coatings

Article
Experimental Evaluation of Polyester and Epoxy–
Polyester Powder Coatings in Aggressive Media
Ivan Stojanović 1, *, Vinko Šimunović 1 , Vesna Alar 1 and Frankica Kapor 2
1 Faculty of Mechanical Engineering and Naval Architecture, University of Zagreb, Zagreb 10002, Croatia;
vinko.simunovic@fsb.hr (V.Š.); vesna.alar@fsb.hr (V.A.)
2 Faculty of Mining, Geology and Petroleum Engineering, University of Zagreb, Zagreb 10002, Croatia;
frankica.kapor@rgn.hr
* Correspondence: ivan.stojanovic@fsb.hr; Tel.: +385-1-6168-343

Received: 13 February 2018; Accepted: 7 March 2018; Published: 8 March 2018

Abstract: Protective coatings are the most widely used corrosion protection method for construction
materials in different environmental conditions. They isolate metals from aggressive media,
making the structure more durable. Today, alongside good anti-corrosive properties, coatings
need to be safe for the environment and harmless to those who apply them. The high volatile
organic compound (VOC) content in conventional solvent-borne coatings presents a huge ecological
problem. A solution for indispensable solvent emission reduction is the application of powder
coatings. This study evaluates the corrosion performance and surface morphology of polyester and
epoxy–polyester powder coatings. Electrochemical impedance spectroscopy (EIS), open circuit
potential (OCP) measurement, salt spray chamber and humidity chamber testing followed by
adhesion testing were used to investigate the protective properties of powder coatings. Scanning
electron microscope (SEM) with energy-dispersive X-ray spectroscopy (EDX) was used to analyse the
surface morphology and chemical composition, whereas the microstructure and coating uniformity
were determined by optical microscope examination. The research revealed a negative influence
of coating surface texture on coating thickness and consequently a lack of barrier and adhesion
properties. The epoxy–polyester powder coating showed a better performance than the polyester
coating. All tested coatings showed uniform structure.

Keywords: electrostatic spraying; powder coatings; corrosion performance; EIS study; SEM analysis

1. Introduction
Electrostatic powder coating originated in the USA in the 1950s. For years, it has been extensively
used for painting processes in the automotive industry. Compared to traditional coatings, it provides
even, uniform and reproducible coatings with less waste [1]. The electrostatic coating process starts
by electrostatically charging the powder. At the spray gun exit, charged particles repel each other,
and spread evenly [2] on the object which is oppositely charged or grounded. The electrostatic
attraction between the powder particles and the object allows the powder to adhere to the surface,
forming an even coating [3,4]. The application of the electrostatic powder coating is followed by a
high-temperature curing process, which provides a smoothly-coated surface. The powder is charged
using either a corona or tribo-charging spray gun [3]. In the case of corona-charging, the powder
particles pass through an ion-rich area and become charged based on their permittivity. Tribo-charging
is based on the frictional charging of powder that is transported through a pipe of a specific material,
such as polytetrafluoroethylene (PTFE), metal or other powder particles [1,5]. The powder particles are
more extensively spread and have a higher transfer efficiency at higher charge [6]. Since tribo-charging
generates less charge on powder particles, corona-charging is generally used for electrostatic powder

Coatings 2018, 8, 98; doi:10.3390/coatings8030098 www.mdpi.com/journal/coatings

Coatings 2018, 8, 98 2 of 12

coating [1]. Today, thanks to the commercial success and wide application of powder coatings,
extensive research is carried out in this field of study, in particular in the powder coating chemistry [5].
Compared to liquid paints, powder coatings feature several advantages including the absence
of volatile organic content, the reduction in coating material loss (up to 68%), the reduction of dust
formation (from 40% to 84%) [1], high utilization rates, fast curing, the minimal health risks involved,
and the elimination of hazardous wastes [7]. However, a major disadvantage of electrostatic coating
technology is that the curing of the powder coating requires a significant amount of heat energy.
For this reason, the future of these technologies will include the development of low temperature
curable (LTC) powder coatings, whose application will enable energy saving solutions and also the
ability to coat heat-sensitive substrates [8]. The second disadvantage is the lack of coating uniformity
in Faraday-cage areas. Aside from several challenges needing improvement, powder coating is an
environmentally-friendly coating process with good performance properties.
There are numerous methods to evaluate the corrosion performance of powder coatings.
Mafi et al. [5] investigated the protective behaviour of powder coatings in 3.5% w/w NaCl solution
using electrochemical impedance spectroscopy (EIS) and open circuit potential (OCP) measurement,
as well as differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA).
Bhadu et al. [9] studied the properties of two polyester-based powder coatings using electrochemical
impedance spectroscopy in 3.5% w/w NaCl solution, the salt spray test, and scanning electron
microscope (SEM) analysis. Both papers [5,9] showed better protective properties of epoxy–polyester
powder coating compared to polyester powder coating, which is attributed to the higher cross-linked
density of the epoxy-based powder.
In this paper, the protective properties of two epoxy–polyester and two polyester powder
coatings with rough and smooth surface textures were evaluated in different aggressive media, that is,
in 4% w/w NaOH solution using the EIS method, evaluated in a humid and warm atmosphere
using humidity chamber testing and in a marine environment using the salt spray chamber testing.
The structure, morphology, and uniformity of powder coatings were analysed by SEM and EDX
analysis. The results were discussed regarding the chemical composition of the binder and coating
thickness, which was strongly affected by surface textures. The coatings were provided by four different
manufacturers, and are commonly used in switch-gear cabinet production.

