Progress in Organic Coatings 54 (2005) 344352

Performance of paint systems with polyurethane topcoats, proposed for

atmospheres with very high corrosivity category
D. Santos , C. Brites, M.R. Costa, M.T. Santos
INETINational Institute of Engineering, Technology and Innovation, I.P. Estrada do Paco do Lumiar, 1649-038 Lisboa, Portugal
Received 11 July 2005; accepted 27 July 2005

Abstract
The EN ISO Standard 12944-5 describes the types of paint and paint systems commonly used for corrosion protection of steel structures.
In this work four paint systems, applied on steel, including polyurethane topcoats, recommended for atmospheres with high corrosivity (C5
category), codified by 14, were studied. Systems 1 and 4 include zinc rich primers and epoxy/polyamide intermediates, system 2 has solvent free
epoxy/polyamide primer and intermediate and, system 3 is a hybrid system with vinylacrylic water based primer and a high solids epoxy/polyamide
intermediate. Systems 24 have acrylicpolyurethane topcoats and, the topcoat of the system 1 was identified as an aliphatic polyurethane.
According to EN ISO 12944-6, water condensation and neutral salt spray tests were performed. Three exposure times were considered taking
into account the durability ranges of paint systems: low, medium and high, respectively. The paint systems were complementary submitted, during
30 days, to ultraviolet radiation with water condensation test according to ASTM G 154. At the same time, natural exposure was conducted in the
marine atmosphere of Sines, with very high corrosivity (>C5).
The paint adhesion, before and after artificial ageing, was evaluated by cross-cut test and, for the systems with dry thickness greater than 250 m,
by pull-off test. Visual inspections were carried out.
For the exposure in UV radiation test chamber and at test site, gloss reduction, colour change and chalking were measured. Chemical changes
on polyurethane topcoats exposed in the UV radiation test chamber were studied by Fourier transform infrared spectroscopy (FTIR).
In spite of the higher aesthetic degradation by UV radiation, of the aliphatic polyurethane topcoat of the system 1 relatively to the
acrylicpolyurethane topcoats of the other systems, system 1 with ethyl silicate zinc rich primer and epoxy intermediate, was the one that
presented the best corrosion protection when exposed in artificial and natural salty environments. At the test site, the worst anticorrosive behaviour
seems to be presented by the system 2 with two coats of solvent free epoxy paint.
Published by Elsevier B.V.
Keywords: Polyurethane; Salty environments; Corrosion protection; Paint systems

1. Introduction
Corrosion may lead to damage of unprotected steel exposed in
different environmental conditions. Steel structures can be protected from corrosion by paint coatings applied on them. The
types of paint and paint systems commonly used for corrosion
protection of steel structures are described in EN ISO 12944-5
[1]. Among them are the polyurethane coatings. Polyurethanes
have been used in the coating industry for approximately 45
years [2]. They have shown excellent performance and great versatility in many applications. In a simple way, urethane coatings
contain urethane linkages, NHCO , that are formed through a

Corresponding author. Tel.: +351 21 0924782; fax: +351 21 7163796.

E-mail address: dulcinea.santos@ineti.pt (D. Santos).

0300-9440/$ see front matter. Published by Elsevier B.V.

doi:10.1016/j.porgcoat.2005.07.010

rearrangement reaction when an hydroxyl group reacts with an

isocyanate group. Other linking groups, like allophanate, urea,
biuret and isocyanurate, may be found in polyurethane coatings
[3].
Two features of polyurethane coatings are high cost and special handling of the potentially hazardous isocyanates that are
used in the manufacture or as curing agents. However, the various industry segments have been able to develop safe handling
and use methods that overcome one of the objections [3].
In this work, four paint systems applied on steel, including polyurethane topcoats, recommended for atmospheres with
high corrosivity category were studied. Three of them have
acrylicpolyurethane topcoats and, the topcoat of the other system is an aliphatic polyurethane.
The performance of the paint systems was evaluated in artificial and natural conditions exposure. EN ISO 12944-6 [4]

