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Case study

Surface investigation of some medieval silver coins cleaned in high-frequency cold plasma
Emil Ghiocel Ioanid a , Aurelia Ioanid a , Dorina Emilia Rusu b, , Florica Doroftei a
a b

Romanian Academy Petru Poni Institute of Macromolecular Chemistry, 41A, Gr. Ghica Voda Alley, 700487, Iasi, Romania Moldova National Museum Complex, 1, Stefan cel Mare si Sfant, 700028, Iasi, Romania

a r t i c l e

i n f o

a b s t r a c t
Processing in cold plasma (cleaning and/or decontamination) represents an ecological alternative for applications in various domains of a diverse range of materials. Considering the advantages it presents, high-frequency cold plasma has been employed to remove the corrosion products found on the surface of some silver coins pertaining to a Polish medieval numismatic collection. The effects of plasma treatment have been evaluated through the investigation of the coin surface before and after the treatment, by means of different analytical techniques: scanning electron microscopyenergy dispersive X-ray microanalysis (SEMEDX), X-ray diffraction (XRD), FTIR spectroscopy and colorimetric measurements. 2010 Elsevier Masson SAS. All rights reserved.

Article history: Received 29 April 2010 Accepted 10 September 2010 Available online xxx Keywords: High-frequency cold plasma Cleaning Silver coins Scanning electron microscopyenergy dispersive X-ray microanalysis (SEMEDX)

1. Introduction and research aim The deterioration of ancient metals, especially coins, represents the undesired effect of some physico-chemical processes, such as those involved in uncontrolled evolution corrosion which gradually alter their aspect, shape, nature and resistance, up to the stage which makes impossible their use as historical evidence of human civilizations or even up to complete destruction of the items [1]. The coins containing non-noble metals (copper, magnesium) show some punctiform spots or more extended corroded zones, on the surface, constituted of chlorides, carbonates, sulfates or metal oxides. Not all of these corrosion products are harmful. For instance, copper oxides found on the surface generate an inert characteristic, which is non-active and should not be removed. However, silver or copper chlorides and suldes have a permanent action on metal, causing serious deterioration of the items, therefore their removal is imperative. In the most recent twenty years, scientists from different research domains have directed their attention to the application of unconventional cleaning methods of metal artifacts highfrequency cold plasma has come to be considered as a viable, non-destructive and ecological method [2,3]. Thus, the effect of O2 /Ar sau H2 /Ar plasma on metals and some of their corrosion

products [4,5], as well as the effect of H2 plasma on silver [6,7], has been studied. Also, it has been proved that hydrogen plasma is efcient in reducing silver chlorides and suldes on metal silver [8,9]. Our study aims to evaluate the effects obtained by highfrequency non-thermal cleaning treatment applied on the surface of some Polish medieval silver coins, chemically and microstructurally. 2. Experimental 2.1. Coins under study The studied coins belong to a thesaurus, containing 82 coins marked as M1 M82 , discovered at Cord reni, Botosani County, a Romania [10]. Two medieval silver coins were selected for study Polish 3 grosz minted during the reign of Sigismund III Wasa. The coins, presented in Fig. 5 ad, were obtained from Vilnius (M6 ) and Riga (M9 ) cities where, it is supposed, they were minted [11] and were identied according to Gumowskis catalogue [12]. Their weight ranges between 1.86 and 2.37 g and diameter between 20 and 22 mm. The coins present specic corrosion, as well as a number of organic deposits. 2.2. Plasma cleaning treatment

Corresponding author. Tel.: +40 232 213 324; fax: +40 232 218 383. E-mail addresses: ioanid eg@yahoo.com (E.G. Ioanid), ioanid aurelia@yahoo.com (A. Ioanid), dorina.emilia@yahoo.com (D.E. Rusu), oricadoroftei@yahoo.com (F. Doroftei). 1296-2074/$ see front matter 2010 Elsevier Masson SAS. All rights reserved. doi:10.1016/j.culher.2010.09.004

For the plasma cleaning treatment of the coins, depending on the goal pursued, a luminescent discharge is performed in a gas or in a mixture of gases. Thus, gases with oxidant character

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Fig. 1. SEM images of the coin surfaces before plasma treatment: a, b: details of M6 surface; c, d: details of M9 surface.

