青铜器锈蚀结构组成及形态的比较研究

采用X射线衍射(XRD)、扫描电镜(SEM)、X射线电子能谱(EDS)和金相显微镜(OM)等方法,分析比较了染有“粉状锈”与未染“粉状锈”的典型青铜残片的锈蚀产物的矿物组成、腐蚀层分层结构及金相组织。结果发现,未染有“粉状锈”的青铜样品腐蚀层一般分为二层,外层是二价铜化合物,合金组织中未见α (α δ)组织,锈蚀产物中不含碱式氯化铜;而染有“粉状锈”的青铜样品都含有碱式氯化铜,其断面腐蚀层分三至四层,且每层锈体的结构和元素组成各不相同,在靠近合金基体层的锈层中发现了大量的CuCl存在。结果表明,青铜文物表面锈蚀覆盖层的致密性、空气中的湿度及锈层中CuCl层状分布的存在,是青铜器表面“粉状锈”形成和发展的根本原因。     

青铜文物研究中CT成像的几个作用

通过计算机断层扫描(CT)检测与成像分析后发现:陈璋圆壶的组成构件有26个,而非最初考古报告表述的19个,分三个部分合成;吴王僚剑的剑体腐蚀严重,剑上铭文为铸造而并非后刻;春秋青铜盘修复前的状态清晰可见。由此说明,CT技术在研究古代青铜器铸造工艺、鉴定青铜器真伪、检验保护修复技术路线等三个方面能起到关键作用。     

黄河流域早期铜器演进初探

黄河流域是中国早期铜器起源与发展的关键区域,早期铜器的演进受社会复杂化程度制约。在文明化进程的视野下,本文通过用铜遗存的考古信息与社会经济背景,将黄河流域早期铜器的演进分为早期用铜的萌芽、发展初期及区域化特征形成三个阶段,初步阐释铜制品从出现到规模化使用的过程。人群流动、定居农业、手工业生产、城市与权力的集中是影响黄河流域早期铜器演进模式的重要因素。大体在公元前2300年至前1400年的文明进程中,黄河上游铜器的制作与使用具有相似的风格及开放共融的特征,而黄河中下游地区防御性城市与权力的发展,推动了铜器技术与社会功用的本土化转变。     

青铜文物缓蚀剂效率及封护剂抗腐蚀能力的比较研究

为评价青铜文物缓蚀剂效率及封护剂抗腐蚀能力进行了两项电化学实验。一是利用直流腐蚀的极化电阻法对缓蚀效率评价,二是应用恒电位交流阻抗法对涂层的抗腐蚀效率评价。实验表明,复合缓蚀剂的缓蚀效率优于单一缓蚀剂如AMT、BTA,在模拟中性土壤介质的水溶液中各自缓蚀效率分别为88.7%、94.6%,两者组成复合缓蚀剂后其缓蚀效率高达98.8%,这是发挥其缓蚀剂各组分的协同效应的结果。应用恒电位交流阻抗实验,可以更好地理解附着有封护层时复杂的腐蚀过程。结果表明,石蜡涂层样品的Nyquist谱图出现扩散过程引起的阻抗特征;聚乙烯醇缩丁醛涂层、Paraloid B72涂层、空白样(缓蚀层BTA)三种样品Nyquist谱图均是由于涂层微孔引起的阻抗特征,在同一浓度下其抗腐蚀性能排序呈依次递减趋势。     

SEM and electrochemical characterization of bronze artifacts from the Francavilla archaeological site

The excavations in the necropolis of the Francavilla Marittima archaeological area, in Calabria, have brought to light the rich burial artifacts and materials, dated between the end of the ninth and sixth centuries BCE. SEM/EDS analysis was conducted on some sections taken from a bronze artifact classifiable as an armilla or fibula fragment. Our aim was to elucidate the nature of the corrosion processes acting on the specimen. SEM investigation detected the segregation of tin towards the outer layer and a depletion of the copper content in the same region. Furthermore, the elemental distribution maps of the sections analyzed evidenced the presence of chloride ions in the border area between the corrosion patina and the metal alloy. Such anion migration of chloride ions into the interior of the alloy leads to a particular variant of the type of corrosion of structure that in the literature has been identified as structure I.A cavity electrode designed for electrochemical measurements of powders was used to perform cyclic voltammetry experiments devoted to explore the activity of the patina covering the surface of the bronze fragment. The surface layer consists mainly of tin and tin oxides; the layer immediately beneath it contains copper oxides. An increase of reactivity was shown in an acidic environment. The activity of the patina is greatly reduced at pH 5 and appears to be zero at neutral pH.     