2. Materials and Methods

Mild steel plates with the dimensions 100 mm × 150 mm × 3 mm were chemically pre-treated
using iron phosphating in a bath and a 0.5−2 µm thick Fe-phosphate coating was obtained.
Subsequently, the epoxy–polyester and polyester powder coatings with different surface textures,
used for indoor and outdoor exposure, were applied to the pre-treated samples using a PG1 electrostatic
spray gun, with spraying parameters of 98 kV, 100 µA, and 17 kHz. The powder-coated samples were
then cured in an oven for about 20 min at 185–200 ◦ C. Table 1 presents technical data for the tested
powder coatings.

Table 1. Technical data for tested powder coatings.

Surface Particle Specific Weight

Sample Chemical Type Purpose Gloss
Appearance Size (µm) (kg dm−3 )
saturated carboxylated polyester
A for indoor use semi-glossy textured (rough) < 100 1.6
resin and solid epoxy resin
saturated carboxylated polyester
river textured
B resin cured with the for outdoor use glossy 30–40 1.7
(rough)
β-hydroxyl-alkyl amide (HAA)
saturated carboxylated polyester
C resin cured with the for outdoor use glossy smooth < 100 1.4-1.7
β-hydroxyl-alkyl amide (HAA)
saturated carboxylated polyester
D for indoor use semi-glossy smooth 30–40 1.65
resin and solid epoxy resin
Coatings 2018, 8, 98 3 of 12

The dry-film thickness (DFT) of the cured powder coated samples was measured with a
non-destructive magnetic induction method using an Elcometer 456 instrument (Elcometer Limited,
Manchester, UK), according to ISO 2808 [10]. Measurements were performed on ten different
locations per sample. The coating adhesion was determined using the Zehntner cross-cut device
(Zehntner GmbH Testing Instruments, Sissach, Switzerland), according to ISO 2409 [11].
The 240-h salt spray and humidity chamber tests were used as accelerated laboratory tests to
predict the corrosion performance of the powder coatings [5,12,13]. The salt chamber testing was
conducted in 5% neutral NaCl solution in an Ascott cabinet, model S450 (Ascott Analytical Equipment
Limited, Staffordshire, UK), according to ISO 9227 [14]. The humidity test was conducted according
to ISO 6270-2 [15]. The samples were periodically examined according to ISO 4628 [16] in order to
evaluate the degradation of coatings [17]. The accelerated testing was performed on two samples per
each powder coating.
The corrosion/stability tendency in the NaOH solution was assessed by measuring the open circuit
potential (OCP) [5]. The open circuit potential of the polyester and epoxy–polyester powder-coated
samples was measured against the saturated calomel electrode (SCE) as the reference electrode [5] in
4% w/w NaOH solution, pH = 12, at room temperature (23 ± 2) ◦ C.
The protective properties of the powder coatings were investigated by electro-chemical impedance
spectroscopy [9,18], with a VersaSTAT 3 Potentiostat/Galvanostat (AMETEK Scientific 131 Instruments,
Princeton applied research, Berwyn, PA, USA). The measurements were carried out after one hour
and after 100 h of immersion in 4% w/w NaOH solution, pH = 12, at room temperature (23 ± 2) ◦ C.
The impedance spectra were performed at open circuit potential (OCP) with a 10 mV sinusoidal
amplitude. The frequency range was from 100 kHz to 100 mHz. A three-electrode cell including a
coated metal sample as the working electrode, a saturated calomel electrode (SCE) as the reference
electrode and graphite sticks as the auxiliary electrodes were used in the experiments [12]. The surface
of the working electrode was 1 cm2 . The EIS measurements were repeated three times for each sample.
The Solartron Z-View 2.2 software was used to interpret data.
The surface morphology and the microstructure of the powder coatings were observed by an
Olympus GX51 (Olympus Corporation, Tokyo, Japan) inverted metallurgical microscope and a Tescan
scanning electron microscope (SEM) (TESCAN Brno, Brno, Czech Republic) equipped with Oxford
Instruments energy dispersive spectroscopy (EDX) (Oxford Instruments, Belfast, UK). The energy used
for analysis was 20 keV.

3. Results and Discussion

3.1. Coating Thickness Measurement

By measuring the coating thickness (ISO 2808), a large scatter of the results for the applied
polyester coating with rough river surface texture (sample B) was found, with a minimum coating
thickness of 40.4 µm. In other samples, greater variations in thickness were not determined.
The average coating thickness was about 100 µm.