(oxygen), gases with reductive character (hydrogen) or their diluted mixtures with argon can be used [13]. The plasma and the treated object are in a stationary interaction (in physical contact, but electrically isolated), the plasma being extended over the whole surface of the object. The cleaning process is achieved under

the action of the active species from plasma, through chemical and mechanical interactions [14]. The treatment is achieved at sufciently low temperatures (up to 60 C), in order to avoid metallographic modications (recrystallized atoms are created with a specic function in the chemical reduction of corrosion products).

Table 1 Mass percentage values of the elements found on the surface of coins, determined by EDXa . Coins Elements C (wt %) M6 obverse Before treatment After O2 treatment After H2 treatment M6 reverse Before treatment After O2 treatment After H2 treatment M9 obverse Before treatment After O2 treatment After H2 treatment M9 reverse Before treatment After O2 treatment After H2 treatment
a

O (wt %) 22.27 13,42 7.40 27.02 37.43 9.90 23.28 32.85 6.06

Al (wt %) 1.81

Mg (wt %) 1.00 1,13 0.89 2.35 0.57

Si (wt %) 0.64 1,89 1.57 2.47 0.80 1.98 1.46 8.93

S (wt %) 0,51 1.04 0.65 0.19

Cl (wt %) 0,38 3.29 0.51 0.14

Ag (wt %) 32.65 72,34 80.50 30.59 90.30 20.04 72.49 2.46 31.78 85.87

Cu (wt %) 20.45 2,23 5.70 14.97 7.36 18.17 7.23 54.95 10.91 2.22

Ca (wt %) 1.79 1.06 0.56

23.00 8,11 4.83 18.98 21.45 7.82 16.69 12.82 5.85

The results listed in the table were obtained for the spots marked by arrows in Fig. 5 (ad).

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Fig. 2. FTIR spectrum of corrosion products.

For performing the cleaning treatment, an installation conceived and built by the authors in the laboratory [15,16] was used. The device consists of a bell-shaped Pyrex reactor, xed onto a stainless steel support. The reactor is coupled capacitively, by means of external electrodes, to a high-frequency generator, which generates and maintains the electrical discharge in plasma. The coin is xed by a Teon clamp on the electrical axis of a micro-motor, producing a rotation movement with a speed of 2 rot/min. The reactor is connected to a vacuum pump and the gas is admitted into the system by means of a needle valve. The experiments have been carried out under the following working conditions: maximum temperature 60 C, frequency 13.5 MHz, electric eld intensity 20 30 V/cm, glow power 100 W, gas used oxygen and/or hydrogen. The vessel was vacuumed at an initial pressure of 5 102 mbar, and then the working gas was introduced with the pressure of 3.5 101 mbar for oxygen, and of 7.5 101 mbar for hydrogen. To avoid the overheating of the coins, the treatment was performed in steps. The optimum duration of a step was established experimentally. For this purpose, a silver disk was manufactured of the same size and shape as the coins, and a thermocouple was introduced into it. The temperature values obtained as a function of the treatment duration, nature and pressure of gas were recorded. Hence, it was estimated that for oxygen, the maximum duration of the treatment is 20 minutes, while for hydrogen it is 30 minutes. The samples were placed directly in the plasma region. The duration of the treatments was varied depending on the corrosion type and penetration depth; the duration of the treatment increased (up to 56 hours), with increasing penetration depth of corrosion. For a rapid and complete elimination of the corrosion products, the treatments were carried out in several steps. In the rst step, the coins were treated in oxygen plasma for removing the contaminants of organic nature. After the treatment, the surface of the object was brushed with a brush of natural hair (squirrel hair) to remove the impurities that were not eliminated by the vac-

uum system. In the second step, pure hydrogen was used for the treatment. 2.3. Method of characterization 2.3.1. SEM/EDX surface analysis The effect of plasma cleaning was assessed by examining the surface of the coins before and after the plasma treatment, by using a non-destructive method of surface analysis scanning electron microscopy (SEM) in conjunction with microscopy energy dispersive X-ray microanalysis (EDX). The analyses were carried out using QUANTA 200 scanning electronic microscope with integrated EDS system, GENESIS XM 2i EDAX with SUTW detector. Scanning electron microscopy was used in the secondary and backscattered imaging mode, by using an ETD detector and a BSED detector. EDAX

Fig. 3. XRD spectrum of corrosion product: 1: Ag2 S (silver sulde, pattern 00-0110688); 2: Cu2 S (copper sulde, pattern 01-070-9135); 3: CaCO3 (calcium carbonate, pattern 00-003-0893); 4: CuCO3 Cu(OH)2 (basic copper carbonate, pattern 00-0010959).

