Progress in Organic Coatings 92 (2016) 29–43

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Progress in Organic Coatings

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Viability of epoxy–siloxane hybrid coatings for preventing steel

corrosion
M. Echeverría a,∗ , C.M. Abreu a , K. Lau b , C.A. Echeverría c
a
ENCOMAT Group, University of Vigo, EEI, University Campus, 36310 Vigo, Spain
b
Florida International University, Dept. of Civil and Env. Eng., 10555 W. Flagler St., Miami, FL 33174, USA
c
Research Center on Anticorrosive and Tensoactive Materials (CEAT), University of Matanzas, 40449 Matanzas, Cuba

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

Article history: In this research work, eight coatings consisting of primers, topcoats and combinations of primers/topcoats
Received 23 March 2015 were evaluated. Salt spray test (SST) and impedance measurements were carried out for evaluat-
Received in revised form 4 December 2015 ing macroscopic failures (blistering, adhesion, etc.) and the electrochemical behaviour of the referred
Accepted 17 December 2015
coatings, respectively, which were supported by surface characterization techniques such as scanning
electron microscopy (SEM), energy dispersive X-ray (EDX) and X-ray mapping (XRM). Coating systems
Keywords:
comprising an epoxy–siloxane topcoat have offered a better corrosion protection of the steel substrate
Epoxy–siloxane coatings
than its counterpart with polyurethane topcoat (comparing coating systems with the same primer: 1A and
Protective properties
EIS
1B, 2A and 2B). Also, the addition of any of the topcoats has outperformed the properties conferred by the
Salt spray test epoxy coating pigmented with zinc phosphate (ZP) and micaceous iron oxide (MIO), which have shown
SEM the worst behaviour as a single coat. The single epoxy–siloxane topcoat and the epoxy–polyurethane
water-based coating system have also provided excellent protective properties, thus allowing to open
up new opportunities to be implemented in real structures.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction reducing considerably the content of volatile organic compounds

Organic coatings are considered the most widespread method
for corrosion prevention of metallic substrates [1,2], where their
anticorrosive protection is achieved via barrier or electrochemical
mechanisms [3]. Their basic components are resin, pigments, sol-
vent and additives. The resin defines relevant properties such as
adhesion between the coating and the substrate, cohesion of the
dry coating, mechanical and chemical resistance, and other prop-
erties [1,4,5]. Generally, coatings are not applied in one single coat
but in a combination (primary/intermediate/topcoat) where each
of them has its own function [4]. The UNE-EN ISO 12944-5 standard
proposes several coating systems for different environments, dif-
ferent surface preparation grades and the durability grade to be
expected [6]. Among the available options, epoxy/polyurethane
coating systems have been widely employed for corrosion protec-
tion of steel structures in aggressive environments due to their high
anticorrosive performance [2,7]. However, more recently, hybrid
organic–inorganic coatings such as epoxy–siloxane coatings (ES)
have outperformed the former, eliminating the isocyanate and
∗ Corresponding author.
E-mail address: mayren1980@uvigo.es (M. Echeverría).
(VOCs) due to their high content of solids [8,9]. These new coatings
offer evident benefits since they synergistically combine the advan-
tages of silicone and epoxy resins, which result in a single polymer
with unique properties such as good corrosion protection, long
life expectancy, low maintenance cost and extreme durability for
materials, equipment and structures exposed to severely corrosive
environments [9]. The anticorrosive protection of ES one-single
coat and traditional two-single coats epoxy/polyurethane coatings
with and without an epoxy or silicate-type zinc-rich primer were
assessed by different techniques [8]. Also, a high anticorrosive per-
formance in acid, alkaline, saline and organic solvent environment
for siloxane-modified epoxy–polyamide coating has been reported
[10]. More recently, a single hybrid coat (an aliphatic epoxy resin
cured with an aminosilane and chemically modified with alkoxysi-
lanes) with high anticorrosive and weathering resistance behaviour
was designed for protecting metal structures with low mainte-
nance requirements [11].
To the best of our knowledge, there is a lack of information about
the study of the anticorrosive protection of ES hybrid coatings with
or without the combination of other protective coats by means
of electrochemical impedance spectroscopy (EIS). It is well known
that this technique offers valuable information of the coatings per-
formance with time, as well as about the kinetics of the corrosive

http://dx.doi.org/10.1016/j.porgcoat.2015.12.005
0300-9440/© 2015 Elsevier B.V. All rights reserved.
30 M. Echeverría et al. / Progress in Organic Coatings 92 (2016) 29–43

Table 1
Main characteristics of the coatings under study.

Coating Group Primer Topcoat Total thicknessa (␮m)

SST EIS

1 1 1 Zinc-rich epoxy (zinc pigments) No topcoat 55 ± 5

2 1 1 Epoxy (ZP and MIO pigments) No topcoat 60 ± 5
1A 2 2 Zinc-rich epoxy (zinc pigments) Epoxy–siloxane 105 ± 5
1B 2 2 Zinc-rich epoxy (zinc pigments) Polyurethane 100 ± 5
2A 2 2 Epoxy (ZP and MIO pigments) Epoxy–siloxane 125 ± 5
2B 2 2 Epoxy (ZP and MIO pigments) Polyurethane 110 ± 5
3 1 2 Water-based epoxy (ZP and MIO pigments) Water-based polyurethane 140 ± 5
4 1 2 No primer Epoxy–siloxane 70 ± 5

SST, salt spray test; EIS, electrochemical impedance spectroscopy test; ZP, zinc phosphate pigments; MIO, micaceous iron oxide pigments.
a
Dry film thickness.

