Anti-Corrosion Methods and Materials

Emerald Article: Accelerated and EIS tests for anticorrosive paints

pigmented with ecological pigments
L.S. Hernández, B. del Amo, R. Romagnoli

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To cite this document: L.S. Hernández, B. del Amo, R. Romagnoli, (1999),"Accelerated and EIS tests for anticorrosive paints
pigmented with ecological pigments", Anti-Corrosion Methods and Materials, Vol. 46 Iss: 3 pp. 194 - 204
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Contributed papers
Accelerated and EIS
tests for anticorrosive
paints pigmented with
ecological pigments
L.S. Hernández,
B. del Amo and
R. Romagnoli
The authors
L.S. Hernández is at the Institute of Metallurgy, UASLP,
San Luis Potosi, Mexico.
B. del Amo and R. Romagnoli are at CIDEPINT, Research
and Development Centre for Paint Technology,
La Plata, Argentina.
Keywords
Corrosion prevention, Health and safety, Paints, Pigments,
Spectroscopy
Abstract
Substitution of zinc chromate or zinc yellow, traditionally
used as anticorrosive pigment, for other phosphate-based
pigments that are not hazardous to health and have the
same anticorrosive behaviour or even better, is studied in
this paper. Four alkyd paints were specially prepared; two
of them contained calcium acid phosphate or micronised
zinc phosphate as anticorrosive pigments respectively. A
paint containing zinc chromate was used as reference and
a paint without anticorrosive pigments was used as a
blank, in which the other ingredients were increased
proportionally to attain the desired PVC relationship. The
corrosion behaviour of low carbon steel panels coated
with these paints in a 3 per cent NaCl solution was
assessed by electrochemical impedance spectroscopy
(EIS). In addition, other painted panels were evaluated by
salt spray and humidity chamber tests. Results of all tests
showed that the paint with calcium acid phosphate and
especially that with micronised zinc phosphate exhibited
better behaviour than paint with zinc chromate. Analysis
of impedance parameters (ionic resistance and capaci-
tance of the paint film) against immersion time allowed
the paints to be ranked in the same order as that obtained
with salt spray and humidity chamber tests.
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Anti-Corrosion Methods and Materials
Volume 46 · Number 3 · 1999 · pp. 198–204
©MCB University Press · ISSN 0003-5599
198
Pigments based on lead oxides and chromates
have proven their efficiency in steel protection
for many years, but are now subjected to
legislative restrictions. Chromates are perhaps
the most effective inhibitors, which is indicat-
ed by their continued use in the most
demanding service in spite of efforts to
replace them with less toxic counterparts
(Hare, 1998). The uncertainties about the
risks attributed to the use of coatings with
these compounds have stimulated the devel-
opment of new corrosion passivating
inhibitors.
The most commercially successful non-
toxic inhibitive pigments have been phos-
phates. Zinc phosphate and their modifica-
tions have been successful in the winning of
markets due to their low cost, reduced risks
(in comparison with those of lead and chromi-
um compounds) and easy application (in
comparison with other lead- and chromate-
free corrosion inhibitors) (Koskiniemi and
Conti, 1996). The use of zinc phosphate
instead of zinc chromate has been often rec-
ommended for the formulation of environ-
mentally compatible anticorrosive priming
compositions. Romagnoli and Vetere (1995)
have pointed out that experimental results
obtained in tests of this pigment have been
contradictory. Accelerated tests of zinc phos-
phate-pigmented coatings were disappoint-
ing, but outdoor long-exposure tests showed
good performance. If compared with oxidis-
ing inhibitors, phosphates (non-oxidising
compounds) require the presence of oxygen
and a higher concentration of the anions to
passivate steel (Hare, 1997). The low solubili-
ty of unmodified zinc phosphate in water and
its extremely coarse crystalline structure
could affect the formation of the protective
layer (Romagnoli and Vetere, 1995). Never-
theless, it has been recognised that the protec-
tive action of zinc phosphate is greater when it
The authors are grateful to CONACYT (Consejo
Nacional de Ciencia y Tecnología, México, con-
tract 3025-A9306), to CONACYT-CONICET
agreement, to CONICET (Consejo Nacional de
Investigaciones Científicas y Técnicas, Argentina)
and to CIC (Comisión de Investigaciones Científi-
cas de la Provincia de Buenos Aires) for their
sponsorship of this research. The authors also
acknowledge the assistance of C. López and
Programa de Corrosión UAC in conducting the
impedance tests. They wish to thank J.M. Miranda
for her assistance in preparation of the manuscript.