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was used for identifying the elemental composition in the areas of interest of the images obtained in BSED mode. 2.3.2. X-ray diffraction The quantitative characterization of the coin was carried out using X-ray diffraction (XRD) (D8 Advance Bruker AXS). The X-rays were generated using a Cu Ka source, with an emission current of 36 mA and a voltage of 30 kV. Scans were collected over the 2 = 270 range using a step size of 0.01 and a count time of 0.5 s/step. The diffractograms were studied with an EVA soft (from DiffracPlus evaluation package).

2.3.3. FTIR Spectroscopy The FTIR analysis was done using ne dispersed samples as KBr pellets. The FTIR spectra were recorded in the range of 3500428 cm1 , using a BRUKER VERTEX 70 Spectrophotometer, in the FTIRATR regime, at the resolution of 2 cm1 and 64 scans. 2.3.4. Color measurement Color modications of the coins were measured by means of a Pocketspect Color QATM device, illuminant D 65. The surface color difference was calculated using the CIE L* a* b* system. According to this color representation, L* is lightness, a* is the red-green compo-

Fig. 4. SEM images of the M6 coin surface before and after plasma treatment: ac: details before treatment; df: details after treatment.

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nent, b* is the yellow-blue component. RGB values provided by the Pocketspec Color QATM device were further processed with Easy RGB database and the L* a* b* were obtained and then used for calculating the color difference, E* , according to the relationship (1) [17]: E* = ( L*2 + a*2 + b*2 )1/2 (1) 2.3.5. Gloss measurement The gloss variation on the surface of the samples was measured with Horiba IG-320 Gloss-Checker apparatus. The gloss values were determined comparing the intensity of the luminous reection on the sample surface with the value recorded for standard surface (polished black glass, an accessory of the apparatus) [18]. 3. Results and discussion 3.1. SEM/EDX analyses The investigated coins were rst cast from coinage silver of high purity. EDX spectrum, obtained for coin M6 (internal layer), reveals the composition of the alloy: 90.30 wt% high-grade silver, low content of copper (7.36 wt%) and magnesium (2.36 wt%). The images presented in Fig. 4 reveal the initial low conservation degree of the coinscorroded surfaces (Fig. 4d), and the presence of a layer of dark brown color, which diminishes the natural shine of silver (Fig. 4ac), as well as some green zones that have been remarked especially on the reverse of coin M6 . The coins were examined directly by SEM and the obtained images are presented in Fig. 1ad. The microphotographs realized evidence rugous surfaces with numerous burrs due to manufacture and some corrosion products both on the obverse (Fig. 1a, c) and on the reverse (Fig. 1b, d). The weight percentage values of the elements identied on the surface of the coins by EDX, (Table 1), evidence a lower grade of silver than the original one, still existent in the coin body, unaffected by corrosion. Additionally, a high content of Cu has been remarked on the corroded areas, in comparison with the one identied in the coin body. EDX spectrum indicates a compositional enrichment in copper, reaching 54.95%. It may be observed that both on the obverse and reverse, but also on different spots from the same side of the coin, the supercial chemical composition of the monetary alloy is non-homogeneous. Besides Ag, Cu and Mg, EDX spectra evidence the presence of Cl, S, Si, Ca, in lower percentages, and higher percentages of C and O. The results obtained by observing the EDX spectra lead to the conclusion that the coins show (Ag2 O) deposits on the surface, identied in the FTIR spectrum, showing an absorption band at 561 cm1 (Fig. 2). There have been identied corrosion products

