Surface and Coatings Technology 155 (2002) 221–230

Electrochemical study on the corrosion resistance of Cr III-based

conversion layers on zinc coatings
T. Bellezze, G. Roventi, R. Fratesi*
Dipartimento di Fisica e Ingegneria dei Materiali e del Territorio, Universita` di Ancona, Via Brecce Bianche, 60131 Ancona, Italy

Received 19 September 2001; accepted in revised form 4 February 2002

Abstract

Zinc coatings submitted to a Cr III-based passivation treatment, with and without a sealing treatment, were studied. For
comparison, similar coatings with a Cr VI-based passivation treatment were also examined. The corrosion behaviour was studied
by polarization resistance (Rp ) measurements, anodic polarization and mainly by electrochemical impedance spectroscopy (EIS)
in aerated 0.85 M NaCl solution. Salt spray tests and morphological observations on the coating surface were also performed.
The results indicate that the Cr III passivated coatings with sealing treatments have a corrosion resistance comparable with that
of coatings with a Cr VI passivation treatment without a sealant; therefore, they could be a less polluting alternative to the
traditional chromated coatings. 䊚 2002 Elsevier Science B.V. All rights reserved.

Keywords: Zinc; Chemical conversion; Impedance spectroscopy; SEM; Salt spray; Pitting corrosion

1. Introduction barrier to humidity and air, but allow chromate ions to

In the last 20 years, zinc plating has seen remarkable
development because of the increasing demand from the
automotive industry for coatings with better corrosion
resistance w1x.
The corrosion resistance of pure zinc coatings can be
improved by means of suitable chemical passivation
treatments, performed generally by immersing the zinc
coated articles in baths containing chromic acid or an
acid solution of Cr VI salts w2–4x. During immersion, a
chemical reaction on the coating surface leads to the
formation of a passivation layer 10–1000 nm thick,
containing zinc oxides and hydroxides, zinc chromate,
mixed Cr III and Cr VI oxides and hydroxides w2x. In
particular, Cr(OH)3 is formed due to Cr VI reduction
and to reduction of either water, hydrogen ion, or
dissolved oxygen to form hydroxyl ions at the metal
surface w2–4x. Chromate passivation baths also contain
‘activators’ such as fluoride, sulfate, acetate, etc., which
lead to thicker conversion layers w3,4x. These layers
protect the zinc coating because they form a non-reactive
*Corresponding author. Tel.: q39 071 2204741; fax: q39 071
2810327.
E-mail address: fratesi@popcsi.unian.it (R. Fratesi).
leach out and to act as corrosion inhibitors w5,6x.
Furthermore, when scratched or mechanically damaged,
enough water is absorbed by the layer to swell and
mend the damaged areas (self-healing effect) w3–6x.
In Europe, the use of Cr VI compounds, considered
a cancer-producing agent w3,6x, must be withdrawn
within a short time, according to the directive 94y60y
CE 20-12-1994. Several alternative passivation treat-
ments have been proposed by researchers w3,6–10x;
these are processes based on molybdates, permanga-
nates, titanates, rare earth metals and Cr III (considered
to be non-carcinogenic) compounds. Promising results
have been found without the need for toxic chemical
additives with application of alternating current together
with the addition of inorganic nitrogen compounds in
an electrochemical bath w11x.
In this work, zinc coatings obtained from a NaOH-
based alkaline bath, with a Cr III-based passivation
treatment leading to Cr VI-free conversion layers, were
studied. After passivation, some samples were submitted
to sealing treatments, which formed layers of Si com-
pounds both in prevalently organic and in prevalently
inorganic matrices. These treatments cover the porosity

0257-8972/02/$ - see front matter 䊚 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 2 5 7 - 8 9 7 2 Ž 0 2 . 0 0 0 4 7 - 6
222 T. Bellezze et al. / Surface and Coatings Technology 155 (2002) 221–230

Table 1
Treatments performed on zinc coatings; identification symbols and chemical–physical characteristics of the obtained coatings