3.2. Chamber Testing Results

The accelerated corrosion tests in the salt spray (ISO 9227) and the humidity (ISO 6270-2) chamber
for a period of 10 days (240 h) did not show any blistering and rusting of the undercoated surface,
according to ISO 4628 [16]. Corrosion appeared only on the hole through which the samples were
suspended on a metal hook for grounding. At the hole, the metal hook physically disabled the access
for coating application. This is certainly a drawback of electrostatic powder coating application because
such places need to be repaired additionally with a brush or spray. The corrosion on the edges of the
samples was not taken into consideration.
After the corrosion test, samples BV 1 and BV 2, which were exposed to the humidity chamber,
showed extremely poor adhesion—Gt = 5 (extreme flaking)—whereas the samples BS 1 and BS 2,
Coatings 2018, 8, 98 4 of 12

after testing in the salt spray chamber, showed excellent adhesion—Gt = 0—according to ISO 2409 [11].
The samples tested in the salt spray chamber were protected with a greater coating thickness.
The adhesion to the other tested samples in the salt spray chamber and the humidity chamber was
classified as Gt = 0. The test revealed a strong negative influence of low coating thickness on the
adhesion of powder coatings in a humid environment. Prior to the corrosion tests, all the samples had
shown excellent adhesion Gt = 0 (no flaking). The chemical composition of the powder coating binder
had no influence on the coating protection properties during 240 h of accelerated chamber testing.
The results of powder coating dry-film thickness and corrosion testing after 240 h in the salt spray
chamber and the humidity chamber, as well as the subsequent adhesion tests, are provided in Tables 2
and 3.
Table 2. Assessment of coating protection properties after 240 h in the humidity chamber.

DFTmin DFTmax DFTmean Cross-Cut

Testing Sample Blistering Rusting
(µm) (µm) (µm) Adhesion
AV 1 83.6 133 104.01 0 0 0
AV 2 100 152 124.1 0 0 0
BV 1 64.5 114 87.98 0 0 5
Humidity BV 2 40.4 130 81.28 0 0 5
chamber CV 1 96.7 116 107.28 0 0 0
CV 2 91.3 134 115.93 0 0 0
DV 1 80.8 106 94.74 0 0 0
DV 2 83.3 104 92.94 0 0 0

Table 3. Assessment of the coating protection properties after 240 h in the salt spray chamber.

DFTmin DFTmax DFTmean Cross-Cut

Testing Sample Blistering Rusting
(µm) (µm) (µm) Adhesion
AS 1 95 115 103.61 0 0 0
AS 2 89.1 123 106.83 0 0 0
BS 1 76 150 107.73 0 0 0
Salt spray BS 2 73.5 154 117.71 0 0 0
chamber CS 1 97.7 119 107.95 0 0 0
CS 2 101 122 113 0 0 0
DS 1 82.7 103 91.81 0 0 0
DS 2 86.6 118 96.57 0 0 0

3.3. OCP and EIS Study

The open circuit potential (E/Ecorr ) results after stabilization for 30 min in 4% w/w NaOH solution
and the mean coating thickness (DFTmean ) are provided in Table 4.

Table 4. The results of the open circuit potential after stabilization in 4% w/w NaOH solution.

Sample A B C D 01 00
DFTmean (µm) 126.6 114.2 71.4 69.2 – –
Ecorr vs SCE (V) −0.447 −0.240 −0.320 −0.300 −0.253 −0.270

A diagram of the open circuit potential in NaOH solution is shown in Figure 1. The phosphate
coating showed instability when exposed to the alkaline solution (sample 01), while the increase in
the corrosion potential in time could be connected to the creation of a passive film on the mild steel
substrate (sample 00). The epoxy–polyester coating D showed very good protective properties because
of its potential corrosion stability over time.
 Coatings 2018, 8, 98 5 of 12
Coatings 2018, 8, 98 5 of 12
Coatings 2018, 8, 98 5 of 12

