You are on page 1of 7

Nuclear Instruments and Methods in Physics Research B 226 (2004) 172–178

www.elsevier.com/locate/nimb

The application of photon, electron and proton induced
X-ray analysis for the identification and characterisation
of medieval silver coins
R. Linke a, M. Schreiner a,*
, G. Demortier b

a
Institute of Humanities, Sciences and Technologies in Art, Academy of Fine Arts, Schillerplatz 3, A-1010 Vienna, Austria
b
LARN, Facultes Universitaires Notre-Dame de la Paix, Rue de Bruxelles 61, B-5000 Namur, Belgium
Received 21 October 2003; received in revised form 2 March 2004

Abstract

Photons, electrons and protons beams applied to the scientific investigation of archaeological materials provide
complementary information for characterising the state of preservation and the provenance of the objects. Investiga-
tions were carried out on medieval silver coins of the ‘‘Friesacher Pfennig’’ and the ‘‘Tiroler Kreuzer’’ from the
Kunsthistorisches Museum Vienna and the Oesterreichische Nationalbank. Techniques employed were EDXRF,
SEM/EDX and PIXE. By determining the trace elements of the alloys it was possible to assign coins to their mint. The
results outline advantages and disadvantages of EDXRF, SEM/EDX and PIXE when applied to corroded objects. 
2004 Elsevier B.V. All rights reserved.

PACS: 78.70.E; 61.16.B; 82.80.Ej
Keywords: Energy dispersive X-ray fluorescence (EDXRF); Scanning electron microscopy (SEM); Proton induced X-ray emission
(PIXE); Silver coins; Archaeometry

1. Introduction duction was already of interest for Martin Heinrich
Klaproth in the late 18th century, when he inves-
Coins represent important objects of our cul- tigated the chemical composition of a number of
tural heritage and are usually of high artistic and ancient gold and silver coins [1]. For this pioneer-
cultural value. In relation to the iconography, the ing chemical work, he had to dissolve the coins in
archaeological issue concerns questions of dating, nitric acid and develop analytical procedures for
provenance, technology of production or authen- the separation of Ag, Pb, Sn and Cu quantitatively.
ticity. The materials (alloys) used for their pro- Frequently, these questions may only be answered
by means of scientific investigations. Apart from
the identification of the composition, chemical
*
Corresponding author. Tel.: +43-1-58816-200; fax: +43-1-
analyses also enable the determination of the state
58816-121. of preservation in view to develop and apply suit-
E-mail address: m.schreiner@akbild.ac.at (M. Schreiner). able treatments for conservation and restoration.

0168-583X/$ - see front matter  2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.nimb.2004.03.084