Process type Sample Coating Conversion Cr Si

identification thickness layer content content
symbol (mm) thickness (mg cmy2) (mg cmy2)
(mm)
Cr III-based passivation treatment C3 14.7 0.07 4.9 –
Cr III-based passivation treatmentqsealing C3SI 13.6 0.25 4.2 86.9
treatment (layer of Si compounds in
prevalently inorganic matrix)
Cr III-based passivation treatmentqsealing C3SO 12.1 1.20 4.6 327.3
treatment (layer of Si compounds in
prevalently organic matrix)
Cr VI-based passivation treatment C6 13.5 0.36 31.2 –
Cr VI-based passivation treatmentqsealing C6SI 13.3 0.54 20.3 158.9
treatment (layer of Si compounds in
prevalently inorganic matrix)
Cr VI-based passivation treatmentqsealing C6SO 14.0 1.63 13.6 251.5
treatment (layer of Si compounds in
prevalently organic matrix)
No conversion treatment ZN 14.2 – – –

and the cracks in the passivation layer surface and
improve the corrosion behaviour even after heating w12x.
The corrosion behaviour was studied by means of
electrochemical impedance spectroscopy (EIS), polari-
zation resistance measurements (Rp) and anodic polari-
zation in 0.85 M NaCl solution. A discussion on the
analysis of EIS data is also carried out. Electrochemical
test results were compared to those of salt spray tests.
Morphological investigations were performed on the
coating surface by scanning electron microscopy (SEM)
before and after immersion in the corrosive solution.
2. Experimental
Zinc coatings were obtained on mild steel sheets
(total area 56.2 cm2) in an industrial rack plating plant
from a cyanide-free alkaline bath containing Zn2q 11–
19 g ly1, NaOH 110–190 g ly1 and commercial addition
agents (T 25 8C; j 1.5–3 A dmy2). After zinc deposi-
tion, the samples were submitted to different conversion
treatments, shown in Table 1 with the obtained samples
identification symbols. Cr III and Cr VI passivation
treatments were performed using, respectively, Max Blue
and Max Tropical CLN (Glomax s.r.l.). Sealant layers
with prevalently organic and inorganic matrices were
obtained using, respectively, Zinc Protector White and
Zinc Protector 1000 (Glomax s.r.l.).
The composition of the coatings was determined by
means of inductively coupled plasma spectroscopy
(ICP) after stripping the deposits in HCl 1:3 with
hexamethylenetetramine to inhibit dissolution of the iron
substrate. The coating thickness was measured by the
magnetic inductive method.
Before and after corrosion tests, morphological anal-
yses of the coatings were conducted by means of
scanning electron microscopy (SEM) and energy dis-
persive X-ray spectroscopy (EDXS). To evaluate the
conversion layer thickness, the samples were fractured
in liquid N2, and SEM analysis was conducted on the
cross-sections.
The corrosion resistance was studied by means of
electrochemical impedance spectroscopy (EIS) and
polarization resistance (Rp) measurements during an
exposure time of 21 days. Anodic polarization curves
after 1.5 h of immersion were also carried out. The
electrochemical measurements were performed under
potentiostatic control in quiescent aerated 0.85 M (5%)
NaCl solution at 25"1 8C (pH 6.4). The cell was
obtained by securing a plexiglass tube to the sample
with epoxy resin (exposed area 13.7 cm2). The reference
electrode was saturated calomel (SCE) and the counter-
electrode was a platinum sheet. The EIS measurements
were performed using an EG&G P.A.R. 273 potentiostat,
connected to a Solartron 1255 frequency response ana-
lyser. The frequency range used was varied depending
on the coating studied, but was always kept between a
maximum value of 50 or 60 kHz and a minimum value
of 1.5 or 2 mHz. Seven or eight measurementsydecade
were carried out and a sinusoidal signal of 5 mV in
amplitude was applied around the corrosion potential.
The sample integrity was checked by measuring the
corrosion potential after all the tests to confirm that the
change from the initial value was no higher than "5
mV. To correlate the admittance found at high frequen-
cies with the conversion layer damage, some measure-
ments were carried out within 4 h from the start of
immersion in the saline solution. In this case, the
experimental conditions were as described above, but
five measurementsydecade in the frequency range 100
kHz–10 mHz were carried out. Rp measurements were
 T. Bellezze et al. / Surface and Coatings Technology 155 (2002) 221–230
performed using an EG&G P.A.R. 273 potentiostat, with
potentiodynamic scans from Ecorry10 to Ecorrq10 mV.
The scan rate vscan was calculated according to the
equation proposed by Mansfeld and Kendig w13x:
vscanŽmVys.s2y2ØVacŽrms; mV.ØpØfintŽHz.
where Vac is the amplitude of sinusoidal signal used
during impedance measurements and f int is the frequen-
cy obtained from the Bode-NZN diagram in correspon-
dence of the medium point of the horizontal part at low
frequencies. In this case, the criterion defined to choose
the frequency used in the equation above is different
from that proposed by Mansfeld and Kendig w13x. If the
horizontal part was not detected in the Bode diagram,
