Corrosion Science 53 (2011) 28722880

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

The EIS investigation of powder polyester coatings on phosphated low carbon steel:
The effect of NaNO2 in the phosphating bath
B.V. Jegdic a,, J.B. Bajat b, J.P. Popic c, S.I. Stevanovic c, V.B. Mikovic-Stankovic b
a

Institute GOA, Milana Rakica 35, 11000 Belgrade, Serbia

Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, P.O. Box 3503, 11120 Belgrade, Serbia
c
ICTMDepartment of Electrochemistry, University of Belgrade, Njegoeva 12, Belgrade, Serbia
b

a r t i c l e

i n f o

Article history:
Received 19 January 2011
Accepted 7 May 2011
Available online 12 May 2011
Keywords:
A. Steel
A. Organic coatings
B. EIS
B. AFM

a b s t r a c t
The effect of different type of iron-phosphate coatings on corrosion stability and adhesion characteristic
of top powder polyester coating on steel was investigated. Iron-phosphate coatings were deposited on
steel in the novel phosphating bath with or without NaNO2 as an accelerator. The corrosion stability of
the powder polyester coating was evaluated by electrochemical impedance spectroscopy (EIS), adhesion
by pull-off and NMP test, while surface morphology of phosphate coatings were investigated by atomic
force microscopy (AFM).
The adhesion and corrosion stability of powder polyester coatings were improved with pretreatment
based on iron-phosphate coating deposited from NaNO2-free bath.
2011 Elsevier Ltd. All rights reserved.

1. Introduction
The rigorous restrictions in application of traditional solventborne organic coatings are related to the presence of volatile
organic compounds (VOC). Therefore, other formulations and types
of organic coatings were investigated and applied in corrosion protection of metals, especially steel [115]. Besides waterborne
organic coatings containing non-toxic protective pigments [16]
and electrodeposited polymer coatings [712], technologies based
on the powder coatings and thermal spraying of polymeric materials have been greatly used recently [1315]. Powder coatings have
several advantages, such as little or no VOC, high utilization rates,
energy savings, and the application of polymer coatings with high
melt viscosities [14,15]. It is important to notice that technologies
based on the powder coatings eliminated the presence of solvents.
Besides, due to the high kinetic energy of thermal spray processes,
the polymer particles do not need to be fully molten in order to
cover the surface of the substrate [14].
Powder coatings, as well as all polymer coatings, provide corrosion protection by acting as a barrier layer between the substrate
material and the environment. However, polymer coatings are to
a certain degree permeable to water, oxygen and ions, depending
on the thickness and characteristics of the polymer coating, the
type of the substrate and the surface treatment, as well as the
metal/coating interface [16]. The pretreatment of the metal surface
Corresponding author. Tel.: +381 11 2412 222; fax: +381 11 2410 977.
E-mail address: borejegdic@yahoo.com (B.V. Jegdic).
0010-938X/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2011.05.019

usually includes metal degreasing and formation of the conversion

coating on the surface, with the aim to increase the corrosion resistance and adhesion strength between metal and organic coating
[17,18]. Pretreatments based on different zinc phosphate coatings
have usually been used as conversion coatings on steel [1925].
Iron-phosphate coatings were also studied, but they showed less
corrosion stability in respect to zinc phosphate coatings [26,27].
However, if iron-phosphate coatings were used as a pretreatment
on steel, prior to deposition of top-organic coatings, good corrosion
protection could be achieved [2831]. The advantages of ironphosphate pretreatment are simple and cheep equipment and
waste water treatment. All these make the iron-phosphate coating
on steel a promising steel pretreatment prior to organic coating
deposition. Most phosphating baths reported in literature require
very high operating temperatures, usually 6070 C or higher
[17]. There are low temperature phosphating baths, but the phosphating process in these baths is very slow and it needs to be accelerated. The most common accelerators that are added to the
phosphating baths are nitrates, nitrites, chlorates, hydroxylamine
and molybdenum compounds [32]. The morphology and surface
coverage of phosphate coatings depend on many factors, such as
the composition of the deposition bath, bath temperature, deposition time, as well as the additives used in the electrolyte [8,33].
The electrochemical impedance spectroscopy (EIS) is often used
in characterization of corrosion stability of polymer coated metal
specimens during exposure to a corrosive environment [34,35]. It
usually takes months before corrosive agent reaches the metal substrate and the onset of corrosion could be determined by EIS, for

