Arsenical Copper-tin Bronze

Abstract: During rescue work in the north cemetery of ancient Demetrias in Volos, fragments from several gilded wreaths were revealed. These wreaths were made using a number of different materials, including wood, bone, ceramic, organic fibers, various pigments and different metals. A number of fragments of these wreaths were studied in order to understand their manufacturing techniques as well as the composition of the metals used (Cu, Au, Pb), and the gilding practices. The wreaths are dated from the mid 4th up to 2nd centuries BC.

Techniques are understood as the human operation involved in any transformation of matter in material production, along with their broader implications concerning tools, gestures, senses, and their interactions with specific social and cultural systems. This theme is deliberately broad, so as to allow young researchers to examine the topic from different angles, which are further detailed and defined in the call for papers (available under the corresponding tab).

The excavation of the Early and Middle Minoan necropolis of Petras in eastern Crete continues to reveal new and interesting information about the people who were buried there before the foundation of the palace at the same site. In 2018, an EM IIA primary female burial was excavated in a lower level beneath House Tomb 2, founded in Middle Minoan IB. The woman wore a necklace of various types of jewels including a very small cast gold pendant. The iconography of the piece depicts two male bearded figures in an embrace with specific hand and arm gestures as they kneel and face each other. The imagery of the figures, which measure only 1.75 cm in height and show a level of naturalism not normally seen at this time, is quite unique for Early Minoan Crete and for the Aegean region during the Early Bronze Age. The kneeling embrace of two men is an
enigmatic motif among the cultures around the eastern Mediterranean during the Early and Middle Bronze Age. Nevertheless, iconographic features and metallurgical technology among other indicators point farther afield to Uruk or the Sumerian region of Mesopotamia
as the origin of the gold pendant. The meaning of the pendant is explored, and it sheds light on the customs and beliefs of an elite or noble woman from Petras before the palace was built.

Arsenical copper was widely used in the Early Bronze Age, but it was not employed after the introduction of copper-tin alloys in the period around the Middle Bronze Age. Nevertheless the present research showed that a few ornamental objects of particular kind were made of a copper alloy with a silvery surface, containing arsenic, antimony and often some cobalt and nickel still in the Final Bronze Age and in the Iron Age. This alloy is very fragile and can only be cast, it is very difficult to cut and file and shows a characteristic silvery surface. The shiny and silvery grey colour of these objects is due to a segregation phenomenon. During the slow cooling of the metal the As rich a and c compound (eutectic) is pushed to the surface through feeders which look like filaments running into the metal body and forms the typical silvery grey layer. The microstructure of the eutectic shows a solid solution phase a and a compound c, containing 29?65 As (Cu 3 As). The eutectic can develop already with 1-2% of As in the alloy. Ornamental objects made of this distinctive and beautiful material were worn by women who had special powers and exceptional functions in the society of the time and were connected with the cult of the moon and fertility goddess.

Thasos is an island in the north Aegean with a long tradition in mining and metallurgical production the emergence of which could be traced to the end of the Neolithic and the beginning of the Early Bronze Age (c. 3200 BCE). The current study is focused on copper alloy artefacts that were found in several Early Bronze Age settlements on the island to provide an understanding of how they were produced and utilised/consumed by their users. Application of laboratory instrumental techniques, namely compositional analysis by X-ray Fluorescence and metallography coupled by Scanning Electron Microscopy (SEM/EDS) are used to illuminate our understanding of the methods utilised for their fabrication and the choice of certain alloys that were common during the Early Bronze Age. Results have revealed the predominance of arsenical copper fabricated by casting, followed by stages of hammering and annealing. A single example of a leaded copper object shows no parallels among the studied assemblage or other contemporary finds. The average arsenic contents of 2.9 wt% might be the result of accidental alloying of copper with arsenic-bearing copper minerals or indeed a conscious selection of mixed ores that contained both metals. Geological information is taken into consideration attempting to locate the possible sources of copper and arsenic-bearing minerals on the island that were potentially utilised as raw materials. Results point to the possible utilisation of fahlores (tennantite in particular) from a mining location close to Limenaria that could yield arsenical copper in a single stage smelting process. Considering the cooccurrence of arsenic and low silver contents in the fahlores from this location, they match well to the minute silver contents detected in two artefacts of the assemblage under study. Such preliminary findings are of special importance as they contribute to the ongoing discussion concerning the production of arsenical copper across the Aegean during the EBA.

