Progress in Organic Coatings 79 (2015) 8–16

Contents lists available at ScienceDirect

Progress in Organic Coatings

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

The protective properties of epoxy coating electrodeposited on

Zn–Mn alloy substrate
M. Bučko ∗ , V. Mišković-Stanković, J. Rogan, J.B. Bajat
Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, 11120 Belgrade, Serbia

a r t i c l e i n f o a b s t r a c t

Article history: The epoxy coating was cataphoretically deposited on steel and steel modified by electroplated Zn–Mn
Received 7 May 2014 alloy of different chemical contents. The samples were immersed in 0.5 mol dm−3 NaCl solution for 60
Received in revised form 27 August 2014 days. The electrochemical impedance spectroscopy (EIS) analysis showed that the values of pore resis-
Accepted 16 October 2014
tance for epoxy coating on steel and Zn–Mn alloy with 16 at.% Mn were two orders of magnitude higher,
while the capacitance values were two orders of magnitude lower than those for the epoxy coating on
Keywords:
Zn–Mn alloy substrates with 5 and 8 at.% Mn. It was assumed that the main reason for such a difference
Zn–Mn alloy
was metallic substrate dissolution during cataphoretic deposition, due to high pH (12.9). This assumption
Epoxy coating
Impedance spectroscopy
was supported by energy dispersive X-ray spectrometry (EDS) measurements showing that the amount
Cataphoretic deposition of released Zn in epoxy coatings decreased as Mn percent in the Zn–Mn alloys increased. In addition,
Zn–Mn alloy coatings on steel, as well as bare steel, were immersed in 0.1 mol dm−3 NaOH solution, pH
12.9, simulating conditions during cataphoretic deposition, and polarization resistance measurement in
this solution indicated that Mn inclusions in Zn–Mn alloy substrate prevent Zn dissolution in alkaline
medium.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction
Electrodeposition of organic coatings has become worldwide
accepted coating process in automotive and general industry, for
providing the first prime coat to a variety of products. Nowadays,
for example, the anticorrosive protection of almost all automobile
bodywork includes a cataphoretic primer, and 98% of cars are
primed with cathodic electrocoat [1]. The epoxy resin is still
the best material for cathodic electrodeposition, because of its
advantages, such as high chemical and corrosion resistance, good
mechanical and thermal properties, outstanding adhesion to
various substrates, low shrinkage upon cure, flexibility, and good
electrical properties [2].
It is well known that surface characteristics of a metal substrate
are an important factor determining the deposition behaviour and
corrosion behaviour of organic electrocoatings [3]. Nevertheless,
these coatings can be used on a wide variety of substrates, such as
steel, zinc, copper, brass, aluminium, magnesium, chrome plate etc.
[1]. As concerning steel parts, the zinc coatings on steel are widely
used for their sacrificial cathodic protection. Galvanized steel is fur-
ther usually protected from corrosive environment by conversion
∗ Corresponding author. Tel.: +381 11 3303 694; fax: +381 11 3370 387.
E-mail address: mbucko@tmf.bg.ac.rs (M. Bučko).
coating (phosphate, chromate, etc.) and then top-coated with some
organic coating [4].
One of the important problems in galvanizing is the improve-
ment of the protective properties of Zn coatings, which is achieved
by alloying Zn with more noble metals of the iron group (Ni, Co
and Fe). The epoxy coating has been successfully electrodeposited
on these Zn–alloy substrates, and the protective properties of
Zn–alloy–epoxy coating system have been broadly investigated
[5,6].
In the last decade, the Zn–Mn alloy coating on steel substrate has
been reported to show superior corrosion behaviour in compari-
son to other Zn alloys, particularly in aggressive media containing
SO4 2− and Cl− anions [7,8]. The Zn–Mn alloy with Mn content up
to 20 at.% can be easily deposited from various electrolytes such as
sulphate [8], chloride [9], or pyrophosphate [10] based electrolyte.
So, this alloy is a promising protective coating for steel parts. Nev-
ertheless, it should be stressed that there is no scientific report
concerning the electrophoretic deposition of organic coatings on
Zn–Mn alloy substrate. For this reason, the aim of this work was
to investigate the influence of steel surface modification by Zn–Mn
alloys on the protective properties of top epoxy coating.
It is a common practice that prior to the epoxy coating, the steel
is covered with Zn or Zn alloy sub layer, in order to generate a corro-
sion resistant interface and provide a link to the epoxy coating. The
layer of corrosion products formed on Zn alloy as a result of ingress