because of the presence of diffusive processes or because
the minimum values of the frequency range used was
not low enough for the dc-limit, the scan rate used was
0.05 mV sy1. Therefore, the Rp measurement was
performed in any case after the EIS measurement.
Anodic polarization curves were carried out using a
scan rate of 1 mV sy1.
The corrosion resistance of the coatings was also
studied by exposing the samples in a salt spray chamber
(ASTM B 117: NaCl 5%, T 35 8C). The surface
percentage covered by white rust was evaluated at
various exposure times. In order to evaluate the effects
of heat treatment on the corrosion resistance, some
samples were heated at 120 8C for 1 h, before the salt
spray test w14x.
The corrosion behaviour of the passivated materials
strictly depends on the production procedure; therefore
all the tests were repeated three times and the results
obtained for the sample showing the average behaviour
of each series are reported in the figures.
3. Results and discussion
The chemical–physical characteristics of the studied
coatings are reported in Table 1. Coatings submitted to
sealing treatments have a higher conversion layer thick-
ness, in particular when the organic matrix-based sealant
is present. The sealing treatments do not change the
chromium content on coatings with Cr III-based conver-
sion treatment, but cause a decrease in the chromium
content on the coatings submitted to Cr VI-based con-
version treatment, indicating that during the sealing
processes some chromium is lost w12x.
The morphological analysis indicates that the samples
submitted to Cr III-based passivation treatment (C3)
have a rough surface (Fig. 1a). Samples submitted to
Cr III-based passivation treatmentqsealing treatment
(formation of a layer of Si compounds in prevalently
organic matrix) (C3SO) show a network of micro-
cracks on the surface (Fig. 1e). The surface of the
samples submitted to a Cr VI-based passivation treat-
ment (C6, Fig. 1b) has a network of very thin, parallel
223
micro-cracks which are limited to the conversion layer;
the surface of the samples submitted to a Cr VI-based
passivation treatmentqsealing treatment (formation of
a layer of Si compounds in prevalently inorganic matrix)
(C6SI, Fig. 1d) is very similar to that of samples
submitted to a Cr III-based passivation treatmentq
sealing treatment (formation of a layer of Si compounds
in prevalently inorganic matrix) (C3SI, Fig. 1c). The
surface of samples submitted to a Cr VI-based passiva-
tion treatmentqsealing treatment (formation of a layer
of Si compounds in prevalently organic matrix) (C6SO,
Fig. 1f) is almost similar to that of C3SO samples (Fig.
1e), even if the conversion layer thickness is higher
(Table 1).
The corrosion behaviour of chromium-based conver-
sion layers was mainly studied by EIS measurements; a
comparison with Rp measurements was also made. Cor-
rosion potential values for all coatings ranged between
y1018 and y1033 mV SCE at the start of immersion.
During the immersion period they did not change more
than 20 mV from their initial value.
In general, the major difficulty in EIS data analysis
is to find an equivalent electrical circuit model andyor
parameters that give, for the analysed systems, good
corrosion behaviour indications. Some authors have
reported circuit models, which can be used to simulate
EIS data from measurements on chromium- and molyb-
denum-based conversion layers w8,15–17x; other
authors, rather than suggesting circuit models, report
partial analysis based on Nyquist and Bode plots w18–
21x. Normally, after EIS measurements, chromium-based
conversion layers show, at least in the first stage of the
electrolytic solution exposure, two time constants at
different frequency ranges w15–18,21x; data analysis is
particularly problematic in the high frequency region.
Zeller and Savinell w18x limited their analysis to the
distortions in this region of the spectrum. In a subsequent
` et al. w16x judged this interpretation incom-
paper Pirnat
plete and proposed an equivalent circuit with a high
frequency time constant, attributed to the chromate layer
and considered this layer as a capacitor with the plates
formed by the metal substrate and electrolyte solution.
Similar considerations are reported by other authors
w8,15,17x. In other papers, the first loop at high frequen-
cy was not attributed explicitly to the chromate layer,
but the low value of 6 mF cmy2 calculated for the
corresponding capacitance was assumed to be related to
the presence of the chromatation film w20,21x. Finally,
Hazan et al. w19x reported a loop at high frequency with
a low capacitance (8.7 mF cmy2) at the first stage of
immersion, which was identified as ‘double layer capac-
itance’ and related to a surface film.
In the present work, an equivalent circuit model that
could completely describe the corrosion behaviour of
the studied conversion layers during the overall obser-
vation period was not found and, therefore, a ‘corrosion
224 T. Bellezze et al. / Surface and Coatings Technology 155 (2002) 221–230