B.V. Jegdic et al. / Corrosion Science 53 (2011) 28722880

protective systems commonly used in practice. In order to evaluate

the inuence of steel pretreatment by different types of the ironphosphate layers on the adhesion and corrosion stability of powder
polyester coating more accurately, the low thickness polyester
coating was used in this work.
The testing of low thickness powder polyester coating enables
faster detection of defects in organic coating, the appearance of
corrosion processes of metal substrate under the coating, in the
form of pitting or some other type of corrosion degradation, as well
as the dependence of the wet adhesion strength of polyester coating with time. In our earlier work [33] it was shown that the properties of phosphate coating deposited on steel from the plating
bath at various temperatures and with various concentration of
NaNO2 was quite different as compared to phosphate coating
deposited from NaNO2-free phosphating bath. In our other work
(not yet submitted) we have optimized plating conditions for phosphate coating on steel and found the optimal plating parameters
for deposition of phosphate coating of on steel. The aim of this
work is to investigate the effect of NaNO2 on the quality of phosphate coating on steel, as a sublayer for top powder polyester coating. In addition, the morphology of phosphate coatings and
corrosion stability and adhesion of top powder polyester coating
on iron phosphated steel, will be analyzed in order to nd the correlation between them.
2. Experimental
2.1. Substrate preparation
The low carbon steel, of the composition given in Table 1, was
used as a substrate for iron-phosphate coating deposition. The steel
panels (30 mm  50 mm  0.8 mm for EIS and pull-off test,
14 mm  14 mm  0.8 mm for NMP test and 20 mm  20 mm 
0.8 mm for microscopic examination) were used as substrates. The
plating bath used in this work (Table 2) is a simple, novel plating
bath, made in our laboratory. Prior to phosphate coating deposition
the steel panels were abraded with SiC papers 600 grades, and then
degreased in 0.2 g dm 3 nonylphenol ethoxylate at room temperature for 5 min, and rinsed with distilled water. Iron-phosphate coatings were formed chemically by immersion in solution at 50 C
during 5 min. The inuence of the addition of accelerator, 0.5 g dm 3
NaNO2, in the plating bath was also investigated.
2.2. Polyester coatings deposition
Powder polyester coatings TGIC, produced by TIGER Drylac,
ral color 9006, pigment: iriodin (Merck), particle size 12
85 lm, specic gravity 1.19 g cm 3, were deposited on bare steel
and phosphated steel by electrostatic spraying method, using
ITW Gema AG manuel powder system, type OPTI ex 17001
12592, at 80 kV and then baked at 190 C for 20 min, as suggested
by the coating producer. The coating thickness was 30 2 lm.
2.3. Polarization measurements
The corrosion rates of steel and phosphate coatings on steel
were determined in a 3 wt.% NaCl solution using extrapolation of
anodic polarization curves to the open circuit potential. Potential
sweep rate of 0.2 mV s 1 was applied starting from the open circuit

Table 1
Chemical composition of carbon steel used as substrate for phosphating.
Element

Si

Mn

Cr

Ni

wt.%

0.119

0.019

0.250

0.019

0.014

0.012

0.019

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Table 2
Chemical composition of phosphate bath.
Component

