海洋出水木质文物保护中的硫铁化合物问题

海洋出水的木质文物中通常会沉积硫铁化合物。打捞出水后,硫铁化合物遇到空气和水分后会发生氧化,生成硫酸以及各种硫酸盐,并引起有机质的降解。近年来,硫铁化合物对海洋出水木质文物的危害已引起广泛关注。为此,本工作阐述了硫铁化合物相关问题的研究现状,就硫铁化合物的产生原因、危害以及目前控制方法的研究进展进行了总结,同时评述了针对硫铁化合物的处理方法。     

重庆大足大佛湾彩绘绿色和蓝绿色颜料的分析研究

为了确定重庆大足大佛湾彩绘含铜、砷元素的绿色及蓝绿色颜料显色成分,应用便携式X射线荧光光谱仪(XRF)、便携式显微镜等无损调查方法,结合X射线衍射分析仪(XRD)、扫描电镜-能谱仪(SEM-EDX)、X射线光电子能谱分析仪(XPS)、显微拉曼光谱仪(RM)等分析方法,对取自大佛湾塑像的绿色及蓝绿色颜料进行调查和分析。结果表明绿色颜料显色成分为为巴黎绿,蓝绿色颜料显色成分为氯砷钠铜石[NaCaCu₅(AsO₄)₄Cl·5H₂O]。根据研究结论推断,氯砷钠铜石可能为巴黎绿的变色产物。该结果为探讨近代人工合成颜料变色机理提供了新的线索和方法。     

饱水古木材难溶盐分析

为研究饱水古木材中难溶盐的成分和分布,基于电感耦合等离子体光谱、X射线衍射以及显微共聚焦激光拉曼等分析手段对出土出水饱水古木材表面和纵向横向不同取样深度的元素含量和分布、表面凝结物以及纵向横向切面颗粒物的物相进行了分析。分析结果表明饱水古木材含有大量的Fe、S和Ca元素,包含这三种元素的凝结物主要由难溶盐和不溶物组成。难溶盐主要分为两大类,一类为钙盐(包括硫酸盐、碳酸盐和磷酸盐等),一类为硫铁化合物(包括硫铁矿、黄铁矿、磁黄铁矿等);不溶物包括各类铁氧化物(如针铁矿、纤铁矿、赤铁矿和水合氧化铁)以及硫单质等。难溶盐分析结果有助于有针对性地对饱水古木材难溶盐尤其是对古木材危害比较大难溶盐进行预防控制和有效脱除。     

X射线荧光面扫描分析技术在文物保护中的应用

X射线荧光分析法由于其分析速度快、可测元素范围广、检出限低等优点被广泛应用于各个领域。X射线荧光面扫描分析技术将光学图像与元素分析完美地结合,为科研工作者的研究和分析提供了新的分析手段。通过对文物面扫描分析可得到文物整体元素分布图,对研究文物的组成、制作工艺及辩伪有非常重要的意义。     

陕西历史博物馆藏汉代“华仓”瓦当表面析出物的分析研究

陶质文物表面析出物中含有机酸盐的现象在国内鲜有报道。本研究采用离子色谱仪(IC)、扫描电子显微镜-能谱仪(SEM-EDS)、X射线衍射仪(XRD)、傅里叶变化显微红外光谱仪(FTIR)、超景深显微镜(DM)对一件馆藏汉代“华仓”瓦当表面析出物进行了表征和检测。结果表明,瓦当表面析出物主要由少量的二水硫酸钙和大量有机酸钙盐[Ca₃(CH₃COO)₃Cl(NO₃)₂·6H₂O]组成,两种盐的形成与瓦当的制作过程、埋藏环境和灰尘有关,有机酸盐的形成还与馆藏环境中的乙酸有关。这种析出物不仅影响瓦当表面的真实文物信息,还会进一步腐蚀瓦当本体,建议从展柜中取出瓦当进行脱盐处理,存放在无酸的环境中。本检测分析为这件瓦当的保护修复方案的制定提供理论依据,也为类似文物样品的分析提供借鉴。     

