Large scale investigation of chemical composition, structure and corrosion mechanism of bronze archeological artefacts from Mediterranean basin

A large number of Cu-based archaeological artefacts from the Mediterranean basin have been selected for investigation of their chemical composition, metallurgical features and corrosion products (i.e. the patina).The guidelines for the selection of the Cu-based artefacts have taken into account the representativeness of the Mediterranean archaeological context, the manufacturing technique, the degradation state and the expected chemical composition and structure of the objects.The results show wide variation of the chemical composition of the alloys that include all kinds of ancient Cu-based alloys such as low and high tin, and also leaded bronzes, copper and copper-iron alloys.The examination of the alloy matrix shows largely different metallurgical features thus indicating the use of different manufacturing techniques for producing the artefacts. The results of the micro-chemical investigation of the patina show the structures and the chemical composition of the stratified corrosion layers where copper or tin depletion phenomenon are commonly observed with a remarkably surface enrichment of some soil elements such as P, S, Ca, Si, Fe, Al and Cl. This information indicates the strict interaction between soil components and corrosion reactions and products. In particular, the ubiquitous and near constant presence of chlorine in the corrosion layers is observed in the patina of the archaeological Cu-based artefacts found in different contexts in Italy, Turkey, Jordan, Egypt, Spain and Tunisia. This latter occurrence is considered dangerous because it could induce a cyclic corrosion reaction of copper that could disfigure the artefact.The micro-chemical and micro-structural results also show that another source of degradation of the bronze archaeological artefacts, are their intrinsic metallurgical features whose formation is induced during the manufacturing of the objects, carried out in ancient times by repeated cycles of cold or hot mechanical work and thermal treatments. These combined treatments induce crystallisation and segregation phenomena of the impurities along the grain boundaries and could cause mechanical weakness and increase the extent of the inter-granular corrosion phenomena. PACS 68.55.Jk; 68.35.Dv; 68.37.Hk; 68.55.Nq; 81.05.Bx     

Production of reference “ancient” Cu-based alloys and their accelerated degradation methods

A large number of bronze artefacts found during archaeological excavations carried out in Italy in different contexts have been studied. Their chemical composition and metallurgical features have been determined by the combined use of different analytical surface and bulk techniques, such as optical microscopy (OM), scanning electron microscopy with energy dispersive X-ray micro-analysis (SEM-EDS), X-raydiffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The study of the corrosion products grown on the archaeological Cu-based artefacts and of their metallurgical features has revealed the quite ubiquitous and nearly constant presence of chlorine as the main corroding agent, and the different structures of the alloys. This information has been used to produce reference Cu-based alloys, whose chemical composition and micro-chemical structure is similar to that of the ancient alloys, and to propose the guidelines for carrying out the accelerated degradation tests to produce corroded samples for testing corrosion inhibiting products. The proposed tests were based on soil, chemical and (chemical+soil)-induced degradation, and the micro-chemical structure of the artificially produced corrosion layers has been compared to those grown on archaeological artefacts during burial. The comparison shows that the (chemical+soil)-induced degradation produces “patinas” that are similar to those grown on archaeological artefacts from a chemical, structural and micro-morphological point of view. PACS 68.55.Jk; 68.35.Dv; 68.37.Hk; 68.55.Nq; 81.05.Ba     

Combined use of SEM-EDS, OM and XRD for the characterization of corrosion products grown on silver roman coins

In the framework of the PROMET project (European Commission contract No. 509126) aimed to develop new analytical techniques and materials for monitoring and protecting metal artefacts and monuments from the Mediterranean region, the corrosion products grown on silver Roman coins during archaeological burial is studied by means of scanning electron microscopy combined with energy dispersive spectrometry (SEM-EDS), X-ray diffraction (XRD) and optical microscopy (OM) techniques. PACS 68.55.Jk; 68.35.Dv; 68.37.Hk; 68.55.Nq; 81.05.Bx     

Microchemical investigation of Greek and Roman silver and gold plated coins: coating techniques and corrosion mechanisms

Within the framework of a project financially supported by the European Commission (contract Nr. 509126, acronym PROMET) the metallurgical techniques used by Romans and Greeks for coating the copper core of coins with a thin or thick layer of gold or silver are studied by means of the combined use of scanning electron microscopy combined with energy dispersive spectrometry (SEM-EDS) and optical microscopy (OM) techniques.This approach is utilised to gain further insight into the micro-chemical structure of the external regions of the coins as well as into the bulk metallurgical features. The results indicate that several methods were used by the Greek and Roman craftsmen including the mechanical application of a thin malleable gold or silver foils to be welded via thermal treatment. The analytical approach is also used for investigating the corrosion products grown on the coins during the long-term burial and for identifying degradation mechanisms.PACS 68.55Jk; 68.35 Dv; 68.37Hk; 68.55 Nq; 81.05 Bx     