Concentration (g dm

H3PO4
NaOH
Nonylphenol ethoxylate

0.92
0.34
0.125

potential (OCP), after the constant OCP was established (up to

25 min).
2.4. Electrochemical impedance spectroscopy
For electrochemical impedance spectroscopy (EIS) measurements the coated samples were exposed to 3 wt.% NaCl in distilled
water, for 120150 days, depending on the time when values of Rp
were around 30 kX cm2. A three-electrode cell arrangement was
used in the experiments. The working electrode was a coated sample situated in a special holder. The counter electrode was a platinum mesh with a surface area considerably greater than that of the
working electrode. The reference electrode was a saturated calomel electrode (SCE). The EIS data were obtained at the open-circuit
potential using GAMRY Reference 600 potentiostatgalvanostat/
ZRA. The impedance measurements were carried out over a frequency range of 300kHz10 mHz using 10 mV amplitude of sinusoidal voltage. The impedance spectra were analyzed using
Gamry Elchem Analyst tting procedure.
2.5. Adhesion measurements
The adhesion strength of polyester coatings on bare steel and
steel pretreated with different iron-phosphate coatings was determined by two methods: by a direct pull-off standardized procedure [36] and by determining the N-methyl-2-pyrrolidone
retention time [37].
2.5.1. Pull-off test
The adhesion strength of polyester coatings on bare steel and
iron phosphated steel was determined by a direct pull-off standardized procedure, using ERICHSEN ADHESIONMASTER 513 MC/
525 MC. The adhesion measurements were performed prior to
exposure to 3 wt.% NaCl solution (dry adhesion), and during exposure to 3% NaCl solution at room temperature (wet adhesion). At
certain time intervals the panels were removed from the solution,
rinsed with distilled water, dried in air at room temperature for
1 h, and dollies were then glued to panels.
According to ISO 4624 [36], prior to bonding the dollies of
20 mm diameter were degreased by ethanol. After that, polyester
coating was rmly abraded by ne emery paper (No. 1000) and
also degreased by ethanol. The industrial grade German super
adhesive PASCO FIX was used. After curing of the adhesive for
24 h the polyester coating was cut around the dolly and the dolly
was pulled-off vertically (force increase speed of 100 N s 1) while
measuring the necessary force, i.e. adhesion strength. For each type
of protective system ve samples were tested and the average value was taken, and only those samples with the interfacial failure
were considered.
2.5.2. NMP test
In the NMP determination test panels of 2 cm2 area were immersed in the N-methyl-2-pyrrolidone (NMP) at 60 C. The paint
always delaminated from the edges inwards. The time when the
paint had completely come off was recorded. The experiment
was done ve times per panel and the average value was calculated
as NMP retention time, or the time for the paint lm to delaminate

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completely and intact from the substrate (NMPRT). Each panel was
always treated in a fresh NMP.

bare steel surface, and that a phosphate coating deposited on steel

from a bath with NaNO2 showed better corrosion stability in respect to phosphate coating without NaNO2.

2.6. Microscopic examinations

Corrosion stability of the polyester coatings on bare steel and
steel with different types of iron-phosphate coatings was investigated by immersion in aqueous 3 wt.% NaCl solution at room temperature. The protective systems were degreased by ethanol and
immersed in 3% NaCl solution. After 15 days of exposure to corrosive environment, one set of samples were taken from the solution,
rinsed with distilled water, degreased with ethanol and treated
with N-methyl-2-pyrolidone solution at 60 C, in order to remove
polyester coating. The samples without polyester coating were
rinsed with distilled water, dried and analyzed by optical microscope type Olympus CX 41, with microscopic camera Olympus
UC 30, with the aim of identifying the corrosion damage of the
samples, as pitting or some other type of corrosion degradation.
The same procedure was performed with other set of samples after
30 days of exposure to 3 wt.% NaCl solution.
2.7. Surface morphology
The surface morphology of bare steel and steel with different
types of iron-phosphate coatings was investigated by atomic force
microscopy (AFM), with NanoScope 3D (Veeco, USA) microscope
operated in contact mode under ambient conditions. Etched silicon
probes with spring constant of 2080 Nm 1 were used.
3. Results and discussion
3.1. Polarization measurements
Polarization curves in a small range of potential near to open
circuit potential (OCP) were obtained in a 3 wt.% NaCl solution.
The E log j dependences obtained are shown in Fig. 1 for phosphate coatings deposited with or without NaNO2, as well as for
bare steel, as a reference. The corrosion current densities, jcorr, were
estimated from the intersections of the anodic Tafel plots with the
corrosion potentials, Ecorr. The corresponding corrosion current
densities obtained for the different samples are: 46.7 lA cm 2 for
bare steel, 16.9 and 20.4 lA cm 2 for steel phosphated with and
without NaNO2 in the bath, respectively. It could be concluded that
both phosphate coatings on steel have smaller jcorr as compared to