http://dx.doi.org/10.1016/j.porgcoat.2014.10.010
0300-9440/© 2014 Elsevier B.V. All rights reserved.
 M. Bučko et al. / Progress in Organic Coatings 79 (2015) 8–16
of corrosive agent, extends the protection of steel substrate. Nev-
ertheless, the main scope of the present work was to investigate
the corrosion behaviour of the top epoxy coating itself. Thin, non-
pigmented epoxy coating, as primer, was electrodeposited on steel
modified by Zn–Mn alloys of different composition, as well as on
a steel surface, as a reference. The Zn–Mn coatings with high Mn
content (30–50 at.% or more) showed in the past excellent results
in corrosion tests [11,12], but also, they are often dendritic [11]
and obtained with low current efficiency [13]. On the contrary,
many authors have stated that Zn–Mn alloys with up to 20 at.%
Mn posses better corrosion resistance than pure Zn [7–9]. Thus, the
epoxy coating deposited on the Zn–Mn alloys containing maximum
16 at.% Mn was examined in this article.
2. Materials and methods
2.1. Electrodeposition of Zn–Mn alloys
Zn–Mn alloy coatings, 10 ␮m thicknesses, were deposited on
a steel panel from chloride electrolyte using PAR M173 potentio-
stat/galvanostat in galvanostatic mode. The employed electrolytes
(Table 1) were prepared using p.a. chemicals and double dis-
tilled water. The levelling agent, 3,4-dimethoxy-benzaldehyde, was
added in order to reduce hydrogen evolution reaction and pre-
vent dendrite formation during Zn–Mn deposition [14]. The AISI
4340 steel panels (20 mm × 20 mm × 0.25 mm) were pre-treated by
mechanical abrading and then degreasing in a saturated solution
of sodium hydroxide in ethanol, pickling in 1:1 hydrochloric acid
solution for 30 s and finally rinsing with distilled water. A Zn plate,
placed parallel to the cathode, was used as a counter electrode.
By applying different deposition current densities, the Zn–Mn
coatings with three different Mn contents were obtained. The
chemical composition of the alloys, shown in Table 1, was deter-
mined by EDX analysis of the deposits, using scanning electron
microscope (SEM) type JEOLJSM 6460LV.
2.2. Electrodeposition of epoxy coatings
Thin non-pigmented epoxy primer was electrodeposited using
a constant voltage method from an epoxy resin modified by amine
and isocyanate (CATOLAC emulsion 543.052, produced by Indus-
trie Vernici Italy under a Pittsburgh Paint and Glass (PPG) licence).
The substrate for deposition was steel and a steel surface previ-
ously modified by Zn–Mn alloy. The resin concentration in the
electrodeposition bath was 10 wt.% solid dispersion in water at pH
5.7; the temperature was 26 ◦ C and the applied voltage was 250 V.
After 2 min deposition the coatings were rinsed with distilled water
and cured for 30 min at 200 ◦ C. The film thickness was 25 ␮m. The
thickness of Zn–Mn coatings and epoxy coatings was measured by
magnetic induction method, using Dualscope MPOR.
2.3. Electrochemical impedance spectroscopy (EIS)
For a.c. impedance measurements, the coated samples were
exposed to 0.5 mol dm−3 NaCl solution for 60 days. A three-
electrode cell arrangement was used. The working electrode was a
coated sample situated in a special Teflon holder, with an exposed
area of 1 cm2 . The counter electrode was a platinum mesh with a
surface area considerably greater than that of the working elec-
trode. The reference electrode was a saturated calomel electrode
(SCE). The impedance data were obtained at the open-circuit poten-
tial using a potentiostat ZRA Reference 600, Gamry Instruments.
The impedance measurements were carried out over the frequency
range of 100 kHz to 10 mHz using a 10 mV sinusoidal voltage.
Gamry Instruments Echem Analyst software was used for the data
fitting of impedance.
9
2.4. Thermogravimetric analysis
Thermal stability of the samples was tested by thermogravimet-
ric analysis (TGA) which was conducted on an SDT Q600 TGA/DSC
instrument (TA Instruments), from 30 to 600 ◦ C. The heating rates
were 20 ◦ C min−1 using less than 10 mg sample mass. The furnace
atmosphere was dry nitrogen at a flow rate of 100 cm3 min−1 .
2.5. Scanning electron microscopy
Surface morphology of the coatings was examined by SEM using
a Tescan, VEGA TS 5130 MM instrument. Chemical analysis of
the deposits was performed by an attached energy dispersive X-
ray spectrometer (EDS), INCAPenta-FETex3, Oxford Instruments,
and energy of 20 kV was used for analysis. For the SEM image of
cross-section, the samples were embedded in epoxy resin, cut and
mechanically polished with different emery papers.
2.6. Electrochemical tests of Zn–Mn coatings
Electrochemical testing of Zn–Mn alloy coatings on the steel
substrate was carried out in 0.1 mol dm−3 NaOH solution (pH 12.9),
with a cell arrangement described in Section 2.3. Immediately
after the immersion of the samples in the NaOH solution, the
open circuit potential (Eocp ) was monitored until its constant value
was established. Afterwards, the linear polarization method was
employed and the linear polarization resistance (Rp ) was mea-
sured. Each working electrode was potentiodynamically polarized
in the potential range ±15 mV over the respective Eocp , at a scan
rate of 0.2 mV s−1 . Polarization tests and Eocp measurements were
conducted using Gamry Reference 600 Potentiostat, and three
measurements were performed for each sample, with good repro-
ducibility.
3. Results and discussion
3.1. Electrochemical properties of the epoxy coating
The electrochemical properties of epoxy coatings on steel and
steel modified by Zn–Mn coatings were examined by EIS measure-
ments. The Nyquist impedance plots for the samples 1–4 described
in Table 1, as a function of immersion time in 0.5 mol dm−3 NaCl
solution, are shown in Fig. 1. The influence of the type of substrate
on the corrosion stability of protective systems based on epoxy
coating, can be clearly seen from Fig. 1. Namely, the impedance val-
ues for epoxy coatings on steel modified by Zn–Mn alloy coatings
with small amounts of Mn (5 and 8 at.%) were for about three
orders of magnitude lower as compared to epoxy coatings on steel
modified by Zn–Mn alloy coatings with 16 at.% Mn and bare steel
substrate. In addition, impedance values of the latter seem to show
a typical decrease with time of immersion in a corrosive solution
(Fig. 1c and d). On the other hand, impedance values of epoxy
coatings on low Mn containing Zn–Mn alloy coatings, decreased
in the first 17 days, and than increased during prolonged exposure
time.
There are several reports in literature claiming that the pro-
tective behaviour of the epoxy coating is better on bare steel as
compared to Zn-coated steel substrate, and some explanations
were offered, as follows. Namely, hydrogen evolution by H2 O dis-
charge as the first step in epoxy deposition, can influence the
coating properties. It was reported that hydrogen evolves from an
epoxy polymer solution on steel and Zn-coated steel at almost the
same rate, but the wettability of Zn–alloy surface by polymer solu-
tion is smaller as compared to steel surface. As a consequence of
the greater contact angle, hydrogen accumulates on the Zn–alloy
10 M. Bučko et al. / Progress in Organic Coatings 79 (2015) 8–16

