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Electrochimica Acta 51 (2006) 45894595

Mechanism of one-step voltage pulse detachment of porous


anodic alumina membranes
J.H. Yuan, W. Chen, R.J. Hui, Y.L. Hu, X.H. Xia
Key Laboratory of Analytical Chemistry for Life Science, Department of Chemistry, Nanjing University, Nanjing 210093, China
Received 7 September 2005; received in revised form 18 December 2005; accepted 22 December 2005
Available online 15 February 2006

Abstract
The mechanism for one-step detachment of porous anodic alumina (PAA) membranes by using an electrochemical voltage pulse technique
is systematically studied. Electrochemical oxidation of pretreated aluminum foil results in a thin oxide layer called barrier layer alumina (BLA)
between the formed PAA and the Al substrate. Achievement of through-hole PAA membranes requires electrolytes of highly concentrated perchloric
acid containing biacetyl and a short detaching pulse voltage of 510 V higher than the film forming potential. The influence of the PAA forming
potential, voltage pulse height (010 V), and the nature of electrolytes on the efficiency of detachment have been systematically investigated. The
successful detachment of the PAA could only be achieved with systems giving appropriate transient current upon application of an optimal voltage
pulse. Based on the experimental results and the electropolishing mechanism of aluminum, a two-step detachment process of PAA freestanding
films is proposed. In this mechanism, the detachment of PAA film from the aluminum substrate upon application of a short voltage pulse is followed
by a pores-opening process. The present mechanism is promising for preparation of freestanding PAA films with various pores sizes, which are
important for nanomaterial synthesis.
2006 Elsevier Ltd. All rights reserved.
Keywords: Porous anodic alumina; Voltage pulse; Detachment; Mechanism; Nanomaterials

1. Introduction
Recent years, porous anodic alumina (PAA) film has attracted
increasing interest because it can be used as template to synthesize ordered nanomaterials [1], such as metal microtubules
[2], magnetic metal wires [3], electrochemically conductive
polymer nanostructrue [4], porous metallic wires [5], semiconductor wires [6] etc. Template-directed synthesis method
has been considered as a promising approach to prepare functional nanotube-template hybrid systems or freestanding nanotubules [7]. In addition, other applications in the field of
electrochemistry [8,9], photonic crystal [10] and biochemical analysis [11] are also reported. In spite of the wide
range of advantages, practical fabrication of the PAA films is
severely hampered by the problem in achieving freestanding and
through-hole membrane [12] although commercial availability
of PAA films limited from Whatman (www.2spi.com). Accord-

Corresponding author. Tel.: +86 25 83597436; fax: +86 25 83597436.


E-mail address: xhxia@nju.edu.cn (X.H. Xia).

0013-4686/$ see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2005.12.044

ingly, many efforts have been made on improving fabrication


procedure of the PAA films according to different demands
[1327].
PAA membrane has a packed array of columnar hexagonal cells with central, uniformly sized holes ranging
from 4 to 400 nm in diameter, pores density as high as
1081011 pores/cm2 , and the film thickness varying from 0.1 to
600 m. PAA is usually prepared using electrochemical anodic
oxidation. When pretreated aluminum is anodically oxidized in
certain multiprotic acids (sulfuric-, phosphoric-, chromic-, and
oxalic-acid), as reported previously [28], porous anodic alumina
(PAA) is formed on a thin barrier layer alumina (BLA) covering
the aluminum substrate. The BLA at the U-shaped pores bottom of the PAA has to be removed to achieve a freestanding and
open-through PAA membrane for its further applications in the
above-mentioned areas. Up to now, three methods of chemical
dissolution [2931], electrochemical method [32], and others
[33,34] have been used to remove the BLA. In the chemical dissolution method which is mostly used, Al base is dissolved by
using heavy metal salts such as HgCl2 or CuCl2 and then, the
thinner barrier layer is removed by using H3 PO4 dilute aqueous

