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Department of Industrial Engineering, University of Trento, via Sommarive 9, 38123 Trento, TN, Italy
Akzo Nobel Coatings, Via Monte Tomba 10, 36060 Romano DEzzelino, VI, Italy
a r t i c l e
i n f o
Article history:
Available online 8 April 2014
Keywords:
Environmentally friendly corrosion
inhibitors
Powder coatings
Accelerated tests
Weathering
a b s t r a c t
In the search for viable alternatives to produce environmentally friendly organic coatings systems, this
work presents the study of several inorganic anticorrosive inhibitors and their further incorporation into
a polymeric matrix via powder coating technology. The selected inhibitors are commercially available
belonging to the second and third generations of developed replacement alternatives for hazards chromates. Polarization curves, also in the presence of continuous ow of N2 and air gases, have been used
for the characterization of the inhibitors. Succeeding, the inhibitors were embedded in powder coatings
and subsequently applied onto mild steel substrate. The coated panels have been investigated by means
of accelerated tests (neutral salt spray test, cathodic delamination test), natural weathering alongside
electrochemical techniques such as electrochemical impedance spectroscopy. The effectiveness of the
different corrosion inhibition pigments in the organic coatings has been evaluated and discussed.
2014 Elsevier B.V. All rights reserved.
1. Introduction
Chromium containing paints are well-known for their great
effectiveness for anticorrosive inhibitive protection of steel alongside toxicity and carcinogenic issues [1]. Hence, in the last decades,
a number of strict environmental protection regulations emerged
and they have driven scientists and professionals in the eld of
paints toward the replacement of chromates compounds. More
recent, attention has been given to another important environmental concern, the release of volatile organic compounds (VOCs) which
motivated the same professionals for the development of solvent
free coatings technologies [2,3].
At rst, several new compounds have been proposed for substitute chromates, for instance phosphates, molybdates and silicates.
Among them, phosphates gained attention as soluble inhibitors
and conversion coating materials. Moreover, coating formulations
pigmented with zinc phosphate (ZP) became widely used due to relatively good performance and low cost. It has been demonstrated
that depending on the exposure media ZP pigments were able to
protect steel at the same level or better that the zinc chromate
[4]. On the other hand, paints with ZP did not perform well in
accelerated tests [5], moreover it is claimed that ZP is classied
2134
Chemical composition
Producer/supplier
Sacthoperse
Barium sulfate
Molywhite
Ca phospho-molybdate
carbonates derivate
Zinc calcium phosphate silicate
derivate
Amorphous silicon dioxide
calcium-ion exchanged
Heucophos
Shieldex
Table 2
Average thickness of the coated panels.
Pigment label
% Inhibitor
Thickness (m)
No inhibitor
Sacthoperse
Molywhite
Heucophos
Shieldex
12
7
5
5
17
5
10
12
12
116.4
174.4
102.2
99.9
115.1
7.6
8.1
5.7
7.6
5.4
0.6
0.4
0.2
0.0
-0.2
-0.4
-0.6
-0.8
-1.0
-1.2
-1.4
-1.6
-1.8
2135
a
10
-5
-4
-3
10
10
2
Current Density (A/cm )
10
-2
-0.5
Potential (V vs Ag/AgCl)
Potential (V vs Ag/AgCl)
-0.6
-0.7
-0.8 Heucophos
-0.9
blank (pH6)
-1.0
Molywhite
-1.1
Sachtoperse
-1.2
10
10
-3
10
Potential (V vs Ag/AgCl)
-4
0.6
0.4
0.2
0.0
-0.2
-0.4
-0.6
-0.8
-1.0
-1.2
-1.4
-1.6
-1.8
a
-6
10
-5
-4
-3
10
10
10
2
Current Density (A/cm )
-2
10
Fig. 2. Polarization curves for the Shieldex saturated solutions with pH 7.0.
Heucophos
-0.6
-0.6
-0.7
Blank (pH6)
-0.8
Molywhite
-0.9
Sacthoperse
N2
-1.0
10
-6
10
-5
10
Fig. 3. Cathodic polarization curves with N2 bubbling for the pigments with
pH 6.0; Molywhite, Sacthoperse and Heucophos.
N2
_7
pH
nk
Bla
-0.9
Blank pH_7
Shieldex
-1.1
-6
10
-0.8
-1.0 MolyWhite
Heucophos
10
-4
10
2
Current Density (A/cm )
-3
10
a
-5
Air
-1.2
-5
10
Table 3
Evolution of the delamination extent during exposure in the salt spray chamber.
ex
ld
ie
Sh
Potential (V vs Ag/AgCl)
-0.7
-1.0
Sachtoperse
Fig. 5. Cathodic polarization curves with air bubbling for the pigments with
pH 6.0, Molywhite, Sacthoperse and Heucophos.
-0.8
Blank (pH6)
-4
-0.6
Potential (V vs Ag/AgCl)
Potential (V vs Ag/AgCl)
2136
-4
10
No inhibitor
Heucophos
Molywhite
Shieldex
Sachtoperse
0h
240 h
500 h
1000 h
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
36.0
3.1
0.6
2.6
0.6
100.0
2137
Table 4
Delaminated area after 30 days at 1.1 V (vs Ag/AgCl).
Delaminated area (cm2 )
Heucophos
Molywhite
No inhibitor
Sachtoperse
Shieldex
1.0
1.4
0.8
6.4
1.0
Table 5
Delaminated area after 1 year of outdoor exposure.
Delaminated area (cm2 )
Heucophos
Molywhite
No inhibitor
Sachtoperse
Shieldex
0.2
0.2
0.2
0.4
0.2
Fig. 6. Delaminated area after 30 days at 1.1 V (vs Ag/AgCl) for Heucophos (a) and
Sachtoperse (b).