一种结构对称的破碎青铜文物的数字修复方法

为有效解决结构具有对称性的破碎文物的数字修复问题,本研究利用计算机技术,提出了一种针对结构具有对称性的破碎青铜器文物的数字修复方法。首先利用三维激光扫描仪实现破碎文物的三维建模,然后采用基于特征点集的最小二乘方法计算破碎文物的对称平面,进而利用对称性实现破碎文物的数字修复。针对对称性计算的镜像模型与原始模型几何造型不完全一致的问题,采用非刚性配准方法实现了镜像模型的几何变形。实验结果表明,本方法能够实现破碎文物的数字修复,将为实体修复提供借鉴和指导。     

Synchrotron radiation-based x-ray analysis of bronze artifacts from an Iron Age site in the Judean Hills

Seven bronze bangles from Tell en-Nasbeh, northern Judah, were investigated to understand the phase composition and manufacturing process of the artifacts, and possibly suggest a provenance for their origin. Synchrotron x-ray radiation diffraction (XRD) and fluorescence (XRF) were used in the analysis to avoid any destructive sampling and at the same time penetrate through the surface into the core metal. These techniques enabled us to determine that the bangles were not just tin bronze, but leaded tin bronze. Based on excavation reports, it is unlikely that the metal objects were manufactured locally at Tell en-Nasbeh; rather, preliminary XRD and XRF data point towards the neighboring region of Edom as their origin. Despite their political enmity during the Iron Age II, the data suggest that Judahite social demands for bronze may have fostered a strong economic relationship between these two polities.     

澄城刘家洼遗址出土青铜器腐蚀成因研究

刘家洼遗址出土大量珍贵的青铜器对研究春秋早期芮国历史具有重要价值,但由于青铜器受到长期腐蚀影响,其蕴含的部分信息可能发生损失。为研究刘家洼青铜器的工艺、保存状况与稳定性,揭示关中东部黄土塬区出土青铜器的土壤腐蚀特征,并为文物保护修复提供参考依据,本工作对刘家洼青铜器腐蚀成因进行综合研究。本工作利用金相显微镜观察、扫描电镜-能谱、X射线衍射、拉曼光谱等分析手段对刘家洼遗址出土6件青铜器样品的锈蚀物相与锈层结构进行表征。结果表明,青铜器腐蚀产物以赤铜矿、孔雀石以及白铅矿为主。部分青铜器表面存在浅绿色粉状腐蚀产物,但并非含氯腐蚀产物。刘家洼青铜器锈层结构自金属基体向外依次为过渡层、原始表面内非金属层、原始界面、原始表面外原位沉积层及扩散沉积层。原始界面内非金属层Cu/Sn值低于基体,表明基体内的铜元素腐蚀后向外迁移以及锡元素腐蚀后形成锡石原位沉积。原始界面外Cu/Sn比值显著高于原始界面内非金属层,表明外迁的铜离子在埋藏环境作用下沉积。本工作通过对青铜器附着土壤样品pH值、氧化还原电位以及离子色谱分析,结果表明刘家洼青铜器埋藏环境为弱碱性氧化型环境,土壤中氯离子含量不高,这与出土青铜器的腐蚀...     