Fig. 1. Anodic polarization curves in 3 wt.% NaCl for bare steel (s) and phosphated
steel with (N) and without NaNO2 in plating bath (d).

3.2. Electrochemical impedance spectroscopy

The electrochemical properties of polyester coatings on bare
steel and different types of the iron-phosphate coatings on steel
were examined by EIS measurements. Electrochemical impedance
spectroscopy (EIS) has been greatly used for characterization of
corrosion stability of organic coatings on steel, as well as, on other
metal substrates. This method provides information about the organic coating itself, such as defects, adhesion, barrier properties,
as well as the destruction of the protective system metal/organic
coating, even before the visual deterioration of the coating could
be seen [34,38].
Figs. 24 show the Bode moduo plots for the polyester coatings
deposited on bare steel and steel pretreated with different phosphate coatings, during long time of exposure to 3 wt.% NaCl. The
polyester coating on steel pretreated with phosphate coating
deposited from the NaNO2-free bath showed the best protective
properties. Namely, impedance of this protective system decreased
slowly during the rst 3 weeks of exposure to 3 wt.% NaCl (Fig. 4).
This was followed with slower decrease of impedance values up to
111 days exposure to 3 wt.% NaCl, as compared to more rapid
impedance decrease for other two samples (Figs. 2 and 3). These
results suggest signicantly improved corrosion stability of polyester coating on steel pretreated with phosphate coating deposited
from the NaNO2-free bath, in respect to both steel and steel phosphated with NaNO2 in the bath.
The tting of experimental data obtained was accomplished
using the equivalent electrical circuits shown in Fig. 5 [14,15,39
41], by Gamry Instruments Elchem Analyst tting program. The
equivalent circuits consist of the electrolyte resistance, RO, the
coating pore resistance, Rp, the coating capacitance, Cc, the
charge-transfer resistance, Rct, and CPE, a constant phase element,
which represents all the frequency dependent electrochemical
phenomena, namely double-layer capacitance, Cdl, and diffusion
processes.
The pore resistance of polyester coatings is plotted as a function
of time in Fig. 6. The pore resistance, Rp, sharply decreases, up to 4
5 orders of magnitude, during the rst 20 days of exposure to
3 wt.% NaCl (Fig. 6), as a consequence of the water uptake, for

Fig. 2. Bode plots for polyester coating on bare steel substrate, during exposure to
3 wt.% NaCl.

B.V. Jegdic et al. / Corrosion Science 53 (2011) 28722880

Fig. 3. Bode plots for polyester coating on steel with iron-phosphate coating
deposited with NaNO2 in the plating bath, during exposure to 3 wt.% NaCl.

Fig. 4. Bode plots for polyester coating on steel with iron-phosphate coating
deposited from NaNO2-free plating bath, during exposure to 3 wt.% NaCl.

polyester coating on bare steel and steel phosphated with NaNO2

in the bath. On the other hand, there is a signicantly smaller decrease in Rp for polyester coating on steel phosphated without
NaNO2 in plating bath (up to 3 orders of magnitude during the rst
20 days of exposure to 3 wt.% NaCl). This initial exposure time
could be related to the equivalent circuit shown in Fig. 5a. The
highest values of pore resistance were obtained for polyester

