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Evaluation of the surface treatment effect on the anticorrosive performance

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Article  in  Progress in Organic Coatings · November 2003

DOI: 10.1016/S0300-9440(03)00112-7

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 Progress in Organic Coatings 48 (2003) 50–62

Evaluation of the surface treatment effect on the anticorrosive

performance of paint systems on steel
C.I. Elsner a,∗ , E. Cavalcanti b , O. Ferraz b , A.R. Di Sarli a
a Centro de Investigación y Desarrollo en Tecnologı́a de Pinturas (CIC-CONICET), Av. 52 s/n, Entre 121 y 122, B1900AYB La Plata, Argentina
b Instituto Nacional de Tecnologı́a, Ministério da Ciéncia e Tecnologia, Av. Venezuela 82, CEP 20081-310 Rı́o de Janeiro, Brazil

Accepted 17 June 2003

Abstract
Electrochemical impedance spectroscopy studies were carried out for paint coated carbon steel sheets under free corrosion conditions
when exposed to 3.5% NaCl solution for 405 days. Five anticorrosive primers [epoxy-polyamide/red lead/ferric oxide; alkyd/red lead;
epoxy/zinc–aluminium; zinc-rich ethyl-silicate and epoxy/zinc phosphate] were used while changing the steel surface treatment condition.
The EIS data was interpreted and discussed in terms of the time dependence of the electrical (paint coating) and electrochemical (steel
substrate) parameters associated to interfacial processes describing the metal/paint system deterioration. Furthermore, the progress of the
coating delamination process was estimated by the empirical expression relating the measured/specific double layer capacitance ratio.
Experimental data withdrawn from salt spray cabinet tests performed for 261 days and adhesion measurements are also discussed. On
the basis of the electrochemical, visual inspection and standardized tests results it was concluded that the best corrosion performance was
provided by the epoxy-polyamide/red lead/ferric oxide anticorrosive paint without any marked effect of the surface treatment; followed by
those anticorrosive systems including dry or wet sandblasting in presence of inhibitor. This result has been attributed to the fact that such
surface treatments can improve the barrier properties and/or the inhibiting corrosion protection and the steel/paint adhesion properties or
reduce the osmotic pressure effect.
© 2003 Elsevier B.V. All rights reserved.
Keywords: Surface treatments; Dry sandblasting; Wet sandblasting; Impedance measurements; Painting systems; Equivalent circuits

1. Introduction on acid derusting, phosphating, etc. [4,5]. Adhesion takes

Films and coatings are used in a wide range of technolo-
gies for a variety of purposes (functional, decorative or pro-
tective), and irrespective of their intended function they must
adhere satisfactorily to the underlying substrate [1]. In line
with this definition, the primer is considered the critical el-
ement in most paint coating systems because it is the most
responsible for preserving the metallic state of the substrate,
and it must also anchor the total paint coating to the steel.
Most coatings adhere to metals via purely physical attrac-
tions (e.g. hydrogen bonds) that develop when two surfaces
are brought closely together [2,3]. Paint vehicles with po-
lar groups (–OH, –COOH, etc.) have good wetting prop-
erties and show excellent physical adhesion characteristics
(epoxies, alkyds, oil paints, etc.). Much stronger chemically
bonded adhesion is possible when the primer can actually
react with the metal, as is the case of pretreatments based
∗ Corresponding author. Tel.: +54-221-483-1141;
fax: +54-221-427-1537.
E-mail address: direccion@cidepint.gov.ar (C.I. Elsner).
place when the coating and substrate separation is not more
than approximately 0.5 nm. Any contaminant on the steel
will increase the separation and, consequently, decrease the
paint film adhesion. Furthermore, reactive sites on the steel
surface at which adhesion can occur are masked not only
by contamination, but also by chemically bonded species
which may themselves occupy sites on the steel that would
otherwise be available for reaction with the paint vehicle.
Thorough surface preparation removes such contamination,
and exposes many more reactive sites; thereby dramatically
increasing the amount of surface area where adhesion can
occur [6].
In the case of steel surfaces, debris such as oxides, dirt,
dust, grease, oil, old paint, corrosion products, rust, mois-
ture and/or mill scale, and other foreign matter (chlorides,
sulfates, etc.) play an important role in the adhesion of
paints [7]. When any of these materials is painted over, it
interferes with the mechanical and chemical adhesion of
the paint film to the substrate, promoting the coating fail-
ure. Besides, as they have the capability to attract water or
water vapor through the paint film, they may cause not only

