Progress in Organic Coatings 43 (2001) 274–281

Composition and behaviour of cerium films on galvanised steel

M.F. Montemor∗ , A.M. Simões, M.G.S. Ferreira
DEQ, Instituto Superior Técnico, Av. Rovisco Pais, 1049-001 Lisboa, Portugal
Received 6 April 2001; accepted 19 July 2001

Abstract
The composition and corrosion performance of galvanised steel treated by immersion in cerium nitrate solution was investigated by
electrochemical techniques and surface analysis. The surface film consists of a mixture of Ce(III) and Ce(IV) compounds, being very rich
in Ce(III) in the first instants of the deposition process and becoming gradually enriched in the more oxidised form, Ce(IV). The presence
of this film on the surface hinders the corrosion reaction by reducing the rate of both the cathodic and the anodic reactions. The film
becomes thicker but more uneven when the time of film growth increases, with the development of defects in the film, which in contact with
electrolyte behaves anodic with respect to the covered areas of the surface. These thicker films have revealed lower resistance to corrosion
initiation. © 2001 Elsevier Science B.V. All rights reserved.
Keywords: Galvanised steel; Cerium pre-treatment; Impedance; Auger electron spectroscopy; X-ray photoelectron spectroscopy

1. Introduction or other sub-microscopic features existing in the native

Chromates have been widely applied as corrosion in-
hibitors in aqueous media. Surface pre-treatments based
on the use of chromates have been successfully applied on
a large number of metal and alloys. The success of these
pre-treatments is mainly due to their high protection effi-
ciency/cost ratio. However, hexavalent chromium presents
very high toxicity and its use has been leading to legisla-
tion that will soon prohibit these pre-treatments. Therefore,
new alternative and more environmentally friendly surface
pre-treatments need to be developed. Recent efforts have
been focussed on the use of rare earth salts as corrosion
inhibitors. Among these, cerium has risen as a possible al-
ternative. The first studies on this field are those of Hinton
[1–3], who found that cerium was effective in reducing
the corrosion rate of aluminium alloys by inhibiting the
cathodic reactions. These preliminary studies using cerium
salts, namely CeCl3 , as corrosion inhibitors for aluminium
alloys have shown that the inhibition mechanism is associ-
ated with a reduction in the kinetics of the cathodic reac-
tions. Those authors suggested a mechanism involving the
activation across the metal surface of many electrochemical
cells associated with microscopic features such as grain
boundaries, precipitates, constituent phases and inclusions,
∗ Corresponding author.
E-mail addresses: pcfatima@alfa.ist.utl.pt (M.F. Montemor),
pcsimoes@alfa.ist.utl.pt (A.M. Simões).
oxide films. In that mechanism, the anodic (metal disso-
lution) and the cathodic reactions (oxygen reduction and
hydrogen evolution) occur preferentially at those sites. The
cathodic reactions generate an alkaline environment that
leads to localised precipitation of cerium-hydrated oxides
and thus to the formation of the surface film.
Davenport and coworkers [4,5] have shown that the
formation of the cerium films depends on the reduction
kinetics of oxygen. In aerated solutions, cerium is initially
depositsed as Ce(III) with further evolution to Ce(IV). Ac-
cording to the authors, this process is dependent on the
solution pH and on the amount of dissolved oxygen. The
authors conclude that cerium is oxidized from Ce3+ to
Ce4+ in solution, by dissolved oxygen and by the high pH
generated in the cathodic sites due to oxygen reduction.
In spite of the increasing number of works in this field
[6–10], the mechanism for precipitation and growth of
cerium films, as well as the way they provide corrosion
protection still generates some controversy. The present
work intends to characterise cerium films deposited on zinc
surfaces by simple immersion of the substrate in cerium
nitrate solutions. The modified surfaces were characterised
using X-ray photoelectron spectroscopy (XPS) and Auger
electron spectroscopy (AES). The corrosion behaviour
of the pre-treated substrates under immersion in sodium
chloride was investigated using the scanning kelvin probe
(SKP) technique, d.c. potentiodynamic polarisation and
electrochemical impedance spectroscopy (EIS).