2875

Fig. 6. The time dependence of pore resistance, Rp, for polyester coatings on bare
steel (s) and phosphated steel with (N) and without NaNO2 in plating bath (d),
during exposure to 3 wt.% NaCl.

coating on steel pretreated with iron-phosphate coating deposited

from the NaNO2-free bath, indicating a better corrosion stability of
this protective system as compared to others investigated in this
work.
The saturation period follows when the values of pore resistance remain almost constant over a longer period of time indicating the maintenance of good protective properties of polyester
coating [31]. As electrolyte keeps penetrating at one moment electrolyte reaches the metal surface and once the electrolyte is in contact with the metal surface, corrosion processes start, which leads
to the loss of adhesion and to delamination of the coating [42,43].
Two time constants appear in the EIS diagrams and this electrochemical behavior is related to the equivalent circuit shown in
Fig. 5b. This is characterized by decrease in pore resistance after
saturation period (Fig. 6).
Figs. 79 show the Nyquist plots for the impedance of the polyester coatings deposited on bare steel and steel pretreated with
different phosphate coatings, during exposure to 3 wt.% NaCl. The
solid circles in these gures indicate time when the corrosion of
steel substrate, under the polyester coating, was initiated, i.e. time
when impedance of these protective systems could be characterized with two-time constants, shown in Fig. 5b. Results obtained
point to the initiation of bare steel substrate corrosion, underneath
the polyester coating, after 10 days of exposure to corrosive agent
(Fig. 7a). For the steel pretreated with iron-phosphate coating
deposited with NaNO2 in the plating bath the initiation of steel
corrosion was delayed for 14 days, i.e. the corrosion processes on

Fig. 5. Equivalent electrical circuits of a polymer-coated metal.

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B.V. Jegdic et al. / Corrosion Science 53 (2011) 28722880

Fig. 7a. Nyquist plots for polyester coating on steel, during early exposure to 3 wt.%
NaCl solution.

Fig. 7b. Nyquist plots for polyester coating on steel, during prolonged exposure to
3 wt.% NaCl solution.

steel were initiated after 24 days of exposure to corrosive agent

(Fig. 8a). On the other hand, the corrosion of steel substrate pretreated with phosphate coating deposited from NaNO2-free bath,
underneath the polyester coating, was initiated after 122 days of
exposure to a corrosive agent (Fig. 9).
The impedance data for prolonged exposure are shown in Figs.
7b and 8b and inset in Fig. 9. They illustrate the presence of two
time constants that become more and more distinct with the increase of immersion time, and which correspond well to the model
shown in Fig. 5b. Although the second Nyquist semicircle is not
complete for all investigated samples, it could be related to the
equivalent electrical circuit shown in Fig. 5b [4447]. Namely,
the advancement of the second loop with exposure time in
3 wt.% NaCl for different samples is shown in Figs. 7b, 8b and 9.
It is clearly seen that the second semicircle becomes almost complete during prolonged exposure time for bare steel and steel with
phosphate coating deposited from NaNO2-free bath (122 and 128
days, Figs. 7b and 9, respectively). However, for steel phosphated
with NaNO2 in the bath the second impedance semicircle does
not complete during 122 days of exposure, but for this time of
exposure the appearance of a diffusion tail at the lowest frequencies is observed. Since the second semicircle completes for samples
shown in Figs. 7b and 9 for prolonged exposure to corrosive agent,
the equivalent electrical circuit proposed in Fig. 5b is still suitable.
Alternatively, the impedance spectra at the intermediate and low
frequencies could be interpreted as a diffusion tail, which assumes
that the diffusion process is much slower than the charge-transfer
reaction and that diffusion is rate-controlling [46]. However, since
the n value in CPE was always above 0.6 and on the basis of the
advancement of this second semicircle with time of exposure,
and its complete shape at low frequencies for long exposure time,

Fig. 8a. Nyquist plots for polyester coating on steel pretreated with iron-phosphate
coating deposited with NaNO2 in the plating bath, during exposure to 3 wt.% NaCl
solution.

