Corrosion Science 78 (2014) 251259

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Corrosion Science
jou r n a l h o m ep ag e: www. e l s evi er .c o m /l oca t e/co
rsci

Corrosion behaviour of chromium coatings obtained by direct

and reverse pulse plating electrodeposition in NaCl aqueous solution
N. Imaz a, M. Ostra b, M. Vidal b, J.A. Dez a, M. Sarret c, E. Garca-Lecina a,
a
b
c

Surfaces Division, IK4-CIDETEC, Paseo Miramn 196, 20009 Donostia-San Sebastin, Spain
Department of Applied Chemistry, Universidad del Pas Vasco, Avda. Manuel de Lardizabal 3, 20018 Donostia-San Sebastin, Spain
ELECTRODEP, Department of Physical Chemistry, University of Barcelona, Mart i Franqus 1, 08028 Barcelona, Spain

a r t i c l e

i n f o

Article history:
Received 5 June 2013
Accepted 2 October 2013
Available online 12 October 2013
Keywords:
A. Metal coatings
B. EIS
B. Polarization
B. SEM
C. Passive lms
C. Electrodeposited lms

a b s t r a c t
In this work the corrosion performance in chloride media of chromium coatings obtained by direct current (DC) and pulse current (PC1 and PC2) was studied. The electrochemical corrosion behaviour of the
layers was characterized by means of potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS) techniques. Additionally, metal cation release and morphological evolution of
chromium surfaces as a function of immersion time in chloride solution was analyzed. The obtained
results show similar hardness values and a superior corrosion performance of PC2 coatings, which is
related to their roughness, morphology, wettability and mainly, their crack absence.
2013 Elsevier Ltd. All rights reserved.

1. Introduction
Hard chromium coatings obtained by wet processes are extensively used as the nal surface nishing operation in many industrial applications, such as aerospace, automotive, and general
engineering industries. This is due to the special properties of this
metal, including its resistance to heat, wear, erosion, galling and
low coefcient of friction. However, the electrochemical reactions
and mechanisms involved in plating processes from chromic acid
electrolytes, mainly the dominant hydrogen evolution that takes
place during electrodeposition, cause low current efciency, affect
the nanocrystalline structure of obtained surfaces and lead to the
cracking of chromium deposits, to the detriment of their corrosion
resistance [1,2]. Corrosion is the principal factor limiting the lifetime of hard chromium plated components. Even though some
alternatives to hexavalent chromium are being sought, today hard
chromium coatings are still the nishing required by very demanding industries, since for the time being no other alternative process
that achieves the required mechanical and tribological characteristics has been developed. As a result, many manufacturers and engineers of different industrial elds strongly require to improve the
protective properties of these coatings, while maintaining their
mechanical and tribological properties.

Corresponding author. Tel.: +34 943 309 022; fax: +34 943 309 136.
E-mail address: egarcia@cidetec.es (E. Garca-Lecina).

0010-938X/$ - see front matter

2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.corsci.2013.10.005

Pulse plating, that is, the electrochemical deposition using a

periodic current, could represent an effective and feasible method
to improve the characteristics of metallic coatings. Pulse plating
techniques have a reported inuence into the microstructure, morphology and properties of electrodeposits, as a result of the effect
of pulse parameters on a wide range of electrochemical phenomena including mass transport, charge transfer kinetics, nucleation
rate, adsorption, desorption and recrystallization that take place
during anodic and interruption times [3,4].
Several authors [46] have studied the inuence of some pulse
parameters on the structural and physical properties of electrodeposited chromium coatings. In particular, in a previous work [7] we
studied the effect of reverse pulse plating on chromium coatings,
carrying out a multivariate analysis to establish a relation between
their structure and physical characteristics. The study established
an interrelation among pulse parameters and the structural (crystalline structure, crystal size, cracking, morphology) and physical
properties (appearance, hardness, wettability, corrosion) of chromium layers. Among the different chromium deposits obtained
using the pulse plating conditions studied in the aforementioned
work, two main types of behaviour could be distinguished. Thus,
pulse plating sequences with high Qc/Qa ratio led to cracked
surfaces with structural and physical properties similar to those
presented by DC coatings, while pulse plating sequences with
low Qc/Qa ratio led to chromium surfaces with noticeably different
structural,
morphological, mechanical
and
corrosion
characteristics. Moreover, in those cases the crack formation in