Table 1
Electrolyte composition, plating conditions and Zn–Mn alloys composition.

Electrolyte composition (mol dm−3 ) Sample No. Deposition c.d. (mA cm−2 ) Mn content (at.%)

KCl 1.25 1 50 5
H3 BO3 0.4 2 70 8
ZnCl2 0.3 3 90 16
MnCl2 1.0 4 Steel substrate
Levelling agent, 0.25 g dm−3
3,4-dimethoxy-benzaldehyde

cathode during electrodeposition of epoxy film, and a more porous In order to further investigate the reason for the observed elec-
epoxy structure is formed on this substrate [6]. trochemical behaviour of epoxy coating on different substrates in
The next factor influencing the epoxy coating properties, was the present article, and prior to the EIS plot analysis, the SEM/EDS
proven to be a cathode heating during cataphoretic deposition. techniques were applied.
Since the deposited epoxy coating has high resistivity, so almost all
the applied voltage is located across the film, one can expect Joule
3.2. Chemical composition and morphological studies of the
heat to be evolved during deposition, the magnitude of which will
coatings by SEM
depend on the applied current density, film resistivity and thick-
ness. It was proven that, due to the local heating, the Zn-plated
The surface morphology of the coatings, as well as the metal
cathode reached higher temperatures during deposition process in
content in the epoxy resin, was investigated by SEM method. Fig. 2
comparison to the bare steel cathode, so that the epoxy film showed
shows, as an example, the cross-sectional SEM micrographs of the
a tendency for a viscous flow downwards [15].
epoxy coating on Zn–Mn alloy substrate containing 16 at.% Mn and
Finally, the difference in the corrosion behaviour of epoxy coat-
a bare steel substrate (samples 3 and 4 in Table 1). As it can be
ing on bare steel and Zn-coated steel can arise from the substrate
seen, applied epoxy coating on the metallic substrates provides a
dissolution during cataphoretic deposition, although dissolution of
uniform coating layer, without defects or pinholes.
metals under cathodic polarization is a rather paradoxical phe-
The EDS analysis of the epoxy coatings was applied with the aim
nomenon. The calculation of the OH− concentration shows that
of detecting the presence of Zn, Mn or Fe atoms within the coatings.
the pH-value in cathodic layer during cataphoretic deposition is
Since a very low percent of these elements could be expected, and
about 12.0–13.0 [15]. In view of such an alkaline environment,
in order to minimize a possible error in measurements, the chem-
many authors have asserted that under conditions of cathodic elec-
ical composition was analyzed on approximately ten spots in each
trodeposition, various metal substrates (Zn, Fe, Ni, Al) are dissolved
coating. Three areas were considered, namely the one close to the
chemically without participation of electric current [4,16]. This
substrate, the other in the middle of the epoxy coating, and finally
particularly stands for Zn, which being an amphoteric metal, may
the area close to the outer interface of the epoxy coating. These
dissolve according to the following reaction indicated in Pourbaix
areas are marked in Fig. 2a as a, b, and c, respectively.
diagram [17], and even at very negative potential:
The EDS analysis has revealed that in addition to carbon and
oxygen, originating from the epoxy resin, the metal atoms were
Zn + 2H2 O = ZnO2 2− + 4H+ + 2e− (1) also detected in each sample, as it is presented in Table 2, prov-
ing that metal substrate dissolves during cataphoretic deposition.
Metal ions that pass from the cathode surface to the solution Both Zn and Mn were found in the epoxy coating deposited on the
may incorporate in the deposited epoxy coating, thus increasing its Zn–Mn substrates, whereas Fe was present in the coating sample
electrical conductivity and lowering protective ability [4]. 4 (Table 2). Beside the fact that the metal atoms could be found

