Surface and Coatings Technology 180181 (2004) 308312

0257-8972/04/$ - see front matter 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2003.10.076
Mechanisms to inhibit corrosion of Al alloys by polymeric conversion
coatings
I. Paloumpa *, A. Yfantis , P. Hoffmann , Y. Burkov , D. Yfantis , D. Schmeier
a, b a a b a
Department of Applied Physics-Sensors, Brandenbungische Technische Universitat Cottbus, Universitatsplatz 3-4, 03044 Cottbus, Germany
a

Department of Chemical Engineering, National Technical University of Athens, 9 Ir. Polytehniou str., Zografou Campus, Greece
b
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 alumin-
ium, 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: q49-355-
693931.
E-mail address: paloumpa@tu-cottbus.de (I. Paloumpa).
corrosion of aluminium in the atmosphere or in natural
waters.
Corrosion inhibition is generally achieved by the
deposition either of passive films or of active conversion
coatings on the surface, which is to be protected. In the
first case (lacquers, ceramics, etc.) the inhibition
depends on the thickness of the deposited film, while
for the second systems (e.g. chromates, noble metal
coatings) the inhibition mechanisms are more complex.
They may offer a low density of pores or cause surface
chemical reactions in order to prevent oxidation. The
use of conducting polymers as a corrosion protective
offers additional properties to those of inorganic con-
version coatings due to the electrical and morphological
characteristics of the polymer in each case.
Conducting polymers gain their conductivity due to
doping with counter ions. We use TiF , ZrF and
2y 2y
6 6
Zn ions in an aqueous solution to dope polypyrrole
2q
(Ppy). Polypyrrole shows an excellent physical and
chemical stability and is easy to synthesise. Additionally
the monomer of pyrrole shows a low toxicity.
In our laboratory we prepare active conversion coat-
ings on aluminium panels by chemical oxidationypoly-
merisation of pyrrole monomers
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x
. We study these
309 I. Paloumpa et al. / Surface and Coatings Technology 180181 (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 mAycm ), investigated with different methods
2
Sample code Accelerated PEEM m-NEXAFS SEM EDX
corrosion time
A Non corroded = =
B 4 min = =
C 2 min =
D 1 min =
Fig. 1. Topography (left images) and Ti distribution (right images)
for sample A before (top) and for sample B (bottom) after the cor-
rosion tests. The boxes indicate the sample sections of the spectra
shown in Figs. 2 and 3.
films in order to learn about the reactions of the dopants
and to conclude on the inhibition mechanisms. Reactions
are expected with the Al at the interface or within the
film to cause either intermediate products or even
sacrificial components.
2. Experimental
The polymeric coating of our samples had been
prepared chemically by using an aqueous solution of
pyrrole, fluoro-zirconic acid, fluoro-titanic acid, zinc
oxide and phosphoric acid. Certified aluminium panels
(Q-panel, series 5005) have been used, with a total
exposed surface area of 2500 mm . The aluminium
2
panels were degreased with acetone. The polypyrrole
(Ppy) coating was formed after simple immersion in the
polymer solution for a time period of 6 min. The Ppy-
coated panels were immersed in a beaker with deionised
water and then extensively rinsed, also with deionised
water. Finally the samples were dried at 100 8C for 10
min.
Accelerated corrosion immersion tests were performed
in an environment of 5 wt.% NaCl acidified with acetic
acid (pH 4), by passing a constant current (100 mAy
cm ) for different time intervals of several minutes
2
through the electrolyte. The time intervals of the accel-
erated corrosion tests for each sample and the methods
of investigation for each one of them are shown on the
Table 1.