as crusts, containing (CuCO3 CU(OH)2 ) and (CaCO3 ). These contaminants are identied in the FTIR spectrum, which present absorption bands at 871 cm1 and at 1402 cm1 and are also evidenced by the XRD results (Fig. 3). EDX spectra are characterized by the presence of corrosion species, such as S and Cl. Extremely ne deposits of (Ag2 S) and (Cu2 S) covering different areas of the coins have been evidenced by the XRD. In the rst step of cleaning process aimed at the reduction of the organic compounds, was followed by using oxygen plasma, which is very efcient in removing organic deposits. For this purpose, a mixture of oxygen/argon was used (25/75). Oxygen dissociated in plasma interacts with organic compounds through oxidation reactions, thus resulting in volatile products (CO, CO2 , H2 O), which are evacuated by the evacuation system of the pump. After a 20minute treatment, the results obtained were assessed by the EDX microanalysis of different zones (Table 1). EDX spectra evidence a decrease in carbon and oxygen, while other contaminants are still present. In the second step, the coins were treated in hydrogen plasma for 1 hr and then they were brushed with a squirrel hairbrush. This procedure was repeated four times. Visual examination of the coins, on both the obverse and reverse sides, evidences a cleaning of the surface, conrmed by the electron microscopy images of the areas observed (Fig. 4). Both at a low magnication scale and at a magnication of 1000, no modication of the coin details has been remarked. Notably, the crusts have been removed after plasma treatment; the crusts became fragile and have been removed by repeated brushings. Corrosion products, due to suldes, and, partially, the green corrosion products (carbonates) have also been removed. The possibility of the total removal of the patina layer comprising sulphur is thus ascertained. 3.2. Decolouration measurement CIEL* a* b* parameters and color difference calculated according to relation 1 for the two coins, before treatment, after 20 minutes of treatment in oxygen plasma and after 4 hours in hydrogen plasma, are presented in Table 2. The increase in luminosity on both sides of coin M6 in the rst step of the treatment can be attributed to the removal of organic deposits an action that was evidenced by the analyses performed. The remaining corrosion products are eliminated in the second step of hydrogen plasma treatment. Consequently, after the treatment, luminosity increases signicantly, reaching values of 91.318 on the obverse of the coin and 76.532 on the reverse from the initial value of 36.155. The color difference, calculated according to equation 1 is higher for the obverse of the coin as compared to the reverse, as the

Table 2 Mass percentage values of the elements found on the surface of coins, determined by EDX. Coin Treatment stage CIE L* a* b* parameters L M6 obverse Before treatment After oxygen treatment After hydrogen treatment Before treatment After oxygen treatment After hydrogen treatment Before treatment After oxygen treatment After hydrogen treatment Before treatment After oxygen treatment After hydrogen treatment
*

E* a
*

36.155 56.475 91.318 61.866 70.201 76.532 87.328 81.578 87.414 45.030 60.464 83.077

3.431 8.861 20.787 8.675 9.235 12.004 13.538 8.407 11.544 15.263 23.861 10.0303

13.722 17.909 29.341 18.771 20.764 24.568 24.426 24.837 27.198 15.623 9.119 37.473

21.19 59.99 8,58 26.00 7.71 3.41 18.82 44.18

M6 reverse

M9 obverse

M9 reverse

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surface on the obverse has been more deeply affected by harmful products. Coin M9 behaves similarly with coin M6 , except for the fact that its obverse, which was much better conserved, shows a slight decrease in luminosity in the rst working step due to surface oxidation an effect that was suppressed after the hydrogen treatment.

3.3. Gloss measurement Gloss values measured before and after HF plasma treatment of the two coins are presented in Table 3. An increase in gloss is remarked due to the removal, to a great extent, of the deposits mentioned previously. The low value of gloss recorded for the obverse of coin M9 , after treatment under oxygen, is determined by the effect explained above for the decrease in luminosity. As a consequence, through the removal of mixed organic and inorganic deposits, under oxygen and hydrogen, silver partially recovers its gloss.

Fig. 5. Photographic images of the coins before (ad) and after (eh); HF plasma cleaning: a, e/b,: obverse/reverse coin M6 (Vilnius); c, g/d, h: obverse/reverse coin M9 (Riga).

