IRON IN ANCIENT COPPER

Analysis of early copper-base artifacts invariably reveals traces of iron. Iron enters the copper during the smelting process and the level of iron in the metalwork is an indication of the smelting technology. In areas such as Western Europe where prehistoric slag heaps are absent even in the proximity of undoubted ancient mines, the iron content is low reinforcing the link between smelting technology and iron content. Very occasionally the iron content was deliberately encouraged and alloys containing between 30% and 50% of iron in copper were made, mainly for use in currency. These alloys are without modern parallel and their metallography and method of production are considered in some detail here.     

Internal oxidation of cast iron artifacts from an 18th-century steel cementation furnace

Heavily corroded metal artifacts recovered from the site of an 18th-century steel cementation furnace in Trenton, New Jersey, are cast iron altered by internal oxidation. The progress of the internal oxidation process was followed by comparison with the microstructure of cast iron exposed to high temperature in a wood-burning fireplace. The graphite flake structure of the cast iron allows deep, rapid penetration of oxygen that reacts at the iron–carbon interfaces within the iron to form iron oxides that eventually replace the graphite flakes. Microprobe analyses show that the silicon in the cast iron is converted to knebelite that also serves as the host for phosphorus. Sulfur dispersed in the internal oxidation product and porosity appear to be responsible for rapid rusting of the artifacts. Internal nitriding accompanies the oxidation. The Trenton artifacts are interpreted as grate bars from the fire box of a cementation furnace.     

Microstructural and elemental analyses of slags excavated from Xuxiebian iron‐smelting site,Sichuan, China

Xuxiebian is an iron‐smelting site located in Pujiang county of Sichuan province, China. Two excavations were carried out in 2007 and 2011, and four bowl‐shaped furnaces were excavated. Ten slag samples from the site were prepared and analysed. The present paper reports the results of metallographic and elemental examination of the specimens. It is concluded that both pig‐iron‐smelting and refining process were applied at the Xuxiebian site, and the bowl‐shaped furnaces are possibly refining furnaces. The function of the site was probably to produce pig iron and refine the pig iron into wrought iron.     

The Crofter and the Iron Works: The Material Culture of Structural Crisis, Identity and Making a Living on the Edge

The iron and steel industry has been of the greatest importance to the Swedish economy since medieval times. During the seventeenth century a large number of new iron works were erected in the Värmland region of western Sweden. The iron works brought an urban and industrial culture into an otherwise rural area. They were also of great importance to the local economies, as a number of people could earn their living, or part of their living, by working at the iron works or in other forms of associated employment. In the late nineteenth century a serious structural crisis hit the Swedish iron industry, causing many iron works to close. However, the actual effects, in the form of unemployment and increased poverty, appear, for hitherto unknown reasons, to have been minimal. In this article the household of a crofter family with close links with an iron works at the time of the structural crisis is investigated. Aspects of the crofter’s material culture, identity and consumption pattern are studied, and it is found that although the household shared in an urban and industrial identity, its economic basis was in the rural tradition of a mixed economy, combining wage employment and land-based elements. The mixed economy stands out as one reason why the structural crisis did not have as dramatic an effect as might have been expected.     

Metallurgical Characterization of A Coated Roman Iron Coin By Analytical Investigations

A coated Roman iron coin from Villa Loig in Salzburg, Austria was investigated. The coating is a copper alloy consisting of Cu, Pb, Sn, Zn and negligible amounts of Ag, a variant of gunmetal known as ‘leaded red brass’. The numismatic term for such a coin is subferratus (Latin). From an archaeometallurgical point of view, information about the chemical composition, the microstructure and the manufacturing technique are of interest. To achieve these objectives, different analytical techniques and metallographic examinations were applied. Droplet‐shaped iron inclusions were observed in the red brass coating, while at the grain boundaries, inside the iron core, copper and lead were detected (liquid metal embrittlement). The dendritic microstructure of the coating, the spheroidal‐shaped iron inclusions in the coating and the liquid metal embrittlement show that the iron coin was plated by immersing it in a molten copper alloy. The iron core is a low‐carbon steel with slag stringers, both of which are characteristic of a bloomery iron. Deformation twins (Neumann lines) were observed in the microstructure of the iron core and indicate that the coining was performed after the flan was cooled.     