Coatings 2018, 8, 98 5 of 12

Figure 1. The open1.circuit

Figure potential
The open of powder
circuit potential coating
of powder as aasfunction
coating ofoftime,
a function time,in
in4%
4% w/w NaOH solution.
w/w NaOH
Figure 1. The open circuit potential of powder coating as a function of time, in 4% w/w NaOH
solution.
solution.
The impedance
Figure 1. data
The impedance
The openfordatathefortested
circuit powder
the tested
potential powder coatings
of powder coatingsasataat
coating the the beginning
beginning
function of time,of in ofw/w
exposure
4% exposure
4% w/wto 4% w/w
toNaOH
NaOH solutionThe
NaOH impedance
were fitted by the Randles equivalent electric circuit for a single to
solution
solution. data
were for
fitted the
by tested
the Randlespowder coatings
equivalent at
electric the
circuit beginning
for a single of exposure
electro-chemical 4%
cell.w/w
electro-chemical
NaOH solution
The equivalentwere fitted consisted
circuits by the Randles equivalent
of the solution electricRcircuit
resistance, for a singleresistance,
s, the polarisation electro-chemical
Rp, and cell.
cell. The equivalent circuits consisted of the solution resistance, Rs , the polarisation resistance, Rp ,
The equivalent
double-layer circuits
The impedance consisted
capacitance,
data Cdl,the
for of
[19] the solution
shown
tested in Figure
powder resistance, Rs, beginning
2. For modelling
coatings at the thethe
polarisation
interface of resistance,
a metal
of exposure 4% R
to surfacep, and
w/w
and double-layer
in contact
double-layer
NaOH capacitance,
with
capacitance,
solution were CdlC
an fitted , dl
electrolyte,
by , [19]
[19]
the as
shownshown
well
Randles as
in to in Figure
describe
Figure
equivalent 2.electric
For 2.circuit
non-porous Forcoating
modelling modelling
forthe interface
a single the
behaviour, ainterface
of the cell.of a metal
Randles
metal
electro-chemical surface
surface in
in contact
contact
The with
equivalent
equivalent
with anan
circuit electrolyte,
is often
circuits consisted
electrolyte, as
of well
usedas[20].
well as describe
theassolution
to to describe
resistance, non-porous coating
Rs, the polarisation
non-porous coating behaviour,
resistance,
behaviour, the Randles
theRpRandles
, and
equivalent double-layer
circuitcircuit
equivalent capacitance,
is often usedused
is often C dl, [20].
[20]. [19] shown in Figure 2. For modelling the interface of a metal surface
in contact with an electrolyte, as well as to describe non-porous coating behaviour, the Randles
equivalent circuit is often used [20].

Figure 2. The Randles equivalent circuit [12,19].

After 100 h of exposure

Figure to2.
Figure a 4%
The w/w
2. The NaOH equivalent
Randles
Randles solution, the
equivalent Nyquist
circuit
circuit diagram for all tested powder
[12,19].
[12,19].
coatings showed a two-time constant spectrum, thus the impedance data were fitted with the
equivalent Figure 2. The Randles equivalent circuit [12,19].
After
After 100 h of helectric
100exposure circuit for
of exposureto a to4%aporous
4%
w/ww/w coating.
NaOH
NaOH
The equivalent
solution,
solution, the circuit
theNyquistfor diagram
Nyquist
porous coating
diagram
consisted
for allfor
tested of
powder
all tested powder
the solution resistance, Rs, the coating resistance, Rc, the charge transfer resistance, Rct, the coating
coatingscoatings
showed showed
After 100 Chca
a two-time
capacitance,
two-time
,ofand
exposure
constanttoconstant
double-layer w/wspectrum,
a spectrum,
4% NaOH
capacitance,
thus the
Cdlsolution,
thus the
, [5,21]
impedance
the Nyquist
impedance
shown
datafor
diagram
data
in Figure 3. were
were fittedpowder
withwith
all tested
fitted the
the equivalent
equivalent
coatings electric
showedcircuit for porous
a two-time coating.
constant The equivalent
spectrum, circuit for data
thus the impedance porous werecoating
fitted consisted
with the of
electric circuit for porous coating. The equivalent circuit for porous coating consisted of the solution
theequivalent
solution resistance, Rs, the
electric circuit coatingcoating.
for porous resistance, Rc, the charge
The equivalent transfer
circuit resistance,
for porous coatingRconsisted
ct, the coating
of
resistance, Rs ,solution
the the coating
capacitance, resistance,
Cc,resistance,
and double-layer Rc , the
capacitance,
Rs, the coating charge transfer
Cdl, [5,21]
resistance, R c, theshown
chargeresistance,
intransfer R
3.ct , the coating
Figureresistance, capacitance, Cc ,
Rct, the coating
and double-layer capacitance,
capacitance, Cdl , [5,21]
Cc, and double-layer shownCin
capacitance, Figure
dl, [5,21] 3. in Figure 3.
shown

Figure 3. The two-time constant electrical equivalent circuits for porous coating [5,12,21].

The EIS analysis results at the beginning and after 100 h of exposure of powder coatings to a 4%
w/w NaOH solution are given in Table 5. CPEdl is a constant phase element of the double layer
FigureFigure
3. The3.two-time
The two-time constant
constant electrical equivalent
electrical equivalent circuits forfor
circuits porous coating
porous [5,12,21].
coating [5,12,21].
Figure 3. The two-time constant electrical equivalent circuits for porous coating [5,12,21].