processes taking place in the metallic substrate. Hence, the present Table 2
Coatings composition.
research aims at assessing the corrosion protection properties of
an ES hybrid coating (as a single coat and also being part of coat- Coating Composition
ing systems as topcoat), where an epoxy zinc-rich coating (ZRP) Zinc-rich epoxy Primer based on a low molecular weight epoxy
and an epoxy coating pigmented with micaceous iron oxide (MIO) bisphenol A and F resins which react with an
and zinc phosphate (ZP), identified as (ZPM), will be the primers. amine. Contains metallic zinc in powder at a
Additionally, and for comparative purposes, the ES topcoat will concentration in accordance with SSPC-Paint
20, type 2, level 2.
be changed for a traditional polyurethane (PUR) one and for an
Epoxy (ZP and MIO Epoxy coating based on a low molecular
epoxy–polyurethane water-based coating system. Salt spray test pigments) weight epoxy resin which react with an amine.
(SST), EIS measurements, physical tests and surface characteriza- It contains zinc phosphate and micaceous iron
tion techniques (SEM, EDX and XRM) will help us to shed light on oxide.
Epoxy–siloxane Epoxy–siloxane coating based on a
the anticorrosive performance.
cycloaliphatic epoxy resin which reacts with a
polysiloxane.
Polyurethane Polyurethane coating based on a hydroxylated
2. Experimental acrylic resin with an aliphatic polyisocyanate.
Water-based epoxy Epoxy water based formed by a modified
2.1. Materials aliphatic polyamine dispersion which react
with a bisphenol A epoxide aqueous
dispersion. It contains zinc phosphate as
Cold rolled low carbon steel panels [12], which composition is corrosion inhibiting pigment.
0.04% S, 0.50% Mn and 0.04% P (maximum weight percentages) Water-based Polyurethane water based formed by
were employed as the metallic substrate for evaluating several polyurethane hydroxyfunctional polyurethane modified
organic coatings. The dimensions are 150 mm length, 100 mm polyacrylic dispersion which reacts with a
water dispersible aliphatic polyisocyanate.
width and 1 mm thickness. They were cleaned with detergent to
remove residues of oil and grease, followed by rinsing with high
pressure deionised water to eliminate salts, dust, etc. Then, the
Coatings were kindly donated by HEMPEL, Barcelona. Also, the
metallic surface was submitted to an abrasive blasting (Sa 2½ level)
steel panels were painted by the air-less method at HEMPEL lab-
[13], reaching a surface profile corresponding to Rugotest No. 3.
oratories (Barcelona, Spain) and once the coatings were dry, they
Later, samples were introduced in an oven at 50 ◦ C to stop the
were packed, identified and kept in a desiccator until the beginning
corrosive process before painting.
of the experiment. A digital coating thickness gauge (POSITECTOR® .
Model 6000-1) with standards of 25, 250 and 1000 ␮m for calibra-
2.2. Coating systems tion was used for thickness measurements.

The main characteristics of eight coatings consisting of 2.3. Experimental procedures

single coats (primers and topcoats) and the combination of
both (primers/topcoats) are presented in Table 1. A traditional
polyurethane (PUR) coat was selected for comparison with the
epoxy–siloxane (ES) one. Coatings were divided in groups 1 or 2
for both the accelerated test (salt spray test-SST) and EIS experi-
ments. In the case of SST, the first group includes the two single
coats (1: zinc-rich epoxy primer-ZRP- and 2: epoxy primer with ZP
and MIO pigments-ZPM) and the second one comprises the coating
systems (1A, 1B, 2A, 2B and 3) and the ES single coat (4), where
the letters A (ES) and B (PUR) indicate the type of topcoat and the
numbers 1 and 2 refer to the primers employed (Table 1). Also,
coating 3 is an epoxy–polyurethane water-based coating system.
A more detailed explanation of this organization will be presented
later. For EIS test, coatings were organized in group 1 (single coats
1 and 2) and group 2 (coating systems 1A, 1B, 2A, 2B and 3) and the
ES topcoat (4) (Table 1). More details about coatings composition
can be seen in Table 2, which were provided by the manufacturer
(HEMPEL).
SST and EIS measurements were carried out for evaluating the
anticorrosive properties of the coatings. The former test was per-
formed in a salt fog chamber, in agreement with the UNE-EN ISO
standard 9227 [14]. Due to the great variety of samples under
study, they were divided in two groups (1 and 2) according to their
expected resistance to a corrosive media, in accordance with the
UNE-EN ISO 12944-5 standard [6] and the information of their cor-
responding technical sheets. Group 1 is composed by coatings 1,
2, 3, and 4, while group 2 refers to coating systems 1A, 2A, 1B and
2B (Table 1), which corresponds to a lower (C2) and medium (C3)
aggressive environments category, respectively. In line with the
above-mentioned, only coating systems of group 2, which resist to
C3 or higher corrosive environment, can be submitted to the SST
(fast evaluation), in agreement with the requirements of the UNE-
EN ISO 12944-6 standard [15]. The exposure time of group 2 during
the SST was 120, 240 and 480 h. On the other hand, group 1 with
lower corrosion resistance, was exposed to the SST for 1385 h with
 M. Echeverría et al. / Progress in Organic Coatings 92 (2016) 29–43 31