Fig. 1. (a–d) Nyquist impedance plots for epoxy coating deposited on various substrates, after different immersion periods in 0.5 mol dm−3 NaCl solution.
 M. Bučko et al. / Progress in Organic Coatings 79 (2015) 8–16
Fig. 2. SEM cross-section view of freshly prepared epoxy coatings on Zn–Mn alloy with 16 at.% Mn and bare steel.
Table 2
Cross-section EDS analysis of epoxy coatings freshly deposited on various substrates.
in low concentrations, the two trends could be observed from the
EDS data. Firstly, it can be noticed for all the samples, that the metal
content is the highest in the area closer to the substrate, while there
is a low amount of metal in the outer layer of the epoxy film, prob-
ably due to the slow diffusion of dissolved metal particles through
the coating depth. And secondly, the amount of metal atoms in the
epoxy coatings depends on the metal substrate. The Mn content is
very low in epoxy coatings on Zn–Mn alloys in samples 1–3. How-
ever, the amount of released Zn is somewhat higher, and what is
more, it is clear from the Table 2 that it decreases in order from the
substrate one to the substrate three. In other words, the Zn content
is the lowest in the epoxy coating on the substrate with 16 at.% Mn.
Thus, the EDS confirms the theory that metallic substrate may
dissolve during the cataphoretic deposition of epoxy coating, and
that various substrates release unequal amounts of metal ions.
3.3. Electrochemical impedance plots analysis
The fitting of experimental data was accomplished using the
same equivalent electrical circuit for all samples, as shown in Fig. 3.
It should be emphasized that the impedance response of the sys-
tem consisting of metal substrate and epoxy coating, is described
in some papers with the electrical circuit comprised of two RC time
constants [5,6]. However, in the present article, a much better fit-
ting of the impedance results has been obtained by using the circuit
with three RC time constants (Fig. 3), where it is assumed that the
one at the highest frequencies represents the epoxy coating pore
resistance, Rp , and the coating capacitance, Cp , while the other two
time constants are related to the corrosion processes inside and
underneath the epoxy coating. Namely, metal particles dispersed
11
in epoxy coating may react with penetrated electrolyte and create
new corrosion products, a process which is assumed to be related to
the time constant Rc,1 CPE1 [18,19]. Also, when electrolyte reaches
the metal substrate, its corrosion occurs, which may be presented
by the time constant Rc,2 CPE2 [5,6]. Symbol CPE denotes a con-
stant phase element, which represents all the frequency dependent
electrochemical phenomena, namely double-layer capacitance and
diffusion processes. Finally, R denotes the electrolyte resistance.
By fitting of experimental data, the Rp , Cp , Rc,1 , and Rc,2 values
were determined and are plotted as a function of time in Fig. 4
or presented in Table 3. The time dependence of coating pore
resistance (Fig. 4a) indicates the different steps of electrolyte
penetration through the epoxy coating, according to the model
proposed by Misković-Stanković et al. [20,21] and confirmed
for different protective systems that we have published earlier
[5,6,12,13]. Briefly explained, it is suggested that electrolyte pene-
tration through an organic coating occurs in two steps. The first step
is related to water uptake, when molecules of pure water diffuse
in the micropores of the polymer net according to Fick’s law. This
Fig. 3. Equivalent electrical circuit with three time constants for a polymer-coated
metal.
12 M. Bučko et al. / Progress in Organic Coatings 79 (2015) 8–16

Fig. 4. Time dependence of pore resistance (a) and coating capacitance (b) for epoxy coatings on various substrates during exposure to 0.5 mol dm−3 NaCl solution.