During rescue excavations at Site 1 in Kotowo in 1958, a ceramic tube was discovered in a feature of the Funnel Beaker culture. Currently, XRF analysis suggests that it is a ceramic tuyère associated with copper processing. The feature, radiocarbon dated to 3911–3714 BC (68.3% probability), most likely housed a metalworking workshop. The artefact from Kotowo has several analogues in the Polish lands, mainly from sites of the Lengyel-Polgár culture. With a clear and well-documented cultural context, it testifies to the existence of the oldest metallurgical workshop so far known in the Funnel Beaker culture.

Copper artifacts from Cahokia Mounds, Illinois were analyzed from a materials science perspective to shed light on techniques used by Mississippian copper workers to deform nuggets of native copper into thin sheets. Eight small copper pieces from a copper-working site at Cahokia's Mound 34 were subjected to metallographic examination. Replication experiments thereafter recreated features of the artifacts under controlled conditions. It is concluded that copper sheets were thinned through repeated cycles of hammering and annealing performed at temperatures achievable in an open wood fire. The welding of sheets to create multilayered objects was not observed in any artifacts and could not be accomplished experimentally. Additionally, a possible cutting method used on some artifacts was identified.

A few decades ago, heritage scientists and art historians started to study the ancient surface colouring techniques of metal art pieces. Colouring of copper and silver has already been broadly studied but no works on gold have been reported yet. This knowledge can be very important for art and technology history, conservation-restoration and surface sciences. This paper contributes to the investigation of the oldest recipe known so far to colour fire gildings. The chosen model samples, the mixture and the application of the recipe have been summarised by referring to the ancient writings known as the Arab and Syrian Alchemist Collection of M. Berthelot. The main aim of this research is to study the colour change obtained by applying the above mentioned recipe, and to identify the processes involved during this colour change. Digital imaging and scanning electron microscopy in combination with colorimetric measurements and elemental analysis have been performed to characterise the colour change and to identify its origins.

Durante décadas el material arqueológico procedente de asentamientos coloniales europeos en contexto americano, y particularmente en Colombia, estuvo excluido de análisis científico-técnicos exhaustivos que aportaran datos de mayor relevancia y que sirvieran no solo para dar por sentado esa presencia y contacto europeo con sociedades amerindias. El tema de investigación, en general, ha sido la cultura material procedente de Europa en fundaciones americanas, es decir, en sociedades de contacto, principalmente, durante el siglo XVI. En este estudio se presenta brevemente el caso de unos crisoles cónicos transportados por los españoles a una de las primeras colonias de Terra Firme llamada Santa María de la Antigua del Darién. Dichos crisoles fueron presuntamente usados en el proceso de fundición de oro, metal que los colonos adquirían por medio de saqueos, intercambios y tributos cargados a los cacicazgos de la región. Los resultados analíticos que se expondrán a continuación forman parte de 433 un conjunto más amplio de cultura material cerámica analizada dentro de Cuadro 1-Valores composicionales normalizados de elementos mayores y elementos traza obtenidos por fluorescencia de rayos X (FRX) (Alzate Gallego, 2015

A Moche cast copper alloy object was investigated with focus on three main areas: the alloy composition, the casting technology, and the corrosion process. This complex artifact has thin connective arms between the body and the head, a situation that would be very difficult to cast. The entire artifact was mounted and polished allowing for complete microstructural and microchemical analysis, providing insight into the forming technology. In addition, gigapixel x-ray spectrum imaging was undertaken to explore the alloy composition and the solidification process of the entire sample. This process used four 30 mm2 SDD-EDS detectors to collect the 150 gigabyte file mapping an area of 46 080 × 39 934 pixels. Raman analysis was performed to confirm the corrosion compounds.

A collection of 35 metallic artefacts comprising various typologies, some of which can be attributed to the Bronze Age and others to later periods, were studied to provide detailed information on elemental composition, manufacturing techniques and preservation state. Elemental analysis by micro-EDXRF and SEM-EDS was performed to investigate the use of different alloys and to study the presence of microstructural heterogeneities, as inclusions. X-ray radiography, optical microscopy and SEM-EDS were used to investigate manufacturing techniques and degradation features. Results showed that most of the artefacts were produced in a binary bronze alloy (Cu-Sn) with 10-15 wt% Sn and a low concentration of impurities. Other artefacts were produced in copper or in brass, the latest with varying contents of Zn, Sn and Pb. A variety of inclusions in the metal matrices were also found, some related to specific types of alloys, as (Cu-Ni)S 2 in coppers, or ZnS in brasses. Microstructural observations revealed that the majority of the artefacts were subjected to cycles of thermomechanical processing after casting, being evident that among some artefacts different parts were subjected to distinct treatments. The radiographic images revealed structural heterogeneities related to local corrosion processes and fissures that seem to have developed in wear-tension zones, as in the handle of some daggers. Radiographic images were also useful to detect the use of different materials in one particular brass artefact, revealing the presence of a possible Cu-Sn solder.

