Long‐distance interaction in Urartu?: Provenance and composition of copper alloys from Ayanis,Turkey

The paper analyses tin bronze weaponry found at the first‐half‐of‐the‐seventh‐century‐BCE Urartian fortress in the Lake Van region of eastern Turkey. Examples of finely manufactured artefacts provide evidence for the consumption of high‐quality bronzes in a well‐defined elite context. This study tests for the presence or absence of long‐distance procurement of the raw materials used to produce status objects. The results of quantitative elemental and lead isotope abundance ratio analyses show that the bronzes were produced with varying copper tin alloys, and the copper was procured from several possible locations, including Anatolia and Cyprus.     

Fuel Efficiency of Ancient Copper Alloys: Theoretical Melting Thermodynamics of Copper,Tin and Arsenical Copper and Timber Conservation in the Bronze Age Levant*

The melting of pure or alloyed copper, tin and arsenical copper ingots or recycled objects was a drain on the timber and dung fuel resources of many cultures. This paper suggests formulae grounded in thermodynamic principles in an attempt to estimate the energy requirements necessary to melt copper alloys common to both Old and New World cultures, with the goal of identifying consumption and conservation patterns. It has been suggested that tin bronze metallurgy was first adopted in the Levant during the Early Bronze Age (EB) IV, at the onset of the Late Holocene climate episode (c.2300–2000 bc ), becoming the most desired alloy by the Middle Bronze Age (MB) II (2000–1530 bc ) due to the ease of melting tin. To test this hypothesis, the formulae are applied here to all published Levantine EB IV – MB II copper alloys. Fuel conservation rates are proposed based on the thermodynamic formulae. Tin bronze is demonstrably more fuel efficient than pure copper. Due to the inherent difficulties in predicting the behaviour of arsenical copper compounds, it is suggested that melting experiments with representative alloys are conducted to further test and refine these energy relationships.     

ON THE COMPOSITION AND PROVENANCE OF METAL ARTEFACTS FROM POLIOCHNI ON LEMNOS

Summary. The majority of the well-stratified Early Bronze Age metal objects from Poliochni, with the exclusion of one hoard find, was analyzed for their chemical and lead isotope composition. The results show that a major change occurred in the metal used at Poliochni during periods contemporary with Troy I and Troy II. Unalloyed or arsenical copper with relatively high lead contents during the earliest two periods 'azzurro' and 'verde' is gradually replaced and supplemented by tin bronze which, during period 'giallo', i.e., by the end of Troy II, becomes the dominant metal type. Lead isotope abundance ratios in the earlier artefacts are consistent with a derivation of the metal from regional ore sources but the trace element abundance pattern is not. Concurrent with the appearance of tin bronzes is an increase in the diversity of ore deposits exploited; for about one third of the artefacts from period 'giallo' there is as yet no matching ore source in all Anatolia and the Eastern Mediterranean. It is argued that the tin bronzes have been imported as such but that the lead isotope signature does not provide any direct clues to the origin of the tin.     

Association for Field Archaeology Members

Abstract

This article is dedicated to Ronald F. Tylecote

Archaeologists and historians of metallurgy have attempted to explain the gradual abandonment of arsenic bronze in favor of tin bronze in the ancient Old world by making comparisons between the mechanical properties of the two bronzes. These comparisons purport to show the superiority of copper-tin alloys over alloys of copper and arsenic, despite an absence of data on the physical properties of the copper-arsenic system. The study reported here presents the results of mechanical tests carried out on experimental samples of both types of bronze over a broad range of alloy compositions. Hardness, tensile strength, and elongation determinations were made on cold worked and hot worked (forged) material. Whereas tin bronzes can be work hardened more extensively than arsenic bronzes, the far greater ductility of arsenic bronze makes it a desirable alloy for the manufacture of thin metal sheet. The widespread use of low-arsenic copper-arsenic alloys in the Americas, especially in the Andean culture area, is attributable in part to the tradition there of sheet metal production in the elaboration of three-dimensional forms.     

ANGLO-SAXON COPPER ALLOYS FROM LECHLADE, GLOUCESTERSHIRE

Summary. A range of copper-alloy artefacts from the early Anglo-Saxon cemetery at Lechlade were analysed using X-ray fluorescence. There were few pure bronzes or brasses in the assemblage and most alloys contained significant amounts of zinc, tin and lead in variable ratios. In view of the current theory that supplies of new metals and ores were limited and Anglo-Saxon metalworkers normally used scrap metal, the compositions were used to assess the techniques of the craftsmen supplying this community. It is concluded that re-use of copper alloys was prevalent but that metals were selected quite carefully for particular applications, with regard to the metallurgical characteristics required.     

