Remarkable corrosion resumption of archaeological bronzes, induced by the oxidation of ternary Cu-Sn-S phases in atmosphere, after long-term burial with sulfides

Rémazeilles, C.; Langlet-Marzloff, Véronique; Creus, Juan; Lotte, Guillaume; Deshayes, Christophe; Baleux, François; Robbiola, Luc

doi:10.1016/j.corsci.2020.108865

Cited by 18 publications

(11 citation statements)

References 57 publications

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“…These alteration products are detected also by Raman analysis with the exception of sulphide and this consented also to better define the measurement location, unlike the powder diffraction techniques in which it needs sample grinding. Despite the complexity of corrosion phenomena, it is possible to conclude that a first alteration was due to reaction of main elements of copper alloy and secondly these alteration products degrade into species in which iron has a prominent role [11].…”

Section: Resultsmentioning

confidence: 99%

Corrosion products characterisation aimed at restoration of Bronze Age metal artefacts from Garda Lake

Labate

Sirello²,

Longhi

et al. 2022

J. Phys.: Conf. Ser.

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Conservation is a complex field that needs an exchange of views among different professionals including archaeologists, conservators, restorers and scientists. Diagnostic analyses can give useful information able to lay down the documentation about the artefacts conservation status before and after the restoration; to define the restoration plan and to lead to the most suitable conservation strategies, materials and methods; to evaluate and track the restoration work and to reproduce it in similar contexts. For all of these reasons, a scientific restoration treatments on cultural heritage need materials and alteration products characterisation as a propaedeutic phase. This awareness has guided the study approach of some Bronze Age metal findings from Garda Lake, analysed in order to know the nature of corrosion products in case of upcoming restoration.

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Section: Resultsmentioning

confidence: 99%

Corrosion products characterisation aimed at restoration of Bronze Age metal artefacts from Garda Lake

Labate

Sirello²,

Longhi

et al. 2022

J. Phys.: Conf. Ser.

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“…It is known that the formation of the whole composition ranges of copper sulphides, from covellite to chalcocite (Cu 2 S), is favored by high concentration of sulphides and pH values ranging from 5 to 8 as reported in the Pourbaix diagram. Sulphide ions, whose formation can occur in anaerobic condition by the action of sulphate reducing bacteria (SRBs), can react with the oxidised copper 19 , 32 , 43 . During this interesting biological assisted corrosion process, bacteria participate in different steps of corrosion process thorough their enzymatic systems.…”

Section: Resultsmentioning

confidence: 99%

Microstructure and phase composition of bronze Montefortino helmets discovered Mediterranean seabed to explain an unusual corrosion

Armetta

Saladino

Scherillo

et al. 2021

Sci Rep

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Two Monterfortino helmets, recovered in the Mediterranean seabed, show unusual features with respect to the more common helmets of the same period and found in underwater environments. Hence, they were investigated by a multi-analytical approach, which allowed us to identify the compounds constituting the helmets and to make some considerations about their metallurgy, although all the metal was converted to degradation products. The helmets, originally made in bronze, have maintained their original shape because of copper sulphides formation. The observed differences in composition between the two helmets were attributed to the position modification, of one of them, into the seabed along centuries. For the first time, a microstructural investigation permits to reconstruct the history of the aging processes involved in the total oxidation of roman bronze helmet metal.

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“…Furthermore, until recently it was believed that the corrosion processes are only active while the object is buried in the soil. However, it was recently evidenced that the characteristics of the burial soil, together with the storage conditions after excavation, can play an important role in the reactivation of these corrosion processes (Rémazeilles et al, 2020). The compactness of the patina suggests the lack of carbon compounds (Petean and Arghir 2012), while the diversity of corrosion products can be the result of higher concentration of soil elements, such as chlorine, phosphorous or oxygen (Graziani et al, 2020;Ingo et al, 2020).…”

Section: Resultsmentioning

confidence: 99%

Investigation on Metal Adornments From Ancient Eastern Europe

Ghervase

Dinu

Borș³

et al. 2020

Front. Mater.

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This study focuses on the investigation of certain bronze adornment objects from the First Iron Age (the so-called middle Hallstatt period), dating to the ninth–eighth c. BC. These objects are part of a bronze and iron hoard (labeled Cx 116) discovered in the present Romanian territory, at Tărtăria–Podu Tărtăriei vest archaeological site, in Alba County. Along with a second hoard of bronze and iron objects, this represents a unique discovery for the present Romanian territory, namely, for the inner Carpathian area and the Lower and Middle Danube Basin, where no such votive discovery had been made by archaeological excavations. The objects, approximately 450 bronze and iron objects—weapons, tools, adornments, and harnesses—were found in the two hoards, in the Southern ditch, which outlines the archaeological site. Digital radiography has been used to assess the physical state of the objects and to identify potential specific craftsmanship details. It showed a fairly good preservation status, with incipient corrosion processes located in the core of some of the objects and some specific traces of the crafting process and subsequent mechanical defects were highlighted. The relatively good state of preservation of the objects can result from the fact that they had been protected from the humid environment by the ceramic vessel they were placed in. XRF and LIBS were used to identify the materials and to stratigraphically evaluate the objects. XRF scanned the surface of the objects, revealing elements related to both the raw material—a copper alloy with tin and lead, together with trace elements related to the specific mining location of the ores, and the depositional environment of the objects–such as iron. LIBS allowed a more in-depth stratigraphic analysis, which indicated a higher copper ratio—compared to iron—as the kinetic series advance, fact that sustains the idea that the major iron input was coming from the depositional environment. Both XRF and LIBS results were consistent with high elemental variability, probably due to the nature of the original material and the influence of the deposition soil conditions.

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Remarkable corrosion resumption of archaeological bronzes, induced by the oxidation of ternary Cu-Sn-S phases in atmosphere, after long-term burial with sulfides

Cited by 18 publications

References 57 publications

Corrosion products characterisation aimed at restoration of Bronze Age metal artefacts from Garda Lake

Corrosion products characterisation aimed at restoration of Bronze Age metal artefacts from Garda Lake

Microstructure and phase composition of bronze Montefortino helmets discovered Mediterranean seabed to explain an unusual corrosion

Investigation on Metal Adornments From Ancient Eastern Europe

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