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.     

铁器文物保护方法综述

铁器文物由于其性质活泼以及自身的结构缺陷,若在埋藏过程中已严重锈蚀,出土后因保护措施不到位及保存环境等因素的影响,将加速铁器文物的进一步锈蚀,因此铁器文物的保护就显得尤为重要。本文从铁器文物保护的关键步骤出发,在对铁器文物腐蚀机理、腐蚀的主要产物、分析检测技术进行分析研究的基础上,对目前铁器文物保护方法进行梳理,并对保存环境提出了具体要求,以期对铁器文物的保护工作提供一定的借鉴。     

郑庄秦石料加工场遗址出土铁器的初步研究

为了解郑庄秦石料加工场遗址出土铁器的成分与制作工艺,采用了金相显微法和湿法化学分析对其中6件残铁器进行了取样分析。通过研究可知:这批铁器具有低锰、低硅的工艺特点,为生铁制钢。     

云贵高原出土战国秦汉时期铁器研究

云贵高原李家山、石寨山、羊甫头、石碑村、赫章可乐、中水等战国秦汉时期典型墓地出土铁器的种类、器形以及时代、数量的变化,表明云贵高原的铁器化进程经历了初始(战国中晚期至西汉早期)、发展(西汉中晚期)、普及(东汉时期)三个阶段;出土铁器的区域分布也具有明显的规律性,主要分布于黔西及滇东北、滇池及滇东南、滇西及滇西北的三大区域;出土铁器的种类、器形以及纹饰特征,特别是广为流行的铜铁合制器和输入与仿制的铁器制品,可以看出云贵高原早期铁器时代与相邻区域在铁文化领域的交流与传播,特别是北方地区、中原地区、巴蜀地区的铁器和制作技术的传入对云贵高原的铁文化产生了极大的影响。     

秦汉铁器锈蚀机理探讨及保护方法研究

为了搞清铁器的锈蚀机理,为铁器文物保存提供最佳条件,通过对秦汉两代几件铁器不同部位腐蚀产物分析及不同条件下铁器锈蚀情况实验来研究古代铁器锈蚀机理及保护方法,结果发现,铁器锈蚀成分不仅十分复杂,而且同一锈蚀产物中α、β、γ三种构型的FeO.OH共存,实属罕见,同时采用新的保护方法,使铁器处于一个干燥,无氧,无盐,无水,无有害气体的最佳保护状态。     

汉诸侯王陵墓出土铁器的比较

对徐州狮子山西汉楚王陵、永城保安山西汉梁王墓等7座汉王陵出土铁器的种类、材质、制作技术及功能进行了比较研究,探讨了汉代钢铁技术的发展状况、技术特征等问题。狮子山楚王陵5件炒钢制品的发现表明西汉早期(公元前2世纪中叶）已经发明了炒钢技术,是迄今为止最早的;块炼铁、块炼渗碳钢、生铁、铸铁退火、铸铁脱碳钢、炒钢、局部淬火、冷加工等多种钢铁冶炼和热处理工艺在西汉王陵出土铁器中都得到了广泛的应用,表明西汉时期钢铁技术有了较大发展,当时工匠对钢铁性能的认识提高到新的水平。     

唐九成宫出土铁器的抢救性保护研究

为了探讨九成宫出土铁器严重锈蚀的主要影响因素,为铁器文物研究设计科学有效的保护方法和最佳保存条件,采用X-衍射粉末法分析九成宫出土的11件铁器的锈蚀产物成分。分析结果表明,锈蚀产物的主要成分为α、β、γ三种不同构型的碱式氧化铁和Fe3O4。这是铁器铁碳合金成分Fe-C活性差异引起析氢、吸氧、差异充气等电化学腐蚀产生结构疏松,在九成宫特别潮湿环境中H2O、O2、空气中有害气体不断渗入,铁器粘附土层中溶盐及尘埃中酸、碱、盐溶于铁器表面水膜而进行长期贴附电化学腐蚀的结果。据此,研究设计出对锈蚀严重的出土铁器进行松土,缓蚀松土,络合法除沉积物,冷热交换法脱盐,最后进行缓蚀防腐加固及表面隔氧、防潮、防有害气体的表面封护保护方案。按此方案保护处理了17件锈蚀严重的铁器,保护效果很好,可以作为其它铁器文物保护的重要参考。     

出土铁器文物脱盐缓蚀保护研究

对出土铁器文物采用缓蚀剂、表面活性剂和多种助洗剂组成的碱性脱盐清洗液对铁器文物进行脱盐清洗处理,消除环境污染给铁器文物带来腐蚀因素的影响,并且对铁器文物还有缓蚀作用。通过磷化处理改善铁器表面的耐腐蚀性,提高铁器文物在大气中的抗腐蚀能力。对磷化后的铁器文物进行钝化封闭处理,进一步阻止基体与大气介质的直接接触,从而更有效地抑制腐蚀。对经磷化、钝化处理     