por su apoyo en la realización de los artículos y las interesantes discusiones en torno al tema de la fisicoquímica de escorias y la pirometalurgia del cobre. A mí querido coautor y socio, Dr. Pascal Coursol por‖encurajarme‖ en la realización de artículos científicos, enseñarme los principios de la modelación termodinámica y brindarme todo su apoyo emocional. A todo el personal de la fundición Paipote que acompañó y apoyó mi trabajo durante los años 2008-2009. En especial el superintendente Juan Carlos Vargas, ingenieros César Mardones,

Copper artifacts from Cahokia Mounds, Illinois were analyzed from a materials science perspective to shed light on techniques used by Mississippian copper workers to deform nuggets of native copper into thin sheets. Eight small copper pieces from a copper-working site at Cahokia's Mound 34 were subjected to metallographic examination. Replication experiments thereafter recreated features of the artifacts under controlled conditions. It is concluded that copper sheets were thinned through repeated cycles of hammering and annealing performed at temperatures achievable in an open wood fire. The welding of sheets to create multilayered objects was not observed in any artifacts and could not be accomplished experimentally. Additionally, a possible cutting method used on some artifacts was identified.

Copper artifacts from Cahokia Mounds, Illinois were analyzed from a materials science perspective to shed light on techniques used by Mississippian copper workers to deform nuggets of native copper into thin sheets. Eight small copper pieces from a copper-working site at Cahokia's Mound 34 were subjected to metallographic examination. Replication experiments thereafter recreated features of the artifacts under controlled conditions. It is concluded that copper sheets were thinned through repeated cycles of hammering and annealing performed at temperatures achievable in an open wood fire. The welding of sheets to create multilayered objects was not observed in any artifacts and could not be accomplished experimentally. Additionally, a possible cutting method used on some artifacts was identified.

The following study focuses on a number of Villanovan bronze artefacts of different typologies, coming from a necropolis discovered in 1998 on the site of Orto Granara (Castel S.Pietro Terme – Bologna – Italy). The period of use of the necropolis spanned from the end of the 8th to the first half of the 7th century B. C. Among the metallic finds retrieved during the excavation, a set of samples has been chosen in order to conduct a set of archaeometallurgical analyses aimed at defining their nature (both in the sense of their chemical composition and their microstructure) and evaluating their state of conservation. Samples have been analysed through optical microscopy (OM), stereomicroscopy (SM) and Extended Pressure Scanning Electron Microscope (EP-SEM) in VP-mode with EDS microprobe for the localised evaluation of the composition. The corrosion products were studied by infrared spectroscopy (FTIR) and the alloy composition by Flame Atomic Absorption Spectroscopy (FAAS). The results...

The following study focuses on a number of Villanovan bronze artefacts of different typologies, coming from a necropolis discovered in 1998 on the site of Orto Granara (Castel S.Pietro Terme – Bologna – Italy). The period of use of the necropolis spanned from the end of the 8th to the first half of the 7th century B. C. Among the metallic finds retrieved during the excavation, a set of samples has been chosen in order to conduct a set of archaeometallurgical analyses aimed at defining their nature (both in the sense of their chemical composition and their microstructure) and evaluating their state of conservation. Samples have been analysed through optical microscopy (OM), stereomicroscopy (SM) and Extended Pressure Scanning Electron Microscope (EP-SEM) in VP-mode with EDS microprobe for the localised evaluation of the composition. The corrosion products were studied by infrared spectroscopy (FTIR) and the alloy composition by Flame Atomic Absorption Spectroscopy (FAAS). The results...

ΠΕΡΙΛΗΨΗ : Στην παρούσα εργασία μελετάται η επίδραση των κραματικών στοιχείων Sc & Zr στα ελατά κράματα αλουμινίου της σειράς 5ΧΧΧ. Οι προσθήκες Sc & Zr αυξάνουν σημαντικά το όριο ροής του υλικού λόγω σχηματισμού ενδομεταλλικών φάσεων οι οποίες συμβάλλουν, στην εκλέπτυνση της χυτής μικροδομής, στην παρεμπόδιση της ανακρυστάλλωσης κατά την έλαση και στην ισχυροποίηση του υλικού λόγω καθίζησης. Συνεπώς μελετήθηκε θεωρητικά η επίδραση των λειτουργικών συνθηκών και της συγκέντρωσης κατά τη χύτευση και τις κατεργασίες ομογενοποίησης και ανόπτησης. Τα αποτελέσματα συγκρίθηκαν με δεδομένα από την ανοιχτή βιβλιογραφία, από τα οποία μπορούμε να συμπεράνουμε ότι οι προσομοιώσεις περιγράφουν ικανοποιητικά τους μετασχηματισμούς που λαμβάνουν χώρα και μπορούν να χρησιμοποιηθούν για τον σχεδιασμό της γραμμής παραγωγής κραμάτων Al-Mg-Sc-Zr.