Fig. 8b. Nyquist plots for polyester coating on steel pretreated with iron-phosphate
coating deposited with NaNO2 in the plating bath, during prolonged exposure to
3 wt.% NaCl.

Fig. 9. Nyquist plots for polyester coating on steel pretreated with iron-phosphate
coating deposited from the NaNO2-free bath, during exposure to 3 wt.% NaCl.

we think that it is clear that the second time constant relates to

corrosion processes on metal substrate, under polyester coating.
All these EIS results give clear evidence that steel surface pretreatment by iron-phosphate coating deposited without NaNO2
in the plating bath is efcient as a surface pretreatment.
3.3. Adhesion measurements
In this work, both the dry and wet adhesion of polyester coatings on bare steel and iron-phosphated steel were measured by
the standard pull-off method. Dry adhesion was also determined
by the NMP test. N-methyl-2-pyrrolidone is highly polar solvent

B.V. Jegdic et al. / Corrosion Science 53 (2011) 28722880

and it is capable of forming strong hydrogen bonds, allowing it to

rapidly diffuse into organic coating and causing extensive swelling
[37]. Due to the swelling shear stresses are imposed at the coating/
metal interface. These shear stresses are in many cases relaxed by
delamination of the coating, with longer time until delamination
indicating a better adhesion.
On the basis of the NMPRT values for polyester coatings on bare
steel and steel with different iron-phosphate coatings (Table 3), it
can be seen that the adhesion of polyester coating is the highest on
steel surface pretreated with iron-phosphate coating deposited
from NaNO2-free bath. The adhesion of the polyester coating on
steel pretreated with iron-phosphate coating deposited with
NaNO2 in bath is better than for the polyester coating on the bare
steel substrate. The results of the pull-off measurements for all
investigated protective systems are shown in Table 4. On the basis
of the results presented in Table 4 it can be concluded that the
highest dry adhesion of polyester coating is accomplished by steel
pretreatment with iron-phosphate coating without NaNO2 as an
accelerator. These results are in accordance with the results of
the NMP test.
Besides the measurement of dry adhesion, it is necessary to
determine also the wet adhesion. Namely, it is well known that
the basic function of an organic coating is, rst, to act as a barrier
so that a complete corrosion cell cannot form, and, second, to prevent the spreading of corrosion from the initial site of electrolyte
penetration. Both functions require adequate coating adhesion in
the presence of water and/or electrolyte. Thus, one of the most
important factors in corrosion prevention by protective coating is
the coating adhesion loss under environmental inuence. The
changes in the pull-off adhesion strength with time of immersion
in NaCl solution for polyester coatings on bare steel and steel pretreated with different type of iron-phosphate coatings are given in
Table 4. The general trend of the initial decrease in adhesion
strength is observed for all investigated samples. Both iron-phosphate pretreatments increased dry and wet adhesion of powder
polyester coating on steel. However, the values of wet adhesion
were the highest for polyester coating on steel pretreated with
iron-phosphate coating without accelerator, and the overall increase of wet adhesion for this sample was maintained throughout
the whole investigated time period. These results are in accordance
with the impedance measurements.
Results shown in Figs. 24, 69 and Tables 3 and 4 indicate that
bonds between polyester coating used in this work and iron oxide
and/or iron hydroxide on bare steel are weaker than the ones
formed with porous iron-phosphate coatings, and in addition, are

Table 3
NMPRT time for polyester coatings on different substrates.

Substrate

NMPRT* (min)

Bare steel
Phosphated steel with NaNO2
Phosphated steel without NaNO2

7
30
>50

Data are mean values of ve measurements.

Table 4
The average values of the pull-off strength for the different protective systems.
Substrate

Bare steel
Phosphated steel with NaNO2
Phosphated steel without NaNO2
*

Pull-off strength* (N mm

0h

24 h

48 h

72 h

2.5
3.1
3.7

1.8
2.2
3.3

1.1
1.5
3.2

0.6
1.1
3.0

Data are mean values of ve measurements.