sampling times at 120, 503, 1001, 1290 and 1385 h. Both groups of microscopy (SEM) and energy dispersive X-ray (EDX), for study-
samples were submitted to the same test conditions, but the times ing the morphology and chemical composition, respectively. Also
and requirements for the evaluation were different. Several repli- X-ray mapping (XRM) was used for analyzing the distribution and
cates (coated steel specimens) were prepared for the SST, including relative abundance of chemical elements in specimens. The equip-
three samples for each coating and for each exposure time, as well ment employed was a FE-SEM JEOL JSM6700F model, connected to
as the reference one for comparative purposes (kept in the desic- an energy dispersive X-ray detector EDS Oxford Inca Energy 300.
cator). Samples observed by SEM were cut in cross-sections and then, they
The UNE-EN ISO standard 4628 (first part) [16] defines a system were mounted in a cold resin. After 24 h, samples already fixed in
for the designation of the quantity and size of the defects and the the resin were submitted to different polishing steps to a mirror-
intensity of the appearance changes of the coatings. The assessment like finish. Subsequently, specimens were sputtered with carbon to
was done by visual comparison at specific times between the tested make them conductive for SEM studies. Measurements were car-
panels (three replicates for each coating, at each pick up time) and ried out at least by triplicate in each of the replicates prepared for
standards pictures for each defect, as well as with the reference each coating under study (coated steel) and in the reference one
sample (not exposed) [16]. The defects or failures studied over the (not tested and kept in the desiccator).
coatings were blistering, degradation of the paint film (DPF) and
adhesion, and the results presented for each of them were the aver-
3. Results and discussion
age of the three tested samples at specific times for each system.
Rusting was also evaluated, not as a failure, but as an observation
3.1. Evaluation of macroscopic failures after salt spray test
revealing that a failure has occurred. The DPF failure refers to the
corrosion progress along an incision made on the coating (to the
The assessment of coating failures by accelerated SST offers
metallic substrate). After the SST, coated samples are rinsed (with
valuable information related to the protective performance of the
tap water) and dried (with compressed air). Then, all the detached
coatings. This was carried out following a numeric scale (0–5) in
coating parts are carefully eliminated by putting a knife blade (with
agreement with the UNE-EN ISO standard 4628 [16], where “0”
an inclination angle) in the coating/steel interface and lifting the
means no degradation and “5” represents the maximum degra-
coating. After that, the maximum width with corrosion (at least
dation (see Table 3). This scale allows the comparison among the
in six points uniformly distributed along the incision) is measured
failures under study. The data were obtained as a result of averaging
(transversely from the incision to outside) and the average value is
the three replicated experimental values (for each defect) in each
calculated. The DPF is determined trough an equation that relates
coating, which were represented as integers in accordance with the
the average widths before and after the experiment [15]. In the case
evaluation scale employed.
of coated panels of group 2 (exposed to the fast evaluation in the
The behaviour of the macroscopic failures presented for coatings
SST), the requirement to pass the test states that at least two of
1, 2, 3 and 4 (group 1) during the SST can be visualized indi-
the three replicates under study do not present failures. Moreover,
vidually (for each defect) in Fig. 1. The aforementioned results,
adhesion and DPF can be observed (before – only adhesion – and
with their standard deviations, are listed in Table 4. In general,
after the experiment) in some specific levels, in agreement with the
all the coatings have shown good resistance to blistering, DPF and
demands of the UNE-EN ISO 12944-6 standard [15].
adhesion after 1385 h of exposure in the SST. In agreement with
Adhesion assessments were performed by the tape test, which
this, rusting was almost undetectable on the surface of the tested
include two methods (A and B) according to the total dry thick-
ness of the coating system, following the requirements of the ASTM
D3359 standard [17]. Method A is for coating thicknesses higher Table 3
than 5 mils (125 ␮m) and method B for lower values. Identification of the numeric values according to the UNE-EN ISO 4628-1 [16].
Following the EIS technique, impedance measurements were Scalea Adhesiona , b Adhesiona Blisteringa Rustinga DPFa
carried out in a classical electrochemical cell consisting of a
0 No release No release No blistering Ri 0 No corrosion
polyethylene tube (exposing an area of 10.17 cm2 ) fixed to the
1 Detachment of <5% Scarce Ri 1 Very light
samples with silicon adhesive and three electrodes: the coated flakes of the
sample (as working electrode), a graphite sheet (as counter elec- coating along
trode) and the saturated calomel electrode (SCE) (as reference the incisions or
electrode). Then, coated samples were exposed in 3% by weight in the
intersection
NaCl solution during the experimental time. The tested areas were 2 Coating has 5–15% 2 S2-S5 Ri 2 Light
carefully examined in order to avoid possible failures or defects on flaked along
the surface and for achieving homogeneous thicknesses. Measure- the incisions to
ments were performed at open circuit potential and at different 1/16
inch (1.6 mm of
immersion times by using a potentiostat Autolab® PGSTAT 30 (Eco
any side)
Chemie) with a frequency response analyser FRA module for EIS 3 Coating has 15–35% 3 S2-S5 Ri 3 Moderate
measures. The frequency range scanned was from 100 kHz down flaked along
to 1 mHz and the signal amplitude was 20 mV rms peak to peak. most of the
For impedance data analysis the Simplex Method was employed, incisions to 1/8
inch (3.2 mm of
in agreement with previous investigations [2,18]. Coatings under any side)
study were organized in group 1 (single coats 1 and 2) and group 2 4 Coating has 35–65% 4 S2-S5 Ri 4 Considerable
(coatings systems and the ES topcoat), as explained previously, to flaked of most
ease the analysis and comprehension of the results. EIS measure- of the X area
under the tape
ments were repeated by triplicate (for each coating) in order to get
5 Coating has >65% 5 S2-S5 Ri 5 Severe
the reproducibility of the results. In line with the above-mentioned, flaked far away
at least three replicates (coated steel) for each coating under study of the X area
were prepared. DPF-degradation of the paint film in the incision.
Several techniques were employed for surface characterization a
UNE-EN ISO 4628-1: 2003.
of samples (before and after the tests) such as scanning electron b
Method A.
32 M. Echeverría et al. / Progress in Organic Coatings 92 (2016) 29–43

5 5

Blistering performance

Rusting performance
4 4

3 3

2 2

1 1

0 0
0 120 503 1001 1290 1385 0 120 503 1001 1290 1385

Exposure Time (hours) Exposure Time (hours)

5 5

Adhesion performance
4 4
DPF performance

3 3

2 2

1 1

0 0
0 120 503 1001 1290 1385 0 120 503 1001 1290 1385

Exposure Time (hours) Exposure Time (hours)

System 1 System 2 System 3 System 4

Fig. 1. Macroscopic failures of the coating systems (group 1) during accelerated SST at 1 (0 h), 2 (120 h), 3 (503 h), 4 (1001 h), 5 (1290 h) and 6 (1385 h), respectively.

Table 4 samples, taking into account that it was evaluated, not as a failure,
Data of the coatings performance (0-5 scale, see Table 3) after the salt spray test
but as an indication that a failure has taken place. The ordering of
(group 1).
the group 1 in terms of protection efficiency follows the sequence:
Coatings Time (h) Blistering Rusting DPF Adhesion coating 1 > coating 3 > coating 4 > coating 2. Thus, coating 1 has
1 0 0 0 0 1 shown a slight adhesion loss (<5%) from the beginning to the end,
120 0 0 0 1 which can be considered almost negligible. On the contrary, the
503 0 0 0 1 worst behaviour is observed for coating 2 in almost all the fail-
1001 0 0 0 1
ures considered. This coating presented the lowest performance
1290 0 0 0 1
1385 0 0 0 1 of blistering (Table 3) with a level of 4(S2) from 120 h onwards.
SD 0.10 0.29 0.19 0.19 Also, the lost of adhesion of coating 2 was determined between
2 0 0 0 0 1 5-15% after 120 hours of test (Table 3) and it steadily increased to
120 4 1 0 2
35–65% from 1290 h on. In relation to this, rusting has appeared
503 4 2 0 3
1001 4 3 0 4 on the surface of coating 2 from 120 h onwards (oxidation level
1290 4 4 0 4 Ri3 after 1001 h of exposition, Table 3), similarly to the observa-
1385 4 4 1 4 tions related to blistering defect. This suggests that blistering could
SD 0.19 0.19 0.29 0.19 be the cause of rusting formation. It should be also noticed that
3 0 0 0 0 0
adhesion was taking place gradually, contrarily to blistering, indi-
120 0 0 0 0
503 0 0 0 0 cating that the blistering onset is not associated with the adhesion
1001 1 0 0 0 lost. So the superiority of the epoxy zinc-rich single coat (coating
1290 1 0 0 0 1) is demonstrated, especially when compared with the epoxy sin-
1385 1 0 0 0
gle coat pigmented with zinc phosphate and micaceous iron oxide
SD 0.19 0.29 0.29 0.19
4 0 0 0 0 1
(coating 2).
120 0 0 0 1 Considering that coating systems 1A, 1B, 2A and 2B (group
503 1 0 0 1 2) were submitted to the SST (fast evaluation), where almost no
1001 1 1 1 1 defects were required to pass the assay; it was decided to repre-
1290 1 1 1 2
sent the performance of blistering, rusting, DPF and adhesion in a
1385 1 1 1 2
SD 0.19 0.10 0.38 0.29 table for a better comprehension (Table 5). The standard deviations
and the pass/fail threshold values for each defect (last row of the
table) are presented (Table 5). The standard deviation values repre-
sent the total variation of each failure at the end of the experiment
 M. Echeverría et al. / Progress in Organic Coatings 92 (2016) 29–43 33

