Professional Documents
Culture Documents
+6
Energy and Nuclear Research Institute, IPEN/CNEN-SP, CCTM, Av. Prof. Lineu Prestes, So Paulo, Brazil; 2CIDEPINT: Research and
Development Center in Paint Technology (CICPBA-CONICET), Av.52 s/n entre 121 y 122. CP. B1900AYB, La Plata-Argentina.
Email: tomazuk@gmail.com, direccion@cidepint.gov.ar
Received April 29th, 2010; revised July 22nd, 2010; accepted August 4th, 2010.
ABSTRACT
Hexavalent chromium-based passivation treatments have been successfully used as promoters of conversion coatings
for many years. Their effectiveness is without question although there are many problems with regard to their environmental suitability. Hexavalent chromium compounds are carcinogenic and toxic. These problems have lead researchers
to evaluate other potential systems, with lower toxicity, to ascertain if they can replace chromates as effective passivators. Researchers have proposed several alternative passivation treatments; these are processes based on molybdates,
3+
permanganates, titanates, rare earth metal and Cr (considered to be non-carcinogenic) compounds. In this work, zinc
3+
coatings obtained from free-cyanide alkaline bath and submitted to a Cr based passivation treatment with different
colors were studied. The corrosion behavior was studied by polarization measurements and mainly by electrochemical
impedance spectroscopy in 0.6 N NaCl solution. Morphological observations on the coatings surface were also per3+
formed. The results indicate that the green-colored Cr passivated coatings have a good corrosion resistance followed
by yellow and blue-colored passivation respectively. They could be a less polluting alternative to the traditional chromated coatings.
Keywords: Zinc, Conversion Treatment, Impedance Spectroscopy, Salt Spray, Corrosion
1. Introduction
Electroplated zinc coating is employed as active galvanic
protection for steel. However, as the zinc is an electrochemically highly reactive metal, its corrosion rate may
be also high in indoor but particularly under outdoor exposure conditions [1]. For this reason, it is necessary a
post treatment in order to increase the lifetime of zinc
coatings. In current industrial practice, this treatment
consists of immersion in a chemical bath that forms a
conversion layer on plated zinc. This latter layer is a dielectric passive layer with high corrosion resistance and
is also a better surface for paint adherence. The main
problem of traditionally used post treatments is the pres6+
ence of Cr salts, considered carcinogenic substances
which usage is forbidden by European norms [2]. Responding to increasingly more rigorous environmental
protection activities, recent years have shown progressive
advances in order to reduce the use of environmentally-hazardous materials. In line with this purpose, the
development of various kinds of chromate-free coated
Copyright 2010 SciRes.
+6
203
2. Experimental Details
The overall coating thickness and description of the samples investigated in this work are reported in Table 1. In
it can be seen that these showed similar and uniform
thickness; besides, they also exhibited a bright appearance throughout their extension. Unfortunately, information related with the passive layer thickness was not possible to be obtained.
2.3. Morphology
The coatings morphology was determined from scanning
electron microscopy (SEM) analyses using a LEICA
S440 microscope.
3.1. Morphology
Identification
Thickness
(Zn + conversion
treatment)
(m)
Description
3+
blue-colored Cr
passivation UniFix Zn-3-50
(LABRITS )
yellow-colored Cr
passivation UniYellow 3
(LABRITS)
10.8
3+
3+
green-colored Cr
11.2
10.4
MSA
204
(a)
3+
and C samples, subjected to green-colored Cr passivation, exhibited a gel-like structure (Figure 1(c)). The characteristic cracks of chromate coatings were not present,
perhaps due to its thin thickness [34].
(b)
Conversion Treatment
Ecorr V(SCE)
(c)
1.10
0.2
1.04
0.4
1.04
0.02
MSA
205
where:
its corrosion rate is lower.
jn
Z
Copyright 2010 SciRes.
Y0
MSA
(b)
(a)
(a)
(b)
Figure 4. Equivalent circuit models used for fitting the impedance data.
206
+6
n CPE power: (n = /
constant phase angle of the CPE
(rad)
Y0 part of the CPE independent of the
-1
frequency ( )
Difficulties in providing an accurate physical description of the occurred processes are sometimes found. In
2
-4
such cases, a standard deviation value ( < 10 )
be- tween experimental and fitted impedance data may
be used as final criterion to define the most probable
circuit. The comparison between simulated and
experimental data at different exposure times are omitted
for simplicity, however, in all cases, the experimental data
were in good
agreement with the model predictions.
The more interesting data to discuss are the exposure
time dependent resistance R1 of the passivation treatment
(giving information on the barrier properties of the conversion layer) coupled in parallel with its Q1 (related to
the coating capacitance) and the charge transfer resistance R2 (giving information on the kinetic of the corrosive process). These values, estimated from the fitting
analysis of the impedance spectra, are reported in Figures 5 to 7, respectively.
Copyright 2010 SciRes.
MSA
(a)
(b)
207
MSA
4. Conclusions
Figure 7. R2 as a function of immersion time in 0.6 N NaCl
solution obtained from impedance data fitting for A and B
samples.
5. Acknowledgements
The authors acknowledge CNPq/PROSUL (Process 490
116/2006-0) of Brazil, CAPES/MINCyT (Process 158/09
of Brazil and BR/08/04 of Argentina), and Comisin de
Investigaciones Cientficas de la Provincia de Buenos
Aires (CIC) and Consejo Nacional de Investigaciones
Cientficas y Tcnicas (CONICET) of Argentina by their
+6
MSA
REFERENCES
[1] N. Zaki, Chromate Conversion Coating for Zinc, Metal
Finishing, Vol. 86, No. 2, February 1988, pp. 75-78.
[2] P. L. Hagans and C. M. Haas, ASM Handbook, Surface
Engineering, ASM International, Vol. 5, 1994.
[3] F. Deflorian, S. Rossi, L. Fedrizzi and P. L. Bonora, EIS
Study of Organic Coating on Zinc Surface Pretreated with
Environmentally Friendly Products, Progress in Organic
Coatings, Vol. 52, No. 4, 2005, pp. 271-279.
[4] R. Berger, U. Bexell, T. M. Grehk and S. E. Hrnstrm,
A Comparative Study of the Corrosion Protective Properties of Chromium and Chromium Free Passivation Methods, Surface and Coatings Technology, Vol. 202, No.
2, 2007, pp. 391-397.
[5] K. W. Cho, V. S. Rao and H. Kwon, Microstructure and
Electrochemical Characterization of Trivalent Chromium
Based Conversion Coating on Zinc, Electrochimica Acta,
Vol. 52, No. 13, 2007, pp. 4449-4456.
[6]
209
MSA
MSA