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1.
《文物保护研究》2013,58(3):274-282
AbstractA study of the composition and phase distribution of the corrosion layers on three ferrous objects, excavated at K2 (Bambandyanalo), an archaeological site in South Africa, was conducted. The objective of the study was to obtain information that can contribute to conservation procedures to be performed on the iron artefacts from this site. Examination of cross sections by means of energy-dispersive X-ray spectroscopy coupled to a scanning electron microscope (SEM–EDX), X-ray powder diffraction (XRD), and micro-Raman spectroscopy revealed the same corrosion composition and structure for all the objects under study, namely an internal layer adjacent to the metal surface with ghost inclusions and an external layer containing quartz grains. The study also revealed that the presence of magnetite (Fe3O4), maghemite (γFe2O3), and lepidocrocite (γ-FeOOH) within the internal layer is the only difference between the chemical compositions of iron corrosion products within the two layers. The results also made it possible to retrace the corrosion history during burial and long-term storage. 相似文献
2.
《文物保护研究》2013,58(4):326-337
AbstractAlthough desalination of archaeological iron reduces its chloride concentration and enhances object stability, the reduction in corrosion rate that this produces has never been quantified. This study measures post-treatment corrosion rates in accelerated corrosion environments to identify the impact of removing chloride ions on corrosion rate. Thirty-five archaeological iron nails, treated individually in either alkaline sulphite or nitrogen-deoxygenated sodium hydroxide, were exposed to 75°C and 75% relative humidity together with 31 untreated objects from the same archaeological sites. Object weight change and visual examination of physical change before and after the test period were used to monitor corrosion. 77% of treated objects showed no weight gain and no visible signs of corrosion, while 90% of untreated objects did corrode. The impact of chloride on corrosion of untreated objects was clearly established by a significant linear correlation between chloride content and weight gain. Treated objects with <400 ppm chloride content showed no corrosion behaviour. Corrosion of treated objects was attributed to incomplete treatment: 93% of objects treated to <5 mg/l Cl? in the final solution bath displayed no corrosion behaviour. Based on these results, desalination of iron objects to enhance their stability offers a valuable option for reducing corrosion rates of archaeological iron, which should increase object lifespan. The results also raise the question of whether low levels of post-treatment residual chloride produce corrosion of any significance. Answering this will be an important step forward for managing the preservation of archaeological iron. 相似文献
3.
A technical study was conducted on a group of copper alloy artifacts excavated from the burial tumulus of Lofkënd (fourteenth–ninth century BCE) to identify the alloy compositions and methods of manufacture. The surface corrosion was also examined in order to understand the diagenetic processes affecting the preservation of the finds and their condition. Portable X-ray fluorescence spectroscopy, metallographic examination, and X-ray powder diffraction (XRD) analysis were used to characterize the alloy composition and identify the corrosion products present. XRD analysis showed the presence of brochantite (Cu4SO4(OH)6) on five of the metallic artifacts. Brochantite is not commonly reported on archaeological bronzes from terrestrial sites, but is more readily found on copper alloy objects exposed to sulfur pollutants in the air or soil. The possible conditions that could have led to the formation of this corrosion on the bronzes from Lofkënd are discussed in the context of the particular burial environment found at the tumulus. 相似文献
4.
《文物保护研究》2013,58(4):205-206
AbstractThe deterioration of Bronze Age objects from the archaeological site at Fort-Harrouard (France) has been studied, firstly, in relation to their external appearance and the elemental composition of the sound metal. A relationship between the composition of the corroded surface and the underlying sound metal was deduced. In addition, examination of metallographic sections of one of the bronzes allowed the differentiation of corrosion processes which are related to the shape of the object: the stratification of the corrosion products and the intergranular and transgranular corrosion processes. The existence of a pseudomorphic microstructure suggests that the mechanism of deterioration may be stratigraphic, which may be explained by the growth of the corrosion products in fissures which do not involve periodic precipitation. 相似文献
5.