The stability of coloured gold alloys may be dependent on the environment that involves them. This paper is concerned with the effect of an artificial sweat solution in the stability of several gold base alloys with different colours. The changes in the samples physical properties, colour, brightness, and reflectance were measured for several periods of immersion. Two types of alloys (purple and blue coloured alloys) showed to be sensitive to the artificial sweat solution. The other tested alloys have a high resistance to tarnishing comparable with the results obtained for pure gold.

In this paper, some aspects of heat treatment used in manufacturing copper and bronze artefacts in different periods of Iran's history have been considered. To study heat treatment processes in ancient and historic copper alloys, two complimentary methods used on some copper and bronze artefacts: metallographic investigations to study microstructural features and SEM-EDS analysis to identify chemical composition of samples. The results showed application of annealing and quenching in different systems: copper, brass and bronze artefacts. Metalworkers by applying a cycle of alternative hammering and annealing operations have looked for mechanical characteristics by which to produce intended objects. On the other hand, quenching high tin bronzes prevents formation of brittle intermetallic phase (δ) and improves workability.

Recent research has brought the prolific bronze industry of Bronze Age Colchis (modern western Georgia) into focus, but many aspects are still poorly understood. This study synthesizes and reinterprets legacy Cu alloy compositional data to investigate technological choices and spatial patterning. It reveals a massive injection of fresh copper into the system during the Late Bronze-Early Iron Age, and a high degree of selectivity in the alloys used for different objects, with colour being as important as hardness in determining these choices. Spatial analyses show significant geographical variability in alloying practices, which map onto topo-graphical zones in unexpected ways. We also explore recycling practices and argue that the term encompasses a range of different reuse activities, which may be employed under differing economic conditions. Finally, the data suggest relatively extensive primary alloying of tin and copper in the Late Bronze and Early Iron Ages, which further substantiates the speculation that some local tin sources were exploited.

In this paper the data on arsenic content of Minoan copper-based finds from various sites in Crete, collected during a program of scientific analyses sponsored by the Institute for Aegean Prehistory, Philadelphia, are discussed. The analyses were carried out by X-ray fluorescence (XRF) spectroscopy. The aim of this study is the investigation of the metallurgical habits and skills that can be reconstructed through the research on various Minoan sites in eastern Crete. The metal objects from Early Minoan (EM) IB (ca. 3000–2900 BCE) sites including Hagia Photia Siteias, Kephala Petras, and Livari Skiadi and from the Late Minoan (LM) I (ca. 1625-1450 BCE) settlements of Gournia and Mochlos (see also Soles and Giumlia-Mair in this volume) have been analyzed. In this paper we present the data on the use of arsenic as an alloying element in the copper-based finds from Crete in the different periods, and compare them with data from analyses of finds from other contexts, such as for instance Anatolia, various sites in the Near East, Armenia and Iran.

This paper presents a study carried out on important finds from the House of the Metal Merchant in Mochlos, dated to the LM IB period (c. 1530­1430 BC). The characteristics of the pieces and the results of analyses carried out by XRF illustrate the habits of the metalworkers of this period and their working and finishing processes. The Foundry Hoard, from the House of the Metal Merchant, consists of a large number of pieces, vessels, tools, weapons, ingots, half­worked pieces, casting remains, and a large number of damaged objects, all collected for recycling, and partly burned and fused together.
They certainly come from a burnt workshop. The most important find is the large chunk of arsenicrich material that indicates that the copper­based alloys containing both elements, arsenic and tin, were deliberate, and presumably produced with the intention of exploiting the advantageous properties of both metals. This paper discusses the analysis data and compares them with the data from contemporary contexts.

Abstract
This paper discusses the methods employed to achieve polychromy on metals in Classical times, the ancient textual sources that give indications on how this was done in different periods, and shortly refers to the meaning of the variously coloured metals in antiquity. The first topic in this text relates the ways in which gold was applied on silver and copper-based metals: the mechanical application of gold sheet and foil, leaf gilding, mercury gilding and lead gilding. The paragraphs dedicated to silvery metals comprise silver foil, surface treatments on debased silver, arsenic-rich alloys, incoctilia and tinning. Some experiments that have been carried out on the iridescent copper-based alloy pyropus, mentioned by various Latin authors, but never identified up to now are then described. Artificially patinated alloys, such as the purple-black alloy Corinthium aes containing small amounts of gold and silver, but also red, orange and yellow patinated alloys recently identified on Roman and Romano-Egyptian objects conclude the essay.

