Situla EMT09-554.665 - Tin Bronze - Iron Age - Switzerland

Situla EMT09-554.665 - Tin Bronze - Iron Age - Switzerland

Situla EMT09-554.665

Christian. Degrigny (HE-Arc CR, Neuchâtel, Neuchâtel, Switzerland) & Marie-Jeanne. Scholl (HE-Arc CR, Neuchâtel, Neuchâtel, Switzerland) & Valentin. Boissonnas (HE-Arc CR, Neuchâtel, Neuchâtel, Switzerland)

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Credit HE-Arc CR, M-J.Scholl.

Fig. 1: Tin bronze Celtic situla (Archeodunum (Gollion), 2009) inverted as found in situ,

Copper alloy situla (Fig. 1). Attached to two riveted iron loops is an iron handle terminating in two swan heads (not shown here). Dimensions of the main body: Hmax = 340mm, Ømax = 220mm.

Situla

Mormont sanctuary, La Sarraz, Vaud, Switzerland

Excavated in 2011

Iron Age

La Tène D

Soil

Musée cantonal d’archéologie et d’histoire, Lausanne, Vaud

Musée cantonal d’archéologie et d’histoire, Lausanne, Vaud

EMT09/554.665

Not conserved

Complementary information

The size and quality of the object makes it likely that is was reserved for important occasions or for ritual use. Secondary use could be a votive offering. Burial condition: inside a 3 meters deep hole in upside-down position.

Credit HE-Arc CR, M-J.Scholl.

Fig. 2: Location of sampling area and sample selected from detached fragments,

The schematic representation below gives an overview of the corrosion layers encountered on the situla from a first visual macroscopic observation (additional e and i within the coding correspond to strata in contact with the environment (e) and internal strata (i)).

Credit HE-Arc CR, M-J.Scholl.

Fig. 3: Stratigraphic representation of the situla in cross-section by macroscopic observation,

Credit HE-Arc CR, M-J.Scholl.

Fig. 4: Micrograph of the cross-section showing the location of Fig. 6. Unetched, dark field, 50x,

The sample was cut from a detached fragment of the upper part of the main body of the situla in Fig. 2. The cross-section is representative of the entire thickness (0.5 mm) of the object’s body where on the outside there is a thicker accumulation of corrosion including curly malachite clusters (Fig. 3). A metallic core is still present inside the corrosion products layers (Fig. 4).

Tin Bronze

Cold worked (hammering on a counter-mould), annealed but no final annealing

None

HE-Arc CR, Neuchâtel, Neuchâtel

Musée cantonal d’archéologie et d’histoire, Lausanne, Vaud

2014, metallography and chemical analyses (FTIR, SEM-EDS)

Complementary information

Nothing to report.

Analyses performed:

Metallography (etched with ferric chloride reagent), SEM-EDS, FTIR, Raman spectroscopy and XRD.

The remaining metal is a dense tin bronze (Fig. 7, Table 1), showing no inclusion. In bright field, the etched alloy shows a structure principally consisting of polygonal alpha phase grains (Fig. 8). Some of the grains include twin lines (Fig. 9). The presence of strain lines (slip lines) indicates a final cold work without annealing (Fig. 9).

 

Elements Cu Sn
mass% 90 10

Table 1: Chemical composition of the metal. Method of analysis: SEM-EDS, Lab of Electronic Microscopy and Microanalysis, IMA (Néode), HEI Arc.

Credit HEI Arc, S.Ramseyer.

Fig. 7: SEM image, BSE-mode, of the metal sample from Fig. 4. Area of Fig. 8 is marked by a rectangle,

Credit HE-Arc CR.

Fig. 8: Micrograph of the etched metal structure from Fig. 7 (detail), etched, bright field, 50x. The alpha phase of the alloy shows polygonal grains. Area of Fig. 9 is marked by a rectangle,

Credit HE-Arc CR.

Fig. 9: Micrograph of the selected area of Fig. 8, etched, bright field, 500x. The grains show both twin and strain lines,

Polygonal grain with twin and strain lines

Cu

Sn

Complementary information

Nothing to report.

The corrosion crust is heterogeneous and has in places completely replaced the metal. The metal – corrosion products interface is irregular due to transgranular corrosion (Figs 7-8). In most cases, the corrosion crust can be divided in three main layers: an inner compact blue layer directly on the metal core (CP5, Figs. 6, 10 and 11 and CP3, Fig. 5). In areas of extensive corrosion this blue layer coexists with a friable green layer (CP4, Figs. 6, 10 and 11 and CP2, Fig. 5). Depending on the area either a very fine dark green (CP3, Fig. 6 and Fig. 10) or red corrosion layer (CP2, Fig. 6 and Fig. 10) marks the limit of the original surface. It is followed by an external fourth layer, consisting of friable and sometimes curly pale green corrosion products intermingled with soil products (CP1, Fig. 6 and Fig. 10 and 13). In heavily worked and fragile parts of the object a cleavage between the inner layers of blue and green corrosion is present, rendering the green corrosion vulnerable to loss (Fig. 11).

There are 2 stratigraphies (Fig. 5 corresponding to the interior face of the situla and Fig. 6 to its exterior face). The strata are similar in composition but their coding is different: CP1 to CP3 in Fig. 5 correspond to CP3 to CP5 in Fig. 6. Since the stratigraphy of Fig. 6 is more complete, the composition of each of its strata is given below.