low bremsstrahlung induced by protons. Au. and range from 0. EDXRF was carried out 4] and energy dispersive X-ray microanalysis with using a TRACOR XRAY Inc. On the other hand. better detection limits for high culated for each element. Linke et al. to remove traces of wax.9] was applied non-destructively in investigation has to be non-destructive. The tion of layered structures at the surface [10]. When applied to corroded . Due to varying the element considered and the experimental con.05 mm thickness was used to analyse small sample areas. include the high spatial resolution and the ability A Pd primary filter of 0. surface structures and inhomogeneities of the ditions. Hg etc. During the number lower than 11 (Na). ethanol and benzine in an ultrasonic bath in order Techniques of investigation include energy dis. (PIGE) and Rutherford backscattering spectrom- Apart from silver and copper. For the without sampling. B 226 (2004) 172–178 173 Coins are usually of small size and sometimes of Additionally. ing approximately from Ar to Zr. proton induced X-ray emission high value or even unique. The coins have been selected according to obtain a statistical dis- tribution between all groups of coins. Instr. depending rotations/min in order to average the analysis re- on the atomic number and the matrix composi. The chemical with portable instruments. ment. Drawbacks of elements. a Rh-tube with an acceleration voltage in the sample size. / Nucl. Res. The advantages of SEM/EDX of 50 kV and a beam current of 0. scientific (PIXE) [8.1 wt. SEM/EDX and PIXE composition of the silver alloys can therefore be (PIGE.) could be observed for A main disadvantage of EDXRF is its infor- EDXRF compared to SEM/EDX. the detection limits area of irradiation was of elliptical shape with a of EDXRF depend very much upon the sample. The means that no sample material (including patina) is sensitivity of PIXE is significantly higher com- removed or that the object itself is not permanently pared to EDXRF and SEM/EDX due to the very modified in any way during or after analysis. in Phys. and Meth.04 mA was used. For a sta. which order to detect elements in the trace level. As well as for SEM/EDX. The for trace elements and for elements with an atomic acquisition time was 100 s real time.1 ppm to a few per. both sides of the coins and mean values were cal- Applied to metals.%. The variation of acher Pfennig’’ and ‘‘Tiroler Kreuzer’’) in order to the proton beam energy enables the characterisa- gain information regarding their provenance. SPECTRACE 5000. R. sults and thus to improve the reproducibility. which has been applied persive X-ray fluorescence analysis (EDXRF) [2– for conservation reasons. PIXE Chemical analyses were carried out on two offers the maximum sensitivity for elements rang- groups of Austrian medieval silver coins (‘‘Fries. (Noran) instru- a scanning electron microscope (SEM/EDX) [5–7]. surface composition analyses were performed on centage for elements with low atomic numbers. mation depth [12]. Experimental tistical assignment it has to be considered that silver was imported and that usually old silver Prior to analysis the coins were cleaned with ware and coins were recycled. silver coins from etry (RBS) can be used for the characterisation of these periods usually contain minor and trace light elements and profiling [11]. While EDXRF can be carried out used for the silver production. diameter of approximately 1 cm. These components originate from the these ion beam analysis (IBA) techniques are the different ores or from the (geographically and availability of an accelerator and the correspond- chronologically) varying manufacturing processes ing high costs. RBS respectively) analysis require objects regarded as being characteristic for the various to be brought to the instrument. mintages of the medieval period. in order to increase the signal/noise ratio by sup- SEM/EDX and EDXRF have a poor sensitivity pressing the bremsstrahlung background. although SEM/EDX is limited excitation. Therefore. Z elements (Pb. with a Si(Li)-detector Both techniques can be applied non-destructively of 155 eV resolution at the Mn-Ka line. proton induced c-ray emission Vienna and the Oesterreichische Nationalbank. The tion. The detection limits of analyses the coins were rotated with a speed of 6 SEM/EDX are approximately 0. coins are objects of the Kunsthistorisches Museum Complementarily. 2.