is micronised (Leblanc et al., 1981; Svoboda
and Mleziva, 1984). Modern specifications
recommend a maximum zinc phosphate
content in the dry film of ~20 vol per cent,
with a standard degree of micronisation, for
moderate outdoor exposure (Colores His-
pania SA, 1994). When the particle size
distribution and shape are optimised, zinc
phosphate content can be reduced to 10 per
cent, and the painted panel can resist more
severe exposures. New-engineered phos-
phates can be used to formulate effective
inhibitive metal primers (Hare, 1997).
One of the most successful applications of
Electrochemical Impedance Spectroscopy
(EIS) has been in the evaluation of the perfor-
mance and degradation of organic coatings
applied to metallic substrates when exposed
to aggressive media. EIS is adequate to evalu-
ate the suitability of substituting classic anti-
corrosive pigments with environmentally
acceptable compounds. EIS can provide both
quantitative kinetic and mechanistic informa-
tion, which make it a very useful tool for
developing improved coatings systems
(Granata, 1984).
The aim of the present work is to study the
corrosion resistance of several alkyd primers
pigmented with phosphates of divalent
cations (Ca2+, Zn2+), in order to screen
candidate pigments that eventually could
replace zinc chromate. The anticorrosive
performance of the paints applied on low
carbon steel panels was assessed by electro-
chemical (impedance and corrosion poten-
tial) as well as accelerated (salt spray and
humidity chamber) tests.
Experimental
Cold-rolled low carbon steel panels (SAE
1010) were utilised as substrates. Steel panels
(150 × 75 × 1mm) were sandblasted to Sa 21⁄2
(SIS 055900-67) and then vapour degreased
with toluene before painting. For this investi-
gation four alkyd paints were specially formu-
lated as described in Table I, whereas Table II
shows the anticorrosive pigments used. The
anticorrosive behaviour of phosphate pig-
mented coatings was compared with a refer-
ence paint containing zinc chromate. A paint
without anticorrosive pigments was used as a
blank in which the other components were
increased proportionally to attain the desired
PVC relationship. Paints were brush applied
on the panels. Specimens with an average dry
199
Table I Composition of paints tested
Volume
per cent of solid
Anticorrosive pigment 12.1
Talc 11.7
Titanium dioxide 4.6
Barium sulphate 11.6
Alkyd resin 59.0
Additives 1.0
PVC/CPVC 0.8
Table II Compounds used as anticorrosive pigments
Anticorrosive
pigment Designation
Calcium acid phosphate CP
Zinc phosphate, micronised ZP
Nonea N
Zinc chromate ZC
Note: aThe other ingredients were increased
proportionately
film thickness within the range 60 ± 5µm were
tested.
Impedance measurements were conducted
using a perturbating voltage of 10mV and a
frequency sweep of 100kHz to 1mHz. A
three-electrode cell configuration was
employed. The surface area of painted panels
(9.1cm2) exposed to the electrolyte (a 3 per
cent NaCl solution, pH = 7.0) was delimited
by means of a short piece of glass tubing
attached to the coated steel surface using a
silicon rubber adhesive. The cell contained a
graphite electrode as the counterelectrode
and a saturated calomel electrode (sce) as
reference. All experiments were carried out at
the laboratory temperature. Impedance spec-
tra were performed in the potentiostatic mode
at the corrosion potential using a Solartron
1250 frequency response analyser (FRA)
operated under microcomputer control. The
FRA was connected to the electrochemical
cell through a PAR 273 potentiostat. Two
impedance spectra were collected from sepa-
rate locations on each panel. Impedance
measurements were made for all paints after
different exposure times in the electrolyte up
to 576h. Analysis of impedance data was
performed using a well-known computer
analysis program (Boukamp, 1989).