D. Santos et al. / Progress in Organic Coatings 54 (2005) 344352

specifies laboratory test methods and test conditions for the

assessment of paint systems for corrosion protection of steel
structures. The test results are to be considered as an aid in the
assessment of paint systems for use in the various corrosivity
categories [5] and not as an exact information for determining
durability. Many factors can influence the progress of coating
degradation, so, artificial ageing will not necessarily have the
same effect as natural exposure.
2. Experimental
2.1. Materials
The main composition of the studied paint systems, codified
by 14, are presented in the Table 1. Excluding the system 1
with grey colour, the white coloured systems, were applied on
grit blasted steel to Sa 212 degree according to ISO 8501-1 [6].
2.2. Methods
2.2.1. Laboratory tests
According to EN ISO 12944-6 [4], water condensation [7]
and neutral salt spray [8] tests were made. Taking into account
the durability ranges of paint systems (low, medium and high),
three exposures times were considered: 240, 480 and 720 h for
water condensation and, 480, 720 and 1440 h for salt spray [4]. A
Q-panel test chamber, model QCT/ADO, and an Erichsen cabinet, model 606, were used for water condensation and salt spray
tests, respectively. Visual inspections were performed according
to EN ISO 4628 [911].
EN ISO 12944-6 [4] requires that after salt spray test [8], any
corrosion from the scratch does not exceed 1 mm when calculated according the following equation:
M=

CW
2

(1)

where W is the original width of the scratch and C the maximum

width of corrosion across the scratch, both in millimetres. For
this evaluation, the coating around the scratch was removed by
pickling, after salt spray.

345

The assessment of coating adhesion to the substrate, before

and after ageing, was carried out by cross cut test [12] and, for the
systems with dry thickness greater than 250 m, by pull-off test
[13]. To evaluate the adhesion before exposure, by pull-off test,
the systems were applied on steel with 15 mm thickness, in order
to eliminate the influence of steel thickness in coating adhesion
[14]. An Erichsen, model 202, equipment and a cyanoacrylate
adhesive were used.
The paint systems were complementary exposed to ultraviolet radiation with water condensation in accordance with ASTM
G 154 [15], during 30 days, in an ATLAS UVCON test chamber equipped with fluorescent UVB-313 lamps, operating with a
cycle composed by 4 h UV at (60 3) C black panel temperature and 4 h condensation at (50 3) C black panel temperature.
An insulated black panel thermometer was used to measure and
control temperature [16]. During and after UV exposure, colour
change, gloss and chalking were measured according to ISO
7724-2 and 3 [17], EN ISO 2813 [18] and EN 13523-14 [19],
respectively. For absolute and colour difference measurements,
an X-Rite 948 spectrocolorimeter was used, which provides
0 /45 geometry and allows the acquisition of values in CIELAB
units, with D65 illuminate and 10 observer angle. Gloss and
chalking were measured with a Rhopoint gloss meter, NovoGloss and with an Erichsen chalking master optical instrument,
model 516, respectively.
2.2.2. Outdoor exposure
The paint systems were exposed, during 18 months, in the
marine test site of Sines with very high corrosivity category
(>C5) [5] and high UV radiation.
Visual inspections, colour change, gloss and chalking
measurements were performed as described for laboratory
tests.
2.2.3. Infrared spectroscopy studies
Chemical changes on polyurethane topcoats surfaces exposed
in the UV radiation test chamber were studied by Fourier transform infrared spectroscopy (FTIR). The spectra were obtained
using a spectrophotometer Nicolet Magna system 560, equipped
with a photoacoustic detector (PAS/FTIR) MTEC 300, in the

Table 1
Main composition of paint systems
Code

Primer

Intermediate

Topcoat

Total thickness (m)

Binder

Pigment

Thickness
(m)

Binder

Thickness
(m)

Binder

Thickness
(m)

Nominal

Measured
(mean)

Ethyl silicate

Zinc powder

1 75

Epoxy polyamide

1 150

1 50

275

268

Epoxy
polyamide
without solvents
Vinyl acrylic
water-borne

Anticorrosive
pigments

1 140

Epoxy polyamide
without solvents

1 130

Aliphatic
polyurethane
Acrylicpolyurethane

1 50

320

284

Carbon black
and
anticorrosive
pigments
Zinc powder

80

Epoxy polyamide
high thickness and
high solids

100

Polyurethane high
solids

60

240

254

1 50 5

Epoxy

2 70 5

Acrylicpolyurethane

1 50 5

220260

268

3a

Epoxy
a

Hybrid system.