process is independent of the type and dimensions of other ions in
the corrosive electrolyte. The second step is related to water and ion
penetration through the macropores. Namely, after several days
of immersion, some percentage of micropores increases in radius
and macropores appear, which can absorb both water molecules
and also ions with large radius, such as Cl− , SO4 2− , etc. [5,6,22,23].
It is seen from Fig. 4a that initially, the pore resistance decreases
over time for all coatings (period up to point a) denoting the entry
of electrolyte into the epoxy coating. According to the proposed
model, this is the first step of electrolyte penetration, related to
the diffusion of molecules of pure water to the micropores of the
polymer net. After this period, the values of pore resistance reach a
plateau for the samples 3 and 4 and remain almost constant over a
longer time period (Fig. 4a, periods a and b), indicating the mainte-
nance of good protective properties of epoxy coating. This is the sec-
ond step of electrolyte penetration and it refers to the penetration of
water and ions through the macropores of the coating. The macro-
pores become deeper by the time, until they finally pass through
the epoxy coating and reach the metal surface. This leads to the
beginning of electrochemical processes on the metallic interface,
characterized by the decrease in pore resistance (Fig. 4a, point c).
As concerning the samples 1 and 2, the pore resistance continu-
ously decreases from the very beginning of the immersion test, until
it reaches a minimum value (denoted as point a), and one cannot
observe the period of constant Rp values, i.e. the period with stable
protective properties of epoxy coating on these two samples.
During prolonged exposure to corrosive agent (after point a for
the samples 1, 2 and point c for the samples 3 and 4), the Rp value
for the first two coatings increases and then remains constant, and
for the other two samples it decreases very slowly over the next 30
days (Fig. 4a, periods c and d). This can be explained by plugging
of the pores in epoxy coating with corrosion products [22,23]. Fur-
ther dissolution and desorption of corrosion products is denoted
by Rp value oscillations after the 45th day of immersion. It has been
reported that ZnCl2 ·4Zn(OH)2 was the main corrosion product on
Zn–alloy coatings in chloride media, which forms pseudo passive
layer under the epoxy coating [6,7].
It can be seen from Fig. 4a that the minimum in the Rp values
(suggesting the contact of electrolyte with the metal surface) is
reached much earlier for the samples 1 and 2, as compared to the
coatings three and four. Furthermore, the values of pore resistance
for the samples 1 and 2 are in the range of 104 –106  cm2 , while for
the other two samples the values are much higher, in the range of
106 –108  cm2 . When these results are compared to the EDS analy-
sis, it is seen that higher percent of metal particles in epoxy coating
gives lower Rp values. Such a correlation is known from literature
[18,19] and is ascribed to the fact that higher metal particle content
results in higher porosity of the dry film.
The time evolution of the coating capacitance (Fig. 4b) is in
accordance with the above results. At early stages of exposure the
sharp rise in the capacitance values suggests a rapid water penetra-
tion, followed by a rather low increase of electrolyte diffusion. After
certain immersion time, one can observe sharp decrease in capaci-
tance values followed by new rising. These oscillations correspond
to the trend shown in Fig. 4a for coating pore resistance and they
were explained by plugging of the pores in epoxy coating with cor-
rosion products from the metal substrate, and their desorption. The
first oscillation occurs relatively early for the sample 1 (10 days of
immersion) and sample 2 (15 days). Bearing in mind that these two
samples contain some amount of Zn particles in the organic coating,
such capacitance change may be also attributed to the evolution of
zinc corrosion products throughout the film [18,19]. It is also clear
from Fig. 4b that the coating capacitance for the samples 1 and 2 is
for two orders of magnitude higher as compared to the Cp for the
samples 3 and 4. Significantly higher dielectric permittivity of the
samples 1 and 2 may be correlated to the higher amount of metal

Table 3
Optimum values of charge transfer resistance, in  cm2 .

Time (days) Sample 1, 5 at.% Mn Sample 2, 8 at.% Mn Sample 3, 16 at.% Mn Sample 4, steel