Fig. 1. Microstructure of the studied coatings: (a) C3; (b) C6; (c) C3SI; (d) C6SI; (e) C3SO; (f) C6SO.

parameter’ Rac was proposed. Barcelo´ et al. w20x also
used Rac and measured the value corresponding to a
chromated zinc coating by reading the total resistance
in the Nyquist plot. A parameter representing the cor-
rosion trend was introduced, for example, by Kendig et
al. w22x to study organic coatings and by Almeida et al.
w8x to study conversion layers based on chromium and
molybdenum on zinc; the former named this parameter
‘Rcor’, the latter ‘Rtot’. In both cases a circuit model and
the corrosion parameter expressed by the sum of the
series resistances, corresponding to the impedance at
low frequency, was proposed. In the present work, Rac
was not measured using the Nyquist plot and it was
impossible to calculate a sum of series resistances
because a circuit model was not available. In order to
obtain an indication of impedance in the low frequency
range, for the conversion layer, Rac can be evaluated
from the Bode-NZN plot and taken as equal to the dc-
limit, when present. When the dc-limit was not present
(for example in those cases where a diffusion tail or a
non-closed loop are present in the Nyquist plot), Rac is
taken as equal to the NZN value corresponding to the
minimum frequency of the range employed in EIS
measurements. An approach based on plotting the trend
of the resistance, measured at a fixed frequency, in
function of the immersion time, was proposed by Magal-
˜ et al. w23x.
haes
In Fig. 2a,b the Rac-time and Rp-time curves, respec-
tively, are reported. In general, they give similar infor-
mation and in particular, Cr VI-based coatings have a
better corrosion resistance than Cr III-based coatings.
C6SI, which initially has the highest resistance, shows
 T. Bellezze et al. / Surface and Coatings Technology 155 (2002) 221–230 225

Fig. 2. Rac-time curves (a) and Rp-time curves (b) during immersion in quiescent aerated 0.85 M NaCl solution. (—m—) ZN; (ØØØjØØØ) C3;
(ØØØdØØØ) C3SI; (ØØØ⽧ØØØ ) C3SO; (—j—) C6; (—d—) C6SI; (—⽧—) C6SO. (c) SEM image of some defects on C6SI samples.