0300-9440/$ – see front matter © 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0300-9440(03)00112-7
 C.I. Elsner et al. / Progress in Organic Coatings 48 (2003) 50–62
paint blistering and/or delamination but also accelerated
corrosion of the underlying steel [8].
The mechanism responsible for the protective action of
paint coatings is highly complex because it depends upon si-
multaneous action of different factors. Thus, the organic film
permeability plays an important role in the metallic substrate
corrosion, since this property is directly connected with the
permeation of environmental corrosion-inducing chemicals
through the polymeric matrix, the chemical composition of
the latter and the presence of pores, voids or other defects
in the coating. It is important to note that particularly water
and oxygen can permeate, at least to some extent, even if
neither of those intrinsic structural defects are present.
When any structural steel surface is prepared for paint-
ing, rough or pitted areas may be contaminated with soluble
salts, which often cannot be eliminated by using the most
common method of surface treatment, dry sandblasting. Be-
sides, this method is a source of pollution or silicosis due
to the amount of particulate matter it releases into the envi-
ronment, and such there is a tendency for government legis-
lation regulating its use in urban areas. The effectiveness of
the applied painting system depends upon the method and
quality of the surface preparation, therefore, the develop-
ment of better coating systems must consider such items as
costs, ease of application and probabilities of getting longer
lifetime under service conditions. Wet sandblasting has been
proposed as an alternative and some related questions are
the scope of this paper. With or without inhibitors, wet sand-
blasting was applied to steel samples with different surface
treatment conditions in order to answer the following ques-
tions: (1) Is it always necessary to use corrosion inhibitors?
(2) Can the method of inhibition be detrimental to coatings
performance? (3) In the case of non-inhibited process, what
is the effect of flash rusting on coating adhesion?
As part of a program aimed at defining lifetime pre-
diction models for steel sheets coated with organic films,
an investigation related to the role played by the steel
surface treatment on the deterioration of such systems
has been performed. In this case, the goal was to study
differences in the corrosion protection provided by com-
mercially available Brazilian paint coating primers: (1)
epoxy-polyamide/red lead/ferric oxide; (2) alkyd/red lead;
(3) epoxy/zinc–aluminium; (4) zinc-rich ethyl-silicate, and
(5) epoxy/zinc phosphate, applied to previously treated (dry
sandblasting (A); wet sandblasting with inhibitor + rinsing
with water + drying with compressed air (B); wet sandblast-
ing with inhibitor + drying with compressed air (C); wet
sandblasting with inhibitor + rinsing with water + drying
with compressed air + exposure to air for 1 h (D); and wet
sandblasting with inhibitor + rinsing with water + drying
with compressed air + exposure to air for 4 h (E)), carbon
steel sheets exposed to either 3.5% NaCl solution for 405
days or to the environment of the salt spray cabinet (ASTM
B-117/85) for 261 days. Periodic visual inspections and
EIS measurements were carried out with the goal of un-
derstanding the effect, if any, in terms of the steel surface
51
Table 1
Surface treatments (Swedish standard SIS 05 59 00/67)
Code Description
A Dry sandblasting to white metal (Sa 3◦ )
B Wet sandblasting to near white metal (Sa 2.5◦ ) with
inhibitora + rinsing with water + drying with compressed air
C Wet sandblasting to near white metal (Sa 2.5◦ ) with
inhibitora + drying with compressed air
D Wet sandblasting to near white metal (Sa 2.5◦ ) without
inhibitor + rinsing with water + drying with compressed
air + 1 h exposure to air
E Wet sandblasting to near white metal (Sa 2.5◦ ) without
inhibitor + rinsing with water + drying with compressed air
+ 4 h exposure to air
a Sodium nitrite (90%), sodium carbonate (7%), sodium tripolyphos-
phate (3%).
preparation method on the effectiveness of the anticorrosive
properties provided by different primers through different
mechanisms. Salt spray cabinet and adhesion test results
are also presented and discussed.
2. Experimental
SAE 1020 steel plates (15 cm × 8 cm × 0.2 cm) were used
as the metallic substrate. They were treated according to the
Swedish Standard SIS 05 59 00/67 as shown in Table 1, then
degreased with toluene and coated with the anticorrosive
systems supplied is described in Table 2.
After the paint systems were applied by brushing, the
painted plates were placed in a dessicator at 20 ± 2 ◦ C until
complete drying had occurred (2–3 weeks). Dry film thick-
ness was measured with an Elcometer 256FN coating thick-
ness gauge, using a bare sanded plate and standards of known
thickness as reference. The average values, together with
the adhesion data determined according to the ASTM Stan-
dard D-4541 are summarized in Table 3. In accordance with
this standard, single specimens of each system were sub-
mitted to the pull-off test using the Elcometer tester model
106. The curing conditions for adhesion testing were in an
air-conditioned room (20 ± 2 ◦ C, 50 ± 5% relative humidity)
for 24 h. Mechanical tests were run in the same room.
On each painted plate, and separated by a distance
of 1–1.5 cm, two cylindrical tubes of transparent acrylic,
6.35 cm in diameter, were fixed by using an epoxy adhesive
Table 2
Anticorrosive paint coatingsa
Code Resin/pigments description Protection mechanism
1 Epoxy-polyamide/red Anodic passivation + barrier
lead/ferric oxide
2 Alkyd/red lead Anodic passivation
3 Epoxy/Zn–Al Cathodic + barrier
4 Ethyl-silicate/zinc Cathodic
5 Epoxy/zinc phosphate Anodic passivation
a Supplier: Tintas Renner S.A.® from Brazil.
52 C.I. Elsner et al. / Progress in Organic Coatings 48 (2003) 50–62

Table 3 the results. Duplicates of these samples were subjected to

Adhesion testing, using a direct pull-off method the immersion test in 3.5% NaCl solution for 400 days. In
System Mean thickness, Mean failure load (N cm−2 ) both cases, the dimension and number of blisters as well
␮m (±10%) as the presence of corrosion spots on every painted steel
A1 165 >343a sample were monitored according to the ASTM D-714/87
B1 189 343 ± 10 and B-610/89 standards, respectively.
C1 200 >343
D1 181 274 ± 39
E1 185 >343
3. Experimental results and discussion
A2 117 343 ± 10
B2 142 >343
C2 163 >343 This work is part of an ongoing research performed at
D2 151 >343 CIDEPINT focused to elucidate physicochemical phenom-
E2 166 314 ± 29 ena occurring within and under paint coatings, encompass-
A3 231 235 ± 19 ing defects in films, porous films, metal/coating adhesion,
B3 189 255 ± 10 surface treatment and/or pretreatments, corrosion, blistered
C3 190 333 ± 29 coatings and cathodic protection. Tests conducted under free
D3 223 176 ± 10 corrosion conditions showed that the influence of different
E3 225 78 ± 10
surface preparation procedures could have an effect on the
A4 183 206 ± 29 anticorrosive and barrier properties of five paint coatings. A
B4 174 196 ± 10
large amount of diverse data has been gathered using stan-
C4 170 206 ± 19
D4 178 137 ± 29 dardized tests as well as electrochemical techniques, and
E4 164 167 ± 19 then interpreted on the basis of their correlation with a num-
A5 199 304 ± 29
ber of physicochemical processes that are thought to occur
B5 195 >343 in pre-treated steel/paint film/exposure medium systems.
C5 198 206 ± 39
D5 184 294 ± 39 3.1. Adhesion measurements
E5 168 >343
a >343 implies that adhesion fails at the paint/dolly interface. Table 3 shows that the scatter among the measurements
for each surface treatment (A → E, see Table 1) given by the
in order to get good adhesion to the coated substrate. The direct pull-off adhesion standardized procedure performed
geometrical area of each cell was 31.27 cm2 . A Pt mesh of prior to any other test was rather low. However, it is inter-
high surface area was used as counter-electrode while a sat- esting to note the different trends between the paint coatings
urated calomel electrode (SCE) was employed as reference. (1 → 5, see Table 2) applied on the treated steel surface were
The cell was filled to a depth of 9 cm with 3.5% NaCl solu- observed. It can be seen that the surface treatment influence
tion (pH = 8.2) at room temperature 20 ± 2 ◦ C. Impedance was greater in epoxy/Al–Zn (3) and ethyl-silicate/zinc (4)
spectra in the frequency range 10−3 Hz < f < 104 Hz were painting systems than in the other ones.
recorded in the potentiostatic mode at the corrosion poten- The lowest adhesion values measured on systems D3, E3,
tial as a function of the exposure time in the electrolyte E4 and D4 show the detrimental effect of rust formed during
solution, using the Solartron SI 1280 Electrochemical Mea- the exposure to air on the adhesion forces between zinc-rich
surement Unit controlled by the OMEGA PRO software primers and steel surfaces that were wet sandblasted without
(i.e., the Solartron 1280 Corrosion Monitoring System). inhibitor. In these cases, considerable adhesion failure was
The amplitude of the applied AC voltage was 20 mV peak observed with large coating areas removed from the sub-
to peak. All the measurements were obtained in a Fara- strate. The systems A3, B3, C3 and A4, B4, C4 exhibited
day cage in order to minimize external interference on the intermediate but satisfactory mean failure load values, with
system. The impedance measurements were periodically only slight removal of the coating from the steel surface.
made for all the samples after the same time and under Among these, the highest adhesion value was obtained for
the same experimental conditions. The impedance spectra steel sheets wet sandblasted with inhibitor (system C3).
were analyzed by means of equivalent electrical circuits In general, the highest adhesion strengths were obtained
and the values of the parameters of the circuit optimized by for systems A1 → E1, A2 → E2 and A5 → E5. Here,
Boukamp’s program [9]. no paint removal was detected and the highest values
Triplicate specimens of each coating system were also were reached for systems A1, C1, E1, B2, C2, D2, B5,
tested in a spray cabinet for 261 days according to the ASTM E5 (>343 N cm−2 ), followed by the systems B1, A2, E2,
B-117/85 standard. During the test, the specimen position D5 (>343 N cm−2 ), and then for the systems A5, D1, C5
in the cabinet was changed after each periodical (11, 17, (<343 N cm−2 ).
28, 42, 73, 100, 122, 150, 170 and 261 days) inspection so It is difficult to draw an accurate physical description
as to eliminate the possibility that the position might affect and conclusive trends with regard to the influence of the
 C.I. Elsner et al. / Progress in Organic Coatings 48 (2003) 50–62 53