试论楚国铁器的使用和发展

我国出土的早期铁器大都集中于楚国,目前出土的楚国早期铁器从上个世纪70年代的10余件增加到40余件,时代上限从春秋晚期上溯到了春秋中期。楚国最早的铁器发现在今鄂西,开始使用的铁器主要为农具,还有一些小型利器。至春秋晚期,楚国已有了锻造的铁器。楚国铁器,从战国初开始容器变大,刀剑变长,新器形大量出现。到战国中期,精工铁器和铜铁合铸的铁足铜鼎流行。楚国大约从春秋中期开始冶铁、用铁,到春战之交,社会已进入了铁器时代。     

辽宁桓仁五女山山城遗址出土铁器的锈蚀产物分析与保护修复

文章是对桓仁五女山山城遗址出土铁器保护修复的技术总结。依据此批铁器的保存现状、病害调查及锈蚀产物分析检测结果,有针对性地对其进行预加固、清理去锈、粘接补全、缓蚀和封护等处理,取得了良好的修复效果。为日后系统研究这批铁器提供了珍贵的实物资料,对后续大规模开展该遗址的铁器保护工作也具有重要的指导意义。     

论楚文化对巴文化的影响

楚、巴两国相邻,文化交流频繁,楚国逐渐占领了巴国今忠县以东的长江沿岸地盘,曾经设立巫郡和黔中郡,这些地区楚文化占绝对优势。由于楚人和巴人交错杂居,因此楚文化吸收了巴文化的釜、鼎及花边口沿装饰等因素,形成了颇具特色的"楚文化峡区类型"。楚文化的辐射范围很广,渝东地区和嘉陵江流域巴人遗存中普遍存在着楚文化因素,包括楚式青铜器、铁器和陶器等器物,从楚文化因素的分布范围、各种器物的种类和数量来看,到战国中期,楚文化对巴文化的影响处于鼎盛时期,到战国晚期,秦灭巴、蜀,楚人逐渐退出峡江地区,楚文化的影响日趋减弱。楚文化的西渐,客观上促进了巴人的生产发展和社会进步,加快了中华文明的一体化进程。     

The medieval iron market in Ariège (France). Multidisciplinary analytical approach and multivariate analyses

The medieval iron market in Ariège (French Pyrenees) is characterised by its complexity leading to many questions regarding the ore used in relation to the artefacts encountered in archaeological settings. Despite the conclusive study of the treaty that regulated iron vs. coal exchanges from the 14th to the 19th c. by Verna et al., many questions remain unanswered concerning provenance and circulation of ores and products. Based on a combination of trace elemental analysis and multivariate statistical methods (discriminant analysis, hierarchical clustering analysis), we propose to follow an elemental-based signature from ore to artefacts, suited to the direct iron process, to clarify provenance hypotheses. We define the chemical signature of the Ariège area and compare it to that of slag inclusions in artefacts uncovered in several main archaeological sites from the Ariège area but also outside of this region. The results from this study are consistent with prior knowledge from historical sources. In the Ariège region, results highlight the multiple origins of products encountered at Montréal-de-Sos, a site close to known trade routes, whereas the isolated Castel-Minier site primarily contained objects from local ores and most objects retrieved from the Mirabat castle (Couserans) are coming from outside Ariège, possibly an indirect consequence from the exchange treaty. The presence of pins made of Ariegean ores is also demonstrated in the far more distant Capestang collegiate (near Narbonne, outside Ariège). This opens the way to finer studies in the politico-economical control of the iron supply for the building of medieval monuments in Southern France.     

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.     

Determination of an Optimal Location for an Iron and Steel Plant Based on Iron Ore of the Kursk Magnetic Anomaly

A locational study of the Iron-Steel Design Institute is criticized on the ground that it selected potential plant sites intuitively and then examined them in terms of proximity to iron ore, water availability and minimal transport requirements. An alternative methodology is proposed. The general region for the new plant is first established on the bases of the interregional balance of iron and steel products. The Central European region is found to have a deficit in the entire product range. A more specific location is then derived by calculating potential transport costs with respect to both markets and sources of raw materials (iron ore, coke). The Rzhev area of Kalinin Oblast is found to be optimal in terms of transport costs alone. But when water and, particularly, labor resources are considered, preference shifts in favor of a plant location in the Gor'kiy-Kostroma area.     