N. Imaz
N. Imaz
et al.
et / al.
Corrosion
/ Corrosion
Science
Science
78 (2014)
78 (2014)
251259
251259

25

the deposit provoked by the tensile stress originated by the

grains accommodating boundary mist at grain coalescence
[8] was avoided, leading to crack-free chromium surfaces.
Some authors [911] have studied the corrosion behaviour of
chromium coatings in sulfuric acid media. These works analyzed
the nature and the performance of the passive lm formed on
the chromium surface upon anodic oxidation and studied the
rela- tion between surface-crack density and corrosion resistance.
How- ever, few of the published studies have analyzed the
electrochemical behaviour of pulsed-plated hard chromium deposits in a chloride media [12,13]. Taking into account that most
part of the corrosion specications demanded by different
industrial applications for hard chromed components involve
salt spray chamber tests, there is currently a need to have a deep
understand- ing of the corrosion process involved in chloride
media and its rela- tion with the characteristics of chromium
deposits. In this sense, the present study provides baseline
information to comprehend the mechanisms responsible for the
corrosion in chloride media of hard chromium coatings obtained
by direct and reverse pulse current and gives some insights
regarding their correlation with the morphological and
wettability properties of these surfaces.

2. Materials and methods

Chromium coatings were obtained on polished carbon steel
2
substrates (AISI 1010, Ra
0.0102 lm, 9 cm ) in an electrolyte
con- taining 250 g L 1 of chromic acid and 2.5 g L 1 of sulfuric acid.
Pre- viously, the cathodes were pickled with hydrochloric acid
(50% vol.) during 30 s and activated in a chromium electrolyte by
2
apply- ing an anodic current of
300 mA cm
during 90 s. The
electrode- position process was carried out under galvanostatic
conditions in
a different three-electrode electrochemical cell with a volume of
400 mL, at a temperature of 51 1 C, with magnetic stirring. A
lead-8% tin sheet (20 cm2) was used as anode and a Ag/AgCl/Cl
(3 M) electrode as reference electrode. During the plating process
the distance between the cathode and the anode was kept at
3.5 cm. Direct current (DC) (300 mA cm 2) and two types of
bipolar
pulse sequences (selected as representative of the sequences with
high Qc/Qa ratio and low Qc/Qa ratio from our previous work [7])
were applied to obtain the chromium coatings (Table 1): PC1 (high
Qc/Qa), that corresponds to chromium coatings with similar morphological characteristics as those of coatings obtained using DC,
and PC2 (low Qc/Qa), with a crack-free surface. A constant charge
of 945 C cm 2 was applied for both the direct and pulse plated
deposits, which led to a constant thickness of 20 1 lm. Prior to
applying the corresponding plating sequence, a thin lm of chromium was applied by direct current ( 300 mA cm 2, 1 min), in order to avoid the attack of the substrate during anodic current.
After electroplating, coatings were rinsed with deionised water
and dried with air.
The average roughness (Ra) of chromium surfaces was measured using a Taylor Hobson Talysurf Intra 50 mm prolometer.
Morphological observation and analysis of the composition of the
chromium coatings were undertaken by means of a Carl Zeis Ultra
Plus eld emission scanning electron microscope (FE-SEM)
equipped with an Ametek EDAX Apollo X X-ray electron probe

25

microanalyzer (EDX). The cross-sections of chromium surfaces

were examined using a Nikon Metrology EPIPHOT 200 inverted
optical microscope. Microhardness was evaluated on polished
cross-sectional areas of chromium deposits by using a Helmut
Fischer Fischerscope HM2000 Vickers microindenter with an applied load of 50 mN for 10 s. Ten readings were taken from each
deposit and the values were then averaged. Data are expressed
as mean standard deviation.
In order to assess the wettability of the chromium coatings, the
contact angle of 5 wt.% NaCl drops deposited onto the surface of
the coatings was measured using a KSV Instruments Cam 200
device.
The electrochemical study of the corrosion performance of electrodeposited samples was carried out in a 250 mL EG&G Princeton
Applied Research three electrode Flat Cell by means of a Solartron
Analytical 1287 potentiostatgalvanostat with a 1255B impedance
interface. All measurements were conducted in an aerated 5 wt.%
NaCl solution at room temperature with a geometrical working
area of 1 cm2. A Pt mesh and Ag/AgCl/NaCl (3 M) electrode were
used as counter and reference electrodes respectively. First, the
corrosion potential, Ecorr, was measured and recorded until no fur1
ther changes were observed (less than 10 mV h ). This process
was usually complete within 34 h. Afterwards, a linear potentio1
dynamic sweep at 0.05 mV s , changing the potential between
Ecorr 15 mV was performed and the polarization resistance, Rp,
was calculated. After polarization, the electrode was allowed to
stabilize again at initial Ecorr. In order to obtain the anodic and
cathodic Tafel slopes (ba, bc), partial potentiodynamic scans
1

