巴蜀带斑纹兵器的锈蚀产物分析及机理探讨

带斑纹兵器是巴蜀兵器的一大特色。由于表面有斑纹的青铜兵器锈蚀与一般青铜器锈蚀有所不同,必须针对其特殊性进行锈蚀机理的研究,才能对症下药,达到有效保护的目的。应用矿相分析、SEM EDS、XRD等分析手段对几件巴蜀带斑纹兵器表面与截面锈蚀产物进行分析,并与非斑纹锈蚀进行比较;对斑纹与非斑纹的锈蚀机理进行探讨。分析结果表明,斑纹的锈蚀产物主要是SnO2,其在兵器斑纹表面形成钝性保护膜,防止其进一步腐蚀,对斑纹下面的基体有一定的保护作用。非斑纹层锈蚀向斑纹层下面的基体扩展,膨胀是造成斑纹层凸起甚至脱落的主要原因,对斑纹兵器保护的关键是控制非斑纹层锈蚀的进一步发展。     

应用电位活化理论研究青铜器的腐蚀与保护(二)——关于多孔氧电极的加速腐蚀机理研究

为了探讨铜盐等腐蚀产物对青铜器腐蚀的影响,采用腐蚀膏试验和微电极测试腐蚀电流的方法研究了氯化亚铜、碱式氯化铜、碱式碳酸铜等对青铜试片和铜电极腐蚀的影响,得出氯化亚铜是加速青铜器腐蚀的最有害物质的结论。红外光谱分析表明,以苯骈三氮唑为主钝化剂的高效防护剂同时改变了氯化亚铜的结构,起到了有效抑制青铜器腐蚀的作用。应用电位活化理论阐述了青铜器粉状锈小孔腐蚀的电化学行为,提出了氯化亚铜加速青铜器腐蚀的多孔氧电极催化模型。     

A Better Shade of Black: Effects of Manufacturing Parameters on the Development of Ancient Black Bronzes*

Copper alloys with controlled contents of Sn, Ag and Au were treated with methods and solutions that mimic those used in ancient and traditional procedures for the production of black bronze. Examination of the resulting patinas with colorimetry, SEM–EDS, TEM, Raman spectroscopy and XRD revealed no systematic differences according to the fabrication method, whereas patina homogeneity and colour in those alloys that did not contain precious metal were affected by superficial work. Patina microstructure determines adherence and coverage, and depends upon the solution used irrespective of the alloy composition, but the colour of the patina is mainly related to the alloy composition. Gold promotes the development of cuprite, slowing the oxidation to tenorite in the corrosion process. Gold additions produce a more uniform patina as well as a desirable blue–black tone, which is likely to have been a factor in alloy selection.     

荥阳小胡村墓地出土部分铜器的科学分析

小胡村墓地为殷墟晚期"舌"氏家族墓地,为探讨其出土铜器的腐蚀特征,揭示其所蕴含制作技术和相应考古学信息,从而为器物保护修复提供科学依据,采用金相显微镜和扫描电镜及能谱仪对墓地出土12件铜器进行基体锈层结构和制作技术分析研究。研究表明,相较纯铜、铜锡和铜锡铅合金,铜铅合金耐腐蚀能力较弱,腐蚀严重;铜器经冷热加工处理易造成内部组织结构不均内应力残存,间接加速铜器腐蚀;12件铜器材质:纯铜2件、铜铅合金4件、铜锡合金3件和铜锡铅合金3件;仅2件兵器(刀M28:1、戈M38:1)经有意铸后热锻和冷加工,其余皆直接铸造成型。M21墓4件铜器皆为铜铅合金明器,小胡村墓地作为殷墟周边商文化系统,趋同商文化中心区,亦呈现部分中小贵族随葬铜器明器化现象。研究结果可为器物修复保护提供科学依据。     

Microstructural and Componential Characterization of the Plating Technology on Chinese Han Dynasty Bronze Fragments