The EIS analysis results at the beginning and after 100 h of exposure of powder coatings to a 4%
The EIS analysis results at the beginning and
The EIS analysis results at the beginning andafter 100 100
after h of exposure of powder
h of exposure ofcoatings
powder to acoatings
4% to a
w/w NaOH
w/w NaOH solution
solutionare
aregiven
givenininTable
Table 5.
5. CPE
CPEdl is a constant phase element of the double layer
dl is a constant phase element of the double layer
4% w/w NaOH solution are given in Table 5. CPEdl is a constant phase element of the double layer
showing its capacitive properties, which depend on the empirical constant ndl . The constant n is in
the range from 0 to 1. If n = 0, the CPE acts as a resistor, and if n = 1, the CPE acts as a capacitor [22].
CPEcoat is a constant phase element of the coating, and ncoat is its empirical constant.
Coatings 2018, 8, 98 6 of 12

showing its capacitive properties, which depend on the empirical constant ndl. The constant n is in
the range from 0 to 1. If n = 0, the CPE acts as a resistor, and if n = 1, the CPE acts as a capacitor [22].
CPEcoat is a constant phase element of the coating, and ncoat is its empirical constant.
Coatings 2018, 8, 98 6 of 12

Table 5. The results of the EIS measurement at the begging (A, B, C, D) and after 100 h (A/100 h, B/100
h, C/100
Table 5. h,
TheD/100 h) immersion
results of the EIS in 4% w/w NaOH
measurement solution.
at the begging (A, B, C, D) and after 100 h (A/100 h,
B/100 h,
DFT C/100
mean h, D/100 h) immersion in 4% w/w NaOH solution.
Sample Rs (Ω) CPEcoat (F) ncoat Rcoat (Ω) CPEdl (F) ndl Rp/Rct (Ω)
(µm)
A DFTmean 150.7 – coat (F) – ncoat –coat (Ω) 4.975 × dl10(F) 0.96016 2.8963
Sample Rs (Ω) CPE R CPE −11
ndl Rp /Rct × 106
(Ω)
126.6
(µm)
A/100 h 331.2 7.665 × 10 −5 0.7334 1.323 × 10 4 2.584 × 10−4 1 1.527 × 104
A 150.7 – – – 4.975 × 10−1−11 0.96016 2.8963 × 1066
B
A/100 h
126.6 113.5
331.2
–
7.665 × 10−5
–0.7334 –
1.323 × 104
6.549 × 10 °
2.584 × 10−4
0.94467
1
1.372 × 10
1.527 × 104
114.2
B/100B h 236.9
113.5 7.705 × 10
–
−5 0.4012 – 2.856 × 10
–
2 1.100
6.549 ×
×10
−4
10−1 ◦ 0.6917
0.94467 2.882 106 4
1.372 ××10
114.2
B/100 h 236.9 7.705 × 10−5 2.856 × 102 10−4
1.100 × −11 4
2.882 × 10 6
C 467.8 – –0.4012 – 6.452 × 10 0.6917
0.96166 1.7562 × 10
C 71.4 467.8 – – – 6.452 × 10−11 0.96166 1.7562 × 1063
C/100 h 71.4 121.6 1.064 × 10−4 −4 0.5856 111.8 2.865 × 10−4−4 0.5569 4.252 × 103
C/100 h 121.6 1.064 × 10 0.5856 111.8 2.865 × 10 0.5569 4.252 × 10
DD 672.3
672.3
– – – – – – 7.321 × 10−11
7.321 × 10−11
0.94090
0.94090
1.8189 × 106
1.8189 × 106
69.2
69.2 − 9 4 10−6−6
D/100
D/100hh 100100 2.702 × −9
× 10
2.702 10 0.9620
0.9620 2.809 × 410 3.462
× 10
2.809 3.462××10 0.7897
0.7897 9.830 104 4
9.830 ××10