2877

less stable in the corrosive environment. This is the consequence

of large inner surface area of phosphate coatings, due to the large
number of pores which enable the contact with top-polyester coating and, consequently, the establishment of great number of Van
der Waals and hydrogen bonds. The adhesion of polyester coating
is especially enhanced on steel pretreated with iron-phosphate
coating deposited from NaNO2-free bath, suggesting that this phosphate coating provides many anchor points for powder polyester
coating.
3.4. Microscopic examinations
Fig. 10 shows the microphotographs of the bare steel and the
steel with different types of iron-phosphate coatings, obtained by
optical microscope, after immersion in 3 wt.% NaCl solution. After
immersion in NaCl solution for 15 or 30 days, samples with polyester coating were treated by NMP solution in order to remove polyester coating.
The specimens with iron-phosphate coating obtained from
NaNO2-free bath showed the best corrosion stability. Corrosion
damages as pitting, or similar corrosion degradation, did not appear either after 15 days, or after 30 days of exposure to NaCl solution (Fig. 10a). The samples with iron-phosphate coating obtained
from plating bath with NaNO2 showed signs of corrosion degradation after 30 days of exposure to NaCl solution (indicated with an
arrow in Fig. 10b), while after 15 days of exposure there was no
visible sign of corrosion damage (Fig. 10b). The corrosion degradation of bare steel was clearly visible after 15 days of exposure to
NaCl solution (indicated with an arrow in Fig. 10c). Corrosion degradation of these samples was intensied during time and after
30 days had form of pits (Fig. 10c). These results are in accordance
with EIS results shown in Figs. 69.
3.5. Surface morphology
In order to nd out the reason for the signicant difference in
the corrosion stability and adhesion of polyester coatings on phosphate deposits obtained from NaNO2-free plating bath and bath
with NaNO2, and to have a deeper insight into a surface morphology of these two phosphate deposits, atomic force microscopy
(AFM) images were taken. Figs. 1113 show three-dimensional
(3D) AFM images of the bare steel (Fig. 11) and the iron-phosphate
coatings on steel deposited with (Fig. 12) and without accelerator
NaNO2 (Fig. 13) in the phospate plating bath.
Microphotograph shown in Fig. 11 reveals almost at and uniform surface of bare steel. The sporadical small spots of more
coarse morphology, that is probably the result of the mechanical
damage during abrading, could be seen. AFM analysis of the morphology of the iron-phosphate coatings studied indicates clear difference between deposits obtained from different plating baths.
The deposit obtained from bath with NaNO2 is made up of small
crystallites in the two characteristic forms of phosphate coating:
laminated structure and needle-like forms (Fig. 12). A completely
different surface morphology could be observed for phosphate
coating deposited on steel from NaNO2-free plating bath, where
phosphate crystals are bigger and have the shape of platelets
(Fig. 13). The AFM results suggest that the NaNO2 causes the decrease in the phosphate crystal size. Namely, the smaller crystal
sizes obtained in the bath with NaNO2 indicate that this additive
has an effect on surface activation, favouring phosphate nucleation
and leading to formation of smaller laminated and needle-like
crystals (Fig. 12).
The different surface morphologies of phosphate coatings on
steel resulted in the different adhesion of polyester coating on
the pretreated steel substrate, as it was shown earlier. This could
be explained as follows: theoretically, for optimal adhesion it

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Fig. 10. Optical microphotographs of steel substrate under polyester coating after 15 and 30 days in 3 wt.% NaCl. (a) Steel with iron-phosphate coating deposited from the
NaNO2-free bath (no corrosion), (b) steel with iron-phosphate coating deposited with NaNO2 in the bath (corrosion after 30 days), and (c) bare steel (corrosion after 15 and
30 days).

