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Materials and Corrosion 2014, XXX, No.

XXX

DOI: 10.1002/maco.201407633

Effect of nanosilica on the corrosion behavior of silicate


conversion coatings on hotdip galvanized steel
F. Jamali, I. Danaee* and D. Zaarei
Nanosilica potassium silicate conversion coating was deposited in different
silica ratio on the surface of hotdip galvanized (HDG) steel as an anticorrosion
coating. The ratio of nanosilica/potassium silicate has been optimized in order
to obtain higher corrosion protection. The corrosion behavior of coatings was
examined by means of electrochemical impedance spectroscopy,
potentiodynamic polarization, and surface techniques. The corrosion resistance
was increased with increasing silica ratio of silicate coatings. This can be related
to the size of nanosilica particles and the ability to ll the pores in potassium
silicate coating. SEM images in agreement with the electrochemical results
indicated that the coating obtained from silica ratio 3 was more homogeneous
and without pores. Electrochemical impedance data shows that with increasing
immersion time up to 60 s, the charge transfer resistance increased. Energy
dispersive Xray analysis shows silica ratio increasing in silicate coatings.

1 Introduction
Corrosion resistance, superior mechanical properties, and low
maintenance costs are resulted in applying hotdip galvanized
steels in variant elds such as automobiles, construction
structures, transportation, etc. [14]. The corrosion rate of Zn
is high due to the large potential difference between iron
substrate and zinc layer [5,6]. It is well known that chromate
coatings are very effective anticorrosives and inhibitors with self
healing property [7,8]. However, due to toxicity and carcinogenic
effects of chromate coatings, there have been extensive efforts in
order to nd an appropriate alternative for it [912]. Rare earth
elements, titanium salts, permanganate, and molybdatephosphatesilanesilicate (MPSS) have been investigated as alternative
for chromate conversion coating on HDG. But their performances were not sufcient in comparison with commercial
chromate conversion coatings and it was necessary to investigate
new compounds [1318].
Many studies show that silicate provides environmental
friendly and good corrosion resistant coatings for the substrate
metals [1924]. Previous researches have described the role of
different processing parameters on the corrosion resistance of
F. Jamali, I. Danaee
Abadan Faculty of Petroleum Engineering, Petroleum University of
Technology, Abadan, (Iran)
E-mail: danaee@put.ac.ir
D. Zaarei
Technical Faculty, South Tehran Branch, Islamic Azad University,
Tehran, (Iran)

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silicate conversion coatings on HDG [2126]. Alkali silicates are a


common and general group of silicate coatings. Alkali silicate
solutions contain two fractions: (a) alkali ions, hydroxide ions, and
silicate ions (SiO4
4 ), (b) polymerized (colloidal) fractions. The
very large polymerized particles are a complex mixture of
polysilicate anions and their hydroxylated surfaces consist of
silanol (SiOH) groups and siloxane bridges (SiOSi).
During the drying process, polymerization is continuing and
more silanol groups are converted to the siloxane bridges. The
produced layer on the substrate increases the corrosion
resistance [2126].
At the present work, nanosilica potassium silicate conversion coating was applied on HDG in different nanosilica weight
percents. The corrosion behaviors of these coatings were
investigated by means of electrochemical impedance spectroscopy (EIS) and polarization curves in 5 wt% NaCl solution.
Surface morphology, chemical composition, and microscopic
features of conversion coatings were analyzed by scanning
electron microscopy (SEM) and energy dispersive spectroscopy
(EDS).

2 Materials and methods


HDG sheets were prepared from GAM Company (Iran) and were
degreased with acetone, rinsed with deionized water, and dried in
air. Cool air was used to prevent any heat treatment on substrates.
A 40 wt% aqueous solution of potassium silicate with SiO2/K2O
weight ratio of 2 was prepared from the Sharif Nanopigment
Company and a 30 wt% aqueous solution of colloid nanosilica

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Jamali, Danaee and Zaarei

Materials and Corrosion 2014, XXX, No. XXX

3 Results and discussion


3.1 Electrochemical methods
Figure 1 shows the potentiodynamic polarization curves of HDG
with and without silicate coatings in 5 wt% NaCl solution. Silicate
coatings were obtained by 60 s immersion in different ratio
of potassium silicate solutions. The corresponding corrosion
parameters such as corrosion current density (Icorr), corrosion
potential (Ecorr), anodic slope (ba), cathodic slope (bc), polarization
resistance (Rp), and corrosion rate (CR) are listed in Table 1. The
polarization resistance is calculated by the following equation [29]:

