Nanopore arrays pore size after the second step in contrast to the initial pores, the depth of nanopores could reach seven
Stainless steel times of the previous depth of 10 nm. The analysis of XPS spectrum performed on the nanostructure,
the energy shifts of Cr 2p3/2 , Fe 2p3/2 , O 1s, and Ni 2p3/2 levels showed that principal constituents of the
anodic overlayer are chromium and iron components. No metallic Fe, Cr, and Ni peaks were detected
on the surface after the second anodization. The depth of nanopores was roughly in agreement with the
thickness estimations obtained from depth profiling data and different chemical compositions that exist
at different depths of even a thin anodic overlayer.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction Some performances of nanostructured materials were influ-

In recent years, tremendous scientific interest has been focused
on fabrication of nanostructured materials due to their remarkable
properties which make them very useful for many technological
applications e.g., in magnetic, electronic, photonic, sensing devices
and biomaterials [1–6]. For example, nanoporous materials with
high surface area and pore volume have been used for implantable
drug delivery systems [7–9]. Another example was shown by our
research, i.e., the nanopore arrays on stainless steel substrate as the
template for 3D graphene platelets possesses high electrochem-
ical activity for the determination of uric acid, ascorbic acid and
dopamine [10].
∗ Corresponding author at: The State Key Laboratory of Refractories and Metal-
lurgy, Wuhan University of Science and Technology, Wuhan 430081, China.
Tel.: +86 27 68862856; fax: +86 27 68862811.
E-mail address: nihongwei@wust.edu.cn (H. Ni).
enced strongly by structural parameters, such as pore size, depth
and interpore distance [11,12]. Thus, to facilitate various prac-
tical applications, fabrication of highly ordered and controllable
nanostructured materials is an essential task. Considerable sci-
entific attention has been paid on developing new, simple and
unexpensive methods of synthesis of controllable nanostructured
materials.
Due to the excellent corrosion resistance and mechanical prop-
erties, 316L stainless steel has been extensively employed in
cardiovascular stents, orthopedic implants, and spinal fixation
devices [13–15]. However, the poor adhesion of the high polish
metal surface cannot match the requirement of long-term stability
of an artificial device to modulate cell-substrate interactions. Func-
tionalization of the material surface by applying defined micro-
and nanostructures has been explored to improve osseointegra-
tion and modulation of cellular activity. For example, the nanopore
surfaces fabricated on 316L stainless steel substrates are able
to influence the expression of integrin and direct cell behaviors
such as cell migration, proliferation and focal adhesion formation