surface treatment on adhesion strengths from results of the
direct pull-off adhesion test only. This is due to the fact that
the chemical composition, cleanliness degree and structural
topography of the treated steel surface contribute to the
adhesion. Besides, the strengths of adhesion demonstrated
depend strongly on the properties and the intrinsical char-
acteristics of the applied anticorrosive primer formulation.
3.2. Salt spray cabinet test
The amount of adhesion loss is highly dependent not only
on the exposure aggressiveness but also on the strength of
the specific paint/metal interactions. Thus, different studies
have shown an adhesion loss coincident with the presence
of water at the metal/coating interface [10–12].
Table 4 lists blistering/corrosion data obtained for intact
steel/paint systems similar to those described in Table 3
but, in this case, placed in a salt spray chamber for 261
days. It can be seen that, except for the reduced perfor-
mance of all the steel/alkyd paint systems (2), the rest of
the specimens showed neither corrosion products nor coat-
ings defects on the main body of the panels during the pe-
riodic visual inspections. In general, the data set revealed
that under these experimental conditions, there was no in-
fluence of the steel surface treatment on the behavior of an-
ticorrosive primers based on organic (epoxy) or inorganic
(ethyl-silicate) binders, not even when steel/alkyd paint sys-
tems were considered.
Nevertheless, it is important to emphasize the poor per-
formance of all the steel/alkyd paint systems which failed
completely since not only blistering but also rusting was no-
ticeable on the panels surface. In fact, after almost the same
induction period, the blistering/corrosion displayed by the
steel/alkyd paint systems occurred so readily that their test
was the first to be interrupted. Such an induction period was
attributed to: (1) the coating thickness (>100 ␮m); (2) the
lack of direct pathways through the paint film; (3) the de-
velopment of negative charges in the paint structure, which
through polar interactions with the water molecules delay
their transport towards the steel/paint interface as well as re-
stricts the permeation of ions with the same charge sign (e.g.,
Cl− ). On the other hand, these results confirm that the highly
reactive alkyd paints are not designed to resist the continu-
ous contact with wet environments, since the polymer degra-
dation is accelerated by a feedback mechanism. This takes
place as follows: once a discrete aqueous phase, and as a

Table 4
Blistering (ASTM D-714a )/corrosion (ASTM D-610b ) results as a function of the exposure time in the salt spray cabinet
System Exposure time (days)

11 17 28 42 73 100 122 150 170 261

A1 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10
B1 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10
C1 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10
D1 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10
E1 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10
A2 10/10 10/10 10/10 10/10 – – – – – –
B2 10/10 10/10 10/10 10/10 10/10 10/9 – – – –
C2 10/10 10/10 8F/10 8F/10 8F/10 – – – – –
D2 10/10 10/10 10/10 10/10 10/10 – – – – –
E2 10/10 10/10 10/10 10/10 10/9 – – – – –
A3 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10
B3 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10
C3 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10
D3 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10
E3 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10
A4 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10
B4 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10
C4 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10
D4 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10
E4 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10
A5 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10
B5 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10
C5 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10
D5 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10
E5 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10
a ASTM D-714 specifications guide—frequency: dense (D), size: 10, comment: no blistering; frequency: medium dense (MD), size: 8, comment:

smaller size blister easily seen by the unaided eye; frequency: medium (M), size: 6, 4, comment: progressively larger size; frequency: few (F), size: 2,
comment: progressively larger size.
b ASTM D-610 specifications guide—for rust grade 9, 8, 7, 6, 5, 4, 3, 2 and 1, the percentage area rusted was 0.03, 0.1, 0.3, 1, 3, 10, 16, 33 and

50, respectively.
54 C.I. Elsner et al. / Progress in Organic Coatings 48 (2003) 50–62

Table 5
Blistering (ASTM-D714)/corrosion (ASTM D-610) results as a function of the immersion time in 3.5% NaCl solution
System Exposure time (days)