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J.H. Yuan et al. / Electrochimica Acta 51 (2006) 45894595

solution, resulting in a free standing PAA membrane [29]. In this


chemical procedure, contamination from heavy metal ions and
pores widening [30] cannot be avoided, although some surface
protection layers of mixture of nitrocellulose and polyester resin
in ethylacetate, butylacetate, and heptane [18] or nail polish [31]
were used. Due to the thickness of the BLA is determined solely
by the electrolyzing voltage, the barrier-layer can be eliminated
by application of the voltage reduction method [32]. Another
method has been used to remove the barrier layer by reversing
the polarity of the electrodes at the final stage of anodization
[12,33]. Recently, Xu et al. demonstrated a complicated and
expensive method using Ar+ ion milling technique to remove
the protruding U-shaped bottom caps of the PAA, yet the Al
substrate still needs to be previously removed using HgCl2 solution [34]. In fact, an interesting method for detaching the PAA
from the aluminum substrate by using a short voltage pulse in a
high concentrated solution of HClO4 and (CH3 CO)2 O has been
reported [3537]. This simple and rapid method has advantages
over those reported previously [2937]: the pores size can be
fully controlled; the solution of HClO4 and CH3 COCOCH3 in
the detaching process is environmental friendly and free of heavy
metal ions. Consequently, the problems caused by residues of
metal ions do not exist. Recently we reported an improved
method on the fabrication of the freestanding PAA film [20].
Although many advantages of the electric voltage pulse detachment technique over the others, the detaching mechanism is not
yet fully understood.
In this paper, the mechanism of porous anodic alumina (PAA)
membrane detachment was systematically studied by using additional voltage pulses in a solution of HClO4 containing additives.
The influence of the voltage pulse height (010 V) and the nature
of electrolytes on the efficiency of detachment have been systematically investigated by using electrochemical methods and
surface analytical techniques. Based on the experimental results
and the electropolishing mechanism of aluminum, a plausible
detachment mechanism is proposed.
2. Experimental section
2.1. Chemicals and instruments
Aluminum (thickness: 0.1 mm; purity: 99.99%) was obtained
from Xinjiang Zhonghe limited Corporation (Xinjiang, China).
Analytical grade H3 PO4 (85%), HCl (37%), HNO3 (67%)
and NaOH were purchased from Nanjing chemical companies (China). And other chemicals were of analytical grade
(Shanghai, China). Solutions were prepared with distilled water
(18.2 M, Purelab Classic Corp., USA). A house-made power
supply for the preparation of PAA has a voltage range between
0 and +300 V. The applied voltage could be automatically controlled by a personal computer using AD/DA convertor. The
electrolyzing current could be real time monitored and the
corresponding data could be saved in text files. The electrochemical experiments were carried out using two-electrode
configuration. A cleaned aluminum sheet was used as the
anode and another Al foil with large geometric area as the
cathode.

