Progress in Organic Coatings 77 (2014) 21332139

Contents lists available at ScienceDirect

Progress in Organic Coatings

journal homepage: www.elsevier.com/locate/porgcoat

Study of the effect of corrosion inhibitors on powder coatings applied

on steel
F. Deorian a, , S. Rossi a , M. Fedel a , L.G. Ecco a , R. Paganica b , M. Bastarolo b
a
b

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

Corresponding author. Tel.: +39 0461282437; fax: +39 0461281977.

E-mail address: avio.deorian@unitn.it (F. Deorian).
http://dx.doi.org/10.1016/j.porgcoat.2014.03.014
0300-9440/ 2014 Elsevier B.V. All rights reserved.

as not-hazardous for human health but toxic in an aquatic environment [6].

In order to improve the anticorrosive inhibitive properties of
zinc phosphate, they were chemically and/or physically modied,
therefore, a second and a third generation of pigments have been
developed [7,8]. As an example, with the purpose to merge the corrosion inhibition properties of phosphates and molybdates, zinc
molybdenum phosphate pigments have been created [5]. In addition, it is possible to mention phosphates modied with aluminum
[9] or lithium [10]. Most of them have been successfully tested in
solvent-based coatings [4,11] and they are to be found as commercial products, e.g. K-White 105 and Heucophos ZPA .
Another class of inhibitors that appeared as chromates-free
alternative is the ion-exchanged inhibitive pigments. The anion or
cation can be selected for specic applications depending on their
basic or acidic properties. As an example, the alkaline calcium ion
exchanged silica (Ca/silica). Particularly, it has been demonstrated
that inhibition starts after the ingress of aggressive cations into the
coating layer. Calcium ions are released from the pigments trapping or delaying the movement of aggressive cations toward the
metal surface [12,13]. This non-toxic kind of ion-exchanged pigments have been studied inside a solvent-based coating for steel
protection [12,14] and they are commercially available under the
trade name Shieldex .
Likewise to the previous scenario, strict directives/regulations
has triggered the development and the use of solvent free coatings
technologies for minimizing the emissions of VOCs, e.g. radiation

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F. Deorian et al. / Progress in Organic Coatings 77 (2014) 21332139

curing, water-based and powder coatings [15,16]. Among them,

powder coatings appeared as environmentally friendly [17] alternative to the traditional solvent-based coatings, since only dry
powder particles are required for the processing. In addition, inside
an industrial plant the overspray used for a single application can be
re-processed, reducing the waste of materials [18]. Moreover, in the
last decades the use of powder coatings is demonstrating continuous acceptance in industry, not only due to economic advantages
but also for equivalent protective properties and durability of the
nal coating when compared to solvent-based paints [19,20].
Considering the context above, the present work aims to
investigate the anticorrosive inhibition effectiveness of several
compounds incorporated into an organic coating system applied
onto steel through powder coating technology. The corrosion mitigation pigments selected for this work are commercially available
in the market; they belong to the second and the third generation of chromates-free pigments and are frequently incorporated
into a solvent-based organic coating. Initially, the efciency of the
pigments has been veried by means of potentiodynamic polarization curves with the purpose of comprehend their capacity of
inhibition. As the materials under investigation are not new, their
potential was investigated in particular conditions, such as oxygen
depletion or oxygen enrichment, which are likely to occur during
the service life of the manufacture to protect. Therefore, polarization curves have also been performed in the presence of continuous
nitrogen and air ow, aiming at a comprehensive understanding of
their capacity of inhibition under lower and higher levels of oxygen
at the metal surface.
Secondly, the pigments were incorporated into an epoxypolyester paint formulation applied to cold-rolled steel using
powder coating technology and the anticorrosive efciency of the
coatings have been studied through both accelerated tests, such
as exposure in the salt spray chamber and cathodic delamination
and outdoor natural weathering. Electrochemical impedance spectroscopy (EIS) measurements were also carried out in order to
investigate the effect of the inhibitors on water uptake and barrier properties of the powder deposited organic coatings. In this
sense, the work aims at assessing the potential of commercial available corrosion inhibitors widely used for solvent based paint in the
eld of powder deposited organic coatings. As these coatings are
recognized to show high ohmic resistance of the water saturated
coating lm and low water solubility [21], the efciency of the corrosion inhibitors might be affected. In fact, the reduced availability
of water and the high ion diffusion resistance of the coating might
affect the dissolution kinetic of the inhibitor and the mobility of the
ionic compounds in the polymeric matrix, respectively.
2. Experimental
2.1. Characterization of the corrosion inhibition pigments
Commercial available corrosion inhibition pigments were used
in this study. Table 1 shows the main features of the inorganic
pigments employed.
Table 1
Studied inhibitors.
Pigment label

