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Electrochemical Techniques as a Tool for Testing the Efficiency

of Protection Systems for Historical Steel objects
Emilio Cano1, David M. Bastidas1, Vasilike Argyropoulos2 and Amalia Siatou2
1
National Center for Metallurgical Research (CENIM)-CSIC
2
Dept. of Conservation of Antiquities & Works of Art, T.E.I. of Athens
Avda. Gregorio del Amo 8, 28040 Madrid, Spain
Phone: +34 91 5538900
Fax: +34 91 5347425
e-mail:ecano@cenim.csic.es

The paper addresses the applicability of electrochemical techniques, polarization resistance (Rp), and
electrochemical impedance spectroscopy (EIS), for the evaluation of protective coatings (Paraloid® B-72
and a liquid polyethylene wax, Poligen® ES 91009), with and without addition of commercial corrosion
inhibitors, as innovative protection coating systems developed under the PROMET Project for the protec-
tion of cultural property made of steel. A comparison of results between these techniques is presented.
The electrolytes used are 0.1M NaCl and the dilute Harrison’s electrolyte (0.35% w/v (NH4)2SO4 + 0.05%
w/v NaCl in H2O), to simulate the type of pollutants found in museum environments.

Keywords: Electrochemical, EIS, protection, corrosion inhibitor additives, coating systems, steel

1. INTRODUCTION commonly used by professional conservator-restorers for

metals. Table 1 summarizes the coating systems tested.
Electrochemical techniques are mainly known in the
field of Cultural Heritage conservation as a tool for conser- Table 1: Coatings and corrosion inhibitors tested.
vation treatments of metal objects, usually involving the Identification Type of coating / coating system
cleaning of corrosion layers or stabilization of metals by 0 Reference (No coating)
the removal of chlorides. 1 Renaissance wax
However, electrochemical techniques can be a very 2 Poligen® ES 91009
valuable tool and quick method for assessing the protective 2a Poligen® ES 91009 + M435 CI additive
efficiency against corrosion of the different (both tradi- 2b Poligen® ES 91009 + M370 CI additive
tional and innovative) protective layers or films applied to 3 15% Paraloid® B-72 in Acetone
prevent further degradation of metal objects. Although 3a 15% Paraloid® B-72 in Acetone + M435
these techniques are widely applied in corrosion research CI additive
and industrial applications, their use in conservation and
3b 15% Paraloid® B-72 in Acetone + M109
restoration of cultural heritage is, so far, more limited.
CI additive
The aim of this paper is to investigate the potential effi-
3c 15% Paraloid® B-72 in Acetone +
ciency of traditional and innovative corrosion protection
Alkaterge-T CI additive
systems for metal museum objects.