2138
13
10
12
10
11
10
10
10
10
0h
24 hs
336 hs
480 hs
744 hs
1032 hs
1224 hs
10
10
10
10
10
-3
10
-2
10
-1
10
10
10
10
10
10
10
10
Frequency [Hz]
90
80
- Phase Angle []
70
60
50
0h
24 hs
336 hs
480 hs
744 hs
1032 hs
1224 hs
40
30
20
10
0
-3
-2
-1
0
1
2
3
4
5
6
10 10 10 10 10 10 10 10 10 10
Frequencies [Hz]
Fig. 7. Evolution of the impedance modulus (a) and phase (b) spectrum during
immersion time for the coating containing Sachtoperse inhibitor.
impedance (|Zj |) vs frequency plot was estimated for all the samples under study during the rst 24 h of immersion. The measured
values ranged from 0.97 to 0.98 for all the investigated samples,
indicating a non-ideal capacitive behavior of the organic coatings.
Fig. 8 shows the evolution of the water uptake during immersion
time in the 5 wt% NaCl solution for 24 h, obtained following the
previously discussed procedure (water 80). Notice that within the
0.05
No Inhibitor
Sachtoperse
Molywhite
Heucophos
Shieldex
Water uptake
0.04
0.03
0.02
0.01
0.00
0
10
15
20
25
Time (hours)
Fig. 8. Water uptake evolution during the rst 24 h of immersion calculated using
the BrasherKingsbury formula [28].
4. Discussion
The accelerated and natural exposure tests carried out in this
work evidenced that the presence of anticorrosive pigments inside
powder deposited organic coatings is able to provide a certain
improvement of the durability of the protection system consisting of an epoxy-polyester primer and a polyester top-coat. This
was proved mainly by means of 1000 h of exposure in the salt
spray chamber. In fact, 1 year outdoor exposure test and cathodic
delamination measurements seem not to be able to clearly differentiate the different coatings, except for Sachtoperse inhibitor.
This fact can be mainly attributed to the good adhesion and very
high barrier properties of the powder deposited organic coating
which is recognized to be very efcient in terms of protection
of the substrate. The accelerated test highlighted that Sachtoperse inhibitor has a negative effect on the protection properties
of the primer coating. Polarization curves showed that the presence of Sachtoperse promotes a decrease of the cathodic current
in both aerated and oxygen depleted conditions (Figs. 1 and 3,
respectively). Despite this fact, the presence of this anticorrosive
pigment inside the paint negatively affects the protection properties. Molywhite inhibitor showed a certain efciency in decreasing
the cathodic corrosion current in de-aerated conditions. However,
the tests carried out on the painted panels did not show any benecial effect to the coating compared to the inhibitor-free control
sample. On the other hand, Shieldex showed a certain efciency
in enhancing the corrosion protection properties of the organic
coating. The potentiodynamic measurements highlighted that the
presence of the Shieldex induces a decrease of the cathodic current
density in oxygen depleted conditions.
Based on the discussed data, it is not possible to nd a clear
correlation between the behavior of the inhibitors when they are
dissolved in water and when they are embedded in the polymeric
matrix. In principle, it is not simple to simulate the effect of a corrosion inhibitor by means of potentiodynamic measurements, since
the steel electrode is forced far from the equilibrium conditions in
a relatively short time. In addition, the inhibitors were tested in
water based solution at natural pH (from 6 to 8, depending on the
different materials) but is recognized that when corrosion takes
place local changes in pH takes place on the metal surface: the pH
noticeably increases in correspondence of the cathodic areas (due
to oxygen reduction) and decreases in correspondence of the anodic
areas (due to metal hydrolysis). Generally speaking it is not easy to
reproduce exactly the condition at the polymer/metal interface.
The EIS measurements evidenced that the presence of the different inhibitors affects the water uptake of the different coatings.
It has to be underlined that the efciency of the inhibitor is strongly
related to the water uptake of the organic coating. Also for this reason it is not easy to nd a direct relationship between the potential
of the inhibitors when dissolved in water based solution and when
dispersed inside the organic coating.
2139
5. Conclusion
References
Prog. Org.
[25] Lj.S. Z ivkovic,
c,
Coat. 76 (2013) 13871395.
[26] A. Amirudin, D. Thierry, Prog. Org. Coat. 26 (1995) 128.
[27] A.S. Castela, A.M. Simes, Prog. Org. Coat. 46 (2003) 130134.
[28] D.M. Brasher, A.H. Kingsbury, J. Appl. Chem. 4 (1954) 62.
[29] M.E. Orazem, N. Pebere, B. Tribollet, J. Electrochem. Soc. 153 (2006) B129B136.
May 2012
June 2012
July 2012
August 2012
September 2012
October 2012
November 2012
December 2012
January 2013
February 2013
March 2013
April 2013
Mean T
( C)
Max T
( C)
Min T
( C)
Mean
RH (%)
Rain
(mm)
Solar
radiation
(MJ/m2 )
17.1
22.1
22.8
24.0
17.9
1.6
7.0
0.4
2.3
3.0
7.0
13.2
23.6
27.8
30.1
31.2
24.0
18.5
11.8
5.1
7.0
7.9
11.5
18.2
10.2
16.0
16.4
17.4
12.9
8.3
3.2
3.1
1.3
1.0
3.1
8.8
63.7
64.6
65.6
61.7
75.2
83.8
88.3
78.0
78.5
66.2
71.2
70.3
95
88
131
68
170
121
237
24
14
16
129
106
664.9
618.1
695.6
655.7
411.8
289.4
169.3
143.2
182.3
250.7
339.5
415.9