Combined use of surface and micro-analytical techniques for the study of ancient coins

By means of the combined use of surface and micro-analytical techniques the surface chemical composition of ancient coins and some aspects of their manufacturing techniques and of degradation mechanisms have been elucidated. Two case histories are described concerning silver Roman Republican coins and some coins plated with thin films of silver and gold. In particular, the coinage methods, the silvering and gilding techniques and the origin of the embrittlement of these selected Roman coins have been studied by means of the combined use of selected-area X-ray photoelectron spectroscopy (SA-XPS) and scanning electron microscopy and energy-dispersive spectrometry (SEM+EDS). This innovative approach has been utilised in order to gain further insight into the microchemical structure of the external regions of the coins as well as of the bulk features. The results show the use of mercury to coat a copper or silver core with a thin film of precious metals that could be considered the most important advance in the technology of gilding to be made in antiquity. Furthermore, the microchemical investigation of brittle Roman silver coins has allowed us to identify the origin of this troublesome problem. The microchemical results indicate that brittleness is induced by the presence of a low amount of lead that is retained in supersaturated solution when the cast blank was produced. This latter element segregates at the grain boundaries during the coin production and the subsequent long-term ageing at room temperature, thus inducing the alloy fracturing along the weakened grain boundaries. PACS 68.55.Jk; 68.35.Dv; 68.37.Hk; 68.55.Nq; 81.05.Bx     

Microchemical investigations of historical coins

Microchemical investigations were carried out on ancient silver coins originated from the same country but of different historical periods between the fifth and the second centuries B.C. Energy-Dispersive X-ray microanalysis in a Scanning Electron Microscope (SEM-EDX) was employed to obtain qualitative and semi-quantitative information about the chemical composition of these coins. SEM-EDX analyses employ an electron beam of 20?keV, which interacts with the sample leading to the emission of characteristic X-rays, to determine elements present in the surface patina, closely related to the sample preservation. In the X-ray photoelectron spectroscopy (XPS) analysis a monochromatic Al Kα radiation (1486.6?eV) interacts with the sample and photoelectrons are detected as secondary radiation, to investigate about coins elemental composition. Moreover a beam of Ar⁺ ions with an energy of 3?keV was used for the sputtering procedure in order to perform depth profile measurements, from the surface (patina composition) down to deeper layers. Useful information about production, chronological period and utilization places of coins are obtained to support a correct dating of these samples.     

Microchemical investigation on Renaissance coins minted at Gubbio (Central Italy)

The bulk and surface chemical composition of Renaissance coins minted at Gubbio (Central Italy) from 1508 to 1516 and from 1521 to 1538 by Francesco Maria della Rovere is investigated by means of the combined use of different analytical techniques such as scanning electron microscopy (SEM), energy dispersive spectrometry (EDS), and optical microscopy (OM). The aim of the work is to determine the bulk chemical composition of these commonly used coins at Gubbio, to ascertain their surface nature and if they were coated by a thin film of silver or other white metals similar to silver.The results indicate that the coins were produced by coating a copper core with a thin film of silver and antimony, and also with lead whose thickness is of a few microns which is now scarcely present because the original silvered surface was almost entirely removed by degradation phenomena. Furthermore, the SEM+EDS results show that the surface content of silver and antimony cannot be attributed to long-term selective corrosion phenomena leaving the coin slightly silver or antimony enriched. Therefore, the presence of silver or apparently silver-like metals i.e. antimony and lead, could be considered as a deliberate surface finishing of the coins obtained via inverse segregation or intentional selective corrosion based on pickling solutions or a combination of them. From a historical point of view the presence of a Ag or Sb film on the surface of the coins discloses the occurrence of a period of economic difficulties. PACS 68.55.Jk; 68.35.Dv; 68.37.Hk; 68.55.Nq; 81.05.Bx     