0300-9440/01/$ – see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 3 0 0 - 9 4 4 0 ( 0 1 ) 0 0 2 0 9 - 0
 M.F. Montemor et al. / Progress in Organic Coatings 43 (2001) 274–281 275

2. Experimental Samples previously treated in cerium nitrate were coated

2.1. Materials
In order to produce a cerium surface film, cleaned and
degreased hot-dip galvanised (HDG) steel substrates were
immersed in cerium nitrate solutions (0.01 M) at ambient
temperature. Although long immersion times are not real-
istic in an industrial perspective, it was decided to test a
wide range of immersion times, in order to follow the Ce
deposition process. Therefore, immersion times between
10 s and 24 h were tested. After immersion, the samples
were oven-dried at 150 ◦ C (50 s). For the samples pre-treated
during 10 s and 24 h of immersion, wet adhesion was tested,
by using samples coated with a polyester–melamine primer.
with a polyester primer and tested under immersion in a
5% NaCl solution. The corrosion process was evaluated by
electrochemical impedance using a Gamry Instrument con-
stituted by an ECM8 Multiplexer, a FAS1 Femtostat and a
PC4 controlled board.
3. Results
The evolution of the open circuit potential during im-
mersion in cerium nitrate solution revealed an initial decay,
probably due to dissolution of zinc oxides on the surface,

2.2. Analytical experiments

AES and XPS analysis were performed using a VG

Scientific Microlab 310F. XPS experiments were performed
using a non-monochromatic Mg anode (K␣ = 1253.7 eV).
Auger depth profiles and Auger imaging (SAM) were
obtained using a 10 kV primary electron beam rastered over
a ×2000-magnified area.

2.3. Electrochemical experiments

The surface potential distribution was investigated on an

area of 9 mm2 , using an SKP from UBM.
The corrosion behaviour of the pre-treated samples was
studied during immersion in a 0.3% NaCl solution, using a
three-electrode arrangement. EIS measurements were made
using a 1255 Solartron Frequency Response Analyser and
a 1286 Solartron Electrochemical Interface. Potentiody-
namic polarisation was made using an Eco Chemie Autolab
Potentiostat. The scanning rate was 1 mV/s in the cathodic
or anodic direction, depending on the branch under study.

Fig. 1. Evolution of the open circuit potential obtained on a sample Fig. 2. Auger depth profiles obtained on samples treated with 0.01 M
immersed in 0.01 M Ce(NO3 )3 . Ce(NO3 )3 during different times.
276 M.F. Montemor et al. / Progress in Organic Coatings 43 (2001) 274–281

followed by a gradual shift in the cathodic direction and

finally a stabilisation after approximately 15 min of immer-
sion (Fig. 1). The potential shift in the cathodic direction is
probably caused by the development of a cerium layer on
the surface, and suggests some polarisation of the anodic
reaction.
Auger depth profiles obtained on the samples treated
during 10 s, 30 min and 24 h (Fig. 2) distinctly revealed
the presence of a layer of cerium deposited on the zinc
surface since the first instants of immersion. The thickness

Fig. 4. AES spectra obtained on a sample treated during 30 min P1 on

the spot; P2 outside the spot.

of the film increases with increasing time of immersion,

although most of the final thickness was developed in the
first 30 min, in agreement with the potential evolution. As-
suming an identical etching rate for all the samples, then
approximately half of the final film thickness had been
attained after the first 30 min. The cerium-to-oxygen ratio
also increased with the time of immersion, suggesting an
evolution in the composition of the film.
The elemental distribution on the surface was determined
by scanning Auger microscopy (SAM) (Fig. 3). In these
maps the lighter areas correspond to a high content of the
element under study, whereas the darker areas correspond
to depletion of that element. For the samples treated during
10 s the SAM maps (Fig. 3a) revealed a reasonably uniform
distribution of cerium and oxygen on the surface, with a
very weak signal from zinc. For longer immersion times,
however, the surface became heterogeneous (Fig. 3b and c,
with an increasing number of zinc-rich spots. AES spectra
obtained at these spots (Fig. 4) revealed a strong signal from
zinc and a very weak signal from cerium. The number of
these zinc-rich spots increased with the immersion time.
Their size was variable, but roughly in the range 5–10 ␮m.
Identification of the species formed on the surface was
made by XPS (Fig. 5). After 10 s, the shape of the spectra

