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Electrochemical Study of the Corrosion Behaviour

of Electroplated Copper Plates
A. Bautista, M. Lage, F. Velasco
Materials Science and Engineering Department. Universidad Carlos III de Madrid
Avda. Universidad no 30
Leganés, Madrid 28911, SPAIN
Phone: (34) 91 624 99 14
Fax: (34) 91 624 94 30
e-mail: mbautist@ing.uc3m.es

For enlarging the number of printings, copper chalcographic plates were frequently coated for years (even
nowadays) using electrolytically applied metal coatings of higher hardness. Galvanic coatings present a corro-
sion performance different from that of the copper base, which influences their condition. Our paper has de-
termined the corrosion rates of bare copper plates along with copper plates with electrolytic coatings using ei-
ther chromium or iron in neutral and acid solutions. Two different dc electrochemical techniques have been
used: polarization curves and polarization resistance measurements. Moreover, many of these electrolytically
coated plates have areas of bare copper. The effect of galvanic couplings that can appear on these materials has
been quantified electrochemically.

Keywords: copper plates, chromium coatings, iron coatings, corrosion rates, galvanic couples

1. INTRODUCTION diffraction (XRD) analysis that offers interesting informa-

Copper chalcographic plates have been frequently
coated for years (and they still are nowadays) with metal
electrolytic coatings of higher hardness, in order to enlarge
the number of printings. For instance, in the National
Chalcography of Spain, there are 230 copper plates en-
graved by Francisco de Goya (the 93% of his chalcograph-
ic work), and all of them exhibit electrolytic coatings. A
damage assessment was carried out in a previous study,
which found that 73% of the plates have some kind of dam-
age [1]. Thus, our investigation involves obtaining as much
information as possible about the influence of the presence
of metallic coatings on the copper plates for designing their
optimal conservation and restoration strategies.
The nature of the coatings on the Goya's plates has not
been extensively studied. However, there is some docu-
mented information [1] along with X-ray
tion. X-ray diffractograms shown in Figures 1 and 2 corre-
spond to “Tauromaquia No 8” and “Capricho No 10”. As can
be deduced from the diffractrograms, “Tauromaquia No 8”
is chromium plated, and there are archival documents [1]
that prove that all the “Tauromaquia” series is chromium
plated. “Capricho No 10” is iron plated, and this type of
metallic coating was also detected by XRD analysis on plates
belonging to “Desastres de la Guerra” series, “Disparates”
series and other Goya's plates. Moreover, XRD has also
been used to identify some Ni coatings on Goya's plates[1]
Galvanic coatings were the first conservation issue ap-
plied on the plates. The presence of the coatings on the en-
graving plates not only changes their surface hardness, but
also affects their corrosion behaviour. Nowadays, any con-
servation policy of engraving copper plates should be mod-
ified due to the presence of these coatings, and it specific
strategies should be

Figure 1 - X-ray diffractrogram corresponding Figure 2 - X-ray diffractrogram corresponding

to “Tauromaquia No 8” to “Capricho No 10”
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Electrochemical Study of the Corrosion Behaviour of Electroplated Copper Plates

designed depending on the nature of the coatings and the
characteristics of the environment they are exposed to. In
this paper, a simple approach to the corrosion rate of bare
copper, and iron and chromium electrolytic coatings is pre-
sented. The studies were carried out in neutral medium,
simulating the corrosive conditions of an uncontrolled mu-
seum environment with fluctuating and high RH, as well as
an acid medium, since air borne contaminants can reduce
the pH of water vapour that condensates on the surface of
the objects. Moreover, the influence of galvanic couples,
which can easily occur for engraving plates with electrolytic
coatings, was carefully analyzed in this work.
2. EXPERIMENTAL TECHNIQUES
Copper plates of 2.9 mm width were examined both as
uncoated and coated with electrolytic layer containing
chromium and iron.
Electrochemical measurements were carried out in
neutral media (0.1 M KClO4 solutions) and acid media
(5% H2SO4 solutions). The traditional three electrode con-
figuration was used, using a saturated calomel electrode
(SCE) as reference electrode. The used potentiostat was
PAR 263A from EG&G Instruments.
Polarization curves were carried out after exposing the
copper plates for 120 minutes in the test solutions. The po-
tential was swept from -175 mV vs. the corrosion potential
(Ecorr) to +175 mV vs. Ecorr at a rate of 0.16 mV/s.
Polarization resistance measurements were performed
periodically from -20 mV vs Ecorr to +20 mV vs. Ecorr. The
potential was swept at 0.20 mV/s.
Galvanic intensities were measured using a zero resis-
tance ampmeter. Specimens of similar surface exposed to
the testing solutions were used.
Prior to the electrochemical studies performed on repli-
cas, XRD measurements of original Goya's plated engrav-
ing plates were carried out from 2ı=5o to 2ı=100o, at a
sweeping rate of 0.04o/s, using a X’Pert Phillips equipment.
3. RESULTS AND DISCUSSION
The polarization curves of the bare and coated coppers
in neutral medium can be seen in Figure 3. Polarization re-
sults in acid medium are shown in Figure 4. The most
meaningful parameters that can be calculated from both
figures are summarized in Table 1.
Bare copper plates exhibited low corrosion intensities
(icorr) in both studied media, being slightly higher in acid. In
both media, copper corrosion rate was controlled by the
cathodic process (anodic Tafel slope, ‚a, is always minor
than cathodic Tafel slope, ‚c). In acid medium, the Ecorr is
also less noble, and the cathodic process is less impeded in
acid media (bc is lower). Obviously, the long-term behav-
iour of the copper would depend on the protective ability
of the formed oxides, which is also dependent on the pH of
the media [2,3].
It can be checked that iron coatings dramatically de-
creases the corrosion resistance if it is compared with that
of original bare copper engraving plates. In neutral media,
the corrosion intensity (icorr) of the electrolytic iron is more
than 20 times higher than that of the bare copper plates.
However, in the acid media, both iron coated copper plate
and bare copper plate increases their corrosion rates, but
iron coated copper plate does it at a higher extent than
bare copper. In 5 %