Analysis of the Hoard of Beçin using X‐ray‐based techniques

Four hundred and sixteen silver coins stemming from the Ottoman Empire (16th and 17th centuries) were analyzed to confirm the fineness of the coinage as well as to study the provenance of the alloy used for the coins. As most of the coins showed the typical green patina on their surfaces due to corrosion processes that have led to the depletion of copper in the near surface domains of the silver coins in comparison to their core composition, small samples had to be taken, embedded in synthetic resin, and cross sectioned to investigate the true‐heart metal composition. μ‐synchrotron micro X‐ray fluorescence analysis and μ‐proton‐induced X‐ray emission were applied to determine the silver contents as well as the minor and trace elements. The type of the alloy was investigated as well as if coins minted in different locations demonstrated homogeneous traits concerning the predominant impurities (Au and Bi), which could suggest a common ore. Finally, energy‐dispersive microanalysis in a scanning electron microscope was applied to study the homogeneity/heterogeneity of the coins and the presence of surface enrichments and to explain differences between the μ‐synchrotron micro X‐ray fluorescence analysis and μ‐proton‐induced X‐ray emission measurements concerning the main component. In general, the silver content of the analyzed specimen varies between 90 and 95%. These outcomes have not supported the historical interpretations, which predict that during the period studied, a debasement of approximately 44% of the silver content of the coins should have occurred. Copyright © 2012 John Wiley & Sons, Ltd.     

Celtic gold coins in the light of Mössbauer spectroscopy, electron microprobe analysis and X-ray diffraction

Celtic gold coins found in Southern Germany were studied by Mössbauer spectroscopy, electron microprobe analysis and X-ray diffraction with special attention to coins rich in silver and copper. In such coins the electron microprobe analyses reveal a gold enrichment in a surface layer of more than 100 μm thickness. ¹⁹⁷Au conversion electron Mössbauer spectroscopy also shows that the surface of the coins consists of two phases, one of which is strongly enriched in gold compared to the bulk composition. In comparison with laboratory experiments the observed phenomena suggest that coin production in Celtic times may have involved deliberate heating and etching steps to enrich the surface layer in gold by depleting it of silver and copper.     

Strain-induced structural and phase transitions in superplastic eutectic

The features of diffuse X-ray scattering from samples of the superplastic Pb-62% Sn alloy, (i) subjected to preliminary compression by ～75% and (ii) deformed at room temperature under the conditions optimal for superplastic flow, have been studied. The diffuse peaks revealed are due to the occurrence of short-range stratification in the alloy crystal structure during superplastic deformation. It is found that the superplastic deformation is accompanied by the outflow of Pb atoms from the surface layers, enriched in lead under preliminary compression, to the sample bulk. The formation of viscous amorphous interlayers at grain boundaries under compression facilitates superplastic flow.     

Behavior of hydrogen and defects in zirconium under irradiation

The accumulation of hydrogen and defects in the E-125 zirconium alloy (Zr-2.5% Nb) is investigated. The hydrogen concentration is maximum on the surface of zirconium alloy samples after electrolytic hydrogenation. The hydrogen concentration decreases at a depth of about 0.5 μm and then gradually grows with increasing depth. The surface of the zirconium alloy is strengthened and becomes more fragile after hydrogenation. A plastic deformation of the zirconium alloy gives rise to traps with different binding energies of hydrogen. The primary type of traps, the binding energy, and the amount of hydrogen captured by traps depend on the deformation magnitude and the sequence of deformation and hydrogenation processes. High mobility of hydrogen in plastically deformed samples is observed under bombardment of the surface of the zirconium alloy by a helium ion beam with an energy of 2.34 MeV. The variation of the hydrogen concentration in the near-surface region of zirconium under ion bombardment depends on the extent of deformation: upon bombardment by helium ions, the hydrogen concentration in the near-surface region of the metal increases for deformations from 1 to 3% and decreases for deformations of 4 and 5%.     

Precipitation imaging of deformation structure of age-hardened alloys

Ageing of supersaturated solid solution of Al 20 wt % Zn alloy after cyclic deformation results in a preferential precipitation of Zn in regions of higher dislocation density. Characteristic inhomogeneities of the deformation structure revealed by this precipitation image correspond well to the surface relief observed by optical and scanning electron microscopy. The posibility of using the method of precipitation imaging to study spatial arrangement of high and low dislocation density regions in deformed age-hardened alloys is discussed.     

