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    湖北省博物馆馆藏部分铁质文物的锈蚀产物与锈蚀机制

    Rust Products and Corrosion Mechanism of the Part of Collected Iron-Artifacts in Hubei Provincial Museum

    • 摘要: 湖北省博物馆馆藏部分铁质文物锈蚀严重,造成其出现层状剥落、残缺、裂隙、变形等病害。采用便携式X射线荧光光谱仪(XRF)、激光拉曼光谱、扫描电镜-能谱(SEM-EDS)、X射线衍射(XRD)等现代检测技术,对这批铁器锈蚀产物的形貌、元素、成分与锈蚀机理进行分析。结果表明:这批铁器普遍含有氯(Cl)元素,且Cl含量越高,器物的外观残损程度越大,锈层越厚、越蓬松、多孔。此外,这批铁器中,不含Cl的铁器锈层明显分为三层,且锈蚀内层较为致密,外层相对疏松;三层锈蚀产物中均检测出α-FeOOH、α-Fe2O3、γ-Fe2O3、Fe3O4和γ-FeOOH,前四种为稳定的无害锈,后一种为不稳定的有害锈。含Cl铁器的锈层也存在明显的分层现象,且外层和中间层锈蚀产物较为疏松,主要成分为α-FeOOH、β-FeOOH、γ-FeOOH、γ-Fe2O3,内层锈蚀产物略微致密,主要成分为α-FeOOH、γ-FeOOH、α-Fe2O3、γ-Fe2O3。其中锈蚀产物β-FeOOH、γ-FeOOH不稳定、活性强,会在铁器表面不断重复生长,造成铁器出现层状剥落、裂隙、断裂等严重病害。另外,含Cl的铁器锈蚀产物中β-FeOOH含量往往较高,其含量与Cl的存在密切相关。这批铁器锈蚀产物的组成与含量存在明显差异,不含Cl铁器锈蚀产物中有害锈含量较少,而含Cl铁器锈蚀产物中有害锈含量则随Cl含量的增加而增加,锈层内无害锈与有害锈的质量分数比值(w无害锈/w有害锈)会减小,因此,Cl含量最高的西汉铁刀w无害锈/w有害锈最小为0.40,不含Cl铁刀的w无害锈/w有害锈最大为6.63。

       

      Abstract: Some of the iron cultural relics in the collection of Hubei Provincial Museum are severely corroded, resulting in layered peeling, damage, cracks, deformation and other diseases. Modern detection technologies such as X-ray Fluorescence spectrometer (XRF), laser Raman spectrometry, scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS), X-ray diffraction (XRD), etc. were used to analyze the morphology, elements, composition and corrosion mechanism of these iron corrosion products. The results show that this batch of iron utensils generally contained chlorine (Cl), and the higher the Cl content, the greater the degree of damage to the appearance of the utensils, and the thicker, fluffier, and more porous the rust layer. In addition, among this batch of ironware, the rust layer of the iron without Cl was clearly divided into three layers, and the inner layer of rust was relatively dense, while the outer layer was relatively loose. α-FeOOH、α-Fe2O3、γ-Fe2O3、Fe3O4 and γ-FeOOH were detected in all three layers of rust products, with the first four being stable harmless rust and the latter being unstable harmful rust. The rust layer of Cl containing ironware also exhibited obvious layering, and the outer and middle layers of rust products were relatively loose, mainly composed of α- FeOOH β-FeOOH、γ-FeOOH、γ-Fe2O3. The inner layer rust products were slightly dense, mainly composed of α-FeOOH γ-FeOOH、α-Fe2O3、γ-Fe2O3. Among them, the rust products β - FeOOH and γ - FeOOH were unstable and highly active, and would continue to grow repeatedly on the surface of the iron, causing serious diseases such as layered peeling, cracking, and fracture of the iron. In addition, the content of β-FeOOH in the corrosion products of ironware are containing Cl was often high, and its content was closely related to the presence of Cl. There are significant differences in the composition and content of the rust products of this batch of iron tools. The rust products of iron tools without Cl had less harmful rust content, while the rust products of iron tools with Cl content increased with the increase of Cl content. The ratio of harmless rust to harmful rust in the rust layer (wharmless rust/wharmful rust) would decrease. Therefore, the Western Han iron knife with the highest Cl content had a minimum of 0.40 wharmless rust/wharmful rust while the iron knife without Cl had a maximum of 6.63 wharmless rust/wharmful rust.

       

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