《文物保护研究》2013,58(4):227-236
AbstractThis article compares chemical dechlorination treatments (immersion in sodium hydroxide or alkaline sulphite) and electrochemical treatments of iron bars from the Gallo-Roman period excavated from a marine environment. Some important parameters, such as storage before treatment, temperature, solution composition, and drying after treatment, were varied during the study to assess their influence on the chloride extraction process. The kinetics of these treatments depend mainly on chloride diffusion through the corrosion layers. The kinetics are promoted by high temperatures and, in the case of electrolysis, by the electric field effect. The reduction of corrosion products during electrolysis occurs only for objects previously stored in air. In fact, the manner in which the objects are stored before treatment is critical in the dechlorination processes. The sooner the objects are treated after excavation (with water storage), the better the removal of chloride ions, in both chemical immersion and electrolysis treatments. But if the object is stored in air, material losses occur, and only electrolysis results in complete extraction of the chlorides. These differences are due to modifications in the corrosion products during storage. Drying after treatment also has a significant impact on the composition of the corrosion layers. If the objects are dried too quickly, Fe(OH)2 oxidizes into FeOOH, which thus forms a layer with low cohesion. 相似文献
6.
《文物保护研究》2013,58(3):161-171
AbstractFour iron meteorite fragments and 13 archaeological iron objects were exposed to a lowpressure hydrogen plasma for up to two weeks in a pilot apparatus. In the experiment the objects acted as cathodes in a 600–1600V d.c. electrical field. While the chlorine-containing β-FeOOH, akaganeite, was present in all objects before the test, no akaganeite and no chlorides were present afterwards. The objects, including one meteorite which had been exposed for more than 5000 years to seawater, were found to be stable after the glow discharge treatment. The major mineral after treatment was identified as magnetite, and the objects generally assumed an iron-grey surface colour. No sputtering and no reduction to free iron took place under the test conditions, operating at or below 120°C and at pressures of O·4–1mb hydrogen. 相似文献
7.
《文物保护研究》2013,58(4):232-240
AbstractThe method of removing chlorides from archaeological iron objects using hydrogen plasma at low pressure has been studied and improved. To carry out the initial experiments and to limit the use of ancient material, synthetic samples were made from iron powder and corrosion products consisting mainly of akaganeite. The time and the temperature required for the complete removal of the chlorides were determined. It was also possible to demonstrate that magnetite, and iron above 400°C, are the final reaction products of the reduction of akaganeite. 相似文献
8.
AbstractThe long-term stabilization of marine archaeological iron, whether cast or wrought, continues to challenge conservators responsible for treatment of this material. Results and observations obtained from past treatments highlight the daunting, prolonged, and laborious efforts required to desalinate large and complex ferrous artifacts recovered from the ocean. In general, the higher an artifact's chloride level, the less stable it is. Consequently, any stabilization treatment must involve the removal of as much Cl?1 as possible without affecting the integrity of the corroded artifact. This problem is particularly acute with corroding cast iron objects that have formed thick, fragile, and highly unstable corrosion layers. Over the course of the twentieth century, conservators have used a variety of techniques in an attempt to mitigate the negative effects of chloride ions on iron artifacts and prevent disintegration. In spite of early promise, each of these stabilization techniques has significant disadvantages, particularly with regard to treatment efficiency, duration of treatment, and/or unacceptable risks to the artifact during treatment. For these reasons, conservators and conservation scientists at the Warren Lasch Conservation Center in Charleston, South Carolina, decided to look at the possibility of using subcritical fluids to stabilize archaeological iron. This paper compares the efficiency and effectiveness of traditional stabilization techniques (i.e. alkaline soaking and cathodic polarization) to subcritical fluids on wrought iron rivets and metal shavings from the H.L. Hunley submarine as well as Civil War era cast iron artillery shells recovered from a marine environment. 相似文献
9.
SummaryThe rate at which chloride ions diffuse from archaeological iron into a treatment solution depends on how the chloride ions are initially distributed in the corrosion layer. This paper compares solutions of the diffusion equation for two limiting cases: (1) where the chloride ions are initially spread uniformly through the corrosion layer; and (2) where the chloride ions are initially concentrated at the interface between the iron and the corrosion layer. Although the first model has been used in the past to describe chloride ions diffusing from marine iron, the second is more appropriate in cases where corrosion has drawn chloride ions toward the iron surface. Because diffusion processes in archaeological iron are complicated, the limitations of both these models are discussed. 相似文献
10.