(0.1667 mV s ) on different samples obtained at the same experimental conditions were performed, starting from the open circuit
potential (OCP) in the anodic or cathodic direction. The cathodic
and anodic potentiodynamic scans were never carried out consecutively as it was observed that the cathodic scan modies the
ano- dic response. The corrosion current density (jcorr) was
calculated by means of the SternGeary relation [14] given in
the following equation:

b b

jcorr

a c

2:3Rp bc

ba

where ba and bc are the anodic and cathodic Tafel slopes.

Corrosion data (Rp and jcorr) are referred to the exposed
geomet- ric area of the sample.
Electrochemical impedance spectroscopy (EIS) measurements
were performed at OCP in the frequency range of 10510 3 Hz with
1
an amplitude of 5 mV (7 points dec ) after immersing the samples
into a chloride solution (5 wt.% NaCl) for different time periods
(0 min, 30 min, 60 min, 90 min, 180 min, 360 min, 540 min). All
the impedance data were analyzed and modelled using a Scribner
Associates Zview software.
Electrochemical measurements were performed with the electrochemical cell inside a Faradays cage in order to reduce as much
as possible the effect of disturbances caused by any external electromagnetic signal on the system under study. The reproducibility
of the presented data was generally checked by using 610 replicates, and typical results are reported.

Table 1
Applied plating sequences, where jc is the cathodic current density, tc is the cathodic time, ja is the anodic current density, ta is the anodic time and jav is the average net
current density dened as jav = (jc tc + ja ta)/(tc + ta).
Sequence
DC
PC 1
PC 2

jc (mA cm )

580
400

tc (s)

ja (mA cm )

ta (ms)

9.4
20

0.04
0.90

25
21

|Qc/Qa|
5452
423

jav (mA cm
300
583
395

In order to evaluate the time-dependent release of metal cations from the coatings and their morphological evolution, samples
of the obtained chromium coatings with a geometrical area of
2
2 2 cm were immersed for 24 h in 50 mL of aerated 5 wt.% NaCl
solution at room temperature. The evolution of the surface
appear- ance of the samples with immersion time was
monitored by brighteld images obtained with a charge-coupled
device (CCD) camera. The images were analyzed by means of a
simultaneous treatment of textural and spectral information of
bi-dimensional and RGB digital images [15]. Only the red channel
from the original RGB images was
used and they were
compressed by Discrete Wavelet Transform (DWT) algorithm up
to 377
362 pixels per sample. The percentage of the corroded
area was calculated by multivariate statistical analysis of the
projection of the images of the tested samples over the image
of the non-tested samples. The morphological characterization
of chromium surfaces before and after the 24 h of exposure time
was performed by SEM-EDX analysis. The concentration of
chromium and iron in corrosive solution was analyzed by means
of a Shimadzu
ICPE-9000 multi- type inductively coupled
plasma optical emission spectrometer (ICP-OES).
3. Results and discussion
3.1. Morphology and hardness of chromium samples
As expected, the morphological characterization of the obtained
chromium coatings showed that the applied pulse sequences had
an important effect on their morphological properties (Fig. 1). Surface micrographs of coatings obtained by DC and PC1 sequences
presented a bright nish characterized by a network of large and
thin microcracks. Moreover, the surface of these coatings among
the cracks was smooth (Ra = 0.025 0.010 lm) and nely structured. Cross-section analysis of the coatings indicated a good
adherence between the coating and the substrate, even though in
most of the cases the microcracks penetrate the coating down to
the base material (Fig. 1d and e). On the other hand, chromium
coatings deposited by PC2 sequences presented a uniform, matt
gray appearance and a higher roughness (Ra = 0.210 0.010 lm).
Analysis of the PC2 coating by FE-SEM showed a crack-free surface
composed of dissimilar polyhedral grains that in some cases
exhibit a cubic structure. In this case, cross-section analysis of
the coatings showed a well-adhered and compact lm and no
pres- ence of transversal cracks were detected (Fig. 1f). The
marked ef- fect of pulse plating sequence with low Qc/Qa ratio
(PC2) on the structure and properties of chromium deposits can
be explained

