Electrochimica Acta 52 (2007) 4449–4456

Microstructure and electrochemical characterization of

trivalent chromium based conversion coating on zinc
KeunWoo Cho, V. Shankar Rao, HyukSang Kwon ∗,1
Department of Materials Science and Engineering, Korea Advanced Institute of Science and Technology,
373-1 GuseongDong, YuSeongGu, Daejeon 305-701, Republic of Korea
Received 13 September 2006; received in revised form 5 December 2006; accepted 12 December 2006
Available online 11 January 2007

Abstract
A trivalent chromium based conversion coating (CCC), based on chromium nitrate solution with Co(II) ions, was developed on Zn substrate.
The corrosion resistance of the trivalent CCC, measured in deaerated pH 8.0 borate buffer + 0.01 M NaCl solution using anodic polarization and
electrochemical impedance spectroscopy (EIS), was very sensitive to both immersion time and bath pH. Micro-cracks were found on the surface
of the CCC. Besides, the density of micro-crack and the coating thickness also depended on immersion time and bath pH. With increasing the
coating thickness its pitting potential increased and passive current density decreased. The trivalent CCC formed on Zn for 40 s in pH 1.7 bath
showed the best corrosion resistance, and the pitting potential increased significantly from −355 mVSCE for Zn to 975 mVSCE for the trivalent CCC
on Zn. To explain the corrosion behavior of the trivalent CCC using EIS analysis, a modified equivalent circuit, which considered the micro-cracks
in the coating and chromium corrosion product (CCP) deposited in the micro-cracks, was designed and the variation of each electrical parameter
was examined. Especially, its corrosion behavior was well described by the variation of the resistance of CCP (Rccp ).
© 2007 Elsevier Ltd. All rights reserved.

Keywords: Trivalent chromium based conversion coating; Microstructure; Corrosion resistance; EIS analysis; Equivalent circuit

1. Introduction studied as an alternative to hexavalent CCC [8–12]. The corro-

Electrodeposited Zn coating has been used to protect ferrous
substrates in automobile industries. However, the corrosion rate
of the Zn coating increases rapidly in a humid air, therefore,
various surface treatments have been developed to improve the
corrosion resistance of the Zn coating: hexavalent chromium
based conversion coating (CCC), generally called chromate
conversion coating, phosphate conversion coating and organic
painting, etc. [1–3]. Among them, CCC is widely used because
of its superior corrosion resistance, good paint adhesion and low
cost [4–6].
CCC is performed by immersing Zn coated articles in a
chromic acid bath, which forms a passive layer containing
Zn oxides and mixed Cr(III)–Cr(VI) oxides [7,8]. Because the
Cr(VI) species present in the chromic acid bath and the coat-
ing are toxic and carcinogenic, nontoxic trivalent CCC has been
∗ CCC has not been reported yet.
Corresponding author. Tel.: +82 42 869 3326; fax: +82 42 869 3310.
E-mail address: hskwon@kaist.ac.kr (H. Kwon).
1 ISE member.
sion resistance of the trivalent CCC is generally lower than that
of the hexavalent CCC [8–10]. Thus, many recent studies have
focused on the improvement in the corrosion resistance of the
trivalent CCC by sealing treatments on the CCC and/or by addi-
tions of different additives in a Cr(III) bath. Bellezze et al. [8]
reported the corrosion resistance of the trivalent CCC increased
dramatically through the sealing treatment in Si based solution
and was equivalent to that of the hexavalent CCC. According
to Fonte et al. [11], the trivalent CCC formed in a Cr(III) bath
containing transition metal ions such as Co(II), Ni(II) and Fe(II)
showed superior corrosion resistance than that formed in the
bath without transition metal ions. It is well known that the
microstructure and the corrosion resistance of the hexavalent
CCC largely depend on immersion time and bath pH as well as
bath composition [13,14]. However, the influences of immersion
time and bath pH on those of the trivalent CCC formed on Zn
substrate are rarely studied. Furthermore, correlation between
the microstructure and the corrosion resistance of the trivalent
We have developed a trivalent CCC bath based on chromium
nitrate (Cr(NO3 )3 ) solution with Co(II) ions. In this paper, we

0013-4686/$ – see front matter © 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2006.12.032
4450 K. Cho et al. / Electrochimica Acta 52 (2007) 4449–4456

examined the effects of immersion time and bath pH on the

microstructure and corrosion resistance of the trivalent CCC.
The corrosion behavior of the trivalent CCC was also inves-
tigated to explain the mechanism for the improvement in its
corrosion resistance.