2.2. Pretreatment and anodic oxidization of the aluminum


The detailed fabrication procedure of PAA has been reported
previously [20]. In brief, an aluminum sheet (geometry area ca.
40 mm 40 mm) was degreased in acetone for 12 h and followed
by ultrasonically cleaning with distilled water and then chemically etched in a solution of 3.0 mol/L NaOH. Electrooxidation
was performed at constant voltages (DC) from a vigorously
stirred solution of 0.3 mol/L H2 C2 O4 or other multiprotic acids
(sulfuric or phosphoric acids) under thermostatic condition. Two
steps including a preoxidation and a final oxidation were used
for the preparation of ordered PAA films. In the first step, the
aluminum sheet was anodized at certain voltages (film forming potential) at solution temperature of 20.0 C for 1 h, then
it was immersed in a phosphochromic acid (6% H3 PO4 + 1.8%
H2 CrO4 aqueous solution) at 60 C under ultrasonic condition
for 30 min to remove the preformed PAA film only, leaving the
Al base intact and the formed nucleation centers for the second
step, and followed by thoroughly rinsing with distilled water.
In the second step, the sample was oxidized under the same
conditions as in the first step for 4 h.
2.3. Voltage pulse detaching PAA lm from aluminum
The detachment of the anodic alumina membranes was
tested at a 3 s voltage pulse of 010 V higher than the PAA
forming potential in various detaching solutions. These solutions included HClO4 (70%) and CH3 COCOCH3 (98%) (volume ratio: v/v = 1:1), HClO4 (70%) and (CH3 CO)2 O (98%)
(v/v = 1:1), HClO4 (70%) and polyethylene glycol (PEG)-20000
(4 g/20 mL) (v/v = 1:1), HClO4 (70%) and octane hydroxybenzene polyvinyl chloride aether (TX-10, C34 H62 O11 ) (v/v = 1:1),
HClO4 (70%) and H2 O (v/v = 1:1), HClO4 (70%) and ethanol
(98%) (v/v = 1:1), H3 PO4 (85%) and CH3 COCOCH3 (98%)
(v/v = 1:1), NaOH (3 mol/L) aqueous solution, HCl (30%) aqueous solution, and HNO3 (30%) aqueous solution. After detached
from the aluminum substrate, the freestanding PAA membrane
was then rinsed in distilled water or acetone and distilled water
again.
Electropolishing experiments were performed in a solution
of 70% HClO4 and anhydrous C2 H5 OH (1:4, v/v) for 3 min
and then rinsed ultrasonically in distilled water for XRD and
XPS analysis. X-ray diffraction (XRD) measurements were performed on an X Pert Pr X-ray diffraction (Philips). X-ray photoelectron spectra (XPS) measurements were performed with
ESCALB MK-II equipment of VG Instruments (UK) using nonmonochromatic Mg K 1253.6 radiation. The spectra (Count per
second, Cps versus Energy binding, Eb) were recorded at room
temperature in a vacuum better than 5 109 mbar.
3. Results and discussion
3.1. Achievement of open-through pores by voltage pulse
We have reported on the fabrication of freestanding PAA
using a two-step method [20]. In this method, after the formation
of an ordered PAA film with anodic oxidation of aluminum, a 3 s

J.H. Yuan et al. / Electrochimica Acta 51 (2006) 45894595

Fig. 1. XRD diffraction patterns of a freestanding PAA film (A curve), the


Al substrate (curve B) after the detachment of the PAA by voltage pulse
(3 s and 50 V) in a detaching solution of HClO4 (70%) + CH3 COCOCH3
(98%) (v/v = 1:1) and an electropolished Al (C curve) in a solution of HClO4
(70%) + CH3 CH2 OH (v/v = 1:4) at 15 V for 180 s.

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Fig. 2. X-ray photoelectron spectra in the Al 2p region for a freestanding PAA


film (A) the residue Al base (B) obtained after a voltage pulse (3 s and 50 V) in a
detaching solution of HClO4 (70%) + CH3 COCOCH3 (98%) (v/v = 1:1) and an
electropolished Al (C) in a solution of HClO4 (70%) + CH3 CH2 OH (v/v = 1:4)
at 15 V for 180 s.