http://dx.doi.org/10.1016/j.apsusc.2015.06.083
0169-4332/© 2015 Elsevier B.V. All rights reserved.
1162 B. Zhang et al. / Applied Surface Science 351 (2015) 1161–1168
[11]. The mouse pre-osteoblasts cell attachment, proliferation and
prominent proteins can be modulated on nanometer-sized grains
structure on the 316L stainless steel surface [16].
In the case of stainless steel, few researches have been devoted
to the surface of stainless steel after its anodization. Vignal et al.
[17] have reported that brightening of AISI 316L stainless steel
in perchloric acid-based electrolytes can form a quasi-hexagonal
arrangement of 10 nm depth pores at the sample surface. Martin
et al. [18] have shown the chemical and periodic nanostructures of
the films growing during the electropolishing treatment of 304L
stainless steel and duplex stainless steel (Uranus 50). Zhan and
coworkers [19] have reported that during the process of the direct
anodization after the achievement of a microscopically smooth sur-
face by electropolishing irregular and undesired patterns appear on
the surface of 316L stainless steel.
In spite of recent progress, some difficulties still exist in con-
trolling important structural parameters. Fabrication of regular and
deep pores on stainless steel requires new anodic methods con-
trast to traditional anodization. From the technical point of view, to
remedy these problems on stainless steel, we designed a two-step
anodic method: the use of perchloric acid-based electrolyte fol-
lowed by dihydrogen phosphate-based electrolyte to form a deeper
self-organized nanopore arrays on 316L stainless steel substrate.
The results of studies on the morphology and chemical analysis
of the anodic overlayers after the first and second anodization are
specified. Furthermore, the influence of several parameters such
as current density, applied voltage and anodization time on the
morphology of the surface patterns will be discussed.
2. Experimental methods
The 316L stainless steel plates (Goodfellow, 0.015 wt.% C,
16–18 wt.% Cr, 10–14 wt.% Ni, 0.3 wt.% Mo, and Fe balance) were cut
into 10 mm × 10 mm × 1 mm size. All the specimens were mechan-
ically polished with successive grades of abrasive papers (grade
1000, 1500 and 2000) and smoothed with diamond pastes (from3.5
to 0.25 ␮m). After the above two processes, they were rinsed with
ethanol and double-distilled water under ultrasonic for 10 min. The
initial anodization of the mechanically polished specimens was
performed in ethylene glycol (EG; 99.8% and anhydrous) solution
containing 5 vol% perchloric acid (HClO4 ; 70%) at a constant voltage
of 40–50 V for 10 min. After the first anodization, the foil was then
anodized in 0.3 M sodium dihydrogen phosphate solution with the
applied voltage ranged from 5 V to 45 V. After each anodization, the
samples were ultrasonically cleaned in acetone, ethanol, and dis-
tilled water and dried in air. Anodization was conducted in a stirred
two-electrode electrochemical cell by a direct current power sup-
ply (IT6154, ITECH, Nanjing, China). The electrolytic solution was
stirred by a rotating magnet. Samples (the area of anodic electrode
dipped in the electrolyte was about 1 cm2 ) were positioned verti-
cally in front of the counter electrode, which was a 9 cm2 graphite
cathode, and the distance between both electrodes was kept at
about 6 cm. The electrolytic temperature was maintained between
0 and 10 ◦ C in an ice/water bath.
The morphology of the anodic films was characterized by field
emission SEM (FE-SEM, FEI Nova 400 Nano) with an accelerat-
ing voltage of 20 kV. The micro images of the anodic films were
obtained in “tapping mode” by atomic force microscope (AFM)
Agilent 5500 (Agilent Technologies, Chandler, AZ) with a scan-
ning range of 5 ␮m. X-ray photoelectron spectroscopy (XPS, VG
Multilab 2000, Thermo Electron Corp., America) experiments were
carried out using a VG Escalab MKII spectrometer with a non-
monochromatic Al K␣ X-ray source (1486.6 eV) to investigate the
chemical composition of the anodic films on stainless steel surface,
calibrated by C 1s at 284.5 eV. The thicknesses of the films were
determined by argon-ion sputtering for different time intervals.
The reference sputtering rate was 0.78 nm/s. An inductively cou-
pled plasma emission spectrometer (ICP-AES, IRIS Advantage ER/S,
Thermo Elemental, USA) was employed to determine the compo-
nents of the precipitate formed during the second anodization, the
precipitate was centrifuged out from the electrolyte and dried in
the air.
3. Results and discussion
3.1. 316L stainless steel surface morphology after the first
anodizaton
Surface morphology after the initial anodization was character-
ized using SEM and AFM. The surface appeared smooth without
defects and exhibited a quasi-periodic arrangement of pores. The
pores indeed self-organize locally in a perfect honeycomb lattice.
As in images of AFM and SEM in Fig. 1, the applied voltages are
40 V (Fig. 1a) and 50 V (Fig. 1b), respectively, which gives rise to the
nanopore’s mean dimensions of 85 nm and 120 nm, respectively.
They have a depth of about 10 nm (Fig. 1c and d). The hexagonal
pattern is sensitive to the applied voltage and the hexagons size
increases with the rise of applied voltage. Indeed, these results are
similar to those previously reported [17].
Similar to the mechanism of hexagonal pores appears on Al,
the formation of hexagonal structure on stainless steel is due to a
cracking and self-healing of the oxide layer atop preexisting ridges
on the stainless steel surface and that this forms a barrier layer of
nonuniform thickness [20].
3.2. Effects of two-step anodic method on the morphology of 316L
substrate
Evident is the result from the micrographs in Fig. 2a that the
direct anodization after mechanical polish results in an irregular
pattern on the surface of 316L stainless steel. On the other hand,
as shown in Fig. 2b, the two-step anodic method significantly
improves the ordering degree of nanopore arrays compared with
the direct anodization. The observed ordered nanopore arrays
could be attributed to the periodic pore nucleation sites formed by
the first anodization in perchloric acid-based electrolyte. Thus, in
nanoporous stainless steel, surface pretreatment prior to the actual
anodization plays a crucial role in the formation of nanopores,
greatly influencing their size uniformity.
As previously reported about Al and Ti, the formation of a bar-
rier oxide layer or the prior formation of porous film by a different
electrolyte guarantees not only stable anodization but also homo-
geneous growth of self-ordered oxide nanopore arrays. It has been
suggested that as anodization started, pores would start at cracks
and imperfections in the surface, leaving an electric field concentra-
tion below the regions where the oxide film was thinner, because
the thickness of the barrier oxide layer on a 316L stainless steel
surface is nonuniform, and the center of pores is the thinnest layer,
where the resistance is lowest and the electric field is highest. This
leads to a temporarily increased dissolution rate at the bottom of
pores [21,22]. As a consequence, pore nucleation for the porous
surface is easier than the flat ones.
Solution/oxide and oxide/metal interfaces exist in the pore
channel. Field-enhanced oxidation occurs at the metal/oxide inter-
face near the bottom of pore when the oxygen containing ions
transport from electrolyte to the oxide film, along the direction
of the pore growth. At the same time, metal ions migrate from
metal substrate to the solution/oxide interface and dissolve into
the electrolyte [22].
 B. Zhang et al. / Applied Surface Science 351 (2015) 1161–1168 1163

