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首页> 外文会议>Eurocorr 2004 >Comparative study of the corrosion process of buried Italian bronzeartefacts and of aged copper-based alloys of similar composition
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Comparative study of the corrosion process of buried Italian bronzeartefacts and of aged copper-based alloys of similar composition

机译：埋藏的意大利青铜制品和类似成分的时效铜基合金腐蚀过程的比较研究

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Research activities regarding the conservation of Cultural Heritage have significantlyincreased in recent years in every European and Mediterranean country, as artefacts areimportant remains of our civilisation and valuable signs of how human being evolved in termsof art and history. One major concern of curators and archaeologists is the preservation ofarchaeological objects taken out of excavations and kept in museums. In the case of bronzesand other copper based alloys, the degradation phenomena occurring during burial orexposure to a museum atmosphere usually initiate by the formation of a cuprite layer, whichdarkens the surface, and then, depending on the environment surrounding the sample, variouscorrosion products of copper II can develop, giving either a brown-black colour or a greenone to the surface. This process damages the alloys, as the copper required to form thecorrosion products comes from the metal core, which can then considerably decrease, indeeddisappear, following the corrosion rate. It is therefore crucial to find methods of protectionand conservation of these metallic artefacts that prevent them from getting damaged.In this paper, we present analyses carried out on Italian copper-based archaeological valueartefacts selected as a function of the archaeological context and of the chemical compositionand structure; and on aged copper-based reference alloys of similar composition to that of theancient alloys, in order to characterise their corrosion products and modelize the mechanismof the degradation process.The archaeological artefacts came from two different sites in Sardinia and the riverbanks ofthe Tiber. They were analysed by means of optical and scanning electron microscopy, X-raydiffraction and fluorescence performed with portable instrument and glow discharge opticalemission spectroscopy. The corrosion layer was also characterised by electrochemicalimpedance spectroscopy.The reference alloys were produced with the similar composition determined after theanalyses of a large selection of artefacts. These analyses gave us either ternary or quaternaryalloys of copper, tin, zinc and lead. These alloys were then buried in soils coming from theSardinian and Roman sites, in presence of water. Ageing tests were run on these samples in aclimatic chamber, where the samples were put for 1, 4 and 7 months. The aged samples werecharacterised by means of the same techniques than those used for the artefacts.The first results obtained on the artefacts show the formation of malachite on samples comingfrom sites exposed to a marine and chlorinated atmosphere and a partial mineralisation of thealloys due to their interaction with the soils. Cuprite is also detected as a major component ofthe corrosion layer. For the one-month degraded reference alloys, wide dark red and red spotsof cuprite have formed a first thin corrosion layer. Green traces of malachite are alsonoticeable on samples buried in soils containing higher water content than the field capacity.
机译：近年来，在每个欧洲和地中海国家，有关文化遗产保护的研究活动都大大增加了，因为文物是我们文明的重要遗存，也是人类在艺术和历史上如何发展的宝贵标志。策展人和考古学家的主要关切之一是对从发掘中取出并保存在博物馆中的考古物品的保护。对于青铜和其他铜基合金，在埋葬或暴露于博物馆气氛期间发生的降解现象通常是通过形成使表面变暗的铜矿层而引发的，然后根据样品周围的环境，铜的各种腐蚀产物II可以显影，使表面呈棕黑色或绿色。这个过程会损坏合金，因为形成腐蚀产物所需的铜来自金属芯，然后随着腐蚀速率的增加，铜会大大减少，甚至消失。因此，寻找保护和保存这些金属文物以防止其受损的方法至关重要。在本文中，我们对根据意大利考古背景以及化学成分和功能选择的意大利铜基考古价值文物进行了分析。结构体;为了鉴定其腐蚀产物并模拟降解过程的机理，对老化的铜基参比合金进行了表征。考古文物来自撒丁岛和台伯河两岸。通过光学和扫描电子显微镜，便携式仪器和辉光放电光发射光谱法对它们进行X射线衍射和荧光分析。腐蚀层也通过电化学阻抗谱进行了表征。参比合金是在分析大量人工制品后确定的，其成分相似。这些分析为我们提供了铜，锡，锌和铅的三元或四元合金。然后将这些合金在有水的情况下埋入撒丁岛和罗马遗址的土壤中。在气候室中对这些样品进行老化测试，将样品放置1、4和7个月。使用与人工制品相同的技术对老化后的样品进行表征。在人工制品上获得的第一个结果表明，暴露于海洋和氯化大气的场所样品上形成了孔雀石，并且由于它们的相互作用而使合金部分矿化与土壤。铜盐也被认为是腐蚀层的主要成分。对于一个月降解的参比合金，宽的深红色和红色的铜矿斑形成了第一薄腐蚀层。埋在含水量高于田间持水量的土壤中的样品上也注意到孔雀石的绿色痕迹。

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