2. Experimental

A commercially pure Zn plate was used as a substrate for

the trivalent CCC. The surface of the Zn plate was polished
with 2000 grit silicon carbide paper, degreased with acetone,
ultrasonically cleaned in ethanol for 3 min, rinsed in distilled
water, activated for 2 s in 3 wt.% nitric acid and rinsed in distilled
water again prior to the trivalent CCC.
The composition of the bath for the trivalent CCC was
50 mL/L Cr(NO3 )3 (40%), 20 g/L CoCl2 ·6H2 O and 3 mL/L
H2 SO4 . Bath pH was adjusted to three different values (pH 1.1,
1.7 and 2.3) by adding NaOH to the bath. The trivalent CCCs
were formed on Zn in the bath for 20–60 s at 30 ◦ C. Then these
coatings were rinsed in distilled water, and dried in an oven
for 4 min at 40 ◦ C, and in a desiccator for 48 h at an ambient
temperature (22 ± 2 ◦ C).
The surface morphology of the trivalent CCC was observed
by scanning electron microscope (SEM). The coating thick-
ness was measured using cross-sectional SEM image of the
trivalent CCC and also by Rurherford backscattering spectrom-
etry (RBS). X-ray photoelectron spectroscopy (XPS) was used
to analyze the valence state of Cr in the trivalent CCC. The
spectrum was obtained with VG Scientific, model ESCALAB
200R, using Mg K␣ X-ray source (hν = 15 kV, 20 mA) at 300 W.
The base pressure in the spectrometer chamber was maintained
at 5 × 10−10 Torr throughout the measurement. The binding
energy scale of the spectrophotometer was calibrated using C 1s
(284.8 eV) substrate. The specimen was analyzed by means of
Ar-ion sputtering with primary beam energy of 5 keV, 0.30 ␮A.
The corrosion resistance of the trivalent CCC was evaluated
by anodic polarization test and electrochemical impedance spec-
troscopy (EIS) in deaerated pH 8.0 borate buffer + 0.01 M NaCl
solution at an ambient temperature (22 ± 2 ◦ C). Anodic polar-
ization test was performed at a scan rate of 0.5 mV/s using a
conventional three-electrode polarization cell: specimen as a
working electrode, saturated calomel electrode (SCE) as a ref- Fig. 1. SEM micrographs of the trivalent CCCs formed on Zn for (a) 20 s, (b)
erence electrode and a platinum counter electrode. EIS was 40 s and (c) 60 s, in pH 1.7 bath at 30 ◦ C.
conducted by frequency sweep from 105 to 10−2 Hz using a
superimposed sinusoidal signal of 5 mV rms at the open cir- corrosion resistances of the trivalent CCCs formed on Zn in the
cuit potential. All the potentials in this work are referred to Cr(III) bath from 20 to 60 s.
the SCE. Fig. 1 shows the surface morphologies of the trivalent CCCs
formed on Zn with immersion time of 20, 40 and 60 s in the
3. Results and discussion pH 1.7 bath. After 20 s immersion, trivalent CCC with micro-
cracks was formed on Zn, which was similar to the surface
3.1. Effects of immersion time on the microstructure and morphology of hexavalent CCC [6,10,15]. According to pre-
corrosion resistance of the trivalent CCC vious reports [6,15,16], the hexavalent CCC deposited on Zn
with gel-like structure in an acidic Cr bath, during drying pro-
CCC is generally performed by immersing Zn coated arti- cess the CCC would shrink due to an internal tensile stress in
cles in an acidic Cr bath within 60 s because the thickness of the coating, and finally micro-cracks were formed on the surface
Zn coating decreases due to dissolution of Zn with increasing of the coating. Moreover, with the coating thickness the tensile
immersion time. Thus, it was examined the microstructures and stress increased, resulting in an increase in the density of micro-
 K. Cho et al. / Electrochimica Acta 52 (2007) 4449–4456 4451