Table 5 (Table 4). It is interesting to notice the higher corrosion resistance of

Results of the coatings performance evaluation (0-5 scale, see Table 3) after the salt
the epoxy–siloxane-based coating systems 1A and 2A with regard
spray test (group 2). Pass/fail limit values are represented in the last row.
to those with the traditional polyurethane topcoat (1B and 2B), even
Coatings Time (h) Blistering Rusting DPF Adhesion though a lowest performance of coating 2 was demonstrated pre-
1A 0 0 0 0 1 viously. The absence of rusting could be closely related to the good
120 0 0 0 1 performance of blistering, DPF and adhesion failures with exposure
240 0 0 0 1 time. The best performance of coating 2 may be attributed to the
480 0 0 0 1
beneficial influence of the ES used as topcoat (coating system 2A).
SD 0.14 0.14 0.14 0.29
1B 0 0 0 0 1 This further evidences that coating 2 requires another single coat to
120 0 0 0 1 enhance its anticorrosive protection. These benefits, together with
240 0 0 0 1 widely known epoxy–siloxanes advantages such as their low VOC
480 2a 0 0 2a
levels, absence of isocyanate, high heat and UV radiation stability,
SD 0.29 0.14 0.29 0.29
2A 0 0 0 0 1 excellent chemical resistance and lower oxygen and water vapour
120 0 0 0 1 permeability [8], make them a preferred option to be used as anti-
240 0 0 0 1 corrosive materials. In addition, previous results from our research
480 0 0 0 1 group have proved the low permeation of this hybrid coating by
SD 0.43 0.29 0.14 0.29
determining the values of diffusion coefficients and water volume
2B 0 0 0 0 1
120 0 0 0 1 fraction in a cyclic experiment [19] which underscores the suitabil-
240 0 0 0 1 ity of this kind of coatings.
480 1a 0 1 1
SD 0.14 0.14 0.29 0.58
Pass/fail limit 0 0 1 1

DPF, degradation of the paint film; SD, standard deviation. 3.2. EIS measurements analysis
a
Values over the pass/fail limit.

Impedance data offer valuable information related to the elec-

(1385 h and 480 h, see Tables 4 and 5, respectively). According to trochemical processes taking place in the coating and will influence
the data, the best protective properties of coating systems 1A and its protective properties. As previously explained in Section 2, sam-
2A can be clearly distinguished, since no failures after 480 h in the ples under study were organized in two groups for analysing the
SST are detected. Additionally, data from coating systems 1B and impedance results. The first group comprises the two single coats
2B reveal a good performance against corrosion, although some (1: ZRP and 2: ZPM) and the second group includes the coating
defects at 480 h (blistering and adhesion loss or DPF) can be seen systems (1A, 1B, 2A, 2B and 3) and the ES single coat (4), where

A 30 B 150
day 1
120k 30
1 mHz
day 16
20 1 mHz
- Imaginary Part (ΜΩ. cm )

day 30
- Imaginary Part (kΩ. cm )
2

80k
2

1 Hz 1 Hz

0.01 Hz 10
20 40k 100
0
0 10 20 30
0
0 40k 80k 120k

10 50 0.1 Hz

3.98 mHz
0.1 Hz
99 days
1 Hz 0.1 Hz 204 days
287 days
0 0
0 10 20 30 0 50 100 150
2
Real Part (ΜΩ. cm ) Real Part (kΩ. cm )
2

C 300 D 100
0.8 4
day 5
1 mHz day 10
- Imaginary Part (ΜΩ. cm )

day 29
2

- Imaginary Part (kΩ. cm )

2

0.01 Hz
0.4 75 2 100 Hz 10 kHz
200

0.0 50 0
0.0 0.4 0.8 0 2 4
6.30 mHz
0.1 Hz 0.1 Hz
100
1.58 mHz
1 Hz 25
day 1 0.01 Hz
day 2
day 5 1 mHz
0 0
0 100 200 300 0 25 50 75 100
2
Real Part (ΜΩ. cm ) Real Part (kΩ. cm )
2

Fig. 2. Impedance spectra of coating 1 (A and B) and coating 2 (C and D), respectively, after continuous immersion in 3% by weight NaCl solution.
34 M. Echeverría et al. / Progress in Organic Coatings 92 (2016) 29–43
the letters A (ES) and B (PUR) indicate the type of topcoat and the
numbers 1 and 2 the primer employed (Table 1).
Due to some dispersion in the experimental data (mostly in the
low frequency region) of some specific days of the coatings tested,
the Nyquist and impedance modulus graphs were not represented
in the same day for each coating. Despite this, the data correspond-
ing with the most similar days in each case have been compared.
Also, the small variation observed in days (day selected and finally
plotted) did not motivate any substantial change in the coating
response (impedance values).
3.2.1. Impedance results of ZRP and ZPM single coats
The Nyquist diagram of the zinc-rich epoxy (coating 1: ZRP) and
the epoxy coating containing zinc phosphate and micaceous iron
oxide (coating 2: ZPM) are visualized in Fig. 2. A clear difference in
the electrochemical behaviour of both coatings can be noticed. In
the first minutes of measurements, the coating 1 has recorded high
impedance values (Mohms cm2 ), since the zinc pigments inside the
ZRP have not been activated yet. After a few hours, a fast decay of the
real impedance (around kohms cm2 ) at lower frequency is depicted.
This behaviour is typical for coatings with active pigments in their
composition. The impedance values of coating 2 have also dimin-
ished with time to kohms cm2 , which is indicative of zinc phosphate
particles activation. The faster deterioration of the protective prop-
erties of coating 2 than coating 1 after 30 days of exposure can be
highlighted. On one hand, the sacrificial pigments (zinc particles)
present in zinc-rich coatings are preferentially oxidized to protect
the metallic substrate trough a cathodic protection mechanism. On
the other hand, inhibitors pigments like zinc phosphate release
water-soluble species which go from the coating to the base, thus
inhibiting the corrosive process due to the formation of protective
single coats (passive layers) on the anodic sites through an anodic
passivation mechanism [1]. Water is necessary for pigments acti-
vation which explains the higher impedance values at initial times
(intact coating). Subsequently, the entry of electrolyte through the
pores promotes the rapid activation of the particles, as evidenced
by the fast impedance evolution to lower values [1,18,20].
The activation of zinc pigments occurs once the water wets the
particles and reaches the metallic substrate establishing electrical
contact among zinc particles, and between them and the sub-
strate. A fast elimination (some minutes) of the native oxide film
Fig. 4. Visual aspect of the coated samples at the end of EIS measurements. 1 (287 days), 2 (29 days), 1A (219 days), 1B (200 days), 2A (405 days), 2B (414 days), 3 (467 days)
and 4 (341 days).
-600
(1) (2)
OCP vs SCE (mV)
-750
-900
-1050
0 10 20 30 40 50 60 70
Time (days)
Fig. 3. Evolution with immersion time of the open circuit potential of the epoxy
zinc-rich coating. Horizontal dashed line indicates the end of cathodic protection
mechanism and the vertical one, the limit between period 1 (cathodic protection)
and 2 (barrier protection), respectively.
covering the zinc particles precedes the aforementioned process
[20]. Later, two main periods in the service life of ZRP can be clearly
distinguished in Fig. 3. The first period, “cathodic protection”, is
characterized by an initial decrease of the OCP of the steel/ZRP
system in sodium chloride to more negative values, reaching a
maximum value (around −1000 mV vs SCE) characteristic of a zinc
plate in this medium, which evidences the zinc pigments acti-
vation. Then, a continuous increase to about −850 mV vs SCE is
recorded, in which the cathodic protection is not efficient. Now,
the second period “barrier protection” is started, where the protec-
tion mechanism is mainly based on a barrier effect, reinforced by
the accumulation of zinc corrosion products inside the pores, thus
retarding the corrosion process. After a time, corrosion products
will appear on the surface confirming the end of the protection.
The above-mentioned is in line with previous works [18,20].
On the other hand, the activation of ZP particles also requires the
presence of water. Some authors have pointed out that the mech-
anism behind the anticorrosive action of ZP is complex and not
well understood yet. Zubielewicz et al. suggested that ZP solubil-
ity (in neutral conditions) was too weak to take part in reactions
 M. Echeverría et al. / Progress in Organic Coatings 92 (2016) 29–43 35