《文物保护研究》2013,58(4):297-307
AbstractWet organic archaeological materials extracted from seawater may suffer damage as a result of degradation influenced by micro-organisms. One of the most common phenomena is indirectly induced by sulphate-reducing bacteria (SRB). Due to their metabolic activity in anoxic conditions, SRB generate hydrogen sulphide from sulphate ions present in seawater. When steel items are in contact with organic matter in presence of sulphides, corrosion of the metal leads to the precipitation of Fe(II) sulphides. These phases are responsible for dramatic post-excavation damage: their oxidation during storage or exhibition in museums leads to the formation of voluminous crystals, which may cause cracking and crumbling, and lead to the production of sulphuric acid. In order to characterize Fe(II) sulphides and their by-products, 13 waterlogged samples were analysed by environmental scanning electron microscopy, micro-Raman spectroscopy, and X-ray diffraction. Experiments were performed on untreated wood fragments, on a fragment of rope, and on mineral concretions scratched from the surface of wood remains, all extracted from different shipwrecks. Mackinawite was detected inside the fragments and between the fibres of the rope. Greigite was detected in scattered locations. Pyrite and sulphated phases, like gypsum and iron sulphates, were identified at the surface of the wood fragments and in the mineral concretions. 相似文献
11.
Hongying Duan Xinqiang Zhang Baoqiang Kang Guangyao Wang Liang Qu Yong Lei 《文物保护研究》2013,58(6):311-322
ABSTRACTIn August 2014, a pit containing more than 10000 porcelain shards was excavated in the southwestern area of the Palace Museum. Reign marks and other stylistic criteria dated the manufacture of these fragments from the reign of Hongwu in the Ming Dynasty (1368–98 CE) to the Guangxu reign in the Qing Dynasty (1875–1908 CE). A famille rose (fencai, 粉彩) bowl decorated with a red-ground peony pattern and having the reign mark of Qianlong (1736–96 CE) on the base was studied using several non-destructive analytical methods to determine the variation in overglaze compositions, the colorants, the application sequences, the thickness of the colored layers and the high-temperature porcelain glaze, and the identification of the surface weathering products that formed during burial. The methods include non-destructive X-ray fluorescence, Raman spectroscopy, optical stereomicroscopy, and laser confocal microscopy, as well as X-ray diffraction. 相似文献
12.
《文物保护研究》2013,58(3):136-142
AbstractVarious desalination methods had been used in the past to treat a large collection of archaeological iron objects. In order to establish whether desalination treatments had been effective, the condition of the objects was assessed and the data analyzed using statistical methods. It was found that objects which had been treated using desalination methods were less likely to re-corrode, and the conclusion was that the development of more effective techniques of chloride removal would be useful. 相似文献
13.
《文物保护研究》2013,58(1):17-40
AbstractA study is presented of the growth of sulphidecontaining corrosion products on antiquities in museums. Analysis of the corrosion products suggests that they are dependent on the mode of formation. Techniques for conservation have also been investigated and l-amido-l-cyanoethylene, 2,2-di(sodium thiolate) is recommended for dissolving the sulphide layers, while a treatment with benzotriazole followed by lacquering is recommended for long-term protection. 相似文献
14.
《文物保护研究》2013,58(3):180-197
AbstractCorrosion rates are presented for metals in the aqueous solutions intended for treating both the wood and the metal components of a waterlogged wood-metal composite object. The metals include lead, mild steel, cast iron and the copper alloys of bronze, cast brass and wrought brass. The corrosion rates were determined using a standard weight-loss method in which clean metal surfaces were immersed in the solutions for two months at room temperature. The treatment solutions included Acrysol® G-11O for lead, Witcamine® RAD 1100 for copper alloys and Pluracol® 824 or the corrosion inhibitor Hostacor® KS 1 in PEG 400 for iron. These treatment solutions were prepared in distilled water as well as in a synthetic seawater. For reference, metal corrosion rates were also determined in distilled water, synthetic seawater and PEG 400. The results demonstrate that, in general, clean metal surfaces corrode more slowly in the treatment solutions than in PEG 400 solutions. However, before recommending these solutions for the treatment of composite objects, further testing is needed to determine how effective they are in reducing the corrosion rates of metals covered with a thick corrosion crust, and to see if Acrysol G-110 is capable of bulking and consolidating waterlogged wood. 相似文献
15.