Chemical composition

Producer/supplier

Sacthoperse

Barium sulfate

Molywhite

Ca phospho-molybdate
carbonates derivate
Zinc calcium phosphate silicate
derivate
Amorphous silicon dioxide
calcium-ion exchanged

Krahn Chemie GmbH

(Germany)
Moly White Pigments
Group (USA)
Heubach GmbH
(Germany)
W.R. Grace & Co.-Conn.
(USA)

Heucophos
Shieldex

The inhibition efciency of the pigments was studied by means

of potentiodynamic polarization curves. For that, the saturated
solution of each pigment prepared in distilled water containing
0.3 wt% of Na2 SO4 was used. Sodium sulfate salt was chosen to
guarantee sufcient electrical conductivity of the solutions during
the tests. After the pigment extraction, the pH of each saturated
solution was measured. Potentiodynamic polarization curves were
acquired in the inhibitor containing solutions using a traditional
three electrodes arrangement. An Ag/AgCl reference electrode
(+0.205 V vs SHE), a platinum ring counter electrode and cold
rolled steel (supplied by Q-panel, USA) working electrode were
employed. Measurements were carried out using Princeton Applied
Research PARSTAT 2273 equipment. The surface of the working
electrode was grinded with silicon carbide abrasive paper: 150,
400, 800, 1200 and 4000, washed and ultrasonically degreased
with acetone. Measurements were performed at room temperature, at 0.166 mV/s scan rate, ranging the potential from the OCP
value to 1.2 V for the cathodic polarization and from the OCP
value to +1.2 V for the anodic polarization. An Avesta-Cell [22]
with an exposed area of the working electrode of 1.0 cm2 has been
employed to perform the experimental measurements.
In addition, cathodic polarization curves were performed in the
presence of continuous bubbling of nitrogen (N2 ) and air (air) gases.
The main purpose of bubbling N2 was to create an environment
near the metal surface with minimized oxygen content. Under
these conditions, the measured oxygen level was about 12 ppm.
On the other hand, air bubbling was used with the purpose to
stimulate oxygen diffusion. For that, the gases bubbling time of
at least 15 min were respected before running the measurements.
All the potentiodynamic polarization curves measurements were
performed, at least, for three replicate samples.
2.2. Coated panels characterization
The inhibitors were dispersed in an epoxy-polyester based polymer (supplied by Akzo Nobel, Italy) exploiting a double screw
extruder. Barium sulfate was added as inert ller in the polymeric
matrix. The polymeric paste was melted by means of the extruder in
order to promote a homogeneous dispersion of ller, inhibitor and
additives. The air cooled melt was milled to obtain a ne powder. By
means of an electrostatic powder coating gun, acetone degreased
mild steel Q-panel were coated and subsequently cured in oven at
180 C for 10 min. The obtained lm was considered as a primer
layer. Therefore, following a similar procedure, a polyester based
polymer (supplied by Akzo Nobel, Italy) was applied on the painted
mild steel panels as top-coat. Notice that no inhibitors are contained in the top-coat. Table 2 summarizes the main features of the
coated panels as well as their nal thickness. Notice that the sum %
inhibitor + % ller is maintained constant at 17% for all the primers.
The protective properties of the coating systems were studied
by EIS in presence of 5 wt% NaCl medium. The EIS spectra were
obtained by using the previously discussed electrodes arrangement
using a coated panel as the working electrode. The EIS measurements were carried out on intact coatings at the free corrosion
potential. The AC perturbation amplitude was 30 mV, frequency
range 105 102 Hz and an analyzed area of about 10 cm2 . The

Table 2
Average thickness of the coated panels.
Pigment label

% Inhibitor

% Filler (barium sulfate)

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

Blank solution (pH_6)

Heucophos
Molywhite
Sachtoperse

a
10

-5

-4

-3

10
10
2
Current Density (A/cm )