X‐ray fluorescence analysis on a group of coins from the ancient roman city of Tridentum (Trento,Italy)

A group of 83 coins, found in the archeological excavations of the ancient Roman city of Tridentum (Trento, Italy), was studied for the determination of their composition, finalized to their classification and cataloging. The coins, mainly made of copper‐based alloys, were minted between the republican period (II century BC) and the last decades of the western empire (V century AD). The X‐Ray Fluorescence archaeometric analysis has allowed a revision of the typological classification of the coins through the identification of six broad groups, each one characterized by a peculiar composition of the coins in the group. A tentative assignation of all the unreadable coins to one of the groups identified was proposed, in a way that could suggest also a possible dating of these coins. Copyright © 2014 John Wiley & Sons, Ltd.     

Quantitative auger electron spectroscopy analysis of AgPd and NiPd alloys

The relationship between peak amplitude in derivative Auger spectra and alloy composition was investigated for AgPd and NiPd alloys. Measurements were performed on polished and sputter etched samples as well as on samples fractured in vacuo. For clean alloy surfaces and in the absence of sputtering, a linear relationship between peak amplitude of a given alloy component and atomic concentration was observed. Relative Auger peak amplitudes measured on sputter cleaned surfaces were different from those measured on fractured surfaces. Results were interpreted in terms of a simple model considering surface enrichment of the alloy component with the lower relative sputtering yield.     

On the comparative study of three silver coins of the IIIrd century B.C. minted in Korkyra, Dyrrachion and by the Illyrian king Monounios

The microstructure of three silver coins dating back to the IIIrdcentury B.C. from the Illyrian King Monounios, the ancient Greek city of Dyrrachion and the ancient Greek city of Korkyra was studied with XRF, PIXE, microhardness measurements, and light and electron microscopy. From this investigation it turned out that these coins have different chemical compositions and different microstructures. The as-collected data allow the determination of a possible minting method. The Korkyra coin was probably hot-worked or cold-worked and annealed, while after cooling, it was cold-worked again. The coin of King Monounios is composed by equi-axed grains which are overrun by slip lines. Consequently it is likely that this coin was casted and then cold-struck. Finally the coin from Dyrrachion is characterized by small-sized grains and strain lines and as a result this coin was probably cold-struck. PACS 07.60.Pb; 78.70.En; 68.37.Ef; Hk; Lp; Nq; 61.66.Bi; 61.72.Mm     

Discontinuous decomposition in quenched and deformed alloys

Discontinuous decomposition in quenched and deformed samples of the alloy Cu + 4.3% Ti has been studied by optical metallography and by electron metallography (with replicas and thin foils). The structure of the discontinuous-decomposition regions changes markedly during the continuous metastable decomposition in the matrix. Cells are nucleated within grains in the deformed samples at recrystallization nuclei.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii Fizika, No. 1, pp. 108–112, January, 1969.     

Microchemical surface analysis of two Numidian coins

This work is a contribution to the microchemical surface analysis of two Numidian coins. Numidia was an ancient kingdom of northern Algeria during 2nd and 1st century BC. Investigations were performed with scanning electron microscopy (SEM) coupled with energy dispersive spectrometry (EDS), energy dispersive X-ray fluorescence spectrometry (EDXRF) and X-ray diffraction (XRD). The identification of the coins was done thanks to the name initials and effigy of King Massinissa. SEM observations of coins showed heterogeneous surfaces. SEM and EDXRF analyses showed an alloy structure with copper (65%), antimony (19%) and lead (16%). The XRD identified a metal structure and corrosion products which were on the coin surfaces: Litharge (PbO), Hydrocerussite (Pb₃(CO₃)₂(OH)₂), Bindheimite (Pb₂Sb₂O₇) and Bystromite (MgSb₂O₆).     

Preferred sputtering on binary alloy surfaces of the AlPdSi system

Auger spectroscopy has been used to investigate the behavior of preferred sputtering on surfaces of homogeneous AlPd, SiPd and AlSi alloy films. These combinations of alloys were chosen for studying the effects of mass and bonding differences on preferred sputtering. Experiments have been carried out using a 1 keV Ar ion beam over a range of alloy compositions. Our results can be summarized as follows: (a) The preferred sputtering of these binary alloys cannot be predicted according to the sputter yields of individual elements, e.g. both Al and Si have been observed to be removed preferentially relative to Pd although pure Pd has a higher sputter yield, (b) In the alloys studied, mass difference appears to dominate over bonding difference in controlling the preferred sputtering behavior since the extent of preferred sputtering of Al and Si relative to Pd is about the same. This observation is interpreted on the basis of the binary alloy sputtering theory formulated by Andersen and Sigmund. (c) Judging from the composition change of the sputtered surface, there is no evidence for formation of compounds with specific compositions as a result of preferred sputtering in the AlPd and SiPd alloys investigated.     