Fig. 11. 3D AFM image of bare steel surface (15  15  0.8 lm).
Fig. 12. 3D AFM image of iron-phosphate coating on steel deposited with NaNO2 in
plating bath (20  20  2.5 lm).

would be important that top polyester coating during deposition

fully penetrates into the pores of the surface layer. Penetration of
this top coating into the pores on rough surface depends on the
contact angle and the shape of the pores. If these are favorable, a
signicant penetration may occur at equilibrium [7].

The AFM revealed that the smoothes surface was accomplished

for the bare, polished steel and the most coarse one for phosphate
coating deposited from the NaNO2-free plating bath (Figs. 1113).
Mechanical adhesion is thought to occur when a polyester powder

B.V. Jegdic et al. / Corrosion Science 53 (2011) 28722880

2879

indicate that steel pretreatment with iron-phosphate coating

deposited from NaNO2-free plating bath is favorable in forming initially stronger bonds with powder polyester coating. The higher
surface roughness and greater crystallite size estimated by AFM
analysis of this phosphate coating provided better adhesion of
top polyester coating. As a consequence, top powder polyester
coating formed on the iron-phosphate without nitrites had high
values of pore resistance, which did not change with time of exposure to corrosive agent (up to 120 days), indicating the increased
corrosion stability. In addition, no corrosion damages (pitting) of
this sample could be seen by optical microscopy after 30 days of
exposure to NaCl.
Finally, it was shown that for protective systems investigated in
this work the EIS results and microscopy examinations correlated
well with the adhesion measurements obtained both by pull-off
and the NMP test.
Acknowledgment
Fig. 13. 3D AFM image of iron-phosphate coating on steel deposited from NaNO2free plating bath (20  20  2.5 lm).

sets in pores and cracks of the substrate, which gives a mechanical

key. When mechanical keying occurs adhesion should rise with
roughness of the substrate. Results presented on Figs. 1113 indicate that the higher roughness of phosphate coating deposited on
steel from the NaNO2-free bath in respect to phosphate coating
with NaNO2, along with the bigger crystallite grains, are favorable
in forming a more stable bonds with polyester coating. So, although
the corrosion stability of phosphate coating deposited on steel with
NaNO2 in the bath was a little greater (jcorr = 16.9 lA cm 2) than the
phosphate coating deposited on steel from the NaNO2-free bath
(jcorr = 20.4 lA cm 2), the more rough phosphate coating from
NaNO2-free plating bath, made up of bigger grains, proved to be
benecial as a sublayer, prior to deposition of polyester coating.
All the results presented point to greater corrosion stability and
adhesion achieved for the protective system based on polyester
coating on steel pretreated with iron-phosphate coatings with no
accelerator.
4. Conclusions
Using electrochemical impedance spectroscopy (EIS), standardized pull-off measurement and the NMP test, corrosion stability
and adhesion of top powder polyester coating on steel and steel
pretreated with different iron-phosphate coatings deposited with
and without NaNO2 in the phosphating bath were monitored during exposure to 3 wt.% NaCl. The surface morphology of steel and
steel pretreated with iron-phosphate coatings was determined by
atomic force microscopy (AFM).
It was shown that both phosphate coatings on steel have smaller corrosion current densities as compared to bare steel surface,
while phosphate coating deposited on steel from a bath with
NaNO2 showed the best behavior.
The highest values of top coating pore resistance and longest
time of corrosion onset on metal substrate were obtained for powder polyester coating on steel pretreated with iron-phosphate
coating from NaNO2-free bath, indicating a better corrosion stability of this protective system as compared to others investigated in
this work. It was also shown that both the dry and wet adhesion
depend strongly on the surface pretreatment. Pretreatment of steel
with iron-phosphate coating deposited from NaNO2-free bath increases adhesion strength of the top powder polyester coating,
compared to steel pretreated with iron phosphate coating deposited with NaNO2 in the bath and bare steel. The results presented

This research was nanced by the Ministry of Education and

Science, Republic of Serbia (Grant No. III 45019).
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