Rc,1 Rc,2 Rc,1 Rc,2 Rc,1 Rc,2 Rc,1 Rc,2

1 1.318E+06 1.479E+11 2.344E+05 5.623E+11 2.754E+11 1.905E+15 9.120E+10 4.898E+13

4 2.951E+07 1.820E+11 4.266E+05 1.096E+10 9.550E+09 3.715E+14 1.479E+10 3.890E+13
7 1.230E+06 1.349E+08 5.370E+05 7.244E+09 6.026E+07 1.862E+10 2.754E+08 1.862E+10
11 6.166E+07 3.548E+11 1.585E+06 5.888E+08 3.467E+08 1.071E+10 5.754E+08 9.550E+09
17 2.042E+09 1.349E+13 3.311E+03 4.786E+05 3.715E+08 5.012E+07 3.631E+08 4.365E+09
28 1.349E+07 1.096E+12 1.412E+08 4.467E+06 1.259E+08 8.709E+08 3.020E+08 5.754E+10
35 1.288E+07 3.311E+11 5.623E+09 1.513E+08 2.344E+08 2.002E+09 2.818E+08 3.162E+10
45 1.514E+07 6.166E+11 1.698E+07 3.981E+09 1.585E+08 3.388E+08 3.090E+08 8.318E+08
52 1.549E+12 6.193E+11 3.631E+11 2.138E+10 3.548E+08 4.677E+09 3.548E+08 2.570E+09
60 4.169E+12 7.226E+10 1.659E+11 5.798E+09 8.128E+08 2.353E+09 6.456E+08 1.072E+09
 M. Bučko et al. / Progress in Organic Coatings 79 (2015) 8–16
Fig. 5. (a–c) The change of open-circuit potential of different samples in 0.1 mol dm−3 NaOH.
particles in their epoxy layers. The dispersion of conductive par-
ticles in an epoxy matrix increases the transport properties of the
coating because conductive paths are easily created and diffusion
of water to the metal-coating interface is enhanced [18,19].
The Rc,1 and Rc,2 values, representing charge transfer resistance
to the electrochemical reactions of metal particles in the epoxy
coating and of the metal substrate, are shown in Table 3. The Rc,1
for the samples 3 and 4 initially decreases, and then it has almost
unchanged values during the prolonged exposure. This parameter
for the samples 1 and 2 is initially lower, but it constantly grows
during immersion, probably as a result of transformation of metal
particles dispersed in organic coating, into non-reacting products
[18].
Extremely high Rc,2 values until the 10th day from the beginning
of the test, implicate that there was no corrosion process at the
metal substrates during this time period. For all the samples, the
Rc,2 constantly drops during the immersion test until certain time
point, a trend which indicates the increase in corrosion rate or the
active area of the metal surface [6]. After this point, the Rc,2 values
rise again to the end of the test, owing to the passivation of the metal
substrates [7,24]. It is seen from data in Table 3 that the passivation
effect is more pronounced for the Zn–Mn substrates, comparing to
the bare steel.
According to the impedance data and previous literature analy-
sis, it can be concluded that the Zn–Mn coatings with 5 and 8 at.%
Mn behave similarly to the pure Zn in sense that the epoxy coating
on these substrates has lower protective property than the coating
on steel substrate. However, it is clear that the epoxy coating on
Zn–Mn substrate with increased amount of Mn (16 at.%) has higher
corrosion resistance than the coating on steel.
13
The EDS results suggested the assumption that the reason for
a significant difference in the impedance response of the samples
investigated, is the presence of various contents of metal species in
the epoxy films. Actually, Zn [18] and Fe [19] powders have been
used as protective pigments in epoxy coatings, due to the fact that
the dissolution of active metallic dust takes place after immersion in
the electrolyte, forming a non-conductive corrosion product. How-
ever, it is apparent in this work that metal species which enter
the epoxy coating from the metal substrate during cataphoretic
deposition, do not behave like protective pigments, but they rather
increase the coating porosity and conductivity.
3.4. Substrate dissolution in alkaline medium
It has been concluded in Section 3.2 that Zn release from
Zn–Mn alloy substrates during cataphoretic deposition, decreases
with the increase in Mn content in the alloy, thus indicating that
Mn inclusions prevent Zn dissolution in alkaline medium. As
concerning literature data which could support this conclusion,
it was shown in the investigation of Mn behaviour at high pH
[25], that a spontaneous two-step passivation of Mn occurs on
a steady-state potential. In the first step Mn3 O4 forms, and after
about 30 min its oxidation leads to Mn2 O3 . On the contrary, the
literature on the corrosion behaviour of Zn–Mn alloy in alkaline
medium is rather scarce. Shang et al. [24] studied the effect of
0.4 wt.% Mn addition on Zn passivation in NaOH solution, and
found that Mn dissolves first and then precipitates as oxide nuclei
at the electrode surface, which act as the initiation sites for the
formation of ZnO. In addition, Mn ions act as dopants in the passive
ZnO film and decrease the defect concentration. Therefore, it was
14 M. Bučko et al. / Progress in Organic Coatings 79 (2015) 8–16
Fig. 6. Polarization curves of different electrodes at open circuit potential in the range of ±15 mV, in 0.1 mol dm−3 NaOH.
concluded that Mn had considerable effects on producing uniform
passive film on Zn surface and decreasing the film porosity [24].
In order to further understand the influence of Mn on the dis-
solution of Zn–Mn substrates used in the present article, the four
samples (Zn–Mn alloys with 5, 8 and 16 at.% Mn, and steel) were
immersed in 0.1 mol dm−3 NaOH solution, pH 12.9, simulating con-
ditions during cataphoretic deposition. The open circuit potential
(Eocp ) was monitored immediately after the immersion, and after
reaching its constant value, the polarization resistance (Rp ) was
measured. The potential change at open-circuit conditions of four
electrodes in NaOH are presented in Fig. 5(a–c). The Eocp profiles
are similar for the alloy coatings with 5 and 8 at.% Mn. When these
electrodes were immersed in the solution, the potential constantly