As Ag-La radia. oper. Pb. Friesacher Pfennig compared to Ag-Ka results in an information depth of approximately 10 lm. The coinage of the Friesacher Pfennig (denarius tion originates predominantly from a depth of up Frisacenses) represents one of the most success- to 2 lm in an Ag/Cu alloy. The experi- phase.9 MeV) at the Labo- ratoire d’Analyses par Reactions Nucleaires (LARN) in Namur (Belgium). Coins were selected according to its own silver mine. 12 lm for Cu-Ka and 5 lm for Ag-L. If the order to enhance relatively the X-ray lines of ele- surface is corroded. it has to be considered that Co-absorber (K-absorption edge: 7. Coins of the early period (1125/1130–1168). in Phys. 1). Abensberg coins and mean values were calculated. mint: Friesach. the probing depth of XRF is approximately 100 lm for Ag-Ka. Croatia.000 mesh. B 226 (2004) 172–178 objects non-invasive. Hungary and Slo- ratios of Ag-K/Ag-L intensities it is possible to vakia. Differences in high value of the coins it was not possible to apply this destructive procedure to each object. A 10 lm (1106–1147). the base components of the ments with an atomic number lower than 29 (Cu) alloy (Cu. which support numismatists to assign them to a In order to check the results obtained by ED. Friesacher Pfennig: Archbishop Konrad I. matrix. The measured area was approximately 1 mm in diameter. depletion [14].and Kb-lines of Cu (Cu-Ka: coin is depleted of these elements and a relative 8. v. the surface of the sities of the Ka.e.0 keV (attenuation factor: 20·). In a second element in the coins apart from Ag. ‘‘Pixboy’’ products at the surface of the coins (patina). i.9 keV enrichment of the more noble constituents of the (attenuation factor: 10·)). Instr.7 keV) was the results obtained from the surface do not rep. corrosion products have to be removed prior to For 2. / Nucl. ful currencies in the 12th century AD in Europe L signals obtained in the spectrum enable the (Fig. Carinthia in former times and that each mint had ated at 20 kV. certain mint. Ni-Ka: 7. both the Ag-K and Ag. 1. Res.174 R.5 keV) and to attenuate the inten- from the surface. Linke et al. By using the Austria. mental set-up has already been described previ- stituents of the environment and form corrosion ously [15].g. and Meth.) are oxidised and removed (e. The analy- ses were carried out on obverse and reverse of the Fig. SEM/EDX measurements were carried out assignment are the rich Ag deposits especially in using a JSM 6400 (JEOL Inc. Consequently. the most abundant alloy (Ag and Au) can be measured. a low amount of Cu. Sn etc. For quantitative evaluation.9 MeV PIXE the probe depths in a Ag analysis. Its wide area of circulation included evaluation of the depleted layer [13]. .) instrument. a self-made iterative program. PIXE measurements were performed in air with an external proton beam (2. the leached elements combine with con. Cu-Kb: 8. In an Ag matrix the electron beam range is less than 1 lm and so this technique does not qualify for surface analysis of corroded objects without destructive sample preparation. Analyses of coins with known their state of preservation and polished on their origin reveal that alloys from these mints show edge with SiC paper of 4. These [16] was applied. based on Gupix calculations are 25 lm for For Ag/Cu alloys with a high content of Ag and Ag-Ka. Due to the variations in the trace element levels. and can be used as an indication which are particularly unique or at least very rare whether Ag is enriched at the surface of a coin or and of high value. have no marks or legends. North-Italy. placed between the coin and the Si(Li)-detector in resent the chemical composition of the core. Essential requirements for the XRF. not. and the coins were produced at different obtain some information about the degree of mints. whereas for Cu- Ka the higher absorption of the specific radiation 3.