Fig. 3. SAM obtained on samples treated during different immersion times Fig. 5. XPS spectra obtained after different treatment times in Ce(NO3 )3 :
in 0.01 M Ce(NO3 )3 . (A) 10 s; (B) 30 min; (C) 24 h.
 M.F. Montemor et al. / Progress in Organic Coatings 43 (2001) 274–281
revealed the presence of Ce(III) species, probably Ce(OH)3 .
For longer immersion times, the development of a satellite
at ∼916.0 eV, characteristic of the presence of Ce(IV) [11],
suggests the formation of CeO2 . The film can thus be de-
scribed as a mixture of Ce(III) and Ce(IV) compounds, with
a predominance of Ce(III) in the first instants of immer-
sion followed by an enrichment in Ce(IV). For the samples
treated during 24 h, XPS analysis also revealed the presence
of zinc oxides and/or hydroxides and zinc carbonates on
the surface, resulting from the development of the zinc-rich
spots mentioned above.
The distribution of the surface potential was investigated
using the SKP technique. Fig. 6a shows a potential map
obtained on a zinc sample in which a part of it was treated
with cerium nitrate during 10 s and another part was kept
without treatment. A potential difference up to 350 mV was
detected between the Ce-treated areas and the untreated
areas, the anodic potentials being detected at the untreated
areas. The same effect observed on a sample treated dur-
ing 24 h (Fig. 6b), which was the one that revealed the
largest number of zinc rich features observed during SAM
analysis. The potential map revealed localised potential gra-
dients larger than 400 mV on the surface. The anodic areas
Fig. 6. SKP potential map obtained on HDG steel: (a) untreated and Ce-treated (10 s) areas; (b) sample treated during 24 h in cerium nitrate.
277
(depressed areas in the picture) are probably related with the
presence of the zinc oxides/hydroxides spots observed by
AES and XPS, whereas the cathodic areas (plateaux) are as-
sociated with the presence of the cerium film. These results
are in good agreement with SAM, suggesting that when
the film thickens and becomes more uneven, large potential
gradients are generated on the surface. Given the spatial
resolution of the SKP technique, only the larger zinc spots
can be detected, but it can be assumed that the behaviour
is the same for the smaller ones. The presence of these po-
tential gradients may accelerate the corrosion process when
the samples are exposed to an aggressive environment.
The corrosion behaviour of the samples treated during
different immersion times in cerium nitrate was studied by
EIS, under exposure to 0.3% NaCl solution. Fig. 7 depicts
the impedance spectra obtained on samples treated during
10 s and 24 h, during immersion in NaCl. After 1 h of expo-
sure to NaCl (Fig. 7a) the samples treated during 10 s (those
with the thinner films) revealed the highest impedance val-
ues. This suggests that the presence of the zinc-rich spots
mentioned before may facilitate the initiation of the corro-
sion process. Thus, the thick, but uneven films formed by
24 h immersion did not achieve the protection afforded by
278 M.F. Montemor et al. / Progress in Organic Coatings 43 (2001) 274–281

Fig. 7. EIS spectra of HDG steel with cerium treatment and without treatment. Treatment time is indicated in the plot. Spectra obtained after 1 h (a) and
6 h (b) of immersion in 0.3% NaCl.