Rp

Figure 1. Polarization curves of the silicate coatings of HDG in 5 wt%


NaCl solution. Coatings were obtained from potassium silicate solution
in different ratio: (1) HDG, (2) ratio 2, (3) ratio 3, (4) ratio 4, and (5) ratio 5

with 2030 nm particle size was prepared from Iranian Nanomaterials Pioneers. Potassium silicate solution and nanosilica
colloid were mixed and different silica ratios 2, 3, 4, and 5 were
prepared. Prior to immersion, solutions were agitated by a
magnetic agitator with the velocity of 500 rpm for 30 min at room
temperature. Samples were cured in oven at 100 8C for 30 min.
The coated samples were stored at room temperature for 1 h.
Electrochemical measurements were carried out by Potentiostat/Galvanostat Autolab, model PGSTAT 302N. Electrochemical glass cell contained a reference electrode of Ag/AgCl, an
auxiliary electrode of platinum and a sample of coated HDG as the
working electrode. To provide steady state condition, samples
were stored for 30 min in electrolyte solution before the test. The
scan rate of polarization curves was 0.5 mV/s. The frequency
range of the EIS was 105102 Hz with AC signal amplitude of
10 mV. Fitting of experimental impedance spectroscopy data to
the proposed equivalent circuit was done by means of a home
written least square software based on the Marquardt method for
the optimization of functions and Macdonald weighting for the
real and imaginary parts of the impedance [27,28].
The morphology of the surface was studied by scanning
electron microscopy (SEM, VEGA, TESCANLMU) equipped
with an energydispersive Xray spectroscopy (EDS) probe.

ba bc
1

2:303ba bc I corr

As can be seen, the corrosion current densities were


decreased in the presence of silicate coatings. After curing steps,
trapped water in the conversion coating was evaporated and
silicate networks (siloxane bridges) were created. Potentiodynamic scans and their corresponding parameters indicate that the
increasing nano silica ratio of potassium silicate up to 3, leads to
the increase of the coating resistance. Effect of increasing ratio on
cathodic current was more signicant than on the anodic
branches. This was in good agreement with the barrier property
of silicate lms with respect to oxygen diffusion.
It has been reported that with increasing the silica ratio up to
34 the degree of polymerization of the silicate ions in solution
increases. Consequently, the contraction of microregions and
holes that are possibly formed during the coatforming process
will be signicantly decreased; this leads to the formation of
more compact and uniform coatings [22]. The size of nanosilica
particles is the most important reason which lls the pores and
spaces of silicate networks [24] and improves the uniformity of
silicate layers [30]. The high surface area is another benet of
these particles which provides higher contacts between functional groups and more convenience to create silicate networks [31]. Also, Padavettan et al. [31] has believed that nano
silica particles can decrease the sintering temperature of silicate
coatings and produce stronger siloxane bridges at the same
preparation conditions. Therefore, the increasing of nanosilica
provides greater corrosion protection. In the higher silica ratios,
the corrosion rate is increased due to the internal stress which
decreases its toughness and leads to cracking. By withdrawing
samples from the solution and curing in oven, a few cracks
progressed on the surface due to drying process and decreased
the corrosion resistance of the coatings.

Table 1. Electrochemical parameters of the silicate coatings in 5 wt% NaCl solution

Ratio

Ecorr (V)

Rp (ohm)

Icorr (A/cm2)

bc (V/dec)

ba (V/dec)

CR (mm/year)

HDG
2
3
4
5

0.967
0.926
0.943
0.918
0.932

7.39  103
9.94  103
8.20  104
5.41  103
1.88  103

2.4  106
3.3  107
5.7  108
1.4  106
1.5  106

0.055
0.010
0.012
0.023
0.01

0.159
0.031
0.11
0.085
0.019

2.82  102
3.88  103
6.73  104
1.70  102
1.77  102

Coatings were obtained by 60 s immersion in potassium silicate solution in different ratio.