The inner layers (CP3-CP5) are Sn and O-rich and depleted in Cu (Table 2). The outer layers (CP1 and CP2) are Cu and O-rich, contain no Sn, and are contaminated with Ca, Si, Al and Fe coming from the soil (Fig. 12). The colour of the corrosion crust varies according to the content of Sn (the more Sn, the darker green or blue the corrosion). FTIR on the inner blue (CP5 and Fig. 14) and outer green (CP1 and Fig. 15) layers were difficult to interpret. Only malachite could be identified in both cases. XRD spectra could not be interpreted because of the deficiency of peaks.

The limit of the original surface is well defined (interface of CP1 and CP2) but due to the fragility of the inner corrosion layers it was difficult to uncover.

Elements

 O Cu Sn
Outer green layer (CP1) +++ +++ nd
Inner green layer (CP4) ++ + +++
Inner blue layer (CP5) ++ + +++
Remnant metal phase nd +++ +

Table 2: Chemical composition of the corrosion crust from Fig. 10. SEM-EDS, Lab of Electronic Microscopy and Microanalysis, IMA (Néode) (+++: high concentration, ++ medium concentration, + low concentration, nd: not-detected).

Credit HE-Arc CR.

Fig. 10: Micrograph of the metal sample from Fig. 4, unetched, dark field, 50x. Areas of Fig. 11 (bottom, corresponding to the stratigraphy of Fig. 5) and Figs. 12 and 13 (top, corresponding to the stratigraphy of Fig. 6) are marked by a rectangle. Codes are those of Fig. 6,

Credit HEI Arc, S.Ramseyer.

Fig. 11: SEM image, BSE-mode of the metal sample from Fig. 10 (detail) showing cleavage between the inner blue (CP5) and green (CP4) layers of Fig. 6,

Credit HEI Arc, S.Ramseyer.

Fig. 12: SEM image, SE-mode, and elemental chemical distribution of the selected area of Fig. 10. In red: the limit of the original surface highlighted by the enriched tin layer. Method of examination: SEM-EDS, Lab of Electronic Microscopy and Microanalysis, IMA (Néode), HEI Arc,

Credit HE-Arc CR.

Fig. 13: Micrograph of the metal/corrosion interface (detail of Fig. 10) unetched, dark field, 100x.The outer layer (CP1 of Fig, 6) incorporates soil material and the thin dark layer (CP2 of Fig, 6) highlights the limit of the original surface,

Credit HE-Arc CR.

Fig. 14: FTIR spectrum (ATR mode) of the inner blue layer compared to the silicate and malachite standard spectrum. Method of analysis: FTIR spectroscopy, HE- Arc CR,

Credit HE-Arc CR.

Fig. 15: FTIR spectrum (ATR mode) of the outer green layer compared to the malachite standard spectrum. Method of analysis: FTIR spectroscopy, HE-Arc CR.,

Multiform - transgranular

Type I (Robbiola)

Complementary information

Nothing to report.

Fig. 6: Stratigraphic representation of the object in cross-section using the MiCorr application. The characteristics of the strata are only accessible by clicking on the drawing that redirects you to the search tool by stratigraphy representation. This representation shows the interior face and can be compared to Fig. 10 (top square), Credit HE-Arc CR, M-J.Scholl.
Fig. 5: Stratigraphic representation of the object in cross-section using the MiCorr application. The characteristics of the strata are only accessible by clicking on the drawing that redirects you to the search tool by stratigraphy representation. This representation shows the exterior face and can be compared to Fig. 10 (bottom square), Credit HE-Arc CR, M-J.Scholl.

Based on the analyses carried out, the schematic representation of the stratigraphy of corrosion layers (Fig. 3) was corrected (additional e and i within the coding correspond to strata in contact with the environment (e) and internal strata (i)).

Credit HE-Arc CR, M-J.Scholl.

Fig. 16: Improved stratigraphic representation of the situla from visual observations and analyses,

The metal structure of this low-tin bronze shows extensive cold work and multiple annealing cycles with a final cold work. The total absence of inclusions highlights a highly developed knowledge in bronze metallurgy. The metal is much corroded. Transgranular corrosion is visible. The majority of the internal corrosion products are composed of copper carbonates that have replaced much of the metal. Curly malachite has developed in clusters on the outside of the surface. This pattern is characteristic of a long-term burial period. The presence of inner enriched Sn layers shows a decuprification phenomenon (dissolution of Cu). Because of the friable nature of the inner green layer that supports the limit of the original surface, as well as its cleavage with the blue layer underneath, the original surface has become very fragile. The corrosion is thought to be of type 1 according to Robbiola et al. 1998.

References on object and sample

Reference object

1. Archeodunum (Gollion) (2009). Le Mormont : un sanctuaire des Helvètes en terre vaudoise vers 100 avant J.-C. Section de l'archéologie cantonale, Lausanne.

 

Reference sample

2. Scholl, M.-J (2013) Situle en bronze et anse en fer, EMT09/554.665, vers 100 av. J.-C., La Sarraz/Eclépens, Le Mormont (VD), Musée cantonal d’archéologie et d’histoire, Lausanne. Rapport d’intervention, Haute Ecole Arc de Conservation-restauration, Neuchâtel [not published].
3. Eggert, G. (2007) Pseudomorph or corrosion? The enigma of the curly malachite, in Metal07 - Proceedings of the International Conference on Metals Conservation, Degrigny, C., Van Langh, R., Ankersmit, B. and Joosten, I. (eds), Rijksmuseum, Amsterdam (2007), 1, 57-60.

References on analytic methods and interpretation
4. Robbiola, L., Blengino, J-M., Fiaud, C. (1998) Morphology and mechanisms of formation of natural patinas on archaeological Cu-Sn alloys, Corrosion Science, 40, 12, 2083-2111.