The
The results
results ofof the
the EIS
EIS analysis
analysis at at the
the beginning
beginning of of exposure
exposure to to aa 4%
4% w/w
w/w NaOH
NaOH solution
solution showed
showed
that
that the polyester powder coating B (for outdoor use) had the weakest protective properties, that
the polyester powder coating B (for outdoor use) had the weakest protective properties, that is,
is,
the lowest coating resistance (R p = 1.372 × 10 6Ω). The biggest coating resistance was determined for
6
the lowest coating resistance (Rp = 1.372 × 10 Ω). The biggest coating resistance was determined for
epoxy–polyester
epoxy–polyester coating
coating A. A. The
The coating
coating resistance
resistance features
features the
the ability
ability toto resist
resist electrolyte
electrolyte penetration
penetration
and is often used to assess coating protective performance
and is often used to assess coating protective performance [9,19]. [9,19].
After
After 100
100 hh of
of immersion
immersion in in 4%
4% w/ww/wNaOH NaOHsolution,
solution,allallthe
thetested
testedpowder
powdercoatings
coatingsshowed
showed a
decrease in resistance, thus indicating a porous coating behaviour
a decrease in resistance, thus indicating a porous coating behaviour where the corrosive mediumwhere the corrosive medium
penetrated the
penetrated themetal–coating
metal–coatinginterface
interface[5].[5]. The
The lowest
lowest coating
coating resistance
resistance after
after long-term
long-term immersion
immersion was
was determined for polyester powder coating C, whereas the best
determined for polyester powder coating C, whereas the best protective properties were establishedprotective properties were
established for epoxy–polyester
for epoxy–polyester powder coatingpowder D. coating
Both powderD. Bothcoatings
powder C coatings
and D C and applied
were D were applied with
with similar
similar
thicknessthickness
and hadand had a smooth
a smooth surfacesurface appearance.
appearance. This suggests
This suggests that the that the chemical
chemical composition
composition of the
of the powder coating binder was responsible for the corrosion protection behaviour
powder coating binder was responsible for the corrosion protection behaviour rather than the thickness. rather than the
thickness. Polyester
Polyester resins are notresins aretonot
resistant resistant
alkaline to alkaline
hydrolysis hydrolysis
[23], which has led [23],
to thewhich has led
degradation andto the
lower
degradation andpolyester
resistance of the lower resistance
powder of the polyester
coatings B and Cpowder
compared coatings B and Cepoxy—polyester
to the hybrid compared to thepowderhybrid
epoxy-–polyester powder coating in the presence of NaOH. Alkaline
coating in the presence of NaOH. Alkaline hydrolysis resulted in a cleavage reaction of ester chains hydrolysis resulted in a
cleavage
and a lossreaction of ester
of polyester chains and
protective a loss of The
properties. polyester protective properties.
epoxy–polyester powder coatingThe epoxy–polyester
A was applied
powder coating A was applied with higher mean thickness but showed
with higher mean thickness but showed slightly lower resistance than the epoxy–polyester slightly lower resistance than
powder
the epoxy–polyester powder coating
coating D, due to an uneven texture film. D, due to an uneven texture film.
The
The impedance
impedance results,
results, measured
measured (Msd.)(Msd.) andand fitted
fitted (Calc.),
(Calc.), were
were expressed
expressed by by the Nyquist and
the Nyquist and
Bode diagrams shown in
Bode diagrams shown in Figure 4. Figure 4.

Sample A.txt
Model : R(Q(R(QR))) Wgt : Modulus
Z , Msd.
6,000 Z , Calc.
5,500
158m
5,000 200m
4,500 251m
316m
4,000 398m
- Z '' (ohm)

3,500 501m
631m
3,000
1
2,500 794m
1.26
2,000
2
1.58
1,500
3.16
2.51
1,000 5.01
3.98
10
500
12.6
0
0 1,000 2,000 3,000 4,000 5,000 6,000 7,000 8,000 9,000 10,000
Z ' (ohm)

(a)
Figure 4. Cont.
Coatings 2018, 8, 98 7 of 12
Coatings 2018, 8, 98 7 of 12
Figure 4. Cont.

Sample A.txt
Model : R(Q(R(QR))) Wgt : Modulus
|Z|, Msd.
10,000
50 |Z|, Calc.
Angle, Msd.
45 Angle, Calc.

40

35

Angle (deg)
30
|Z| (ohm)

1,000 25

20

15

10

100 0
0.1 1 10 100 1,000 10,000 100,000
Frequency (Hz)

(b)
Sample B.txt
Model : R(Q(R(QR))) Wgt : Modulus
Z , Msd.
Z , Calc.
3,500
158m
3,000 200m
251m
2,500 316m
- Z '' (ohm)

398m
2,000 501m
631m
794m
1,500 1

1.58
1,000 1.26
2.51
2
5.01
500 3.98
10
12.6
0
0 500 1,000 1,500 2,000 2,500 3,000 3,500 4,000 4,500 5,000 5,500 6,000 6,500 7,000
Z ' (ohm)

(c)
Sample B.txt
Model : R(Q(R(QR))) Wgt : Modulus
|Z|, Msd.
10,000
48 |Z|, Calc.
Angle, Msd.
46
Angle, Calc.
44
42
40
1,000 38
Angle (deg)

36
|Z| (ohm)

34
32
30
100 28
26
24
22
20
18
10
0.1 1 10 100 1,000 10,000 100,000
Frequency (Hz)

(d)
Figure 4. Cont.
Figure 4. Cont.
Coatings 2018, 8, 98 8 of 12
Coatings 2018, 8, 98 8 of 12

Sample C.txt
Model : R(Q(R(QR))) Wgt : Modulus
Z , Msd.
1,200 Z , Calc.

1,100 100m

1,000 158m
126m
900 251m
800 398m 200m
- Z '' (ohm)

631m 316m
700
1 501m
600
794m
500 1.58
1.26
400 2.51
2
3.98
300 3.16
7.94
200 5.01
20
10
100
31.6
0
0 200 400 600 800 1,000 1,200 1,400 1,600 1,800 2,000 2,200 2,400
Z ' (ohm)

(e)
Sample C.txt
Model : R(Q(R(QR))) Wgt : Modulus
|Z|, Msd.
10,000
|Z|, Calc.
40 Angle, Msd.
Angle, Calc.