羟基吡啶酮衍生物用作文物硫铁化合物脱除螯合剂的分析

硫铁化合物是出土出水文物中普遍存在,又危害很大的难溶盐,为此,本研究对温和条件下1,2-二甲基-3-羟基-4-吡啶酮脱除硫化亚铁可行性进行了研究。在此实验研究基础上,采用Gaussian09软件,在B3LYP/6-31G~*水平上对不同的羟基吡啶酮衍生物分子结构进行了分析。分析结果表明,羟基吡啶酮的单官能团氨羧化衍生物N-(α-氨基丁酸基)-3-羟基-4-吡啶酮有可能是一种比1,2-二甲基-3-羟基-4-吡啶酮更为有效的出土出水文物硫铁化合物络合脱除剂。     

浙江瓯海出土一件西周青铜器腐蚀成因研究

为研究浙江温州瓯海M24墓出土的一件青铜器的腐蚀成因,采用扫描电镜（SEM）、X射线荧光光谱仪（XRF）、X射线衍射仪（XRD）、离子色谱分析仪（HPIC）等,对青铜剑腐蚀产物及其埋藏土壤进行了分析。结果表明,青铜剑已严重腐蚀,铜元素大量流失形成以锡元素为主的腐蚀产物。通过测量模拟瓯海土壤环境下的自腐蚀电位并参照CuH₂O体系的电位-pH图,推导出了浙江瓯海出土一件西周青铜器腐蚀反应历程。研究结果对类似出土文物有参考价值。     

三种含Cu、As绿色颜料的拉曼光谱研究

分析和确认古代颜料的成分是文物研究中的一项重要工作。为对四个来自不同地区的含Cu、As元素的绿色颜料进行鉴别,应用拉曼光谱仪并辅助以扫描电镜能谱分析仪(SEMEDX)和X射线衍射仪(XRD)进行研究。结果表明其分别为墨绿砷铜矿、氯砷钠铜石以及巴黎绿。对其来源分别进行了讨论,因巴黎绿在国内青铜修复和古建彩画当中的大量应用,过去对于含有Cu、As的绿色颜料通常鉴定为巴黎绿。墨绿砷铜矿和氯砷钠铜石为在文物彩绘中新发现的两种矿物颜料,为绿色颜料的鉴定提供了新的思路。     

馆藏金属器物上浅蓝色铜锈蚀物的辨别与成因分析

不同于新出土青铜器上的锈蚀物,博物馆藏金属器物上经常可见浅蓝色铜的锈蚀物。为辨别和探析其成因,通过采用扫描电子显微镜-能谱仪(SEM-EDX)、X射线衍射仪(XRD)和激光拉曼光谱仪(Raman)进行元素成分和物相综合分析,发现其为铜的有机盐。这些有机盐包括简单(或碱式)的甲酸铜和乙酸铜,也包括复杂的含有钠离子和碳酸根的乙酸铜NaCu(CO₃)(CH₃CO₂)、含有钠离子和氧离子的水合甲酸铜Cu₄Na₄O(HCOO)₈(OH)₂·4H₂O。这种浅蓝色铜的有机盐形成根源主要有两种:储存或展览环境的不当;用于除锈的化学试剂的残留。要杜绝这类锈蚀物的形成需要确保储存和展览器物的环境低湿度且无有机酸释放材料的存在。对经过化学处理的器物应确保将化学试剂清理干净且无任何残留以绝后患。对复合材料器物的处理更应谨慎,因为对不同材质的处理和保存环境要求不一样,要个例对待。     

同步辐射X射线技术在中国文物分析上的应用

同步辐射光源是一种特殊的新型光源,具有从远红外、可见光、紫外光到X射线范围内的连续光谱。鉴于高亮度、宽频谱、高偏振等优点,基于同步辐射光源的技术,尤其是X射线技术,包括X射线荧光光谱(X-ray fluorescence spectroscopy, XRF)、X射线吸收精细结构谱(X-ray absorption fine structure, XAFS)、X射线衍射谱(X-ray diffraction, XRD)和X射线断层摄影术(X-ray micro computed tomography, X-μCT)等,被广泛地应用到文物分析与保护以及考古研究等领域。主要从基于同步辐射的X射线技术在中国文物分析的角度出发,总结基于我国现有同步辐射X射线装置在相关方面的研究,并对比国外前沿研究给出展望。     