by the inuence of anodic current on the oxidation of absorbed

hydrogen formed during electroplating. Hydrogen acts as a inhibiting specie of the crystal growth and leads to the characteristic
cracked morphology of DC chromium coatings [2,8,16]. Meanwhile, the anodic current density involved in the PC1 sequence
(high Qc/Qa ratio) was insufcient to totally oxidize structurally
incorporated hydrogen, leading place to cracks in chromium surfaces. Moreover, the hardness of PC2 coatings (967 61 HV) was
slightly lower than the one presented by DC (1024 21 HV) and
PC1 (1097 26 HV) layers, but high enough for the majority of
functional applications of hard chromium coatings. The slight decrease in hardness observed for crack-free chromium coatings
can be explained by the changes on crystalline structure provoked
by PC2 sequence [8]. A more detailed description of the relations
between the structural and physical properties of chromium coatings, as well as with applied pulse parameters was made in our
previous work [7].
3.2. Electrochemical corrosion behavior and contact angle
measurements
Table 2 summarizes the electrochemical corrosion parameters
obtained using direct current techniques (Ecorr, Rp, ba, bc, jcorr) for
DC, PC1 and PC2 chromium coatings. As observed in the table,
the corrosion potential (Ecorr) was very similar for all the chromium
surfaces (
500 50 mV vs. Ag/AgCl), in agreement with their
analogous chemical composition and with the values reported by
other authors [13]. However, the polarization resistance of crackfree PC2 coatings (170 31 kohm cm2) was two orders of magnitude
higher
than
those
achieved by
cracked
DC
2
2
(6.4 0.5 kohm cm ) and PC1 coatings (6.5 2.4 kohm cm ), indicating a better corrosion behaviour.
Fig. 2 illustrates the overall potentiodynamic behaviour of DC,
PC1 and PC2 chromium coatings in 5 wt.% NaCl aerated media.
The anodic polarization branches related to cracked deposits (DC
and PC1 chromium coatings, Fig. 2 curves a and b, respectively)
present similar characteristics. The anodic curves show a monotonic increase of current with potential and display anodic Tafel regions of 70 mV dec 1 slope (Table 2). This behaviour corresponds
to a uniform corrosion mechanism, probably related to metal dissolution. However, the crack-free chromium layers (PC2) (Fig. 2,
curve c) reveal a different behaviour, showing an anodic current
depletion with regard to the cracked chromium coatings. Moreover, a considerable increase in the anodic Tafel slope
1
( 350 mV dec ) (Table 2) is observed and the curve shows a
280300 mV region of stabilized current that would indicate a

Fig. 1. Surface morphology and cross section images of chromium coatings obtained by (a and d) DC, (b and e) PC1 and (c and f) PC2 sequences.

Table 2
Electrochemical corrosion parameters obtained for DC, PC1 and PC2 chromium coatings in 5 wt.% NaCl. Data are expressed as mean standard deviation (n = 610).
Sample
DC
PC1
PC2

Ecorr (mV vs. Ag/AgCl)

507 19
476 28
504 9

Rp (kohm cm )

ba (mV dec

6.4 0.5
6.5 2.4
170 31

78 2
65 2
356 41

Fig. 2. Polarization diagrams for (a) DC, (b) PC1 and (c) PC2 coatings.

pseudo-passive effect that initially blocks the dissolution of the

coatings. This effect can be associated with the response of a
non-conductive oxide thin lm (525 ) spontaneously formed
on the chromium surface in contact with air that according to
pre- vious studies [8,1719], is composed of a non-crystalline
chro- mium hydroxide outer part with crystalline Cr2O3
islands dispersed in the inner part. This passive region extends up
to high potential values ( 803 mV vs. Ag/AgCl), followed by a
sharp in- crease in current density, related to the local breakdown
of the pro- tective oxide lm and the growth of a stable pit [20].
On the other hand, the cathodic branch of the polarization
curves of DC and PC1 chromium coatings show a current plateau,
which, taking into account that experiments were carried out in
near-neutral chloride solution, can be presumably associated with
the oxygen reduction reaction (ORR). At more negative potentials,
hydrogen evolution reaction (HER) related to the water discharge
appears, characterized by a new slope in the polarization curve.
1
However, the measure slope of approximately 170 mV dec is
1
higher than the theoretical value (bc = 118 mV dec ), probably
related to the HER inhibition. In the case of PC2 chromium coatings, an increase in the cathodic current and a cathodic slope
with a lower Tafel value (
300 mV dec 1) than those
observed for cracked coatings was observed (Table 2), indicating
that the catho- dic process is not mass transport controlled. It has
been reported that chromium hydroxide lms catalyze the
hydrogen evolution by decreasing its reaction overpotential.
Simultaneously, these chromium hydroxide lms can hinder
side
reactions, including the reduction of oxygen, increasing
even more the current ef- ciency for HER [2123]. Taking into
account the presence of a chro- mium hydroxide and Cr2O3 thin
lm on the surface of PC2 sample, its preferential cathodic
reaction could presumably correspond to the HER instead of the
ORR, which would explain the depolariza- tion of the cathodic
branch regarding to cracked layers.
The estimated corrosion current density (jcorr) by SternGeary
approach was 3.1 0.3 lA cm 2 for DC and 3.6 0.2 lA cm 2 for
PC1 coatings, while one order of magnitude lower values of current
2
density were obtained for PC2 samples (0.4 0.1 lA cm ) (Table 2). Taking into account the obtained results, it can be concluded
that, crack-free PC2 chromium coatings present a reduced
corrosion current density due to an anodic barrier effect and a