inhibiting corrosion [21]. In line with this, previous authors have A 13

10
demonstrated the improvement of the barrier properties of ZP pig-
mented coatings [22]. In addition, an active corrosion protection

Impedance Modulus (Ω. cm )

11

2
10
motivated by the phosphatisation of the iron surface [23], or the
formation of ZP and hydroxides thin coats adsorbed on the iron
9
surface [24], has been reported. Some of the most important ele- 10
ments influencing the ZP efficiency are the hydration ratio [25], the
7
pigment volume concentration (PVC) [26], the morphology [27], 10
and possible interactions with the binder (e.g. epoxy resin) [22]. As
was noted, the activation mechanism of ZP pigments is not com- 10
5

pletely clear, but the improvement of the protective properties of

the coatings due to its presence has been validated. 10 -3
3
-2 -1 0 1 2 3 4 5
The MIO pigments are also included in the composition of the 10 10 10 10 10 10 10 10 10
epoxy coating (coating 2), together with ZP ones, for getting a com- B 10
12

bined action and an improvement of the corrosion protection of 10

11

Impedance Modulus (Ω. cm )

2
the substrate. It is an inert particle with lamellar shape which is 10
10
known for its benefits as a barrier pigment. Its function is to isolate
9
the metallic substrate from the aggressive media [5,28,29]. 10
In summary, coating 2 has shown a fast diminution of the global 10
8

impedance with time, leading to a deterioration of its protective 7

10
properties in just 1 month (29 days), as expected from the occur-
6
rence of blistering from day 8 on and the observation of rusting 10
(Fig. 4), contrarily to the behaviour observed for coating 1 during 10
5

287 days. Fig. 4 depicts the visual aspect of coatings tested at the 4
10 -3
end of EIS measurements. In most of the cases, the experiments 10 10
-2
10
-1
10
0
10
1
10
2
10
3
10
4
10
5

have ended when some defects have appeared on the surface.

Frequency (Hz)

3.2.2. Coating systems and topcoat impedance results Fig. 5. Comparison of the impedance modulus between 1A and 1B (A) and between
The impedance modulus and phase angle comparison (at ini- 2A and 2B (B) coating systems, respectively, at initial and final times of EIS test. 1A:
d 1 (䊐) and d 220 (), 2A: d 30 (䊐) and d 405 (), 1B: d 2 (䊏) and d 200 (), 2B: d
tial and final times of exposure) of the coatings 1 and 2 with
30 (䊏) and d 401 ().

1.4

A 500 B 30
day 1 day 140
day 30 day 190
day 101 0.7
day 219 8
- Imaginary Part (ΜΩ. cm )
- Imaginary Part (GΩ. cm )

1 mHz
2

400 1.58 mHz

10 Hz

20 0.0
300 4 0.0 0.7 1.4

0.3 1 kHz
1 Hz 1 mHz

200 0.2 0
10 0 4 8
1 mHz
0.1 1 mHz
100 0.1 Hz
100 Hz 1 Hz

0.0
0.0 0.1 0.2 0.3
0 0
0 100 200 300 400 500 0 10 20 30
2
Real Part (GΩ. cm )
2
Real Part (ΜΩ. cm )
0.12
C 30
day 2
D 6
120M day 108
day 30 day 143
days 60
- Imaginary Part (GΩ. cm )

day 200
- Imaginary Part (ΜΩ. cm )
2

0.06 1 mHz
1 Hz 0.8
60M 100 Hz
20 1 mHz 4
0.00
0.4 0.00 0.06 0.12
0
0 60M 120M
0.1 Hz
10 2 0.0
0.0 0.4 0.8
1 mHz

3.98 mHz

0 0
0 10 20 30 0 2 4 6
2
Real Part (GΩ. cm ) Real Part (ΜΩ. cm )
2

Fig. 6. Nyquist diagrams of coating systems 1A (A and B) and 1B (C and D), respectively, for immersion in 3% by weight NaCl solution.
36 M. Echeverría et al. / Progress in Organic Coatings 92 (2016) 29–43

A 60 B 28
day 1 day 198
day 30 day 305 6
39.85 mHz
day 101

- Imaginary Part (GΩ. cm )

- Imaginary Part (GΩ. cm )

day 405

2
21
40 3
20 0.01 Hz
0.1 Hz
14 1 Hz
0
0 3 6
10 0.1 Hz
20
1 mHz 7
0.1 Hz 1 mHz
1 mHz
0
0 10 20 1 mHz

0 0
0 20 40 60 0 7 14 21 28
2 2
C Real Part (GΩ. cm ) D Real Part (GΩ. cm )
40 100
day 1 day 197
day 30 4.0 day 304

- Imaginary Part (ΜΩ. cm )

day 414
- Imaginary Part (GΩ. cm )

2
2

day 100
30 75
2.0 10 Hz
0.1 Hz
1 mHz
20 160M 50
0.0
0.0 2.0 4.0

80M
10 25
1 mHz 1 mHz
10 Hz
1 mHz
0
0 80M 160M
0 0
0 10 20 30 40 0 25 50 75 100
2 2
Real Part (GΩ. cm ) Real Part (ΜΩ. cm )

Fig. 7. Impedance spectra evolution of coating systems 2A (A and B) and 2B (C and D), respectively, for immersion in 3% by weight NaCl solution.