2. EXPERIMENTAL Two coatings commonly used in conservation-restora-

Low carbon steel coupons of 2.5 cm × 5 cm were cut
from a hot-rolled sheet of 3 mm of thickness. Samples were
mechanically polished with emery paper with successive
grades down to grade 600, ultrasonically cleaned in ethanol
and stored with silica gel until application of a protective
coating system. Before the application of the coating, the
surface was degreased using cotton swabs with acetone.
The composition of the steel, obtained by glow dis-
charge-optical emission spectroscopy was: 0.12% C,
<0.05% Si, 0.55% Mn, 0.010% P, 0.015% S, and balance Fe.
Coupons where coated using a nylon-bristle brush
121
tion (C-R) treatments were included in our investigation
for comparison to the new coating systems: Paraloid® B-
72 (acrylic resin) and Renaissance wax (microcrystalline +
polyethylene wax). A new wax coating was tested, bought
as a ready-to-use liquid that dries within 24 hours upon ap-
plication, known as Poligen® ES 91009 (BASF) (aqueous
emulsion of an ethylene copolymer). Additionally, corro-
sion inhibitor (CI) additives were added either to Par-
aloid® B-72 or Poligen® ES 91009. The CI tested were
bis-oxazoline (Alkaterge-T) (Dow Chemical Co.), calcium
sulfonate (M109), a blend of triazoles (M435), and ammo-
nium salt of tricarboxylic acid (M370) (Cortec Co.).
AP°YPO¶OY§OY TELOS 30-01-08 11:02 ™ÂÏ›‰·122
E. Cano et al.
Two different electrochemical tests where carried out,
polarization resistance (Rp) and electrochemical imped-
ance spectroscopy (EIS). A classical three electrode elec-
trochemical cell was used. The working electrode was the
surface (area 4.15 cm2) of the coupon exposed to the elec-
trolyte, the counter electrode was a large area platinum
mesh, and the reference electrode was a saturated calomel
electrode (SCE). All experiments were performed after 1 h
of stabilization of the open circuit potential in the elec-
trolytic solution. Figure 1 shows a photograph of the elec-
trochemical cell used for these experiments.
Two electrolytes were used to simulate the type of pol-
lutants found in most museum environments in the
Mediterranean region:
ñ 0.1M NaCl, named electrolyte N.
ñ dilute Harrison’s electrolyte (0.35% w/v (NH4)2SO4 +
0.05% w/v NaCl in H2O), named electrolyte S.
Figure 1 - Photograph of the electrochemical cell used
for the experiments
For Rp measurements a EG&G PARC 273A potentio-
stat/galvanostat was used. The potential was swept from -
10 to +10 mV vs. open circuit potential, at a scan rate of
0.16 mV/s.
For EIS, a Solartron 1250 frequency response analyzer
was connected to the potentiostat. A logarithmic sweeping
frequency of 5 steps/decade was used, from 64 kHz to 64
mHz. Impedance measurements were obtained at the
open circuit potential, imposing a sinusoidal signal of 10
mV amplitude. EIS measurements were made only with
electrolyte N.
The thickness of the coatings was measured using an
Elcometer 300 thickness gauge, using a probe for magnetic
materials based on electromagnetic induction.
SEM images of coatings, shown in Figure 8, applied to
pre-corroded samples (not tested here) were taken using a
JEOL JSM-5310 Scanning Electron Microscope, with a
voltage of 3kV to avoid any damage to the coatings.
122
3. RESULTS AND DISCUSSION
The visual appearance of the specimens is a very im-
portant parameter to take into account when dealing
with coatings intended to be used for the C-R treatments
of cultural property. Even though this is a subjective
opinion, it is very important that the coatings applied to
metals do not alter their aesthetic appearance, in terms
of color changes. From this point of view, all coatings
studied were considered suitable, since all of them are
transparent [1].
Additionally, in the case of bare metals, the metallic
shine needs to be preserved. From this point of view,
there are important differences between the coatings.
For the bare steel coupons, the best appearance is given
by Renaissance wax, since this aspect of the metal is
completely natural. On the contrary, the Paraloid® B-
72 coatings have a plastic appearance, and it is difficult
to obtain a uniform coating appearance. The visual ap-
pearance of the Poligen® coated samples lies some-
where in between the previous two. It gives a slightly
plastic aspect, but the layer is more uniform than the
Paraloid® B-72.
Figure 2 - Average thickness of the coatings.
Figure 2 shows the average thickness of the different
coating systems investigated on bare steel coupons. The re-
ported thickness is an average of 20 points in different ar-
eas of two different samples. It can be observed that there
are important differences in the thickness of the coatings
and, therefore, for the comparison of the protective char-
acter of the different coatings this should be taken into ac-
count.
Figure 3 shows the corrosion potential (Ecorr) of the
coated steel coupons after 1 hour of immersion in different
electrolytic solutions. It can be seen that the application of
the coatings shifts the Ecorr towards more noble values (i.e.,
less negative potentials) except in the case of coating 1, Re-
naissance wax, which gives potential values similar to the
uncoated samples. The amount for the shift in potential
differs for the different coating systems, where coating 2a
had the best behavior.
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Electrochemical Techniques as a Tool for Testing the Efficiency of Protection Systems for Historical Steel objects
Figure 3 - Corrosion potential of the different samples
after 1 hour of immersion
Figure 4 shows the polarization resistance of the differ-
ent samples.
Figure 4 - Polarization resistance of the different samples