bc (mV dec
1
1
296 62

jcorr (lA cm

3.1 0.3
3.6 0.4
0.4 0.1

cathodic inhibition of oxygen reduction reaction, both effects

attributed to the continuous protective oxide/hydroxide lm
formed on their surface. Thus, the Rp and the anodic Tafel slope increase, while the cathodic slope, corresponding to HER, decreases.
The predicted different behaviour among samples was corroborated by their visual inspection after an anodic polarization test.
In particular, DC and PC1 electrodeposits showed clear signs of corrosion products such as stains of rust on their whole surface,
whereas crack-free PC2 layers were macroscopically unaltered, except for only a few pitting points (Fig. 3).
The differences in the corrosion behaviour of the chromium
coatings studied could be partially ascribed to differences in their
morphology. Hence, accelerated corrosion of the cracked DC and
PC1 coatings would be expected due to the penetration of chloride
ions through the cracks (as shown in Fig. 1), which become preferential corrosion initiation sites [24]. However, the more pronounced effect of corrosive media on these samples than on PC2
deposits could also be partly attributed to their wettability. Thus,
a correlation is usually observed between the wettability of a
given material and its anticorrosion performance. Materials with
more hydrophobic character are typically more resistant against
corro- sion in aqueous environments [25]. Since liquidchromium
inter- facial tension is not easy to measure directly, the contact
angle of a sodium chloride solution droplet on chromium surface
was used to indicate surface wettability. Our results (Fig. 4)
indicate that the abovementioned roughness and morphology
differences caused markedly larger contact angles for PC2 coatings
(120.0 ) than for DC (81.0 ) and PC1 deposits (91.3 ), which are
related to the inter- facial energy of the samples [26]. Thus, in a
rst approximation, the Youngs equation correlates the existing
interfacial tensions with the contact angle:

csv csl clv cos h

where csv, csl and clv are the solidvapor, solidliquid and liquid
vapor interfacial energy respectively and h is the equilibrium contact angle.
Our results indicate that PC2 coatings exhibit larger contact angles than DC and PC1 coatings, that is, they present a more hydrophobic character. Since clv mainly depends on the liquid used for
the experiments, its value can be regarded as constant. Hence,
the differences in contact angle between cracked and crack-free
chromium coatings have to be ascribed to variations in csv and
csl, mainly attributed to variations in the interfacial tensions
caused by differences in electric charge and the presence of an
oxide/hydroxide lm at the solid interface. Thus, in the case of
PC2 coatings, the solution comes in contact with the hydrophobic
chromium oxide/hydroxide lm, which decreases the wettability
of the solution. Moreover, it is known that Cl ions from the solution can be differentially adsorbed in solid defects, which can
change the intensity of the electrostatic eld at the interfaces electrical double layer, promoting an increase in wettability [27]. Taking into account the results of contact angle measurements, the
penetration capacity of chloride solution would be easier on DC
and PC1 surfaces, increasing the probability of accelerated corrosion phenomena by differential aeration cells that can be formed
in solution drops [28].

Fig. 3. (a) DC, (b) PC1 and (c) PC2 chromium surfaces after anodic polarization measurements.

Fig. 4. Contact angle of studied chromium surfaces.