The investigation of the corrosion mechanism on the
surface of the polymer-covered Al samples was made
with several microscopic and spectroscopic methods (see
Table 1), mainly photo-emission electron microscopy
(PEEM) and scanning electron microscopy (SEMy
EDX). In our studies we employ the FOCUS-PEEM
with modified sample stage. That instrument can deliver
topographic contrast, elemental contrast, and chemical
information with spatial resolution. Topographic contrast
is obtained by imaging the secondary electrons. For
elemental contrast we take two images, off and on the
XAS resonance of a particular element, and build the
difference. For chemical information we record the total
intensity of the imaged electrons as a function of the
energy of the incoming photon (m-NEXAFS). An excel-
lent variable X-ray source for PEEM is our Undulator
beam line U49y2-PGM2 at BESSY-II in Berlin, because
of its tunability, high brilliance and high energy resolu-
tion (plane grating monochromator, resolution EyDE
above 10 000, flux of approximately 10 photonsys,
13
energy range from 80 up to 1500 eV). The SEMyEDX
analysis was done with a ZEISS Digital Scanning
Electron Microscope DSM 962, equipped with an Isis-
Oxford Link EDX System.
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 Ppy-
film we attribute the double peak structure with a
characteristic splitting of 2.7 eV to the existence of
TiO particles. This is a first indication that the TiF
2-
2 6
ions must have reacted upon the film deposition. A
310 I. Paloumpa et al. / Surface and Coatings Technology 180181 (2004) 308312
Fig. 2. O1s-mNEXAFS spectra of the as deposited conversion coating
(black dash-dot line) and after corrosion tests (grey solid line).
Fig. 3. Ti2p-mNEXAFS spectra taken on the non corroded sample A
(dashdot) and on the marked sample sections of the corroded sample
B (solid black and grey line, see also Fig. 2).
Fig. 4. SEM image of the sample C. Upper half (dark) of the image:
non corroded. Lower half (light): corroded.
possible explanation is that they link to defects in the
native Al O of the Al sample. Thereby the Ti-fluorites
2 3
convert to TiO nanoparticles
w
3
x
.
2
The O1s spectrum of the sample B (after corrosion
test) has significantly changed. Now only a weak shoul-
der remains from the absorption doublet of the TiO
2
particles, while a broad unstructured feature is indicative
of other oxides, probably the native Al O .
2 3
In the NEXAFS spectrum of the Ti2p signal we find
our assignment of TiO particles supported by the sharp
2
features at approximately 460 eV, which reflect the
transitions into the empty Ti3d states of TiO (Fig. 3,
2
dashdot curve)
w
1,2,5
x
. After the corrosion tests the
spectrum changes only subtle, there is a weak change
in the relative intensities and a small increase in the
width of the 3d-features. However, there is a much
lower intensity. We show two spectra which are taken
in the marked regions of the sample (Fig. 3, black and
grey solid line) and indicate that the Ti concentration
varies significantly and has almost completely disap-
peared in the lower spectrum. These data indicate that
the TiO particles may act as a sacrificial material in
2
the conversion coating to getter oxidants and become
washed out afterwards
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6
x
.
Fig. 4 shows the SEM image (=200) of the border
between the corroded and the non-corroded part of an
Al panel, which was partly corroded (sample C). The
region above is not corroded, while the region below is
the corroded one. In this image it can be seen, that the
corrosion takes place locally, at certain points and
parallel to the rolling lines. The homogeneity of the Ppy
layer is interrupted, even on the non corroded part of
the sample. These sites, as shown from the SEM analysis
of the sample, are metal phases containing a high
percentage of iron (see also Spectra 2 and 3, Figs. 6
and 7). Their presence seem to play a significant role
for the beginning of the corrosion.
The SEM image of the Fig. 5, shows another region
of the same sample, in its corroded part. It shows the
border between a corroded stain (upper left) and an
intact corrosion protection (lower right). One can see
here, that the phenomenon of the corrosion starts at
specific spots and spreads further on the area next to
them.