The polarization resistance of a material is defined as
the slope of the potential–current density (¢E/¢i) curve at
the free corrosion potential:
Rp = B
icorr
where Rp is the polarization resistance, icorr is the corro-
sion current and B is a constant that can be related to the
anodic (ba) and cathodic (bc) Tafel slopes according to:
Rp = b·bc
2.3(b· + bc)
Faraday’s law can be used to calculate the corrosion
rate (in mass/time units) from icorr .
The determination of constant B to calculate icorr from
the experimentally determined Rp can be done by different
means, being the most immediate the determination of the
Tafel slopes. However, a rough estimation can be done us-
ing an intermediate value of 0.026 V [2].
In our case, since the experimental electrolyte is not
the media to which the metals will be exposed (since this
coatings are intended for atmospheric corrosion protec-
tion), the calculation of the exact corrosion rate is not im-
portant, and it is enough to see that the corrosion rate is in-
versely proportional to the polarization resistance.
According to data in Figure 4, coating 1 showed no pro-
tective effect, with a polarization resistance similar to the
uncoated steel (~103 ø cm2). Coatings based on Poligen®
ES 91009 showed a better protection, especially with the CI
additives (coatings 2a and 2b), yielding an Rp of ~106
øcm2. Coating systems using Paraloid® B-72 also provide a
good protection (~105 ø cm2), but in this case the addition
of corrosion inhibitors does not improve the protection in
all cases: the protection is better for coating 3b, is similar in
coating 3c, and in the case of coating 3a the additive impairs
the protective character of the Paraloid® B-72.
Figure 5 shows the Bode plots of the EIS data obtained
for the metal without coating, and with coatings 1, 2, 2a and
2b. It can be seen that coatings 1 and 2 do not provide a sig-
nificant protection of the base metal, since the values of the
impedance are quite close to the uncoated samples. On the
other hand, coatings 2a and 2b show an increase of two and
three orders of magnitude in the values of |Z| respectively.
Bode plots for coatings 3, 3a, 3b and 3c are shown in
Figure 6, along with the reference sample. Coatings 3, 3b
and 3c show a good protective character, but the addition
of the corrosion inhibitor decreases the corrosion protec-
tion properties of the coating.
EIS data are usually studied by means of an equivalent
circuit that reproduces the properties of the metal/coating
system. A simple corrosion process is usually modelled us-
ing the equivalent circuit shown in Figure 7a, composed of a
resistance (Rs), modelling the resistance of the electrolyte,
in series with a constant phase element (CPE1) in parallel
with a resistance (R1), usually modelling the double layer
capacitance and the polarization resistance, respectively [3].
EIS data obtained from a coated metal are usually mod-
elled using two sub-circuits, each one composed by a resis-
tance in parallel with a capacitor or CPE [4,5].
(1)
(2)
Figure 5 - Bode plots obtained from samples
without coating and with coatings 1, 2, 2a and 2b.
123
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E. Cano et al.
Figure 6 - Bode plots obtained from samples
without coating and with coatings 3, 3a, 3b and 3c.
The CPE is commonly used instead of a capacitor to
model the behaviour of many electrochemical systems
showing depressed semicircles in the Nyquist plot. The im-
pedance of a CPE is defined by
∑CPE = 1
Àn(jˆ)· (3)
where Yn is a constant, j=(-1)1/2, ø=2f, and the exponent ·
takes values from -1 to 1: when · =0, the CPE is a resistor;
EIS data of the sample without coating has been mod-
elled using the equivalent circuit of Figure 7a. The equiva-
lent circuit of Figure 7c has been used to model the spectra
of coating 1. The values of the exponent of the CPEs are
about 0.8, and therefore can be interpreted as “imperfect”
capacitors. According to the interpretation of the classical
circuit for coated metals, CPE1 and R1 can be assigned to
the coating behaviour, and CPE2 and R2 to the corrosion
process at the bottom of the pores on the coating [5]. It can
be observed that the values of the double layer and polar-
ization resistance are very similar to the uncoated sample,
and that the resistance of the coating is extremely low, only
124
when · =1, the CPE is a capacitor; and when · =-1, the
CPE is an inductor. Finally, if · =0.5, the CPE is the War-
burg impedance, that is, models a diffusion process [6].
The use of a CPE instead of a “pure” capacitor can be at-
tributed to different reasons, such as surface roughness, in-
homogeneous distribution of the reaction rates or the cur-
rent or differences in the thickness or properties of a coating.
Figure 7 show the equivalent electrical circuits that
have been used to model the EIS spectra obtained from
our samples. Table 2 shows the values of the different ele-
ments, according to Figure 7, obtained from the fitting of
the experimental data to the equivalent circuits.
Figure 7 - Equivalent electrical circuits used
to model EIS spectra.
22.86 ø cm2, indicating that the protective character of this
coating is almost null.
EIS data of coatings 2, 2a and 2b have been modelled
using the equivalent circuit in Figure 7b. The “nested cir-
cuit” model is applicable only to coatings that have defects
or pores that allow the electrolyte to penetrate the coating
down to the metal. Figure 8 shows SEM images of the dif-
ferent coatings applied to pre-corroded metal samples (not
investigated here), which help to interpret EIS spectra. It
can be observed that in the case of coating 1, large pores
are visible, and justify the use of the equivalent circuit in