75 100 125 150 180 200 250 300 400

A1 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10

B1 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10
C1 10/10 8M/10 8M/10 8M/10 8M/10 8M/10 8M/10 8M/10 6M/10
D1 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10
E1 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10
A2 10/10 10/10 10/10 8F/10 8F/10 8F/10 8F/8 – –
B2 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/9
C2 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10
D2 10/10 10/10 10/10 10/10 6F/9 6F/5 – – –
E2 10/10 10/10 10/10 10/10 10/9 10/6 – – –
A3 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10
B3 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10
C3 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10
D3 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10
E3 10/10 10/10 10/10 10/10 10/10 10/10 10/10 6M/10 2M/10
A4 10/10 10/10 10/10 10/10 10/10 8F/10 8F/10 8F/10 8F/10
B4 10/10 10/10 10/10 10/10 10/10 10/10 10/10 8M/10 6M/10
C4 10/10 10/10 10/10 10/10 10/10 10/10 10/10 8F/10 8F/10
D4 10/10 8F/10 4M/10 4M/10 4M/10 4M/10 4M/10 4M/10 2M/10
E4 10/10 8F/10 6F/10 6MD/10 6MD/10 6MD/10 6MD/10 6MD/10 –
A5 10/10 10/10 10/10 10/10 10/10 8F/10 8F/10 8F/10 8F/10
B5 10/10 10/10 10/10 10/10 8F/10 8F/10 8F/10 8F/10 8F/10
C5 10/10 10/10 10/10 10/10 10/10 10/10 10/10 10/10 8F/10
D5 10/10 10/10 8F/10 8M/10 6M/10 6M/10 6M/10 6M/10 6M/10
E5 10/10 10/10 10/10 6F/10 6F/10 6F/10 6F/10 4F/10 4F/10

consequence an electrochemical double layer, forms at the
steel/paint interface, Fe start to dissolve as Fe2+ [13] in the
anodic areas whilst, in the cathodic ones, OH− ions develop
from the oxygen reduction as the main cathodic reaction.
As the process progresses, the alkaline medium created at
cathodic sites rapidly attacks the oil base of the alkyd film,
saponifying it. In addition to having some plasticizing effect
on the internal structure of this film, the absorbed water
favors the diffusion through the coating film for molecules
of a number of reactive species.
3.3. Immersion test in 3.5% NaCl solution
Table 5 summarizes blistering/corrosion data obtained
for intact steel/paint systems similar to those described in
Table 3 but, in this case, subjected to continuous immersion
in 3.5% NaCl solution for 400 days.
According to Ritter and Kruger [14], it may be supposed
that during the first stage of immersion in NaCl containing
solutions, different amounts of water, oxygen, Na+ and Cl−
can permeate the paint coating. As a consequence of this
mass transport, the blistering caused by the water permeation
proceeds as follows.
The mechanism of formation and growth related to the
paint film blistering, which involves a number of frequencies
and sizes, may be explained assuming that water permeation
through organic coating develops at small localized regions
where local failure of the paint film adhesion takes place.
As the exposure to the aqueous electrolyte continues, these
areas grow and coalesce into larger units resulting in part or
the total exposed area to become delaminated. The periodic
visual inspection and standardized characterization of the
painted surface allowed the monitoring of the starting and
evolution of the blistering/corrosion processes leading to re-
duce aesthetic and mechanical properties of each sample.
As can be seen in Table 5, most of the systems failed
by blistering before the end of the test. System C1 (8M/10)
and (6M/10) failed at 100 and 400 days immersion, respec-
tively, illustrating the range in painted steel performance un-
der the present experimental condition. When the steel cor-
rosion was effectively inhibited by both the barrier and anti-
corrosive action provided by the strongly adhered epoxy/red
lead-ferric oxide paint, a lesser density of blistering was
observed. Such a result allows inferring that this painting
scheme is not compatible with the NaNO2 left on the treated
surface. The reason is, perhaps, a significant increase of the
osmotic phenomena caused by this salt deposit. Fortunately,
for the other surface treatments, no change was noticed on
visual inspection.
On the contrary, systems A2, D2 and E2 exhibited the
detrimental effect on the blistering/corrosion performance
due to both the low barrier properties and the high chemical
 C.I. Elsner et al. / Progress in Organic Coatings 48 (2003) 50–62
reactivity of alkyd-based schemes. The lack of a corrosion
inhibitor in the wet sandblasting should also be taken into
account. The behavior of systems D2 and E2 allows the
conclusion that the corrosion degree is enhanced when the
surface of electrochemically active bare steel is exposed to
air for a certain length of time. The three cases also demon-
strate that under continuous immersion conditions, the an-
odic passivation afforded by the red lead pigment alone is
not enough to avoid the underlying steel corrosion. The red
lead, an active alkaline oxidizer, content in the paint formu-
lation provides the mechanism of such passivation, helps to
neutralize the acidity of the medium, and also forms soaps
of lead with the alkyd resin. By repelling the water, these
soaps reduce the corrosive action at the steel/paint interface.
On the other hand, systems B2 and C2 were able to de-
velop very good resistance properties, since they remained
almost similar to the control samples. Indeed, the better per-
formance of these two systems should be attributed to the
fact that residual (in panels B) or permanent (in panels C)
action of the NaNO2 , improves and/or longer preserves the
intrinsic protective properties of the alkyd system.
The results obtained for systems A3, B3, C3 and D3 are
indicative of the high protective effectiveness developed by
the paint system, which was applied on panels with different
surface treatments. An exception was system E3 which, in
agreement with the lowest measured mean adhesion value
(88 N cm−2 , see Table 3), showed the worst blistering de-
gree. Such data coherence suggests that the addition of an
inhibitor either to the water or to the steel surface immedi-
ately after the wet sandblasting is essential in order to tem-
porarily prevent formation of a rust layer.
The response to continuous immersion in the electrolyte of
systems 4 (ZRP ethyl-silicate) and 5 (epoxy/zinc phosphate)
was fairly poor. Some of the samples (samples D4, E4 and
D5) showed an important blistering degree from 100 to 125
days exposure, respectively. Nevertheless, disregarding the
surface treatment every sample presented a certain degree of
blistering at the end of the test. In spite of this, no corrosion
forms were visually noticed after 400 days immersion in the
strongly corrosive 3.5% NaCl solution. Therefore, in terms
of its anticorrosive behavior, it can be said that the inhibitive
action of the zinc alone in the ZRP (system 4) as well as
that coming from the zinc phosphate (system 5) pigment,
added to the barrier effect supplied by the respective binders
was very effective. Concerning to the pigments anticorrosive
mechanism, it can be explained assuming that a high PVC
(>85%) of zinc particles provides initially cathodic and then
barrier protection to the steel substrate [15]. On the other
hand, the slightly soluble (in this electrolyte) zinc phosphate
not only forms an alkaline buffer (sodium zincate) inhibiting
the corrosion at anodic areas but also polarizes the cathodic
reaction through precipitation of scarcely soluble salts (ferric
phosphate and hydrated iron oxides) on the steel surface.
A certain relationship associating low adhesion values
with blistering results was found for system 4 but not for
system 5. Systems B4 and C4 with higher failure load val-
55
ues than A4, D4 and E4 showed few or medium blistering
after 300 days exposure, while they appeared after 100 days
and grew to complete delamination of the layer for systems
D4 and E4, or after 200 days and they remained stable un-
til the end of the test for system A4. The better results ob-
tained for systems B4 and C4 suggest again that if the flash
rust formation is avoided by using a corrosion inhibitor dur-
ing or just after the wet surface treatment, the blistering ap-
pearance could be delayed longer when a painting system
based on an ethyl-silicate binder is chosen for covering the
so treated steel surfaces. Such an improvement was also ver-
ified for system C5 (where the inhibitor was not removed
after the surface treatment) but not for the rest (A5, B5, D5
and E5) of the panels coated with the same epoxy paint. Al-
though this product has good resistance to water permeation
and adhesion properties, it was unable to avoid the devel-
opment of certain blistering degree (from few to medium).
Both types appeared and grew gradually in frequency and
size with different kinetics and immersion times. Due to the
proper and complex characteristics of the epoxy-based paint
and its interaction with the treated steel surface, it is perhaps
not surprising that it was very difficult, if not impossible, to
determine a clear differentiation about the surface treatment
influence on the blistering degree for this painting system.
An exception to this rule could be the time at which the
blisters appear.
The analysis of the entire data set obtained from this test
indicates that only systems B2 and C2 performed clearly bet-
ter when the corrosion inhibitor was used during the wet sur-
face treatment. Sometimes, however, this improvement has
no practical significance because the coating performance
could become classified as not satisfactory or poorly satis-
factory when, although minimum, a certain blistering degree
is detected.
3.4. Electrochemical measurements
Corrosion potential and impedance data as a function of
the immersion time in 3.5% NaCl solution have been ob-
tained. Then, impedance data were fitted using the transfer
function and algorithms from electrical equivalent circuit
models, and interpreted from their association with pro-
cesses occurring within the paint film and at the substrate/
paint interface.
Rest or corrosion potential measurements for painted met-
als and their variation with time have been questioned with
regard to their use as a technique for evaluating the anticor-
rosive resistance of organic coatings [16]. Depending upon
the microstructure of the paint coating, especially its poly-
merization degree, a certain period elapses until electrolyte
penetration channels are established through which the un-
derlying metal comes into contact with the medium. So, it
is not surprising that, when a compact structure and a high
crosslinking level are accompanied by a high film thickness,
a few days of testing are not enough time for the electrolyte
to enter in contact with the base metal of coated specimens,
56 C.I. Elsner et al. / Progress in Organic Coatings 48 (2003) 50–62