the mean value is 80. Pb. 3). 103 coins which have been minted in Hall and 33 coins of uncertain origin. the data were clustered and on 180 coins in order to compare coins minted in evaluated separately according to the specific Merano with those produced in Hall and to assign question of provenance. The Ag concen. Linke et al. Res.6 wt. main currencies in the 15th century AD (Fig. Hg and Ni). Hg. (‘‘M’’) with coins from the mints of Laufen (‘‘L’’) and Salzburg (‘‘S’’).0 wt. R. mint: Merano. ‘‘Factor 1’’ and ‘‘Factor 2’’ refer to the elements Pb. clear separation between the coins from Laufen Cu. Detailed results have been coins with an unknown mint. Therefore. Veit. project. gated included 44 objects. and Meth.4 ± 2. . Bi. Ag-K/Ag-L data treatment. Laufen. ferred to Hall (Austria). Coin of the ‘‘Tiroler Kreuzer’’ by Archduke Sigismund Hg and Au. Comparison of coins from Archbishop Adalbert II. potential assignments. Fig. in Phys. Instr. nearly 80% of all (221) coins investigated SEM/EDX investigations revealed a homoge. Bi. a Aquileia and Cologne. The coins of Adalbert II (‘‘M’’) appear to have a The Ag values appeared independent from any similar composition to coins from Salzburg.0 ± 2. Adalbert II (1183–1200). Analyses were carried out ment. the coins were produced in the mints of possible to obtain significant differences between Merano (Italy) and in 1477 the mint was trans- all 221 coins within a single statistical data treat. it can be 4. 3. 2. Tiroler Kreuzer assumed that the results obtained by EDXRF were a good approximation of the core composition of The ‘‘Tiroler Kreuzer’’ represents one of the the coins. Fe and Sb. Mints included in this survey are the locations could be Salzburg or Laufen. Au.2 wt.2 ± 1. Pb and Bi) and trace elements (Fe. For multivariate data evaluation it was not Initially. ratios were calculated for all coins leading to re- sults comparable with uncorroded Ag/Cu stan- dards of varying composition. which have been minted ciency of statistical data evaluation is stressed by in Merano. Elements measured are Ag.% to (‘‘S’’) were obtained by means of factor analysis.%. There exist no hints in EDXRF analyses were carried out on 221 coins the archives concerning the identification of the in order to enable geographical or chronological mint producing this coinage. EDXRF was applied non-destructively in order to determine the Ag contents as well as minor constituents (Cu. 89. which is towns of Friesach. (‘‘L’’ followed by the coin number) and Salzburg tration in the coins varies from 63. Au. just 60 km next to Salzburg. The Ag concentrations vary Fig. As shown in Fig. / Nucl. B 226 (2004) 172–178 175 the chemical composition originate from the the results obtained on the mintage of Archbishop technology of refining or from the ore itself. However. of Tyrol. could be assigned to a mint on the base of their neous elemental distribution and no leaching of chemical composition by means of multivariate the surface layer has been measured. Salzburg. For example the effi.%. Therefore. The coins investi- published elsewhere [17]. 2. St. In the chronology.