10

-2

-0.5

Potential (V vs Ag/AgCl)

spectra of each coating system were collected hourly for 24 h and,

afterwards, daily during about 1200 h.
Cathodic delamination test was performed in the presence of a
2 cm long (about 200 m wide) articial defect over the coated panels. The scratched samples were conditioned at a cathodic potential
of 1.1 V (vs Ag/AgCl, +205 mV vs SHE) for 30 days. 5 wt% NaCl solution was used as electrolyte. The delamination was evaluated at the
end of the test.
Exposure in neutral salt spray chamber in compliance with UNI
EN ISO 9227 standard was carried out. A cross cut was performed
on each sample using a 0.6 cm width cutting tool. Maximum delamination from the articial scribe was measured after 0, 240, 500 and
1000 h of exposure, respectively.
Natural weathering of the organic coatings containing the different inhibitors was carried out. The panels were exposed with 45 of
inclination in the South direction in a site by Trento (North of Italy,
situated 180 m above sea level, geographical coordinates 46 04 N,
11 08 E) characterized by a continental weather [23,24]. Scratched
panels were used: a 2 cm long articial defect was performed
using a cutter. During 365 days of exposure time (from 01.05.2012
to 30.04.2013) the main meteorological data (i.e. temperature,
humidity, rain, solar radiation) were measured and collected (see
Appendix 1 for the average meteorological data). At the end of
the exposure time, the delaminated area starting from the articial scratch was measured. Whenever necessary, the evaluation of
the delaminated area was performed by means of ImageJ software.

Potential (V vs Ag/AgCl)

F. Deorian et al. / Progress in Organic Coatings 77 (2014) 21332139

3. Results and discussion

-0.6
-0.7
-0.8 Heucophos
-0.9
blank (pH6)

-1.0
Molywhite

-1.1

Sachtoperse

-1.2

3.1. Corrosion inhibitors in solution

-5

10

10

-3

10

Current Density (A/cm )

Fig. 1. Polarization curves for the pigments saturated solutions with pH 6.0:
Molywhite, Sacthoperse, Heucophos and blank solution (a) and enlarged cathodic
polarization curve of the same solutions (b).

Potential (V vs Ag/AgCl)

According to literature, a possible method for understanding the

mechanisms which pigments can protect steel is the immersion of
the bare metal into the compounds extracts solution, i.e. saturated
solution [4,11]. The measured pH of all the saturated solutions was
between 5.9 and 6.4 for Sacthoperse, Heucophos ZCP and Molywhite, and around 7 for Shieldex saturated solution. As the pH
of each pigment saturated solution varied between 6 and 7, for
a proper comparison, two different blank solutions were prepared
with the pH balanced to 6.0 and 7.0, respectively. As the saturated
solution of each pigment was obtained with 0.3 wt.% of Na2 SO4 in
distilled water, for the potentiodynamic polarization curves, the
term blank describes the sulfate solution without the presence of
any pigment.
Fig. 1 shows the potentiodynamic polarization curves for mild
steel electrodes immersed in the saturated solutions with measured pH at around 6.0. The corrosion potential (Ecorr ) of steel after
contact with the blank solution was found to be 0.60 V. In the cases
of the pigment containing solutions, no signicant changes in the
Ecorr , neither in the anodic curves have been noticed. However, a
slight shift of the cathodic current toward lower current densities
was given by these solutions. Fig. 1(b) enlarges the cathodic curves
and one can notice that between the potential values of 0.6 and
1.2 V, the pigments containing solutions decreased the corrosion
current. The lowest cathodic current is attributed to the Heucophos
pigment.
Differently from the above, the saturated solution of Shieldex
showed pH equal to 7. Fig. 2 shows the polarization curves compared with the proper blank solution. From this, the cathodic
polarization curve of the saturated Shieldex is to be considered
equivalent to the blank solution.
From Fig. 1(a), although the corrosion potential was not modied, the reduction of the cathodic current suggested an inhibitive
effect promoted by the presence of the inhibitors inside the
solutions. In order to get more insight into the mechanisms of

-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

Blank solution pH 7.0

Shieldex

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.

protection given by the pigments, cathodic polarization curves in

the presence of continuous bubbling of nitrogen (N2 ) were likewise carried out. The cathodic polarization curves with continuous
N2 bubbling for the solutions with pH at around 6.0 are plotted in
Fig. 3. Since the gas was kept continuously owing into the solutions under evaluation, a small physical disturbance in the signal is
commonly expected. As can be seen from the cathodic curves, no
signicant displacement in the corrosion potential was observed.
Ecorr was found to be around 0.60 V for all the tested solutions.

F. Deorian et al. / Progress in Organic Coatings 77 (2014) 21332139

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.