form the electrochemical double layer, and enable the mea-
surement of a corrosion potential.
It is fairly obvious that a significant potential difference
exists between the uncoated active steel surface at the bot-
tom of paint coatings defects (typical electrodes potentials
<−0.65 V/SHE) and the intact, strongly adhered steel/paint
interface, where anodic potentials (>0 V/SHE) are measured.
In essence, being characteristics of passive iron [17], these
last potential values demonstrate the presence of a strong
inhibition to the steel corrosion. Therefore, a function of the
specific conditions of each steel/painting scheme/electrolyte
system, one point or more probably a region of the transi-
tion between positive and negative potential values denotes
the beginning of the painted steel corrosion.
Based on this statement and the Ecorr values measured for
all the sandblasted and then painted steel panels (Fig. 1a,
systems A1 → E1, epoxy/read lead-ferric oxide), it is clear
1 A1
B1
C1
0 D1
-Ecorr / V(SCE)
that in no case any type of corrosion could be detected. The
initial values of Ecorr were characterized by a large scatter
(>0.7 V/SCE), although all of them ranged between +0.9
and +1.6 V/SCE. Such noble values were attributed to the
excellent barrier effect and presumably enhanced by the
significant adhesion forces, afforded by the different paint-
ing systems. Then, during the first week immersion, they
moved steeply (0.2–0.4 V) towards less positive values but
later, when the anticorrosive action of the pigments started
to be effective, they changed more slowly, +0.8 V/SCE
being the lower potential measured for sample E1 at 400
days immersion. Consequently, considering these and also
the data showed in Table 3 for A1 → E1 systems, it is
assumed that strong (although not conclusive) evidence
was found that the steel surface stayed effectively pro-
tected from corrosion-inducing chemicals, particularly Cl−
ions, coming from the electrolyte throughout the exposure
time.
From Fig. 1b (alkyd/red lead paint, systems A2 → E2); it
is evident that immediately after immersion the Ecorr values
ranged between +1 and +1.5 V/SCE. The higher permeabil-
ity to water and other corrosive species of the alkyd paint

E1 caused the protection mechanisms provided by the different

-1
pigments to work rapidly, causing the sharp movement of
(a ) -2 potentials in direction to more positive (noble) values. Such
situation went on until almost 175 days immersion. There-
1 A2 after the samples, except system C2, which maintained this
B2
C2
trend (systems A2, B2, D2, and E2) exhibited a drastic de-
0
D2 crease of their Ecorr , which reached values between −0.4
-1
E2
and −0.8 V/SCE, i.e. near or equal to the bare steel in this
medium. Keeping in mind that, in essence, the more nega-
(b ) -2
tive the measured potentials becomes, the more susceptible
1 A3
to corrosion is the underlying steel surface, the visual in-
B3 spection led to the determination that no corrosion signal
C3
0 D3
was visible by the human eye. However, it will be discussed
E3 later, the steel surface had already been attacked. From this
-1
time, systems A2, D2 and E2 suffered a quick and uniform
(c ) -2 deterioration; therefore their test was interrupted. Neverthe-
less, the inhibitive surface treatments B2 and C2 showed to
1 A4
be much more effective than A2, D2 and E2 since they con-
B4