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E.G. Ioanid et al. / Journal of Cultural Heritage xxx (2010) xxxxxx 7 [2] E.G. Ioanid, A. Ioanid, D.E. P rp uta, Plasma pre-treatment and polymerization a a on the surface of heritage objects, Revue Roumaine de Chimie 52 (4) (2007) 441447. [3] E.G. Ioanid, D.Rusu, Noi frontiere n conservarea obiectelor de patrimoniu. Plasma de nalt frecventa, Ed. Pim, Iasi, 2008. a [4] V.D. Daniels, M.W. Pascoe, L. Holland, Gas plasma reactions for the conservation of antiquities, Studies in Conservation 24 (1979) 8592. [5] K. Schmidt-Ott, V. Boissonnas, Low-pressure hydrogen plasma: an assessment of its application on archaeological iron, Studies in Conservation 47 (2002) 8187. [6] K. Schmidt-Ott. Plasma-reduction: its potential for use in conservation of metals, in metal 04, proceedings of the international conference on metals conservation, Camberra, October 2004, 247260. [7] K. Schmidt-Ott, Plasma reduction of silver surfaces, exposure 2001: corrosion, conservation & study of historic metals in situ, on display & in storage, Archetype, London, 2004. [8] S. Veprek, J. Patscheider, J. Elmer, Restoration and conservation of ancient artifacts: a new area of application of plasma chemistry, Plasma Chemistry and Plasma Processing 5 (2) (1985) 201209. [9] J. Patscheider, S. Vepek, Application of low-pressure hydrogen plasma to the r conservation of ancient iron artifacts, Studies in Conservation 31 (1986) 2937. [10] Viorica Enachiuc, Relatiile comerciale ale Moldovei in secoleleXVIXVII, ilustrata in tezaurul monetar descoperit la Cordareni, judetul Botosani, Acta Moldavie Meridionalis, Vaslui, XIIXIV, (19901992), 9399. [11] http://www.geocities.com/Athens/Olympus/5539/index.html, the coinage of Poland in Riga Sigismund III Vasa, 15871632. [12] M. Gumowski. Handbuch der Polnischen Heraldik [Handbook of Polish Heraldry], Akad. Dr. U. Verl. Anst: Graz, 1969. [13] H. Keppner, U. Kroll, P. Torres, M. Goetz, J. Meier, Process-enhancement of hydrogen-plasma treatment by Argon? Zeitschrift fr Schweizerische Archologie und Kunstgeschichte 54 (2) (1997) 528. [14] E.G. Ioanid, D.E. P rp uta, Aplicatii ale plasmei reci de nalt frecventa n domea a a niul restaur riiconserv rii, Ed Performantica, Iasi, 2005. a a [15] M. Totolin, I. Neamtu, E.G. Ioanid, Plasma rece in tratamentul materialelor: de la fundamental la aplicatii, Ed Performantica, Iasi, 2007. [16] G. Ioanid, D. Rusu, A. Ioanid, S. Dunca, A. Muresan Patent: RO 122 396, (2009). [17] E. Franceschia, P. Letardib, G. Lucianoc, Colour measurements on patinas and coating system for outdoor bronze monuments, Journal of Cultural Heritage 7 (2006) 166170. [18] B.-H. Lee, H.-J. Kim, Inuence of isocyanate type of acrylated urethane oligomer and of additives on weathering of UV-cured lms, Polymer Degradation and Stability 91 (2006) 10251035.

Photographic images showing the aspect (initial and nal) of the coins are presented in Fig. 5 dg. These support the analyses performed before and after the treatment, conrming the effects of HF plasma in partially removing the corrosion products identied and the degradative agents of organic nature. If the qualitative and quantitative analyses reveal the structural and compositional modications of the surface of coins, the photographic images offer the possibility for an aesthetic appreciation of the results obtained an aspect that can not be neglected in the conservation of heritage objects. 4. Conclusions By the application of plasma treatment, we succeeded in preserving the original patina to a great extent, achieving a uniform aspect of the surface, revealing some coin reliefs and stopping the corrosion process. The coins have partially recovered the specic gloss of silver, which does not however confer the aspect of new, and hence, the principle of the minimum intervention on patrimony objects is respected. The utilization of gases with reductive character in the HF plasma cleaning processes of silver patrimony pieces permits to remove selectively the harmful corrosion products. The method is ecological, non-invasive, easy to apply and is in accordance with the European norms recommending the reduction of using solvents and toxic substances whenever possible. References
[1] W. Mourey, Conservarea antichitatilor metalice de la sapatura la muzeu, Ed Tehnica, Bucuresti, 1998.

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