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。     

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...     

一件中国国家博物馆馆藏铜雕塑锈蚀产物的分析研究

铜雕塑作为现代艺术品因其历史价值、文化价值、审美价值、科技价值和时代价值被越来越多的博物馆收藏。经过岁月的洗礼,雕塑上有时也会出现锈蚀产物,锈蚀产物或影响艺术品的美感或进一步损害雕塑,因此需要对锈蚀产物进行鉴别,然后采取适合的方法将其去除。为此,通过超景深三维视频显微观察、扫描电子显微镜-能谱仪、显微激光拉曼光谱和傅立叶变换显微红外光谱对一件中国国家博物馆馆藏铜雕塑锈蚀产物进行取样分析。能谱结果表明该锈蚀产物中没有氯离子,再结合拉曼光谱和显微红外光谱结果可以确定锈蚀产物是蓝铜钠石[Na₂Cu(CO₃)₂·3H₂O]和含有钠离子和氧离子的水合甲酸铜[Cu₄Na₄O(HCOO)₈(OH)₂·4H₂O],这种铜锈蚀产物在国内报道较少。为防止它们进一步腐蚀和损害雕塑,选择使用物理方法将锈蚀产物清除。科学的检测方法和分析手段为铜雕塑保护方案的制定提供了重要信息支撑和理论依据。     

Assessing the Impact of Typhoons on Historic Iron Shipwrecks in Chuuk Lagoon Through Changes in the Corrosion Microenvironment

The corrosion microenvironment of a dozen Second World War iron shipwrecks in Chuuk Lagoon, Federated States of Micronesia, was investigated to see if there were any measurable changes caused by a recent major typhoon. Seven previously inspected wreck sites were used for calibration to assess the environmental impacts. Five new wrecks, including the Fumitzuki, a destroyer of the Imperial Japanese Navy, were assessed at up to twice the depth of previous studies. The new data showed that the logarithm of the corrosion rate falls linearly with depth to 36 m. Measurements of corrosion potentials, concretion thickness and pH showed that many of the vessels suffered partial deconcretion during the typhoon Maysak in April 2015 with concomitant increases in the rate of decay. Regrowth of the colonising marine organisms are presently ameliorating the impact of the typhoon.     

Chemical durability of lead-bearing glazes in sulphuric acid solutions — Laboratory experiments performed on Zsolnay architectural ceramics from Budapest (Hungary)

This study aims to simulate the long-term deterioration of architectural glazes exposed to open air in a highly polluted urban environment. A laboratory experiment—a 14-day long accelerated weathering test—on glazed roof tiles has been performed to reveal the damaging influence of contacting acid solutions originating from dissolved gaseous pollutants, mainly SO₂. The studied tiles are made by the Hungarian Zsolnay factory and applied on two buildings in Budapest in the 19th and 20th century. The ceramics were covered mainly by lead glazes in the construction and lead-bearing alkali glazes in the renovation periods.

The solution of pH2 induced a greater dissolution, especially of alkali and alkaline earth metals (up to 2886 ppm), but less lead (up to 21 ppm) from the lead glazes of the construction periods. Newly formed lead sulphate (anglesite) on the corroded glaze parts precipitated on some lead-bearing alkali glazes, with moderate dissolution of alkali and alkaline earth metals (up to 396 ppm) accompanied by higher amount of lead (28–39 ppm). Based on the results, the main determining factor in the durability of glazes is mostly their chemical composition and less their preliminary degradation state.     

不稳定青铜器的处理方法

“青铜病”的稳定问题对文物保护工作者来说还是一个挑战。文献报道了不少的处理方法,每种方法都有其优点及不足之处。本文对“青铜病”的处理方法进行了考察,主要讨论了化学封护法的应用及其未来的研究方向。     

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。     

Galvanic removal of metallic wrought iron from marine encrustations

Historic shipwrecks frequently contain a large proportion of wrought-iron tools, fasteners, and other types of artefacts. Encrustations readily form around such objects in many marine environments. Depending on many factors, the iron objects inside these encrustations may be well preserved, completely disintegrated, or poorly preserved but still present. The latter type of encrustation is every conservator's nightmare because removing the encrustation yields merely a poorly preserved artefact still in need of extensive additional conservation. Neatly separating the artefact from its encrustation in order to obtain a natural mould for casting is generally impossible. Having encountered this problem many times, the authors began to experiment with the extraction of metallic iron from poorly preserved encrusted artefacts using galvanic dissolution. Data on rates of dissolution were gathered for three experimental configurations. The results of a test conducted on an encrusted artefact were promising, but inconclusive.     

Conservation and Management Strategies Applied to Post-Recovery Analysis of the American Civil War Submarine H. L. Hunley (1864)

The 12-m long submarine H. L. [Horace Lawson] Hunley was successfully recovered from the Atlantic in August 2000 after nearly 140 years of immersion, and immediately brought to the Warren Lasch Conservation Center to be excavated in a controlled environment. In 2001 a multi-disciplinary team excavated the crew compartment and uncovered numerous fragile artefacts and human remains. This paper describes the conduct of the excavation and technological advancements developed to work with this complex and unstable iron vessel. Impressed current technologies, automated tank controls and water monitoring systems; laser mapping; fibre-optics; database management; in situ x and gamma rays; moulding and protection of fragile archaeological features; and protocols for moving artefacts to the laboratory will also be discussed.
© 2004 The Nautical Archaeology Society     

长江口咸淡水混合水域腐蚀性细菌的筛选及其对文物的腐蚀作用

近年来,针对文物在海水中的细菌性腐蚀研究主要集中于海域沉积,但关于咸淡水混合水域的腐蚀性细菌研究鲜有报道。河口及近海岸水域是水下文物较为丰富的区域,咸淡水交互作用影响水下文物的埋藏环境和文物遗存。本研究采集长江口北港拦门沙Ⅱ号沉船附近海底不同层次的海泥,通过非定向富集培养基培养,分离纯化得到18株菌,经16S rDNA鉴定出4种具有腐蚀性的细菌：哈夫尼希瓦氏菌(Shewanella hafniensis)、越南芽孢杆菌(Bacillus wiedmannii)、金橙微小杆菌(Exiguobacterium aquaticum)和微小杆菌(Exiguobacterium indicum)。将分离得到的细菌作用于瓷质、陶质和木质等常见文物材料,置于30℃摇床220 r/min转速下培养7 d,喷金干燥,扫描电镜下观察,均可见在材料表面上产生生物膜。生物膜与微生物腐蚀的发生密切相关,除了已报道具有腐蚀性的菌株外,还发现了2株先前并未报道但也在材料表面产生生物膜的菌类：萘醌对希瓦氏菌(Shewanella xiamenensis)和嗜水气单胞菌(Aeromonas hydrophila)。实验...