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...     

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。     

屈家岭遗址出土铜矿石标本初步研究

近年来屈家岭遗址的屈家岭文化晚期至石家河文化早期地层中出土了20余件铜矿石。本文采用光学显微镜、扫描电镜能谱仪(ESD)、X射线衍射仪(XRD)和拉曼光谱仪(Raman)等科学分析仪器对部分铜矿石标本进行检测分析。结果表明这些矿石多为含磷的假孔雀石和磷铜矿伴生矿,少量为孔雀石。部分矿石表面覆盖一层黑色氧化铜,属矿石经焙烧后的产物。由于目前未发现其它冶炼遗迹,这些焙烧产物是否与冶炼活动直接相关还须进一步研究。     

昆明羊甫头墓地出土青铜器的分析研究

为了对羊甫头出土青铜器的保存状况、锈蚀结构有全面的了解,同时对出土青铜器的原料配比、冶金技术、制作工艺进行研究。从不同的器物及残片上采集了32个青铜样品,应用扫描电镜、面探测器X射线衍射仪等方法对样品进行了合金成分分析及锈蚀产物检测。分析结果表明,羊甫头墓地青铜器物是用多种金属制作而成,器物主要是Cu-Sn合金,其次是红铜、Cu-Sn-Pb、Cu-Pb-Sb等合金;锈蚀产物主要以孔雀石、锡石、石英、赤铜矿等为主。     

古代青铜器的腐蚀及其控制研究

采用现代分析仪器及实验方法,对青铜器腐蚀过程进行了剖析,结果表明。（1）青铜器腐蚀产物所含元素与腐蚀环境——土壤和大气内微物质组分具有对应关系,这说明青铜器腐蚀与外界腐蚀环境存在物质交换。（2）有害粉状锈具有物理吸附与扩散性能,因而具有物理活性,腐蚀反应是通过锈层的空穴和缺陷,借助于腐蚀产物的物理活性而进行交换的。（3）有害氯元素在腐蚀产物内层有较高分布,在与最内层锈相邻之基体金属一定深度内,存在纵横交错的腐蚀沟槽,在这些沟槽内氯元素有较高分布。这揭示了对青铜器有害的C1离子难以彻底脱除的原因。进而提示对腐蚀青铜器的保护应从控制腐蚀环境入手。     

青铜文物缓蚀剂概谈

中国古代青铜器具有很高的历史价值、研究价值和艺术欣赏价值,是我国文物宝库中的明珠。青铜文物的主要成分是铜、锡、铅。经过长期腐蚀环境的作用,青铜文物在铸造过程中产生的缺陷会形成各种不同类型的腐蚀产物,常见的有氧化铜、碱式碳酸铜、碱式氯化铜、氯化亚铜等等。在这些锈蚀物中有些是相当稳定的（如碱式碳酸铜）,对青铜文物的进一步腐蚀起抑制作用。     

九连墩墓地1、2号墓出土青铜器上锈蚀产物分析

采用XRD、XRF和显微照相等方法,测试分析了九连墩1、2墓中出土青铜器锈蚀产物的成分和物相组成,发现该产物的物相主要为氧化亚铜.结合埋藏环境土壤的理化分析,探讨了这些锈蚀产物的形成原因,以及其对青铜文物的影响.同时使用XRD分析方法研究了这批青铜器在大气中的腐蚀情况,发现了一部分文物已经滋生了"粉状锈".     

开县余家坝遗址出土青铜兵器与工具金相学研究

兵器和兵器工具是青铜时代中两类非常重要的青铜器,体现了一个区域在一定时期科技的发展水平。余家坝遗址出土青铜器含有8.20％的Sn元素,表明青铜合金具有良好的机械强度。同时,这些大多数经过了热处理、热锻处理的青铜器,可以减少或者消除8相,或者形成小晶粒,都能够改变青铜的组织结构,有效地提高青铜合金的塑性。总而言之,余家坝遗址出土青铜兵器和工具中较多地使用了铸造热处理技术以及热锻冷加工技术,可以提高青铜器的塑性,这些表明重庆地区早在战国时期已经掌握了利用热处理、机械加工技术提高青铜合金性能的技术,反映出该地在青铜器制作方面已经具备了高超的水平。     

新干商墓青铜器铜绿脱落现象解析

本文从新干商代大墓部分出土青铜器上发生铜绿脱落的腐蚀现象入手,利用现代分析仪器对腐蚀产物进行分析。分析结果表明,在腐蚀过程中锡元素形成胶状沉淀物是导致表面铜绿脱落的原因。     

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。     

Characterisation of the raw metal sources used for the production of copper and copper-based objects with copper isotopes