7 38. as shown in Fig.176 R.1 )20.1 41.8 35. The surface of the coins shows cavities.0 no provenance assignment could be performed for S36 79. has the S50 69. Therefore. However. Therefore. investigations of cross-sections were carried out using SEM/EDX in order to determine the stage of corrosion and the Ag concentration of the core of the coins. Backscattered electron image of a cross-section of a corroded ‘‘Tiroler Kreuzer’’ coin in the SEM. 4) the Fig.6 ± 2.1 to 81.1 ± 1.2 wt.6 S37 71. the coin became S29 77.9 38. S30 78.4 )15.8 44.6 40.4 ± 1.0 39.3 the coins investigated on the basis of the EDXRF S39 74.9 ± 0.4 ± 0.5 )14. applied at 2.7 ± 0. which have been caused by leaching and Ag concentrations of a selection of the ‘‘Tiroler Kreuzer’’ coins diffusion of oxidised Cu during the corrosion obtained non-destructively by EDXRF and on cross-sections process.0 )14.% could be measured.6 )15. S45 64.5 brittle leading to a crack.6 44. which could be analysed neither by EDXRF . a detailed re- port has been published elsewhere [18].3 ± 4.6 36. Ni. Sb. 4 has an Ag concentration by SEM/EDX of 74. In the backscattered electron image (Fig.5 wt. B 226 (2004) 172–178 from 55.9 ± 1.4 to approximately 5–25 lm in metals. 4.8 ± 0.1 ± 4.5 )15.4% lower compared to Ag/Cu standards.4 )18. PIXE.0 )9.2 )10.3 )16.%) (%) dissolution and diffusion of Cu.5 ± 4.5 ± 1. Due to the no.3 ± 1.3 )16.1% ± 4.1 ± 1. Res.1 ± 2.5 ± 2.1 40. Therefore.3 )13.6 ± 3.8 ± 2. Fe. Ni.9 preparation.1 means of EDXRF and SEM/EDX due to corro- S43 75.5 45.1 ± 2.0 ± 1.9 ± 3.0 ± 0. a number of S40 79.4 38.4 ± 2. black in Table 1 the image.%. S35 67.3 )17. domains where Cu was leached out can be ob- served. as only very low brems- S56 75.9 ± 2. while in area 2 an Ag content of Coin EDXRF SEM/EDX Ag-K/Ag-L 95.6 )2.7 41.8 38.6 ± 1.3 ± 3. ment.7 ± 3.5 ± 2.2 ± 4. Bi.2 74.1 )10.%) Ag (wt.7 centrations between measurements carried out by S42 71.4 )13. Area 1 in Fig.7 ± 3.9 MeV.6 )11.7 order to measure trace elements (Pb.0 S44 72.5 sion processes. The results for the Ag-K/Ag-L ratio reveal values 13.3 41.5 )20. The results showed differ- ences up to 50% between the composition of the core and the surface.8 this technique cannot provide quantitative analysis S54 77.0 ± 2.9 ± 5.7 of the high background of the bremsstrahlung in- S34 79.8 duced by the electron bombardment.1 strahlung is induced by the protons.3 ± 1.6 ± 3.3 Compared to EDXRF.2 measurements. and Meth.6 ± 2.%.6 ± 2. Linke et al. 4. which is obviously due to corrosion pro- cesses.4 Finally. / Nucl.1 )11. an ele- Cu standards of similar composition.0 ± 4. Instr.4 ± 2. PIXE measurements were carried out in S46 67.4 76.2 41.3 coins shows significant deviations in the Ag con- S41 73.4 ± 2.1 disadvantage of low penetration depths of just up S51 76.5 71.8 ments could be determined apart from Cu because S33 73.6 )13.0 41.4 nique enables lower detection limits compared Ag-K/Ag-L values reveal the deviation from non-corroded Ag/ to EDXRF and SEM/EDX.3 ± 1.6 39.9 )7. S53 73.9 ± 1.7 ± 0.4 Au and Hg).6 ± 1.6 41.5 ± 1.6 )6. indicating that Ag is relatively enriched at the surfaces of the coins due to corrosion processes (Table 1).5 )5.4 ± 2. this tech- Mean 74.8 43.8 S52 78.5 ± 2. S47 76.2 S31 76. Therefore.9 ± 2.6 ± 4. Ag (wt.9 38.0 ± 0.5 when applied to corroded objects without sample S55 71.0 ± 1.8 ± 2. The dark areas show the originally Cu-rich and the bright areas represent the Ag-rich phase.6 35.3 ± 1.0 )13. in Phys.1 ± 2.9 35.1 ± 1. As shown in Table 1.0 )13. no minor and trace ele- S32 72.7 )14.5 ± 0.3 wt.5 ± 1.5 ± 6.