Fig. 1. Morphologies of 316L stainless steel surface after the first anodization at (a) 40 V and (b) 50 V. (c) Profile along the white segment in Fig. 1a and (d) profile along the
white segment in Fig. 1b showing the relief amplitude. The measured depths both are about 10 nm, a value which may depend on the tip shape. Scale bar = 500 nm.

3.3. Morphology of 316L stainless steel surface after the second
anodization
Because of the nanopore diameter’s decrease toward the sub-
strate, it is hard to define accurately the diameter and the wall
thickness of the nanopores. Therefore, we will concentrate on
reporting the influence of the growth parameters on the inner
diameter measured from SEM images and the depth of pores.
We used nanoporous surface which was generated by the ini-
tial anodization to fabricate deeper self-organized nanopores in
0.3 M sodium dihydrogen phosphate-based electrolyte. A perfect
self-organized nanopore arrays were obtained through the second
anodization under suitable conditions. Similar to the first anodiza-
tion results, the distribution of the pores was uniform on the
surface, but the pores are deeper. The domain boundaries are also
shown in Fig. 3, as indicated by the white arrows. The domains grew
by alignments and the mergers of pores were regular at domain
boundaries. Maybe the bottoms of the pores could move around
[22]. As the pores moved and merged, the orientation of adjacent
domains could change gradually, so domains matched each other.
In contrast to the polished 316L stainless steel, no color change
appears on the sample surface after anodization.
For a better understanding of this nanostructured surface, AFM
observations in air have been performed. With the AFM, the mea-
sure may depend on the geometry of the tip and its apex. As
revealed in pictures of SEM (Fig. 4a) and AFM (Fig. 4b), the voltage
applied at the first anodizing step was 40 V after 10 min anodiza-
tion in sodium dihydrogen phosphate-based electrolyte at 15 V. The