The composition of the copper alloys used by the Greek,etruscan and Roman civilisations: 2. The Archaic,Classical and Hellenistic Greeks

This paper is the second dealing with the composition of copper alloys used by the Greeks. About 500 analyses of Archaic, Classical and Hellenistic objects are published here pp. 117–123 together with comments upon the alloys used. The data are arranged chronologically within broad limits and further subdivided typologically. The techniques of sampling and analysis are discussed in depth in the first part of this project (Craddock, 1976).The development of casting technology is one of the principal features of bronze-working during this period. Our knowledge of Greek casting technology comes both from archaeological excavation and from a careful examination of the castings themselves. Evidence from these sources has been brought together here for the first time together with the comments of medieval, renaissance, and modern technical authors to attempt a coherent picture of the way the superb Greek bronzes were produced and adorned.It was during this period that the Greeks started using mercury gilding on copper and bronze; and the techniques and range of gilded metal are discussed.     

湖北郧县乔家院墓地出土战国及东汉铜器的成分与金相分析

2006年3 ～12月,在南水北调中线工程中,湖北省文物考古研究所等单位对郧县五峰乡乔家院墓群进行了考古勘探和发掘工作.限于考古发掘材料和学者关注度等因素,利用科技手段对该墓地出土战国及东汉时期青铜器的研究尚未见报道.同时,关于鄂西北地区出土古代青铜器的科学分析研究目前并不多见.鉴于此,本研究利用金相显微镜、XRF等方法分析了湖北省郧县乔家院墓地出土的14件战国及东汉时期铜器样品.分析表明除铜壶镶嵌丝为低锡二元(Cu-Sn)合金外,其他13件均为Cu-Sn-Pb三元合金;其制作工艺以铸造为主,另外还采用了热锻、热锻后冷加工、铜质芯撑、错红铜等工艺.以上分析数据为湖北地区战国及东汉时期青铜合金构成及成型工艺积累了相关数据.     

贵州红营盘墓地铜器技术研究

为研究贵州青铜时代铜器技术特征,本文对红营盘墓地出土的17件铜器进行金相观察和扫描电镜能谱分析,结果表明:春秋晚期至战国早中期,红营盘青铜技术进入相对成熟阶段;铜器材质以锡青铜为主,锡含量较稳定,配比较合理;工艺以热锻及冷加工为主;柳叶形铜剑可能产自红营盘当地。     

THE ISOTOPIC COMPOSITION OF TIN IN SOME ANCIENT METALS AND THE RECYCLING PROBLEM IN METAL PROVENANCING

A recent suggestion that some ancient metallurgical processes might give rise to large changes (> 0.5%) in the isotopic composition of tin gave hope that it might be possible to identify ancient bronze samples which had undergone recycling and mixing processes. This paper describes a method for the analysis of the isotopic composition of tin by thermal ionization mass spectrometry and applies it to analyse a number of ancient bronzes and tin metal objects from the Bronze Age Mediterranean. No observable isotopic fractionation of tin was found above $0.1% in the ratio¹²² Sn/¹¹⁶. Consequently, either recycling of bronze in the Late Bronze Age Mediterranean was not so common as supposed, or the isotopic composition of tin is not fractionated by anthropogenic metallurgical processes to the extent predicted by the Bradford group.     

A Comparison Study of Middle Bronze Age II Daggers and Their Rivets as a Tool for a Better Understanding of Their Production

The Middle Bronze Age II is a period during which there exists a contemporaneous usage of arsenic copper and tin bronze for metal weaponry production. In order to learn more about the alloys used in this period, the blades and rivets from 65 daggers of two significantly different types, which were discovered at the Rishon LeZion (RL) cemetery, Israel, were tested by the non‐destructive method of X‐ray fluorescence (XRF). The results reveal new knowledge of the alloys selected for dagger and rivet production, both of which represent fine examples of the Middle Bronze Age II Southern Levant in metal industry.     