Differently than before, Heucophos pigment has not shown

inhibitive effect. On the other hand, the saturated solutions containing both pigments, Sachtoperse and Molywhite, up to some extent,
have promoted reduction of the cathodic currents.
The cathodic polarization curves with N2 bubbling for the pigment Shieldex is shown in Fig. 4. One can observe that although the
Ecorr showed small shift in the direction of more active potentials,
the cathodic current is found to be shifted toward lower current
densities. As previously mentioned, powder coatings are to be considered with higher barrier properties if compared to the similar
solvent-based coating. Thus, it can be highlighted that the performance observed for the pigments, Molywhite and Sachtoperse
are suggestive for inhibitive protection inside a paint system that
offer superior barrier properties against water permeation, in other
words when the content of oxygen is expected to be low.
Fig. 5 shows the cathodic polarization curves performed in the
presence of continuous air ow for the saturated solutions with
measured pH near 6.0. It is possible to see a slight reduction of
the cathodic current for Molywhite and Heucophos pigment. Apart
from these, no signicant changes were seen for the Sachtoperse
pigment in the cathodic curve when compared to the blank solution. One can notice a shift toward higher currents densities for the
curves with air when compared with N2 bubbling due to the higher
content of oxygen into the electrolyte leading to a more remarkable
corrosion rate. Therefore, the Molywhite and Heucophos pigments

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

showed, to some extent, capability to inhibit corrosion on the metal

surface when oxygen diffusion is stimulated.
For the pigment Shieldex, the cathodic polarization curves with
air bubbling are not shown in the present document since neither
the Ecorr nor the cathodic curves were found to have no signicant
changes when compared to the blank solution.
3.2. Corrosion inhibitors inside powder deposited organic
coatings
The inhibitors under investigation were dispersed in the polymeric paste following the previously discussed procedure. The
samples under investigation are reported in Table 2. Notice that
the organic coatings are named like the inhibitor which is contained inside. The properties of the coatings containing the different
inhibitors were investigated by means of accelerate tests (cathodic
delamination test and exposure in neutral salt spray chamber), natural weathering exposure and electrochemical measurements such
as electrochemical impedance spectroscopy.
Neutral salt spray test was carried out on scratched samples.
The maximum delamination extent was measured after 0, 240, 500
and 1000 h of continuous exposure. Notice that the starting value,
corresponding to 0.6 mm, corresponds to the width of the cutter.
Table 3 shows the delamination extent for the different samples
under investigation.
After about 500 h of continuous exposure, only the coatings containing Sachtoperse show a noticeable increase of the delaminated
area. It is worth noticing that after 500 h of exposure the coating
containing no anticorrosive pigments shows no evidence of delamination. After 1000 h of exposure in the salt spray chamber the
coatings containing Sachtoperse show a remarkable detachment
of the paint layer from the steel substrate. The coatings containing
Molywhite and No inhibitor showed a delamination front which
is about 23 mm, while if Shieldex or Heucophos are present the
coatings show no delamination.

Delamination extent (mm)

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

Current Density (A/cm )

-0.6

Potential (V vs Ag/AgCl)

Potential (V vs Ag/AgCl)

2136

-4

10

Current Density (A/cm )

Fig. 4. Cathodic polarization curves with N2 bubbling for the Shieldex saturated
solution with pH 7.0.