35

1,000 30

Angle (deg)
|Z| (ohm)

25

20
100

15

10

10
0.1 1 10 100 1,000 10,000 100,000
Frequency (Hz)

(f)
Sample D.txt
Model : R(Q(R(QR))) Wgt : Modulus
Z , Msd.
3.20E+05 Z , Calc.
3.00E+05
2.80E+05 158m
2.60E+05
2.40E+05 200m
2.20E+05
2.00E+05
- Z '' (ohm)

251m
1.80E+05
1.60E+05 316m
1.40E+05 398m
1.20E+05 501m
1.00E+05
8.00E+04 794m 631m
6.00E+04 1.26 1
4.00E+04 2 1.58
2.00E+04
7.94
0.00E+00
0.00E+00 1.00E+05 2.00E+05 3.00E+05 4.00E+05 5.00E+05
Z ' (ohm)

(g)
Figure 4. Cont.
Figure 4. Cont.
Coatings 2018,
Coatings 2018,8,8,98
98 99of
of 12
12
Coatings 2018, 8, 98 9 of 12
Sample D.txt
Model : R(Q(R(QR))) Wgt : Modulus
Sample D.txt
|Z|, Msd.
1.00E+06 Model : R(Q(R(QR))) Wgt : Modulus 85 |Z|, Calc.
Msd.
1.00E+06 85
80 Angle, Msd.
|Z|, Calc.
80
75 Angle, Calc.
Msd.
75
70 Angle, Calc.
1.00E+05 70
65
1.00E+05 65
60
60
55

Angle
(ohm)
55
50

Angle
(ohm)
1.00E+04 50
45

(deg)
1.00E+04 45
40
|Z| |Z|

(deg)
40
35
35
30
1.00E+03 30
25
1.00E+03 25
20
20
15
15
10
1.00E+02 510
1.00E+02 0.1 1 10 100 1,000 10,000 5
100,000
0.1 1 10 Frequency
100 (Hz) 1,000 10,000 100,000
Frequency (Hz)
(h)
(h)

Figure 4.
Figure TheNyquist
4. The Nyquist diagram
diagram (a,c,e,g)
(a,c,e,g) andand
BodeBode diagram
diagram (b,d,f,h)
(b,d,f,h) of tested
of tested powder powder coatings
coatings after
Figure 4. h
afterh 100 The Nyquist diagram
immersion (a,c,e,g) and Bode diagram (b,d,f,h) of tested powder(e,f)coatings after
100 immersion in 4%inw/w
4% NaOH
w/w NaOH solution:
solution: (a,b) Sample
(a,b) Sample A;Sample
A; (c,d) (c,d) Sample
B; (e,f)B;Sample
Sample C;
C; (g,h)
100 h immersion
(g,h) Sample in 4% w/w NaOH solution: (a,b) Sample A; (c,d) Sample B; (e,f) Sample C; (g,h)
Sample D. D.
Sample D.
3.4.
3.4. Morphology
Morphology and
and EDX
EDX Spectra
Spectra
3.4. Morphology and EDX Spectra
The
The cross-section
cross-section of
of the representative
representative polyester
polyester and
and epoxy–polyester
epoxy–polyester powder
powder coatings
coatings on
on aa
The cross-section of the representative polyester and epoxy–polyester powder coatings on a
phosphate steel surface are shown in Figure 5. It can
can be
be seen
seen that
that the
the coatings
coatings applied
applied on
on the
the samples
samples
phosphate steel surface are shown in Figure 5. It can be seen that the coatings applied on the samples
appear
appear to
to be adequately
adequately cured and uniform, with no defects and pores. A slightly higher coating
appear to be adequately cured and uniform, with no defects and pores. A slightly higher coating
thickness
thickness of
of the polyester coating C can be observed. The cracks and pores are not visible.
thickness of the polyester coating C can be observed. The cracks and pores are not visible.

(a) (b)
(a) (b)
Figure
Figure 5. Cross-sectional photographs
photographs of
of powder coatings: (a)
(a) Sample A (epoxy-polyester),
(epoxy-polyester), coating
Figure 5. Cross-sectional
5. Cross-sectional photographs of powder
powder coatings:
coatings: (a) Sample
Sample AA (epoxy-polyester), coating
coating
thickness
thickness 60–100
60–100 µm;
µm; (b)
(b) Sample C (polyester), coating thickness 80–120
80–120 µm.
thickness 60–100 µm; (b) Sample
Sample C
C (polyester),
(polyester), coating
coating thickness
thickness 80–120 µm.
µm.
The SEM micrograph with an EDX spectrum is shown in Figure 6. The SEM micrograph
The SEM
SEMmicrograph
micrographwith
withan an
EDX spectrum
EDX is shown
spectrum in Figure
is shown 6. The SEM
in Figure micrograph
6. The indicated
SEM micrograph
indicated that the tested epoxy–polyester and polyester coating adhered firmly to the phosphate
that the tested
indicated epoxy–polyester
that the and polyester
tested epoxy–polyester coating adhered
and polyester coatingfirmly to the
adhered phosphate
firmly substrate
to the phosphate
substrate following the morphology of the substrate. The peak of the Ti pigment materials on the
following following
substrate the morphology of the substrate.
the morphology of the The peak ofThe
substrate. the peak
Ti pigment
of the materials
Ti pigmentonmaterials
the EDX spectra
on the
EDX spectra was predominant in both cases.
was predominant
EDX in both cases.in both cases.
spectra was predominant
Coatings 2018, 8, 98 10 of 12
Coatings 2018, 8, 98 10 of 12