electric field-assisted dissolution of aluminum as in the case of


electropolishing of aluminum.
anodic voltage pulse with 10 V higher than the forming voltage
of PAA films was applied in a solution of 70% HClO4 + 98%
CH3 COCOCH3 at 20 C. A complete separation of the membrane from the barrier layer immediately was achieved. Voltage
pulse detachment resulted in freestanding PAA film with all
pores open, although the pore size is slight smaller than that
of the top surface [20,37].
Fig. 1 presents the XRD results of a freestanding PAA film
obtained using the present method (curve A), the Al substrate
after the detachment of the PAA (curve B) and a freshly electropolished aluminum sheet (curve C). The XRD diffraction
pattern of the PAA film shows only a broad peak located in
the 2 angle range of 2030 , indicating that the composition
of the PAA film is consisted of amorphous alumina (curve A)
without contamination of Al. In contrast, the XRD diffraction
patterns of the other two samples only showed strong diffraction
peaks for crystal aluminum. No similar broad diffraction pattern
corresponding to the amorphous alumina is observed, indicating that no electrochemically formed alumina existed on these
samples. These results were supported by XPS measurements
on the above three samples. The Al(2p) region of the spectra is
shown in Fig. 2. Curve A shows the spectrum of a freestanding
PAA film. Only one peak located at 74.4 eV appeared, indicating
the sample only consisting of tripositive Al(III). The other two
curves for the Al substrate (curve B) and a freshly electropolished aluminum sheet (curve C) show the similar features. Two
broad peaks appeared at the binding energy of 71.3 and 74.4 eV
correspond to the aluminum Al(0) and the oxidized aluminum
Al(III), respectively. Integration of the peak areas gives the same
atomic ratio of Al(0) to Al(III) in these two samples. Existence
of trivial Al(III) in the polished aluminum and the aluminum
substrate after the PAA detachment may be due to the oxidation
of the fresh Al surfaces in the air or might come from residual
PAA. These results demonstrate that voltage pulse detachment
of the PAA films should occur at the Al substrate surface via the

3.2. Inuence of pulse voltage on the PAA detachment


Short pulse voltages of 015 V higher than the film forming
potentials were applied to the PAA/Al hybrid anodes formed at
30 or 40 V in a 0.3 M H2 C2 O4 solution. The recorded currenttime profiles during the voltage pulse detachment in a solution
of 70% HClO4 + 98% CH3 COCOCH3 at 20 C are shown in
Fig. 3. When the pulse voltage was the same as the film forming
potential, no significant anodic current transient was observed
(Fig. 3, crosses) and detachment of the PAA film failed. When a
pulse voltage higher than the film forming potential was applied,
a significant peak-like current transient could be observed. This
transient current increased rapidly at the beginning and reached

Fig. 3. Effect of different detaching voltage () 5 + 40 V; () 5 + 30 V; ()


10 + 40 V; () 0 + 40 V on the current density in a solution of 70% HClO4 + 98%
CH3 COCOCH3 (v/v = 1:1) at 25 C for 3 s. The PAA filmAl hybrids were
formed at different anodic oxidation voltage (40 or 30 V) in a 0.3 M H2 C2 O4
solution at 25 C for 4 h.

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a current peak in a very short time of ca. 0.5 s. Then the transient
current decreased to a quasi-steady-state value. In addition, the
peak current increased with the increase of the pulse voltage. For
a pulse voltage of 5 V higher than the film forming potential, a
peak current density of 120 mA/cm2 was obtained (Fig. 3, open
stars). In this case, partial detachment of the PAA membrane
from the base occurred. Complete detachment of the PAA film
from the substrate required a few 5 V voltage pulses higher than
the film forming potentials. Alternatively, complete detachment
of the PAA film could be achieved by increasing the pulse voltage, e.g. 10 V higher than the film forming potential (Fig. 3, solid
circles). In this case, the transient peak current density reached
392 mA/cm2 and automatic detachment of the PAA film from
the substrate was observed. For pulse voltage of 15 V higher
than the film forming potential, the transient current is too high,
leading overload of the instrument in our case. The detachment
process disrupts the balance between the formation and dissolution of BLA. Therefore, the currents are determined by the
difference between the detaching voltage and the PAA forming potential. Higher potential differences will result in larger
transient currents. We also found that successful detachment of
the PAA film does not depend on the film formation potentials
when it is not higher than 70 V. For example, for a lower PAA
forming potential of 30 V, a similar current transient (Fig. 3,
open squares) was also observed upon application of a pulse
voltage of 35 V. The peak current is similar to that for a film
formed at 40 V (Fig. 3, open stars), however, the increase in
transient current is delayed by 0.55 s upon the application of
voltage pulse. This transient delay could be due to slower polishing rate at lower pulse voltage and implies that in this case,
an initial process for the formation of local heat is essential (see
Section 3.4). These results demonstrate that pulse voltages of
510 V higher than the film forming potential should be applied
in order to achieve successful detachment of the PAA film and
an optimal pulse voltage of 10 V higher than the film forming
potential seems to be appropriate for the detachment of the PAA
film from the Al base. For each case, pores with full through
hole were observed as shown by SEM characterization. Fig. 4