Fig. 2. SEM images of 316L surface after two different treatments: (a) the direct anodization after mechanical polish and (b) the nanopore arrays that formed through
two-step anodic method. The inset in (a) is the image of mechanically polished surface. Samples were anodized at 25 V.
1164 B. Zhang et al. / Applied Surface Science 351 (2015) 1161–1168
Fig. 3. Domain boundaries and pore merging along the domain boundaries. The
white arrows show the merging of pores.
measured mean dimension of pores was about 90 nm and the depth
was of 30–40 nm (Fig. 4c), which is three to four times that of initial
pores. Self-organized pores were shown in Fig. 4d and e that was
obtained at 20 V potential for 15 min after the initial achievement
of a 120 nm nanoporous surface at 50 V in perchloric acid-based
electrolyte. The mean size of nanopores is about 130 nm and they
are about 70–80 nm deep (Fig. 4f), which is about seven to eight
times that of the initial depth of the pores. Obviously, there is no
appreciable difference between the pore dimensions after the sec-
ond anodization and the initial one. The measured thickness of the
walls is 20–50 nm without correction due to the tip shape [18]. As
shown in SEM (Fig. 4a and d) and AFM (Fig. 4b and e) images, all the
white spots can be associated with defects in the nanopore arrays.
3.4. Chemical analysis of the nanostructure and the mechanisms
of anodization
Fig. 5a and b revealed some qualitative information on the com-
position depth profiles for 316L stainless steel after the first step
Fig. 4. (a) SEM and (b) AFM images of stainless steel anodized at 15 V. (c) Profile along the white segment in Fig. 4b showing the relief amplitude, the measured depth is
about 30–40 nm. (d) SEM and (e) AFM images show the surface morphology anodized at 20 V for 15 min after the first anodization at 50 V. (f) Profile along the white segment
in Fig. 4e showing the relief amplitude, the measured depth is about 70–80 nm, a value which may depend on the tip shape. Scale bar = 500 nm.
of anodization at 40 V and the second step at 20 V for 15 min. The
profiles present the relative concentrations of Cr, Fe, O, and Ni. The
precise stoichiometry of the oxide cannot be determined due to the
ion-sputtering-induced effects, such as the reduction of the oxi-
dation state and the influence of nanostructured morphology of
the surface [18,23]. Oxygen is enhanced toward the outer regions,
where the signals from Fe species are increased. As the depth ranges
from the surface to 15 s (∼10 nm) and 80 s (∼60 nm), the XPS quan-
titative analysis shows that the content of O element is nearly zero
compared with about 52 at% and 78 at% of the surface. Obviously,
the O fraction in the second anodized sample was higher than the
initial surface. In the first anodized sample, the Cr fraction was
slightly decreased. In contrast, the Cr fraction was slightly increased
in the second anodized sample.
Fig. S1 showed the overview XPS spectra of 316L stainless steel
surfaces after mechanical polishing, the first anodization, and the
second anodization, respectively. The peaks of Fe 2p, Cr 2p, and Ni
2p are obvious on the bare 316L stainless steel surface. In contrast
with bare 316L flat, the intensity of O 1s signal increases, Cr 2p peak
is almost consistent, and Fe, Ni peaks decreases on the first anodized
sample surface. After the second anodization, O 1s signal increases
greatly, while the Cr, Ni peaks are almost completely vanished from
the sample surface.
The high-resolution spectra of Cr 2p3/2 , Fe 2p3/2 and O 1s at dif-
ferent depths from the surface were all analyzed in Fig. 5. As shown
in Fig. 5c, e and g, the spectra of Cr 2p3/2 , Fe 2p3/2 and O 1s for the first
anodized film reveals the presence of metallic Cr (573.6 eV), Cr2 O3
(576.1 eV), Fe (706.3 eV), FeO (708.4 eV) and Fe2 O3 (710.9 eV) on the
surface [24–26]. The spectrum shows visible changes in chemical
composition of Cr and Fe after 10 s or 20 s etching [27].
The Cr 2p3/2 , Fe 2p3/2 and O 1s spectrum obtained from the sec-
ond anodized overlayer was revealed in Fig. 5d, f and h. For Cr,
Fe, no metallic Fe and Cr peaks were detected at the surface while
another peak of FeOOH (711.8 eV) emerges. The peaks of metallic
Fe (706.4 eV), FeO (708.4 eV), Fe2 O3 (710.9 eV) were detected after
45 s etching [27–29]. The Cr 2p3/2 spectra show two types of bonds,
such as metallic Cr and Cr2 O3 . After 90 s etching, the main peak in Cr
2p3/2 can be separated into two possible peaks. As shown in Fig. 5f,
similar case is also found in the spectra of Fe, which are related to
metallic Fe and FeO and two kinds of Fe oxide components appear
 B. Zhang et al. / Applied Surface Science 351 (2015) 1161–1168 1165