Fig. 2. Anodic polarization curves of Zn with and without the trivalent CCC in
deaerated pH 8.0 borate buffer + 0.01 M NaCl solution at 22 ± 2 ◦ C. The CCCs
were formed on Zn substrate for 20, 40 and 60 s in pH 1.7 bath at 30 ◦ C.

crack. With increasing immersion time to 40 s the Zn surface

was uniformly covered with the trivalent CCC, and the density
of micro-crack on the surface increased. However, the density
of micro-crack decreased significantly with further increasing
immersion time to 60 s. The coating thickness also decreased
from 1 to 0.35 ␮m with increasing immersion time from 40 to
60 s. Gigandet et al. [17] suggested that both the growth of CCC
and the dissolution of the deposited CCC progressed at the same
time during immersion of Zn in an acidic Cr bath. Thus, it is
considered that the thickness of trivalent CCC increases until
40 s immersion because the growth rate of the trivalent CCC is
faster than its dissolution rate. However, with further increasing
immersion time its growth rate becomes less than dissolution
rate, and finally the coating thickness decreases.
The anodic polarization curves for the Zn substrate and the
trivalent CCCs formed on Zn in the pH 1.7 bath for 20, 40 and
60 s, obtained in deaerated pH 8.0 borate buffer + 0.01 M NaCl
solution, are presented in Fig. 2. After trivalent CCC, the pitting
corrosion resistance of Zn greatly improved as confirmed by
an increase in the pitting potential from −355 mVSCE for Zn
to 975 mVSCE for the trivalent CCC on Zn for 40 s. Moreover,
Fig. 3. SEM micrographs of the trivalent CCCs on Zn for 40 s at 30 ◦ C in (a)
the pitting potential increased with increasing immersion time to pH 1.1, (b) pH 1.7 and (c) pH 2.3 bath.
40 s, but decreased with immersion time above 40 s. The passive
current density decreased gradually with increasing immersion
time to 40 s, but increased with further increasing immersion the coating formed in the pH 1.1 bath surface was very rough
time. Thus, the pitting potential and passive current density of the with high defect density, whereas for the coating formed in the
trivalent CCC largely depended on its thickness. With the coating pH 1.7 bath micro-cracks were found on the surface and the its
thickness, the pitting potential of the trivalent CCC increased, surface roughness decreased compared to the CCC formed in
and the passive current density decreased. The best corrosion the pH 1.1 bath. The surface of the CCC formed in the pH 2.3
resistance of the trivalent CCC with maximum coating thickness bath was very smooth and no micro-crack was observed on the
was obtained for immersion time of 40 s. surface. These results indicate that with the bath pH the surface
roughness of the trivalent CCC decreases. Further, the uniform
3.2. Effects of bath pH on the microstructure and corrosion growth of the trivalent CCC becomes difficult in low pH bath
resistance of the trivalent CCC due to the high dissolution rate of both the Zn substrate and the
trivalent CCC.
Fig. 3 shows the surface morphologies of the trivalent CCCs Fig. 4 shows the variation of the trivalent CCC thickness as
formed on Zn for 40 s in the bath of pH 1.1, 1.7 and 2.3. For a function of bath pH. The thickness of the CCC increased with
4452 K. Cho et al. / Electrochimica Acta 52 (2007) 4449–4456
Fig. 4. Effects of bath pH on the thickness of the trivalent CCC. The CCCs were
formed on Zn for 40 s in pH 1.1, 1.7 and 2.3 bath at 30 ◦ C.
increasing bath pH to 1.7, and then decreased above pH 1.7. It
was reported that bath pH affected the dissolution rate of Zn,
which provided electrons for deposition of CCC, as well as that
of the deposited CCC [14]. Therefore, it is considered that the
trivalent CCC formed in the pH 1.7 bath shows the maximum
thickness because at pH less than 1.7 the dissolution rate of
the deposited CCC is very fast and at pH more than 1.7 the
dissolution rate of Zn providing electrons for the deposition of
the CCC is very slow.
The anodic polarization curves of the trivalent CCC on Zn
for 40 s in the pH 1.1, 1.7 and 2.3 bath, which were mea-
sured in deaerated pH 8.0 borate buffer + 0.01 M NaCl solution,
are presented in Fig. 5. The pitting potential increased with
increasing bath pH from 1.1 to 1.7, but decreased with further
increasing pH to 2.3. The passive current density decreased with
increasing bath pH to 1.7, but increased with bath pH above
pH 1.7. From Figs. 4 and 5, it was found that the thickness
and corrosion resistance of the trivalent CCC increased with
increasing pH to 1.7, and with a further increase in pH they
decreased.
Fig. 5. Anodic polarization curves of the trivalent CCCs in deaerated pH 8.0