gives the SEM images of the anodic alumina layer formed at


40 V in 0.3 mol/L H2 C2 O4 at 25 C. The ordered pores diameter
from the top surface (Fig. 4(A)) is ca. 40 nm, while the pores
from the bottom surface of PAA could be clearly seen although
they have smaller pores diameter (Fig. 4(B)). The pores at the
bottom of the anodized oxide seem to be somewhat less ordered
as compared to the top surface. This can be explained by the fact
that the dissolution of pores bottom in the detachment process
occurs in homogeneously, resulting in not very flat bottom. But
in reality, the bottom pores are indeed more ordered than those
on the top surface if we dissolved away the aluminum base by
chemical process as reported previously [2931].
For PAA films formed with higher oxidation potential, the
barrier layers are relatively thick. Therefore, detachment of such
PAA films with full pores open requires several times of voltage
pulse (160 V, 3 s). Fig. 5 shows the SEM images of the anodic
alumina layer formed at 150 V in 0.3 mol/L H3 PO4 at 25 C. It
is clear that the pores size ranged from 200 to 250 nm in the top
surface (Fig. 5(A)). Upon application of a single voltage pulse
(160 V, 3 s) in a solution of 70% HClO4 + 98% CH3 COCOCH3
(v/v = 1:1) at 25 C, no pores structure at the bottom of the PAA
was observed although the PAA film could be detached from aluminum base (Fig. 5(B)). In this case, partial connection between
the PAA and the substrate certainly remains. Therefore, more
than one time voltage pulse can be applied, e.g. application of
three-time voltage pulses results in partial pores-opening of the
PAA film as indicated by Fig. 5(C). This result lets us make conclusion that PAA film-detaching and pores-opening processes
are involved in the preparation of freestanding PAA films upon
application of short voltage pulses. The former occurs at the
interface of the Al anode and the barrier layer alumina (Al/BLA)
at suitable electric field (e.g. short voltage pulse). This step gives
a transient current due to fast electrochemical dissolution of the
Al base. The latter takes place due to accelerated electric-assisted
dissolution of the BLA by fast formation of localized heat at the
interface between BLA and solution. Thus, a freestanding and
open-through PAA film can be detached from Al base upon voltage pulses with suitable height and period.

Fig. 4. SEM images of the anodic alumina layer formed at 40 V in 0.3 mol/L H2 C2 O4 at 25 C. (A) Top surface; (B) bottom surface. The freestanding PAA membrane
was detached with a 3 s voltage pulse (50 V) in a solution of 70% HClO4 + 98% CH3 COCOCH3 (v/v = 1:1).

J.H. Yuan et al. / Electrochimica Acta 51 (2006) 45894595

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Fig. 5. SEM images of the anodic alumina layer formed at 150 V in 0.3 mol/L H3 PO4 at 25 C. (A) Top surface; (B) bottom surface after single a voltage pulse; (C)
bottom surface after three-time voltage pulses in a solution of 70% HClO4 + 98% CH3 COCOCH3 (v/v = 1:1) at 25 C. Pulse duration: 3 s; voltage height: 160 V.