0 C4 tributed to increase the resistance to corrosion of steel/alkyd

D4
E4
paint systems. The reasons for such a response have been
-1 described in a previous paragraph (see Immersion test).
(d ) -2 Results of Ecorr evolution for systems A3 → E3 (steel/
epoxy-Al–Zn paint) are shown in Fig. 1c. It can be seen
1 A5 that, except for system C3, from the beginning until almost
B5
C5
the end of the immersion test, the scatter and subsequent
0 D5 evolution of painted steel corrosion potentials are like those
found for systems A1 → E1. This is presumably due to
E5
-1
the fact that the most important but not unique form of
(e ) -2
protection is supplied by the barrier properties of the epoxy
0 100 200 300 400 500 coating film. The active function (either anodic or cathodic
protection) exerted by the anticorrosive pigments should also
time / days
be considered. Although no corrosion spots were visually
Fig. 1. (a–e) Time dependence of the corrosion potential (Ecorr ) of all the detected (see also Table 5), in system C3 at 6 days and E3
painted steel systems immersed in 3.5% NaCl solution. (with development of high blistering degree) after 350 days
 C.I. Elsner et al. / Progress in Organic Coatings 48 (2003) 50–62
exposure, a transition from positive to negative corrosion
potentials values was observed.
Fig. 1d presents the Ecorr changes obtained for system 4
(steel/ZRP). It can again be seen that the corrosion potential
of the dry sandblasted and then painted steel surface (sys-
tem A4) showed more positive values (between +1.7 and
+1.1 V/SCE) than those treated with the wet sandblasted
procedure (systems B4 → E4). Among these, the worst
performance was provided by the system C4, whose Ecorr
was −0.7 V/SCE at the beginning of the exposure, although
corrosion spots could be visually detected only after 200
days immersion (see Table 5). However, disregarding the
type of wet surface treatment employed, i.e. with or without
inhibitor or exposure to air, the corrosion potential results
together with the low adhesion values shown in Table 3,
demonstrated that, when used alone and subjected to con-
tinuous immersion in aggressive aqueous electrolytes, this
type of ZRP does not provide effective cathodic protection
for a long time. The high permeability and weak adhesion
of the paint film due to its high PVC (near or greater than
the CPVC), allow us to account for such behavior. Despite
this, except in system E4 from 200 days, no corrosion spots
were observed in the other systems.
More positive (noble) and stable Ecorr values were mea-
sured for system A5 than for systems B5 → E5, which de-
teriorated more or less quickly, as shown in Fig. 1e. Whilst
the corrosion potential of the painted steel in system A5
(dry sandblasting) remained at about +1.8 ± 0.2 V/SCE
throughout the test, values corresponding to the other sys-
tems changed from +0.5 V/SCE (system B5) or +0.2 ±
0.2 V/SCE (systems C5, D5, E5) to −0.4 ± 0.2 V/SCE. It is
important to emphasize that, in this case, there was a dis-
tribution of transition times since for systems B5, C5, D5 it
appeared at 100 ± 25 days exposure, whilst for system E5
it did so at 260 days exposure. Whereas all painting sys-
tems showed some degree of blistering, no corrosion spots
were observed during the visual inspections. Therefore, it
Fig. 2. Equivalent circuit model where R is the electrolyte resistance; R1 and C1 are ionic resistance and dielectric capacitance of the paint film; R2 and
C2 are charge transfer resistance and electrochemical double layer associated with the corrosion process.
57
may be inferred that if there was any type of corrosion at
the steel/painting system interface, it took place at a rate and
to an extent depending more on the wet surface treatment
than on the intrinsic physicochemical characteristics of the
steel/epoxy painting system used.
3.5. Equivalent circuit models
Impedance spectra allow us to obtain useful information
on the evolution of both the organic coating protective prop-
erties and the kinetics of the underlying steel corrosion pro-
cess as a function of the immersion time in the electrolyte.
The dynamic character of the membrane barrier effect, the
anticorrosive action of the pigments, the rust formation, and
also changes in the disbonded area account for the variations
of the coated steel/electrolyte impedance spectra throughout
the exposure time. In general, an explanation of such perfor-
mance can be given by fitting the experimental impedance
data with non-linear least squares algorithms involving the
transfer function derived from the equivalent circuit model
shown in Fig. 2 [5,18–20]. This figure represents the parallel
and/or series connection of a number of resistors and capac-
itors, simulating a heterogeneous arrangement of electrolyt-
ically conducting paths. Thus, R represents the electrolyte
resistance between the reference and working (coated steel)
electrodes, R1 the resistance to the ionic flux through paths
(pores, low crosslinking) short-circuiting the paint film, and
(C1 ≡Q1 ) the dielectric capacitance of the same film’s in-
tact part [21]. Once the permeating and corrosion-inducing
chemicals (water, oxygen and ionic species) reach elec-
trochemically active areas of the substrate, particularly at
the bottom of the paint film pores, the metallic corrosion
becomes measurable so that its associated parameters, the
double layer capacitance (C2 ≡Q2 ) and the charge transfer
resistance, R2 , can be estimated. It is important to remark
that R2 and C2 values vary directly (R2 ) and inversely (C2 )
with the size of the attacked metallic area. Sometimes, when
58 C.I. Elsner et al. / Progress in Organic Coatings 48 (2003) 50–62

the strength of the bonding forces at the paint/substrate in- 13

log (R1 / Ωcm )
2

terface are affected (e.g., by wet adhesion), facilitating lat- (a)

eral diffusion of the electrolyte, other processes under and/or 12
within intact parts of the coating film could be graphically
and/or numerically separated [22], causing the appearance 11
of additional time constants (Ri Ci ).
On the other hand, distortions observed in these resistive– 10
log (Q1 / Fcm )

capacitive contributions indicate a deviation from the the- (b)

-2

-12
oretical models in terms of a time constants distribution
due to either lateral penetration of the electrolyte at the -13
steel/paint interface (usually started at the base of intrin-
sic or artificial coating defects), underlying steel surface -14
heterogeneity (topological, chemical composition, surface
energy) and/or diffusional processes that could take place (c)
along the test [23,24]. Since all these factors cause the 1.0
n1

impedance/frequency relationship to be non-linear, they are 0.8 A1

taken into consideration by replacing one or more capacitive B1
0.6 C1
components (Ci ) of the equivalent circuit transfer function D1
by the corresponding constant phase element (CPE), Qi [9], 0.4 E1

for which the impedance may be expressed as [25]: 0 100 200 300 400 500
(jω)−n time / days
Z= (1)
Y0
Fig. 3. Time dependence of: (a) R1 , (b) Q1 and (c) n1 of A1 → E1
where Z(ω) is the impedance of the CPE (Z = Z
+jZ

) (); painted steel systems immersed in 3.5% NaCl solution.

j the imaginary number (j2 = −1); ω the angular frequency

9
log (Q1 / Fcm ) log (R1 / Ωcm )

(d)
log (Q2 / Fcm ) log (R2 / Ωcm )

(a)
2

12
8
9
7
6
6
-6 (b) (e)
-2

-2

-6
-9

-12 -8

-15
-10
(c) A2 (f)
1.0 B2 1.0
n1

n2

C2
0.8 D2 0.8
E2
0.6 0.6
0.4 0.4
0 100 200 300 400 500 0 100 200 300 400 500
time / days time / days

0.6
(g)
Ad / cm2

0.4

0.2

0.0
0 100 200 300 400 500
time / days

Fig. 4. Time dependence of: (a) R1 , (b) Q1 , (c) n1 , (d) R2 , (e) Q2 , (f) n2 and (g) Ad of A2 → E2 painted steel systems immersed in 3.5% NaCl solution.
 C.I. Elsner et al. / Progress in Organic Coatings 48 (2003) 50–62 59

