Materials and Corrosion 47, 439445 (1996)
Corrosion prevention with an organic metal
(polyaniline): surface ennobling, passivation,
corrosion test results
Korrosionsschutz mit HiIfe eines organischen MetaIIs (PoIyaniIin):
Oberflachenveredelung, Passivierung, Korrosionstest-Ergebnisse
Progress on the area of passivation of metallic materials by poly-
aniline is being presented. The redoxcatalytic reaction leading to
the formation of a passivating oxide layer has been evaluated,
and a reaction scheme is shown. Results of corrosion tests are de-
scribed as well.
1 First breakthrough results
In 1985 D. DeBerry [I] found that polyaniline, electro-de-
posited on passivated steel in strong acid environment, was
enhancing the corrosion protection of this metal. No further
research was done to find out what mechanism was reducing
the corrosion rate and - even more important - if polyaniline
deposited by other than electrochemical means on nonprepas-
sivated metal surfaces would lead to any kind of corrosion
protection, until our laboratory had developed first polyani-
line containing paints and published first corrosion inhibition
by such paints in 1988 [ 2 ] .It took another 5 years to come to
reproducible results first by using pure polyaniline coatings
from organic dispersions [3], which were deposited on un-
treated metals like normal steel, stainless steel and copper.
We found that the corrosion potential was shifted to the
more noble region and that the corrosion current was signifi-
cally reduced or even completely eliminated at comparable
corrosion potentials (Fig. 1).The SEM revealed that an oxide
layer was formed between the PAni coating and the metal
surface (Fig. 2). Our research was continued together with
R. Elsenbaumer and Wei-Kang Lu [4], where we found the
corrosion rate being reduced by several orders of magnitude
and the oxide layer being composed mainly by Fe,O, above a
very thin Fe,O, layer (Fig. 3).
2 Passivation reaction mechanism
We suspected earlier [3] that the passivation reaction lead-
ing to the oxide could occur via a catalytic redox reaction of
PAni. Our group later succeeded in developing dispersed PAni
containing paints [5] which are capable of inducing the same
* Dr. B. Wessling
Zipperling Kessler & Co. (GmbH & Co.)
Postfach 14 64, D-22904 Ahrensburg (Germany)
0 VCH Verlagsgesellschaft mbH, D-69451 Weinheim, 1996
Corrosion prevention with polyaniline 439
B. Wessling*
Fortschritte auf dem Gebiet der Passivierung von metallischen
Werkstoffen mittels Polyanilin werden vorgestellt. Die redoxkata-
lytische Reaktion, die zur Ausbildung einer passivierenden Oxid-
schicht fuhrt, wurde untersucht, ein Reaktionsschema konnte auf-
gestellt werden. Ergebnisse von Korrosionsprufungen werden pra-
sentiert.
passivation effect, but moreover industrially applicable and
effective as corrosion prevention primer [7]. The present
work [6] was intended to find out what kind of reaction se-
quence is responsible for the passivation (oxide layer forma-
tion) and the corrosion protection induced by the PAni layer.
2.1 Experimental
A polypropylene film (480 p, supplied by BP-ETIMEX)
was coated in a laboratory coating machine with PAni from
dispersion [3] which contained 5% of suspended iron powder
(10 p diameter “pro analysi” made by reduction, Fa. Merck).
The u. v. and visible spectrum was recorded using a UV-VIS-
spectrometer (Hitachi, model U-2000). The spectroscopy was
made using coated films with and without iron powder in a
quartz kuvette using 2 different solutions:
a) 1 M NaCl / water
b) 0,l M p-toluene sulfonic acid / water
Due to the reason that the colour of polyaniline is changed
in the presence of iron and water very quickly, the recording of
spectra was started as soon as the coated film was placed into
the solution. The spectra were recorded at different time in-
tervals after the reaction start. The colour changes from green
to yellowish green and later a pale yellow (reduction step,
Figs. 4a and b) which later turns back to green (back-reac-
tion, Figs. 5a and b). In the neutral salt solution the green
has got a more blueish undertone (Fig. 5b), in contrast to
the acid solution which leads to the original nice PAni green
(Fig. 5a). Without iron powder there is no colour change to be
seen (Fig. 6). Figs. 4a and 4b are showing the change of the
spectrum of polyaniline with suspended iron powder in pTs
and NaCl solution, Figs. 5a and 5b the back reaction over
1 day.
A calibration (see Table 1) shows that 90% PAni has been
reduced during the first 5 minutes, with a subsequent loss of
extinction during the following 2 hours (in pTs, Fig. 4a) or 10
min. (in NaCl, Fig. 4b) with no further spectral change in the
0947-5 117/96/0808-0439$10.00+.25/0
440 Wessling Materials and Corrosion 47, 439-445 (1996)