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Materials and Corrosion 2014, XXX, No. XXX

Effect of nano-silica on the corrosion

Electrochemical impedance was employed to conrm the


anticorrosion behavior of the silicate coatings. Figure 2 shows the
Nyquist plots of silicate coated HDG obtained by 60 s immersion
in different silica ratio. Impedance was measured at open
circuit potential in 5 wt% NaCl solution. The data revealed that
impedance diagram consist of two overlapped capacitive semicircles which were depressed towards the real axis. The depressed
semicircle in the low frequency region can be related to the
combination of charge transfer resistance and the double layer
capacitance. The high frequency semicircle was related to the
resistance and capacitance of silicate coatings. The equivalent
circuit compatible with the Nyquist diagram was depicted in
Fig. 3. In this electrical equivalent circuit, Rs, Qdl, and Rct represent
solution resistance, a constant phase element corresponding to the
double layer capacitance and the charge transfer resistance of
zinc dissolution. CPEc and Rc are the electrical elements related to
the resistance and capacitance of coatings. To obtain a satisfactory
impedance simulation of silicate coated HDG, it is necessary to
replace the capacitor (C) with a constant phase element (CPE) Q in
the equivalent circuit. The most widely accepted explanation for
the presence of CPE behavior and depressed semicircles on solid
electrodes is microscopic roughness, causing an inhomogeneous
distribution in the solution resistance as well as in the double
layer capacitance [32,33]. The simplest approach requires the
theoretical transfer function Z(v) to be represented by:

Rc
1=1 Z ct v=Rc ivn Rc Qc
Rct
Z ct v
n
iv Qdl Rct 1
Zv Rs

v is the frequency in rad/s, v 2pf and f is frequency in Hz. To


corroborate the equivalent circuit, the experimental data are tted
to equivalent circuit and the circuit elements are obtained. Table 2
illustrates the equivalent circuit parameters for the impedance
spectra of corrosion of silicate coated HDG in NaCl solution.
According to Table 2, with increasing silica ratio, the coating
resistance increased which is due to the presence of the more
uniform silicate coating on the surface of HDG, and it would
decrease the active area of the substrate. Also higher charge
transfer resistance was obtained for ratio 3.
The data indicate that increasing charge transfer resistance is
associated with a decrease in the double layer capacitance. The
decrease in Q values indicated that the exposed area decreased.
On the other hand, a decrease in Q, was caused by a decrease in
local dielectric constant due to decreased water penetration in the
conversion layer which leads to increased protection behavior of
the coatings. As the exponent (n) is a measure of the surface
heterogeneity, values of n indicates that the electrode surface
becomes more and more homogeneous for ratio 3.
Figure 4 presents the impedance diagrams of silicate coated
HDG obtained from silica ratio 3 in different immersion times.
Impedance was measured at open circuit potential in 5%wt. NaCl
solution. The impedance data showed two depressed capacitive
loops which were due to the conversion coatings and charge
transfer resistances. The experimental data are tted to equivalent
circuit and the circuit elements are obtained in Table 3. It can be
seen that by increasing immersion time from 30 to 60 s, Icorr
decreased and the corrosion resistance of the coated samples
increased. But after 60 s immersion, corrosion rate was increased.
In lower immersion time very thin conversion layer was formed or
Table 2. EIS parameters of the silicate coatings in 5 wt% NaCl solution

Sample
HDG
Ratio
Ratio
Ratio
Ratio
Figure 2. Electrochemical impedance spectroscopy diagrams of
potassium silicate coatings of HDG in 5 wt% NaCl solution. Coatings
were obtained from potassium silicate solution in different ratio:
(1) HDG, (2) ratio 2, (3) ratio 3, (4) ratio 4, and (5) ratio 5

Figure 3. Equivalent circuit compatible with the Nyquist diagram of


potassium silicate conversion coatings of AA2024

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2
3
4
5

Rc (V)

Qc (F)

n1

Rct (V)

Qdl (F)

n2

5.1  103
9.1  103
2.4  104
6.1  103
5.6  103

5  105
4  105
1  105
4  105
3  105

0.65
0.69
0.72
0.67
0.62

1.8  103
1.2  104
4.3  104
1.1  104
4.5  103

3  103
3  104
2  104
4  104
1  103

0.75
0.78
0.82
0.78
0.73

Coatings were obtained by 60 s immersion in potassium silicate solution


in different ratio.