A 280 B 400
1.58 mHz day 1
day 28
1.58 mHz
- Imaginary Part (GΩ. cm )

- Imaginary Part (GΩ. cm )

day 106
2

210 300
2.51 mHz
0.01 Hz 3.98 mHz

40
140 200
0.01 Hz
0.1 Hz
20
1 mHz
70 100 0.01 Hz
day 206
day 302
0 day 341
0 20 40
0 0
0 70 140 210 280 0 100 200 300 400
2
Real Part (GΩ. cm ) Real Part (GΩ. cm )
2

5
C 100 D 80
day 1 18
day 33
3
- Imaginary Part (GΩ. cm )

- Imaginary Part (GΩ. cm )

day 103
2

75 60 9 0.1 Hz
1 mHz day 198
0
0 3 5 day 303
50 40 day 467
0
0 9 18
0.1 Hz
0.01 Hz

25 20
1 mHz
1 mHz
0.01 Hz 1 mHz
0 0
0 25 50 75 100 0 20 40 60 80
2 2
Real Part (GΩ. cm ) Real Part (GΩ. cm )

Fig. 8. Impedance spectra evolution of the epoxy–siloxane topcoat (A and B) and the epoxy–polyurethane water-based coating system (C and D), respectively, for immersion
in 3% by weight NaCl solution.
 M. Echeverría et al. / Progress in Organic Coatings 92 (2016) 29–43 37

A 10
5
40
B 10
6
80
Measured Measured
Fitted Fitted

Impedance Modulus (Ω. cm )

Impedance Modulus (Ω. cm ) IZI

2
2

5
10

-Phase Angle (degree)

-Phase Angle (degree)
4
10 θ 60
IZI θ
4
10
3
10 20 40
3
10

2
10 2
20
10

1 1
10 -3 0 10 -3 0
-2 -1 0 1 2 3 4 5 -2 -1 0 1 2 3 4 5
10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10
Frequency (Hz) Frequency (Hz)

C C2 D Cp

Rsol Rsol Cdl

R2 Rp
Ccp
Zfb
Rct
Rcp

Fig. 9. Bode diagram of the measured and fitted data of coating 1 (A) and coating 2 (B), after 204 and 29 days of EIS experiments, respectively. Their corresponding equivalent
circuits C and D are presented, which electrical parameters are summarized in the work.

the two different topcoats are represented in Fig. 5. All the sam- A 10
8
100
ples have demonstrated excellent protective properties after the Measured
Fitted
Impedance Modulus (Ω. cm )

7
EIS assessment. However, there is a clear difference in the elec-
2

10
80

-Phase Angle (degree)

trochemical behaviour between coating systems 1A and 1B and
10
6 IZI θ
between 2A and 2B. The impedance modulus of coating system
1A with the ES topcoat is higher than 1B with the traditional PUR 10
5 60
topcoat, at the beginning and final times, respectively (Fig. 5A).
4
Similar behaviour is observed for coating systems with the coat- 10 40
ing 2 (2A and 2B) (Fig. 5B). In addition, the coating system 2A 3
10
has shown the highest impedance module (around Gohm cm2 ) in
20
accordance with the excellent protective properties after more than 10
2

a year of continuous immersion time in 3% by weight NaCl solu-

1
tion. Although the similar coating system containing PUR topcoat 10 -3 -2 -1 0 1 2 3 4
0
5
10 10 10 10 10 10 10 10 10
(2B) has entailed a lower impedance module (around Mohm cm2 )
after similar exposure time, this result is considered positive. On Frequency (Hz)
the other hand, coating systems 1A and 1B, even with lower values B 10
11
100
(about Mohm cm2 and hundreds of kohm cm2 , respectively) at the
Impedance Modulus (Ω. cm )
2

end of the test, have demonstrated good protective properties. The 9 IZI 80
10
-Phase Angle (degree)

results afforded have indicated an improvement of the corrosion θ

protection efficiency of the coating 2 when a topcoat is added.
7
The Nyquist diagrams of the coated samples (1A and 1B /2A and 10 60
2B) are presented in Figs. 6 and 7, and support previous conclu-
sions. At initial time the global impedance is very high in the order 10
5
40
of Gohms cm2 , which is characteristic of an intact coating (dielec-
tric properties) and it is also related to the first time constant at the 3
20
10
high frequency domain. Subsequently, water and oxygen penetrate Measured
the coating trough pores, affecting the coating resistance and lead- Fitted
1
ing to a decay of the impedance with the immersion time in the 10 -3 0
-2 -1 0 1 2 3 4 5
10 10 10 10 10 10 10 10 10
electrolyte. In line with this, new time constants in the middle and
Frequency (Hz)
low frequency can be appreciated for specimens 1A and 1B (Fig. 6)
and only a second one, in the low frequency region, for 2A (not very Fig. 10. Impedance spectra of the measured and fitted data of coating systems 1A
well defined) and 2B. The visual aspect of the coated panels after (A) and 2A (B), after 190 and 305 days, respectively.
the EIS measurements confirms these results (Fig. 4).
The Nyquist spectra of the ES topcoat are presented in Fig. 8A
and B. The excellent protective properties after 341 days of
38 M. Echeverría et al. / Progress in Organic Coatings 92 (2016) 29–43

Fig. 11. SEM images of the coated panels before and after continuous immersion in 3% by weight NaCl solution. A, C and E represent coating 1, coating 2 and the epoxy–siloxane
topcoat (4) before the test and B, D and F the same coatings at the end of the EIS test. The substrate, the coating and the resin can be observed in each image (from the bottom
to the top).