Figure 4 - Polarization curves corresponding

to the studied materials in acid medium

Table 1. Parameters calculated from polarization curves

Medium Material Ecorr icorr ‚a ‚c

(mV) (A/cm2) (mV) (mV)
Cu 26 6.0e-7 16 236
Neutral Cr -240 7.1e-8 255 210
Fe -490 1.5e-5 260 260
Cu -78 1.1e-6 74 140
Acid Cr 11 1.0e-7 46 250
Fe -506 1.0e-4 185 120
Figure 3 - Polarization curves corresponding
to the studied materials in neutral medium
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A. Bautista et al.
H2SO4 solution, electrolytic iron coated copper plate cor-
rodes 100 times faster than bare copper plate. This data ex-
plains the extent and frequency of the damages that iron
coated engraved plates shown all over their surface (see ex-
ample in Figure 5).
XRD carried out on the back side of some iron coated
plates, where relatively large deposits of corrosion prod-
ucts had been detected, are compatible with hematite
(Fe2O3) (Figure 6).
On the other hand, chromium coated copper plates ex-
hibit better corrosion behaviour than bare copper plates in
both media (Table 1). The corrosion rates of the electrolyt-
ic coating in both studied media are more than one order
of magnitude lower than those of the bare copper.
These results about the good corrosion resistance of
chromium corresponds to lack of corrosive attack that are
usually observed in chromium coated engraving plates.
In spite of being a relatively simple method to estimate
the corrosion rate of the metals, polarization curves imply
the imposition of high overpotentials to the studied system,
so they are a destructive test. Polarization resistance (Rp)
measurements are faster, non-destructive, and they can be
applied several times to the same specimen to observe how
the corrosion rate changes with time. In Figure 7, Rp mea-
surements
Figure 5 - Appearance of “Disparate no 4”, that is iron
coated, and where extensive corrosion damage can be easi-
ly observed.
Figure 6 - X-ray diffractrogram of oxide powders detached
from the back side of the Goya's plate “Felipe IV” where
peaks compatible with Fe2O3 (▲) can be identified.
corresponding to bare copper exposed for different times
in H2SO4 solutions are shown. A decrease can be observed
112
in the slopes of the lines, that indicate that the Rp of the
studied material decreases with time.
The Rp values can be used to calculate icorr, using the
Stern-Geary equation [4] and the ba and bc values obtained
from the polarization curves (Table 1). Adequate similarity
can be observed between corrosion rates calculated from
Rp measurements and from polarization curves (Figure 8).
Moreover, the amount of metal transformed into oxide
during the tests can be calculated from the icorr values using
the Faraday’s law [5]. Using the results from Rp measure-
ments, weight loss for the studied plates, in Figures 9 and
10 were estimated. The higher corrosion rates suffered by
iron coated copper plates indicated that the weight losses
corresponding to this coating should be represented in dif-
ferent vertical axis than those corresponding to bare cop-
per or chromium coated copper plates.
Figure 7 - Temporal evolution of the Rp of bare copper
in acid medium.
Figure 8 - Relationship of icorr values obtained using differ-
ent electrochemical techniques for the studied materials
after similar exposure times.
Figures 9 and 10 indicates that initially, all the studied
plates tend to corrode faster, but after the formation of a
certain amount of oxides on their surface, the corrosion at-
tack slows down. This phenomenon is evident when a large
amount of oxides is formed (see curve corresponding to
iron coating in acid, in Figure 10) or when the formed ox-
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Electrochemical Study of the Corrosion Behaviour of Electroplated Copper Plates

ides are highly protective, as chromia (see curve corre-

sponding to chromium coated copper plate in Figure 9).
However, the electrolytic metal coatings do not usually
cover the entire surface of the copper engraving plates.
Quite often, coated plates have evidence of areas without
coating. These areas can have different origins:
ñ Suction pads placed at the back of the plate to hold the
plate in the electrolytic bath [6] (Figure 11).
ñ Clamps placed on edges for holding in the electrolytic
bath the plates when they are engraved on both sides
(Figure 12).
Figure 11 - Bare copper region caused by a suction pad
on the back side of “Capricho No 36”.