the thinner and uniform films formed on the samples treated
during 10 s. After 6 h of immersion (Fig. 7b), the impedance
of the sample treated during 10 s had decreased to about half
of its initial value, approaching that of the sample treated
during 24 h. The samples treated for 24 h thus seem to be
less protective in a first stage, but to be more stable during
immersion in NaCl. This is possibly because the corrosion
process occurs mainly in the defective areas of the film,
where the zinc is exposed.
The electrochemical behaviour of samples with differ-
ent treatment times in Ce(NO3 )3 during exposure to 0.3%
NaCl was also studied by potentiodynamic polarisation. It
was observed that the cerium layer decreased the rate of
both the anodic and the cathodic reactions (Fig. 8). The
treatment time affected the anodic response of the system
(Fig. 8A). Samples treated during 10 s and 30 min showed
higher corrosion potentials and lower corrosion currents
than the untreated HDG steel samples. The samples treated
during 24 h revealed the lowest corrosion potential, whereas
the corrosion current similar to the one measured on the
untreated HDG steel. The surface film formed on the sam-
ples treated during 10 s and 30 min slightly decreased the
anodic currents. Thus, the anodic dissolution of zinc seems
to be decreased in the presence of the thinner, but more
homogeneous films. In the cathodic branch, both the re-
duction of oxygen and the reduction of zinc oxides [8,12]
may occur. The presence of the cerium film also decreased
the rate of the cathodic reactions. The treatment time also
exerts a strong influence on the cathodic response of the
system (Fig. 8B). The sample treated during 10 s revealed
 M.F. Montemor et al. / Progress in Organic Coatings 43 (2001) 274–281
Fig. 8. Potentiodynamic polarisation curves obtained under immersion in
0.3% NaCl: (A) anodic curves; (B) cathodic curves.
the lowest cathodic current. Samples treated during 30 min
revealed cathodic currents slightly lower than HDG steel
and the behaviour of the sample treated during 24 h was
very close to that of untreated HDG.
Since the sample treated during 10 s revealed the best
corrosion resistance, its behaviour was compared with that
of a substrate pre-treated with Cr (Fig. 9). Relative to the
untreated HDG substrate, the treatments with Ce-10 s and
Cr resulted in a decrease of the cathodic currents, the lowest
values being obtained with the Ce treatment. The corrosion
current and corrosion potential were very similar for these
two samples. Thus, the presence of a uniform Ce(III)-rich
film seems to lead to increased cathodic protection. On the
other hand, the anodic response shows that Cr seems to
be more effective than Ce in constraining the anodic reac-
tions. Cr and Ce revealed anodic currents lower than those
of untreated HDG. These results suggest that for HDG
substrates, Ce exerts its influence mainly in the cathodic
reactions, whereas Cr affects more significantly the anodic
processes.
Following the results obtained above, pre-treated samples
were coated with a primer. After 1 day of immersion in 5%
NaCl, the sample with the thinner film (Fig. 10a) clearly re-
vealed a capacitive response over the frequency range under
279
Fig. 9. Potentiodynamic polarisation curves obtained under immersion in
0.3% NaCl: (A) anodic curves; (B) cathodic curves.
study, which can be correlated with the coating capacitance.
The sample treated during 24 h revealed a distinct behaviour.
At high frequencies the response was capacitive, however, at
low frequencies the resistance of the coating was observed,
with a value of ∼1 M cm2 . A time constant developing
at low frequencies reveals some corrosion activity. After 1
week of immersion, the shape of the spectra was identical
for both samples (Fig. 10b). At this stage, the coating re-
sistance is determined at the high frequencies, and it was
approximately 5 × 104  cm2 in the sample treated during
10 s, in comparison with a value of ∼2 × 103  cm2 in the
other sample. Also the charge transfer resistance was higher
in the sample with the 10 s treatment, although its exact
value cannot be observed in the spectrum. The EIS results
obtained on the coated samples has shown that the corro-
sion initiation was delayed in the presence of the uniform
Ce(III)-rich film. The presence of the spots observed on the
films formed during longer immersion times seems to help
to decrease the corrosion resistance, in accordance with the
previous electrochemical results obtained on the uncoated
samples.
280 M.F. Montemor et al. / Progress in Organic Coatings 43 (2001) 274–281
Fig. 10. EIS spectra of HDG steel with Ce pre-treatment (two different immersion times) and coated with primer after: (a) 1 day; (b) 7 days of immersion
in 5% NaCl.
4. Discussion
Cerium is known to act as a cathodic inhibitor for alu-
minium, zinc and steel in solutions of sodium and cerium
chlorides [3]. Further to this inhibiting effect, it has been
shown that the deposition of a film of cerium oxides and/or
hydroxides can be beneficial as a pre-treatment. The mech-
anism widely accepted for the formation of cerium films is
strictly correlated with the cathodic process occurring in the
surface. Thus, the production of alkaline conditions in the
cathodic areas due to oxygen reduction leads to precipitation
of cerium oxides and/or hydroxides. These compounds block
the cathodic sites, leading to a decrease of the corrosion
rate [13]. This effect has been shown for copper-containing
aluminium alloys [4,14,15], where a cerium-rich film was
detected over the copper precipitates as a consequence of
the increased cathodic activity at these sites.
In this work, the nature of the surface film was associated
with the presence of cerium oxides and hydroxides, namely,
Ce(OH)3 and CeO2 , its amount depending on the treatment
time. Film thickening and development of more heteroge-
neous films where anodic sites were identified, seems to