秦始皇帝陵园出土彩绘青铜水禽铜矿料来源探索

关于秦始皇帝陵出土彩绘青铜水禽铜矿料来源的研究,对进一步研究秦代的物质文化、青铜器冶铸工艺、装饰工艺以及铜矿来源均具有重要意义。本研究对部分秦始皇帝陵园出土彩绘青铜水禽基体进行了铅同位素分析及微量元素分析。并在此基础之上,与甘肃东部及关中西部出土的部分早期秦文化铜器、国墓地出土的部分铜器、周原李家铸铜作坊出土的部分铜器、山西中条山、江西瑞昌、江西铜岭、安徽铜陵以及湖北大冶铜绿山古铜矿以及秦岭山区的部分现代铜矿的相关数据进行了对比研究。结果发现,秦始皇帝陵园出土的青铜水禽使用了相同的矿料,且与绝大多数早期秦文化铜器所使用的矿料基本相同,但与国墓地以及李家铸铜作坊出土西周铜器的矿料明显有别。秦人使用的铜矿与秦岭山区现代铜矿较为接近,表明秦人的铜矿来源可能与秦岭山区有关。     

安徽南陵出土部分青铜器研究

安徽省南陵县是长江下游地区最早而且规模最大的冶炼中心之一,其古代矿冶遗址可上溯至西周晚期。本研究对南陵出土的不同年代和类别的青铜器样品进行了金相检测及合金成分定量分析。结果表明,只有容器存在铜铅二元合金和铜锡铅三元合金,但是热锻淬火的容器却不含铅,含锡量恰好位于适合该工艺操作并具有良好性能的区间。兵器、工具、车马饰均为铜锡二元合金,说明当时的工匠对于合金成分配比与性能的关系有明确的认识。越式鼎腹部样品具有热锻淬火马氏体组织,同样的金属结构还见于汉代铜锣等乐器、峡江地区战国中晚期青铜剑、江都大桥镇南朝青铜器窖藏出土的多件青铜容器,而镇江地区出土吴国青铜戈则具有铸造淬火组织,工艺稍有差别。这些器物中发现高锡青铜淬火组织不是偶然的,高锡青铜热锻淬火技术至少可以上溯至春秋战国时期,用以改善高锡青铜的机械性能。     

EARLY BRONZE AGE TROJAN METAL SOURCES AND ANATOLIANS IN THE CYCLADES

Summary. New chemical analyses of EB II copper-alloy artefacts from Troy show that about seventy per cent are of high tin, low arsenic, bronze; the remaining Trojan objects are of arsenical copper but contain no more than 3 per cent of arsenic. Lead-isotope analyses suggest that at this time the Trojans made use of at least five different copper-ore deposits and that at least two of these were not in the immediate vicinity of Troy itself.
At this period tin bronze was unknown in the Early Helladic, Cycladic or Minoan cultures. Low-arsenic tin bronzes do however constitute sixty-nine per cent of the copper-alloy artefacts excavated at the fortified hilltop EC IIIA settlement at Kastri on Syros, but lead-isotope analyses show that the copper in these objects is derived from three different ore deposits which are different from those exploited by the early Cycladic peoples on Amorgos, Paros, Kythnos and Chalandriani on Syros. For Kastri the alloy types are closely similar to and the copper ore sources used are identical with those employed in Troy II; in addition there are good Anatolian parallels for some of the metal types occurring at Kastri. Taken together with evidence from the pottery, the architecture and the nature of the site it seems inescapable that Kastri was a short-lived settlement of Anatolians who lived, perhaps, in somewhat uneasy juxtaposition with their Cycladic neighbours. These Anatolians came most probably from Troy or the Troad since tin bronze was virtually unknown at this period elsewhere in Anatolia, and certainly not in Cilicia, except at the central Anatolian sites of Ahlatlibel, Alishar and Alaca Hüyük.     

铅同位素考古研究的可行性问题——浅议“青铜器铅同位素指示意义的范铸实验研究”

国际上对铅同位素示踪方法在青铜器原料产地研究中的应用做过很多探讨。《范铸》一文再次提出有关问题,认为铅同位素分析结果不能确切指示青铜器铜锡铅原料的来源信息。本文考察了其依据的实验数据,它们似乎与其观点互相矛盾,其结论说服力相当有限。     

Special alloys from remote frontiers of the Shang Kingdom: scientific study of the Hanzhong bronzes from southwest Shaanxi, China

More than 200 bronze objects found in Hanzhong, southwest Shaanxi Province, China, a frontier region of the Shang Kingdom during the Shang dynasty, have been analysed for their composition and microstructure. Forty-three typologically distinct, and probably culturally indigenous, items have been found to be compositionally distinctive as well. This paper presents analytical results of the two types of local Hanzhong bronzes, namely the sickle-shaped and sceptre-shaped objects. Three special alloys, arsenic bronze, antimonial bronze and copper–nickel–arsenic ternary alloy, are particularly emphasized and discussed. The archaeological context of Hanzhong bronzes and their significance for the archaeometallurgy research of the Shang period are discussed as well.     