Copper isotopes can be successfully used to determine the origin of copper or bronze artefacts from either primary or supergene sulphide or hydrocarbonate ores. In conjunction with lead isotopes, they provide information on the origin and type of the metal ore. We demonstrate this in this paper from the combination of literature and own data on metal ores and artefacts (coins and ingots). Low-temperature hydrocarbonates (esp. malachite and azurite) do not fractionate the copper isotopes amongst each other and have identical lead isotopes. Substantial fractionation of copper isotopes, however, occurs between copper sulphides and hydrocarbonates (malachite, azurite) such that the ⁶⁵Cu isotope is always enriched in the oxidised relative to the sulphide phase with a clear distinction between the two ore types. Expressed in the δ⁶⁵Cu notation, we assigned supergene sulphides to values less than −0.4‰ down to negative values of −2‰ and more, primary sulphides to a range between −0.4 and +0.3‰ and hydrocarbonates to positive values higher than +0.3‰. We have applied these boundaries to copper coins and ingots from the time of the Roman emperors with known ages from Augustus up to 250 AD. The deposit fields of the metal used for the production of the coins were previously identified from the lead isotope ratios to lie in the Southwest and the Central South of Spain. From the combination of the lead and copper isotopes and the exact time constrains, we could develop a picture of the change in mining activities in Spain involving continued mining sulphide ore deposits and, indicated by positive δ⁶⁵Cu values as proxies for malachite and azurite, the opening of new mines in various time slots. This first application shows that copper isotopes will become the most important tool in archaeometallurgy to distinguish between the exploitation of deeper-seated primary and supergene sulphide ores and shallower, secondary hydrocarbonate ores. This will become especially relevant for archaeometric questions regarding the distinction between occasional and intentionally produced alloys.     

LEAD ISOTOPIC ANALYSIS OF COPPER ORES FROM THE SIERRA EL ARAMO (ASTURIAS,SPAIN)*

This study presents the first ever lead isotope ratio data for copper ore samples (malachite and azurite) from the Sierra El Aramo (Asturias, northwestern Spain). The aim of this study was to supplement information in the existing reference database on the lead isotopic composition of Spanish ores. The Sierra El Aramo is particularly important because, while no data for the Asturian ores have been published so far, this northern province of Spain has played a significant role in terms of copper exploitation and metallurgy since the Copper Age.     

Electrochemical Characterization and Dating of Archaeological Leaded Bronze Objects Using the Voltammetry of Immobilized Particles

The application of solid state electrochemistry techniques for the characterization and dating of leaded bronze objects is described. Characteristic voltammetric signatures of copper and lead corrosion products were used as markers of more or less prolonged corrosion periods. The proposed methodology was applied to samples from the Roman archaeological sites of Valeria (Spain) and Gadara (Jordan), Roman and medieval sites in Xàtiva (Spain), and modern statuary exhibited outdoors, on the campus of the Universitat Politècnica of Valencia, Spain, covering a time interval between the fourth to second century bc and the 20th century ad . For such samples, the ratio between the signals for copper and lead corrosion products decreased monotonically with the corrosion time. This variation was modelled on the basis of thermochemical and kinetic considerations, the experimental data being consistent with a potential rate law for the corrosion process.     

UNIQUE PRE‐ROMANESQUE MURALS IN KOSTOĽANY POD TRÍBEČOM,SLOVAKIA: THE PAINTING TECHNIQUE AND CAUSES OF DAMAGE

Pre‐Romanesque murals at Kosto?any pod Tríbe?om, Slovakia, have been investigated by portable X‐ray fluorescence and by microanalytical methods to identify painting materials (pigments and binders), and to explain the degradation of colours. Today, missing green and blue shades have been reconstructed according to residual concentrations of Cu, which correspond to copper chlorides—products of salt corrosion of the copper carbonates azurite and/or malachite, accelerated by micro‐organisms. As confirmed by powder X‐ray microdiffraction, original minium (Pb₃O₄) has been transformed to brown–black plattnerite (PbO₂). In increased humidity, even insoluble pigments are washing down from the walls and the intensity of colours further diminishes.     

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。     

一件东汉时期铜鼓的分析与保护研究

本文对一件东汉时期铜鼓的保存状况和病害进行了初步调查,并采用金相显微镜、X-射线荧光光谱分析仪(XRF)、X-射线衍射仪(XRD)等仪器分析了铜鼓本体材质及其腐蚀产物。结果表明,该铜鼓本体材质为典型的铜锡铅三元合金,推测为泥范法铸造:铜鼓锈蚀产物主要是孔雀石,此外夹杂有针铁矿和石英。根据检测结果,结合局部实验效果,对铜鼓采取了表面清理、脱盐清洗、缓蚀、封护等针对性的保护处理措施。历经三年多沿海地区馆藏环境的考验,铜鼓保存状况稳定。     

Copper Mines,Chromite Copper Ores and Slags of the Ishkinino Bronze Age Archaeological Microregion,The Southern Urals

The study addresses copper mines structure and composition of copper ores and slags at the Ishkinino archaeological microregion, Orenburg Province. Both ores and slags contain chromites derived from the host ultrabasite rock. Chromites were subdivided into three categories in terms of Cr2O3 content: 45–50%, 50–55%, and 55–61%. The proportions are similar to those observed in chromites of the malachite ores of the Ishkinino cobalt-copper-pyrite deposit. The reguli found in the slag contain copper sul?des and iron phosphides with a high content of nickel. Our results evidence the exploitation of local copper mines in the Late Bronze Age. Finds of chromite ores and slag at the archaeological sites of the Southern Urals are listed, and goals for future research are outlined.     

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。     

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。