D. Santos et al. / Progress in Organic Coatings 54 (2005) 344352

346

4000400 cm1 range. OMNIC software was used for data

acquisition and processing.
3. Results and discussion
The systems under study presented good behaviour when
submitted to 720 h of water condensation [7]. A small quantity
of blisters of very small size on the panel surface of systems
1 and 2 after 480 h exposure was only verified. However, for
the system 1, the appearing of blisters was verified only on the
surface of some panels (the panels were exposed in triplicate for
each test time) and seems to be due to troubles with the coating
application on those panels. This is supported by the results
of pull-off test, because some panels showed nature of failure
different from that of the greatest part of the tested panels. The
scratch made on the coating only presented larger or smaller
amount of corrosion (red and/or white), not having blistering
around it, for all systems.
Table 2 presents the results of salt spray test [8] and Fig. 1
shows the aspects of the samples after the three exposure times
considered [4].
For systems 1, 2 and 4, the results of adhesion before and
after ageing, obtained using pull-off test, are presented in
Fig. 2. All these systems presented good adhesion (rupture
strength higher than 5 MPa when applied on steel with 15 mm
thickness), which did not change significantly after ageing. The
same thing occurred for the system 3, with cross-cut adhesion
having classification 1, before and after water condensation and
salt spray tests.

Concerning the results of laboratory tests obtained and,

mainly those of neutral salt spray, which in this study are more
limitative, the systems can be considered suitable for use in
C5-M atmospheres, the system 1 being classified as medium
durability and the other three systems as low durability.
The results of chalking, colour change and gloss measurements obtained after UV radiation test are presented in Fig. 3.
This laboratory test did not give rise to any other coating defect,
excluding corrosion on the scratch.
Fig. 4 shows aspects of the paint systems after 18 months
exposure at Sines test site and Fig. 5 presents the results of chalking, colour change and gloss measurements performed each 6
months during 18 months at the same test site.
As occurred for salt spray test (Fig. 1), at Sines test site the
best behaviour was verified for system 1 (Fig. 4) including ethyl
silicate zinc rich primer and epoxy intermediate. This was the
only system that did not present blisters near the scratch after 18
months exposure. Blisters near the scratch were more significant
for system 2 with two coats of solvent free epoxy paint under the
acrylicpolyurethane topcoat. For this system, filiform corrosion
was also observed (Fig. 4).
Good correlation between the chalking values obtained in
the UV radiation test chamber exposure (Fig. 3) and at the test
site (Fig. 5) was verified. Concerning gloss reduction values,
for systems 1 and 3 these were similar after 30 days exposure
in the UV radiation test chamber and after 18 months exposure
at test site. However, the acrylicpolyurethane topcoats of systems 2 and 4 suffered higher gloss reduction in the UV radiation
test chamber. Differences in the spectral energy distribution can

Table 2
Results of salt spray test
Code

480 h

720 h

1440 h

Corrosion

Blistering

Corrosion

Blistering

Corrosion

Blistering

Panel

Ri0

Ri0

Ri0

Scratch

White, M = 0 mm

3 (S4)
Max = 3 mm
3 (S5)
2 (S4)
Max = 4 mm

White along all the

scratch, M = 0 mm

2 (S4)
Max = 8 mm
3 (S4)
Max = 5 mm

Ditto with dripping,

M = 3 mm

1 blister (S4) near

bottom edge
4 (S4)
Max = 4 mm

Panel
Scratch

Ri0
Red in all the scratch
with corr. products
around the scratch,
M = 1 mm

0
2 (S4)
Max = 3 mm

Ri0
Ditto, M = 5 mm

0
2 (S4)
Max = 4 mm

Ri0
Ditto, M = 7 mm

0
4 (S4)
Max = 5 mm

Panel
Scratch

Ri0
Red along all the
scratch with corr.
products around the
scratch and dripping,
M = 0.5 mm