Unpublished poster presentation presented at the 42nd International Symposium on Archaeometry, Merida, Mexico, 20-26 May, 2018.

As one of the earliest alloys of the ancient world, the study of the production and use of arsenic bronze is of significant interest to archaeometallurgists and archaeologists alike. However, archaeometric investigations of ancient arsenic bronze alloys and artefacts have been hampered by a lack of available reference standards, with only three arsenic bronze reference standards having been commercially produced to date: BCR-691 C, MBH-36XCUAS3 A, and MBH-36XCUAS4 A [1]. Additionally, the fabrication of arsenic bronze alloys analytically suitable for use as reference standards is complicated by segregation processes which take place in these alloys during the casting and cooling stages of manufacture [2]. This poster presents the preliminary results of ongoing efforts to create new arsenic bronze reference standards through the use of graphite mold casting, slow cooling, and prolonged annealing techniques under reducing conditions. Using these fabrication techniques, it is possible to fabricate arsenic bronze alloys of sufficient homogeneity for use as reference standards for chemical analysis. It is the intention of the authors to use these techniques to fabricate a suite of reference standards which would provide new opportunities for interlaboratory collaborations and comparative research on arsenic bronze alloys and artefacts.

[1] Heginbotham, A., Bassett, J., Bourgarit, D., Eveleigh, C., Glinsman, L., Hook, D., Smith, D., Speakman, R., Shugar, A., and Van Langh, R., 2014, The Copper CHARM Set: A New Set of Certified Reference Materials for the Standardization of Quantitative X-Ray Fluorescence Analysis of Heritage Copper Alloys, Archaeometry, 57(5), 856-868.

[2] Mödlinger, M., and Sabatini, B., 2016, A Re-evaluation of inverse segregation in prehistoric As-Cu objects, Journal of Archaeological Science, 74, 60-74.

Αργύρης Βουγιουκλάκης Α.Μ:1052493 ΑΣΚΗΣΗ ΓΕΩΧΗΜΕΙΑΣ 6 α) ΜΕΤΑΛΛΑ: Τα μέταλλα είναι μια μεγάλη κατηγορία χημικών στοιχείων που εμφανίζουν ορισμένες κοινές ιδιότητες, όπως είναι η λάμψη, η υψηλή ηλεκτρική και θερμική αγωγιμότητα, η δυνατότητα σχηματισμού ελασμάτων (ελατά) και συρμάτων (όλκιμα). Τα περισσότερα, αλλά όχι όλα, έχουν μεγάλη πυκνότητα και είναι σκληρά και ανθεκτικά. Διακρίνονται από τα αμέταλλα, που αποτελούν επίσης τη δεύτερη μεγάλη κατηγορία των στοιχείων, τόσο από τις φυσικές όσο, κυρίως, από τις χημικές τους ιδιότητες.

In this paper we discuss chemical compositions, lead isotope ratios and results of metallographic analysis of some copper based alloys extremely rich in ar-senic (15.8-27.6 wt% ) and touch upon technological aspects of producing of such an extraordinary alloy.

The chemical composition of ancient copper-based metal changes over time due to repetitive recycling and mixing of old metal. Prehistoric copper usually contains impurities from the copper ores themselves, and some have been used as evidence of anthropomorphically induced chemical change. Research into these changes has historically relied upon the assumption of element loss linearity, which is highly misleading and in fact varies with a multitude of factors. To illustrate the complexity of such losses for prehistoric alloys, we have selected arsenical bronze (Cu-As alloys) for study. The mass loss of several Cu-As-alloys under reducing atmosphere were measured by DTA/TGA. From our comparison of the experimental results to thermodynamic calculations and literature data, it was unclear whether weight losses were solely caused by the elemental loss of arsenic. However, a prolonged time temperature-cycling run demonstrated that mainly arsenic volatilizes, hence the non-linear mass loss from the alloy can be directly attributed to arsenic. Keywords DTA – TGA – arsenical bronze – prehistory – recycling