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     

Micro-chemical and micro-structural investigation of archaeological bronze weapons from the Ayanis fortress (lake Van, Eastern Anatolia, Turkey)

Bronze weapons (VII cen BC) found during the archaeological excavation of the Ayanis fortress (lake Van, eastern Anatolia, Turkey) are investigated in order to determine their chemical composition and metallurgical features as well as to identify the micro-chemical and micro-structural nature of the corrosion products grown during long-term burial. Small fragments were sampled from the artefacts and analysed by means of the combined use of optical microscopy (OM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and energy dispersive spectrometry (EDS). The results show that the bronze artefacts have been manufactured by using alloys with a controlled and refined chemical composition demonstrating the high level metallurgical competence and skill of the Urartian craftsmen and artists. Furthermore, the micro-structural and metallurgical investigations evidence the presence of equiaxed grains in the matrix, indicating that the artefact were produced by repeated cycles of mechanical shaping and thermal annealing treatments to restore the alloy ductility. From the degradation point of view, the results show the structures and the chemical composition of the stratified corrosion layers (i.e. the patina) where the copper or tin depletion phenomenon is commonly observed with the surface enrichment of some elements coming from the burial soil, mainly Cl, which is related to the high concentration of chlorides in the Ayanis soil. The results reveal also that another source of degradation is the inter-granular corrosion phenomenon likely increased by the metallurgical features of the alloys caused by the high temperature manufacturing process that induces crystallisation and segregation phenomena along the grain boundaries.     

Investigations of corrosion phenomena on gold coins with SIMS

In order to establish a new handling procedure for contaminated coins, the Coin Cabinet and the Conservation Science Department of the Kunsthistorisches Museum, Vienna, initiated a research project on corrosion effects of gold coins. By now, investigations on historic and contemporary coins included optical microscopy, scanning electron microscopy (SEM), Auger electron microscopy (AES), X-ray photoelectron microscopy (XPS), and electrochemical methods showing the distribution of pollutants.This work focuses on secondary ion mass spectrometry (SIMS) investigations merely showing the distribution of electronegative elements, such as sulfur, oxygen, and chlorine on the surface. Sulfur is highly suspected of causing the observed corrosion phenomena, and is indeed enriched near polluting splints. Since SIMS is a destructive method, the investigated samples are test coins with intentionally added impurities. These coins were manufactured in cooperation with the Austrian Mint. They were treated with potassium polysulfide (K₂S_x) for 8 h gaining a rapid corrosion of the surface.SIMS mass spectra, depth profiles, and images were done (a) at non-polluted areas, (b) near polluted areas with slight coloring, and (c) directly at polluting stains showing enrichments of sulfur and chlorine. Due to the success of these investigations further studies on historic coins are intended.     

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).     

Integrated approach to the characterization and conservation of artefacts of the Brazilian colonial period

Several common-use artifacts (coins, faience, cult objects, etc.) coming from two excavations sites near Rio de Janeiro, two sugar farms Historico do Rochedo and Cruzeiro, have been the subject of this investigation, which aimed to integrate physico-chemical characterizations with the identification of degradation mechanisms, and the proposal of innovative conservation methods, such as PECVD deposition of SiO₂-like films for protection of metallic artifacts. For the microchemical, micromorphological and microstructural analysis, optical microscopy-OM, X-ray diffraction XRD, X-ray fluorescence-XRF, and scanning electron microscopy equipped with electron microprobe-SEM+EDS have been employed.A cleaning step followed by a consolidation step has been carried out on glassy artefacts, while on metallic artefacts the mechanical cleaning has been followed by a stabilization treatment when necessary.For long-term protection the deposition by PECVD of SiO₂-like films has been performed on a series of copper-based alloys in a home made reactor fed with an tetraethoxysilane-oxygen-argon mixture. The coatings show a good barrier effect against the diffusion of water and oxygen from the environment to the metal surface, that increases with increasing the oxygen to monomer ratio in the feeding gas mixture and the input power density. Moreover, the coating adhesion increases if the deposition process is performed after a hydrogen plasma treatment. PACS 68.55.Jk; 68.35.Dv; 68.37.Hk; 68.55.Nq; 81.05.Bx     

Raman study of a deuterated iron hydroxycarbonate to assess long‐term corrosion mechanisms in anoxic soils

In several contexts such as cultural heritage, oil and gas or nuclear waste disposal, the long‐term corrosion mechanisms of iron in anoxic soils are studied. For this purpose, corrosion layers formed on ferrous archaeological artefacts from the site of Glinet (16th century, Normandy, France) were characterised. The main phases identified are siderite (FeCO₃), chukanovite (iron hydroxycarbonate: Fe₂(OH)₂CO₃ and magnetite (Fe₃O₄). In order to provide reliable Raman references for further studies on carbonated systems, the iron hydroxycarbonate (chukanovite) was synthesised on iron discs. The corrosion mechanisms were investigated by re‐corroding the archaeological samples in a deuterated solution. Raman characterisation on cross sections inside the layer revealed the presence of deuterated chukanovite, allowing the deuterium tracing of the spreading of the corrosion. A set of chukanovite samples was synthesised with various D/H ratios. Using these reference data, the proportion of deuterated chukanovite in re‐corroded artefacts was evaluated, and the corrosion rate was estimated as less than 1.6 µm/year. Copyright © 2010 John Wiley & Sons, Ltd.     