20

14

1
potential U-H2 [vl

:I
-10 -c- 2) iron St-37, passivated

-14
-12
-16
I t3) stainless steel VZA, no treatment
+ 4) stainless steel V2A. passivated
t5) copper, no treatment

Fig. 1. Corrosion current density-potential curves of various metals, both original and passivated.
Abb. 1. Korrosionsstromdichte-Potential-Kurven verschiedener Metalle, beide original und passiviert

w740 730 720

Binding Energy (ev)

710

Fig. 2. SEM image showing that the second phase seems to be the
deposition of an oxide, initially extremely thin
Abb. 2. SEM-Bild, das zeigt, dalj die zweite Phase der Passivie-
rung die Ablagerung eines anfanglich extrem dunnen Oxides zu
sein scheint
following 2 hours, All leuco-emeraldine has reacted back to
PAni during the next 24 hours.
For understanding the back reaction we have made two key
experiments:
a) with the use of additional oxygen in the quartz kuvette
b) using degassed solutions
during spectroscopy.
Fig. 3. XPS analysis of passive iron oxide layers form in the pre-
sence of doped polyaniline
Abb. 3. XPS-Analyse von passivierenden Eisenoxid-Schichten in
der Anwesenheit von Polyanilin
The reaction with additional oxygen is shown in Figs. 7a
and 7b. It can be seen, that now only 55% of the PAni is re-
duced with the reduction proceeding at much slower reaction
rate. All leuco is re-oxidized, but much faster within 6 hours.
For the spectroscopy in degassed solutions, the solution was
degassed at 60 "C under ultrasonic action and vacuum
(25 mbar) and then stored under nitrogen. The spectroscopic
changes are shown in Fig. 9a (degassed, reduction step) and
Fig. 9b (back reaction). They document, that PAni is first re-
duced also to a degree of 90% (obviously at a slower reaction
rate) compared to only 55% under additional oxygen. The
back reaction is proceeding at comparable rates, but under
Materials and Corrosion 47, 439-445 (1996) Corrosion prevention with polyaniline 441

j +original 1 I

I
250 450 650 850 1050 250 450 650 850 1050
wavelength [nm] wavelength [nm]

1.2
b)
3

0.8
0

0,6
::
Q 04

02

0
250 450 650 650 1050
wavelength [nm]

Fig. 4. Spectral change of PAni on PP film with suspended iron Fig. 6. Spectral change of PAni on PP film without iron
(reduction step) a) measured in 0.1 M pTS
a) measured in 0.1 M pTS b) measured in 1 M NaCl
b) measured in 1 M NaCl Abb. 6. Spektralanderung von PAni auf PP-Film ohne Eisen
Abb. 4. Spektralanderung von PAni auf PP-Film mit verteiltem a) gemessen in 0,l M pTS
Eisen (Reduktionsschritt) b) gemessen in 1 M NaCL
a) gemessen in 0,l M pTS
b) gemessen in 1 M NaCL
the green to the yellow form, which can be understood as the
reduction of polyaniline from the emeraldine salt to the leuco-
gas evolution (H2?). Table 2 shows a summary with the role of emeraldine. This requires an equivalent oxidation of iron (to
oxygen. Fe2+). The back reaction shown in Figs. 5a and 5b is leading
back to the normal polyaniline, although with some blueish
component (emeraldine base or nigraniline) in the neutral en-
2.2 Conclusions vironment. This back reaction is performed with the help of
oxygen as can be seen from the comparison of spectra in Figs.
Figs. 4a and 5a are showing that the contact of polyaniline 7a and 7b with Figs. 5 d 5 b and Figs. 8d8b. In the degassed
with iron in the presence of water changes polyaniline from water solutions we also observe the reoxidation of the leuco-