The bronze wares of the Han Dynasty excavated in Chongqing are decorated with plating patterns, maintaining an exquisite lustre right up to modern times after the covering patina is cleared away. In this paper, a plated fragment of the Han Dynasty from the Wushan County Museum was characterized by combining optical microscopy (OM), scanning electron microscopy with X‐ray energy‐dispersive spectrometry (SEM–EDS), X‐ray fluorescence analysis (XRF), X‐ray diffraction (XRD) and X‐ray photoelectron spectroscopy (XPS). The results showed that the bronze fragment was gilded with a ~ 3 μm thick gilded layer and a ~ 20 μm thick silvered layer. The high concentration of Hg and Hg‐rich intermetallic compounds confirmed the existence of mercury gilding/silvering technology, for example, Au₉Hg in the gilded layer and Ag₁₃Hg₇ in the silvered layer. An ordered stripe structure was observed in the gilded surface, corresponding to the formation of rod‐like, intermetallic Au–Hg compounds. Specifically, a high concentration of Au was detected in the silvered layer. The exploration of gilded/silvered bronze casts light on this ancient technology and the benefit of identifying, protecting and reproducing it.     

青铜古镜表面层富硅的考察

运用扫描电子显微镜、电子探针微量分析、X射线衍射、原子力显微镜和红外反射光谱等分析手段对16块古青铜镜残片的合金基体及表面层进行了分析比较,结果发现表面层内Cu含量低于基体,而Sn．O的含量则明显增高;表面层内有Si元素的富集,并且是以SiO_2非晶形态存在;对于不同种类的青铜镜,表面层深度不同,含Si量有差异,其表面光亮度和釉质感亦有区别。对古铜镜颜色的变化,SiO_2的保护作用及铜镜表面的加工工艺进行了分析探讨。     

A Second Investigation into the Chemical Composition of the Roman Provincial (Procuratorial) Coinage of Judaea,AD 6–66*

An investigation of the chemical composition of the first Roman provincial coinage of Judaea, minted in ad 6–66, was conducted. A total of 103 copper‐alloy coins were analysed by ICP‐AES. It was determined that different copper alloys were used for the coinage, a leaded tin‐bronze and a pure tin‐bronze alloy. The investigation also showed that the copper alloy was made in four different formulae with regard to the alloying elements added to copper. Trace element profiles point to the existence of a shared pool of metal for Roman coins and metalwork.     

IDENTIFICATION OF FORGERIES BY MEASURING TIN ISOTOPES IN CORRODED BRONZE OBJECTS*

The reliable identification of fakes consisting of bronze often presents problems, because traditional methods such as stylistic studies, optical microscopy, chemical analysis or X‐ray diffraction of the corrosion may not be conclusive. We present a method that is based on the comparison of the tin isotope ratios ¹²²Sn/¹¹⁶Sn and ¹¹⁷Sn/¹¹⁹Sn in the metal and in the adherent corrosion layer. An artificial patina is usually generated within a short time period. It has been observed that such a procedure leads to a depletion of the light tin isotopes in the corrosion layer, while in naturally corroded authentic archaeological objects no isotopic fractionation has been detected. The method has also been applied to archaeological objects and it could be confirmed, among other examples, that the famous ‘Sky Disc of Nebra’ is authentic.     

Technical Studies on the Bronze Age Metal Artefacts from the Graveyard of Deh Dumen,South‐Western Iran (Third Millennium BC)

During the excavations of the graveyard at the site of Deh Dumen in south‐western Iran, 15 graves from the Early/Middle Bronze Age were uncovered that contained a variety of metallic artefacts. This paper reports on the analysis of nine metal artefacts, including eight broken vessels and a decorative strip that covered the handle of a dagger. The ICP–MS results showed that the bodies of the vessels are made of tin bronze alloy with variable amounts of tin, while the internal piece of the base of one vessel is made from an arsenical copper alloy. Further, the metallic strip is a thin sheet manufactured with partially pure silver. Microanalytical and microstructural information yielded by SEM–EDS revealed elongated Cu–S inclusions and lead globules as various phases formed in bronze solid solution. This study presents some information about the transition from arsenical copper to bronze metallurgy in the third millennium bc in south‐western Iran.     