3.3. EIS measurements as a function of immersion time

To account for the corrosion behaviour of Cr coatings at their
respective open circuit potentials, Nyquist and Bode diagrams obtained by EIS measurements as a function of immersion time (from
0 to 24 h) in 5 wt.% NaCl were recorded.
Two time constants could be differentiated in the impedance
spectra for all the samples (Fig. 5). The rst time constant appearing at high frequencies may be related to the behaviour of the
elec- trolyte/coating interface for cracked samples and of the
electrolyte/ oxide layer interface for crack-free coatings. On the
other hand, the second time constant at lower frequencies
would correspond to the
electrolyte/substrate
interface.
Furthermore, from the Bode diagrams it can be observed that the
phase angle did not reach zero at high frequencies, as can be
expected for a purely resistive behav- iour [29], suggesting the
presence of defects or weak spots in the studied surfaces.
The comparison of the three types of coatings at initial immersion time showed a greater semicircle diameter in Nyquist diagrams and higher Z module in Bode diagrams for crack-free PC2
coatings, suggesting a higher corrosion resistance regarding to
DC and PC1 layers. It is important to point out the selected different scale in vertical axis between graphs in Fig. 5. Additionally, it
was observed that in PC2 coatings, the abovementioned two time
constants appeared at lower frequencies, indicating slower corrosion reaction rates.
The results obtained in EIS measurements with immersion time
corroborate that the corrosion process started immediately after
the exposition of DC and PC1 coatings to the NaCl solution. Thus,
the semicircle diameter and Z module of mentioned samples decreased considerably after just 30 min of exposure to corrosive
solution, suggesting an electrochemically active interface. Moreover, a considerable weakening and shifting to higher frequencies
of the phase angle associated with the rst time constant was detected. This is presumably due to a more severe corrosion inside
the cracks and defects of DC and PC1 coatings. The shift was
signif- icantly lower in the PC2 deposits, indicating a superior
corrosion

performance of these coatings with immersion time. This behaviour is in agreement with that inferred from polarization curves
measurements and conrmed that crack-free PC2 coatings yielded
a better barrier effect due to the more compact structure of the
coating and the presence of the uniform oxide/hydroxide chromium lm.
Various equivalent circuits were proposed to t the impedance
data. A fairly good description of the impedance data evolution
associated with the systems under study is showed in Fig. 6. In order to account for the non-ideal frequency response, constant
phase elements (CPE) were used in the equivalent circuit instead
of capacitive components (Ci) [30]. The non-ideal capacitive response of the system can be attributed to several factors such as
distributed surface reactivity, surface inhomogeneity, roughness
or electrode porosity [31]. The impedance of CPE (ZCPE) can be dened by the following equation:

Z CPE

1
a
Y jx

where Y is the part of the CPE independent of the frequency (f), j is

an imaginary number (j = ( 1)1/2), x is the angular frequency
(x = 2pf) and a is a parameter that measures how far the interface
was from an ideal capacitor (0 < a < 1). The Zview software employed in this study uses two parameters to dene CPE (Eq. (4)): T
indicates the value of capacitance of the CPE element and P is related to a and accounts for the change of the compressed semicircle
from an ideal one [32].

CPE T

j2pf

Although the proposed equivalent circuit was the same for all the
studied coatings, the physical meaning of their parameters was different for DC and PC1 (Fig. 6a) regarding to PC2 samples (Fig. 6b). In
all the cases, R0 is the high frequency limit series impedance and is
associated with the electrolyte resistance. In regard to cracked layers, CPE-1 accounts for the double layer capacitance of chromium
coatings, R1 corresponds to the coatings resistance and electrolyte
resistance in uncovered regions and pores, CPE-2 represents the redox capacitance and R2 accounts for the charge transfer resistance
of the corrosion process on the substrate. Concerning PC2 sample,
CPE-1 accounts for the dielectric contribution of the chromium
oxide lm, whereas R1 corresponds to this passive lm resistance.
On the other hand, CPE-2 represents the double layer capacitance
and R2 accounts for the charge transfer resistance of the corrosion
process through the chromium layer. The impedance function for
the described equivalent circuit corresponds to the following
equation:

1
Zx R0 a

1
1R
2 2 a
R R
1jxR C
jxR1 C 1
a
jxR C
1

R2

A good tting between experimental and theoretical data was

achieved.

Fig. 5. Nyquist and bode diagrams after (j) 0, (

) 0.5, (

) 1, (

) 1.5, (

) 3, ( ) 6 ( ) 9 and ( ) 24 h of immersion in 5% wt. NaCl for (a) DC, (b) PC1 and (c) PC2 coatings.

Fig. 6. Schematic representation of chromium layers and corresponding equivalent

circuit proposed for simulation of the experimental data for (a) DC/PC1 and (b) PC2
samples.