Fig. 5. (a) The XPS depth profiles and high resolution XPS spectra of (c) Cr 2p3/2 , (e) Fe 2p3/2 , and (g) O 1s peaks collected from the anodic films that formed after the first
anodization at 50 V for 10 min. (b) The XPS depth profiles and detailed XPS spectra of (d) Cr 2p3/2 , (f) Fe 2p3/2 , and (h) O 1s peaks collected from the anodic films that formed
after the second anodization at 20 V for 15 min, the first anodization was performed at 50 V for 10 min.

in Fe 2p3/2 peaks after 45 s etching. These two components corre- composition exist at different depths of even a thin anodic overlayer
spond to Fe oxide stoichiometry changing with depth from FeOOH [31].
to FeO and Fe2 O3 . As showed in Fig. S2, nickel existing in different depth of the
Fig. 5g and h displays the detailed XPS spectra of O 1s generated anodic films that formed during the process of the first or the second
from anodic films that formed during the first and second anodizing anodization in the form of metallic nickel and NiO. No metallic Ni
steps. The O 1s spectra show two types of bonds in Fig. 5g, such as 2p peak was detected on the surface after the second anodization
O2− in oxide species and OH− in hydroxide species. Fig. 5b shows [30]. During the first step of anodization, the formation of oxides is
the spectra of O 1s fitted by OH− in hydroxide species on the surface. described as the following reactions [32]:
After 45 s or 90 s etching, two peaks of O 1s correspond to O2− in
oxide species at binding energies of 530.2 eV and OH− in hydroxide 2H2 O → O2 + 4H+ + 4e−
species at binding energies of 531.5 eV, respectively [30]. It appears
that the nanostructured surface was consistent with a mixture of y
Cr and Fe components. This may suggest that different chemical xM(Fe, Cr, Ni) + O2 → Mx Oy (FeO, Fe2 O3 , Cr2 O3 , NiO)
2
1166 B. Zhang et al. / Applied Surface Science 351 (2015) 1161–1168

Fig. 6. (a) Examples of j–t curves characteristic of nanopores that formed and morphology evolution of the anodized 316L stainless steel surface upon the experimental
conditions. (b) Relationship between the applied voltages and pore dimensions during the second anodizing step after the first anodization at 40 V and 50 V, respectively.
(c) Inner dimension-time anodization curve during the second anodizing step. The dimension increases linearly with bias voltage in a certain range. Scale bar = 500 nm. The
error bars represent the standard deviations from the mean of each measured quantity.

The anodization process was further investigated by determina-

tion of the metal ions in the electrolyte after the first anodization, The dissolved metallic cations (Cr3+ , Ni2+ ) can react with hydrogen
as shown in Fig. S3. The color of the electrolyte turned to brown phosphate, and form phosphates [36,37]:
yellow after the first step of anodization, indicating the existence Cr3+ + 2HPO2− −
4 → [Cr(HPO4 )2 ]
of Fe3+ in the electrolyte. The results suggest that the dissolution of
these metal oxides including Fe2 O3 , NiO, and Cr2 O3 , appears during Ni2+ + 2HPO2−
4 → [Ni(HPO4 )2 ]
2−

the first step of anodization [18,33–35]:

The precipitate should be attributed to the hydrolysis of Fe3+ in
Fe2 O3 + 6H+ → 2Fe3+ + 3H2 O the solution of sodium dihydrogen phosphate [36]:

Cr2 O3 + 6H+ → 2Cr3+ + 3H2 O Fe3+ + 2H2 O → FeOOH + 3H+

NiO + 2H+ → Ni2+ + H2 O

The enrichment of Cr atoms in the anodic layer is attributed to
the less proportion of Cr atoms in the solution than that in the bulk
material of 316L stainless steel.
The formation of the nanostructures during the second anodiza-
tion is described as the following reactions [32]:
2H2 O → O2 + 4H+ + 4e−
y of nanostructure. The applied voltage was regulated from 5 V up to
xM(Fe, Cr, Ni) + O2 → Mx Oy (FeO, Fe2 O3 , Cr2 O3 , NiO)
2
According to the chemical composition of precipitate after the
second anodization step (Fig. S4), the precipitate was mainly com-
posed of iron compound. The trace amount of Cr and Ni in the
precipitate should be ascribed to the absorption on the precipitate.
3.5. Nanostructure growth parameters
The morphology of the nanostructured surface is influenced by
the physico-chemical conditions of the second anodizing process
[38]. Besides the applied voltage, the current density and temper-
ature have been investigated. By changing the temperature of the
electrolyte from 0 ◦ C up to 10 ◦ C, no change in the morphology of
the nanostructured surface was noticed. Further experiments have
been performed to investigate the influence of anodizing voltage
and the current density changes on the formation and morphology
45 V. Average values of the current density recorded during steady-
state growth of porous anodic 316L stainless steel in 0.3 M sodium
dihydrogen phosphate solution show a dependency on the anodiz-
ing potential independently of the electrolyte temperature. The
reaction was strongly affected by the current density. Fig. 6a depicts
the influence of applied voltages on the current density and the
 B. Zhang et al. / Applied Surface Science 351 (2015) 1161–1168
morphology of nanostructures in the second anodization process.
The current density increased with the voltage. At 5 V the current
was very steady; the morphology has almost no obvious changes
compared with the first anodization. At 45 V the current density
showed large fluctuations and the interpore walls are etched during
the anodization process. Following the applied voltages increase in
range of 5–45 V, the chemical dissolution rate at the layer/solution
interface increases. Local temperature may rise and rates of heat
dissipation may become nonuniform, thus causing fluctuations in
the anodization current density [22]. As shown in Fig. 6b, it was
found that the applied voltage has a strong influence on the mor-
phology of the surface, and that the pore dimension increases with
the potential in a certain range.
Surprisingly, as we can see from Fig. 6c, the dimension of pore
increases linearly with the second anodization time in the process
of the second step at 20 V, the first step was performed at 50 V
in perchloric acid-based electrolyte. In the range of 5–15 min, the
dimension of pores increases from about 90 nm to 130 nm. How-
ever, the walls were etching when the anodization time amounts
to 20 min. This fact is enough to demonstrate that these parame-
ters have significant effects on the achieved nanostructure on 316L
stainless steel surface.
4. Conclusions
It was found that a porous anodic film that formed on initial
anodized 316L stainless steel before the second anodization pro-
cess can effectively suppress undesired surface events, and that the
initial pores left in the first anodized surface actually guided pore
nucleation during the second step. The two-step anodic method
significantly improves the ordering degree of nanopore arrays com-
pared to the direct anodization after mechanically polished surface.
In the second anodization, our results indicated that a linearly rela-
tionship exists between the mean inner dimension and anodization
time, and that the surface morphology is also influenced by the
applied voltage and current density in a certain range. At the
premise of no significant diameter expansion in contrast to that
of the initial pores, we found that the measured mean depth after