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。     

Sulfur and iron analyses of marine archaeological wood in shipwrecks from the Baltic Sea and Scandinavian waters

Analyses of marine archaeological wood from shipwrecks in the Baltic Sea area, Kronan, Riksnyckeln, Tattran, the Puck Bay Boat and the Ghost wreck, and at the Scandinavian West coast, the Göta wreck, Stora Sofia and the Viking shipwrecks of Skuldelev, show accumulation of sulfur compounds. The penetration profiles of sulfur and iron into the wood and the speciation of characteristic sulfur groups were evaluated by combining X-ray spectroscopic analyses, in particular S K-edge XANES (X-ray absorption near edge structure) and X-ray fluorescence, with ESCA and elemental analyses. The combined analyses support the hypothesis that hydrogen sulfide produced by sulfate-reducing bacteria reacts and accumulates at low iron concentration mainly as organically bound sulfur, which as in previous studies was found by X-ray spectro-microscopy to accumulate in lignin-rich parts of the wood cell walls. The presence of iron(II) ions from corroding iron promotes formation of pyrite and other iron(II) sulfides, which easily oxidise in aerobic conditions with high humidity. No significant differences in sulfur and iron accumulation were found in wood from shipwrecks in the east coast brackish water and the west coast seawater. Sediments from three wreck sites, the Göta wreck, Stora Sofia and Kronan, were analyzed to a depth of a few decimeters and showed especially at the Stora Sofia high sulfur concentrations, exceeding 3 mass%. S K-edge XANES analyses of the sediments showed mainly reduced forms of sulfur, in particular pyrite and iron(II) sulfides together with elemental sulfur.     

Investigating the processes necessary for satisfactory freeze-drying of waterlogged archaeological wood

Preliminary studies into methods for improving and safeguarding the preservation of waterlogged archaeological wooden artefacts are presented. Mannitol, sorbitol and trehalose have been tested as replacements for polyethylene glycol (PEG) as a treatment prior to freeze-drying of wooden archaeological objects. The highest anti-shrink efficiency achieved in this short experiment was (70 ± 15) % using a 20% weight per volume solution of sorbitol after soaking for one week. The collapse or eutectic temperature of each solution used was determined using a freeze-drying microscope. Importantly, it was noted that the collapse temperature of the solutions was reduced by several degrees after use for treatment of the wood samples for one month. A freeze-drying microscope with a cold light source has been used to observe the real-time freeze-drying behaviour of various treatments inside a thin section of wood, confirming that this novel technique is indeed possible and useful. Lastly, the effects of magnesium phytate as an iron chelator have been studied. It was found that the treatment lowers the collapse temperature of a PEG 600/2000 solution by roughly 3 °C meaning that objects must be freeze-dried at a correspondingly lower temperature. Iron K-edge X-ray absorption near-edge spectroscopy analysis showed that the treatment extracted approximately half of the iron(III) ions present in the timbers.     

长沙风篷岭M1出土漆器检测研究

长沙市风篷岭M1出土漆器百余件,为研究该批漆器的制造工艺及保护修复方法。选取多个样品采用扫描电子显微镜、X荧光光谱仪、红外光谱仪、X射线衍射仪等进行含水率、木胎种质、漆膜和漆灰成分多项检测。结果显示:木胎漆器含水率远大于夹纻胎;木胎漆器材质有楠木、梓木等;底漆层厚度大于面漆层;漆膜中的红色颜料为HgS,黑色颜料为C,白色颜料中含Ag较高;漆灰中含有大量SiO_2和CaO。本研究成果为研究夹苎胎漆器制作工艺提供了可靠依据。     

Chemical analysis of 17th century Millefiori glasses excavated in the Monastery of Sta. Clara-a-Velha,Portugal: comparison with Venetian and façon-de-Venise production