0
0

Ri0
Ditto, M = 1.5 mm

0
(deposition of corr.
products do not allow
the detection of
probable blistering)

Ri0
Ditto, M = 11 mm

0
4 (S5)
Max = 18 mm

Panel
Scratch

Ri0
Red in all the scratch
with corr. products
around the scratch and
dripping M = 0 mm

0
2 (S2)
Max = 1 mm, in
one of the panels

Ri0
Ditto, M = 1.5 mm

0
(S2), (S3) and (S4)
Max = 3 mm

Ri0
Ditto, M = 3 mm

0
2 (S4)
Max = 4 mm

D. Santos et al. / Progress in Organic Coatings 54 (2005) 344352

Fig. 1. Appearance observed after different times of salt spray test: (a) system 1; (b) system 2; (c) system 3 and (d) system 4.

347

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D. Santos et al. / Progress in Organic Coatings 54 (2005) 344352

Fig. 2. Results of pull-off test: (a) system 1; (b) system 2 and (c) system 4.

Fig. 3. Results of UV radiation test: (a) chalking; (b) colour change and (c) gloss.

D. Santos et al. / Progress in Organic Coatings 54 (2005) 344352

Fig. 4. Appearance of paint systems after 18 months exposure at Sines test site: (a) system 1; (b) system 2; (c) system 3 and (d) system 4.

349

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D. Santos et al. / Progress in Organic Coatings 54 (2005) 344352

Fig. 5. Results of chalking (a), colour change (b) and gloss (c) measurements performed on panels exposed at Sines test site.

cause significant differences in the test results, depending on the

coating nature. The distribution of light intensity as a function
of wavelength seems to be the most likely cause of unnatural
chemistry in accelerated tests [20].
The polyurethane based topcoats did not suffer significant
colour change (Figs. 3 and 5). However, system 3 showed some
yellowing when exposed in the UV test chamber. Nonyellowing
polyurethane coatings have been developed, with colour retention equal, if not superior, to that of some of the better acrylic
coatings [21].
System 1, which allowed higher anticorrosion protection in
artificial and natural environments, was composed by the topcoat that presented the highest aesthetic degradation, due to the
significant development of chalking. Light-induced degradation
of the binder along the pigment interfaces, followed by the dissolution of the polymeric breakdown products in water allowed to
loosening of the pigment. UV-induced oxidative and hydrolytic
changes in the surface of the film resulted also in significant
loss of gloss. After 18 months exposure at the test site, system
1 presented gloss reduction higher than the other studied paint
systems. Photolytically induced degradation depends not only
on the nature of coating binder, but also on pigments and other
sorts of extraneous matter (additives, etc.) present.
Higher oxidative degradation by UV light of the topcoat of
the system 1 was also shown by the PAS/FTIR spectra presented
in Fig. 6, corresponding to unexposed coatings and to coatings
exposed 30 days in the UV radiation test chamber.
Bands near 17251705 cm1 and 15401520 cm1 corresponding to carbonyl (C O) and secondary urethane (N H)
respectively, are observed.

The degradation of polymeric coating binders by UV light

is a multi-stage process involving initiation, propagation and
termination phases [22]. To initiate degradation change in a paint
film binder, the radiation must be absorbed by the binder, where
the UV absorbing groups are known as chromophores. When
a chromophore in the coating absorbs UV light, the electronic
energy of the molecule increases and, the excited molecule can
undergo bond cleavage with production of free radicals. These
highly reactive species react with oxygen, forming peroxy-free
radicals [22,23]. Peroxy radicals attack the binder, abstracting
hydrogen atoms from the polymer forming a hydroperoxide and
a new carbon centred radical.
Hydroperoxides produced in the propagation step are themselves chromophoric and very unstable and, they readily undergo
photolysis, breaking down to form alkoxy and free radicals
[22,23]. These very active species will also abstract hydrogen
atoms from the polymer molecule with the formation of still
more peroxy radicals. So, the degradation proceeds until two
free radicals species recombine in the termination step to form
crosslinks. The alkoxy radicals formed by the breakdown of
hydroperoxides can also induce cleavage in the polymer chain
[22]. The two main structural results of UV degradation are
crosslinking and chain scission.
Carbonyl is one of the groups formed from photooxidation
reactions in paint coatings. So, relative extent of photooxidation
can be determined by measuring the increase in carbonyl band
of infrared spectra after weathering [23].
Comparing the FTIR spectra obtained before exposure and
after 30 days exposure in the UV radiation test site, it was verified that the aliphatic polyurethane topcoat of the system 1 was

