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Mechanisms To Inhibit Corrosion of Al Alloys by Polymeric Conversion
Mechanisms To Inhibit Corrosion of Al Alloys by Polymeric Conversion
Cottbus, Universitatsplatz
Abstract
We introduce a recently developed novel polypyrrole-based coating, which can be formed on the aluminium surface from an
aqueous pyrrole solution of fluorozirconic and fluorotitanic acid neutralised with zinc oxide. The composite layer consists of
polypyrrole (Ppy) chemisorbed on titanium and zinc oxides and exhibits advanced corrosion resistance. For the investigation of
the structure and the corrosion mechanism of the composite corrosion resistant layer we use a photo-electron emission microscope
(PEEM). PEEM is especially suitable because it can deliver topographic contrast as well as elemental contrast and chemical
information in connection with a variable X-ray source. Additionally, in order to investigate further the corrosion mechanism, but
also the role of the alloy in the corrosion process, we examine the aluminium samples with SEMyEDX. The structure of the
corrosion resistant layer was investigated before and after accelerated corrosion tests. Our results pointed out the important role
of titanium oxide and zinc in the corrosion resistance of our Ppy coating on aluminium.
2003 Elsevier B.V. All rights reserved.
Keywords: Polypyrrole; Fluorozirconates; Fluorotitanates; Aluminium; Corrosion
1. Introduction
Aluminium is a reactive metal that owes its corrosion
resistance to a thin, protective oxide surface layer, which
is generally stable in air and aqueous solutions. Although
aluminium oxide is generally protective, pores and other
defects caused from alloying elements can lead to
localised corrosion.
Corrosion of metals generally involves two half-cell
reactions: an oxidation reaction at the anode and a
reduction reaction at the cathode. In the case of aluminium, the pits act as microgalvanic cells, where active
metal dissolution is taking place in the crater of the pit,
which is anodic, and reduction reactions are taking place
in the periphery, which acts as a cathode. Corrosive
anions like chlorides are attracted to these anodic sites
anddue to the low local pHare transformed to the
corresponding acid. This model allows the pits to
become self catalytic and proceed fast until the final
perforation. Localised corrosion is the main form of
*Corresponding author. Tel.: q49-355-693099; fax: q49-355693931.
E-mail address: paloumpa@tu-cottbus.de (I. Paloumpa).
0257-8972/04/$ - see front matter 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2003.10.076
I. Paloumpa et al. / Surface and Coatings Technology 180 181 (2004) 308312
Table 1
Aluminium panels covered with polypyrrole coating and corroded in
5% wt. NaCl acidified with acetic acid (pH 4.3), by passing a constant
current (100 mAycm2), investigated with different methods
Sample code
Accelerated
corrosion time
PEEM
m-NEXAFS
A
B
C
D
Non corroded
4 min
2 min
1 min
=
=
=
=
SEM
EDX
309
=
=
3. Results
PEEM images of two Al samples coated with our
polymeric conversion coating are shown in Fig. 1. The
sample A is imaged before corroding and the sample B
(Table 1) after the accelerated corrosion tests. We
studied the Ti distribution (difference image taken at
the Ti2p absorption edge) in the same sample section.
The two difference images on the right hand side of
Fig. 1 reveal that the elemental distribution of Ti is not
homogeneous. Furthermore, it is not correlated to the
sample topography caused by rolling lines and other
irregularities, seen in the topography images. Finally,
there is no evidence for pitting corrosion.
The elemental images of the other dopants show
similar non homogeneous behaviour. The difference
images of zinc qualitatively scale with the distribution
of titanium, while the behaviour of fluorine is reversed.
Chemical information is obtained from the O1s and
Ti2p NEXAFS data. In Fig. 2 we compare the O1s
NEXAFS of the two samples. In the as-deposited Ppyfilm we attribute the double peak structure with a
characteristic splitting of 2.7 eV to the existence of
TiO2 particles. This is a first indication that the TiF26
ions must have reacted upon the film deposition. A
310
I. Paloumpa et al. / Surface and Coatings Technology 180 181 (2004) 308312
Fig. 4. SEM image of the sample C. Upper half (dark) of the image:
non corroded. Lower half (light): corroded.
I. Paloumpa et al. / Surface and Coatings Technology 180 181 (2004) 308312
311
312
I. Paloumpa et al. / Surface and Coatings Technology 180 181 (2004) 308312
lines). The corrosion occurs through the non-homogeneity of the samples, dominated by the elemental distribution, which is not homogeneous on the surface.
By the use of PEEM for our analysis, we demonstrated that it is a powerful tool for the investigation of
inhomogeneous reactions at technological interfaces. We
learned that already in the corrosion protection layer the
titanium occurs as TiO2 and we found a non-homogenous spatial distribution. The PEEM results show that
corrosion does not depend on topographic irregularities
and does not proceed via etch pits but reduces the total
intensity of the TiO2. Further details of the reactions
occurring among the dopants within the Ppy film are
currently investigated with the aim to understand the
complex inhibition mechanisms.
Our SEMyEDX investigations pointed out the importance of the presence of iron in the main body of our
panels. The traces of this metal cause a homogeneity on
the surface of the non-coated alloy, as well as in the
Ppy film which is supposed to protect the aluminium
alloy against corrosion. This lack of homogeneity is
fatal for our films. Not only are the Fe phases the points
from where the corrosion begins, but they avoid zinc to
play its cathodic-protective role vs. aluminium. There-
by the Max-Grunebaum-Stiftung
(2000).
w4x A. Yfantis, D. Schmeier, Greek Industrial Property Org.,
Patent Nr. 100 37 63 (2002).
w5x Y. Harada, et al., Phys. Rev. B 61 (2000) 12854.
w6x D. Schmeier, I. Paloumpa, P. Hoffmann, Y. Burkov, A.
Yfantis, D. Yfantis, BESSY Annual ReportyHighlights, 2002,
p. 24.