Figure 9 - Weight loss suffered by the metals due to expo- Figure 12 - Bare copper region caused by clamps on the
sure in neutral medium. The results are calculated from Rp one of the edges of “Tauromaquia No 8”.
measurements.

Figure 13 - Improper metal coating due to greasy contami-

Figure 10 - Weight losses suffered by the metals due to ex-
posure to acid medium. The results are calculated from Rp
measurements.
ñ Detachments of the coating due to scarce careful appli-
cation or manipulation of the plates (Figure 13).
ñ Loss of the coating due to corrosive attack (Figure 5).
The strength of the galvanic couples that can appear on
iron and chromium coated engraving plates was measured
during this research in neutral and acid solutions. Curves
as that shown in Figure 14 are obtained. During the mea-
surements the bare copper and the coated copper coupons
are connected in such a way that a positive the galvanic cur-
rent (igalv) indicates that the metallic coating favours the
corrosion of the bare copper, and a negative igalv means that
the copper reduces its corrosion rate due to the presence of
the coating and it speed the attack on the coating.
nation from finger prints prior to the electrolytic process
on “Capricho No5”.
The bare copper, when is short-circuited to electroplat-
ed chromium in H2SO4 solutions, tend to be polarized by
the electrolytic coatings. Initially the Ecorr of isolated Cu is
more noble than the Ecorr of isolated Cr (Figure 14). That
means that when both metals are short-circuited, copper
protects itself and favours the attack on the chromium.
However, this only occurs during the first few minutes.
While the Ecorr of the Cu hardly changes during exposure,
the Cr coated plate in 5% H2SO4 passivates in a very effec-
tive way. A very isolating oxide layer grows on this surface,
as can be checked by the marked increase on its Ecorr.
Hence, after a short time, the chromium becomes more
corrosion resistant than copper in acid, and the sign of the
galvanic current changes. After the few minutes of stabi-
lization, the Ecorr of the galvanic couple is 30 mV

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A. Bautista et al.
Figure 14 - Galvanic current measured between bare Cu
and chromium plated Cu in acid medium. Time evolution
of the corrosion potentials of both isolated materials in
that medium are also included.
Figure 15 - igalv measured between bare Cu and the studied
electrolytic coatings. Currents that favour the corrosion of
the copper are marked in black. Currents that favour the
corrosion of the coating are marked in grey.
vs SCE, very close to the Ecorr of isolated Cr. When the stabi-
lization is reached, the corrosion of the copper is accelerated
by the presence of electrolytic chromium. It is true that the
igalv is lower than the icorr of isolated copper in acid (Table 1),
but data in Figure 14 has been obtained exposing identical
surfaces of bare copper and electrolytic chromium to the so-
lution. In practice, the surface of bare copper on coated
plates is small in comparison with that electrolytic coating
(Figures 5 and 11-13), so it is probably that if this kind of gal-
vanic coupling appears on engraving plates, it was more dan-
gerous for the copper than in the designed laboratory test.
The ability of chromium to accelerate the attack on cop-
per plates has also been detected in neutral media (Figure
15). As expected, the strength of the galvanic couple is minor
than in acid solutions, due to the minor aggressivity of the
medium. Copper oxides have been identified by XRD in the
boundary between chromium and copper caused by the suc-
tion pads (as those shown in Figure 11). A small peak com-
patible with Cu2O is found in measurements performed in
that region (Figure 16). In Figure 15, it can also be seen that
copper forms intense galvanic couples with iron coating.
These galvanic couples favour iron corrosion. For these ma-
terials, the measured igalv are higher than the icorr of the elec-
trolytic iron in the studied media (Table 1). In practice, the
effect of the galvanic couple could be reduced by the area ra-
tio. In this case, the anodic area on engraving plates (iron) is
much higher than cathodic area (copper). In summary, both
chromium and iron coatings can have adverse effects for
the conservation of copper plates. It is not advisable to ap-
114
ply such kind of conservative technique in pieces with artis-
tic value. It will be interesting to carry out studies that ana-
lyze the possibility of removing the coating without affect-
ing the copper base. Besides, the original artefact of the
artist could be appreciated without the metallic coating.
Figure 16 - X-ray diffractrogram of Goya's plate “Tauro-
maquia 8” where peak compatible with Cu2O can be iden-
tified. Diffractogram taken on a bare copper region of a
chromium coated plate.
4. CONCLUSIONS
Galvanic coatings increase the hardness of the surface
of engraving plates, but our study has shown disadvantages
from the corrosion point of view:
ñ Iron coatings exhibit a low corrosion resistance and cor-
rode easily, increasing the difficulty of the conservation
of the engraving plates.
ñ Chromium coatings increase the corrosion resistance of
the copper, but tend to form galvanic couples with it, so
it can favour the corrosion of copper in those regions
where the copper of the engraving plate is exposed to
the environment.
REFERENCES
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