Other series of painted panels were submit-
ted to exposure in a salt spray chamber in
accordance with the ASTM B 117-90 Stan-
dard or in a humidity chamber according to
 the ASTM D 2247-87 Standard. The panels,
with an area of 112cm2, were inspected visu-
ally at regular intervals up to 500h in the salt
spray chamber and up to 2,000h in the
humidity chamber. The panels were evaluated
using the system described by ASTM D 610
Standard for corrosion sites or for blisters
given by ASTM D 714 Standard. In the series
of panels exposed in the salt spray chamber, a
scratch line was made through the coating
with a sharp instrument so as to expose the
underlying metal to the aggressive environ-
ment. In order to assess failure at the scribe
ASTM D 1654 Standard was performed. In
all cases experiences were carried out in
triplicate and determining the mean value of
the results obtained in the test.
Results and discussion
Electrochemical tests
According to Van Westing et al. (1994), it is
necessary to have an independent parameter
such as the corrosion potential (Ecorr), mea-
sured at the same time the impedance spec-
trum is obtained, to support the interpreta-
tion of the mentioned spectra. The depen-
dence of the Ecorr on immersion time in the 3
per cent NaCl solution is shown in Figure 1.
Ecorr was recorded before each impedance
measurement. Although all paints show noble
values from Ecorr at the beginning of the
immersion, the paints CP and ZP maintain
these values for at least 200h, afterwards they
fall abruptly to more negative potentials. This
fall is observed at the few hours of immersion
for paints N and ZC. Nevertheless, it was
observed that, after 576h immersion, the
Ecorr values of the four paints were very near
Figure 1 Evolution of the corrosion potential (Ecorr) as a function of
immersion time in 3 per cent NaCl for steel panels coated with alkyd paints
300
200 Key
100 CP
0 ZP
Ecorr mV (sce)
–100 N N
ZC
–200
–300
–400
–500
–600
–700
0 100 200 300 400 500
Immersion Time (hours)
to the known free corrosion potential of
uncoated steel under equivalent environmen-
tal conditions, i.e. ~ –650mV/sce.
Most impedance data reported in the litera-
ture for polymer coated metals exposed to
corrosive media, agree with the simple model
shown in Figure 2 (Tsai and Mansfeld, 1993).
This model corresponds to a defective or
porous coating system. It was also used to
analyse the EIS data obtained in the present
work. It has two time constants: RiCp for the
paint film and RtCd related to the corrosion
cell formed at the base of the defects, Ri being
the ionic resistance of the paint film impreg-
nated with electrolyte, Cp the paint film
capacitance, Rt the charge transfer resistance,
and Cd the metal double-layer capacitance.
Re was related to the resistance of the elec-
trolyte and the ohmic resistance in electrical
leads.
Impedance spectra from the painted steel
specimens, for 1h and 576h immersion times
are depicted in Figures 3 and 4, respectively.
Scarcely after 1h immersion, the spectra in
Figure 2 Model of a defective insulating coating on a metallic substrate
Figure 3 Bode plots for steel panels coated with alkyd paints immersed in
3 per cent NaCl for 1h
10
Key
9 CP
Log Z (Ohms.cm2)
ZP
8
7
ZC
6
5
4
3
600
10–2 10–1 100 101 102 103 104 105 106
Log w (rads/s)
200
Figure 4 Bode plots for steel panels coated with alkyd paints immersed in
3 per cent NaCl for 576h (Rf corresponds to the overall system resistance)
10
9 Rf Key
CP
Log Z (Ohms.cm2)
8 ZP
7 N
ZC
6
5
4 5
3 4
10–2 10–1 100 101 102 103 104 105
Log w (rads/s)
the Bode plot format showed a high difference
in impedance response for these paints and a
relatively sharp transition from capacitive to
resistive behaviour. Paints ZP, CP and N
showed the highest resistance values at the
lowest frequencies (Rf), greater than
108Ω.cm2. Rf will eventually represent the
sum of coating resistance, charge transfer
resistance, and solution resistance. Paint ZC
exhibited a lower Rf value indicative of a lower
corrosion protection. After 576h of immer-
sion (Figure 4), Rf values decreased for all
paints and they were all close neighbours
indicating that a quick and constant deteriora-
tion took place during immersion time. Prob-
ably it is due to the inherently porous nature
of the primers. Rf values ranging from 107 to
1.9 × 105 Ω.cm2 for paints ZP and N respec-
tively. It has been proposed that coatings
showing a resistance of less than 107 ohms for
1cm2 of measured surface area are not protec-
tive (Leidheiser, 1991). At this immersion
time (576h), corrosion beneath all paints
except paint ZP would be expected to occur.