ABSTRACTHafez’s tomb was constructed on the grave of the well-known Iranian poet in Shiraz, in the 1930s. The dome of this monument is made of copper metal and has been exposed to the urban environment for 80 years. In this study, corrosion mechanisms and conservation conditions of the metallic dome of the Hafez’s tomb are investigated by analytical methods including optical microscopy, ICP-MS, SEM-EDX, and X-ray diffraction. The results showed that the dome is constructed from many copper sheets that are hammered to shape the dome. The corrosion products formed on the surface of copper sheets include copper oxide and copper trihydroxichlorides. In fact, the corrosion mechanism occurring in the metallic dome consists of copper oxidation and redeposition of copper II products because of reaction with air pollutants. 相似文献
16.
《文物保护研究》2013,58(3):108-124
AbstractThe causes of deterioration of the gilded bronze doors of the Baptistery in Florence have been examined and the mechanism of corrosion discussed. An apparatus for thermal conditioning has been proposed and tested either on the north door of the Baptistery, or on samples exposed to the urban atmosphere in Milan and by laboratory tests on an electrochemical model. The effectiveness of the proposed apparatus has been verified by weight losses, by assessing soluble salts, by visual observations, by local chemical microanalyses, by morphological examinations with a scanning electron microscope equipped with an X-spectrometer and by X-ray diffraction. 相似文献
17.
《文物保护研究》2012,57(1):28-36
ABSTRACTA pre-restoration diagnosis revealed a high amount of pyrite in the wood of the Lyon Saint-Georges 4 shipwreck (end of the second century). The occurrence of this phase is supposed to result from the microbiologically influenced corrosion of the iron fasteners. So, all the nails and metallic elements were removed from the remains before treatment and the wreck was consolidated by polyethylene glycol impregnation coupled to a specific desalination process. Treated and non-treated samples extracted from the wreck were studied in order to identify the iron/sulfur-containing compounds present in the wood before and after treatment and figure out its effect. Sample analyses relied on an original approach combining magnetic characterization methods and more common elemental and structural analysis methods. The results showed that the treatment was effective in removing soluble salts. However, a large amount of unstable iron sulfides remained inside the wood. 相似文献
18.
19.
Discoloured 18-carat gold decorations from Sweden have been analysed by scanning electron microscopy with energy dispersive X-ray spectroscopy and X-ray electron spectroscopy (XPS)/electron spectroscopy for chemical analysis (electron spectroscopy).The original gold composition was close to 75% gold, 13% silver, and 12% copper. After manufacture, many details were boiled in sulphuric acid. As a consequence of this, the surfaces are irregular and porous with a gold concentration around 90% and with less than 1% copper. With XPS the outermost 10–20 atomic layers could be examined. No copper was present here, and the silver concentration was significantly higher. Also carbon, sulphur, oxygen, and (in one case) chlorine were present. The valence numbers indicated that gold only occurred in its metallic state, while silver (as Ag+) was preferably associated with sulphur to form black silver sulphide (Ag2S). The grey discolorations are basically due to silver sulphide and organic dirt. Sometimes green, violet, and ‘copper-shining’ colours occur, presumably as a result of light refraction phenomena. 相似文献
20.
《文物保护研究》2013,58(1):29-41
AbstractChloride-contaminated archaeological iron is unstable and problematic to store and display within museum collections. Reducing its chloride ion content using aqueous desalination followed by storage in controlled relative humidity offers one treatment option. This study reports a quantitative assessment of chloride extraction by aqueous deoxygenated alkaline desalination solutions from 120 individual archaeological iron nails. The three treatment methods comprised alkaline sulphite solution (0.1 M NaOH/0.05 M Na2SO3) at room temperature and at 60°C and sodium hydroxide solution (0.1 M) deoxygenated using a nitrogen gas positive pressure system at room temperature. Chloride extraction was monitored using a specific ion meter. The nails were digested after treatment to measure their residual chloride content. A wide range of extraction patterns emerged, with the majority of individual treatments extracting 60–99% of the chloride present. Residual chloride levels for 87% of the objects fell below 1000 ppm and 42% were below 200 ppm. Although no treatment extracted 100% of the chloride in the object, alkaline desalination produced very significant reductions in chloride content. The impact of this on future corrosion of the objects is discussed. This quantitative and statistically viable assessment of deoxygenated desalination treatments provides evidence to support their use in conservation practice, which will impact on procedures for the preservation and management of archaeological heritage. 相似文献