A set of ten Millefiori glass fragments dating from the 17th century, originated from archaeological excavations carried out at the Monastery of Sta. Clara-a-Velha (Coimbra, Portugal), were characterized by X-ray electron probe microanalysis (EPMA), Raman microscopy and UV–Visible absorption spectroscopy. All glasses are of soda-lime-silica type. The use of coastal plant ash is suggested by the relatively high content of MgO, K₂O and P₂O₅, as well as by the presence of chlorine. Tin oxide or calcium antimonate were the opacifiers used in the opaque glasses, cobalt in the blue glasses, copper in the turquoise glasses, iron in the yellow and greenish glasses, and iron and copper were found in the opaque red and aventurine glasses. Based on the concentrations of alumina and silica four different sources of silica were identified, allowing the classification of the glasses into the following compositional groups: low alumina (<2 wt%), which includes a sub-group of cristallo samples with SiO₂ > 70 wt%, medium alumina (2–3 wt%), high alumina (3–6 wt%) and very high alumina (>6 wt%). Comparison with genuine Venetian and façon-de-Venise compositions showed that two fragments are of Venetian production, one of Venetian or Spanish production and the remaining are of unknown provenance. In two fragments the glass of the decoration is probably Venetian or Spanish but the glass used in the body is also of unknown provenance.     

Comparative microstructural and elemental analysis of iron artefacts from Kaveri valley archaeological sites

Iron has been one of the most critical technotraditions that had lasting impact on social formation throughout the Iron Age and historical period. Iron was used in warfare and subsistence economy. Our knowledge on ancient iron smelting and working have generally been derived from ethnography and ethnohistory, which is by all means, time, region, and raw material specific. Scientific analyses of ancient iron have contributed in understanding this heritage to a respectable extent, yet a comprehensive knowledge about the evolution of iron making through time and space in India eludes us. In this work, a comparative study of iron artefacts from two Iron Age/Megalithic-Early Historic sites of Tamil Nadu, south India, that is, Mangadu (burial site) and Ambal (habitation-cum-burial site) is carried out to understand the iron thermal-processing capabilities. The retrieved artefacts were examined using X-ray fluorescence (XRF) for elemental composition. The imaging of the artefacts was done using Scanning Electron Microscopy (SEM), Electron Backscatter Diffraction (EBSD), and Optical Microscopy (OM). In addition, phase identification was performed using X-ray diffraction (XRD) and Energy Dispersive X-ray Spectroscopy (EDS). Combination of these analyses illustrates that inhabitants of Mangadu and Ambal were aware of the iron alloy manufacturing/processing techniques such as forging and hammering.     

济南运署街汉代铁工场遗址的相关问题探讨

为探讨济南运署街汉代铁工场遗址的性质和冶炼技术,应用X-射线荧光、X-射线衍射、热膨胀测温等方法,对遗址出土的部分遗物进行了相关分析。结合出土实物和测试结果,可以推断运署街遗址是汉代一处兼有冶炼和铸造的铁作坊。陶范、耐火砖、铁渣及矿石原料等冶铸遗物的分析指出,当时的矿石分选、加工、冶炼、铸造技术已经十分成熟,在一定程度上反映了汉代冶铁业的工艺水平。     

Large-scale 2nd to 3rd century AD bloomery iron smelting in Korea

Iron production in Korea has traditionally been seen in the shadow of developments in cast iron technology in China, with limited indication for a northern influence via Russia’s Maritime Province. The possibility of the existence of bloomery iron production in ancient Korea has been little explored, and relevant discussion is fraught with speculations based primarily on the early use of cast iron. The recent excavation of a site in South Korea recovered substantial amounts of slag providing direct evidence of bloomery smelting. The accelerator mass spectrometric dating of burnt wood from inside one of the slag pieces showed that the site was in use in the early 3rd century AD or earlier, which is in agreement with the assessment based on ceramic typology. The traits of a bloomery process evident in the slags’ microstructure, shape, composition and excavation context are discussed along with the implications for historical iron technology in Korea, where cast iron and the influence from China have been overly emphasised.