铜-铁复合兵器铁刃的分析

对上海博物馆馆藏新品王件春秋早期的铜一铁复合兵器中铁的类型、制成方法、机械性能和材料组织进行了分析,以判明铁刃的原料来源和制作工艺。结果表明：铁刃基体成分为较纯的铁,没有发现镍元素,铁刃组织呈层状分布,结构疏松,合较多夹杂物和孔洞,夹杂物由硅酸盐类复相组成,证实了三件铜一铁复合兵器的铁刃是由人工冶铁锻制而麻     

5,000 years old Egyptian iron beads made from hammered meteoritic iron

The earliest known iron artefacts are nine small beads securely dated to circa 3200 BC, from two burials in Gerzeh, northern Egypt. We show that these beads were made from meteoritic iron, and shaped by careful hammering the metal into thin sheets before rolling them into tubes. The study demonstrates the ability of neutron and X-ray methods to determine the nature of the material even after complete corrosion of the iron metal. The iron beads were strung into a necklace together with other exotic minerals such as lapis lazuli, gold and carnelian, revealing the status of meteoritic iron as a special material on a par with precious metal and gem stones. The results confirm that already in the fourth millennium BC metalworkers had mastered the smithing of meteoritic iron, an iron–nickel alloy much harder and more brittle than the more commonly worked copper. This is of wider significance as it demonstrates that metalworkers had already nearly two millennia of experience to hot-work meteoritic iron when iron smelting was introduced. This knowledge was essential for the development of iron smelting, which produced metal in a solid state process and hence depended on this ability in order to replace copper and bronze as the main utilitarian metals.     

Investigating the production provenance of iron artifacts with multivariate methods

The quest for suitable data, data treatments and statistical methods for identifying the provenance of iron artifacts has led to a variety of analytical strategies. Researchers working on the problem have been slow to develop or adopt the use of multivariate statistical techniques, despite their successful implementation in other archaeomaterials sourcing frameworks. This paper explores the analytical potential of a comprehensive multivariate statistical strategy for identifying the primary production origins of bloomery iron artifacts using bulk chemical analyses of bloomery smelting slag and slag inclusions in iron artifacts. This strategy includes a multivariate model for identifying distinct slag inclusion types introduced during smelting and refining. Principal component analysis and linear discriminant analysis are then applied to smelting slag training sets to create multivariate provenance fields, the chemical distributions of which are defined by kernel density estimation. Single and multi-group evaluation methods are examined. Appropriate data transformations are discussed to facilitate the projection of the chemistry of “unknown” slag inclusions into the multidimensional space generated by the smelting slag groups of known provenance. The efficacy of this strategy is demonstrated through its application to a previously examined data set derived from three iron production experiments and a published archaeological example. Results indicate that an appropriately designed multivariate strategy can be an effective tool for evaluating provenance hypotheses for bloomery iron artifacts.     

Transitions in cast iron technology of the nomads in Mongolia

Metallurgical study of seven cast iron artifacts recovered from sites of the former Xiongnu (BC 3rd to AD 1st), Turk (AD 6th to 8th), Khitan (AD 10th to 12th), and Mongolian empires (AD 12th to 15th) shows that the earlier Xiongnu and Turk artifacts were made of cast iron alloys of near eutectic composition. The later Khitan and Mongol objects had greatly reduced carbon content in the range of ultrahigh carbon steel rather than cast iron, and contained more than 0.5 mass % silicon as an alloying element. Inclusions high in sulfur, phosphorus or silicon are also present. These differences suggest that Mongolia experienced a technical transition a few centuries before the establishment of the Mongolian empire, which is in agreement with some written accounts. The microstructures of the cast iron artifacts are compared with the related archaeological and documentary evidence. The results suggest that the use of fossil coal in smelting and the state policy of controlling iron production were the major factors responsible for the transition.     

