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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 Legans, 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 corrosion performance different from that of the copper base, which influences their condition. Our paper has determined the corrosion rates of bare copper plates along with copper plates with electrolytic coatings using either 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 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 engraved by Francisco de Goya (the 93% of his chalcographic 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 damage [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 documented information [1] along with X-ray diffraction (XRD) analysis that offers interesting information. X-ray diffractograms shown in Figures 1 and 2 correspond 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 applied on the plates. The presence of the coatings on the engraving plates not only changes their surface hardness, but also affects their corrosion behaviour. Nowadays, any conservation policy of engraving copper plates should be modified due to the presence of these coatings, and it specific strategies should be

Figure 1 - X-ray diffractrogram corresponding to Tauromaquia No 8 110

Figure 2 - X-ray diffractrogram corresponding 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 presented. The studies were carried out in neutral medium, simulating the corrosive conditions of an uncontrolled museum 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 configuration 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 potential 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 resistance ampmeter. Specimens of similar surface exposed to the testing solutions were used. Prior to the electrochemical studies performed on replicas, XRD measurements of original Goya's plated engraving plates were carried out from 2=5o to 2=100o, at a sweeping rate of 0.04o/s, using a XPert 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 results 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 behaviour 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 decreases 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 Cu Cr Fe Cu Cr Fe Ecorr (mV) 26 -240 -490 -78 11 -506 icorr (A/cm2) 6.0e-7 7.1e-8 1.5e-5 1.1e-6 1.0e-7 1.0e-4 a c (mV) (mV) 16 236 255 210 260 260 74 140 46 250 185 120

Neutral

Acid Figure 3 - Polarization curves corresponding to the studied materials in neutral medium 111

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A. Bautista et al. H2SO4 solution, electrolytic iron coated copper plate corrodes 100 times faster than bare copper plate. This data explains the extent and frequency of the damages that iron coated engraved plates shown all over their surface (see example in Figure 5). XRD carried out on the back side of some iron coated plates, where relatively large deposits of corrosion products had been detected, are compatible with hematite (Fe2O3) (Figure 6). On the other hand, chromium coated copper plates exhibit better corrosion behaviour than bare copper plates in both media (Table 1). The corrosion rates of the electrolytic 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 measurements 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 Faradays law [5]. Using the results from Rp measurements, 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 different vertical axis than those corresponding to bare copper or chromium coated copper plates.

Figure 7 - Temporal evolution of the Rp of bare copper in acid medium.

Figure 5 - Appearance of Disparate no 4, that is iron coated, and where extensive corrosion damage can be easily observed.

Figure 8 - Relationship of icorr values obtained using different electrochemical techniques for the studied materials after similar exposure times. 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 (v) can be identified. corresponding to bare copper exposed for different times in H2SO4 solutions are shown. A decrease can be observed 112 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 attack 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 corresponding 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: Suction pads placed at the back of the plate to hold the plate in the electrolytic bath [6] (Figure 11). 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 exposure in neutral medium. The results are calculated from Rp measurements.

Figure 12 - Bare copper region caused by clamps on the one of the edges of Tauromaquia No 8.

Figure 13 - Improper metal coating due to greasy contamination from finger prints prior to the electrolytic process on Capricho No5. Figure 10 - Weight losses suffered by the metals due to exposure to acid medium. The results are calculated from Rp measurements. Detachments of the coating due to scarce careful application or manipulation of the plates (Figure 13). 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 measurements the bare copper and the coated copper coupons are connected in such a way that a positive the galvanic current (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. 113

The bare copper, when is short-circuited to electroplated 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 effective 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 stabilization, 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. ply such kind of conservative technique in pieces with artistic value. It will be interesting to carry out studies that analyze the possibility of removing the coating without affecting the copper base. Besides, the original artefact of the artist could be appreciated without the metallic coating.

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.

Figure 16 - X-ray diffractrogram of Goya's plate Tauromaquia 8 where peak compatible with Cu2O can be identified. 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: Iron coatings exhibit a low corrosion resistance and corrode easily, increasing the difficulty of the conservation of the engraving plates. 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 [1] Lage, M.: "Goya, ciencia y tecnologa para la conservacin de sus matrices de grabado calcogrfico", In Lage, M., Mota, J.M. (eds.): "Ciencia y Tecnologa para la conservacin de matrices de grabado calcogrfico". Fundacin BBVA, Bilbao, pp. 143-166 (2005). [2] Mora, N., Cano, E., Mora, E.M., Bastidas, J.M.: "Influence of pH and oxygen on copper corrosion in simulated uterine fluid", Biomaterials, Vol. 23, pp. 667-671 (2002). [3] Palit, A., Pehkonen, S.O.: "Copper corrosion in distribution systems: a evaluation of homogeneous Cu2O film and natural corrosion scale as corrosion inhibitors", Corros. Sci., Vol. 42, pp. 1801-1822 (2000). [4] Stern, M., Geary, E.D.: "Electrochemical polarization I. A theoretical analysis of the shape of the polarization curves". J. Electrochem. Soc. Vol. 104, pp. 56-63 (1957). [5] Otero, E.: "Corrosin y degradacin de materiales". Editorial Sntesis S.A., Madrid, p.60 (1997). [6] Bautista, A., Velasco, F.: "La electrodeposicin en las planchas calcogrficas", In Lage, M., Mota, J.M. (eds.): "Ciencia y Tecnologa para la conservacin de matrices de grabado calcogrfico". Fundacin BBVA, Bilbao, pp. 37-58 (2005). 114

vs SCE, very close to the Ecorr of isolated Cr. When the stabilization 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 solution. 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 galvanic coupling appears on engraving plates, it was more dangerous for the copper than in the designed laboratory test. The ability of chromium to accelerate the attack on copper 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 suction pads (as those shown in Figure 11). A small peak compatible 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 materials, the measured igalv are higher than the icorr of the electrolytic iron in the studied media (Table 1). In practice, the effect of the galvanic couple could be reduced by the area ratio. 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-