3.3. Inuence of electrolytes on the lm detachment


Successful detachment of PAA from the substrate is also
determined by the nature of detaching solution besides the height
and width of the pulse voltage. Therefore, voltage pulse was
applied to the PAA films formed at 40 V in various detaching solutions to study the influence of the electrolytes on the
film detachment. These solutions were all volume ratio = 1:1,
including HClO4 (70%) mixtures of CH3 COCOCH3 (98%), or
(CH3 CO)2 O (98%), or PEG-20000 (4 g/20 mL), or TX-10, or
H2 O, or ethanol (98%); other mixtures of H3 PO4 (85%) and
CH3 COCOCH3 (98%), HCl (30%), and HNO3 (30%) aqueous solutions, and pure NaOH (3 M). The detaching results and
the corresponding parameters for all the studied systems are
listed in Table 1. For better comparison, results of typical systems at the pulse voltage of 50 V for 3 s are also displayed
in Fig. 6. We found that highly concentrated HClO4 , HNO3
or HCl aqueous solution could give instant separation of the
PAA film from the aluminum base. Solution of HClO4 containing C2 H5 OH (Fig. 6, solid stars) or CH3 COCOCH3 (Fig. 6,
solid circles) gave similar current transient curves and successful film-detachment upon applying a pulse voltage to the
electrode. We also found that although HClO4 + PEG-20000 or
H2 O, or C2 H5 OH gave successful detachment of the PAA film,
the resulted PAA films were fragile which is probably due to
the very high current transient (the real reason is not clear yet).

Solution of HClO4 containing viscous TX-10 gave very low transient current density (3 mA/cm2 ), thus detachment of the PAA
film failed. These results demonstrate that the electrolytes giving successful detachment of the PAA film from the aluminum
base should include those in which the electric field assisted dissolution rate of the anodic alumina should be much faster than
Table 1
Detaching results and the corresponding parameters of some electrolytes
Electrolyte (v/v = 1:1)

Peak current
density
(mA/cm2 )

Detaching results

HClO4 + CH3 COCOCH3

392

HClO4 + (CH3 CO)2 O

178

HClO4 20 mL + PEG-20000
(4 g/20 mL)

588

HClO4 + H2 O
HClO4 + C2 H5 OH
HClO4 + TX-10
HCl (30%)

630
416
3
Overload

HNO3 (30%)
NaOH (3 M)
H3 PO4 (72%) + CH3 COCOCH3

189
13
8

Yes, negligible
dissolution
Yes, negligible
dissolution
Yes, negligible
dissolution, but the
film is fragile
Yes, slight dissolution
Yes, slight dissolution
No
Yes, part dissolution
and Cl2 formation
Yes, part dissolution
No
No

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J.H. Yuan et al. / Electrochimica Acta 51 (2006) 45894595

Fig. 6. Effect of the detaching electrolytes () HClO4 + C2 H5 OH; ()


HClO4 + (CH3 CO)2 ; () NaOH; () H3 PO4 + (CH3 CO)2 on the current transients of the PAA films upon application of a voltage pulse (50 V and 3 s) at
20 C. The PAAAl hybrids were formed at an anodic oxidation potential of
40 V in a 0.3 M H2 C2 O4 solution at 20 C for 4 h.

its electrochemical formation rate. Therefore, multiprotic acids


cannot be used as detaching electrolytes since the formation rate
of the alumina is balanced by its dissolution rate in these acidic
solutions [25]. For example, successful detachment of the PAA
film in a mixture of H3 PO4 and CH3 COCOCH3 (Fig. 6, crosses)
could not be observed, although solution of H3 PO4 can dissolve
both the BLA and the PAA. This fact can also explain why NaOH
solution could not give detachment of the PAA film (Fig. 6, open
squares). Aqueous solution of HCl, HNO3 or HClO4 could give
successful detachment of the PAA film with high transient current, but they dissolve the PAA as well, resulting in the widening
of the pores. In addition, in the case of HCl solution, strong
evolution of chlorine gas during voltage pulse occurs. Taking
account of the quality of the PAA membranes and the safety,
these two systems should not be adopted.
Based on the above results, we proposed to prepare freestanding PAA membranes via detachment in a controlled fashion
using perchloric acid containing biacetyl or ethanol system. In
this case, the resulted PAA film can be easily cleaned by acetone
and has high quality.
3.4. Film detachment mechanism
The above measurements can be summarized as follows: successful detachment of the PAA films with high quality from the
aluminum base can be achieved by using a 510 V pulse voltage
higher than its forming potential in a solution of HClO4 containing CH3 COCOCH3 or (CH3 CO)2 O. All these systems gave
relative high current transients upon applying pulse voltage.
The detachment mechanism of PAA membranes upon applying a voltage pulse is schematically presented in Fig. 7. By
anodic oxidizing in multiprotic acid solution, porous anodic
alumina can be formed over the BLA that is closely contacted
with the Al substrate (Fig. 7(A)). Upon application of a voltage pulse to the PAAAl hybrid in highly concentrated solution
of monoprotic inorganic acids, the electric field is mainly distributed across the insulated BLA. In this case, although the Al