after 1 day, an abrupt decrease both in Rac and in Rp
values; after 7 days they strongly increase and the C6SI
resistance becomes once again the highest. Visual obser-
vation of the sample after 5 days of immersion did not
show the presence of localised attack, contrary to what
happens for C3 sample. This anomalous behaviour could
be attributed to the presence on its surface of small
defects which can act as an electrical shunt (Fig. 2c);
on prolonging the immersion these pits are occluded
and the resistance increases. Between Cr III-based coat-
ings, C3SO shows the best corrosion resistance. For
comparison, Fig. 2 also shows the non-passivated zinc
corrosion behaviour. From 1 to 5 days of immersion,
zinc shows excessively high resistance values (;40–
80 kV cm2) probably related to the presence of a layer
of white corrosion products on its surface. This layer
breaks off after 7 days and the resistance then assumes
lower values.
Subsequently, an EIS data analysis in the high fre-
quency region of the spectrum was performed in order
to obtain a representative indication of the degree of
coating damage. Fig. 3 shows the variation in the Bode-
NZN curves for the C3 coating during 4 h of exposure.
In the high frequency region, it is clear that the oblique
line shifts towards low frequencies. From the hypothesis
that the Bode plot high frequency region is sensitive to
the coating damage, a linear fitting procedure, which
characterises quantitatively the line considered above,
has been developed. At first, the linear trend at high
frequency was assigned to a constant-phase element
(CPE), whose admittance is YsYo( jv)n w24x; from the
slope and the intercept corresponding to the fitted line,
226 T. Bellezze et al. / Surface and Coatings Technology 155 (2002) 221–230

Fig. 3. Bode-NZN plot for C3 coating at different immersion times in

quiescent aerated 0.85 M NaCl solution. (—⽧—) 5 min; (—m—)
40 min; (—d—) 100 min; (—j—)240 min.

it is possible to calculate n and Yo, after correction for

solution resistance. This fitting procedure is similar to
that applied by Shih and Mansfeld w25–27x.
On plotting Yo and n constants as a function of time,
it is possible to observe the increase in the first quantity
and the decrease in the second quantity, as indications
of coating damage. This approach has been used by
other authors for coatings with passivation layers
w19,25,27,28x, although they used the capacitance Fig. 4. Yo-time curves during short (a) and long (b) immersion in
increase rather than the admittance increase. quiescent aerated 0.85 M NaCl solution. (ØØØjØØØ) C3; (ØØØdØØØ)
The high frequency data analysis results, for an C3SI; (ØØØ⽧ØØØ ) C3SO; (—j—) C6; (—d—) C6SI; (—⽧—)
immersion time of 4 h in a NaCl 5% solution, are C6SO.
shown in Fig. 4a. The admittance Yo, for the C3 coating,
increases sharply in comparison to the other coatings ides), which changes in the presence of the two different
whose values remain almost constant, close to their sealants, then, for the same exposed area, a lower
initial ones. This trend indicates a high degree of damage capacitance corresponds to a higher conversion layer
on the C3 coating, whereas no damage was revealed on thickness. The results reported in Tables 1 and 2 agree
the other coatings because the corresponding Yo-time with this hypothesis (CC6-CC3; CC6SI-CC3SI; CC6SO-
curves show the same trend, irrespective of their relative CC3SO) confirming that, in the early stages of immersion,
positions. In the present work, the n-time trends did not the high frequency loop could be physically related to
give significant indications on the corrosion resistance; the conversion layer. On passing from the conversion
in fact, for all the samples, the n quantity slightly layer without sealant to the conversion layers with the
decreased and ranged between 0.9 and 0.7. two sealants, both in Cr III and in Cr VI series, the
Even though it was not possible in this work to use
an equivalent circuits approach to analyse the impedance Table 2
data during the overall observation period, the two time Conversion layer capacitance values obtained from the high frequency
constant models could be useful in the early stages of region of the impedance spectrum after 5 min of immersion in salt
solution
immersion to characterise physically the conversion
layers w17x. In the present case, at 5 min of immersion Coating Capacitance
n is close to 1 and Yo could be approximated to a (mF cmy2)
capacitance quantity C. Table 2 shows the calculated C3 0.62
capacitance values for the conversion layers examined; C3SI 7.28
similar low values were obtained by other authors C3SO 1.93
w8,17,21x. On assuming that Cr III- and Cr VI-based C6 0.21
passivation layers have the same dielectric constant C6SI 5.97
C6SO 0.91
(they basically contain chromium oxides and hydrox-
 T. Bellezze et al. / Surface and Coatings Technology 155 (2002) 221–230 227