(rad); n the CPE power (n = α/(π/2)); α the constant phase
angle of the CPE (rad); Y0 the part of the CPE independent
of the frequency (−1 ).
Difficulties in providing an accurate physical description
of the occurred processes are sometimes found. In such
cases, a standard deviation value (χ2 < 10−4 ) between ex-
perimental and fitted impedance data may be used as final
criterion to define the most probable circuit.
The delaminated corroding area Ad can be estimated by
means of the following empirical equation [5]:
Q2 (t)
Ad =
20
where Ad is the delaminated area (cm2 ); Q2 (t) ≈ C2 (t) is
electrochemical double layer capacitance measured at any
time t (␮F); 20 the typical value of the bare steel double
layer capacitance, adopted to estimate the underlying metal-
lic active surface (␮F cm−2 ).
3.6. Impedance results
Fig. 3a shows a representative plot for the resistive compo-
nent (R1 ) of the impedance corresponding to the five treated
steel/epoxy-red lead-ferric oxide paint systems (A1 → E1).
log (Q1 / Fcm ) log (R1 / Ωcm )
It can be seen that no difference was detected among the val-
ues corresponding to all of them, in spite of the significant
differences between the steel surface treatments used be-
fore painting. The extremely high values (R1 > 1011  cm2 )
measured for 400 days of continuous immersion in 3.5%
NaCl solution, confirm the excellent barrier properties af-
forded by the epoxy base paint. Besides, its stability allows
one to infer that, in accordance with results reported by other
authors [26,27], the paint film was in all cases able to keep
the steel substrate isolated from the action of the corrosive
electrolyte. Fig. 3b shows that the capacitive component of
(2) the paint film impedance is drawn as a CPE (Q1 ). Also here
its stability around 10−13 to 10−14 F cm−2 with the immer-
sion time is noteworthy. Likewise, typical values of n ob-
tained for the corresponding CPE are shown for systems
A1 → E1 in Fig. 3c; it can be seen that low Q1 values, as-
sociated with the capacitance of the intact part of the epoxy
film, gives 0.9 ≤ n1 ≤ 1. Therefore, the magnitude of these
two parameters also contributes to demonstrate that the paint
coating actually behaved like a dielectric capacitor through-
out the test. The agreement among the whole experimental
data obtained for systems A1 → E1, confirms the excellent
anticorrosive protection provided to steel structures through
the combined barrier + anodic passivation mechanisms of
log (R2 / Ωcm )
2

(a) (d)
2

12 12

10
10
8
8
log (Q2 / Fcm )

(b) (e)
-2

-2

A3
B3

-12 C3 -10
D3
E3
-14 -12

-16 -14
(c) (f)
1.0 1.0
n2
n1

0.8 0.8
0.6 0.6
0.4 0.4
0 100 200 300 400 500 0 100 200 300 400 500
time / days time / days

60
2

(g)
Ad 10 / cm

40
7

20

0
0 100 200 300 400 500
time / days

Fig. 5. Time dependence of: (a) R1 , (b) Q1 , (c) n1 , (d) R2 , (e) Q2 , (f) n2 and (g) Ad of A3 → E3 painted steel systems immersed in 3.5% NaCl solution.
60 C.I. Elsner et al. / Progress in Organic Coatings 48 (2003) 50–62

this painting system. The relevant importance of such a per-
formance is that it was obtained regardless the type of steel
surface treatment or test conditions considered.
Results shown in Fig. 4a–g indicate that the evolution of
systems A2 → E2 was diverse. Whilst the evolution of the
resistive and capacitive components of the electrochemical
impedance indicate that systems B2 and C2 were able to
keep their protective properties along 400 days of the test, the
systems A2, D2 and E2 show considerable changes. It can
be seen that a steep decrease of the resistance to ionic flux
(R1 , Fig. 4a) from about 1012  cm2 to ∼ =106 to 107  cm2
for systems D2 and E2 at 180 days and for system A2 at
270 days immersion took place. Simultaneously, the coat-
ing deterioration was illustrated by the sharp increases of
the corresponding capacitance Q1 (Fig. 4b), whose initial
magnitude was 10−13 to 10−14 F cm−2 but then reached val-
ues greater than 10−9 F cm−2 , a clear signal of the dielec-
tric properties deterioration. However, the small fluctuation
of the CPE power (n1 , Fig. 4c) shows that whether such
degradation was in progress, it was much more significant
for system E2.
Simultaneously with the painting system changes, the cor-
rosive attack to steel substrate was detected, Fig. 4d–f. Com-
log (Q1 / Fcm ) log (R1 / Ωcm2)
paring the appearance time of electrochemical parameters
(R2 , C2 , n2 ) associated with this Faradaic process for sys-
tems A2, D2 and E2, a longer induction period for system
A2 is observed. Again, the dry sandblasting was more effec-
tive than the wet procedure when the latter procedure was
performed in absence of an inhibitor and leaving the active
steel surface exposed for 1 h (system D2) or 4 h (system E2)
in contact with atmospheric air. It is thought that the layer of
corrosion products, formed and deposited on the bare steel
before applying the paint system enhanced the osmotic phe-
nomena and, consequently, the faster formation of the elec-
trochemical double layer. The poor performance of system
E2 is an example of it. Of course, this fact must be added to
the intrinsic characteristics of the alkyd-based coatings dis-
cussed in previous paragraphs. It is also important to note
that, just after the corrosion process was initiated, a quick
paint delamination occurred (initial values of Ad ≈ 1.66%
for system D2; 0.096% for system E2; 0.032 for system A2,
Fig. 4g) followed by an overall system deterioration. For
this reason the test had to be interrupted before the next in-
spection.
In Fig. 5a–g the relative performance of systems A3 →
E3 in contact with the electrolyte is shown through the

log (Q2 / Fcm ) log (R2 / Ωcm )

12 (a) (d) 12
2

10 10
8
8
6
6
(e)
-2

(b)
-2

A4

-9
B4 -8
C4
D4 -10
-12 E4
-12
-15
-14
(c) (f)
1.0 1.0
n1

n2

0.8 0.8
0.6 0.6
0.4 0.4
0 100 200 300 400 500 0 100 200 300 400 500
time / days time / days