continuous exposition in 3% by weight NaCl solution is evidenced, equivalent circuit, since only one time constant was observed in
and no macroscopic failures on the surface are detected (Fig. 4). both specimens.
The capacitive behaviour observed during the entire test, typical of
barrier coats at initial times (Fig. 8A and B) is in accordance with 3.3.1. ZRP and ZPM single coats
previous investigations [2]. It is highlighted the excellent corrosion The impedance data of the ZRP were fitted by using a trans-
protection offered by the ES single coat to the metallic substrate. mission line model, for which Eq. (1) is applicable, as previously
reported [18].
3.2.3. Epoxy–polyurethane water-based coating system
√
The impedance diagram of coating system 3 reflects its excel- Zm Rei L (Zm 2 + Rei 2 ) cosh (L ) + 2Zm Rei
ZTL = + √ √ (1)
lent electrochemical performance, with a very high real impedance Zm + Rei (Zm + Rei )  sinh (L )
value in the low frequency region (about 50 Gohm cm2 ) after more
than a year of constant immersion in the electrolyte (Fig. 8C and ZTL is the impedance of the transmission line, L (cm) the thickness of
D). This is in line with the behaviour observed during the SST and the coating, Zm the contact impedance between zinc particles along
the visual appearance of the coated specimens at the end of EIS the transmission line, Rei ( cm) the resistance of the electrolyte
measures (Fig. 4). This coating system has a good combination of inside the coating and  is calculated through the Eq. (2) [18]:
coats, such as a water-based epoxy primer, followed by a water- Zm + Rei
based polyurethane topcoat, promoting a good barrier protection = (2)
Z1
against the electrolyte uptake. The existence of ZP and MIO pig-
ments in the epoxy resin enhances the protective action of the where Z1 is the interfacial impedance of a small area between zinc
coating (ZPM), as previously explained. This is also supported by particles and the electrolyte inside the pores (in parallel to the steel
the polyurethane topcoat, which has been widely employed in substrate) and Zm can be expressed by the Eq. (3), considering the
aggressive marine environments due to its high environmental same performance as in the dry film [18]:
resistance [2,30]. Moreover, the TiO2 pigments presented in both
Rm
coats (primer and topcoat) reinforce the high anti-corrosion, chem- Zm = ˛m (3)
1 + (jωRm Cm )
ical stability at high temperatures as well as permanent stability
under UV exposure [31]. Rm ( cm) and Cm (F/cm) are the contact resistance and contact √
capacitance, respectively, ω (rad/s) the angular frequency, j = −1
3.3. Modelling of the EIS data to equivalent circuit models and ˛m is the dispersion of the contact impedance along the trans-
mission line. Z1 is determined by considering the double layer
The experimental impedance data were fitted to the convenient capacitance (C1 , F/cm) and the faradaic resistance (R1 ,  cm3 )
equivalent electrical circuit model with the aim of shedding more related to the zinc dissolution, which can be stated by the Eq. (4) as
light on the electrochemical processes taking place in the system [18]:
composed by electrolyte/steel/coating.
The epoxy–polyurethane water-based coating system (3) R1
Z1 = ˛1 (4)
and the epoxy–siloxane topcoat (4) were not modelled to an 1 + (jωR1 C1 )
 M. Echeverría et al. / Progress in Organic Coatings 92 (2016) 29–43 39

Fig. 12. Mapping of chemical elements of the ZRP coated steel cross-section surface at the end of EIS test.

where ˛1 is the dispersion of the interfacial impedance. Also, Rsol = 133.05  cm2 , R2 = 1.80 × 104  cm2 , C2 = 3.14 × 10−9 F/cm2 ,
additional resistance (R2 ,  cm2 ) and capacitance (C2 , F/cm2 ) are ˛2 = 0.75.
required at lower frequencies, which are associated with the Rm = 2.24 × 104 k cm, Cm = 0.14 × 10−9 F/cm, ˛m = 0.9,
cathodic reaction (oxygen reduction) taking place over the zinc par- R1 = 2.30 × 103  cm3 , C1 = 0.12 F/cm, ˛1 = 0.55,
ticles in the upper part of the coating (close to the electrolyte). R2 is Rei = 2.00 × 103 k cm, L = 5.5 × 10−3 cm
in series with the impedance of the transmission line ZTL and ˛2 is
the dispersion parameter of the R2 C2 time constant. Moreover, R2 is These values are referred to the sample surface (10.17 cm2 ) and
in series with another resistance, Rsol ( cm2 ), related to the solu- the thickness of the coating (L, see Table 1) taking into account
tion resistance outside the coating. Hence, the global impedance for that both Zm and Rei act perpendicularly to the steel surface and Z1
a zinc-rich coating at the end of its service life (last stage of period parallel to it.
2, three time constants) is calculated through the Eq. (5) [18] On the other hand, the fitting results of the ZPM after 29 days of
experiments are presented below:

R2
Z(ω) = Rsol +   (5) Rsol = 52  cm2 , Rp = 1.40 × 103  cm2 , Cp = 3.70 × 10−9 F/cm2 ,
˛2 R2
1 + (jωR2 C2 ) + R2 +ZTL ˛p = 0.54
Rct = 1.44 × 103  cm2 , Cdl = 175.42 × 10−6 F/cm2 , ˛ct = 0.73,
Rcp = 13.13 × 103  cm2 , Ccp = 167.48 × 10−6 F/cm2 , ˛cp = 0.68
The good agreement between measured and fitted data can be
visualized in Fig. 9A, together with the equivalent circuit model The good agreement between experimental and calculated data
employed (Fig. 9C), after 204 days of experiment. The calculated is presented (Fig. 9B). An electrical equivalent circuit (Fig. 9D) with
parameters are listed below: three time constants (in parallel) hierarchically distributed was
40 M. Echeverría et al. / Progress in Organic Coatings 92 (2016) 29–43
Fig. 13. Mapping of chemical elements of the coating 2 coated steel cross-section surface after continuous immersion in 3% by weight NaCl solution.
considered, where Rp Cp is the high frequency time constant associ-
ated with the barrier characteristics and gives us information about
the pore resistance and coating capacitance respectively. Rct Cdl is
the second time constant, related to the resistance and capacitance
of the electrochemical double layer (corrosion processes develop-
ing at the metal-coating interface) and a third time constant (Rcp Ccp )
in the lowest frequency domain, related to the corrosion products
formation. Moreover, Rsol represents the electrolyte resistance, as
explained before.
3.3.2. Coating systems with ES and PUR topcoats (1A, 1B, 2A and
2B)
Coating systems 1A and 1B have shown three time constants
located in the high, medium and low frequency range, respectively,
as was already noted. To model the experimental impedance data,
the same electrical circuit model employed by coating 2 (with the
same meaning of each electrical parameter) was used. The good
agreement between experimental and calculated data for coating
system 1A, after 190 days of constant immersion in the electrolyte,
can be observed (Fig. 10A). The calculated parameters are compiled
and presented below:
Rsol = 0.25  cm2 , Rp = 2.21 × 106  cm2 , Cp = 93.00 × 10−12 F/cm2 ,
˛p = 0.94
Rct = 4.57 × 106  cm2 , Cdl = 0.12 × 10−6 F/cm2 , ˛ct = 0.5,
Rcp = 6.00 × 106  cm2 , Ccp = 0.24 × 10−3 F/cm2 , ˛cp = 0.27
A similar behaviour was also checked for 1B coating system
(data not shown). Moreover, the experimental EIS measurements of
coating system 2A were modelled with a two time constants equiv-
alent circuit, where the first constant (Rp Cp ) and the second one
(Rct Cdl ) have the same meaning previously mentioned for coating
2. The former circuit (for 1A and 1B coating systems) was employed,
but only the first and the second time constants were considered.
The measured and calculated data of the coating system 2A after
305 days of experiments were suitably fitted (Fig. 10B). The fitting
parameters of coating system 2A after 305 days of experiment are
summarized below:
Rsol = 10.01  cm2 , Rp = 7.14 × 109  cm2 ,
Cp = 115.70 × 10−12 F/cm2 , ˛p = 0.93
Rct = 9.45 × 109  cm2 , Cdl = 43.39 × 10−9 F/cm2 , ˛ct = 0.53,
 M. Echeverría et al. / Progress in Organic Coatings 92 (2016) 29–43 41