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

F. Deorian et al. / Progress in Organic Coatings 77 (2014) 21332139

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

Cathodic delamination test was also carried out to assess

the wet adhesion of the coating when the reduction of oxygen
(H2 O + O2 + 2e 2OH ) is forced on the steel substrate, thus
promoting a local increase of the pH in correspondence of the
metal/coating interface. As previously explained, a 2 cm long scribe
was performed on the coatings, reaching the underling metal.
The samples were conditioned for 30 days at 1.1 V (vs Ag/AgCl).
Afterwards, the delaminated area around the articial defect was
measured. The results are reported in Table 4, while Fig. 6 shows
the appearance of the coatings containing Heucophos (Fig. 6(a))
and Sachtoperse (Fig. 6(b)) at the end of the test. Observe that the
delaminated area is all around the articial scribes.
The coating containing Sachtoperse shows a huge extent of
delamination. As far as the other samples are concerned, the disbonded area is remarkably lower, in the range 0.81.4 cm2 . For
samples containing no inhibitors, Shieldex and Heucophos the
delamination is relatively low (1 cm2 ) at the end of the test.
In accordance with neutral salt spray test results, cathodic
delamination test evidenced that the corrosion inhibitor named
Sachtoperse seem not suitable for the protection system under
investigation. In fact, the corresponding delamination rates were
proved to be higher than for the coating containing no inhibitor.
As previously anticipated, outdoor exposure test was carried out
employing scratched samples. The main meteorological data were
collected to dene the aggressiveness of the environment. Details
about the evolution of the collected meteorological data during the
exposure period are reported in Appendix 1. Table 5 reports the
delaminated area at the end of the outdoor exposure.
Also in this case the coatings containing Sachtoperse showed the
most noticeable extent of delamination among the studied samples, thus indicating that they do not bring any benecial effect to
the protection system. As far as the other samples are concerned,
the total delamination is comparable. Based on the natural weathering results it seems that Sachtoperse inhibitors do not enhance
the outdoor resistance of the coating but, actually, their presence
in the polymeric matrix negatively affects the protection system.
However, the relatively limited duration of the outdoor test do not
allow a clear assessment of the effectiveness of the most of the
studied inhibitors.
To evaluate the effect of the inhibitors on water uptake and
barrier properties of the organic coating used in this study, electrochemical impedance spectroscopy measurements were carried
out in 5 wt% NaCl solution. Fig. 7 shows, for example, the evolution of the impedance modulus and phase during immersion
time for the coating containing Sachtoperse. All the investigated
samples follow the trend depicted in Fig. 7, characterized by very
high values of impedance in the low frequency domain (around

Fig. 6. Delaminated area after 30 days at 1.1 V (vs Ag/AgCl) for Heucophos (a) and
Sachtoperse (b).

1011 1012  cm2 ), in accordance with similar results obtained by

other authors [25]. Regardless of the different inhibitors, considering the impedance modulus in the low frequency range (0.01 Hz)
[26], all the investigated coatings show very high protection performance. At this level, due to the relatively short immersion time,
it is not possible to differentiate the investigated samples in terms
of barrier properties even after about 1224 h of continuous immersion.
The shape of the impedance plots indicates an almost capacitive behavior of the coated mild steel electrodes. The imaginary
impedance |Zj | value was exploited to estimate the effective value
of the capacitance of the coatings in order to measure the water
uptake during the rst 24 h of immersion [27] by means of the
BrasherKingsbury formula [28]. To calculate the effective capacitance of the coatings during immersion, the equation proposed
by Orazem et al. [29] was employed. For this purpose, the |Zj | values at 104 Hz were used for calculation. The slope of the imaginary

2138

F. Deorian et al. / Progress in Organic Coatings 77 (2014) 21332139

rst 15 h of immersion all the different samples reach a plateau

value which can be related to water saturation.
As powder coatings are known to show low water uptake, it
is not an unexpected result that the water saturation values are
exiguous for all the investigated samples. From Fig. 8 it is possible to observe that the presence of the inhibitor pigments causes
a decrease of the water uptake of the organic coating. In particular, the presence of Shieldex and Molywhite seems very effective in
decreasing the water absorption. However, based on the EIS measurement performed in this work, it is not possible to highlight a
clear relationship between the effect of the different inhibitors on
the water uptake and on the delamination rate, as measured by
means of accelerated (neutral salt spray test and cathodic disbonding) and outdoor exposure tests.

13

10

12

10

11

|Z| Impedance [cm ]

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.

F. Deorian et al. / Progress in Organic Coatings 77 (2014) 21332139

2139

5. Conclusion

References

The effect of commercial corrosion inhibitor pigments on

the corrosion protection properties of powder deposited organic
coatings was investigated. Natural weathering (1 year of exposure
in Trento, continental weather), cathodic delamination measurements and neutral salt spray tests were carried out the assess the
effect of different corrosion inhibitors widely used in the liquid
paint industry. The experimental tests indicated that Sachtoperse inhibitor do not provide any benecial effect to the powder
deposited organic coating while the other materials, such as
Shieldex, increase the durability of the organic coatings, as highlighted by 1000 h of exposure in neutral salt spray chamber. The
efciency of the different pigments was also evaluated analyzing
the electrochemical behavior of mild steel electrodes immersed in
water based solution saturated with the different inhibitors. The
measurements indicated a certain cathodic inhibition activity for
several pigments, both in aerated and oxygen depleted conditions.
It was not possible to nd a direct relationship between the potential of the inhibitors when dissolved in water based solution and
when dispersed inside the organic coating.

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Appendix 1. Main weather parameters from 1 May 2012 to

30 April 2013

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