decayed in the cathodic direction, denoting an active dissolution
of Zn–Mn alloy. On the other hand, for the sample with 16 at.%
Mn, the Eocp shifted towards cathodic value at the beginning, but
after exhibiting a minimum it increased gradually and the steady-
state was reached at −1050 mV. Quite similar potential profile was
described for pure Mn electrode in highly alkaline medium by other
authors [25], and such a variation was explained by a spontaneous
passivation of the electrode in 0.1 mol dm−3 NaOH. After immer-
sion of Fe substrate in NaOH solution (Fig. 5c) the potential shifted
to negative values, and after 500 s, a single hump appeared, denot-
ing that some passive layer was formed. However, it was not stable
enough, so the active dissolution of Fe further took place, until the
steady-state potential was reached.
Besides the Eocp recording, a linear polarization resistance, as a
fast corrosion testing method, was used to investigate the substrate
dissolution in NaOH. After obtaining steady-state potential (the
time of 120 min was chosen for all samples), polarization curves
in a small potential range near to Eocp were obtained for Zn–Mn
alloys with different Mn content, and for Fe substrate. Polarization
resistance (Rp ) was determined from the slope of the experimental
curve (dE/dj) at the open circuit potential, and the results are pre-
sented in Fig. 6(a–c). The Rp value is significantly higher for Fe and
for Zn–Mn alloy with 16 at. % Mn, denoting that these substrates
dissolve much slower in alkaline solution.
To conclude, the data obtained from the investigation of sub-
strate dissolution in alkaline medium show that the increase in Mn
content in Zn–Mn alloy from 5 to 16 at.%, strongly decreases its
dissolution rate. What is more, the open circuit potential monitor-
ing leads to the conclusion that a passive layer forms on Zn–Mn
substrate with 16 at.% Mn, almost immediately after immersion in
the test solution. Therefore, the corrosion tests strongly support
the assumption from Sections 3.2 and 3.3, i.e. that the main rea-
son for a huge difference in impedance of epoxy coating formed on
various substrates, may be a different metal content in the epoxy
coating, which, in turn, results from the cathode dissolution during
cataphoretic deposition.
3.5. Thermal properties of epoxy coatings
TGA was used to investigate the influence of the metallic
substrate on the thermal stability of epoxy coating, and its elec-
trolyte absorption properties. A Fig. 7a shows the TG curves of the
epoxy coatings electrodeposited on four different substrates, after
 M. Bučko et al. / Progress in Organic Coatings 79 (2015) 8–16
Fig. 7. (a) TG curves for epoxy coatings on steel and steel modified by Zn–Mn alloys, after 48 h exposure to 0.5 mol dm−3 NaCl; (b) reduced TG curves; (c) reduced TG curves
up to 190 ◦ C; (d) DTG curves from reduced TG curves. The various substrates are marked in figures.
immersion in 0.5 mol dm−3 NaCl for 48 h. As can be seen, a stable
residue at 600 ◦ C differs significantly for the samples, ranging from
18 to even 49 wt.%. Taking into account that the epoxy formula-
tion does not have any mineral filler, the residue must arise as a
consequence of a carbonization process [26], and especially from
NaCl particles present in the coating pores, or metallic particles
which ended up in the samples while scratching the epoxy coating
from the substrate. In order to eliminate the influence of the resid-
ual mass on the shape of TG curves, the reduced TG curves were
calculated using Eq. (2), where wred is reduced weight, wt weight
at temperature t, w0 initial weight and wr residual weight. The
reduced TG curves are shown in Fig. 7b and c, while DTG thermo-
grams obtained from the reduced TG curves are presented in Fig. 7d.
wt − wr
wred =
w0 − wr
Fig. 7c shows the TG curves up to 190 ◦ C, where the amount of
absorbed water during immersion in NaCl for 48 h, and the final
dehydration temperature are given for each sample. There are two
weight loss steps for all samples. The first, rather sharp, weight
loss step occurs at temperatures around 80 ◦ C, and it is related to
loss of water from macropores of epoxy coating. The second step is
slow and gradual and takes place between 80 and 190 ◦ C. It prob-
ably relates to the delivering of chemically linked water. It is clear
that the lowest water uptake was for the epoxy coating at bare
steel substrate (2.0 wt.%), the coating with the high electrochemi-
cal impedance, while the highest amount of absorbed water was for
the coating on Zn–Mn alloy with 8 at.% Mn (3.3 wt.%), which pos-
sessed much lower impedance in NaCl. Nevertheless, for the other
15
two epoxy coatings on Zn–Mn alloys, the mass of absorbed water
was equal (3.0 wt.%). So, it seems that the porosity of the epoxy
coatings, measured via water absorption, is in agreement with EIS
results, but is not the most important factor causing such a big dif-
ference in the electrochemical impedance response in NaCl, among
the coatings obtained at Zn–Mn substrates.
As can be seen from DTG curves (Fig. 7d) the epoxy resin
degrades in mainly two different steps, and the DTG peak tem-
perature values are presented in the figure. If the first stage is the
releasing of the absorbed water up to 190 ◦ C, then the second stage
occurs, depending on the substrate, at the temperatures between
190 and nearly 300 ◦ C, which may be due to the breaking of unre-
acted epoxy resin or other impurity traces, apart from the cured
epoxy resin [27]. Finally, the third stage takes place from 300 and
(2) up to about 500 ◦ C, probably corresponding to thermal degrada-
tion of the cured epoxy network [27]. It is evident from Fig. 7d that
DTG peaks shift towards higher temperature as Mn content in the