Fig. 14. Chemical elements mapping of the epoxy–siloxane coated steel cross-section surface after continuous immersion in 3% by weight NaCl solution.

It is of our interest to further study the electrochemical mecha-
nism of the epoxy–siloxane coating as a single coat and as a topcoat
in a multilayer system in future studies. This will allow a better
comprehension of these new coating materials.
3.4. Surface characterization analysis
SEM images of the ZRP and ZPM single coats (coatings 1 and 2)
and the ES single coat (coating 4), before and after EIS measure-
ments, can be visualized in Fig. 11. The images of the ZRP reveal
some slight colour changes (from white to light brown) of the zinc
particles (located from the middle to the upper part of the single
coat), at the end of the EIS measurements (Fig. 11B). The detec-
tion of a higher quantity of chlorine, oxygen and zinc in this area at
the end of the experiment (after 287 days of EIS test), by analyzing
the X-ray map obtained (Fig. 12); suggests the formation of zinc
corrosion products. The typical products formed are zinc hydrox-
ide or zinc hydroxichlorides, depending on the local pH (formation
of OH− due to the oxygen reduction) and the chloride concentra-
tion, which are located in the upper part of the coating film. This
behaviour is in agreement with the end of the service life of a ZRP
(barrier protection reference period), in agreement with previous
studies [18]. In relation to coating 2, some notorious morphological
changes after continuous immersion in 3% by weight NaCl solution

Fig. 15. SEM images of the coated panels before and after continuous immersion in 3% by weight NaCl solution. A, C and E are the coating systems 1A, 1B and 2A, respectively,
before the test and B, D and F the same ones at the end of the assay. The substrate, the primer, the topcoat and the resin (of each coating system) can be observed in each
image (from the bottom to the top).
42 M. Echeverría et al. / Progress in Organic Coatings 92 (2016) 29–43
Fig. 16. Chemical elements mapping of the 1B coated steel cross-section surface after constant immersion in 3% by weight NaCl solution.
are detected, as a consequence of the formation of a thick single
coat between the coating and the metallic substrate (Fig. 11D).
The X-ray map analysis of this area (after the test) indicates the
existence of iron and oxygen which is probably associated to fer-
rous corrosion products formed (Fig. 13). Additionally, the ES coat
seems to remain morphologically unaltered after 1 year of contin-
uous immersion in the electrolyte (Fig. 11F). This is related to the
beneficial effect of the siloxane chains (Si O Si) distributed in the
whole coating but more reinforced in the upper border (more con-
centration of Si and O), as can be observed in Fig. 14. Titanium was
also detected by mapping in the topcoat, which should be related
to the good properties of TiO2 pigments, as already pointed out.
On the other hand, morphological changes of coated panels 1A, 1B
and 2A (2B similar to 2A, not shown) before and after EIS measure-
ment are depicted in Fig. 15. Only the coating system 1B presented
changes in the morphology, since a thick and little cracked single
coat in the coating/substrate interface can be inferred, as a result of
a higher content of oxygen and iron in this area (Fig. 16) related to
the presence of iron oxides compounds. No morphological changes
appeared in the cross-section of the epoxy–polyurethane water-
based coated samples before and after EIS test. Thus, no images
were shown. The detection of zinc, phosphorous, iron, oxygen and
titanium elements in the water-based epoxy primer (by X-ray map-
ping, figure not shown), closely related to the presence of ZP, MIO
and TiO2 anticorrosive pigments in the formulation; promoted
the good corrosion protection. Finally, the surface characteriza-
tion findings are in agreement with the accelerated SST and the
impedance measurements results, respectively.
4. Conclusions
The good protective properties of the ZRP, the epoxy–
polyurethane water-based coating system and the epoxy–siloxane
topcoat (group 1) have been demonstrated after 1385 h in the SST
without macroscopic defects. A better anticorrosive performance of
the coating systems with the epoxy–siloxane topcoat (1A and 2A)
than for those (1B and 2B) with the traditional polyurethane top-
coat was evidenced for the same test. An important improvement
of the protective action of coating 2 (ZPM) was concluded when
the topcoats were added. Similarly, coating 1 (ZRP) offered good
protection to the base during 287 days of constant immersion in
3% by weight NaCl solution, motivated by the combined action of
the cathodic and barrier protection mechanisms. The impedance
module of coating system 1A with the epoxy–siloxane topcoat
 M. Echeverría et al. / Progress in Organic Coatings 92 (2016) 29–43
was higher than 1B with the traditional polyurethane topcoat, at
the beginning and final times, respectively. Similar behaviour was
observed for coating systems with coating 2 (2A and 2B). Besides,
coating system 2A led to the highest impedance module (around
Gohm cm2 ) after more than a year of experiment. The capacitive
behaviour of the top epoxy–siloxane coat after 341 days of expo-
sure, confirmed the excellent protection offered to the substrate,
probably due to its high resistance to water uptake. Furthermore,
the suitable combination of the water-based epoxy and the water-
based polyurethane coats, together with the higher thickness of
this system, led to the observed good electrochemical performance
(global impedance value around Gohm cm2 ) recorded for more
than a year. A higher concentration of silicon and oxygen in the
epoxy–siloxane single coat (determined by X-ray mapping) vali-
dated its excellent corrosion protection.
Acknowledgements
The authors are very grateful to the University of Vigo (Spain) for
funding through a PhD grant and a study stay grant in Florida Inter-
national University. Also, we thank the valuable support received
by ENCOMAT group from the University of Vigo. Additionally,
the authors thank the important support of HEMPEL laboratories
(Barcelona, Spain) for the supply of coatings and samples prepara-
tion.
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