400000 (g)
2
Ad 10 / cm

400
7

200

0
0 100 200 300 400 500
time / days

Fig. 6. Time dependence of: (a) R1 , (b) Q1 , (c) n1 , (d) R2 , (e) Q2 , (f) n2 and (g) Ad of A4 → E4 painted steel systems immersed in 3.5% NaCl solution.
 C.I. Elsner et al. / Progress in Organic Coatings 48 (2003) 50–62 61

variation of Ri , Ci and ni parameters with immersion time.
The high resistance to water and corrosive species perme-
ation of the epoxy coating remained almost constant dur-
ing the entire test, with R1 ≥ 1010  cm2 , 10−14 F cm−2 ≤
Q1 ≤ 10−12 F cm−2 and 0.8 ≤ n1 ≤ 1, Fig. 5a–c. In ad-
dition to this barrier effect, the cathodic protection afforded
by the pigment was also effective since no steel corrosion
was detected. The corrosion parameters R2 , C2 and n2 were
associated with the zinc self-corrosion which, regardless of
the surface treatment considered, initiated in each case (sys-
tems C3, D3 and E3) after a relatively short induction pe-
riod. However, it occurred at very low rates and over a very
small extended area (Ad ≈ 2 × 10−6 cm2 , Fig. 5g) of the
active pigments, since the estimated values for R2 ranged
1010 to 1012  cm2 and its parallel connected capacitance
Q2 between 10−12 to 10−14 F cm−2 , whilst its power varied
as 1 ≤ n2 ≤ 0.8.
A similar behavior was seen for systems A4 → E4,
Fig. 6a–f. Thus, systems A4, B4 and C4 with R1 ≥
1010  cm2 , Q1 ≤ 10−12 F cm−2 and 0.8 ≤ n1 ≤ 1 did
not exhibit changes, but systems D4 and particularly E4
showed some increase of their ionic conductivity (Fig. 6a)
and capacity of water absorption (Fig. 6b, system E4). The
higher permeability of this ZRP coating, which facilitates
a faster development of osmotic phenomena, was indicated
log (Q1 / Fcm ) log (R1 / Ωcm )
by the resistive–capacitive (R2 , C2 , n2 ) components, related
with a slow corrosion process, just after immersion (system
C4), after a week (system D4) or about 50 days (system
E4). Such parameters remained almost stabilized for system
C4 and D4, but they started to show the progressive deteri-
oration of system E4 until its test was interrupted because
of its strong deterioration. This was manifested by the high
degree of coating film blistering, precipitation of massive
amounts of zinc corrosion products, and a delaminated cor-
roded area close to 4 × 10−2 cm2 in size (Fig. 6g). In this
case, the magnitude of such changes was probably associ-
ated with the corrosion rates of the zinc particles contained
within the ethyl-silicate structure. From these results we
can infer, therefore, that both the dry sandblasting proce-
dure (code A, Table 1) and the inhibited wet one + rinsing
with water (code B) introduce very significant delays of
the development of osmotic processes. This is attributed to
the fact that in both cases the respective surface treatments
provide much cleaner steel surfaces than in the other three.
In Fig. 7a–f the values of the electrical (R1 , Q1 , n1 ) and
electrochemical (R2 , C2 , n2 ) parameters show very good
agreement with the experimental results obtained when
similar samples of systems A5 → E5 were submitted to a
number of tests (see Tables 3–5, and Fig. 1f). All of them are
consistent in proving independently of the previously used

log (Q2 / Fcm ) log (R2 / Ωcm )

12 (a) (d)
2

12
2

10 10
8
8
6
6
A5
-2

-2

(b) (e)
B5
-9 C5 -8
D5
E5 -10
-12
-12
-15
-14
(c) (f)
1.0 1.0
n2
n1

0.8 0.8
0.6 0.6

0.4 0.4

0 100 200 300 400 500 0 100 200 300 400 500
time / days time / days

(g)
2

300
Ad 10 / cm

200
7

100

0
0 100 200 300 400 500
time / days

Fig. 7. Time dependence of: (a) R1 , (b) Q1 , (c) n1 , (d) R2 , (e) Q2 , (f) n2 and (g) Ad of A5 → E5 painted steel systems immersed in 3.5% NaCl solution.
 62 C.I. Elsner et al. / Progress in Organic Coatings 48 (2003) 50–62
surface treatment, the epoxy/zinc phosphate paint can be
classified as having fairly effective anticorrosive properties
for protecting steel panels under the present service condi-
tion. So, R1 ≥ 109  cm2 , Q1 ≤ 10−12 F cm−2 and 0.8 ≤
n1 ≤ 1 are representative values of polymeric coatings hav-
ing intact protective properties. Despite this and the fact
that no corrosion was detected during visual inspections, the
electrochemical parameters (R2 , Q2 , n2 ) denoting the pres-
ence of substrate corrosion in systems B5, C5, E5 and D5
could be estimated. Their appearance was just after immer-
sion (systems B5, C5, E5) or after an induction period of
about 40 days for system D5. The stable values of those
parameters during the test, with R2 ≥ 109  cm2 , Q2 ≤
10−12 F cm−2 and 0.8 ≤ n2 ≤ 1, allow the presumption that
steel corrosion took place at extremely localized areas. Such
assumption is in agreement with the actually small values
of delaminated area calculated, where the worst result was
Ad ≤ 10−5 cm2 (Fig. 7g, system C5); it is to say, 0.000032%
of the whole painted area.
4. Conclusions
• The adhesion strength as well as the development of the
corrosion process beneath the coating film were strongly
dependent on the characteristic properties of the anticor-
rosive primer formulation.
• Whatever the surface treatment was, the general perfor-
mance of the anticorrosive primer based on the epoxy-
polyamide binder was always the best; in not one case
was the development of any type of corrosion observed.
• For paint systems using Zn as anticorrosive pigment, the
surface treatments that provided satisfactory protective
performance were dry sandblasting (A) and wet sandblast-
ing with inhibitor + subsequent rinsing (B).
• For the epoxy/zinc-phosphate coatings the only surface
treatment that did not allow the development of corrosion
is the dry sandblasting (A).
• Except for alkyd/red lead primers, dry sandblasting (A)
was the surface treatment that showed the best perfor-
mance. For those coatings, wet sandblasting with inhibitor
(B or C) showed to be useful for delaying the corrosion
process development.
Acknowledgements
The authors would like to thank the Comisión de Investi-
gaciones Cientı́ficas de la Provincia de Buenos Aires (CIC),
the Consejo Nacional de Investigaciones Cientı́ficas y
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Técnicas (CONICET) and the Conselho Nacional de
Pesquisas (CNPq) de Brasil for their financial support of this
research work. They also thank Technicians J.H. Asurmendi
and N.B. Alvarez for their efficient experimental work.
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