重庆忠县洞天堡墓地出土西汉青铜钫的腐蚀研究

为了解重庆洞天堡墓地出土青铜器的保存状况、腐蚀产物种类和埋藏环境特征等,并探索其锈蚀成因,为即将进行的保护修复工作提供科学的依据,利用三维视频显微镜、激光共聚焦拉曼光谱仪和扫描电子显微镜等对重庆忠县洞天堡墓地出土青铜钫残片进行微观形貌观察和锈蚀物结构成分分析,并利用X射线荧光和微生物分析技术对青铜钫附着土壤进行成分和微生物分析。结果表明:该青铜钫锈蚀物含孔雀石、白铅矿、铅钒、磷氯铅矿、砷铅矿和赤铜矿等;外层锈蚀存在磷和氯元素富集现象;土壤中的磷、硫和氯等元素向青铜器迁移,青铜器中铜、锡和铅元素因腐蚀向土壤中流失;附着土富含多种真菌类微生物,促进了磷氯铅矿和砷铅矿的形成。     

咸阳龚西战国秦墓出土铜壶制作工艺研究

咸阳龚西战国秦墓出土的青铜器为研究战国时期秦青铜容器的铸造技术提供了重要实物资料。本文对龚西战国晚期秦墓M8出土的两件铜壶,通过表面观察结合X光摄像考察其制作工艺痕迹,利用金相显微镜、扫描电镜能谱分析等手段开展成分及显微结构分析,揭示两件铜壶壶身及表面装饰的制作工艺、材质特征。结果显示,两件铜壶均为铸造,器底和铜环预先铸好后置于范中,与器身铸为一体。器身和器底均为铅锡青铜(铜锡铅三元合金),但成分有一定差异,镶嵌的装饰金属片为高铅青铜。铜壶的器底分铸工艺和高铅青铜镶嵌工艺为古代青铜器制作工艺研究提供了重要的新材料。     

东周青铜复合剑制作技术研究

东周时期,吴越出现了一种奇特的青铜复合剑,剑的中脊和两刃是用两种不同成分的青铜铸接而成。为充分了解青铜复合剑的制作,对上海博物馆馆藏的4把青铜复合剑残剑进行了分析,通过X-射线荧光能谱仪分析残剑的剑刃和剑脊的成分,金相显微镜分析剑刃和剑脊的组织,发现中国古代工匠采用低锡青铜制作韧性好的剑脊,高锡青铜制作强度和硬度高的剑从,通过榫卯结构以铸接法将剑脊与剑从结合成一体,得到刚柔兼具的青铜复合剑。在测试分析的基础上进行模拟实验,先以陶范铸造法铸造出两侧带榫头的青铜剑脊,剑脊的成分采用88％铜、10％锡、2％铅的低锡青铜;然后将青铜剑脊置入铸造剑从的陶范内,两侧的榫头伸入陶范型腔中,剑从的成分采用78％铜、20％锡、2％铅的高锡青铜,当剑从凝固时产生的收缩使剑脊和剑从牢固地结合成整体,再分1次或多次以铸接法铸上剑格、剑茎、剑箍和剑首,成功地复制了青铜复合剑,再现了东周时期青铜复合剑的制作工艺。     

COPPER ALLOYS FROM THE ‘ENOT SHUNI CEMETERY AND THE ORIGINS OF BRONZE METALLURGY IN THE EB IV – MB II LEVANT

Tin bronze replaced arsenical copper as the preferred alloy in the Levant for reasons that have long been debated. Found almost exclusively in graves, these two types of copper alloys share nearly identical mechanical properties. The Bronze Age cemetery of ‘Enot Shuni has yielded the first metals ever analysed from an uninterrupted stratigraphic sequence in the Levant, spanning the earliest adoption of tin bronze from the Early Bronze Age (EB) IV through the Middle Bronze Age (MB) II (c. 2300–1530 bc ). SEM–EDS analysis of these artefacts, combined with a compositional meta‐database of all previously published EB IV – MB II alloys, reveals diachronic alloy progression as selected by populations of the Levant. It has long been qualitatively understood that bronze became the primary alloy by the MB II. These results verify this trend and quantify human demand, showing that tin importation increased by 103% and arsenic content decreased by 49% throughout these periods. This shift in technological choice is attributed to cultural reorientation from the Egyptian to Mesopotamian sphere of influence, as well as to tin's appreciable fuel efficiency over pure copper and arsenical copper in light of unprecedented timber shortages.     

