Background: Archaeological metallic artefacts buried in soils deteriorate by means of various environmental as well as internal factors and mechanisms over time such as change in composition and microstructure of metal and corrosive factors due to long-term burial environment. Corrosion in metals occurs in different morphologies and results in different types of corrosion products based on soil composition. Identification of corrosion mechanisms and morphology in archaeological metals can help conservators to characterize deterioration occurred in metals and make decisions to protect artefacts about preventing further deterioration. In archaeological bronzes, different layers may form on the surface of artefacts and their composition, depth and shape depends on factors noted above. Results: In this paper, results of investigation carried out on ancient bronzes discovered from Haft Tappeh archaeological site, southwestern Iran, are presented. The ancient bronze samples are dated to the Middle Elamite period about 14th century BC. Some of the Haft Tappeh bronze artefacts corroded completely and a multilayer structure has formed. To study the stratigraphy of corrosion layers and their composition, some bronze artefacts have been analyzed using SEM-EDS (Scanning Electron Microscopy Energy Dispersive Spectrometry) and Optical Microscopy analyses. The results show difference between the amount of Cu and Sn in layers that may follow from copper leaching from inner layers and formation of copper trihydroxychlorides because of bronze disease. Conclusions: Based on the results, it can be concluded that SEM-EDS analysis and Microscopy observations can help to characterize compositional difference between corrosion layers in the micro scale as well as corrosion mechanisms occurring in archaeological metal artefacts.

Gypsum (calcium sulfate dihydrate) is one of the most used inorganic binding materials in the world. During calcination, calcium sulfate subhydrates are formed and, for technical reasons, are mixed with water to form dihydrate again. Therefore, the dehydration process of gypsum and the rehydration of hemihydrate were investigated. This dehydration process is technically performed in three different ways. Heating up, i.e., in a rotary kiln, leads to a preferred formation of β-hemihydrate, which crystallizes in comparatively small crystals. Similar results can be achieved by recrystallization from gypsum slurry around 100 °C in an autoclave or under a water steam atmosphere. However, in contrast, the recrystallization process here leads to the formation of a larger, needle-like morphology and sometimes branched α-hemihydrate crystals. The synthesis of β-hemihydrate was investigated in detail with a special thermal stage for optical microscopy on natural single gypsum crystals. It was observed that the crystal loses transparency because of the breaking surface of the crystals due to water evaporation. Furthermore, within a deeper layer of the crystal, new crystals become visible but disappear during dehydration of the upper layers. These are expected to be α-hemihydrate. This theory of the formation of α-hemihydrate inside of a gypsum crystal is experimentally proven in the present work. This work firstly shows that the observed crystallization inside of gypsum during dehydration is the formation of alpha-hemihydrate.

High-resolution microscopy investigations on ancient ceramics recommend the complex progression of crystalline phases in an antique object via the sintering process. Based on materials-science point of view, sintering is not a routinely reaction in all crystalline phases with the same crystallographic pattern, but also is a transition pathway. Sintering depends on the processing of raw materials via the manufacturing process. Five samples are chosen for this analytical approach from two different periods from Tappeh Zaghe, Iran (5100 millennium BC). A multimicroscopical approach was carried out by means of polarized light microscopy, environmental scanning electron microscopy, and atomic force microscopy. Crystalline phases were determined by X-ray diffraction and refined after Rietveld method. The observation of the behavior of phase-interphase boundaries of a crystalline part in the nano area suggests that the partial sintering is the point at which the mineral began to be decomposed, and the conditions of the occurrences of this phenomenon depend on crystallographic properties.