In Figures 3 and 4, paint ZP pigmented with
micronised zinc phosphate, showed the high-
est Rf values and paint ZC, pigmented with
zinc chromate, showed values of the lowest
ones.
A better estimate of the paints deteriora-
tion evolution can be obtained by considering
the variation of Ri and Cp as a function of
immersion time. As can be seen from Figure
5, Ri values decreased continuously from the
beginning for paints CP, ZP and N. The first
datumpoint for paint ZP in the Figure repre-
sents a measurement after 24hr, insufficient
accuracy in the impedance spectrum before
this time was expected as a result of the high
impedance measured. Ri, which represents
Figure 5 Evolution of the paint ionic resistance (Ri) as a function of
immersion time in 3 per cent NaCl for steel panels coated with alkyd paints
10
Key
CP
9
ZP
Log Ri (Ohms.cm2)
8 N
ZC
7
6
106 0 100 200 300 400 500 600
Immersion time (hours)
the extent of ionic conduction through the
polymer in electrolytic environments,
decreased over time, indicating an increasing
ionic conductivity for the coating and lower
protective properties as a result of electrolyte
penetration. Ri has been described as a het-
erogeneous assembly of electrolytically con-
ducting paths across the coating (Deflorian et
al., 1994; Kending et al., 1983). For paint ZC,
it was observed an initial increase in Ri values
up to 24h and then a sharp decrease up to
120h, greater than 4 orders of magnitude;
afterwards they increased slightly again and
finally decreased until 576h immersion. This
erratic behaviour, especially in the beginning
of the testing time, is usually attributed to the
plugging of the pores with products of paint
decomposition or corrosion products which
explains the initial increase of Ri values; while
the appearance of other localised weak points,
means that Ri decreases again. The decrease
and minimum of Ri values have been associat-
ed to the formation and rupture of blisters
and the subsequent increase and maximum to
the deposition of corrosion products in the
blister (Van Westing et al., 1994). Cavalcanti
and co-workers (1993) claimed that this
dynamic behaviour accounts for the 4-5
orders of magnitude fluctuations exhibited by
the Ri values during the tests.
One way to verify the behaviour of paint
ZC consists in a close examination of Figure 6
that shows the time dependence of Cp. As it is
widely known, as the coatings degrade, the
paint film resistance decreases and the coating
capacitance increases. Increasing capacitance
values are indicative of increased uptake of
water (electrolyte) (Skerry et al., 1992). Ini-
tially Cp of paint ZC decreased but after 120h
continued growing until 216 hours, where it
201
Figure 6 Evolution of the paint capacitance (Cp) as a function of immersion phase angle format (log frequency v. phase
time in 3 per cent NaCl for steel panels coated with alkyd paints angle) for the four paints is shown in Figure 7.
However, this Figure does not show clearly
10–6
Key and without doubt such a time constant,
CP
ZP
mainly for a non-skilful eye. Apparently, there
N is a second time constant for all paint except
10–7
Cp (F/cm2)

ZC for paint ZP. To obtain more detailed infor-

10–8
10–9
0 100 200 300 400 500 600
Immersion time (hours)
reached a plateau. This suggests that the
water uptake reached a steady state after 216h
of immersion (Compere et al., 1993). The
increase of Cp values for the other paints was
approximately continuous with time, which
agreed with the trend observed for Ri data
shown in Figure 5. So, Cp value was the
lowest for paint ZP after 576h immersion
(<10–8 F/cm2) corresponding to a good
dielectric properties coating and this same
paint exhibited the highest Ri value at the end
of the immersion time. According to Di Sarli
and co-workers (1990), the results obtained
from the electrochemical measurements show
that, comparatively, there is agreement with
mation about the extent of corrosion at the
paint/steel interface it is easier to examine the
Nyquist diagrams of these four alkyd paints
after 576h immersion. The corresponding
Nyquist diagrams showed two frequency-
dependent components for all paints. Figure 8
presents the Nyquist diagram for paint ZP.