the second anodization is about three to seven times of the initial
pores; this is also a clear improvement over previous syntheses.
The analysis of shifts of Cr 2p 3/2 , Fe 2p 3/2 , O 1s, and Ni 2p 3/2
levels in XPS spectra suggested that the depth of nanopores were
roughly consistent with thickness estimations obtained from depth
profiling data, and that different chemical composition of Cr and Fe
exist at different depths of even a thin oxide layer. At the same
time, the possible mechanisms of the anodization were proposed
by us. We believe that the present results may facilitate the further
investigations of other porous oxides.
Acknowledgement
This work was supported by the National Natural Science Foun-
dation of China (No. 51471122, No. 51171133) and the Program for
New Century Excellent Talents in University (No. NCET-07-0650).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.apsusc.2015.06.
083
References
[1] V. Balzani, Nanoscience and nanotechnology: the bottom-up construction of
molecular devices and machines, Pure Appl. Chem. 80 (2008) 1631–1650.
1167
[2] D. Ho, D. Garcia, C.M. Ho, Nanomanufacturing and characterization modalities
for bio-nano-informatics systems, J. Nanosci. Nanotechnol. 6 (2006) 875–891.
[3] D. Grieshaber, R. MacKenzie, J. Voros, E. Reimhult, Electrochemical biosensors
– sensor principles and architectures, Sensors 8 (2008) 1400–1458.
[4] X. Li, Strain induced semiconductor nanotubes: from formation process to
device applications, J. Phys. D: Appl. Phys. 41 (2008) 193001–193013.
[5] J.B. Dai, J.K. Tang, S.T. Hsu, W. Pan, Magnetic nanostructures and materi-
als in magnetic random access memory, J. Nanosci. Nanotechnol. 2 (2002)
281–291.
[6] S. Oh, K.S. Brammer, Y.S. Julie Li, D. Teng, A.J. Engler, S. Chien, S. Jin, Stem cell
fate dictated solely by altered nanotube dimension, Proc. Natl. Acad. Sci. U. S.
A. 106 (2009) 2130–2135.
[7] D. Losic, S. Simovic, Self-ordered nanopore and nanotube platforms for drug
delivery applications, Exp. Opin. Drug Deliv. 6 (2009) 1363–1381.
[8] E.A. Jackson, M.A. Hillmyer, Nanoporous membranes derived from block
copolymers: from drug delivery to water filtration, ACS Nano 4 (2010)
3548–3553.
[9] E. Gultepe, D. Nagesha, S. Sridhar, M. Amiji, Nanoporous inorganic membranes
or coatings for sustained drug delivery in implantable devices, Adv. Drug Deliv.
Rev. 62 (2010) 305–315.
[10] Z. Wang, H. Ni, R. Chen, W. Zhan, C. Zhang, R. Lei, B. Zhang, Enhanced perfor-
mance of multilayer graphene platelet film via three dimensional configuration
with efficient exposure of graphitic edge planes, Electrochem. Commun. 47
(2014) 75–79.
[11] H.-A. Pan, J.-Y. Liang, Y.-C. Hung, C.-H. Lee, J.-C. Chiou, G.S. Huang, The spa-
tial and temporal control of cell migration by nanoporous surfaces through
the regulation of ERK and integrins in fibroblasts, Biomaterials 34 (2013)
841–853.
[12] S.H. Chung, S.J. Son, J. Min, The nanostructure effect on the adhesion and
growth rates of epithelial cells with well-defined nanoporous alumina sub-
strates, Nanotechnology 21 (2010) 125104–125111.
[13] L. Cardenas, J. MacLeod, J. Lipton-Duffin, D.G. Seifu, F. Popescu, M. Siaj, D. Man-
tovani, F. Rosei, Reduced graphene oxide growth on 316L stainless steel for
medical applications, Nanoscale 6 (2014) 8664–8670.
[14] P. Elter, F. Sickel, A. Ewald, Nanoscaled periodic surface structures of medi-
cal stainless steel and their effect on osteoblast cells, Acta Biomater. 5 (2009)
1468–1473.
[15] A. Latifi, M. Imani, M.T. Khorasani, M.D. Joupari, Electrochemical and chem-
ical methods for improving surface characteristics of 316L stainless steel for
biomedical applications, Surf. Coat. Technol. 221 (2013) 1–12.
[16] R.D.K. Misra, C. Nune, T.C. Pesacreta, M.C. Somani, L.P. Karjalainen, Understand-
ing the impact of grain structure in austenitic stainless steel from a nanograined
regime to a coarse-grained regime on osteoblast functions using a novel metal
deformation–annealing sequence, Acta Biomater. 9 (2013) 6245–6258.
[17] V. Vignal, J.C. Roux, S. Flandrois, A. Fevrier, Nanoscopic studies of stainless steel