The R1, CPE 1, R2, CPE-2 parameter values estimated from the
impedance spectra tting analysis are graphically presented in
Fig. 7. The dynamic behaviour of the processes taking place at DC
and PC1 interfaces are reected by the changing value of the
parameters associated with these processes. Thus, a decrease of
R2 resistance with exposure time is observed, indicating a
reduction of charge transfer resistance, that is, the increase of

redox processes on the substrate with time. Moreover, the redox

capacitance, CPE-2, of DC and PC1 coatings increases with immersion time, presumably due to an increase of the area involved in
the electrochemical reaction and to a more severe corrosion phenomena occurring inside their cracks and defects. The increase of
R1 and CPE-1 during the rst 67 h of immersion can be attributed
to the accumulation of corrosive products in the coatings cracks
that can partially act as a barrier, blocking the penetration of chloride ions to the substrate. At higher immersion times, the values of
these parameters decrease, probably as a consequence of the
detachment of part of these corrosion products towards the electrolyte, contributing to the diminishment of the coating resistive
and capacitive properties.
In the case of the PC2 chromium coatings, practically constant
values of CPE-2 with time were observed, indicating that the characteristic of the redox capacitance of PC2 chromium coatings remained practically unaltered. Furthermore, the CPE-2 values were
lower than those corresponding to DC and PC1 coatings, indicating
a lower corrosion. A decrease of R2 resistance with exposure time
is observed but in all the cases the R2 values of PC2 chromium
coat- ings were considerably higher than those corresponding to
DC and PC1 coatings, indicating a lower degradation rate and a
better

Fig. 7. Evolution of best R1, R2, CPE-1 and CPE-2 tting parameters for (x) DC, (

) PC1 and (

) PC2 samples with immersion time in 5% wt. NaCl solution.

corrosion resistance. On the other hand, R1 and CPE-1 increase (in

this last case slightly) with time, which can be related to an increase of the thickness of the chromium oxide/hydroxide layer
on PC2 coatings surface.
The results obtained in the initial impedance measurements
suggest a superior corrosion performance of crack-free PC2 coatings, which present a higher charge transfer resistance, a lower
corrosion rate and less substrate area involved in redox reactions.
Moreover, this behaviour was maintained with exposure time to
chloride media in comparison with DC and PC1 coatings. Taking
into account the observations made in the impedance diagrams,
the different response of the studied samples against corrosion
can be attributed mainly to the ease of penetration of chloride ions
into the substrate, which would be markedly inhibited by the
pres- ence of a barrier oxide lm, the absence of cracks (Fig. 1)
and the decrease of the wettability (Fig. 4) of the PC2 surfaces.
3.4. Metal cation release and morphological evolution of chromium
surfaces as a function of immersion time
In order to get a better understanding of the corrosion
phenom- ena of the chromium coatings, samples obtained under
different conditions were immersed during 24 h into 5 wt.% NaCl
solution under non-polarized conditions. Fig. 8 shows the
evolution of chro- mium surfaces with immersion time,
characterized by brighteld images obtained with a CCD camera
of a confocal microscope, including the percentage of corroded
area estimated by image analysis. From the results, a fast
formation of corrosion products for DC and PC1 chromium
coatings exposed to NaCl solution can be observed. Thus, after 1
h of immersion, approximately 20% of their area was corroded
and this corroded area increased up to
80% after 24 h. On the other side, crack-free PC2 layers did not
present any macroscopically noticeable alteration during the 24 h
of test. The small percentage of corrosion detected in PC2 coatings
by image analysis can be considered negligible, included in the error associated to the method, particularly taking into account that
different specimens were used for each of the immersion tests.
A more detailed inspection of chromium coatings after the
immersion experiments was performed by FE-SEM (Fig. 9). The

Fig. 8. Brighteld images of chromium surfaces obtained by a CCD camera of

confocal microscope after different immersion times and estimated percentage of
corroded area for (x) DC, ( ) PC1 and ( ) PC2 samples.

surface micrographs showed that while PC2 coatings remained

practically the same after immersion, in the case of DC and PC1
coatings some changes were observed. Thus, these coatings presented some protruding formations on the cracked regions formed
by blade-like crystals that ll the cracks and spread to the surrounding area. The compositional analyses performed by EDX on
the corroded areas of the sample revealed the presence of iron
oxi- des, probably originated from the faster dissolution rate of the
steel substrate through the cracks compared to the chromium
coating. These observations are in agreement with the results of
the elec- trochemical corrosion tests previously described.