Composition and structure-property relationships of chromium-diboride/molybdenum-disulphide PVD nanocomposite hard coatings deposited by pulsed magnetron sputtering

The composition and structure-property relationships of physical vapour deposited coatings containing mixtures of CrB₂ and MoS₂ are reported. The coatings were produced by pulsed magnetron sputtering of loosely-packed powder targets formed from a blend of chromium and boron powders, alloyed with 12.8, 18.9 and 24.0 atom percent MoS₂. Results of coating characterisation (by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Auger electron spectroscopy and nanoindentation measurement of hardness and elastic modulus) revealed that increasing amounts of MoS₂ produced the following effects: frustration of crystallisation and phase separation; a decrease in average grain sizes (from ∼5.5 to ∼ 4.3 nm) and a decrease in coating hardness (from ∼15 to ∼ 10 GPa). Scratch testing also showed that the load-bearing capability of coatings was altered; coatings possessing an intermediate concentration of MoS₂ exhibited the best behaviour with no failure observed in mechanical testing, due to an optimal nanocomposite structure. The corrosion resistance (investigated by potentiodynamic polarisation tests) however tended to improve as more MoS₂ was introduced. An investigation of the effects of generating an amorphous structure by adding Ti and C into Cr-B-MoS₂ coatings revealed improved corrosion behaviour, which significantly exceeded that of uncoated stainless steel and CrB₂-coated samples. PACS 68.37.Lp; 68.55.A-; 68.55.Ln; 68.55.Nq; 68.60.Bs     

Unusual surface degradation products grown on archaeological bronze artefacts

Within the framework of the EFESTUS project funded by the European Commission a large number of Cu-based archaeological artefacts from the Mediterranean basin have been studied to investigate their chemical composition, metallurgical features and corrosion products nature (i.e. the patina). By means of the combined use of X-ray photoelectron spectroscopy (XPS), optical microscopy (OM), scanning electron microscopy with energy dispersive X-ray spectrometry (SEM-EDS) and X-ray diffraction (XRD) the bronze artefacts have been studied for the detailed identification of the corrosion products and their micro-chemical structure in order to achieve information about degradation agents and mechanisms. In the present work, some examples of unusual corrosion products formed on the objects during the long-term burial are presented and related to the peculiar local context revealing the strong interaction between the bronze artefact and the chemical components found in the archaeological site.     

A complementary set of electrochemical and X-ray synchrotron techniques to determine the passivation mechanism of iron treated in a new corrosion inhibitor solution specifically developed for the preservation of metallic artefacts

Metallic artefacts of the cultural heritage are often stored in uncontrolled environmental conditions. They are very sensitive to atmospheric corrosion caused by a succession of wet and dry periods due to variations of relative humidity and temperature. To avoid the complete degradation of the metallic artefacts, new preventive strategies must be developed. In this context, we have studied new compounds based on sodium carboxylates solutions CH₃(CH₂) _n−2COO⁻, Na⁺ hereafter called NaC _n . They allow the formation of a passive layer at the metallic surface composed of a metal–carboxylate complex. To understand the action of those inhibitors in the passivation process of iron we have performed electrochemical measurements and surface characterisation. Moreover, to monitor in real time the growth of the coating, in situ X-ray absorption spectroscopy (XAS) experiments at iron K-edge were carried out in an electrochemical cell. These analyses have shown that in the case of NaC₁₀ solution, the protection of iron surface is correlated to the precipitation of a well-organised layer of FeC₁₀. These experiments confirmed that this compound is a fully oxidised trinuclear Fe(III) complex containing decanoate anions as ligands. Such information concerning the passive layer is a key factor to evaluate its stability and finally the long-term efficiency of the protection treatment.     