be closely associated with the formation of CeO2 . This
result suggests that a number of defects need to develop
in order to support the film thickening. In that case some
non-covered zinc zones must be observed on the surface.
This behaviour was confirmed for the thicker films formed
by immersion. The non-uniformity of the film is correlated
with the presence of some anodic sites. These results are in
accordance with Hinton et al. [2,16], who have pointed out
the need for the existence of anodic sites to promote further
growth of the film.
In another work, Geary and Breslin [17] observed the
presence of a non-uniform cerium film, however, protective,
on the surface of Sn/Zn alloy coatings. The non-uniformity
of the film was attributed to the fact that anodic and ca-
thodic processes continue through sub-microscopic defects
in the film. The electrochemical results correlate well with
the analytical data; the formation of a uniform film hinders
the initiation of the corrosion process (as shown by EIS)
and significantly reduces the rate of the cathodic reactions
(as shown by polarisation). On the other hand, the presence
of defects in the film, irrespective of its thickness, decreases
the resistance against corrosion initiation.
Therefore, the presence of anodic sites on the film facili-
tates the initiation of the corrosion process upon immersion
in sodium chloride solution. In this situation, the covered
areas may still remain protected, but the presence of defects
is determinant in the initiation of the corrosion process.
Thus, the treatment time seems to play a determinant role
on the characteristics of the surface film. Short treatment
times have resulted in a surface with better resistance to
chloride-induced corrosion.
Polarisation data provided evidence that the cerium
pre-treatment reduces the corrosion rate, by hindering the
rates of both the anodic (zinc dissolution) and the cathodic
(oxygen reduction) reactions. The inhibition of the anodic
reaction was also observed by Lu and Ives [6,18]. The
 M.F. Montemor et al. / Progress in Organic Coatings 43 (2001) 274–281
effect of the Ce film on the cathodic branch is in accordance
with results obtained by other authors [6,16,18] and can be
explained by the existence of a surface barrier to the sup-
ply of oxygen or electrons [16] (due to its high electrical
resistivity) to the oxygen reaction site. As consequence, the
reduction of oxygen, which is the rate-controlling step of
the corrosion process, is constrained.
The evolution of the potential revealed three stages in
the process of cerium deposition. A first stage of activation,
characterised by a potential decrease of only a few milli-
volts, followed by a potential growth during approximately
10–12 min, and a potential stabilisation after that. In the first
stage, a very thin layer of Ce(OH)3 precipitates, while proba-
bly some of the zinc oxides dissolve from the surface. During
the second stage, zinc dissolution occurs, and concomitantly
with that, cerium oxides precipitate as a consequence of the
cathodic reaction. Assuming that there are no preferential
sites for the cathodic reaction to occur, the deposition pro-
cess occurs in a practically uniform way, covering the surface
with a thin film of cerium oxides that, due to its impedance,
limits the cathodic reaction at its outer surface. The rise
of the potential to less anodic values, however, reveals that
the film hinders also the anodic reaction. In the third stage,
the potential practically becomes constant. The film grows
slowly, although with a separation between the partial reac-
tions at the surface. The cathodic reaction can only take place
at the surface of the cerium oxide film, whereas the anodic
sites are essentially located at the zinc-exposed areas, i.e.,
at the defects of the film. At this stage, the composition of
the film has changed, with enrichment in Ce(IV). Although
this evolution is not fully understood, one possible explana-
tion is that when the Ce(III) film becomes reasonably thick,
oxidation of Ce(III) can occur at the surface, according to
the scheme:
2Ce(OH)3 + 2OH− → 2CeO2 + 4H2 O + 2e−
H2 O + 21 O2 + 2e− → 2OH−
These reaction lead to the oxidation of cerium, but will not
affect the pH at the surface.
Since the aim of these pre-treatments is the formation
of a surface film for the application of coil coatings, it is
essential to ensure good adhesion and reasonable corrosion
protection. The results obtained in this work show that the
coated samples performance is strongly influenced by the
characteristics of the surface film. A uniform and thin film
helps to coating adhesion and consequently to increased
corrosion resistance. Comparatively, in the presence of the
thicker and defects-rich films the corrosion process of the
coated samples is significantly accelerated.
281
5. Conclusions
The deposition of cerium nitrate results in a surface film,
whose thickness increases with the treatment time. The
presence of the Ce film constrains the cathodic reduction
of oxygen and the anodic dissolution of zinc resulting in a
decrease of the corrosion rate.
Short treatment times result in uniform surface films
mainly composed by Ce(III) species, which are more
resistant to the initiation of the corrosion process both for
uncoated and coated substrates.
For long immersion times, the film becomes uneven and
is mainly composed by Ce(IV) oxides. The heterogeneity of
the surface results in areas where the zinc is exposed and
that work as anodic sites.
A solid-state mechanism for the oxidation of the Ce(III)
to Ce(IV) is proposed.
Acknowledgements
The authors acknowledge funding from the ECSC pro-
gramme (Contract No. 7210-C-066) and the support from
POCTI. Our project co-ordinators, Dr. H. Edwards and Dr.
D. Hammond from CORUS WTC, Port Talbot, UK, are
also acknowledged for providing the coated samples and
for several interesting discussions.
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