borate buffer + 0.01 M NaCl solution at 22 ± 2 ◦ C. The CCCs were formed on
Zn for 40 s in pH 1.1, 1.7 and 2.3 bath at 30 ◦ C.
Fig. 6. SEM micrograph showing cross-section of the trivalent CCC formed on
Zn for 40 s in pH 1.7 bath at 30 ◦ C.
From the results until now, it was revealed that the corrosion
resistance of the trivalent CCC was proportional to the coating
thickness. The trivalent CCC formed on Zn for 40 s in the pH
1.7 bath showed the best corrosion resistance with maximum
thickness about 1 ␮m (Fig. 6).
3.3. XPS analysis of the trivalent CCC
XPS analysis of the trivalent CCC was performed to examine
the valence state of Cr present in the coating. Fig. 7 shows the
XPS spectrum of Cr in the trivalent CCC formed on Zn for 40 s in
the pH 1.7 bath, which showed the best corrosion resistance. This
spectrum was obtained after sputtering for 2 min from the top
surface by Ar-ion. In Fig. 7, the two peaks appeared at 586.0 and
576.2 eV correspond to Cr2p1/2 and Cr2p3/2 , respectively [18].
For the hexavalent CCC, it is well known that the Cr2p3/2 peak
can be resolved into more than two peaks representing the Cr
compound with the Cr(III) and Cr(VI) states [6,15,19]. However,
the Cr2p3/2 peak, obtained from the trivalent CCC, was composed
of only one peak corresponding to the Cr2p3/2 peak of Cr2 O3
[6,9,10].
From XPS analysis, it was confirmed that Cr in the triva-
lent CCC was in the form of Cr2 O3 and there was no Cr(VI)
component in the coating.
Fig. 7. XPS spectrum of Cr present in the trivalent CCC formed on Zn for 40 s
in pH 1.7 bath at 30 ◦ C (after Ar sputtering for 2 min).
 K. Cho et al. / Electrochimica Acta 52 (2007) 4449–4456
Fig. 8. Effect of immersion time on the Nyquist plots of the trivalent CCC in
deaerated pH 8.0 borate buffer + 0.01 M NaCl solution at 22 ± 2 ◦ C. The CCC
was formed on Zn for 40 s in pH 1.7 bath at 30 ◦ C.
3.4. The corrosion behavior of the trivalent CCC
The polarization results in Sections 3.1 and 3.2 show that the
trivalent CCC formed on Zn for 40 s in the pH 1.7 bath exhibits
the best corrosion resistance. To examine its corrosion behavior,
impedance analysis of the trivalent CCC on Zn was performed
in deaerated pH 8.0 borate buffer + 0.01 M NaCl solution (expo-
sure area: 0.32 cm2 ). Nyquist plots of the trivalent CCC obtained
after immersion for 10–80 h showed a distorted semi-circle at
a low frequency region (Fig. 8). It is suggested that the dis-
tortion of the low frequency region is caused by a diffusion
control reaction and affected by Warburg impedance. The radius
of this semi-circle increased with immersion time to 50 h, and
then decreased. The increase in the radius of the semi-circle can
be interpreted to an increase in the surface resistance caused by
surface passivation. However, the decrease in the radius of the
semi-circle with increasing immersion time above 50 h cannot
be explained by only the surface passivation. Therefore, in order
to analyze the corrosion behavior of the trivalent CCC clearly,
it is necessary to find an equivalent circuit for the trivalent CCC
and measure electrical parameters of the equivalent circuit.
Fig. 9. Bode plot of the trivalent CCC after 50 h in deaerated pH 8.0 borate
buffer + 0.01 M NaCl solution at 22 ± 2 ◦ C. The CCC was formed on Zn for 40 s
in pH 1.7 bath at 30 ◦ C.
4453
Fig. 10. Equivalent circuit models of porous layer (a) without and (b) with
corrosion product.
Fig. 11. Equivalent circuit of the trivalent CCC formed on Zn for 40 s in deaer-
ated pH 1.7 bath at 30 ◦ C.
Fig. 9 shows Bode plot of the trivalent CCC obtained after
50 h immersion. Three different time constants were observed
from the Bode plot of the trivalent CCC, indicating that the
equivalent circuit of the trivalent CCC is composed with more
than three capacitive components. Pang et al. [20] has proposed
a simple circuit, with two time constants (Fig. 10(a)), to describe
the impedance behavior of a porous coating. In this case, Rs cor-
responds to the electrolyte resistance, Rcoat and Qcoat represent
the resistive and capacitive responses of the pores and defects of
the layer, respectively. Rct models the charge transfer resistance
and Qdl describes double layer capacitance. However, this model
cannot explain the three time constants observed in the Bode plot
of the trivalent CCC (Fig. 9). Bonora et al. [21] suggested that
corrosion products could deposit in a porous coating and affect
Fig. 12. Spectrum fitting of the trivalent CCC after 50 h in deaerated pH 8.0
borate buffer + 0.01 M NaCl solution at 22 ± 2 ◦ C. The CCC was formed on Zn
for 40 s in pH 1.7 bath at 30 ◦ C.
4454 K. Cho et al. / Electrochimica Acta 52 (2007) 4449–4456