(a) (b)
Figure 6. The SEM micrograph with EDX spectra of the powder coatings: (a) Sample A (epoxy-
Figure 6. The SEM micrograph with EDX spectra of the powder coatings: (a) Sample A
polyester), good penetration of coating into the substrate, no visible cracks, and pores, Ti pigment is
(epoxy-polyester), good penetration of coating into the substrate, no visible cracks, and pores,
dominant; (b) Sample C (polyester), no visible cracks and pores, finely micro-rough appearance of
Ti pigment is dominant; (b) Sample C (polyester), no visible cracks and pores, finely micro-rough
upper layer surface, Ti pigment is dominant.
appearance of upper layer surface, Ti pigment is dominant.

4. Conclusions
4. Conclusions
The tests performed in this study showed that the powder coatings exhibited very good
The tests performed in this study showed that the powder coatings exhibited very good properties
properties in humid and marine environments as well as in an alkali medium, but also displayed
in humid and marine environments as well as in an alkali medium, but also displayed some failures.
some failures. Extremely good protective properties were displayed in the epoxy–polyester coatings,
Extremely good protective properties were displayed in the epoxy–polyester coatings, which are
which are intended for indoor use, while the worst performance was delivered by polyester powder
intended for indoor use, while the worst performance was delivered by polyester powder coating B,
coating B, intended for outdoor use, which lost of adhesion after exposure to the humid and warm
intended for outdoor use, which lost of adhesion after exposure to the humid and warm atmosphere
atmosphere (ISO 6270-2). A possible cause of this adhesion loss was the distinct relief surface of
(ISO 6270-2). A possible cause of this adhesion loss was the distinct relief surface of coating B, for which
coating B, for which insufficient coating thickness was determined (DFTmin = 40.4 µm), which led to
insufficient coating thickness was determined (DFTmin = 40.4 µm), which led to an early penetration
an early penetration of water to the steel surface. The protective efficiency of an organic coating is
of water to the steel surface. The protective efficiency of an organic coating is generally achieved
generally achieved through the barrier mechanism, which confirms the strong influence of coating
through the barrier mechanism, which confirms the strong influence of coating thickness on corrosion
thickness on corrosion protection behaviour. Taking into account that the size of the particles in most
protection behaviour. Taking into account that the size of the particles in most powders used for
powders used for electrostatic spraying is 30–50 µm, the coating thickness should exceed 50 µm to
electrostatic spraying is 30–50 µm, the coating thickness should exceed 50 µm to obtain a satisfactory
obtain a satisfactory protective film.
protective film.
According to the EIS results, the coating resistance for all the tested coatings at the beginning of
According to the EIS results, the coating resistance for all the tested coatings at the beginning of
exposure showed an acceptable value (1066 Ω·cm22) for protective coatings [19], but after 100 h in 4%
exposure showed an acceptable value (10 Ω·cm ) for protective coatings [19], but after 100 h in 4%
w/w NaOH, this decreased for all tested coatings. The worst coating resistance was established for
w/w NaOH, this decreased for all tested coatings. The worst coating resistance was established
polyester coating sample C. The established difference in corrosive durability between the epoxy–
for polyester coating sample C. The established difference in corrosive durability between the
polyester powder coating and the polyester powder coating determined by EIS can be related to the
epoxy–polyester powder coating and the polyester powder coating determined by EIS can be related
better corrosion properties and the higher cross-link density of the epoxy-based binder [5,9,13], as
to the better corrosion properties and the higher cross-link density of the epoxy-based binder [5,9,13],
well as the instability of polyester to alkaline hydrolysis [23]. The cross-sectional examination showed
as well as the instability of polyester to alkaline hydrolysis [23]. The cross-sectional examination
that all tested coatings were fully cured with no cracks and pores and with good adhesion to the
substrate.
Coatings 2018, 8, 98 11 of 12

showed that all tested coatings were fully cured with no cracks and pores and with good adhesion to
the substrate.

Author Contributions: Ivan Stojanović and Vesna Alar conceived and designed the experiments; Ivan Stojanović
and Vinko Šimunović performed the experiments and analysed the data; Frankica Kapor contributed with
materials/analysis tools and to the experimental work; Ivan Stojanović wrote the paper; Vesna Alar revised
the paper.
Conflicts of Interest: The authors declare no conflict of interest.

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