Figure 7c, but in the case of coating 2, the coating seems to
be intact without any signs of defects. For coatings without
AP°YPO¶OY§OY TELOS 30-01-08 11:02 ™ÂÏ›‰·125
Electrochemical Techniques as a Tool for Testing the Efficiency of Protection Systems for Historical Steel objects
defects, Skale et al. [7] have proposed that diffusion of
species through the coating control the corrosion rate, and
therefore can be modelled using Warburg impedance. In
our case, the exponents of CPE2 are around 0.5, and there-
fore the CPE is a Warburg impedance, indicating a diffu-
sion process. The values of the exponent of CPE1, on the
other side, range from 0.76 to 0.96, and can be attributed to
an imperfect capacitance of the coating. The values of R1 in-
creases in order from coating 2, to coating 2a and coating 2b
indicating that the later has the best protective properties.
Impedance spectra from coatings 3, 3a, 3b and 3c have
been modelled using circuit in Figure 7c. However, in this
Figure 8 - SEM images of coating 1 (a), coating 2 (b) and coating 3 (c), applied on pre-corroded steel samples.
In general, EIS results completely agree with results
obtained by Rp. The main advantage of the polarization
resistance method is that it is a very fast technique and
that the interpretation of the results is usually much
easier than EIS. On the contrary, EIS provides more in-
depth information concerning the behaviour of the
coating and the corrosion and diffusion processes tak-
ing place. The main disadvantage of EIS is that the in-
terpretation of the results is much more complicated
than Rp, due to the complexity of the information it
provides.
To summarize, the best protection for iron without
corrosion products is provided by coating 2b (Poligen®
ES 91009 + M370 inhibitor) and coating 3b (Paraloid®
B-72 + M109 inhibitor). But when dealing with coatings
it is very important to consider the thickness of the coat-
ing, and the Poligen coatings yielded a good protection
with a thickness of about one half of the thickness of the
Paraloid® B-72 (see Figure 2). Poligen is also favoured
by its uniform and natural appearance, which is an im-
portant factor to take into account for coatings to be
used in C-R treatments. On the other hand, Paraloid®
B-72 has the advantage of being a coating well known
amongst the conservators-restorers for its good aging
properties and reversibility. Nevertheless, regarding this
aspect, it should be noted that the addition of the corro-
sion inhibitors may change these good properties.
125
case, the low values of the exponents of both CPEs do not
allow for a classical interpretation of the elements. SEM
image in Figure 8c shows that coating systems with Par-
aloid B-72 are not as uniform as in the case of Poligen
(coating 2), since they show cracking and irregularities.
The values of the exponents are close to 0.5, indicating a
diffusion process, probably through the corrosion products
formed upon inmersion inside the cracks and defects of the
coating. The higher values of resistances, and therefore the
best protective character, are given by coating 3b. On the
contrary, the values of coating 3a are much lower than the
coating without additive.
The worst protection is provided by coating 3a (Par-
aloid® B-72 + M435 inhibitor) and especially coating 1
(Renaissance wax). This later coating does not provide any
measurable protection to the base metal, and therefore its
use as a corrosion protection system for metallic objects is
not recommended.
4. CONCLUSIONS
Electrochemical techniques make possible a quantita-
tive comparison between the different coating systems and,
therefore, the selection of the most appropriate coatings to
be applied to real objects.
The best protection is provided by Poligen® ES 91009
along with the M370 CI additive, and by Paraloid® B-72
with the addition of M109 CI additive.
Poligen® ES 91009 seems to be a very promising coat-
ing for C-R of metal objects made of steel, since it provides
good protection against corrosion.
ACKNOWLEDGMENTS
Authors wish to acknowledge the European Communi-
ty for funding this research under the 6th Framework Pro-
gram project PROMET.
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E. Cano et al.
REFERENCES
[1] Siatou, A., Argyropoulos, V., Charalambous, D., Po-
likreti, K., Kaminari, A.; “Testing New Coating Sys-
tems for the Long-Term Protection of Copper and
Iron Alloy Collections Exposed in Uncontrolled Mu-
seum Environment” paper submitted in the CSSIM
conference
[2] González, J.A.; “Control de la corrosión. Estudio y
medida por técnicas electroquímicas” CSIC, Madrid,
pp. 101-134 (1999), (in Spanish).
[3] Loveday, D., Peterson, P., Rodgers, B.; “Evaluation
of organic coatings with electrochemical impedande
spectroscopy. Part 1: Fundamentals of electrochemi-
cal impedande spectroscopy”, JCT Coatingstech,
Vol. 1, pp. 46-52 (2004).
126
[4] Murray, J. N.; “Electrochemical test methods for eval-
uating organic coatings on metals: an update. Part III:
Multiple test parameter measurements”, Prog. Org.
Coat., Vol. 31, pp. 375-391 (1997).
[5] Loveday, D., Peterson, P., Rodgers, B.; “Evaluation of
organic coatings with electrochemical impedande
spectroscopy. Part 2: Application of EIS to coatings”,
JCT Coatingstech, Vol. 1, pp. 88-93 (2004).
[6] Bastidas, J. M., Polo, J. L., Torres, C. L., Cano, E.; “A
study on the stability of AISI 316L stainless steel pit-
ting corrosion through its transfer function”, Corros.
Sci., Vol. 43, pp. 269-281 (2001).
[7] Skale, S., Dolecek, V., Slemnik, M.; “Substitution of
the constant phase element by Warburg impedance
for protective coatings”, Corros. Sci., Vol. 49, pp.
1045-1055 (2007).