Fig. 5. Morphology of the corrosion attack on the studied coatings after 21 days of immersion in quiescent aerated 0.85 M NaCl solution. (a)
C3; (b) C6; (c) C3SI; (d) C6SI; (e) C3SO; (f) C6SO.

values reported in Table 2 demonstrate that the dielectric
constant changes significantly, because a decrease in
conversion layer thickness (Table 1) does not lead to
an increase in capacitance (Table 2).
In Fig. 4b, the Yo-time curves for long immersion
times are reported. Again, the C3 coating curve increases
sharply, indicating a high degree of damage; the sharp
increase in C6 Yo-time curve indicates that pitting
corrosion affects a wide area. The C3SO and C3SI show
a similar behaviour: the pitting corrosion starts before
that of C6, but the area affected is smaller w27x. The
C6SI coating shows an abrupt increase in Yo, which
remains high until 7 days of immersion, confirming the
Rac and Rp measurements (Fig. 2a,b). It is clear that
C6SO is the coating with the best resistance to corrosive
agents. For all the coatings, the quantity n (not shown)
slightly decreased with time and ranged between 1 and
0.6. Shih and Mansfeld, for conversion layers obtained
by CeCl3-based treatments on aluminium, previously
correlated the capacitance increase with the corrosion
initiation by the pitting mechanism w25,27x. SEM obser-
vations after 2 days of immersion showed that the
corrosion of the coatings studied in this work initiates
with a pitting mechanism w29x. The dimensions of the
pits correlate well with the increase in Yo-time curves,
indicating that pitting corrosion can be revealed by the
admittance increase.
Morphological analysis confirms the indications
offered by Yo quantity (Fig. 4b). Fig. 5 shows the
morphology of the corrosion attack on the studied
228 T. Bellezze et al. / Surface and Coatings Technology 155 (2002) 221–230

formation of corrosion products, which exerts a barrier

effect. The decrease occurs more markedly and at
potentials more negative for the coatings with lower
corrosion resistance w30x. These results indicate that C3
has the lowest corrosion resistance while C6SI has the
highest.
Fig. 7 shows the surface percentage covered by white
rust vs. time during the salt spray exposure of the
samples without (Fig. 7a) and with (Fig. 7b) heat
treatment at 120 8C for 1 h. The C3 coating shows very
poor corrosion resistance. The C3SO and C3SI coatings
have better corrosion resistance than C6, particularly
when the coatings have been submitted to heat treatment
(Fig. 7b). Usually, the conversion coatings have worse
corrosion resistance after heat treatment; on the contrary,
the C3SO coating shows a considerable improvement in
its corrosion behaviour after heat treatment and this, in
agreement with other authors w12x, is an effect due to
the sealant. The results of the salt spray exposure tests
correlate well with the indications offered by the
increase in Yo quantity (Fig. 4), in particular they
confirm the lower corrosion resistance of C6 with
respect to that of C3SI and C3SO. On the other hand,

Fig. 6. Anodic polarization curves in quiescent aerated 0.85 M NaCl

solution. (—m—) ZN; (ØØØhØØØ) C3; (ØØØsØØØ) C3SI; (ØØØeØØØ)
C3SO; (—j—) C6; (—d—) C6SI; (—⽧—) C6SO. Scan rate: 1
mV sy1.