郑韩故城出土战国晚期铁器腐蚀产物分析

为了分析郑韩故城遗址出土战国晚期铁器的锈蚀产物类型,采用X射线衍射和金相显微观察等现代科技手段,对郑韩故城遗址内仓城铸铁遗址出土的13件样品进行综合研究。通过分析比较样品间的锈蚀程度,发现铁质文物的锈蚀机理复杂,成分多样;一些锈蚀产物中出现明显的分层,锈蚀不均;部分铁器中还存在着活性锈蚀物,其保存状态与金相组织有着密切关系。     

Geographical Problems in the Iron and Steel Industry of the USSR

Technological advances in the Soviet iron and steel industry are producing changes in the locational pattern of the industry. The increasing concentration of production in large iron and steel plants requires the use of large iron-mining establishments of the order of 30 million tons of crude ore. Iron and steel plants were once viewed in the Soviet Union as oriented toward the market of a particular economic region. But the growing plant capacity and a trend toward specialization in particular types of finished products tend to expand the marketing zone of individual plants far beyond the boundaries of single economic regions. Future planning of the industry is in terms of five basic iron and steel zones: Central Russia, Urals, South, Siberia and Kazakhstan, of which the Urals and the South are fully integrated and the three others are in varying stages of formation. The declining share of coke in the blast-furnace charge tends to shift the locational pattern increasingly toward iron-ore sources, and this accounts to a certain extend for the gradual shift of iron and steel capacity toward Central Russia, with its ore reserves of the Kursk Magnetic Anomaly.     

Characterization of a Historical Cannonball from the Fortress of San Juan De Ulúa Exposed to a Marine Environment

Metallurgical analyses and chemical characterizations were carried out on historical cannonballs from the Fortress of San Juan de Ulúa, Veracruz, México. Cannonballs dating from the 18th and 19th centuries share metallurgical characteristics similar to those of material coming from a shipment of ammunition found in the wreck of a sunken French ship from the battle of Trafalgar. The analyses show that the base material is grey cast iron with a carbon equivalent of 4.94 and a ferritic–perlitic matrix, in which the high phosphorus content has led to the formation of iron phosphide compounds in conjunction with a homogeneous distribution of carbon graphite flakes of Type C. In addition, corrosion products from samples revealed the presence of various crystalline iron compounds (X‐ray diffraction), mostly highly chlorinated iron compounds identified as akaganeite. X‐ray fluorescence identified various characteristics of the corrosion products as a function of the sampling depth. FT–IR spectroscopy revealed that the main difference between the corrosion products (internal and external) is determined by the number of organic species. Differential scanning calorimetry corroborated that these corrosion products are thermally stable compounds at elevated temperatures.     

Composition of white paste inlay on the pottery from sites of the 10th–8th centuries bce in the northern Pontic region

For the first time, the mineralogical–geochemical compositions of the white paste inlay found on vessels from sites (10th–8th centuries bce ) in the northern Pontic region are investigated. Samples of the white paste on vessels from settlements, burials of sedentary groups and graves of early nomads were analysed by means of scanning electron microscopy with energy-dispersive X-ray spectrometry (SEM-EDX) and X-ray diffraction (XRD) methods. Between the 10th and eighth centuries bce , various innovations occurred in the working area. Iron processing technology and the manufacture of iron products also appeared. Other innovations were changes in the manufacturing technology of ceramics. A high-quality, polished/burnished surface and ornaments with white paste inlay are characteristic of this pottery. When collating white paste mixtures of different European sites, similarities in the preparation of white paste recipes for vessels from the Balkan and northern Pontic regions are evident. During the Early Iron Age, further changes in the manufacture of the white paste were discovered in the northern Pontic region, namely the application of high-temperature firing to obtain more resistant synthesized material such as calcium alumosilicates and silicates (wollastonite). The development of iron metallurgy in this period could provide a basis for the elaboration of new techniques in ceramic manufacture.     

铁器文物脱盐清洗溶液中硅酸盐缓蚀性能的研究

硅酸盐是一种环保型的缓蚀剂,研究水溶液中硅酸盐与铁表面氧化物的相互作用对铁器文物脱盐清洗液的实际应用有较大的指导意义。本工作研究了羟基氧化铁对硅酸盐的吸附作用以及多种因素对Fe/FeOOH/Na_2SiO_3体系电化学行为的影响,并运用XRD技术分析研究了硅酸盐水溶液处理对钢铁表面氧化物形态的影响。结果表明,在Fe/FEOOH/Na_2SiO_3体系中,硅酸盐吸附在钢铁表面羟基氧化物上,反应生成了新的物质,形成了较为致密的缓蚀膜,可同时抑制钢铁的阴、阳极反应,且对阴极反应的抑制作用较强。     

Early ironworking in Iron Age South India: New evidence for the social organization of production from northern Karnataka

Abstract

Iron production was integral to political and ritual practices during the South Indian Iron Age (ca. 1200–300 b.c.), yet the investigation of the social relations of metals production during this period has been overshadowed by studies of iron consumption, particularly of iron objects in megalithic mortuary contexts. Recent archaeological research in the Tungabhadra River Corridor, Karnataka, has revealed iron production debris within and between settlements in more ephemeral occupational contexts, such as rockshelters. One notable discovery is the earliest ironworking facility in South India at Bukkasagara. The regional pattern suggests that iron production involved at least two classes of specialist producers—smelters and smiths—who exercised varying degrees of control over the practice and products of their craft. It also suggests that iron production was an important component in the construction and negotiation of Iron Age social differences, affiliations, and inequalities.