Figure 4. Electrochemical impedance spectroscopy diagrams of


potassium silicate coatings of HDG in 5 wt% NaCl solution. Coatings
were obtained in ratio 3 of potassium silicate solution from different
immersion times: (1) 30, (2) 60, and (3) 120 s

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Jamali, Danaee and Zaarei

Materials and Corrosion 2014, XXX, No. XXX

Table 3. EIS parameters of the silicate coatings in 5 wt% NaCl solution

Sample Rc (V)
30 s
60 s
120 s

Qc (F)

n1

Rct (V)

Qdl (F)

n2

7.1  103 5  105 0.63 2.2  104 4  104 0.77


2.4  104 1  105 0.72 4.3  104 2  104 0.82
1.5  104 1  104 0.75 3.1  104 4  104 0.8

cannot release from the coating because of the presence of the top
hard layer and leads to cracking and porous structures.
3.2 Surface analysis

still a lot of parts of sample remained bare. In longer immersion


time the lm will be cracked and pored due to its high thickness.
Propagation of cracks and pores on the lm related to growth of
the lms thickness which caused decreased toughness. These
features were attributed to the curing process in oven. The upper
layer of the coating will be hardened during the curing process and
water was trapped in the inner silicate layer. So the trapped water

Figures 58 show the SEM images and the corresponding EDS


spectrum of the surface of silicate conversion coatings obtained
from higher ratio of silica. The EDS result represents the weight
percentages of the coating elements. The potassium silicate
conversion coatings obtained from ratio 2 contained discontinuities, pores, and cracks which related to the silicate networks
and the defects of these layers. The coating defects are the
susceptible zones for the corrosion attacks. Fig. 6 shows the
surface of silicate conversion coatings obtained from silica ratio 3.
Coating surfaces was homogeneous without discontinuities and
irregularities on the surfaces. In the higher silica ratio, conversion
coatings show pores and cracks on the surface due to the internal

Figure 5. (a) SEM and (b) EDX analysis of the potassium silicate
conversion coating of HDG obtained from potassium silicate with ratio 2
and immersion time 60 s

Figure 6. (a) SEM and (b) EDX analysis of the potassium silicate
conversion coating of HDG obtained from potassium silicate with ratio 3
and immersion time 60 s

Coatings were obtained from ratio 3 of potassium silicate solution in


different immersion time.

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Materials and Corrosion 2014, XXX, No. XXX

Effect of nano-silica on the corrosion

Figure 7. (a) SEM and (b) EDX analysis of the potassium silicate
conversion coating of HDG obtained from potassium silicate with ratio 4
and immersion time 60 s

Figure 8. (a) SEM and (b) EDX analysis of the potassium silicate
conversion coating of HDG obtained from potassium silicate with ratio 5
and immersion time 60 s

stress. The results of EDS analysis are shown in Table 4. The


results indicate that the Si:K weight ratio increased in the
conversion coatings in presence of nanosilica.
Figure 9a and b presented the silicate conversion coatings of
HDG obtained in different immersion time in ratio 3 of silicate
solution. It can be seen that, in lower immersion time the coatings
were not uniform and did not cover the whole surface. In
comparison with Fig. 6a, in higher immersion time, a very thick
lm formed on the surface and caused to increase stress in the
coating structure. SEM reveals the porous structures and pinholes
on the surface which was created due to releasing the trapped water.

Table 4. EDS results of the potassium silicate surface coatings obtained


from different ratio of silica

4 Conclusions
The corrosion behavior of nanosilica potassium silicate conversion coatings on the HDG was investigated in 5 wt% NaCl
solution. Potassium silicate coatings improve the corrosion

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Ratio
2
3
4
5

Si (wt%)

K (wt%)

15.58
16.39
17.39
21.47

1.05
0.57
0.46
0.30

resistance of the HDG due to the formation of silicate lm.


Presence of nanosilica improves the silicate networks and
decreases the existing defects. The ratio of nanosilica plays an
important role to provide a high corrosion protection. The lm
that formed with ratio 3 nanosilica is relatively more protective
and continuous. The size of nanoparticles is the main reason for
this phenomena and the corrosion resistance is mainly due to the
formation of compact and perfect silicate layers on the surface.
2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Jamali, Danaee and Zaarei

Figure 9. SEM of the potassium silicate conversion coating HDG


obtained from potassium silicate with ratio 3 in different immersion
times: (a) 30 s and (b) 120 s

Immersion time in the silicate solution had an important


inuence on the corrosion properties and the optimum coating
behavior was obtained by 60 s immersion.