L-10 [min]
+

+
5[hl
24[h]

I
250 450 650 850 1050
250 450 650 650 1050
wavelength [nm] wavelength [nm]

Fig. 5. Spectral change of PAni on PPfilm with suspended iron Abb. 5. Spektralanderung von PAni auf PP-Film mit verteiltem
(back reaction) Eisen (Riickreaktion)
a) measured in 0.1 M pTS a) gemessen in 0,1 M pTS
b) measured in 1 M NaCl b) gemessen in 1 M NaCL
442 Wessling Materials and Corrosion 47, 439-445 (1996)

Table 1. Calibration from cyclic voltammetry combined with uv-visible absorption spectroscopy measured on an SnO, coated conduction
glass (5052km)
Tabelle 1. Kalibrierung basierend auf Cyclovoltametrie und UV-VIS-Spektroskopie einer Beschichtung auf leitfahigem Sn0,-Glas
(5052km).

potential wavelength absorption relative percentages

measured [nml 730 nm absorption Emeraldinsalt
against 730 nm
H,/Pt

-0.22 887 0.154 0 0

-0.11 883 0.172 0.018 3.3
0 882 0.188 0.034 6.3
0.1 874 0.208 0.054 10
0.2 865 0.256 0.102 18.9
0.3 848 0.369 0.215 39.8
0.4 835 0.449 0.295 54.6
0.5 821 0.505 0.351 65
0.6 803 0.579 0.425 78.7
0.7 786 0.694 0.54 100

Talbe 2. Reaction time and percent leucoemeraldine for different reaction conditions
Tabelle 2. Reaktionszeiten und Prozentanteil von Leuco-Emeraldine unter verschiedenen Bedingungen

time [%I leucoemeraldine

reaction max. for the for the at the after reduction after the
conditions wavelength reduction backoxidation beginning step backoxidation
[nm] * I [min] Ihl "2
pTS with normal 0, 874 5 24 20 90 20
degassed pTS 877 12 24 20 90 20
pTS with additional 0, 842 30 6 20 55 20
"1 achieved during reduction step
*2 estimated from calibration table at max. wavelength

f 0.B

2W 390 480 590 8M 790 891 190 (090

Wwelenglh Inm]

Fig. 7. Spectral change of PAni on PP film with suspended iron Fig. 8. Spectral change of PAni on PP film with suspended iron
measured in 0.1 M pTS with additional 0, measured in degassed 0.1 M pTS
Abb. 7. Spektralanderung von PAni auf PP-Film mit verteiltem Abb. 8. Spektralanderung von PAni auf PP-Film mit verteiltem
Eisen, gemessen in 0,l M pTS zusatzlich mit 0, Eisen, gemessen in entlufteter 0,l M pTS
Materials and Corrosion 47, 439445 (1996) Corrosion prevention with polyaniline 443

0.5 0 2 + H20 ,OH--, a> describing the whole passivation reaction sequence of poly-
aniline on the iron surface, showing that polyaniline is acting
thildst.p
as a redox catalyst and as a noble metal with respect to iron (or
2 Fe 2 Fe" 2Fe"' A
t
Fep3 + 3 H 2 0 copper, stainless steel, aluminum, zinc and others (Fig. 9a).