Fig. 9. Morphology of chromium surfaces characterized by FE-SEM after 24 h of immersion in 5% wt. NaCl and weight percent composition on corrosion products analyzed by
EDX for (a) DC, (b) PC1 and (c) PC2 coatings.
Table 3
Fe and Cr concentration in 5 wt.% NaCl solution after 24 h of immersion test.

Sequence

Cr (mg L )

Fe (mg L )

DC
PC 1

0.09
0.01

6.50
5.30

The PC
superior
corrosion Lower
resistance
of crack-free layers was0.10cor2
than detection limit
The metal dissolution of the chromium coatings in the NaCl
solution was investigated by assessing the levels of metal cations
released from the samples. Table 3 shows the concentration of
chromium and iron ions in the NaCl solution after 24 h of immersion time, obtained by ICP-OES measurements. The results indicate
that the release of Cr ions from DC and PC1 samples is low but surpasses the levels of the PC2 sample (in the latter, the
concentration of Cr ions was below the detection limit of the
equipment). How- ever, the concentration of Fe ions notoriously
increases after 24 h of immersion in the case of DC and PC1 but
remains at low values for PC2 samples. Thus, the results
obtained by ICP-OES measure- ment of corrosive solution,
demonstrate once again the superior corrosion resistance of PC2
deposits and more importantly, that the corrosion in studied
coatings is due to the substrate dissolution through the cracks
more than due to the dissolution of the chro- mium layer itself.
4. Conclusions
The corrosion characteristics of hard chromium coatings obtained by direct current (DC) and pulse current (PC1 and PC2)
were compared in this work. DC and PC1 (high Qc/Qa) sequences
led to smooth chromium surfaces with a network of cracks,
while PC2 (low Qc/Qa) coating presented higher roughness and a
crack-free surface composed of dissimilar polyhedral grains.
The electrochemical corrosion measurements show the high
sensitivity of chromium layers to NaCl aqueous solution, having a
great corrosion rate in this media. Polarization measurements
demonstrated a uniform corrosion performance for DC and PC1
cracked-coatings, while localized corrosion mechanism was obtained for PC2 crack-free deposits. The evolution of the anodic
and cathodic branches of the polarization curves and the
estimated corrosion parameters
demonstrate
a
reduced
corrosion current density for PC2 chromium coatings, due to an
anodic barrier effect and a cathodic inhibition of oxygen reduction
reaction, both effects

attributed to the continuous protective chromium oxide/hydroxide

lm formed on their surfaces. Thus, Rp and the anodic Tafel slope of
crack-free PC2 coatings increase, while the cathodic slope,
predominantly corresponding to HER, decreases compared to the cracked
DC and PC1 deposits.
roborated by means of EIS measurements. PC2 coatings showed a
greater
semicircle
diameter
in Nyquist
diagrams
and higher
Z module in Bode
diagrams
regarding
to cracked
coatings.
Moreover,
the
simulation of EIS data permitted a quantitative evaluation of resistance and capacitance parameters, demonstrating the superior corrosion performance of PC2 deposits with immersion time.
The corrosion study was rounded out by means of appearance
and morphology characterization, as well as by analyzing the composition of coatings and test solution. The different techniques utilized to characterize the developed chromium coatings show a
superior corrosion performance of PC2 deposits compared to DC
and PC1, which is related to their roughness, morphology, wettability and mainly, their crack absence and the presence of an
oxide/hydroxide chromium lm in the surface. The study of the
performance of the surfaces with immersion time in chloride media show that at long immersion periods the corrosion is widely
spread on cracked surfaces and a weakening of the protective ability of crack-free coatings was detected. Moreover, it was demonstrated that the corrosion process in hard chromium coatings is
not related to reactions of chromium itself, but to the penetration
of chloride ions through the cracks and defects towards the substrate, causing its dissolution and oxidation, which in turn makes
these coatings so susceptible to corrosive media.
The developed PC2 coatings showed a uniform matt and gray
appearance, high hardness value and superior corrosion
resistance than conventional hard chromium surfaces (DC), which
would al- low their use in many functional and engineering
components ex- posed to severe corrosion environments for
numerous industrial sectors, such as aeronautic, thermosolar or
chemistry industries.

Acknowledgements
The authors would like to thank the MINECO of the Spanish
government (Project MAT2011-27380-C02) and the Gobierno Vasco-Eusko Jaurlaritza (Project No. S-PE11UN042) for their nancial
support. Moreover, the contribution of IkanKronitek S.L. company
is gratefully acknowledged.

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with

blocking electrodes,