5 References
[1] G. Ebell, A. Burkert, J. Lehmann, J. Mietz, Mater. Corros.
2012, 63, 791.

Materials and Corrosion 2014, XXX, No. XXX

[2] U. Nrnberger, Mater. Corros. 2012, 63, 1173.


[3] W. J. Yang, P. Yang, X. M. Li, W. L. Feng, Mater. Corros. 2012,
63, 401.
[4] T. Bellezze, G. Roventi, E. Barbaresi, N. Rufni, R. Fratesi,
Mater. Corros. 2011, 62, 155.
[5] H. J. Kim, J. Zhang, R. H. Yoon, R. Gandour, Surf. Coat.
Technol. 2004, 188189, 762.
[6] N. LeBozec, D. Thierry, A. Peltola, L. Luxem, G. Luckeneder,
G. Marchiaro, M. Rohwerder, Mater. Corros. 2013, 64,
969.
[7] L. Jiang, M. Wolpers, P. Volovitch, K. Ogle, Surf. Coat. Technol.
2012, 206, 3151.
[8] X. Zhang, S. Bhm, A. J. Bosch, E. P. M. van Westing,
J. H. W. de Wit, Mater. Corros. 2004, 55, 501.
[9] I. Aziz, Q. Zhang, Mater. Corros. 2010, 61, 568.
[10] B. Chen, Q. Li, H. Gao, J. M. Fan, X. Tan, Mater. Corros. 2009,
60, 521.
[11] C. F. Malfatti, T. L. Menezes, C. Radtke, J. Esteban, F. Ansart,
J. P. Bonino, Mater. Corros. 2012, 63, 819.
[12] S. K}oszegi, I. Felh}osi, E. Klmn, Mater. Corros. 2008, 59,
744.
[13] E. P. Banczek, S. R. Moraes, S. L. Assis, I. Costa, A. J.
Motheo, Mater. Corros. 2013, 64, 199206.
[14] Y. K. Song, F. Mansfeld, Corros. Sci. 2006, 48, 154.
[15] M. F. Montemor, W. Trabelsi, M. Zheludevich, M. G. S.
Ferreira, Prog. Org. Coat. 2006, 57, 67.
[16] H. Hasannejad, T. Shahrabi, M. Jafarian, Mater. Corros. 2013,
64, 1104.
[17] I. M. Zin, R. L. Howard, S. J. Badger, J. D. Scantlebury, S. B.
Lyon, Prog. Org. Coat. 1998, 33, 203.
[18] A. A. O. Magalhes, I. C. P. Margarit, O. R. Mattos, Electrochim.
Acta 1999, 44, 4281.
[19] L. T. Zhuravlev, Colloid. Surf. 2000, 173, 1.
[20] K. Aramaki, Corros. Sci. 2002, 44, 1621.
[21] J. Min, J. H. Park, H. K. Sohn, J. M. Park, J. Ind. Eng. Chem.
2012, 18, 655.
[22] M. R. Yuan, J. T. Lu, G. Kong, C. S. Che, Surf. Coat. Technol.
2011, 205, 4466.
[23] M. Hara, R. Ichino, M. Okido, N. Wada, Surf. Coat. Technol.
2003, 169170, 679.
[24] S. Dalbin, G. Maurin, R. P. Nogueira, J. Persello, N. Pommier,
Surf. Coat. Technol. 2005, 194, 363.
[25] M. R. Yuan, J. T. Lu, G. Kong, Surf. Coat. Technol. 2010, 204,
1229.
[26] M. R. Yuan, J. T. Lu, G. Kong, C. S. Che, Surf. Coat. Technol.
2011, 205, 4507.
[27] I. Danaee, J. Electroanal. Chem. 2011, 662, 415.
[28] J. R. Macdonald, Solid State Ion. 1984, 13, 147.
[29] I. Danaee, O. Ghasemi, G. R. Rashed, M. Rashvand Avei,
M. H. Maddahy, J. Mol. Struct. 2013, 1035, 247.
[30] K. J. Klabunde, Nanoscale Materials in Chemistry, Wiley
Interscience, New York 2001.
[31] V. Padavettan, I. Ab Rahman, J. Nanomater. 2012, 2012, 1.
[32] I. Danaee, S. Noori, Int. J. Hydrogen Energy 2011, 36,
12102.
[33] I. Danaee, M. NiknejadKhomami, A. A. Attar, Mater. Chem.
Phys. 2012, 135, 658.
(Received: January 26, 2014)
(Accepted: March 2, 2014)

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