D. Santos et al. / Progress in Organic Coatings 54 (2005) 344352

351

Fig. 6. PAS/FTIR spectra obtained with different coatings before and after artificial high UV weathering: (a) system 1; (b) system 2; (c) system 3 and (d) system 4.

the one that presented the highest increase in intensity of the

carbonyl band 1720 cm1 , indicative of photooxidation and
the highest loss of intensity in the secondary urethane band
1520 cm1 resulting form scission of urethane crosslinking
(Fig. 6). According to Bauer et al. [20] the last referred change
is more easily quantified than the oxidation, and they used the
loss of amide II signal to determine the acceleration factors, by
comparison of rates of loss of amide II signal in accelerated tests
with that verified in a test site.
4. Conclusions
From the results of laboratory performance tests [4], mainly
from neutral salt spray test [8], it was possible to work out
the Table 3, which presents the suitability of the studied paint
system for C5-M corrosivity category [5] an their durability.
One of the studied paint systems was classified as being of
medium durability and the other three systems of low durability. However, none of the studied paint systems, including
polyurethane topcoats, presented the requirements needed for
high durability classification.
Concerning the exposure at the marine atmosphere of Sines,
after 18 months, the best performance was shown by system
1 followed by systems 3, 4 and finally by system 2.

As occurred for outdoor exposure, system 1 including ethyl

silicate zinc rich primer, epoxy/polyamide intermediate and
aliphatic polyurethane topcoat, when submitted to neutral salt
spray test [8] presented also higher performance than all the
other studied paint systems. However, the topcoat of system 1
was the one that presented the highest chalking values and also
great gloss reduction, in the UV radiation test chamber and
at the test site. This is in agreement with PAS/FTIR results,
showing the spectrum of system 1 higher increase of intensity
of the carbonyl band (photooxidation) and higher decrease of
intensity of secondary urethane band (scission).
System 3 is a hybrid system, environmentally friendly, including water-borne primer and high solids intermediate and topcoat, which presented relatively good performance.
Good correlation between the results of chalking obtained
after 18 months exposure at Sines test site and 30 days exposure in the UV radiation test chamber was verified. However,
for acrylicpolyurethane topcoats of systems 2 and 4, gloss
reduction was more significant in the UV weathering than at
high UV radiation Sines test site. The results confirmed that
differences in the distribution of light intensity as a function
of wavelength between exposure environments, lead to significant differences in the degradation results, depending on
coating nature.

D. Santos et al. / Progress in Organic Coatings 54 (2005) 344352

352

Table 3
Selection of paint systems for C5-M corrosivity category
Code

Durability

Remarks

Low

Medium

High

Y*

N**

* After 480 h of water condensation test, some small blisters were

verified for some panels. But, these can be due to troubles with
application
** After 1440 h of salt spray test, corrosion from the scratch exceeded
1 mm

N*

* After 720 h of salt spray test, corrosion from the scratch exceeded
1 mm
After 480 h of water condensation test, some blisters of very small
size were observed

N*

* After 720 h of salt spray test, corrosion from the scratch exceeded
1 mm

N*

* After 720 h of salt spray test, corrosion from the scratch exceeded
1 mm

Y: yes; N: no; low (L): 25 years; medium (M): 515 years; high (H): more than 15 years before the first maintenance.

Acknowledgements
The authors would like to thank APS, CELBI, CIN,

EDP Produca o, EURONAVY, HENKEL IBERICA,

HEMPEL,
PROET, REFER, REN, ROBBIALAC SLM and TECOR companies for products supply, surface preparation, paint application, availability of test sites and financial support. They also
thank INETI/LTR team that collaborated in this work, specially
Jose Alves.
References
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