Additionally. The comparison of a coin produced in the mint of Hall are usually heavily corroded. Fiat. X-Ray Spectrom. 6. 28 (1999) 86. 6. the low X-ray intensities of most nor by SEM/EDX. differs from the chemical composition of the core. Zambon. Cosma.F. . Museum Vienna for their fruitful co-operation. C. Radioanal. 5). 5. to the application of a Co-absorber between the reduce the high X-ray intensity of Cu. Schreiner. 7026) is gratefully acknowledged for financial support. where the chemical (continuous line) and one from the mint of Merano (dotted composition of the near-surface domain markedly line) reveals a clear difference regarding the content of Ni. Nucl. M. Linke et al. Guerriero. References [1] M. a comparison of the concentrations of the elements Ni and Bi (limit of detection <100 ppm) relative to the Ag concen. M. Alram elements are characteristic accompanying elements and H. PIXE. The better XRF instruments commercially available hampers detection limits for Ni (<100 ppm) originate from the use of selective X-ray filters such as Co. The scatter plot of concentration ratios of Ni/Ag and Bi/ (2000) 39. Additionally. 29 Fig. and Meth. Experimental-Philosophie 3. K. Al-Tarawneh.H. / Nucl.01% Ni). Chem. coins of unknown prov.1% Ni) and Hall (approximately Merano and Hall. 201 (1995) 447. from Hall. R. Abhandlungen der K€ oniglichen Akademie der Wissenschaften und sch€onen K€ unste zu Berlin (1792– 1797). As shown in Fig. which were produced from Ag gained directly from ores and which have a high Ag content. B 226 (2004) 172–178 177 enance could clearly be identified as being minted in Merano. P.J. Daraban. [2] M. X-Ray Spectrom. Conclusion The investigations carried out on medieval sil- ver coins (‘‘Friesacher Pfennig’’ and ‘‘Tiroler Kreuzer’’) have shown that XRF is a valuable tool for the identification and characterisation of coins. 29 (2000) 3. as mentioned previously thanks to its high X-ray yields and low back- (Fig. Res. T. sample and the detector. Instr. Kunsthistorisches in Cu ores. The ‘‘Jubil€aumsfonds der Oesterreichischen Na- tionalbank’’ (Project No.M. R. Al-Kofahi. could be detected. The concentration of Ni shows a clear ground has enabled a clear differentiation of ‘‘Ti- difference between the coins from Merano roler Kreuzer’’ coins produced in the mints of (approximately 0. Both The authors express their thanks to M. Calliari. 0. Acknowledgements tration yields a definite differentiation of coins minted in Merano from those minted in Hall. in Phys. X-Ray Spectrom. [4] M. coin-cabinet. Ag enables a clear distinction between coins from Merano and [5] I. PIXE mea- surements were carried out within a short term scientific mission of COST G1-Action. Klaproth. Sil- ver coins with a high amount of Cu and excavated Fig. Mantler. A. [3] L. Winter. Martini. 5. Magrini.

32 (2003) 373. and Meth. H€artel. Mikrochim. Hasler. 317. Mathot. Prehistoric Gold in [8] N.P.. Oddy. S. B. [18] R. Jembrih-Simb€ urger. Schreiner. Schreiner. I. Constantinescu. Friesacher Pfennigs. 109 (2001) 125.). Neelmeijer. M. Martinek. Vol. and Meth. Linke et al.J. Stern. 2002. Neelmeijer. Schramm.P. A. Spectrom.R. Morteani. 1995.2004. V. [13] R. M. G. p. M. M. H.). Int. Archaeometry 35 [15] G. A. doi:10. [17] M. Nucl. and Meth. 94. John Kennedy. Oeconomides. [11] D. Alram. Numismatische Zeitschrift 108 and j. Katsanos.). Van Oystaeyen. [9] B. Res. H. J. On non-destructive analysis of gold objects. Kallithrakas-Kontos. Linke. Instr. Acta 133 (2000) 165. W. in: W. Alram. C.A. Demortier. Schreiner (Eds. Demortier. Nucl.178 R. [16] G. B 118 (1996) 338. and Meth. .03. [10] C. PIXE 9 (1999) 487. in Phys. in: No. Kluwer Academic. B 85 (1993) 265. Y. Demortier.P. Demortier. this issue.1016/ Spindler. Bubert. Instr. M. Wagner. Touratsoglou. M. Klockenk€ amper. Cowell (Eds. M. J. X-Ray 41 (1999) 311. Europe. Die Fr€ uhzeit des and Meth.nimb. Special Publication [14] W.A. Instr. Schreiner. G. Amsterdam. K. 4. G. Vienna. G. p. Linke. Northover. M. M€ader. Schreiner. M. Aravantinos. R. London 1999. 30. Instr. M. P. Instr. Northover (Eds. [7] J. B 49 (1990) 46. B 226 (2004) 172–178 [6] R. Morciaux. (1994) 112.075. Nucl. / Nucl. Demortier. K. Nucl. Metallurgy in Numismatics. Archaeometry [12] R. Alram.B. Linke.