3 Corrosion test results

The main question for practical applications is, if this new,
proven and convincing passivation procedure does also pro-
vide significant improvements in internationally accepted cor-
rosion tests and later in continuous use. For the tests reported
below, PAni containing primers [8] have been applied with a
ES + 4H+ b) thickness of 20 p and coated as described.
Especially the behaviour of the coating system with the
passivation primer in scratches and other inquiries is of con-
4Ht siderable interest. We had observed very early, that crossed
scratches do not corrode under various corrosion conditions
including laboratory tests and atmospheric corrosion, if the
Fig. 9. Reaction scheme. a) reduction step, b) back reaction
scratches are up to 2 mm wide.
Abb. 9. Reaktionsschema. a) Reduktionsschritt, b) Riickreaktion Actual research [9] shows, that the passive oxide layer for-

CORRPASSIV
PAni-Primer

\
Fe,OLr
/
steel
-
1
scratch
-
I
CORRPASSIV
P i-Primer
9"
mation is observable for at least 400 nm towards the scratch
center from the primer edge (Fig. 10). This might explain the
extraordinary positive results in the corrosion tests described
below.

3.1 Tests at DECHEMA Institute

Fig. 10. Schematic view of passivation influence of PAni in a
scratch
Abb. 10. Schematischer Uberblick bezuglich des Einflusses von
PAni auf die Passivierung in einem Kratzer
Fig. 11. Corrosion was found to be considerably less marked with
the PAni primer
Abb. 11. Mit der PAni-Grundierung wurde ein wesentlich geringe-
rer Rost-Angriff festgestellt
The polyaniline primer CORRPASSIV (with Wilckens
Eposist 2000 epoxy resin top coat) on sandblasted St 37 steel
was compared with specimens coated with only an epoxy top
coat or with a zinc-rich primer (Wilckens Epoxid Zinkstaub-
farbe EPB 7601) and the same epoxy resin top coat.
The test investigated crevice and pitting corrosion in accor-
dance with ASTM G-48in FeC1, solution and contact corro-
sion with copper (with short-circuit - in accordance with DIN
50 919 - and without short circuit). Crevice and pitting corro-
sion testing was performed on specimens with intact coatings
and specimens with deliberately damaged coatings.
The results were as follows:
Of the steel specimens with damaged coatings, only those
treated with the polyaniline primer CORRPASSIV passed

Fig. 12. Crevice corrosion of specimen with zinc-rich epoxy pn-

mer
Abb. 12. Spaltkorrosion an der Probe mit Zinkstaub-Epoxid-Grun-
dierung

emeraldine into the emeraldine salt, but very interestingly we

can see a gas formation at the surface of the film which we
suppose is hydrogen.
Further observations using polyaniline containing paints
have shown that the occurence of hydroxyl ions is very prob-
able. We therefore come to the following reaction scheme
Fig. 13. All specimens exhibited formation of corrosion products
in the crevice, but in the case of CORRPASSIV this was only slight
Abb. 13. Alle Proben zeigten im Spalt die Bildung von Korrosi-
onsprodukten, jedoch bei CORRPASSIV nur in leichtem AusmaS
444 Wessling Materials and Corrosion 47, 439-445 (1996)

the test. With intact coatings the specimens with zinc-rich

primer and with CORRPASSIV primer passed. Corrosion
was nevertheless found to be considerably less marked
with the PAni primer, (Fig. 11.) Fig. 12 shows crevice corro-
sion of specimen with zinc-rich epoxy primer.
The contact corrosion tests were performed in each case
with a defined cruciform injury to the coating and an insulat-
ing bolted joint to copper.
In the test without short-circuit only the steel specimen trea-
ted with polyaniline primer displayed no corrosion attack at
the damage site and no undermining of the coating. The com- Fig. 15. Standard system: corrosion attack even under two-compo-
parison specimens displayed more or less marked rust forma- nent primer
tion at the damage site. Abb. 15. Standard-Aufbau: Korrosionsangriff auch unter 2K-Pri-
In the test in accordance with DIN 50 919 with short-circuit mer
by an external electrical connection to the contact corrosion
element the cell current is measured directly.
All specimens exhibited formation of corrosion products in
the crevice, but in the case of CORRPASSIV this was only
slight (Fig. 13).
The specimen coated with polyaniline primer recorded a
current of only approx. 1 mA, whereas the comparison speci-
mens with and without zinc-rich primer showed much higher
readings (around 2.5 - 3 mA).