Analysis of the internal structure of ancient copper coins by neutron tomography

The internal structure of copper coins—a Golden Horde pulo of the 14th century AD and an ancient coin found in Phanagoria at sites of the 5–4th centuries BC—are studied by neutron tomography method. From a set of angular projections of neutron absorption, three-dimensional models of the analyzed objects are reconstructed and the analysis of their physical state is performed. In the copper pulo, a region characterized by a greater neutron beam attenuation coefficient is found. It is assumed that this region was formed due to the gradual penetration of patina into the coin. The neutron tomography data also make it possible to analyze the remnants of an antique coin found in underwater archeological studies. Areas of surface damage and cracks in the antique coin are shown, visually separated from the corrosion layer.     

Emergence of the Sierpinski Gasket in Coin-Dividing Problems

The present paper proposes a generation mechanism of a fractal pattern related to a coin system. The problem is formulated in terms of a situation of dividing coins among people. Remarkably, a fractal pattern like the Sierpinski gasket is obtained, by marking all the possible division of coins as a point set. The mechanism for this fractal structure is reduced to nested relations, owing to a hierarchical property of coin denominations. Relevance to dynamical systems is also discussed.     

Au80Sn20合金焊料制备工艺

针对高功率二极管激光器的封装要求,通过磁控溅射的方法制备了Au80Sn20合金焊料,使用扫描电子显微镜（SEM）观察其微结构和表面形貌;利用能谱仪（EDX）和X射线荧光测试仪分析其成分;采用差热分析法（DTA）测试其熔化温度,并用制备的Au80Sn20合金焊料进行了可焊性实验。结果表明:磁控溅射法可以制备Au80Sn20合金焊料,其制备的Au80Sn20合金焊料表面无明显缺陷,结构致密;成分与理论值接近;熔点与理论熔点接近;焊接浸润性好,空洞率小,强度大。     

Fabrication of superhydrophobic nanostructured surface on aluminum alloy

A superhydrophobic surface was prepared by consecutive immersion in boiling water and sputtering of polytetrafluoroethylene (PTFE or Teflon®) on the surface of an aluminum alloy substrate. Immersion in boiling water was used to create a micro-nanostructure on the alloy substrate. Then, the rough surface was coated with RF-sputtered Teflon film. The immersion time in boiling water plays an important role in surface morphology and water repellency of the deposited Teflon coating. Scanning electron microscopy images showed a “flower-like” structure in first few minutes of immersion. And as the immersion time lengthened, a “cornflake” structure appeared. FTIR analyses of Teflon-like coating deposited on water treated aluminum alloy surfaces showed fluorinated groups, which effectively reduce surface energy. The Teflon-like coating deposited on a rough surface achieved with five-minute immersion in boiling water provided a high static contact angle (～164°) and low contact angle hysteresis (～4°).     

Deformation chaos and self-organization at the prefracture stage of 5556 alloy

Based on the analysis of the data of high-speed video recording of the surface of the deformed aluminum-magnesium alloy 5556, it has been found that the unstable plastic deformation associated with the deformation band dynamics tends to deformation chaos with increasing deformation. It has been shown that the ductile fracture of the 5556 alloy with a recrystallized structure should be considered as a global self-organization in a nonlinear nonequilibrium system being in the state of deterministic chaos.     

Composition and structure of coatings formed on a VT16 titanium alloy by electro-plasma spraying combined with microarc oxidation

The composition, the structure, and the microhardness of the oxide coating formed during a combined plasma process on a VT16 titanium alloy are studied. The structure of plasma-sputtered aluminum oxide after microarc oxidation is found to change: the coating has a lower density and is melted. The phase composition of the aluminum oxide formed by electro-plasma sputtering and then subjected to microarc oxidation remains unchanged.