According to the interpretation for this type of
complex plane plots, an initial high frequency
semicircle can be seen, which contains infor-
mation on the coating properties, and a very
clearly defined second semicircle indicating
that corrosion is effectively present. This little
second semicircle is approximately one-third
of the first semicircle, indicating that corro-
sion is incipient. The other paints exhibited a
Figure 7 Bode phase angle plots for steel panels coated with alkyd paints
immersed in 3 per cent NaCl for 576h
0
–10
Phase Angle (degree)

the results of Ecorr, Ri and Cp. The more –30

positive corrosion potential values (smaller
Key
areas exposed to corrosion) correspond to the –50 CP
higher values for the resistance to the flow of ZP
ions of the electrolyte through the membrane, –70
N
and with the minimum capacitance values. An ZC
example of this agreement is obtained when
–90
comparing the variation with the exposure 10–2 10–1 100 101 102 103 104 105 106
time of Ecorr and Ri for paint ZC in Figures 1 Log ω (rad/s)
and 5 respectively. A coincidence point by
point is observed in both Figures.
Figure 8 Complex plane plot for steel panels coated with paint pigmented
Nevertheless, it should be noted that all
with micronised zinc phosphate (ZP) immersed in 3 per cent NaCl for 576h
paints exhibited Ecorr values ~ –650mV/sce
after 576h immersion, which would indicate 7 ZP
that corrosion is being developed at the
6
Z imaginary/106 (Ohms.cm2)

paint/steel interface. These results agree with

5
those shown in Figure 4, Rf values for all
paints are less than 107 Ω.cm2 except for paint 4
ZP. To clarify this apparent contradiction it is 3
required to analyse impedance data by means 2
of other methods. At least, there are two
1
alternatives to identify a second time constant
which is associated with the metallic corrosion 0
0 2 4 6 8 10 12
for the electrode coated with paint ZP, Bode Z real/106 (Ohms.cm2)
phase angle plots and Nyquist diagrams. The
202
 semicircle and a diffusion tail (Hernández et
al., 1998). A diffusion tail (Warburg imped-
ance) appeared as consequence of a diffusion-
controlled corrosion process at the paint/steel
interface. Plotting the same data in both
formats (Bode and Nyquist) is a common
practice used by most researchers who assess
organic coatings by means of EIS. Granata
(1984) claims that Nyquist and other data
representation forms should be used for
more detailed data analysis, after the full data
range has been examined using the Bode plot
format.
A good agreement of results was also
achieved between Ri values and the break-
point frequency method as it has been
described elsewhere (Hernández et al., 1998).
An important characteristic of this method is
that the values for its application can be deter-
mined directly from the diagrams without a fit
to the model in Figure 2. The same paint
ranking was even obtained comparing the
results of both methods; this is in order of
growing protection against the corrosion
after 576h immersion in the saline electrolyte,
N < ZC < CP < ZP. The same ranking may be
obtained considering the visual appearance of
the immersed areas once the test was conclud-
ed (Table III). It should be noted that only a
corrosion spot was found when removing the
glass tubing from the painted surface. Seem-
ingly, the silicon rubber adhesive masked this
corrosion spot. Paint ZC presented fading
that suggests a loss of leachable chromate
from the paint.