the impedance spectrum of the coating, when the coating was
exposed to corrosive environment, and they proposed an equiva-
lent circuit model shown in Fig. 10(b). In this model, Rcp and Qcp
represent the resistive and capacitive responses of the corrosion
products, respectively. The equivalent circuit of Fig. 10(b) can
explain three capacitive components observed from the Bode
plot of the trivalent CCC. However, it was impossible to fit the
impedance spectrum of the trivalent CCC into the equivalent
circuit of Fig. 10(b). We could fit the impedance data using a
modified equivalent circuit shown in Fig. 11, which considered
Warburg impedance observed in Fig. 8 and the deposition of
chromium corrosion product (CCP) in the micro-cracks of the
trivalent CCC. Definitions of the electrical parameters in the
modified equivalent circuit are presented in Table 1. Fig. 12
shows the impedance data of the trivalent CCC obtained after
50 h immersion and the fitting results, demonstrating that the
experimental results are well described by the equivalent circuit
proposed for the trivalent CCC in Fig. 11.

Fig. 13. Variation of (a) coating resistance (Rcoat ), (b) admittance (Yo ) of coating capacitance (Qcoat ), (c) charge transfer resistance (Rct ), (d) Yo of double layer
capacitance (Qdl ), (e) Yo of Warburg impedance (W), (f) CCP resistance (Rccp ) and (g) Yo of CCP capacitance (Qccp ) of the trivalent CCC with immersion time.
 K. Cho et al. / Electrochimica Acta 52 (2007) 4449–4456 4455

Table 1
Definitions of the electrical parameters
Rs Solution resistance
Rcoat Resistance of trivalent chromium based conversion coating
Qcoat Capacitance of trivalent chromium based conversion coating
Rct Charge transfer resistance
Qdl Double layer capacitance
W Warburg impedance
Rccp Resistance of chromium corrosion product
Qccp Capacitance of chromium corrosion product