An intriguing set of twelve concave metal discs were recovered during excavations in the Pre- and Protopalatial
cemetery at Petras, all in Protopalatial contexts, between 2011 and 2014. Five had been placed inside
Room 2 of House Tomb 10, and several more were found in the exterior space north of the same Ceremonial
Area 2. e discs are small and have a shallow but noticeably concave pro!le. Where preserved the upper
surface is o"en polished, but there are no other visible traces of decoration or piercing that might shed
light on their use in antiquity. To determine their function, we employed a combination of contextual and
material analysis. e discs form part of a large deposit of small copper, bronze, silver and gold objects in
Tomb 10. Ten of the discs were examined by XRF and the results reveal interesting choices of metal. One
is made of a silver alloy. e others are copper alloys with a high percentage of arsenic which indicates that
they originally had a silvery color. e use of such a special alloy suggests the discs had a speci!c function
and meaning. Various possibilities are explored including their use as balances, mirrors and ornaments.

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Here we present the results obtained in the study of metallurgical debris of the Copper Age settlement of Agua Amarga (Fuensanta, Lorca). A preliminary description of the different types of debris has been made. This classification has been related to the first metallurgy documented in Iberian Peninsula based on crucible smelting. A selection of materials has been analysed through pFRX, PIXE, XRD, optical microscopy and SEM-EDS. The exceptionality of materials of Agua Amarga allows us to answer questions highly debated about arsenical copper production during Copper Age. Reconstructing ore supplies at Agua Amarga was achieved thanks to regional archaeomining survey and geochemical study of copper deposits.

Lead alloys characterized by the addition of selenium exhibit a fine grain structure even at very low antimony contents (less than 2%). This structure yields acceptable castability and quality of the castings. The hardness which is necessary for handling the battery plates is achieved by age hardening due to finely dispersed antimony. Corrosion stability at constant potential or constant current proves to be slightly superior, but in the same order of magnitude compared to conventional antimony alloys (≥ 4%). However, at constant cell voltage the amount of antimony released from the positive acid grid is too small to affect the potential of the negative electrode markedly. Therefore, the very low initial gassing rate, which is of the same order as experienced with antimony free batteries, remains almost constant. Of special importance, is that the well known stabilizing effect of antimony in respect to the positive active material is virtually maintained with these selenium alloys. This results in capacity stability as well as rather good cycling performance.

Zusammenfassung:
Im Rahmen der Forschungen auf dem Çukuriçi Höyük, Westtürkei, konnte eine Siedlung ausgegraben werden, die in die Frühbronzezeit 1 zu stellen ist. Die durchgeführten 14C-Analysen ermöglichen es, diese in den Zeitraum von 2850–2750 calBC zu datieren. In den aufgedeckten Räumen und Gebäuden fanden sich diverse Siedlungsreste, die auf allgemeine Haushaltsaktivitäten, wie etwa Kochen oder Spinnen, hinweisen. Gleichzeitig konnten aber in diesen Räumen umfangreiche metallurgische Ensembles ausgegraben werden, die darauf schließen lassen, dass dort auch eine intensive Metallverarbeitung stattfand. Tiegelfragmente, Düsen, Gussreste, Halbfertigprodukte, Fertigprodukte und auch Öfen fanden sich in großer Zahl auf dem Tell. An den verschlackten Innenflächen der Tiegel fanden sich zahlreiche Metalleinschlüsse mit sehr hohen Arsenkonzentrationen (18–20 Masse%) sowie andere intermetallische Phasen. Diesee bemerkenswert hohe Arsenkonzentration lässt in Kombination mit den Resultaten eines weiteren Fundstückes, das Kupferstein und Speis enthält, darauf schließen, dass auf dem Tell auch Arsenkupfer produziert wurde. Die Untersuchung dieser metallurgischen Reste, die sich unter dem Begriff „Tiegelmetallurgie“ subsummieren lassen, ermöglichte es, nahezu alle Produktionsstufen von Arsenkupfergegenständen zu beschreiben.

Schlüsselwörter: Türkei, Westanatolien, Frühbronzezeit 1, Entwicklung der Metallurgie, Arsenkupfer, Arsenopyrit, Kupferverarbeitung, Bronze, Archäometallurgie

An investigation was carried out by Mintek to examine the influence of a range of alloying additions (titanium, vanadium, chromium, molybdenum, cobalt, zirconium, boron, aluminium, silicon, zinc, platinum, palladium, rhodium, iridium and ruthenium) on the formability, hardenability and colour of 18 carat gold alloys. This paper provides chemical formulae for yellow 18 carat gold alloys that have hardnesses which are higher than the hardnesses of the corresponding conventional 18 carat alloys, in particular in excess of 300 HV, but with colours similar to conventional 18 carat gold. A preparation method for the alloys will also be described, which includes the steps of melting, annealing, quenching, cold working and age hardening.