coatings at the end of the immersion period. For all the

coatings, the corrosion occurs by localised attack: the
conversion film breaks off from the zinc substrate and
the aggressive solution can penetrate to give corrosion
products, which cause new cracks. EDXS analysis
revealed the presence of chlorides in the inner points of
the pit and around it, indicating the formation of corro-
sion products below the conversion layer. In the case of
the C3 coating (Fig. 5a), the attack affects a very wide
area; on the other coatings the attacked zones are smaller
and C6SO (Fig. 5f) is the less damaged coating. The
pits observed on C6SI (Fig. 5d) are small, confirming
that the trends of Rac, Rp and Yo in the 2–7 day range
are anomalous.
Fig. 6 shows anodic polarization curves performed on
the studied coatings and, for comparison, on bare zinc
coating. At potentials of approximately y850 mV bare
zinc has the highest current density. The C3 sample
shows behaviour similar to that of bare zinc, according
to its very thin conversion layer. The other coatings
have a lower current density and, in particular, show a
curve inflection at approximately y900 mV, which
Fig. 7. Surface damage during salt fog exposure of samples without
indicates a passive behaviour. At potentials from y350 (a) and with (b) heat treatment at 120 8C for 1 h. (ØØØjØØØ) C3;
to q250 mV a minimum in current density was found (ØØØdØØØ) C3SI; (ØØØ⽧ØØØ) C3SO; (—j—) C6; (—d—) C6SI;
for all the coatings; this decrease can be related to the (—⽧—) C6SO.
 T. Bellezze et al. / Surface and Coatings Technology 155 (2002) 221–230
Rac, determined from EIS measurements (Fig. 2a), over-
estimates the performance of the C6 coating which has
Rac values similar to that of C6SO, while salt spray test
results indicate that its corrosion resistance is lower than
that of C3SI, C3SO, C6SO and C6SI. This can be
explained by considering that Rac could include the
contributions from the impedance due to the intact
conversion layer, as well as to corrosion products, while
Yo could be related to the intact conversion layer only.
4. Conclusions
The corrosion behaviour of zinc coatings submitted
to a Cr III-based passivation treatment, with and without
sealing treatment, were studied. For comparison, similar
coatings with Cr VI-based passivation treatment were
also examined. The investigations were performed by
electrochemical tests in aerated 0.85 M NaCl solution
(impedance measurements, polarization resistance meas-
urements and anodic polarization curve registration), by
salt spray tests and by morphological observations on
the coating surface.
Consideration of EIS data analysis has not been able
to provide an equivalent circuit model capable of com-
pletely describing the corrosion behaviour of the studied
conversion layers on zinc coatings on steel during the
overall observation period. Therefore, two quantities,
the impedance modulus Rac and the factor Yo of a CPE,
were obtained from the Bode-NZN plot: the first one was
obtained from the low frequency range data and the
second was calculated by a linear fitting of the high
frequency region data. These quantities Rac and Yo give
similar information, but Rac overestimates the corrosion
behaviour, for example, of the unsealed Cr VI coating
(C6) in comparison with the corresponding sealed coat-
ing with prevalently organic matrix (C6SO), whereas
Yo, for long immersion times, shows that C6 corrodes
before C6SO. Besides the anomalous behaviour of the
C6SI, the results obtained in this work show that Yo is
a parameter able to give rapid indications on the corro-
sion properties of the conversion layers and correlates
well with salt spray test results. It is noteworthy that the
salt spray test required more than 15 days to give the
indications offered by Yo after 5 days. Probably, the Yo
increase, as a function of immersion time, is related to
corrosion initiation occurring by the pitting mechanism.
At least during the early stages of salt solution exposure,
Yo could be related to the physical properties of the
conversion layer.
In general, the coatings based on Cr VI showed a
better corrosion behaviour compared with the Cr III-
based coatings, but it is noteworthy that the sealed Cr
III coatings, in particular C3SO, have a higher corrosion
resistance than the unsealed Cr VI coating C6. These
results indicate that the presence of the sealant consid-
229
erably improves the corrosion behaviour of the Cr III
conversion layer and can be used as alternative to the
traditional chromating treatment.
Acknowledgments
The authors are grateful to Dr G. Faranda (Glomax
s.r.l.) for the samples preparation.
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