From the EIS results shown, it is apparent
that the only mechanism that shared in the
metallic substrate protection was a barrier
effect for paints CP, ZP and N. Chemical
protection by plugging the coating pores by
means of corrosion products was only present
Table III Comparison between paint resistance (Ri) values and visual
appearance of the coating surface after 576h immersion in 3 per cent NaCl
solution
Sample Ri (KΩ.cm2) Visual appearance
CP 1,000 Few larger blisters, some of them
burst
ZP 7,080 No significant loss of protection
N 52 Many small burst blisters. One large
burst blister. Whole surface stained
by corrosion products
ZC 132 Few small blisters, some of them
burst. Fading
203
for paint ZC. The electrochemical mechanism
which involves the build-up of permanently
passive conditions at the metal surface was
hindered by chloride ions action forming
soluble ion complexes of iron which may
diffuse away and be converted to insoluble
rust products, as it has been pointed out by
Rammelt and Reinhard (1994). In accor-
dance with these authors, protection can only
be given by the chemical reaction of divalent
cations to produce solid compounds with
barrier properties, for example metallic soaps
or basic carbonates.
Accelerated tests
Tables IV and V illustrate paint deterioration
after 500h testing in the salt spray chamber or
2,000h in the humidity cabinet. None of the
paints showed blistering after the salt spray
test. There was rusting in and adjacent to the
scribe lines showing variable coating delami-
nation around them. The paint film was
removed and the panels observed to determine
the rusting degree (Table IV) at the conclusion
of the test. The anticorrosive protection was
improved when zinc phosphate and calcium
acid phosphate were employed, reaching
oxidation degrees of 10 and 8 respectively. The
underlying rusting in both cases was 2mm.
These paints behaved slightly better than that
formulated with zinc chromate (rusting degree
8), which showed an important underlying
rusting value (11mm). Buchheit et al. (1998)
claim that EIS and salt spray tests could be
sensitive discriminators of corrosion protec-
tion, but EIS was more discriminating in the
extremes of coating performance. When both
tests were sensitive, regression analysis showed
a linear relationship between the log of Ri and
the qualification obtained for a coating in salt
spray test.
Table V presents the results of the humidity
chamber test. The temperature during expo-
sure was 38oC. All paints except the paint
without anticorrosive pigment exhibited
Table IV Rusting degree (ASTM D610 and D1654) after
500h in the salt spray chamber
Rusting degree
Painted Panel after At scratch
Sample panel paint removal line, mm
CP 10 8 2
ZP 10 10 2
N 6 2 15
ZC 8 8 11
Table V Blistering (ASTM D714) and rusting degree (ASTM
D610) after 2,000h in the humidity chamber
Rusting degree
Painted Panel after
Sample Blistering panel paint removal
CP 8F 10 9 Boukamp, B.A. (1989), Equivalent Circuit (EQUIVCRT.PAS)
ZP 8F 10 10
N 6F 8 6
ZC 8F 8 8
relatively little degradation after this test. The
anticorrosive performance was related to the
observed blistering. The best behaviour was
also exhibited for the paint pigmented with
micronised zinc phosphate but it was very near
to the calcium acid phosphate one. Taking into
account the results of both accelerated tests,
paints can be classified in order of increasing
corrosion protection as N < ZC < CP < ZP.
This is the same order obtained with the other
three methods, Ri, breakpoint frequency and
visual appearance.
Conclusions
(1) Divalent cation phosphates are suitable
pigments to replace chromates in anticor-
rosive paints. In addition to the known
protective properties of zinc phosphate,
calcium acid phosphate showed promis-
ing results.
(2) A very good correlation was obtained
between the results of electrochemical
(Ri, Cp, breakpoint frequency and open
circuit corrosion potential) and accelerat-
ed (salt spray and humidity chamber)
tests. Results indicated the micronised
zinc phosphate containing paint as having
the best results, with the non-anticorro-
sive pigment containing paint as the
worst. Visual appearance after 576 h
immersion complements these results.
(3) From the EIS results, it is apparent that
the only mechanism that shared in the
metallic substrate protection was a barrier
effect for all paints except for paint pig-
mented with zinc chromate. Chemical
protection by build-up of compounds
plugging the coating pores was only
present for the same paint.
(4) Although the results observed between
the EIS and salt spray tests indicate that
there is a good correlation in the diagnosis
204
made by both types of tests, more experi-
mental work is required to arrive at true
relationships.
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