The paper presents the results of archaeological and metallurgical research performed on a hoard of three metal objects: a double spiral ornament, a dagger and a hammer-axe. The artefacts were discovered at site 2 in Kałdus, Chełmno commune, kujawsko-pomorskie voivodeship. The objects were discovered within the Wiórek phase of a Funnel Beaker culture context. They were probably deposited into a votive pit. Typological analyses have been carried out. The relative chronology of the objects was determined by the results of typological analyses. The dagger is of Usatovo type and the typological classification of the other objects causes difficulties. The hoard is dated to the second half of the 4th millennium cal. BC. The artefacts’ chemical composition and macrostructure analyses were also performed. It has been concluded that all the objects from the hoard were made of arsenic copper with the dagger also enriched with arsenic minerals. The manufacture technique and objects’ usage traces have been recognized. Using the results of typological and chemical analyses the provenance of the hoard from Kałdus is discussed.

Precious metals have been often employed to manufacture various decorative artefacts at Pre-Islamic Iran. One of the most outstanding phenomena from this period of Iran was the extraordinary occurrence of the silver application to make various decorative objects. Indeed, application of silver and its alloys was extended for making different vessels and other decorative and royal objects in historic time, especially in Achaemenid (550-330 BC) and Sasanian (224-642 AD) Empires. In this paper, four silver artefacts dated to Achaemenid period, found in Hamedan region, Western Iran, are investigated to identify manufacturing/ shaping process as well as alloy composition. The examined objects consist of two bowls, one decorated plate and one decorated spoon with the head of a felidae. Scanning Electron Microscopy-Energy Dispersive X-ray Spectrometry (SEM-EDS) method has been applied on cross section samples to determine chemical composition of the alloys and the phases and optical microscopy (Metallography) and SEM techniques were used to study of microstructure and manufacturing/shaping procedure. The results showed that all samples were made of silver-copper alloys with different amount of copper in each artefact. Other elements have detected in minor/trace contents such as As, Pb, Cd, Al, S. The microstructure of samples showed interesting features that are related to manufacturing/shaping process to make silver artefacts and compositional aspects of the objects because of copper amount. In fact, two-phased microstructure could be observed in two Achaemenian silver bowls because of the high amount of copper in alloy composition. Two other artefacts include single phase microstructure depending on low content of copper in alloy composition.

The analysis of brasses regarding their microstructure, mechanical properties and ecological characteristics has been
presented. The influence of characteristic alloying elements contained in the brasses and the possibilities of replacing them
with other elements have been assessed. The paper contains the results of studies on the influence of chosen additional elements shaping the structure and properties of unleaded alloys based on Cu-Zn system as the matrix. The research aimed at determining the mechanism and the intensity of influence of such additives as tellurium and bismuth. The microstructures were investigated with the help of light microscopy and scanning electron microscopy with X-ray microanalysis (SEM-EDS) for determining significant changes of the properties.

A Moche cast copper alloy object was investigated with focus on three main areas: the alloy composition, the casting technology, and the corrosion process. This complex artifact has thin connective arms between the body and the head, a situation that would be very difficult to cast. The entire artifact was mounted and polished allowing for complete microstructural and microchemical analysis, providing insight into the forming technology. In addition, gigapixel x-ray spectrum imaging was undertaken to explore the alloy composition and the solidification process of the entire sample. This process used four 30 mm 2 SDD-EDS detectors to collect the 150 gigabyte file mapping an area of 46 080 × 39 934 pixels. Raman analysis was performed to confirm the corrosion compounds.

CuMgSn alloys are investigated as a high-strength substitute for CuPb alloys in journal bearings, based on the tribological compatibility of Mg with steel. While the incorporation of Mg into a copper alloy presents considerable technical difficulties, it was found that its effect on hardness is extraordinary; there are good indications that Mg reduces the tendency for adhesive wear. Higher amounts of alloying elements, as well as slower cooling rates during solidification increase the presence of a brittle interdendritic eutectic, forbidding cold-working. Below 2 wt% of Sn and Mg and using high cooling rates, the slabs can be cold-rolled up to 80% reduction. Isothermal recrystallisation treatments at 600°C provoke highly heterogeneous intermediate microstructures, with some zones fully recrystallised and others showing a cold-rolled structure. Dispersed intermetallic particles separating zones with different kinetics prevent excessive grain growth, allowing the subsequent recrystallisation of slower grains, mitigating the heterogeneity of the final product.