Late horizon silver,copper, and tin from Machu Picchu,Peru

Analyses of silver–copper alloy artifacts from Machu Picchu show silver contents ranging from 24 to 81%. The tin present, ranging up to 3%, originated with the copper, perhaps from admixture of recycled bronze. The presence of 0.4–0.9% lead in the silver-rich phase indicates use of silver prepared by cupellation. All the objects had been forged after casting, some extensively. All have surface enhancement of the silver arising from depletion of the copper-rich phase. Some of the tin found at the site contains inclusions of hardhead (FeSn₂) and of a nickel–arsenic–copper compound. Forming trials with duplicate silver–copper alloys show that intermediate anneals at temperatures between 500 and 600 °C facilitate making thin sheet artifacts. Mechanical tests show that the most commonly used alloys, containing 25–30% silver, are particularly well adapted to forging because of their uniform work hardening during plastic deformation. Annealing of the laboratory-made alloys in air followed by boiling in salty weak acid creates a silver-rich surface layer comparable to that found in the artifacts. Depletion forms a dense silver surface on the alloy containing more silver than the eutectic composition, but a porous surface layer on the 25% silver alloys.     

Sourcing copper ores for production of bronzes excavated at Shuangyantang,a Western Zhou (1046–771 <Emphasis Type="SmallCaps">bc</Emphasis>) site in Chongqing (Southwest China): evidence from lead isotope analysis

Energy-dispersive X-ray fluorescence (EDXRF) and lead isotope analyses were applied to 12 Western Zhou (1046–771 bc) bronzes unearthed from the Shuangyantang site in Wushan County, Chongqing (southwest China), to investigate their chemical compositions and possible mineral source(s). The results showed that (1) the investigated bronzes were mostly bronzes with low, common lead and (2) their lead isotopic values almost all fall into a relatively narrow range, suggesting possibly the use of raw materials from a common copper mine. The comparison between lead isotopic values for Shuangyantang bronzes and those already published for copper mines and other bronzes produced and used about at the same times leads us to believe that the Shuangyantang bronzes probably used the same copper ores as used in bronzes from the Peng and Jin states in Shanxi Province. However, it would not be possible at this point to come up with a clear idea of where exactly these copper ores may come from. Candidate copper mines might be the Tonglvshan mines in Hubei Province, the Zhongtiaoshan mines in Shanxi Province, or the Dajing copper mines in Inner Mongolia.     

山东莱芜嬴城遗址炼铜渣初步研究

为了解山东地区早期冶金技术的发展情况,采用扫描电子显微镜分析等方法,对莱芜赢城冶炼遗址出土的3件炉渣进行了检测。结果表明其中2件为红铜还原渣,1件为砷铜熔炼渣。由此推测该遗址铜的还原可能存在两种工序,并且掌握了利用含砷矿物"点炼"铜液得到砷铜的技术。遗址所利用的铜可能来自于北江水铜矿,砷可能来自于鲁中山区,炉渣所属的时代应与遗址出土的商周青铜器年代相近。     

湖北宜城跑马堤墓地出土铜器的科学分析研究

跑马堤墓地是位于湖北省宜城市郑集镇的一处战国至汉代墓地。该墓地出土了大量青铜器,为研究从战国到汉代青铜器的制作技术变迁提供了系统性的资料。本研究对该墓地出土的部分铜器进行了金相组织观察和元素成分分析。结果显示,战国晚期铜器的材质包括铅锡青铜和锡青铜两类,不同类型功用的器物,在材质的选择上也有所不同;西汉铜器的材质则以铅锡青铜为主,合金元素总量相对于战国晚期铜器要低,而且变化范围较大。整体上,该批铜器主要为铸造成型,但其中有3件汉代青铜容器为锻造而成,这三件锻造铜器均为敞口薄壁器物。研究结果可为汉代以后考古学和金属技术史研究提供资料,并为中国古代金属技术史演进序列的补充完善提供科学数据。     

EARLY BRONZE AGE TIN PROCESSING AT KESTEL/GÖLTEPE,ANATOLIA

Chemical analysis of statistically significant numbers of samples including minerals, sediments, soil, host rock as well as powdered materials, crucible accretions and metal artefacts revealed information about the distribution of cassiterite at Kestel and the tin smelting processes that took place at Göltepe c. 2600 BC. Using the ancient technique of vanning for the isolation of tin ore (cassiterite), followed by assaying by blowpipe/charcoal block, as well as crucible smelting with a blowpipe, good tin metal suitable for alloying with copper to make bronze was obtained. There is every indication that tin was mined and smelted in the Early Bronze Age at the Kestel/Göltepe sites.