Fig. 13 shows the trend of each component of the equivalent

circuit as a function of immersion time. The coating resistance
of the trivalent CCC (Rcoat ) increased with immersion time to
50 h, and then decreased (Fig. 13(a)). Rcoat varied about from 30
to 70  cm2 , which was very small in comparison to the charge
transfer resistance of the trivalent CCC (Rct ) and the resistance
of CCP (Rccp ). Thus, this indicates that the effect of Rcoat on
the corrosion resistance of the trivalent CCC is negligible. The
admittance Yo of the coating capacitance of the trivalent CCC
(Qcoat ) increased with immersion time (Fig. 13(b)). According
to previous reports [8,14], the increase in the admittance Yo of
Qcoat can be interpreted such that the surface area of the CCC
increases due to the corrosion of the coating and/or its dielectric
constant increases because of water uptake. The charge transfer
resistance of the trivalent CCC (Rct ) increased with increasing
immersion time (Fig. 13(c)). This means that the charge transfer
between the CCC and solution becomes more difficult due to the Fig. 14. SEM micrographs of the trivalent CCC (a) before immersion and (b)
passivation property of the trivalent CCC. Thus, it is suggested after immersion for 80 h in deaerated pH 8.0 borate buffer + 0.01 M NaCl solution
at ambient 22 ± 2 ◦ C. The CCC was formed on Zn for 40 s in pH 1.7 bath at
that the trivalent CCC acts as a barrier, which prevents the contact
30 ◦ C.
of substrate Zn with corrosive environment. The admittance Yo
of the double layer capacitance (Qdl ) increased with immersion
fusivity of oxidation species; Dred is the diffusivity of reduction
time (Fig. 13(d)). The admittance Yo of Qdl is proportional to the
species.
area involved in the electrochemical reaction, i.e. surface area of
The resistance of the CCP (Rccp ) increased with increas-
micro-cracks in contact with the solution. Therefore, the increase
ing immersion time to 50 h, and then decreased dramatically
in the admittance Yo of Qdl indicates that the corrosion inside
(Fig. 13(f)). Campestrini et al. [22] reported that dense CCPs,
the micro-cracks becomes more severe and the surface area of
which were deposited inside the micro-cracks of the CCC dur-
the micro-cracks increases with immersion time. The admittance
ing immersion in corrosive environment, affected the charge
Yo of Warburg impedance (W) decreased rapidly with increasing
carrier diffusion through the CCC. Thus, the increase in Rccp
immersion time from 10 to 20 h, and then decreased gradually
is concerned with the increase in the amount of dense CCP,
(Fig. 13(e)). W is inversely proportional to the Yo according to
which acts as a diffusion barrier of ion such as chloride ion
Eq. 1. Thus, it means that mass transfer through the micro-cracks
through the trivalent CCC. With further increasing immersion
in the trivalent CCC becomes more difficult with immersion
time, it can be expected that the corrosion inside the micro-
time. This may be caused by the deposition of CCP in the micro-
cracks becomes more severe and the crack propagation occurs.
cracks.
Finally, the CCP deposited in the micro-cracks will be loosened
σ 1 and cannot act as the diffusion barrier after critical immersion
W = σω−1/2 − jσω−1/2 = √ = (1a)
2(jω) 1/2 Y o (jω) 1/2 time. Therefore, it is considered that the decrease in Rccp after
√ 50 h immersion results from the crack propagation of the triva-
2 lent CCC. The admittance Yo of the capacitance of the CCP
Yo = (1b)
σ (Qccp ) did not change significantly with immersion time until
 