electropolishing, Corros. Sci. 42 (2000) 1041–1053.
[18] F. Martin, D. Del Frari, J. Coustya, C. Bataillon, Self-organisation of nanoscaled
pores in anodic oxide overlayer on stainless steels, Electrochim. Acta 54 (2009)
3086–3091.
[19] W.T. Zhan, H.W. Ni, R.S. Chen, Z.Y. Wang, Y.W. Li, J.H. Li, One-step hydrothermal
preparation of TiO2 /WO3 nanocomposite films on anodized stainless steel for
photocatalytic degradation of organic pollutants, Thin Solid Films 548 (2013)
299–305.
[20] K. Shimizu, K. Kobayashi, G.E. Thompson, Development of porous anodic films
on aluminium, Philos. Mag. A 66 (1992) 643–652.
[21] W. Lee, K. Nielsch, U. Gösele, Self-ordering behavior of nanoporous anodic alu-
minum oxide (AAO) in malonic acid anodization, Nanotechnology 18 (2007)
475713–475721.
[22] F. Li, L. Zhang, R.M. Metzger, On the growth of highly ordered pores in anodized
aluminum oxide, Chem. Mater. 10 (1998) 2470–2480.
[23] W.H. Hocking, F.W. Stanchell, E. McAlpine, D.H. Lister, Mechanisms of corro-
sion of stellite-6 in lithiated high temperature water, Corros. Sci. 25 (1985)
531–557.
[24] A. Kocijan, Č. Donik, M. Jenko, Electrochemical and XPS studies of the passive
film formed on stainless steels in borate buffer and chloride solutions, Corros.
Sci. 49 (2007) 2083–2098.
[25] S.J. Yuan, S.O. Pehkonen, Microbiologically influenced corrosion of 304 stain-
less steel by aerobic Pseudomonas NCIMB 2021 bacteria: AFM and XPS study,
Colloids Surf. B: Biointerfaces 59 (2007) 87–99.
[26] J. Xu, X. Wu, E.-H. Han, The evolution of electrochemical behaviour and oxide
film properties of 304 stainless steel in high temperature aqueous environment,
Electrochim. Acta 71 (2012) 219–226.
[27] A.L. Neal, K. Lowe, T.L. Daulton, J. Jones-Meehan, B.J. Little, Oxidation state of
chromium associated with cell surfaces of Shewanella oneidensis during chro-
mate reduction, Appl. Surf. Sci. 202 (2002) 150–159.
[28] C.Q. Cheng, J. Zhao, T.S. Cao, Q.Q. Fu, M.K. Lei, D.W. Deng, Facile chromaticity
approach for the inspection of passive films on austenitic stainless steel, Corros.
Sci. 70 (2013) 235–242.
[29] W. Fredriksson, K. Edström, XPS study of duplex stainless steel as a possible
current collector in a Li-ion battery, Electrochim. Acta 79 (2012) 82–94.
[30] X. Cheng, Z. Feng, C. Li, C. Dong, X. Li, Investigation of oxide film formation on
316L stainless steel in high-temperature aqueous environments, Electrochim.
Acta 56 (2011) 5860–5865.
[31] C. Donik, D. Mandrino, M. Jenko, Depth profiling and angular dependent XPS
analysis of ultra thin oxide film on duplex stainless steel, Vacuum 84 (2010)
1266–1269.
1168 B. Zhang et al. / Applied Surface Science 351 (2015) 1161–1168
[32] M. Paulose, K. Shankar, S. Yoriya, H.E. Prakasam, O.K. Varghese, G.K. Mor, T.A.
Latempa, A. Fitzgerald, C.A. Grimes, Anodic growth of highly ordered TiO2 nano-
tube arrays to 134 ␮m in length, J. Phys. Chem. B 110 (2006) 16179–16184.
[33] A.V. Kuzin, I.G. Gorichev, Y.A. Lainer, Stimulating effect of phosphate ions on the
dissolution kinetics of iron oxides in an acidic medium, Russ. Metall. (Metally)
9 (2013) 652–657.
[34] T. Grygar, P. Bezdička, Electrochemical dissolution of CrIII and CrIV oxides, J.
Solid State Electrochem. 3 (1998) 31–38.
[35] E.J. Underwood, J.F. Filmer, Enzootic Marasmus: the determination of the bio-
logically potent element (cobalt) in limonite, Aust. Vet. J. 11 (1935) 84–92.
[36] L. Fu, H. Yu, Y. Li, C. Zhang, X. Wang, Z. Shao, B. Yia, Ethylene glycol adjusted
nanorod hematite film for active photoelectrochemical water splitting, Phys.
Chem. Chem. Phys. 16 (2014) 4284–4290.
[37] B.F. Alfonso, C. Piqué, C. Trobajo, J.R. García, E. Kampert, U. Zeitler, J. Rodríguez
Fernández, M.T. Fernández-Díaz, J.A. Blanco, Double magnetic phase transition
in ND4 Fe(DPO4 )2 and NH4 Fe(HPO4 )2 , Phys. Rev. B 82 (2010) 1–10.
[38] S. Yoriya, W. Kittimeteeworakul, N. Punprasert, Effect of anodization parame-
ters on morphologies of TiO2 nanotube arrays and their surface properties, J.
Chem. Chem. Eng. 6 (2012) 686–691.