3.2 Salt spray test

The (physically wetting) polyaniline primer CORRPASSIV
was compared with a fast-drying two-component epoxy resin
primer (Messrs. Finalin, Type 144) and a metal-reactive two-
component primer with adhesion-promoting properties (Type
918). All three primers were coated with a two-component
polyurethane paint (B412). CORRPASSIV, both with and
without top coat, exhibited no rust formation beneath the
primer. The slight undermining receded after the test, and
even within the cross and scratch injuries it was virtually im-
possible to detect any corrosion.
The salt spray test was performed in accordance with DIN
50021 with an exposure time of 288 hours.
The primer was tested on one plate without top coat (with a
cruciform injury site), and on another with top coat (with
scratch damage).
Both coating systems were also assessed after the test for
adhesion, using the cross-hatch test (Fig. 14).
The cross-hatch test made it clear that the polyaniline
primer displayed the best adhesion, and also that here the cor-
rosion was confined solely to the damaged cross-hatch area
and the undermining effect was by far the smallest.
Fig. 14. CORRPASSIV without top coat: no rust under cross-hatch
cut
Abb. 14. CORRPASSIV ohne Decklack: kein Rost unter Gitter-
schnitt
Fig. 16. Metal-reactive two component primer with top coat: crak-
king and considerable undermining by rust
Abb. 16. Metallreaktive 2-K-Grundierung mit Decklack: Verspro-
dung und starke Rostunterwanderung
Fig. 17. CORRPASSIV with top coat: hardly any undermining, no
flaking of paint system at cross-hatch
Abb. 17. CORRPASSIV mit Decklack: kaum Untenvanderung,
kein Abplatzen des Lackaufbaus am Gitterschnitt
The epoxy resin primers used for corrosion protection proved
distinctly brittle and exhibited considerable rust formation
beneath the layers peeling off (Fig. 15).
On the comparison specimens with clearly poorer adhesion
properties, corrosion products were even found beneath the
intact areas of primer, and the coatings displayed either con-
siderable blistering or marked undermining in the region of
the cross (Fig. 16).
These results were confirmed in the specimens with poly-
urethane top coats. Here too CORRPASSIV displayed out-
standing results thanks to its excellent adhesion to substrate
and top coat.
With all three coatings corrosion was visible at the scratch.
Here CORRPASSIV displayed considerably less “bleeding”
of corrosion products than the comparison specimens.
The combination of polyaniline primer / polyurethane top
coat showed only a very small measure of undermining
(0 - 0.5 mm) (Fig. 17).
Materials and Corrosion 47, 439-445 (1996)
The comparison specimens exhibited varying degrees of
marked undermining of the coating (up to 4 mm), sometimes
with blistering as well.
4 Conclusions
The new organic metal polyaniline, almost a noble metal,
ennobles steel and other metal surfaces while shifting their
surface potential. It also passivates the conventional metal
by forming a metal oxide layer of up to 1 p thickness.
The passivation is “self healing” as can be seen from the
weak corrosion in scratches and other inquiries of the coating.
5 References
[l] D. W DeBeriy: J. Electrochem. SOC.132 (1985) 1022.
121 German Patent P 37 29 566.7, 1987, Zipperling Kessler & Co.
Corrosion prevention with polyaniline 445
131 B. Wessling: Adv. Mater (1994) 6.
[4l B. Wessling, Wei-Kang Lu, Ronald L. Elsenbaurner: “Corrosion
Protection of Mild Steel by Coatings Containing Polyaniline”,
JSCM 1994, SEOUL (Proc. Synth. Mat., in press).
PI B. Wessling: “Polyaniline an organic metal”, information bro-
chure of Firma Zipperling Kessler & Co.
r61 together with S.Schrodel; S.Gleeson, H. Merkle, E Baron.
t71 U. Ruhrberg: DECHEMA, test report: Tests on “passivated”
steel specimens, for Zipperling Kessler & Co., 1994.
[8] see technical informations “CORRPASSIV’, Zipperling Kess-
ler & Co, cf. http:flwwv Zipperling.de/.
P I together with Technische Fakultat Universitat Kiel, ongoing
research, unpublished.
(Received: April 14, 1995, W 3104
Revised version: November 10, 1995)