RT 1 1 50 h (Fig. 13(g)). Then, however, the admittance Yo of Qccp
σ= √ + (1c) increased abruptly, suggesting that the surface area of CCP
n2 F 2 2 Cox (Dox )1/2 Cred (Dred )1/2
contacting with the solution increased because of the crack
ω is the angular frequency; j = (−1)1/2 ; R the ideal gas constant; propagation of CCC after 50 h immersion. Fig. 14 shows the
T the absolute temperature; n the number of electron trans- surface morphologies of the trivalent CCC before and after
ferred; F Faraday’s constant; Cox the concentration of oxidation the impedance test. After 80 h immersion, propagation of the
species; Cred the concentration of reduction species; Dox the dif- micro-cracks and pitting initiation were observed. This is well
4456 K. Cho et al. / Electrochimica Acta 52 (2007) 4449–4456
Fig. 15. Schematic representation for corrosion behavior of the trivalent CCC
formed on Zn: (a) initial stage, (b) formation of CCP, (c) dense CCP acting as a
diffusion barrier and (d) crack propagation.
corresponded with the analysis of the impedance spectra of the
trivalent CCC, especially with the decrease in Rccp after 50 h
immersion.
From EIS analysis, the impedance spectra for the triva-
lent CCC on Zn with immersion time in the buffer solution
containing chloride ions were well described by the modified
equivalent circuit considering both the micro-cracks in the coat-
ing and the CCP deposited in the micro-cracks. Besides, the
corrosion behavior of the trivalent CCC was well explained by
the variation of Rccp . A schematic diagram of the corrosion
behavior of the trivalent CCC based on the above discussion
is shown in Fig. 15. The trivalent CCC with micro-cracks is
formed on Zn in the Cr(III) bath (Fig. 15(a)). After immersion
of the trivalent CCC in corrosive environment, dense CCP is
deposited in the micro-cracks and it acts as a diffusion bar-
rier, which inhibits the movement of an ion through the CCC
(Fig. 15(b)). With increasing immersion time, the amount of
dense CCP increases, and hence the resistance of the CCP also
increases (Fig. 15(c)). However, with further increasing immer-
sion time, the CCP deposited in the micro-cracks is loosened
due to crack propagation and pit growth, and finally the resis-
tance of CCP to inhibit corrosion decreases. These results well
corresponded with other researchers’ work for the hexavalent
CCC [22].
4. Conclusions
A trivalent CCC was formed on Zn substrate in chromium
nitrate solution with cobalt chloride and sulfuric acid. The
microstructure and corrosion resistance of the trivalent CCC
were found to largely depend on bath pH and immersion time.
Conclusions drawn from this study are as follows:
1. In the Cr(III) bath of pH 1.7, the density of micro-crack
and thickness of the trivalent CCC increased with increasing
immersion time from 20 to 40 s, and thereafter decreased with
further increase in the immersion time. This indicates that
both the growth of the CCC on Zn and the dissolution of the
deposited CCC progress competitively during the immersion
of Zn in the bath.
2. The surface roughness and surface defect concentration of the
trivalent CCC decreased with increasing bath pH. The triva-
lent CCC formed in the pH 1.7 bath showed the maximum
thickness because at pH less than 1.7 the dissolution rate of
the CCC was very fast and at pH more than 1.7 the dissolu-
tion rate of Zn, which provided electrons for the deposition
of the CCC, was very slow.
3. The trivalent CCC formed for 40 s in the pH 1.7 bath showed
the best corrosion resistance, as confirmed by the significant
increase its pitting potential from −355 mVSCE for Zn to
975 mVSCE for the trivalent CCC formed on Zn.
4. The impedance spectra for the trivalent CCC on Zn with
immersion time in the buffer solution containing chloride
ions were well described by the modified equivalent circuit
considering both the micro-cracks in the CCC and the CCP
deposited in the micro-cracks.
5. The corrosion behavior of the trivalent CCC was explained
by the variation of the resistance of CCP (Rccp ), which
increased with immersion time to 50 h, and then decreased.
The increase in Rccp indicates an increase in the amount
of dense CCP in the micro-cracks, which acts as a diffu-
sion barrier of chloride ion through the CCC. However, with
further increasing immersion time, the corrosion inside the
micro-cracks becomes more severe and the crack propaga-
tion occurs. Finally, Rccp decreases drastically because the
CCP cannot act as the diffusion barrier.
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