Arsenical copper was widely used in the Early Bronze Age, but it was not employed after the introduction of copper–tin alloys in the period around the Middle Bronze Age.
Nevertheless the present research showed that a few ornamental objects of particular kind were made of a copper alloy with a silvery surface, containing arsenic, antimony and often some cobalt and nickel still in the Final Bronze Age and in the Iron Age. This alloy is very fragile and can only be cast, it is very difficult to cut and file and shows a characteristic silvery surface.
The shiny and silvery grey colour of these objects is due to a segregation phenomenon. During the slow cooling of the metal the As rich a and c compound (eutectic) is pushed to the surface through feeders which look like filaments running into the metal body and forms the typical silvery grey layer. The microstructure of the eutectic shows a solid solution phase a and a compound c, containing 29?65 As (Cu3As). The eutectic can develop already with 1–2% of As in the alloy.
Ornamental objects made of this distinctive and beautiful material were worn by women who had special powers and exceptional functions in the society of the time and were connected with the cult of the moon and fertility goddess.

Η παραγωγή μολύβδου στο Αρχαίο Λαύριο στη διάρκεια των Κλασικών και των Ρωμαϊκών χρόνων 1. Εισαγωγή Η ΠΑΡΟΥΣΑ ΑΝΑΚΟΙΝΩΣΗ αποτελεί συνέχιση και ολοκλήρωση μιας άλλης σχετικής ανακοίνωσης που παρουσίασα στην ΣΤ´ συνάντηση Νοτιοανατολικής Αττικής (Παπαδημητρίου 1995), με θέμα τον λιθάργυρο, ως παραπροϊόν της μεταλλουργίας αργύρου στο Αρχαίο Λαύριο. Μεταξύ των άλλων χρήσεων του λιθαργύρου είχα αναφέρει τότε και τη χρησιμοποίησή του για παραγωγή μολύβδου και είχα διατυπώσει ορισμένες απόψεις βασισμένες σε προκαταρκτικές παρατηρήσεις. Στο διάστημα που πέρασε από τότε είχα την ευκαιρία να εξετάσω διεξοδικά και με σύγχρονες εργαστηριακές μεθόδους, όπως η ηλεκτρονική μικροσκοπία, η σημειακή μικροανάλυση και η περίθλαση ακτίνων Χ, πολυάριθμα δείγματα σκουριάς και καμινείας από το Αρχαίο Λαύριο, που επιτρέπουν να δώσουμε μία πιο ολοκληρωμένη εικόνα του τρόπου παραγωγής του μολύβδου από τον λιθάργυρο και να απαντήσουμε σε ορισμένα ερωτήματα σχετικά με ευρήματα των ανασκαφών στα αρχαία πλυντήρια. Στο φως αυτών των νέων δεδομένων είναι δυνατόν να επανεξετάσουμε τα θέματα του κόστους παραγωγής, της προσφοράς και της ζήτησης του μολύβδου και τις εφαρμογές του και να εκφράσουμε απόψεις για το ιδιοκτησιακό καθεστώς των καμίνων.

H παρούσα διάλεξη Γ.Δ. Παπαδημητρίου: «Η εξέλιξη των κραμάτων χαλκού στον ελλαδικό χώρο από τα προϊστορικά χρόνια ως την έναρξη της Γεωμετρικής περιόδου» παρουσιάστηκε την 5 Νοεμβρίου 2012 στην αίθουσα του ΜΟΥΣΕΙΟΥ ΤΗΣ ΠΟΛΕΩΣ ΤΩΝ ΑΘΗΝΩΝ (Παπαρρηγοπούλου 5-7,Πλατεία Κλαυθμώνος) στο πλαίσιο των ομιλιών της Εταιρείας Μελέτης Αρχαίας Ελληνικής Τεχνολογίας (ΕΜΑΕΤ).

A direct corrélation exists between the com position o f ancient bronze objects and the art o f their fabrication. T h is is p articularly valid for the bronzes o f the G eom etric period in G reece, w h en a sh o rta g e o f tin an d o f good q u a lit y c o p p er has c o n stra in e d the m etalsm iths to adapt their casting and m etalw orking techniques properly.

In this article is presented the study of the cutting edges of about 40 axes and palstaves from the Iberian Peninsula, with a chronology ranging from Chalcolithic to Late Bronze Age. Using metallography, SEM-EDS, XRF-ED analysis and micro-hardness testing, some insights into the technological processes involved in the manufacture of these items can be obtained, and some proposals about the “chaînes opératoires”, or operative chains, and their relationship with the possible functions of the objects can be proposed. The study also comprises the influence of impurities and segregations in the metal, and some suggestions about the “quality” of the items as tools, in relationship with the possible raw materials they worked upon, are included as well.