Zn–Mn substrate increases, and the highest decomposition tem-
perature (peak placed at the highest T) is observed for the epoxy
coating deposited on steel substrate. So, the influence of metallic
substrate on the thermal stability of epoxy coating is in correlation
with the results from previous sections, since the thermal stabil-
ity rises as the corrosion behaviour improves, i.e. as the dispersed
metal content in the epoxy coating decreases. This is understand-
able because higher temperature of degradation indicates higher
cross-linking density achieved during the curing reaction, which
results in lower porosity of epoxy coating [1]. Actually, the metal
particles trapped in epoxy coating can reduce the mobility of the
molecules of epoxy resin and the cross-linking agent, and as a result,
16 M. Bučko et al. / Progress in Organic Coatings 79 (2015) 8–16
a linking degree may be lower in the coating with higher percent
of metal particles [1].
4. Conclusion
In this article, the role of Zn–Mn alloy coating, as a corrosion
barrier for steel and a substrate for the top epoxy coating, was inves-
tigated. A significant difference in the properties of epoxy coatings
obtained on steel and Zn–Mn alloy coatings with 5, 8 and 16 at.%
Mn was observed.
It has been shown by the electrochemical impedance spec-
troscopy that the corrosion protection behaviour in 0.5 mol dm−3
NaCl during 60 days, is weaker for the epoxy coating on Zn–Mn
alloy with 5 and 8 at.%, and better for the coating on Zn–Mn alloy
with 16 at.%, as compared to the epoxy coating on bare steel.
The EDS analysis of the epoxy coatings was applied with the
aim of detecting the presence of Zn, Mn or Fe atoms within the
coatings. It was shown that the amount of released atoms of Zn
in the epoxy coating, decreases with the increase in Mn content
in Zn–Mn alloy substrates. Since the impedance of the epoxy sam-
ples increases in the same manner, the EDS analysis supports the
assumption that the main reason for a significant difference in the
coating conductivity for the samples investigated, is the presence
of various content of metal atoms in the epoxy films.
In order to further understand the influence of Mn inclusions
on the dissolution of Zn–Mn substrates during cataphoretic deposi-
tion, the corrosion tests were applied on four different substrates in
alkaline medium. It was concluded that the increase in Mn content
in Zn–Mn alloy from 5 to 16 at.% strongly decreases its dissolution
rate in NaOH solution.
The thermogravimetric analysis revealed that the epoxy coat-
ing porosity measured through water absorption, is lower for the
coatings with higher impedance and vice versa. However, it was
shown that different water absorption is not the only reason for
a huge difference in the impedance between the epoxy coatings
on various Zn–Mn substrates. So, it may be concluded from cou-
pled EDS and TGA analysis, that the main influence on corrosion
behaviour of epoxy coating is probably the substrate dissolution
during cataphoretic deposition.
The best coating to be used as an additional barrier for steel
protection and a substrate for epoxy coating, is the Zn–Mn alloy
with 16 at.% Mn.
Acknowledgment
This research was financed by the Ministry of Education, Science
and Technological Development, Republic of Serbia (Grant No. III
45019).
References
[1] S.J. García, J. Suay, Prog. Org. Coat. 66 (2009) 306–313.
[2] M. Tomić, B. Dunjić, V. Likić, J.B. Bajat, J. Rogan, J. Djonlagić, Prog. Org. Coat. 77
(2014) 518–527.
[3] M. Poelman, I. Recloux, N. Cornil, N. Blandin, L. Deronne, Y. LeDisert, M.G.
Olivier, Prog. Org. Coat. 74 (2012) 453–460.
[4] I. Krylova, Prog. Org. Coat. 42 (2001) 119–131.
[5] J.B. Bajat, V. Mišković-Stanković, D. Dražić, J. Serb. Chem. Soc. 72 (2007)
1383–1392.
[6] J.B. Bajat, M. Maksimović, V. Mišković-Stanković, S. Zec, J. Appl. Electrochem.
31 (2001) 355–361.
[7] Z. Ortiz, P. Díaz-Arista, Y. Meas, R. Ortega-Borges, G. Trejo, Corr. Sci. 51 (2009)
2703–2715.
[8] M. Bučko, J. Rogan, S.I. Stevanović, S. Stanković, J.B. Bajat, Surf. Coat. Technol.
228 (2013) 221–228.
[9] S. Ganesan, G. Prabhu, B.N. Popov, Surf. Coat. Technol. 238 (2014) 143–151.
[10] M. Bučko, J. Rogan, S.I. Stevanović, A. Perić-Grujić, J.B. Bajat, Corr. Sci. 53 (2011)
2861–2871.
[11] B. Bozzini, E. Griskonis, A. Fanigliulo, A. Sulcius, Surf. Coat. Technol. 154 (2002)
294–303.
[12] M.R. Kalantary, Plat. Surf. Finish. (1994) 80–89.
[13] C. Muller, M. Sarret, T. Andreu, Electrochim. Acta 48 (2003) 2397–2404.
[14] M. Bučko, U. Lačnjevac, J.B. Bajat, J. Serb. Chem. Soc. 78 (2013) 1–22.
[15] N. Aćamović, D. Dražić, V.B. Mišković-Stanković, Prog. Org. Coat. 25 (1995)
293–307.
[16] Z. Ranjbar, S. Moradian, Prog. Org. Coat. 54 (2005) 292–295.
[17] A.T. Al-Hinai, M.H. Al-Hinai, J. Dutta, Mater. Res. Bull. 49 (2014) 645–650.
[18] E. Akbarinezhad, M. Ebrahimi, F. Sharif, A. Ghanbarzadeh, Prog. Org. Coat. 77
(2014) 1299–1308.
[19] N. Kouloumbi, G.M. Tsangaris, A. Skordos, S. Kyvelidis, Prog. Org. Coat. 28 (1996)
117–124.
[20] V. Mišković-Stanković, D. Dražić, M. Teodorović, Corr. Sci. 37 (1995)
241–252.
[21] V. Mišković-Stanković, D. Dražić, Z. Kačarević-Popović, Corr. Sci. 38 (1996)
1513–1523.
[22] J.B. Bajat, V.B. Mišković-Stanković, N. Bibić, D. Dražić, Prog. Org. Coat. 58 (2007)
323–330.
[23] J.B. Bajat, V.B. Mišković-Stanković, J. Popić, D. Dražić, Prog. Org. Coat. 63 (2008)
201–208.
[24] X. Shang, B. Zhang, E. Han, W. Ke, Electrochim. Acta 56 (2011) 1417–1425.
[25] B. Messaoudi, S. Joiret, M. Keddam, H. Takenouti, Electrochim. Acta 46 (2001)
2487–2498.
[26] F. Cadena, L. Irusta, M.J. Fernandez-Berridi, Prog. Org. Coat. 76 (2013)
1273–1278.
[27] F.L. Jin, S.J. Park, Polym. Degrad. Stab. 97 (2012) 2148–2153.