An integrated approach to reconstructing primary activities from pit deposits: iron smithing and other activities at Tel Dor under Neo-Assyrian domination

Secondary pit deposits in historical occupations of Near Eastern mounds are usually regarded as uninteresting and are seldom analyzed. We used an integrated approach to study all the artifacts as well as the sediments in a pit at Tel Dor, on Israel's Carmel coast, dating to the 7th c. BCE – a period when the site served as an Assyrian administrative center. This pit was unusually large, had a peculiar ceramic assemblage, and many macroscopic metallurgical wastes. A detailed excavation and analysis revealed that the pit served intermittently as a waste disposal site for an iron smithy and for pottery that was presumably involved in maritime trading. On two occasions the area was also used for animal penning. Despite the obvious importance of the iron industry to the Neo-Assyrian Empire, actual workshops are rare in its archaeological record. Hence the new information regarding an Iron Age iron smithy in the southern Levant contributes to the study of this industry, and also to the history of Dor in this period.     

宁波“小白礁I号”清代木质沉船中硫铁化合物脱除技术研究

近年来的分析与研究表明,海洋出水沉船的木材中普遍存在大量的以Fe S2和Fe S为代表的硫铁化合物难溶盐,它们在空气中和一定湿度条件下,会氧化生成硫酸,使木材纤维素发生快速降解,从而对木船造成毁灭性的破坏。目前,硫铁化合物的脱除仍然是世界性难题,很多国家发现的木质沉船都面临这方面的困扰。为此,本研究以宁波象山"小白礁I号"清代沉船遗址出水的船体木材构件为研究对象,研发了金属络合剂与氧化剂复配材料EDTAHO,开展了海洋出水木材中沉积的二硫化亚铁的去除技术初步研究,取得了良好的保护效果。本研究结果可为后续脱水定型和加固修复打下良好的基础,有利于海洋出水木质船体的长期保存。     

Early use and production of iron in the northern Shaanxi: A perspective on iron objects excavated from the Yuejiazhuang cemetery site

Yuejiazhuang is a cemetery site of Qin people in the Northern Shaanxi, China, and it is dated to the mid-late Warring States Period. Ninety-two iron objects were excavated from the Yuejiazhuang cemetery site, which provide an opportunity to understand the use and production of iron in the Northern Shaanxi. The metallurgical and statistical study has revealed that bloomery iron, cast iron, and steel made from cast iron were adopted in the Northern Shaanxi during the mid-late Warring States Period. In the meanwhile, cast iron and steel made from cast iron became dominant in the Northern Shaanxi.     

Prehistoric iron production technologies in the Upper Thai-Malay Peninsula: metallography and slag inclusion analyses of iron artefacts from Khao Sam Kaeo and Phu Khao Thong

This article presents a preliminary attempt to characterise Upper Thai-Malay Peninsula prehistoric iron technologies based on assemblages from two recently excavated coastal sites: Khao Sam Kaeo and Phu Khao Thong. These are the earliest known sites involved in the early trans-Asian exchange that connected the eastern Indian Ocean to the South China Sea from the mid-first millennium bc. It is from this period that iron assemblages start appearing at both continental and insular Southeast Asian sites. Three models have been offered confronting an indigenous vs. Chinese or South Asian impetus for the introduction of iron metallurgy in Southeast Asia. These models are discussed in the light of the metallographic and compositional analyses of iron and slag assemblages from these two sites using optical microscopy, scanning electron microscopy with energy dispersive spectrometry, energy dispersive X-ray fluorescence and slag inclusion analysis techniques, together with other production materials from these and other contemporaneous Southeast Asian sites.     

Cargoes of Iron Semi‐Products Recovered from Shipwrecks off the Carmel Coast,Israel

Underwater surveys along the Israeli Carmel coast have revealed six cargoes of iron semi‐products associated with shipwrecks. They are described and dated according to the associated artefacts. Metallographic and chemical analyses on samples from the biggest cargo have determined the stages of the chaîne opératoire, identified the properties of the iron and characterized the iron trade along the Israeli coast. The new discoveries contribute to our understanding of the circulation of iron in the South Levant, which was characterized by an almost complete absence of local iron production. During the Byzantine and Crusader periods, this absence was compensated by long‐distance sea trade, depending on political circumstances and restrictions. Three main types of iron semi‐products were identified: (a) partly consolidated blooms, (b) short pointed bars and (c) elongated pointed bars. The cargoes discovered represent a time period of nearly a millennium. Altogether, 148 iron semi‐products were studied. Of these, 166 were from cargo a, which was dated by coins to around 1130–1200 ce . Those coins could have been imported from Europe for Crusader military and civil uses in the Levant. The iron from cargoes b, d and f, dated perhaps to the Byzantine period, could have been imported from Anatolia or Venice for military and civil purposes.     