贵州银子坛墓地出土铜锡器的初步分析

为研究黔西地区铜器时代金属制作技术及水平,本文采用金相显微镜和扫描电镜,对贵州银子坛墓地出土13件铜器和2件锡器进行了金相观察和化学成分分析,发现中水银子坛墓地出土的战国到西汉时代的铜器,有红铜、锡青铜和铜锡铅合金多种材质,而锡器有纯锡器以及锡铅合金,合金配比已具有一定的水平。制作技术有铸造和锻造工艺,并能应用冷热加工技艺。本文对研究古夜郎地区金属器的制作技术有一定的价值。     

在SO2存在下青铜腐蚀与相对湿度的关系

采用光度法和亚硫酸氢钢静态分解法研究了不同相对湿度0．1％SO2存在条件下,仿古铜-锡-铝合金的腐蚀情况。在无可溶性氯离子存在下,青铜腐蚀的第一和第二临界相对湿度值分别为50％和65％左右;在有可溶性氯离子存在下,其两个临界相对湿度值均有所降低。从而给出了青铜保存的最佳湿度范围。     

QUANTITATIVE ANALYSIS OF COPPER-TIN BRONZES BY MEANS OF GLOW DISCHARGE OPTICAL EMISSION SPECTROMETRY

Glow discharge optical emission spectrometry (GDOES) has been used for obtaining calibration curves for copper, tin, lead, silver, antimony, arsenic, zinc and iron from standards including copper-base alloys (Cu 61.33-99.95%) and from bronze Punic coins. The GDOES results were calibrated using atomic absorption spectroscopy with inductively coupled plasma atomization (ICPAAS) to analyse the standards and coins. For all these materials, the results show that via GDOES it is possible to obtain reliable and reproducible calibration curves for copper, tin, lead, zinc and iron with a linear behaviour as a function of the content. The quantitative GDOES and ICPAAS data for the coins have been also compared with those obtained via X-ray fluorescence (XRF) and it is shown that GDOES, ICPAAS and XRF agree well with one another considering that the bronze coins are inhomogeneous to some degree. As an example of GDOES analytical features, a depth concentration profile through a thin bronze patina is shown and briefly discussed.     

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.     

周原遗址及鱼国墓地出土青铜器锈蚀研究

运用等离子体发射光谱（ＩＣＰ）、Ｘ射线衍射（ＸＲＤ）、扫描电镜（ＳＥＭ）、Ｘ射线电子能谱 （ＥＤＡＸ）、金相分析等现代仪器,对从周原遗址及宝鸡国墓地所采集的青铜残片的成分、结构进行 了剖析,比较了合金基体与表面层的成分变化及表面的结构形态。结果表明腐蚀呈现明显电化学特 性,有选择性腐蚀,高锡相优先被腐蚀,在完全矿化层与合金基体之间形成部分腐蚀区的过渡层。因 自然腐蚀导致表面层富集Ｓｎ、Ｐｂ、Ｓｉ、Ｆｅ。氯离子可穿过腐蚀层沉积于表面层并向基体延伸。     

明代铜镜科学考察

通过对部分明代铜镜的科学分析,了解到明代也使用过与战国汉唐成分相近的合金来铸镜;除了锡汞齐外,此时还使用了铅汞齐和铅锡汞齐来开镜或磨镜。     

古铜镜“水银沁”表面形成机理的研究

对加工纯铜、黄铜、锡青铜和铸造高锡镜青铜样品的基体及“磨镜药”处理前后表面进行检测,发现在磨镜处理时,“磨镜药”中的Sn原子通过Hg的作用首先以置换方式扩散渗入铜材表面的α固溶体中,当Sn元素浓度达到饱和时,将首先在晶体缺陷处生成Cu41Sn11新相并逐渐长大,使表面形成“水银沁”富锡层。富锡层逐渐氧化生成致密的、显微晶态的SnO2膜。此即古铜镜“水银沁”表面的形成机理。