五种含氯铜合金腐蚀产物的拉曼光谱及扫描电镜的分析研究

为深入研究五种含氯铜合金腐蚀产物(氯铜矿、斜氯铜矿、羟氯铜矿、氯磷钠铜石和铜氯矾)的拉曼光谱图,进一步补充金属锈蚀物的拉曼光谱库,采集不同考古来源的铜合金上腐蚀产物的拉曼光谱,并结合扫描电镜观察了腐蚀产物的形貌特征。研究结果表明,氯铜矿、斜氯铜矿和羟氯铜矿3个同分异构体的拉曼光谱并不相同:氯铜矿和斜氯铜矿较为常见,且经常混合在一起;羟氯铜矿不稳定,非常少见,一般与其他两种混合在一起。扫描电镜观察氯铜矿主要为粒状形貌,同时也发现有葡萄状、皮壳状、钟乳状等形貌;羟氯铜矿因少见,目前只观察到板状形貌。氯磷钠铜石腐蚀产物较厚且疏松柔软,常发现于干旱地区有动物或人遗骸墓葬的出土器物上,扫描电镜观察呈花瓣形状的蓓蕾形貌。铜氯矾更为少见,笔者目前只在2件器物上发现。同时对5种腐蚀产物的形成原因进行了讨论。     

山西定襄中霍墓地出土铜器的初步科学分析

中霍墓地出土青铜器是研究春秋晚期和战国早期青铜文化特征、制作技术以及探讨该时期中原和北方少数民族相互关系等学术问题的重要资料。为进一步揭示该墓地出土青铜器所包含的科学信息,对该墓地出土17件铜器的37个样品进行了科学分析检测。结果显示,这批青铜器的制作工艺以铸造为主,另外还有热锻、热锻后冷加工等;其合金成分有铜锡二元合金和铜锡铅三元合金两种,铜锡二元合金全部用于制作工具,铜锡铅三元合金用于制造容器。这显示中霍墓地铜器的合金成分和器物类型之间的关系明显,表明制作者已经能根据青铜器的用途而选择合适的制作材料。研究结果对研究中原和北方少数民族冶金术及在此基础上的文化交流有较大的指示性意义。     

昆明呈贡天子庙和呈贡石碑村出土铜铁器的科学分析

为了解中国古滇地区铜铁农具、兵器和工具的制作工艺,采用金相显微镜组织观察和扫描电子显微镜分析的方法,对昆明呈贡天子庙和呈贡石碑村出土的战国至西汉时代11件铜器和2件铁器样品进行分析。分析结果表明,铜器的材质有红铜和铜锡合金两种,相同的器物有较稳定的化学成分。铜器中农具、兵器和工具为铸造制作而成。2件铜柄铁刃剑的材质为亚共析钢,作为兵器,具有优良的性能。本研究成果对进一步研究古滇地区铜铁器具的工艺技术有一定的价值。     

云南祥云县检村石棺墓出土铜器的初步研究

为研究滇西地区青铜文化及相关铜器的制作技术,本研究采用扫描电镜和金相分析的方法,对云南祥云检村石棺墓出土的17件样品进行取样分析,结果表明祥云检村石棺墓出土的铜器以红铜为主,少数为Cu-Sn合金。这些器物的制作工艺主要是铸造、铸后冷加工等,制作工艺相对单一。3件编钟均为Cu-Sn合金,并且锡成分具有等比递增的现象。兵器矛经过鉴定后说明由于墓主身份的不同,随葬的矛也有实用器和随葬器两类。农具锸和工具锥和凿的鉴定表明有冷加工或使用过的痕迹,可能曾是实用器;而农具锄经鉴定并没有在农作中使用过,仅作为随葬品,进一步证明随葬铜锄是青铜时代滇西地区的一种丧葬习俗。分析表明,当时已根据不同器物的用途进行了不同的制作和加工。本研究结果对研究滇西青铜文化及金属技术有一定的意义。     

郑州商城青铜大方鼎造型与纹饰研究

郑州商城的三处青铜器窖藏共出土了八件青铜大方鼎,目前学界一般认为铜方鼎的原型与陶方鼎有关。但通过造型与纹饰的细节分析,可发现大方鼎的原型应为方形木质容器,乳钉纹带模仿了容器边套、箍圈上的成排铆钉。南顺城街窖藏的四件大方鼎,其纹饰的演变体现出从模仿铆钉原型到向装饰化发展的过程。     