Implications of Reappraising the Iron‐Deficiency Anemia Hypothesis

In 2009, Walker and colleagues questioned the validity of the iron‐deficiency anemia hypothesis as an explanatory mechanism for the presence of porotic hyperostosis (PH) and cribra orbitalia. They presented evidence demonstrating that iron deficiency inhibits, rather than promotes, marrow hypertrophy and argued a link between both PH and hemolytic or megaloblasic anemias (including vitamin B₁₂ deficiency). This paper suggests that dismissing the iron‐deficiency anemia hypothesis may be premature, but, if dismissed, may result in unforeseen consequences. Vitamin B₁₂ deficiency and iron deficiency often result from similar proximate causes, i.e. lack of animal protein in the diet and sanitation problems that lead to parasitic or diarrheal diseases, thereby promoting nutrient losses. As a result, vitamin B₁₂ deficiency and iron deficiency commonly co‐occur. In individuals with a co‐occurrence of iron deficiency and vitamin B₁₂ deficiency, a possible inhibition of marrow hypertrophy caused by iron deficiency may prevent the development of PH, despite the presence of (vitamin B₁₂) nutritional deficiency. The implications of dismissing the iron‐deficiency anemia hypothesis are that many skeletal populations may exhibit hidden heterogeneity, i.e. individuals who are the most nutritionally stressed, with multiple nutrient deficiencies, would mimic the non‐stressed individuals and neither would show evidence of PH. However, the inclusion of multiple stress indicators and greater understanding of biocultural context in bioarchaeological analyses may mitigate the potential impacts of hidden heterogeneity in the expression of PH. Copyright © 2013 John Wiley & Sons, Ltd.     

铁器文物腐蚀与保护的研究现状

影响铁器文物腐蚀的主要因素有氧化气氛、潮湿环境、土壤的酸碱性环境和可溶性环境.本文介绍了铁器腐蚀的主要产物以及研究铁器文物腐蚀的主要方法,综述了目前国内外对铁器文物腐蚀和保护研究的最新进展.     

出土铁器文物的脱盐清洗研究

测试了铁在含不同浓度Cl~-、SO4~(2-)水溶液中的腐蚀速度和电化学极化曲线。结果表明,在通空气的情况下,Cl~-和SO4~(2-)浓度的增大能加速铁的腐蚀,而在密闭情况下就没有这种影响,说明铁器在地下不通空气的环境中相对较稳定。但出土铁器在大气环境中会受到Cl~-和SO4~(2-)的加速腐蚀,只有及时地排除这些有害物质,才有可能减缓铁器在大气环境中的腐蚀。根据铁在水溶液中腐蚀行为的电位-pH图判断,在pH=9－13的碱性水溶液中铁的腐蚀较小,因而可用添加有缓蚀剂、表面活性剂和多种助洗剂成分的复配碱性脱盐清洗液来处理出土铁器。它比铁在蒸馏水中的腐蚀速度小四十多倍,且去污和脱盐效率高。这对恢复出土铁器的面貌及进一步化学稳定转化铁器表面的锈层都具有重要的作用。     

‘Guard the Good Deposit’: Technology,Provenance and Dating of Bipyramidal Iron Semi‐Products of the Durrenentzen Deposit (Haut‐Rhin,France)

In the early days of iron metallurgy in Western Europe, the most widespread type of ‘trade iron’ (semi‐product) was bipyramidal in shape. Although they are frequently found, little is known about how they were manufactured and circulated, or even about their age. An interdisciplinary approach was applied to the Durrenentzen deposit (Haut‐Rhin, France), the third‐largest in Europe in terms of artefact quantities, in an attempt to reconstruct the technological, social and economic context that caused them to be abandoned. A morphometric study of the 51 iron bars revealed a high degree of homogeneity, despite variations in detail. Four objects were selected for archaeometric studies. Metallographic analyses show internal differences (quality of the material, nature of the alloys and manufacturing techniques). Chemical analyses also showed different provenances. Finally, radiocarbon analyses of the carbon in steel (iron/carbon alloy) linked this deposit to the early Iron Age. This study provided the first benchmark for more general research, significantly changing perceptions of the economics of iron at the beginning of the Iron Age.