The presence of the iron-phases in our aluminium
alloys increases the corrosion-grade. Polypyrrole is not
that adhesive on iron as on aluminium and therefore, on
these locations of iron, the Ppy film is clearly thinner
than on the rest of the surface of the panels. Through
this fact, the homogeneity of the protective layer is
damaged. Therefore, our Ppy protective layer loses its
passivity much quicker, through its bad corrosion pro-
tection properties on the iron phases contained in our
alloys. Additionally, the zinc present in the protective
layer, will now be faster corroded, since it is in an
311 I. Paloumpa et al. / Surface and Coatings Technology 180181 (2004) 308312
Fig. 5. SEM image of the sample C. Detail of the corroded part of
Fig. 4.
Fig. 6. Spectrum 1: EDX spectrum of the sample D (corroded area,
on a point with intact corrosion protectiondarker area).
Fig. 7. Spectrum 2: EDX spectrum of the sample D (corroded area,
on a further corroded stainlight area).
environment containing iron. In this way, the cathodic
corrosion protection of the Zn against the Al will be
decreased and the corrosion process will be accelerated.
Spectrum 1 (Fig. 6) is the EDX spectrum of the
sample D. It is taken on the corroded surface, but on a
point with an intact corrosion protection (from the darker
area on the surface), while Spectrum 2 (Fig. 7) is a
spectrum from an already further corroded stain (light).
The presence of Fe is evident, which is clearly more on
the further corroded stain. Additionally, the quantity of
Fe changes between the two spectra that strong as by
almost no other element. This is also a proof, that the
iron phases play a strong role for the corrosion process
of our Al alloys. This quantitative difference of the Fe
peaks is seen, becauseduring and after the corrosion
the iron will be uncovered from the thin film of the
polypyrrole. It is, however, already known, that when
Fe is contained in the alloys of Al, its presence is
generally responsible for the accelerating of the corro-
sion of these alloys.
Another obvious change on the same spectra is this
of the Zn. As mentioned before, Zn should protect the
aluminium surface, through the corrosion of itself. How-
ever, in our case, since the iron phases are practically
uncovered, the corrosion of the Zn will be much faster,
than in the case where only Al would exist in its
environment. Conclusively, zinc will not be enough or
maybe even not present at all in order to protect the
aluminium, when the corrosive factors will already have
penetrated the polymer layer and are in contact with the
surface of the metallic aluminium. In this way, the
relationship between the iron phases and the zinc seem
to be very important for our alloys and our passivating
method of their surface.
4. Conclusions
We studied the reactions upon accelerated corrosion
of aluminium alloys coated with a conductive Ppy film
doped by TiF , ZrF and ZnO. Our film shows an
2y 2y
6 6
excellent corrosion resistance under usual corrosion
conditions. Only under the extreme conditions of low
pH and electric current flow the film loses its durability
(after 5 min the surface of the Al alloy is practically
uncovered).
The investigations with PEEM and SEMyEDX point-
ed out that the corrosion proceeds via random distributed
spots. The morphological irregularities of the samples
are, however, not directly related to the corrosion pattern
(e.g. there is no corrosion concentrated along the rolling
312 I. Paloumpa et al. / Surface and Coatings Technology 180181 (2004) 308312
lines). The corrosion occurs through the non-homoge-
neity of the samples, dominated by the elemental distri-
bution, which is not homogeneous on the surface.
By the use of PEEM for our analysis, we demonstrat-
ed 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 TiO and we found a non-homoge-
2
nous 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 TiO . Further details of the reactions
2
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 impor-
tance 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-
fore, testing our Ppy film on other alloys of aluminium,
containing smaller quantities of iron, should be one of
our further aims, with the expectation that we shall have
even stronger corrosion protection properties.
Acknowledgments
We would like to acknowledge Dr Wiehe for the
SEMyEDX measurements and Guido Beuckert for his
skilful experimental assistance. Furthermore, we would
like to thank Carola Schwierz, Karsten Henkel, Marian
Sterzel and Torsten Lehmann for their support.
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