The bronze artifacts from the Yejiashan site and the political presence of the Zhou dynasty in the middle Yangtze Plain: an application of lead isotope analysis

Lead isotope ratios of 15 Chinese bronze artifacts from the Yejiashan site (Suizhou City, Hubei Province) were analyzed and compared with copper ores across China. This study attempts to provide a new perspective to discuss the role that Zeng State played among all the vassal states in the early Zhou dynasty (ca. 1046–977 BC). The political presence of the Zhou dynasty in the middle Yangtze Plain is another main content of this paper. The lead isotopic characteristics of Chinese bronze artifacts between different historical periods are also in the scope of the study. By comparison, the lead isotopic ratios of the tested bronzes and copper deposits in the north Jiangxi Province show numerous overlaps. It indicates that the tested bronzes might have a single ore source, and this source was in the south of the Zhou dynasty. Combined with history and archaeological records, it is highly likely that the middle Yangtze Plain might be a part of the Zhou dynasty since the very beginning. Moreover, Zeng State might have a great influence in the ancient middle Yangtze Plain, and the nobles of Zeng State might even have authority to supervise certain area extending to Jiujiang. As lead isotopes of the bronzes appear to show a clear relation to chronology, the change of lead isotope patterns across times may further serve to distinguish the bronzes of the Western Zhou dynasty from the late Shang ones.     

廊坊市出土的汉唐至辽金时期铜镜

我国铜镜的历史,大约可追溯至4000多年前的齐家化时期,它形成于东周时期,盛行于汉唐,衰于宋元。不同历史时期铜镜的制作、形制、纹饰和铭都有其特点,反映着当时的政治、经济、思想化、社会生活及时代风尚。历史上青铜镜铸造还出现了如西汉的透光镜,唐代的金银平脱、嵌螺钿、捶金银、鎏金、彩漆绘、嵌琉璃等特种工艺,     

競之定铜器群考

澳门出现的一组楚器,数量大。组合比较完整,且大多数铸有铭文,是近年来楚国青铜器的一次重要发现,它对于研究春秋战国时期楚国的历史、楚王世系、青铜器铸造,以及楚国与少数部族之间的关系,都有着重要的价值。根据其形制、纹饰以及铭文等方面所表现出的特征,其时代应在春秋晚期后段。盘、匜的作器者楚王酓(熊)恷,金文首次出现,亦不见于史书。经考证熊恷就是楚平王熊居,恷、居一名一字。您读为休,休,息止也。居,也有止息之义。名与字意义相因。鼎、簋、豆、鬲的作器者競之定是楚国的一位封君。盘、匜是楚平王所赐。     

A re-assessment of bronze age wool

Measurements of twelve new samples of Danish Bronze Age wool showed them to be hairy medium fleeces. Supporting evidence was obtained that a high proportion of fine fibres in a yarn results from the plucking of wool during the moult before the hairy fibres have been released from the skin. The fine fibres were closer in diameter to the underwool of the wild ancestor than to those of the Soay sheep (supposedly a Bronze Age survivor), indicating a more primitive fleece. The samples described include the first white Bronze Age wool. Those with natural pigmentation in every fibre could be black or brown, while those with pigmented and white fibres are thought to be a mixture of brown and white (by analogy with the Soay) rather than grey, which is unknown in the Soay.     

Traditions and transitions in Korean bronze technology

Metallurgical examination of Korean bronze artifacts shows that a technical tradition based on casting and use of leaded high-tin alloys was established in Korea at the early stages of bronze use. After the subsequent discovery of quenching methods that suppress formation of the brittle δ phase, new thermo-mechanical techniques were introduced between the 7th and 10th centuries AD. Lead-free alloys were used, and tin contents near that of the peritectic point in the Cu–Sn phase diagram were chosen. Leaded high tin alloys continued in use, but only in cast objects, and with significant composition variation. The unique conditions during the time of innovation suggest that the transition to new metallurgical techniques was gradually achieved through domestic technical innovation inspired by external influences.