Fig. 7. Schematic representation of the mechanism for two-step voltage pulse


detachment of porous anodic alumina membrane. (A) PAA formed on the barrier
layer alumina (BLA) covered Al substrate by anodic oxidation. (B) PAABLA
separated from the Al substrate upon application of a voltage pulse. (C) Freestanding PAA film obtained via dissolution of BLA at the pore bottom.

base is in close contact with the oxide instead of direct contact


with the solution, highly concentrated protons through the BLA
film out and in are normally responsible for the electropolishing process. Under the same conditions, for example, we find
that anodic currents generated during the electrooxidation process increase with the increase of proton concentrations. As
a result, electrochemical-polishing process occurs at the BLA
bottom, leading to a rapid increase in current [36]. With the
electropolishing process ongoing, the microstructure of the Al
substrate near the pores bottom will be soon smoothed, thus the
current for the electropolishing process decreases. At certain
time (e.g. 2 s in Fig. 3), the Al surface is polished and the current for the electropolishing process reaches a stable stage. In
this electropolishing process, the dissolution rate of alumina is
much faster than its formation rate. Therefore, no net alumina
will be accumulated at the Al substrate, resulting in detachment
of the anodic alumina layer from the Al substrate (Fig. 7(B)).
Accompanying this detachment process, another electric field
accelerated dissolution of BLA at the solution front occurs. This
BLA dissolution rate increases exponentially with the applied
electric field [28]. In addition, the current transient results in
localized heat that in turn could accelerate the dissolution of
the BLA at the interface between BLA and Al substrate. Due
to these two dissolution processes, the BLA dissolves in the
nanometer range in very short time period if the pulse voltage
is highly enough. In the end, freestanding PAA with all pores
open is separated from the Al base (Fig. 7(C)).
Based on our experimental results, the appropriate current
transient is essential for successful detachment. Highly enough
current shows more Al dissolved to achieve separation from alumina and high heat generated is helpful to dissolve the BLA.
Concentration of water in the system is also very important
for obtaining high quality PAA film. Higher concentration of
water will give higher transient current, thus, the detached PAA
films are fragile. Addition of additive biacetyl to the system can
decrease the water concentration for obtaining high quality PAA
films.

J.H. Yuan et al. / Electrochimica Acta 51 (2006) 45894595

4. Conclusions
Achievement of high quality PAA membranes with all pores
open requires detaching electrolytes of highly concentrated perchloric acid containing biacetyl [20] or acetic anhydride [29],
short pulse voltage of 510 V higher than the film forming
potential, and suitable pulse period. The detachment mechanism
can be explained by the electropolishing of the aluminum substrate and electric field accelerated dissolution of the BLA upon
application of voltage pulse to the PAABLAAl system. The
electropolishing process can be explained by the electric field
assisted transport of ions in the BLA, while the accelerated dissolution of the BLA is due to the pulse-generated heat. Therefore,
PAA film with all pores open detaches from the Al base automatically. The present mechanism is promising for preparation
of freestanding PAA films with various pores sizes, which are
important for non-material synthesis. Further research is undergoing.
Acknowledgement
This work was supported by grants from the National Natural
Science Foundation of China (NSFC, No. 20125515; 20375016;
20299030).
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