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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-
0013-4686/$ see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2005.12.044
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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
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).
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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.
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
392
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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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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