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     

Bronze roman mirrors: the secret of brightness

The surface microchemical structure of high tin leaded bronze Roman mirrors has been studied by means of scanning electron microscopy combined with energy dispersive spectrometry (SEM-EDS), X-ray diffraction (XRD) and optical microscopy (OM) techniques. The results allowed understanding of the origin of their high chemical stability and silvery-lustrous appearance. Indeed, some areas of the selected Roman mirrors are still characterised by a highly reflective and silver coloured surface even though they have been buried in the soil for about 2000 years. The micro-chemical results obtained from these areas have revealed that the mirror surface was tin enriched via inverse-segregation phenomenon by tailoring the cooling parameters. Furthermore, the presence of tin could be likely enhanced via cycles of oxidation and selective copper corrosion processes, thus resulting in a tin surface enrichment as a semi-transparent amorphous-like tin oxide (SnO₂) film, as well as a copper depletion at the outer surfaces.     

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.     

Investigation of Cl corrosion products of iron archaeological artefacts using micro-focused synchrotron X-ray absorption spectroscopy

Synchrotron-based micro-X-ray absorption spectroscopy is used in the present study to obtain chemical information at the microscopic scale such as coordination and oxidation state of Fe atoms in phases constituting corrosion products within archaeological iron artefacts buried in soil. This technique is required in order to answer questions about the iron corrosion process related to the presence of chloride, particularly for restoration and conservation of metallic artefacts of the cultural heritage. The samples available for X-ray microprobe analyses are cross sections from corroded iron archaeological objects. Previously, complementary techniques have been used such as μXRD and μRaman. This specific study applies micro-X-ray absorption spectroscopy to determine the spatial variation of the predominant Fe oxidation state and to identify the corresponding crystallographic phase. The analyses performed at Fe and Cl K-edges (μXANES) reveal the correlation between the valence distribution in the corrosion products and the evolution of the chloride concentration. In addition to the presence of the well-known iron oxyhydroxide β-FeOOH: akaganeite, we highlight the presence of another important phase, the β-Fe₂(OH)₃Clhydroxychloride. These important findings help to gain new insights concerning the influence of such phases in the iron corrosion mechanism within their precise characterization. PACS 61.10.Ht; 61.10.-i; 68.49.Uv     

Synchrotron PEEM and ToF‐SIMS study of oxidized heterogeneous pentlandite,pyrrhotite and chalcopyrite

Synchrotron‐based photoemission electron microscopy (PEEM; probing the surface region) and time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS; probing the uppermost surface layer) have been used to image naturally heterogeneous samples containing chalcopyrite (CuFeS₂), pentlandite [(Ni,Fe)₉S₈] and monoclinic pyrrhotite (Fe₇S₈) both freshly polished and exposed to pH 9 KOH for 30 min. PEEM images constructed from the metal L₃ absorption edges were acquired for the freshly prepared and solution‐exposed mineral samples. These images were also used to produce near‐edge X‐ray absorption fine‐structure spectra from regions of the images, allowing the chemistry of the surface of each mineral to be interrogated, and the effect of solution exposure on the mineral surface chemistry to be determined. The PEEM results indicate that the iron in the monoclinic pyrrhotite oxidized preferentially and extensively, while the iron in the chalcopyrite and pentlandite underwent only mild oxidation. The ToF‐SIMS data gave a clearer picture of the changes happening in the uppermost surface layer, with oxidation products being observed on all three minerals, and significant polysulfide formation and copper activation being detected for pyrrhotite.     

Characteristics of the Raman spectra of archaeological Malachites

Archaeological malachites, represented by the malachites found on the ancient Chinese and Vietnamese copper/bronze coins, may also incorporate those on other archaeological objects. The Raman spectra with Ar laser of these malachites differ slightly from those of the natural malachites found in mines. In this study, 120 measurements of the malachites on 40 coins identified 26 bands, while only around 18 of them are frequently observed. The wavenumbers (cm⁻¹), shifts (±)and relative intensities (in parentheses) of the 18 common bands read, respectively: 153±4 (0‐vs), 179±7 (m‐vs), 217±8 (m‐vs), 274±7 (0‐vs), 355±5 (0‐m), 431±4 (0‐vs), 514±3 (0‐m), 533±5 (0‐s), 566±3 (0‐m), 599±2 (0‐m), 718±6 (0‐m), 754±2 (0‐m), 1061±7 (0‐m), 1093±10 (0‐m), 1365±9 (0‐m), 1491±7 (0‐vs), 3321±11 (0‐vs) and 3380±7 (0‐vs). In comparison with those of the 105 measurements on the natural malachites in five mines, the Raman spectra of the archaeological malachites tend to show less bands, higher backgrounds and greater shifts in the wavenumber position. The weakening or loss of bands is in the order of the OH stretch (3300 cm⁻¹) (most severe), CO₃ (600–1500 cm⁻¹) and CuO (<600 cm⁻¹) (less severe) groups, indicating successive stages of corrosion. The malachites on the coins from three climate zones show their own characteristics. Several coins may have experienced two or more climatic or geologic episodes and show complex Raman spectra different from those of the natural malachites. Copyright © 2012 John Wiley & Sons, Ltd.